WorldWideScience

Sample records for di-hydroxybenzenes catechol resorcinol

  1. Di-hydroxybenzenes: Catechol, resorcinol, and hydroquinone

    Energy Technology Data Exchange (ETDEWEB)

    Verevkin, Sergey P. [Department of Physical Chemistry, University of Rostock, 18055 Rostock (Germany)], E-mail: sergey.verevkin@uni-rostock.de; Kozlova, Svetlana A. [Department of Physical Chemistry, University of Rostock, 18055 Rostock (Germany)

    2008-05-30

    Molar enthalpies of sublimation of 1,2-di-hydroxybenzene, 1,3-di-hydroxybenzene, and 1,4-di-hydroxybenzene were obtained from the temperature dependence of the vapor pressure measured by the transpiration method. The molar enthalpies of fusion of 1,2- and 1,4-isomers were measured by differential scanning calorimetry (DSC). A large number of the primary experimental results on the temperature dependences of vapor pressure and phase transitions have been collected from the literature and have been treated in a uniform manner in order to derive sublimation, vaporization and fusion enthalpies of di-hydroxybenzenes at the reference temperature 298.15 K. The data sets on phase transitions were checked for internal consistency. This collection together with the new experimental results reported here has helped to resolve contradictions in the available thermochemical data and to recommend consistent and reliable sublimation, vaporization and fusion enthalpies for all three isomers under study.

  2. Application of an easily water-compatible hypercrosslinked polymeric adsorbent for efficient removal of catechol and resorcinol in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Huang Jianhan, E-mail: xiaomeijiangou@yahoo.com.cn [College of Chemistry and Chemical Engineering, Central South University, Changsha 410083 (China); Huang Kelong; Yan Cheng [College of Chemistry and Chemical Engineering, Central South University, Changsha 410083 (China)

    2009-08-15

    An easily water-compatible hypercrosslinked resin HJ-1 was developed for adsorbing catechol and resorcinol in aqueous solution in this study. Its adsorption performances for catechol and resorcinol were investigated in aqueous solution by using the commercial Amberlite XAD-4 as a reference. The adsorption dynamic curves were measured and the adsorption obeyed the pseudo-second-order rate equation of Boyer and Hsu. The adsorption isotherms were scaled and Freundlich isotherm model characterized the adsorption better. The adsorption thermodynamic parameters were calculated and the adsorption was an exothermic, favorable, and more ordered process. The fact that the adsorption capacity of catechol was larger than resorcinol and the adsorption enthalpy of catechol was more negative than resorcinol can be explained in terms of the solubility and the polarity of two adsorbates.

  3. Simultaneous Determination of Hydroquinone, Catechol and Resorcinol at Graphene Doped Carbon Ionic Liquid Electrode

    Directory of Open Access Journals (Sweden)

    Li Ma

    2012-01-01

    Full Text Available A new composite electrode has been prepared with doping graphene into the paste consisting graphite and ionic liquid, n-octyl-pyridinum hexafluorophosphate (OPFP. This electrode shows an excellent electrochemical activity for the redox of hydroquinone (HQ, catechol (CC, and resorcinol (RS. In comparison with bare paste electrode, the redox peaks of three isomers of dihydroxybenzene can be obviously, simultaneously observed at graphene doping paste electrode. Under the optimized condition, the simultaneous determination of HQ, CC, and RS in their ternary mixture can be carried out with a differential pulse voltammetric technique. The peak currents are linear to the concentration of HQ, CC, and RS in the range form 1×10−5 to 4×10−4, 1×10−5 to 3×10−4, and 1×10−6 to 1.7×10−4 mol L−1, respectively. The limits of detection are 1.8×10−6 mol L−1 for HQ, 7.4×10−7 mol L−1 for CC, and 3.6×10−7 M for RS, respectively.

  4. Fabrication of Graphene/polydopamine Modified Electrode and Simultaneous Determination of Hydroquinone, Catechol and Resorcinol

    Institute of Scientific and Technical Information of China (English)

    QI; Ya’e; SONG; Hai; REN; Xuefeng; XU; Li

    2015-01-01

    Graphite oxide(GO) prepared by an improved Hummers method was reduced to graphene(Gr) by a hydrothermal method with Na BH4 as a reductant. Gr sample was characterized by scanning electron microscopy, X-ray diffraction and BET specific surface area analysis, respectively. The Gr-PDA modified glass carbon electrode(Gr-PDA/GCE) was designed and constructed for the simultaneous determination of hydroquinone(HQ), catechol(CC) and resorcinol(RC). The electrochemical behaviors of HQ, CC and RC on the Gr-PDA/GCE were investigated by cyclic voltammetry(CV) and differential pulse voltammetry(DPV) techniques. The results show that there are the three detections with a high peak current on the modified electrode duo to the synergetic effects of Gr and PDA, the linear response ranges for HQ and CC are 40.2–1559.6 and 24.7–1105.0 μM and the detection limits(S/N=3) are 13.4 and 8.2 μM, respectively.

  5. Simultaneous Detection and Estimation of Catechol, Hydroquinone, and Resorcinol in Binary and Ternary Mixtures Using Electrochemical Techniques.

    Science.gov (United States)

    Hossain, Md Uzzal; Rahman, Md Toufiqur; Ehsan, Md Qamrul

    2015-01-01

    Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) were performed with a glassy carbon electrode (GCE) modified with polyglutamic acid (PGA) on the three dihydroxybenzene isomers, catechol (CT), hydroquinone (HQ), and resorcinol (RS). At bare GCE, these isomers exhibited voltammograms with highly overlapped redox peaks that impeded their simultaneous detection in binary and ternary mixtures. On the contrary, at PGA modified GCE binary and ternary mixtures of the dihydroxybenzene isomers showed well-resolved redox peaks in both CV and DPV experiments. This resolving ability of PGA modified GCE proves its potential to be exploited as an electrochemical sensor for the simultaneous detection of these isomers.

  6. Simultaneous Detection and Estimation of Catechol, Hydroquinone, and Resorcinol in Binary and Ternary Mixtures Using Electrochemical Techniques

    Directory of Open Access Journals (Sweden)

    Md. Uzzal Hossain

    2015-01-01

    Full Text Available Cyclic voltammetry (CV and differential pulse voltammetry (DPV were performed with a glassy carbon electrode (GCE modified with polyglutamic acid (PGA on the three dihydroxybenzene isomers, catechol (CT, hydroquinone (HQ, and resorcinol (RS. At bare GCE, these isomers exhibited voltammograms with highly overlapped redox peaks that impeded their simultaneous detection in binary and ternary mixtures. On the contrary, at PGA modified GCE binary and ternary mixtures of the dihydroxybenzene isomers showed well-resolved redox peaks in both CV and DPV experiments. This resolving ability of PGA modified GCE proves its potential to be exploited as an electrochemical sensor for the simultaneous detection of these isomers.

  7. The Nitrite-Scavenging Properties of Catechol, Resorcinol, and Hydroquinone: A Comparative Study on Their Nitration and Nitrosation Reactions.

    Science.gov (United States)

    Lu, Yunhao; Dong, Yanzuo; Li, Xueli; He, Qiang

    2016-10-14

    The nitration and nitrosation reactions of catechol, resorcinol, and hydroquinone (0.05 mmol/L) with sodium nitrite (0.05 mmol/L) at pH 3 and 37 °C were studied by using liquid chromatography and mass spectrometry (LC-MS) and atom charge analysis, which was aimed to provide chemical insight into the nitrite-scavenging behavior of polyphenols. The 3 benzenediols showed different mechanisms to scavenge nitrite due to their differences in hydroxyl position. Catechol was nitrated with 1 NO2 group at the hydroxyl oxygen, and resorcinol was nitrosated with 2 NO groups at the C2 and C4 (or C6 ) positions of the benzene ring. Hydroquinone could scavenge nitrite through both nitration and nitrosation mechanisms. The nitrated hydroquinone had 1 NO2 group at the hydroxyl oxygen in the molecule, while the nitrosated 1 containing 2 NO groups at the benzene ring might have 3 structure probabilities. The results may provide a structure-activity understanding on the nitrite-scavenging property of polyphenols, so as to promote their application in the food industry for the removal of possibly toxic nitrites found in many vegetables and often in processed meat products. © 2016 Institute of Food Technologists®.

  8. INHIBITION KINETICS DURING THE OXIDATION OF BINARY MIXTURES OF PHENOL WITH CATECHOL, RESORCINOL AND HYDROQUINONE BY PHENOL ACCLIMATED ACTIVATED SLUDGE

    Directory of Open Access Journals (Sweden)

    C. C. Lobo

    Full Text Available Abstract In this work the aerobic degradation of phenol (PH, catechol (CA, resorcinol (RE, hydroquinone (HY and of the binary mixtures PH+CA, PH+RE, PH+HY by phenol-acclimated activated sludge was studied. Single substrate experiments show a Haldane-type dependence of the respiration rate on PH, RE and HY, while CA corresponded to the Monod model. Binary substrate experiments demonstrated that the presence of a second substrate only affected the kinetics, but not the stoichiometry of the oxidation of the compounds tested. While CA inhibited the oxidation of PH, PH inhibited the oxidation of RE and HY. A mathematical model was developed to represent the aerobic biodegradation of the phenolic compounds tested. The agreement between the proposed model and the experimental data indicates that the proposed model can be useful for predicting substrate and dissolved oxygen concentrations in bioreactors treating phenolic wastewaters.

  9. Simultaneous determination of hydroquinone, catechol and resorcinol by voltammetry using graphene screen-printed electrodes and partial least squares calibration.

    Science.gov (United States)

    Aragó, Miriam; Ariño, Cristina; Dago, Àngela; Díaz-Cruz, José Manuel; Esteban, Miquel

    2016-11-01

    Catechol (CC), resorcinol (RC) and hydroquinone (HQ) are dihydroxybenzene isomers that usually coexist in different samples and can be determined using voltammetric techniques taking profit of their fast response, high sensitivity and selectivity, cheap instrumentation, simple and timesaving operation modes. However, a strong overlapping of CC and HQ signals is observed hindering their accurate analysis. In the present work, the combination of differential pulse voltammetry with graphene screen-printed electrodes (allowing detection limits of 2.7, 1.7 and 2.4µmolL(-1) for HQ, CC and RC respectively) and the data analysis by partial least squares calibration (giving root mean square errors of prediction, RMSEP values, of 2.6, 4.1 and 2.3 for HQ, CC and RC respectively) has been proposed as a powerful tool for the quantification of mixtures of these dihydroxybenzene isomers. The commercial availability of the screen-printed devices and the low cost and simplicity of the analysis suggest that the proposed method can be a valuable alternative to chromatographic and electrophoretic methods for the considered species. The method has been applied to the analysis of these isomers in spiked tap water.

  10. Molecular, spectroscopic and thermal studies on catechol, 4,5-dibromocatechol, resorcinol, hydroquinone and 4-4‧-dihydroxybiphenyl derivatives armed with benzothiazole moieties

    Science.gov (United States)

    Alshargabi, Arwa; Yeap, Guan-Yeow; Mahmood, Wan Ahmad Kamil; Samikannu, Rakesh

    2013-05-01

    A new series of catechol, 4,5-dibromocatechol, resorcinol, hydroquinone and 4-4'-dihydroxybiphenyl derivatives possessing two benzothiazole moieties at respective positions of 1,2, 1,3, 1,4 and/or 4,4' has successfully been synthesized. The molecular structures were fully elucidated by spectroscopic techniques (1H NMR, 13C NMR and two dimensional COSY, HMBC, HMQC, DEPT-135 and DEPT-90). The connectivity study between the cause of using different core systems in the target compounds and the anisotropic behavior as inferred from phase transition temperature and relevant morphology studies has led to some unique features arising from this series. Compounds with ortho substituent exhibit enantiotropic N and SmA phases. The analogues containing resorcinol and 4,4'-disubstituentbiphenyl show enanotiotropic nematic behavior while the hydroquinone derivative induces the formation of monotropic nematogen. An extensive study to further substantiate the relationship between the stability of the nematic phase and associated transition temperatures due to different core systems is also reported.

  11. Simultaneous Electrochemical Determination of Hydroquinone, Catechol and Resorcinol at Nitrogen Doped Porous Carbon Nanopolyhedrons-multiwall Carbon Nanotubes Hybrid Materials Modified Glassy Carbon Electrode

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Wei; Wu, Liang; Zhang, Xiaohua; Chen, Jinhua [Hunan Univ., Changsha (China)

    2014-01-15

    The nitrogen doped porous carbon nanopolyhedrons (N-PCNPs)-multi-walled carbon nanotubes (MWCNTs) hybrid materials were prepared for the first time. Combining the excellent catalytic activities, good electrical conductivities and high surface areas of N-PCNPs and MWCNTs, the simultaneous determination of hydroquinone (HQ), catechol (CC) and resorcinol (RE) with good analytical performance was achieved at the N-PCNPs-MWCNTs modified electrode. The linear response ranges for HQ, CC and RE are 0.2-455 μM, 0.7-440 μM and 3.0-365 μM, respectively, and the detection limits (S/N = 3) are 0.03 μM, 0.11 μM and 0.38 μM, respectively. These results are much better than that obtained on some graphene or CNTs-based materials modified electrodes. Furthermore, the developed sensor was successfully applied to simultaneously detect HQ, CC and RE in the local river water samples.

  12. Electrochemical behavior of catechol, resorcinol and hydroquinone at graphene-chitosan composite film modified glassy carbon electrode and their simultaneous determination in water samples

    Energy Technology Data Exchange (ETDEWEB)

    Yin Huanshun [College of Chemistry and Material Science, Shandong Agricultural University, Taian, 271018 Shandong (China); College of Resources and Environment, Shandong Agricultural University, Taian 271018, Shandong (China); Zhang Qingming [College of Resources and Environment, Shandong Agricultural University, Taian 271018, Shandong (China); College of Chemistry and Pharmaceutical Sciences, Qingdao Agriculture University, Qingdao 266109 (China); Zhou Yunlei [College of Life Science, Beijing Normal University, 100875 Beijing (China); Ma Qiang; Liu Tao [College of Chemistry and Material Science, Shandong Agricultural University, Taian, 271018 Shandong (China); Zhu Lusheng, E-mail: lushzhu@sdau.edu.c [College of Resources and Environment, Shandong Agricultural University, Taian 271018, Shandong (China); Ai Shiyun, E-mail: ashy@sdau.edu.c [College of Chemistry and Material Science, Shandong Agricultural University, Taian, 271018 Shandong (China)

    2011-02-15

    Graphene-chitosan composite film modified glassy carbon electrode was prepared and characterized. The fabricated electrode showed excellent electrochemical catalytic activities towards the oxidation of catechol (CT), resorcinol (RS) and hydroquinone (HQ). The oxidation overpotentials of CT, RS and HQ decreased significantly and the corresponding oxidation currents increased remarkably compared with those obtained at the bare GCE and chitosan modified GCE. Some kinetic parameters, such as the electron transfer number (n), proton transfer number (m), charge transfer coefficient ({alpha}) and the apparent heterogeneous electron transfer rate constant (k{sub s}), were calculated. Differential pulse voltammetry was used for the simultaneous determination of CT, RS and HQ in their ternary mixture. The peak-to-peak potential separations between CT and RS, RS and HQ, and HQ and CT were 0.388, 0.484 and 0.096 V, respectively. The calibration curves for CT, RS and HQ were obtained in the range of 1 x 10{sup -6} to 4 x 10{sup -4}, 1 x 10{sup -6} to 5.5 x 10{sup -4} and 1 x 10{sup -6} to 3 x 10{sup -4} mol L{sup -1}, respectively. The detection limits were 7.5 x 10{sup -7} mol L{sup -1} (S/N = 3).

  13. Theoretical Study on Reaction Pathways Leading to CO and CO2 in the Pyrolysis of Resorcinol.

    Science.gov (United States)

    Furutani, Yuki; Kudo, Shinji; Hayashi, Jun-Ichiro; Norinaga, Koyo

    2017-01-26

    Possible pathways for the pyrolysis of resorcinol with the formation of CO and CO2 as final products were proposed and evaluated using ab initio calculations. Our experimental study revealed that large quantities of CO2 are generated in the pyrolysis of 1,3-dihydroxybenzene (resorcinol), while the pyrolysis of the dihydroxybenzene isomers 1,2-dihydroxybenzene (catechol) and 1,4-dihydroxybenzene (hydroquinone) produces little CO2. The fate of oxygen atoms in catechol and hydroquinone was essentially the formation of CO. In the proposed pathways, the triplet ground state m-benzoquinone was generated initially from simultaneous cleavage of the two O-H bonds in resorcinol. Subsequently, the direct cleavage of a C-C bond of the m-benzoquinone diradical yields 2-oxidanylcyclopenta-2,4-dien-1-yl-methanone, which can be converted via two channels: release of CO from the aldehyde radical group and combination of the ketone radical and carbon atom in the aldehyde radical group to form the 6-oxabicyclo[3.2.0]hepta-2,4-dien-7-one, resulting in the release of CO2. Potential energy surfaces along the proposed reaction pathways were calculated employing the CBS-QB3 method, and the rate constants at the high-pressure limit were also evaluated based on transition-state theory to assess the feasibility of the proposed reaction pathways.

  14. Biodegradation of resorcinol by Pseudomonas sp.

    Directory of Open Access Journals (Sweden)

    Nader Hajizadeh

    2016-11-01

    Full Text Available Objective: To investigate the ability of Pseudomonas sp. isolated from East Azarbaijan, Iran in bioremediation of resorcinol. Methods: Resorcinol biodegradation was evaluated using spectrophotometry and confirmed by gas chromatography-mass spectroscopy. Results: This isolate was able to remove up to 37.12% of resorcinol from contaminated water. Reusability experiments had confirmed the biodegradation process which produced seven intermediate compounds. These intermediates were characterized by gas chromatographymass spectroscopy technique. The products of resorcinol biodegradation were apparently 1, 4-cyclohexadiene, nonadecene, 2-heptadecanone, 1-isopropyl-2-methoxy-4-methylbenzene, hexadecanoic acid, 9-octadecenoic acid, phenol and 5-methyl-2-(1-methylethyl. Conclusions: The findings revealed that Pseudomonas sp. is able to degrade resorcinol. Because of being an indigenous organism, this isolate is more compatible with the climate of the northwest region of Iran and possibly will be used for degradation of other similar aromatic compounds.

  15. Biodegradation of resorcinol byPseudomonas sp.

    Institute of Scientific and Technical Information of China (English)

    Nader Hajizadeh; Najibeh Shirzad; Ali Farzi; Mojtaba Salouti; Azra Momeni

    2016-01-01

    ABSTRACT Objective:To investigate the ability ofPseudomonas sp. isolated from East Azarbaijan, Iran in bioremediation of resorcinol. Methods: Resorcinol biodegradation was evaluated using spectrophotometry and confirmed by gas chromatography-mass spectroscopy. Results:This isolate was able to remove up to 37.12% of resorcinol from contaminated water. Reusability experiments had confirmed the biodegradation process which produced seven intermediate compounds. These intermediates were characterized by gas chromatography-mass spectroscopy technique. The products of resorcinol biodegradation were apparently 1, 4-cyclohexadiene, nonadecene, 2-heptadecanone, 1-isopropyl-2-methoxy-4-methylbenzene, hexadecanoic acid, 9-octadecenoic acid, phenol and 5-methyl-2-(1-methylethyl). Conclusions: The findings revealed thatPseudomonas sp. is able to degrade resorcinol. Because of being an indigenous organism, this isolate is more compatible with the climate of the northwest region of Iran and possibly will be used for degradation of other similar aromatic compounds.

  16. Antidermatophytic Action of Resorcinol Derivatives: Ultrastructural Evidence of the Activity of Phenylethyl Resorcinol against Microsporum gypseum

    Directory of Open Access Journals (Sweden)

    Carlo Romagnoli

    2016-09-01

    Full Text Available In this work, we evaluated the antidermatophytic activities of three resorcinol derivatives that have a history of use in dermo-cosmetic applications to discover molecules with multiple dermatological activities (i.e., multi-target drugs, thereby reducing the cost and time necessary for new drug development. The antidermatophytic activities of the three skin lighteners were evaluated relative to the known antifungal drug fluconazole on nine dermatophytes responsible for the most common dermatomycoses: Microsporum gypseum, Microsporum canis, Trichophyton violaceum, Arthroderma cajetani, Trichophyton mentagrophytes, Epidermophyton floccosum, Nannizzia gypsea, Trichophyton rubrum and Trichophyton tonsurans. Among the three tested resorcinols, only two showed promising properties, with the ability to inhibit the growth of all tested dermatophytes; additionally, the IC50 values of these two resorcinols against the nine dermatophytes confirmed their good antifungal activity, particularly for phenylethyl resorcinol against M. gypseum. Ultrastructural alterations exhibited by the fungus were observed using scanning electron microscopy and transmission electron microscopy and reflected a dose-dependent response to treatment with the activation of defence and self-preservation strategies.

  17. Antidermatophytic Action of Resorcinol Derivatives: Ultrastructural Evidence of the Activity of Phenylethyl Resorcinol against Microsporum gypseum.

    Science.gov (United States)

    Romagnoli, Carlo; Baldisserotto, Anna; Vicentini, Chiara B; Mares, Donatella; Andreotti, Elisa; Vertuani, Silvia; Manfredini, Stefano

    2016-09-30

    In this work, we evaluated the antidermatophytic activities of three resorcinol derivatives that have a history of use in dermo-cosmetic applications to discover molecules with multiple dermatological activities (i.e., multi-target drugs), thereby reducing the cost and time necessary for new drug development. The antidermatophytic activities of the three skin lighteners were evaluated relative to the known antifungal drug fluconazole on nine dermatophytes responsible for the most common dermatomycoses: Microsporum gypseum, Microsporum canis, Trichophyton violaceum, Arthroderma cajetani, Trichophyton mentagrophytes, Epidermophyton floccosum, Nannizzia gypsea, Trichophyton rubrum and Trichophyton tonsurans. Among the three tested resorcinols, only two showed promising properties, with the ability to inhibit the growth of all tested dermatophytes; additionally, the IC50 values of these two resorcinols against the nine dermatophytes confirmed their good antifungal activity, particularly for phenylethyl resorcinol against M. gypseum. Ultrastructural alterations exhibited by the fungus were observed using scanning electron microscopy and transmission electron microscopy and reflected a dose-dependent response to treatment with the activation of defence and self-preservation strategies.

  18. How Many Drugs Are Catecholics

    Directory of Open Access Journals (Sweden)

    Da-Peng Yang

    2007-04-01

    Full Text Available By examination of the 8659 drugs recorded in the Comprehensive Medicinal Chemistry (CMC database, 78 catecholics (including five pyrogallolics were identified, of which 17 are currently prescribed by FDA. Through analyzing the substitutent patterns, ClogPs and O-H bond dissociation enthalpies(BDEs of the catecholic drugs, some molecular features that may benefit circumventing the toxicity of catecholics were revealed: i strong electron-donating substituents are excluded; ii ClogP 3; iii an energy penalty exists for quinone formation. Besides, the present analyses also suggest that the clinical usage and dosage of currently prescribed catecholic drugs are of importance in designing or screening catecholic antioxidants.

  19. Synthesis and Analysis of Resorcinol-Acetone Copolymer

    Directory of Open Access Journals (Sweden)

    Gen-ichi Konishi

    2009-01-01

    Full Text Available Synthesis and characterization of resorcinol-acetone copolymer is described. The polymer was prepared by trifluoroacetic acid-catalyzed polymerization of resorcinol with acetone. According to the 1H-NMR, 13C-NMR, and MALDI-TOF Mass spectra data, the obtained polymer had three types of repeating units: isopropylidene bridged-resorcinol, chromane ring, and spiro-shaped double chromane ring, indicating that polymerization proceeded via simultaneous addition-condensation and cyclization of resorcinol with acetone. The obtained polymer can be useful not only for the development of plastic materials such as thermosets, adhesives, and coatings but also for the synthesis of biomaterials such as antimicrobial agents, pesticides, and medicines.

  20. Alkyl resorcinols in grains from plants from the family Gramineae

    Directory of Open Access Journals (Sweden)

    Grzegorz Kubus

    2014-02-01

    Full Text Available 5-n-alkylresorcinols were found in 22 of the 27 studied species of grasses. In Agropyron caninum and Bromus macrostachys only the content of alkyl resorcinols was determined, in Agropyron repens, Bromus mollis and Elymus arenarius the composition of alkyl resorcinol homologues was also established. When calculated per gram of dry mass of air-dried grains, the content of alkyl resorcinols was found to be: in the genus Agropyron - approximately 715 µg, in the genus Bromus approximately 60 µg and in Elymus arenarius, 272 µg. The homologues of alkyl resorcinods in the studied genera of grasses differ from the homologues found in wheat or rye by their greater content of long-chain fractions.

  1. Boron complexing with H-resorcinol and acidic hydroxyxanthene dyes

    Energy Technology Data Exchange (ETDEWEB)

    Nazarenko, V.A.; Flyantikova, G.V.; Chekirda, T.N. (AN Ukrainskoj SSR, Odessa. Fiziko-Khimicheskij Inst.)

    1984-01-01

    Complex formation of boron with H-resorcinol (hr; 2,4-dihydroxybenzene-azo -8-hydroxynaphtalene-3,6-disulfonic acid) and acidic hydroxyxanthene dyes (hxd: fluorescein, eosine, erathrosine). Mixed-ligand complexes with a ratio of r:hr:hxd=1:1:1 are formed at pH=5-6. The chemism of the complex formation of boron with H-resorcinol and fluorescein has been studied. The stability constant of the complex is 1.12x10/sup 21/, the conditional molar absorptivitis 1.80x10/sup 0/. This complex formation reaction was used for photometric determination of boron in natural water.

  2. The Three Catecholics Benserazide, Catechol and Pyrogallol are GPR35 Agonists

    Directory of Open Access Journals (Sweden)

    Huayun Deng

    2013-04-01

    Full Text Available Nearly 1% of all clinically used drugs are catecholics, a family of catechol-containing compounds. Using label-free dynamic mass redistribution and Tango β-arrestin translocation assays, we show that several catecholics, including benserazide, catechol, 3-methoxycatechol, pyrogallol, (+-taxifolin and fenoldopam, display agonistic activity against GPR35.

  3. Sol-Gel Synthesis of Carbon Xerogel-ZnO Composite for Detection of Catechol

    Directory of Open Access Journals (Sweden)

    Dawei Li

    2016-04-01

    Full Text Available Carbon xerogel-zinc oxide (CXZnO composites were synthesized by a simple method of sol-gel condensation polymerization of formaldehyde and resorcinol solution containing zinc salt followed by drying and thermal treatment. ZnO nanoparticles were observed to be evenly dispersed on the surfaces of the carbon xerogel microspheres. The as-prepared CXZnO composites were mixed with laccase (Lac and Nafion to obtain a mixture solution, which was further modified on an electrode surface to construct a novel biosensing platform. Finally, the prepared electrochemical biosensor was employed to detect the environmental pollutant, catechol. The analysis result was satisfactory, the sensor showed excellent electrocatalysis towards catechol with high sensitivity (31.2 µA·mM−1, a low detection limit (2.17 µM, and a wide linear range (6.91–453 µM. Moreover, the biosensor also displayed favorable repeatability, reproducibility, selectivity, and stability besides being successfully used in the trace detection of catechol existing in lake water environments.

  4. Catechol biodegradation kinetics using Candida parapsilopsis

    OpenAIRE

    Maurício Rigo; Ranulfo Monte Alegre; José Raniere Mazile Vidal Bezerra; Narjara Coelho; Reinaldo Gaspar Bastos

    2010-01-01

    This study evaluated the biodegradation of catechol by a yeast strain of Candida parapsilopsis in standard medium in Erlenmeyer flasks. Results shown that the highest concentration of catechol caused the longer lag period, demonstrating that acclimatized cultures could completely degrade an initial catechol concentration of 910 mg/L within 48 h. Haldane's model validated the experimental data adequately for growth kinetics over the studied catechol concentration ranges of 36 to 910 mg/L. The ...

  5. Electrochemical sensor for catechol and dopamine based on a catalytic molecularly imprinted polymer-conducting polymer hybrid recognition element.

    Science.gov (United States)

    Lakshmi, Dhana; Bossi, Alessandra; Whitcombe, Michael J; Chianella, Iva; Fowler, Steven A; Subrahmanyam, Sreenath; Piletska, Elena V; Piletsky, Sergey A

    2009-05-01

    One of the difficulties with using molecularly imprinted polymers (MIPs) and other electrically insulating materials as the recognition element in electrochemical sensors is the lack of a direct path for the conduction of electrons from the active sites to the electrode. We have sought to address this problem through the preparation and characterization of novel hybrid materials combining a catalytic MIP, capable of oxidizing the template, catechol, with an electrically conducting polymer. In this way a network of "molecular wires" assists in the conduction of electrons from the active sites within the MIP to the electrode surface. This was made possible by the design of a new monomer that combines orthogonal polymerizable functionality; comprising an aniline group and a methacrylamide. Conducting films were prepared on the surface of electrodes (Au on glass) by electropolymerization of the aniline moiety. A layer of MIP was photochemically grafted over the polyaniline, via N,N'-diethyldithiocarbamic acid benzyl ester (iniferter) activation of the methacrylamide groups. Detection of catechol by the hybrid-MIP sensor was found to be specific, and catechol oxidation was detected by cyclic voltammetry at the optimized operating conditions: potential range -0.6 V to +0.8 V (vs Ag/AgCl), scan rate 50 mV/s, PBS pH 7.4. The calibration curve for catechol was found to be linear to 144 microM, with a limit of detection of 228 nM. Catechol and dopamine were detected by the sensor, whereas analogues and potentially interfering compounds, including phenol, resorcinol, hydroquinone, serotonin, and ascorbic acid, had minimal effect (< or = 3%) on the detection of either analyte. Non-imprinted hybrid electrodes and bare gold electrodes failed to give any response to catechol at concentrations below 0.5 mM. Finally, the catalytic properties of the sensor were characterized by chronoamperometry and were found to be consistent with Michaelis-Menten kinetics.

  6. Solar photocatalytic degradation of resorcinol a model endocrine disrupter in water using zinc oxide

    Energy Technology Data Exchange (ETDEWEB)

    Pardeshi, S.K. [Department of Chemistry, University of Pune, Ganeshkhind, Pune 411007 (India)], E-mail: skpar@chem.unipune.ernet.in; Patil, A.B. [Department of Chemistry, University of Pune, Ganeshkhind, Pune 411007 (India)

    2009-04-15

    Photocatalytic degradation (PCD) of resorcinol a potent endocrine disrupting chemical in aqueous medium was investigated by ZnO under sunlight irradiation in a batch photoreactor. The influence of various parameters such as photocatalyst amount, initial concentration of resorcinol and pH was examined for maximum PCD of resorcinol. A considerable influence of pH upon the chemical oxygen demand (COD) disappearance was observed. In general, neutral or basic pH is favorable for COD removal of resorcinol. PCD intermediates were identified using FTIR and GC/MS. Two of the initial oxidation intermediates detected were 1,2,4-trihydroxy-benzene and 1,2,3-trihydroxy-benzene. FTIR studies revealed 1,2,4-trihydroxy-benzene as the major PCD intermediate. A working photodegradation mechanism is also suggested for PCD of resorcinol. This work envisages the great potential that sunlight mediated photocatalysis has in the removal of resorcinol from waste water.

  7. Characterization of the action of tyrosinase on resorcinols.

    Science.gov (United States)

    Garcia-Jimenez, Antonio; Teruel-Puche, Jose Antonio; Berna, José; Rodriguez-Lopez, José Neptuno; Tudela, Jose; Garcia-Ruiz, Pedro Antonio; Garcia-Canovas, Francisco

    2016-09-15

    The action of tyrosinase on resorcinol and some derivatives (4-ethylresorcinol, 2-methylresorcinol and 4-methylresorcinol) was investigated. If the catalytic cycle is completed with a reductant such as ascorbic acid or an o-diphenol such as 4-tert-butylcatechol, these compounds act as substrates of tyrosinase in all cases. The reaction can also be carried out, adding hydrogen peroxide to the medium. All the above compounds were characterized as substrates of the enzyme and their kinetic constants, KM (Michaelis constant) and kcat (catalytic constant) were determined. Measurement of the activity of the enzyme after pre-incubation with resorcinol, 4-ethylresorcinol or 4-methylresorcinol points to an apparent loss of activity at short times, which could correspond to an enzymatic inactivation process. However, if the measurements are extended over longer times, a burst is observed and the enzymatic activity is recovered, demonstrating that these compounds are not suicide substrates of the enzyme. These effects are not observed with 2-methylresorcinol. The docking results indicate that the binding of met-tyrosinase with these resorcinols occurs in the same way, but not with 2-methylresorcinol, due to steric hindrance.

  8. Permeability changes of erythrocytes and liposomes by 5-(n-alk(en)yl) resorcinols from rye

    NARCIS (Netherlands)

    Kozubek, A.; Demel, R.A.

    1980-01-01

    5-(n-Alk(en)yl) resorcinols can induce potassium release from liposomes and erythrocytes. The results suggest that 5-(n-pentyl)resorcinol can induce a specific permeability to protons as well as to potassium and other small molecules. The highest permeability changes were found in the presence of 5-

  9. Synthesis of resorcinolic lipids bearing structural similarities to cytosporone A

    Directory of Open Access Journals (Sweden)

    Edson dos Anjos dos Santos

    2009-01-01

    Full Text Available Inspired by the structure and biological activities of resorcinolic lipids and, particularly cytosporone A- a potent inhibitor of plantule germination and growth, we have performed the synthesis of the analogs 3-heptyl-3-hydroxy-5,7-dimethoxy-2-benzofuran-1(3H-one (1 and 3-heptyl-3-hydroxy-4,6-dimethoxy-2-benzofuran-1(3H-one (2. The intermediates and products were submitted to allelopathic test using Lactuca sativa L. seeds. Target compound 1 showed an inhibitory effect on germination and growth of hypocotyl and radicle in milimolar range.

  10. Synthesis of resorcinolic lipids bearing structural similarities to cytosporone A

    Energy Technology Data Exchange (ETDEWEB)

    Santos, Edson dos Anjos dos; Beatriz, Adilson; Lima, Denis Pires de [Universidade Federal Mato Grosso do Sul (UFMS), Campo Grande, MS (Brazil). Centro de Ciencias Exatas e Tecnologia. Dept. de Quimica], e-mail: dlima@nin.ufms.br; Marques, Maria Rita; Leite, Carla Braga [Universidade Federal Mato Grosso do Sul (UFMS), Campo Grande, MS (Brazil). Centro de Ciencias Biologicas. Dept. de Morfofisiologia

    2009-07-01

    Inspired by the structure and biological activities of resorcinolic lipids and, particularly cytosporone A- a potent inhibitor of plantule germination and growth, we have performed the synthesis of the analogs 3-heptyl-3-hydroxy-5,7-dimethoxy-2-benzofuran-1(3H)-one (1) and 3-heptyl-3-hydroxy-4,6-dimethoxy-2-benzofuran-1(3H)-one (2). The intermediates and products were submitted to allelopathic test using Lactuca sativa L. seeds. Target compound 1 showed an inhibitory effect on germination and growth of hypocotyl and radicle in millimolar range. (author)

  11. Production of catechols: microbiology and technology

    NARCIS (Netherlands)

    Krab-Hüsken, L.E.

    2002-01-01

    Catechols play an important role in the fine-chemical and flavour industry, as well as in photography, dyeing fur, rubber and plastic production. Many of these compounds cannot easily be synthesised chemically, but some micro-organisms are capable of producing catechols fro

  12. A redox-neutral catechol synthesis

    Science.gov (United States)

    Wu, Qian; Yan, Dingyuan; Chen, Ying; Wang, Ting; Xiong, Feng; Wei, Wei; Lu, Yi; Sun, Wei-Yin; Li, Jie Jack; Zhao, Jing

    2017-01-01

    Ubiquitous tyrosinase catalyses the aerobic oxidation of phenols to catechols through the binuclear copper centres. Here, inspired by the Fischer indole synthesis, we report an iridium-catalysed tyrosinase-like approach to catechols, employing an oxyacetamide-directed C-H hydroxylation on phenols. This method achieves one-step, redox-neutral synthesis of catechols with diverse substituent groups under mild conditions. Mechanistic studies confirm that the directing group (DG) oxyacetamide acts as the oxygen source. This strategy has been applied to the synthesis of different important catechols with fluorescent property and bioactivity from the corresponding phenols. Finally, our method also provides a convenient route to 18O-labelled catechols using 18O-labelled acetic acid.

  13. A redox-neutral catechol synthesis.

    Science.gov (United States)

    Wu, Qian; Yan, Dingyuan; Chen, Ying; Wang, Ting; Xiong, Feng; Wei, Wei; Lu, Yi; Sun, Wei-Yin; Li, Jie Jack; Zhao, Jing

    2017-01-27

    Ubiquitous tyrosinase catalyses the aerobic oxidation of phenols to catechols through the binuclear copper centres. Here, inspired by the Fischer indole synthesis, we report an iridium-catalysed tyrosinase-like approach to catechols, employing an oxyacetamide-directed C-H hydroxylation on phenols. This method achieves one-step, redox-neutral synthesis of catechols with diverse substituent groups under mild conditions. Mechanistic studies confirm that the directing group (DG) oxyacetamide acts as the oxygen source. This strategy has been applied to the synthesis of different important catechols with fluorescent property and bioactivity from the corresponding phenols. Finally, our method also provides a convenient route to (18)O-labelled catechols using (18)O-labelled acetic acid.

  14. REACTIVITY OF RESORCINOL FORMALDEHYDE RESIN WITH NITRIC ACID

    Energy Technology Data Exchange (ETDEWEB)

    King, W; Fernando Fondeur, F; Bill Wilmarth, B; Myra Pettis, M; Shirley Mccollum, S

    2006-06-14

    Solid-state infrared spectroscopy, differential scanning calorimetry, and elemental analysis have been used to evaluate the reactivity of resorcinol formaldehyde resin with nitric acid and characterize the solid product. Two distinct reactions were identified within the temperature range 25-55 C. The first reaction is primarily associated with resin nitration, while the second involves bulk oxidation and degradation of the polymer network leading to dissolution and off-gassing. Reaction was confirmed with nitric acid concentrations as low as 3 M at 25 C applied temperature and 0.625 M at 66 C. Although a nitrated resin product can be isolated under appropriate experimental conditions, calorimetry testing indicates no significant hazard associated with handling the dry material.

  15. Reactivity of Resorcinol Formaldehyde Resin with Nitric Acid

    Energy Technology Data Exchange (ETDEWEB)

    King, William D.; Fondeur, Fernando F.; Wilmarth, William R.; Pettis, Myra E.

    2005-10-25

    Solid-state infrared spectroscopy, differential scanning calorimetry, and elemental analysis have been used to evaluate the reactivity of resorcinol formaldehyde resin with nitric acid and characterize the solid product. Two distinct reactions were identified within the temperature range 25-55 C. The first reaction is primarily associated with resin nitration, while the second involves bulk oxidation and degradation of the polymer network leading to dissolution and off-gassing. The threshold conditions promoting reaction have been identified. Reaction was confirmed with nitric acid concentrations as low as 3 M at 25 C applied temperature and 0.625 M at 66 C. Although a nitrated resin product can be isolated under appropriate experimental conditions, calorimetry testing indicates no significant hazard associated with handling the dry material.

  16. Spherical Resorcinol-Formaldehyde Synthesis by Inverse Suspension Polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Ray, Robert J.; Scrivens, Walter A.; Nash, Charles

    2005-10-21

    Base catalyzed sol-gel polycondensation of resorcinol (1,3-dihydroxybenzene) with formaldehyde by inverse suspension polymerization leads to the formation of uniform, highly cross-linked, translucent, spherical gels, which have increased selectivity and capacity for cesium ion removal from high alkaline solutions. Because of its high selectivity for cesium ion, resorcinol-formaldehyde (R-F) resins are being considered for process scale column radioactive cesium removal by ion-exchange at the Waste Treatment and Immobilization Plant (WTP), which is now under construction at the Hanford site. Other specialty resins such as Superlig{reg_sign} 644 have been ground and sieved and column tested for process scale radioactive cesium removal but show high pressure drops across the resin bed during transition from column regeneration to loading and elution. Furthermore, van Deemter considerations indicate better displacement column chromatography by the use of spherical particle beads rather than irregularly shaped ground or granular particles. In our studies batch contact equilibrium experiments using a high alkaline simulant show a definite increase in cesium loading onto spherical R-F resin. Distribution coefficient (Kd) values ranged from 777 to 429 mL/g in the presence of 0.1M and 0.7M potassium ions, respectively. Though other techniques for making R-F resins have been employed, to our knowledge no one has made spherical R-F resins by inverse suspension polymerization. Moreover, in this study we discuss the data comparisons to known algebraic isotherms used to evaluate ion-exchange resins for WTP plant scale cesium removal operations.

  17. A NOVEL EOR POLYMER(Ⅰ)——STUDY ON GELATION OF RESORCINOL FORMALDEHYDE SYSTEMS

    Institute of Scientific and Technical Information of China (English)

    ZHUANG Yinfeng; Stanley McCool; G. Paul Willhite; Don W. Green

    1995-01-01

    Factors affecting the gelation of resorcinol-formaldehyde systems have been examined over variable ranges applicable to oilfield use. Gelation of resorcinol-formaldehyde (RF)system was sensitive to pH,salinity and hardness. Generally,this gel system could be used in fresh water or low salinity brine at pH higher than about 9. The application would require careful monitoring of injection fluids to avoid premature gelation or prolonged shut-in times ,especially under conditions of low salinity and high pH. Salinity and hardness compatibilities of the system were improved by sulfomethylation of resorcinol. Aqueous sulfomethylated resorcinol formaldehyde (SMRF)system could be used in brine with higher salinity and hardness and at a wider pH range of 5-10.

  18. Reaction of pyrocatechol and resorcinol with styrene in the presence of aluminum phenolate

    Energy Technology Data Exchange (ETDEWEB)

    Kozlikovskii, Y.B.; Butov, S.A.; Koshchii, V.A.

    1986-08-01

    The alkylation of pyrocatechol and resorcinol with styrene in the presence of aluminum phenolate leads to a mixture of isomeric (..cap alpha..-methylbenzyl)dihydroxybenzenes, in which the ortho-alkylation products as a rule predominate.

  19. 40 CFR 721.9480 - Resorcinol, formaldehyde substituted carbomonocycle resin (generic).

    Science.gov (United States)

    2010-07-01

    ... carbomonocycle resin (generic). 721.9480 Section 721.9480 Protection of Environment ENVIRONMENTAL PROTECTION... carbomonocycle resin (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as resorcinol, formaldehyde substituted carbomonocycle resin...

  20. Growth-induced incommensurability observed in the organic co-crystal hexamethylenetetramine resorcinol.

    Science.gov (United States)

    Rodriguez, Soraya Maria Belluga; Palatinus, Lukás; Petrícek, Václav; Chapuis, Gervais

    2006-12-01

    Co-crystals of hexamethylenetetramine and resorcinol were investigated by X-ray diffraction. The structure was refined in the superspace group Xmcm(0beta0)s0s, X=(1/2 1/2 0 1/2). In the average structure the resorcinol molecules are disordered between two orientations. The main effect of the modulation in the structure is a harmonic modulation of the occupation probabilities of the two orientations of the resorcinol molecule. However, the modulated order is not perfect and the resorcinol molecules remain partially disordered. Below 270 K the crystal undergoes a phase transition to a commensurately modulated structure with modulation vector q=(0 1/2 1/4) and superspace group X2/m(0betagamma)0s. The structure of the low-temperature phase could not be determined owing to the poor quality of the crystals affected by the reconstructive phase transition.

  1. Resorcinol degradation by a Penicillium chrysogenum strain under osmotic stress: mono and binary substrate matrices with phenol.

    Science.gov (United States)

    Guedes, Sumaya Ferreira; Mendes, Benilde; Leitão, Ana Lúcia

    2011-04-01

    A phenol-degrading Penicillium chrysogenum strain previously isolated from a salt mine was able to grow at 1,000 mg l(-1) of resorcinol on solid medium. The aerobic degradation of resorcinol by P. chrysogenum CLONA2 was studied in batch cultures in minimal mineral medium with 58.5 g l(-1) of sodium chloride using resorcinol as the sole carbon source. The fungal strain showed the ability to degrade up to 250 mg l(-1) of resorcinol. Resorcinol and phenol efficiency degradation by P. chrysogenum CLONA2 was compared. This strain removes phenol faster than resorcinol. When phenol and resorcinol were in binary substrate matrices, phenol enhanced resorcinol degradation, and organic load decreased with respect to the mono substrate matrices. The acute toxicity of phenol and resorcinol, individually and in combination, to Artemia franciscana larvae has been verified before and after the bioremediation process with P. chrysogenum CLONA2. The remediation process was effective in mono and binary substrate systems.

  2. Bimodal activated carbons derived from resorcinol-formaldehyde cryogels

    Energy Technology Data Exchange (ETDEWEB)

    Szczurek, Andrzej; Amaral-Labat, Gisele; Fierro, Vanessa; Celzard, Alain [Institut Jean Lamour-UMR CNRS 7198, CNRS-Nancy-Universite-UPV-Metz, Departement Chimie et Physique des Solides et des Surfaces. ENSTIB, 27 rue Philippe Seguin, BP 1041, 88051 Epinal cedex 9 (France); Pizzi, Antonio, E-mail: Alain.Celzard@enstib.uhp-nancy.fr [ENSTIB-LERMAB, Nancy-Universite, 27 rue Philippe Seguin, BP1041, 88051 Epinal cedex 9 (France)

    2011-06-15

    Resorcinol-formaldehyde cryogels prepared at different dilution ratios have been activated with phosphoric acid at 450 deg. C and compared with their carbonaceous counterparts obtained by pyrolysis at 900 deg. C. Whereas the latter were, as expected, highly mesoporous carbons, the former cryogels had very different pore textures. Highly diluted cryogels allowed preparation of microporous materials with high surface areas, but activation of initially dense cryogels led to almost non-porous carbons, with much lower surface areas than those obtained by pyrolysis. The optimal acid concentration for activation, corresponding to stoichiometry between molecules of acid and hydroxyl groups, was 2 M l{sup -1}, and the acid-cryogel contact time also had an optimal value. Such optimization allowed us to achieve surface areas and micropore volumes among the highest ever obtained by activation with H{sub 3}PO{sub 4}, close to 2200 m{sup 2} g{sup -1} and 0.7 cm{sup 3} g{sup -1}, respectively. Activation of diluted cryogels with a lower acid concentration of 1.2 M l{sup -1} led to authentic bimodal activated carbons, having a surface area as high as 1780 m{sup 2} g{sup -1} and 0.6 cm{sup 3} g{sup -1} of microporous volume easily accessible through a widely developed macroporosity.

  3. Boronate Derivatives of Functionally Diverse Catechols: Stability Studies

    Directory of Open Access Journals (Sweden)

    Kamal Aziz Ketuly

    2010-03-01

    Full Text Available Benzeneboronate of catecholic carboxyl methyl esters, N-acetyldopamine, coumarin and catechol estrogens were prepared as crystalline derivatives in high yield. Related catechol compounds with extra polar functional group(s (OH, NH2 do not form or only partially form unstable cyclic boronate derivatives.

  4. Adsorbent for resorcinol removal based on cellulose functionalized with magnetic poly(dopamine).

    Science.gov (United States)

    Ding, Chaofan; Sun, Yuanling; Wang, Yanhui; Li, Jianbo; Lin, Yanna; Sun, Weiyan; Luo, Chuannan

    2017-06-01

    A simple chemical bonding method to synthesize magnetic cellulose-poly(dopamine) (Fe3O4@CMC@PDA) was reported. The adsorption behaviors of resorcinol in aqueous solution on Fe3O4@CMC@PDA were systematically investigated. As the results shown that, with the advantage of high surface area, abundant hydroxyl and amino groups of Fe3O4@CMC@PDA, and the magnetic property of Fe3O4, the resorcinol can be easily and rapidly extracted from the water by magnetic attraction under investigation. The adsorption equilibrium of Fe3O4@CMC@PDA for resorcinol corresponded with Freundlich isotherm, and the novel adsorbent exhibited better resorcinol removal efficiency in solutions with low pH. It was found that the resorcinol adsorption performance of Fe3O4@CMC@PDA strongly depends on their surface charge concentration and specific surface area. These results provide evidences for estimating and optimizing the removal of phenols from the wastewater by using of Fe3O4@CMC@PDA composites in the future. Copyright © 2017 Elsevier B.V. All rights reserved.

  5. The role of catechol-O-methyltransferase in catechol-enhanced erythroid differentiation of K562 cells

    Energy Technology Data Exchange (ETDEWEB)

    Suriguga,; Li, Xiao-Fei; Li, Yang; Yu, Chun-Hong; Li, Yi-Ran; Yi, Zong-Chun, E-mail: yizc@buaa.edu.cn

    2013-12-15

    Catechol is widely used in pharmaceutical and chemical industries. Catechol is also one of phenolic metabolites of benzene in vivo. Our previous study showed that catechol improved erythroid differentiation potency of K562 cells, which was associated with decreased DNA methylation in erythroid specific genes. Catechol is a substrate for the catechol-O-methyltransferase (COMT)-mediated methylation. In the present study, the role of COMT in catechol-enhanced erythroid differentiation of K562 cells was investigated. Benzidine staining showed that exposure to catechol enhanced hemin-induced hemoglobin accumulation and induced mRNA expression of erythroid specific genes in K562 cells. Treatment with catechol caused a time- and concentration-dependent increase in guaiacol concentration in the medium of cultured K562 cells. When COMT expression was knocked down by COMT shRNA expression in K562 cells, the production of guaiacol significantly reduced, and the sensitivity of K562 cells to cytotoxicity of catechol significantly increased. Knockdown of COMT expression by COMT shRNA expression also eliminated catechol-enhanced erythroid differentiation of K562 cells. In addition, the pre-treatment with methyl donor S-adenosyl-L-methionine or its demethylated product S-adenosyl-L-homocysteine induced a significant increase in hemin-induced Hb synthesis in K562 cells and the mRNA expression of erythroid specific genes. These findings indicated that O-methylation catalyzed by COMT acted as detoxication of catechol and involved in catechol-enhanced erythroid differentiation of K562 cells, and the production of S-adenosyl-L-homocysteine partly explained catechol-enhanced erythroid differentiation. - Highlights: • Catechol enhanced hemin-induced hemoglobin accumulation. • COMT-catalyzed methylation acted as detoxication of catechol. • COMT involved in catechol-enhanced erythroid differentiation.

  6. Solution-state NMR analysis of hydroxymethylated resorcinol cured in the presence of crude milled-wood lignin from Acer saccharum

    Science.gov (United States)

    Daniel J. Yelle

    2017-01-01

    Resorcinol-formaldehyde adhesives can reinforce stress fractures that appear from wood surface preparation. Researchers have found that applying the resorcinol-formaldehyde prepolymer, hydroxymethylated resorcinol is thought to plasticize lignin components and stabilize stress fractures through reactions with lignin subunits and hemicelluloses in wood. In this study, a...

  7. Biodegradation dynamics of high catechol concentrations by Aspergillus awamori.

    Science.gov (United States)

    Stanchev, Veselin; Stoilova, Ivanka; Krastanov, Albert

    2008-06-15

    The biodegradation process of high catechol concentrations by Aspergillus awamori was investigated. The values of the kinetic constants for a model of specific growth rate at different initial conditions were determined. At 1.0 g/L catechol concentration, the biodegradation process proceeded in the conditions of substrate limitation. At higher catechol concentrations (2.0 and 3.0 g/L) a presence of substrate inhibition was established. The dynamics of the specific catechol degradation rate was studied and the values of catechol and biomass concentrations, maximizing the specific catechol degradation rate, were estimated analytically. The specified ratio catechol/biomass could serve as a starting base for determination of the initial conditions for a batch process, for specifying the moment of feeding for a fed-batch process, and for monitoring and control of a continuous process by the aim of time-optimal control.

  8. Spectrophotometric determination of tetrazene in primers and primer mixes by use of resorcinol.

    Science.gov (United States)

    Norwitz, G; Keliher, P N

    1979-06-01

    A spectrophotometric method is proposed for the determination of tetrazene (tetracene) in primers and primer mixes that involves treatment of the tetrazene with resorcinol solution and measurement of the intensity of the yellow colour of the diazo-dye produced. In the application of the method, lead styphnate and barium nitrate are first removed by extraction with ammonium acetate solution and then nitrocellulose and PETN are removed by extraction with acetone. The insoluble matter containing the tetrazene is boiled with resorcinol reagent, the solution filtered, and the absorbance measured at 400 nm. Conditions for optimum colour development are studied and the nature of the reaction is considered.

  9. Production of catechols : microbiology and technology

    NARCIS (Netherlands)

    Krab-Hüsken, L.

    2002-01-01

    Catechols play an important role in the fine-chemical and flavour industry, as well as in photography, dyeing fur, rubber and plastic production. Many of these compounds cannot easily be synthesised chemically, but some micro-organisms are capable of producin

  10. An Engineering Evaluation of Spherical Resorcinol Formaldehyde Resin

    Energy Technology Data Exchange (ETDEWEB)

    Birdwell Jr, Joseph F [ORNL; Lee, Denise L [ORNL; Taylor, Paul Allen [ORNL; Collins, Robert T [ORNL; Hunt, Rodney Dale [ORNL

    2010-09-01

    A small column ion exchange (SCIX) system has been proposed for removal of cesium from caustic, supernatant, and dissolved salt solutions stored or generated from high-level tank wastes at the US Department of Energy (DOE) Hanford Site and Savannah River Sites. In both instances, deployment of SCIX systems, either in-tank or near-tank, is a means of expediting waste pretreatment and dispositioning with minimal or no new infrastructure requirements. Conceptually, the treatment approach can utilize a range of ion exchange media. Previously, both crystalline silicotitanate (CST), an inorganic, nonelutable sorbent, and resorcinol-formaldehyde (RF), an organic, elutable resin, have been considered for cesium removal from tank waste. More recently, Pacific Northwest National Laboratory (PNNL) evaluated use of SuperLig{reg_sign} 644, an elutable ion exchange medium, for the subject application. Results of testing indicate hydraulic limitations of the SuperLig{reg_sign} resin, specifically a high pressure drop through packed ion exchange columns. This limitation is likely the result of swelling and shrinkage of the irregularly shaped (granular) resin during repeated conversions between sodium and hydrogen forms as the resin is first loaded then eluted. It is anticipated that a similar flow limitation would exist in columns packed with conventional, granular RF resin. However, use of spherical RF resin is a likely means of mitigating processing limitations due to excessive pressure drop. Although size changes occur as the spherical resin is cycled through loading and elution operations, the geometry of the resin is expected to effectively mitigate the close packing that leads to high pressure drops across ion exchange columns. Multiple evaluations have been performed to determine the feasibility of using spherical RF resin and to obtain data necessary for design of an SCIX process. The work performed consisted of examination of radiation effects on resin performance

  11. CHARACTERIZATION OF CYCLED SPHERICAL RESORCINOL-FORMALDEHYDE ION EXCHANGE RESIN

    Energy Technology Data Exchange (ETDEWEB)

    Nash, C.; Duignan, M.

    2010-02-23

    This report presents characterization data for two spherical resorcinol-formaldehyde (sRF) resin beds that had processed cesium in non-radioactive and radioactive cycles. All column cycle operations for the resin beds including loading, displacements, elution, regeneration, breakthroughs, and solution analyses are reported in Nash and Duignan, 2009a. That report covered four ion exchange (IX) campaigns using the two {approx}11 mL beds in columns in a lead-lag arrangement. The first two campaigns used Savannah River Site (SRS) Tank 2F nonradioactive simulant while the latter two were fed with actual dissolved salt in the Savannah River National Laboratory (SRNL) Shielded Cells. Both radioactive cycles ran to cesium breakthrough of the lead column. The resin beds saw in excess of 400 bed volumes of feed in each cycle. Resin disposal plans in tank farm processing depend on characterizations of resin used with actual tank feed. Following a final 30 bed volume (BV) elution with nitric acid, the resin beds were found to contain detectable chromium, barium, boron, aluminum, iron, sodium, sulfur, plutonium, cesium, and mercury. Resin affinity for plutonium is important in criticality safety considerations. Cesium-137 was found to be less than 10E+7 dpm/g of resin, similar to past work with sRF resin. Sulfur levels are reasonably consistent with other work and are expected to represent sulfur chemistry used in the resin manufacture. There were low but detectable levels of technetium, americium, and curium. Toxicity Characteristic Leaching Procedure (TCLP) work on the used (eluted) resin samples showed significant contents of mercury, barium, and chromium. One resin sample exceeded the TCLP level for mercury while the other metals were below TCLP levels. TCLP organics measurements indicated measurable benzene in one case, though the source was unknown. Results of this work were compared with other work on similar sRF resin characterizations in this report. This is the first

  12. Endogenous catechol thioethers may be pro-oxidant or antioxidant.

    Science.gov (United States)

    Picklo, M J; Amarnath, V; Graham, D G; Montine, T J

    1999-08-01

    Increased catechol thioether formation is associated with Parkinson's disease. In this study, we examined whether catechol thioethers, having a lower oxidation potential than their parent catechols, would cause greater oxidative damage than their parent catechols. We synthesized 5'-S-glutathionyl, cysteinyl, and N-acetylcysteinyl derivatives of dopamine and dopac, encompassing the known catechol thioethers of the mercapturate pathway. Cyclic voltametry studies showed that catechol thioethers had higher reduction potentials than their parent catechols. A higher reduction potential did not correlate with an increase in oxidative damage, measured by metal-catalyzed DNA strand breakage. 5'-S-Glutathionyldopamine and the cysteinyl adducts of dopamine and dopac mediated less oxidative damage than their parent catechols. In contrast, both N-acetylcysteinyl analogs were equipotent to dopamine. Oxygen consumption corresponded to DNA damage except for 5'-S-glutathionyldopamine. The glutathionyl and cysteinyl adducts of dopamine inhibited dopamine-mediated DNA damage indicating that these adducts may have antioxidant properties. 5'-S-Glutathionyldopamine potentiated H2O2-mediated damage whereas 5-S-cysteinyldopamine was inhibitory. Our results show that the ability of catechol thioethers to cause oxidative damage in vitro is not based simply upon the reduction potential but rather, reflects a complex relationship among structures of the parent catechol and thiol adduct, metal catalyst, and oxidant.

  13. Aluminum complexation by catechol as determined by ultraviolet spectrophotometry

    Energy Technology Data Exchange (ETDEWEB)

    Sikora, F.J.; McBride, M.B.

    1989-03-01

    Methods of ultraviolet (UV) spectrophotometry were used to determine the stoichiometry and association constant for the Al-catechol complex from pH 3.8 to 4.6. Job's method of continuous variation indicated the Al-catechol complex had a 1:1 stoichiometry in the pH range studied. Aluminum titrations of catechol and pH titrations of catechol plus Al resulted in a shift in the UV spectra due to the formation of an Al-catechol complex absorbing UV radiation uniquely different than that of free catechol. General equations were developed for the determination of association constants assuming an organic and Al-organic complex absorb UV radiation. Aluminum titrations with constant catechol concentration yielded a log k/sub 0.1//sup c/ of 16.22 for a 1:1 Al-catechol complex. Calculated absorbance as a function of pH agree dwell with experimental pH titrations of solutions containing catechol plus Al. The fact that Al can be complexed by catechol at low pH indicates the o-hydroxy group provides a potential source for Al complexation in soil and surface waters.

  14. Synthesis and characterization of resorcinol-formaldehyde resin chars doped by zinc oxide

    Science.gov (United States)

    Gun'ko, Vladimir M.; Bogatyrov, Viktor M.; Oranska, Olena I.; Urubkov, Iliya V.; Leboda, Roman; Charmas, Barbara; Skubiszewska-Zięba, Jadwiga

    2014-06-01

    Polycondensation polymerization of resorcinol-formaldehyde (RF) mixtures in water with addition of different amounts of zinc acetate and then carbonization of dried gels are studied to prepare ZnO doped chars. Zinc acetate as a catalyst of resorcinol-formaldehyde polycondensation affects structural features of the RF resin (RFR) and, therefore, the texture of chars prepared from Zn-doped RFR. The ZnO doped chars are characterized using thermogravimetry, low temperature nitrogen adsorption/desorption, Raman spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), and high resolution transmission electron microscopy (HRTEM). At a relatively high content of zinc acetate (1 mol per 10-40 mol of resorcinol) in the reaction mixture, the formation of crystallites of ZnO (zincite) occurs in a shape of straight nanorods of 20-130 nm in diameter and 1-3 μm in length. At a small content of zinc acetate (1 mol per 100-500 mol of resorcinol), ZnO in composites is XRD amorphous and does not form individual particles. The ZnO doped chars are pure nanoporous at a minimal ZnO content and nano-mesoporous or nano-meso-macroporous at a higher ZnO content.

  15. Sol-gel coating of inorganic nanostructures with resorcinol-formaldehyde resin.

    Science.gov (United States)

    Li, Na; Zhang, Qiao; Liu, Jian; Joo, Jibong; Lee, Austin; Gan, Yang; Yin, Yadong

    2013-06-07

    A general sol-gel process has been developed to form a coating of resorcinol-formaldehyde (RF) resin on inorganic nanostructures of various compositions and morphologies. The RF shell can be conveniently converted into carbon through high temperature carbonization under an inert atmosphere.

  16. The role of catechol-O-methyltransferase in catechol-enhanced erythroid differentiation of K562 cells.

    Science.gov (United States)

    Suriguga; Li, Xiao-Fei; Li, Yang; Yu, Chun-Hong; Li, Yi-Ran; Yi, Zong-Chun

    2013-12-15

    Catechol is widely used in pharmaceutical and chemical industries. Catechol is also one of phenolic metabolites of benzene in vivo. Our previous study showed that catechol improved erythroid differentiation potency of K562 cells, which was associated with decreased DNA methylation in erythroid specific genes. Catechol is a substrate for the catechol-O-methyltransferase (COMT)-mediated methylation. In the present study, the role of COMT in catechol-enhanced erythroid differentiation of K562 cells was investigated. Benzidine staining showed that exposure to catechol enhanced hemin-induced hemoglobin accumulation and induced mRNA expression of erythroid specific genes in K562 cells. Treatment with catechol caused a time- and concentration-dependent increase in guaiacol concentration in the medium of cultured K562 cells. When COMT expression was knocked down by COMT shRNA expression in K562 cells, the production of guaiacol significantly reduced, and the sensitivity of K562 cells to cytotoxicity of catechol significantly increased. Knockdown of COMT expression by COMT shRNA expression also eliminated catechol-enhanced erythroid differentiation of K562 cells. In addition, the pre-treatment with methyl donor S-adenosyl-L-methionine or its demethylated product S-adenosyl-L-homocysteine induced a significant increase in hemin-induced Hb synthesis in K562 cells and the mRNA expression of erythroid specific genes. These findings indicated that O-methylation catalyzed by COMT acted as detoxication of catechol and involved in catechol-enhanced erythroid differentiation of K562 cells, and the production of S-adenosyl-L-homocysteine partly explained catechol-enhanced erythroid differentiation.

  17. Catechol-based biomimetic functional materials

    OpenAIRE

    Sedó, Josep; Saiz-Poseu, Javier; Busqué, Félix; Ruiz Molina, Daniel

    2013-01-01

    Catechols are found in nature taking part in a remarkably broad scope of biochemical processes and functions. Though not exclusively, such versatility may be traced back to several properties uniquely found together in the o-dihydroxyaryl chemical function; namely, its ability to establish reversible equilibria at moderate redox potentials and pHs and to irreversibly cross-link through complex oxidation mechanisms; its excellent chelating properties, greatly exemplified by, but by no means ex...

  18. Catechol Siderophore Transport by Vibrio cholerae

    OpenAIRE

    Wyckoff, Elizabeth E.; Allred, Benjamin E.; Raymond, Kenneth N.; Payne, Shelley M

    2015-01-01

    Siderophores, small iron-binding molecules secreted by many microbial species, capture environmental iron for transport back into the cell. Vibrio cholerae synthesizes and uses the catechol siderophore vibriobactin and also uses siderophores secreted by other species, including enterobactin produced by Escherichia coli. E. coli secretes both canonical cyclic enterobactin and linear enterobactin derivatives likely derived from its cleavage by the enterobactin esterase Fes. We show here that V....

  19. Catechol-O-methyltransferase and Parkinson's disease.

    OpenAIRE

    Tai CH; Wu RM

    2002-01-01

    Parkinson's disease (PD) is one of the main causes of neurological disability in the elderly. Levodopa is the gold standard for treating this disease, but chronic levodopa therapy is complicated by motor fluctuation and dyskinesia. The catechol-O-methyltransferase (COMT) inhibitors represent a new class of antiparkinsonian drugs. When coadministered with levodopa/decarboxylase inhibitor, 2 COMT inhibitors, tolcapone and entacapone have been shown to improve the clinical benefit of levodopa. C...

  20. Catechol biodegradation kinetics using Candida parapsilopsis

    Directory of Open Access Journals (Sweden)

    Maurício Rigo

    2010-04-01

    Full Text Available This study evaluated the biodegradation of catechol by a yeast strain of Candida parapsilopsis in standard medium in Erlenmeyer flasks. Results shown that the highest concentration of catechol caused the longer lag period, demonstrating that acclimatized cultures could completely degrade an initial catechol concentration of 910 mg/L within 48 h. Haldane's model validated the experimental data adequately for growth kinetics over the studied catechol concentration ranges of 36 to 910 mg/L. The constants obtained for this model were µmax = 0.246 h-1, Ks = 16.95 mg/L and Ki = 604.85 mg/L.Neste trabalho foi estudada a biodegradação de catecol em frascos de Erlenmeyers em água residuária sintética pela levedura Candida parapsilopsis. As respostas dos ensaios cinéticos mostraram que altas concentrações de catecol ocasionaram uma fase lag longa para a levedura. Portanto, a aclimatização da cultura de levedura empregada para biodegradação de catecol é de fundamental importância, sendo possível reduzir toda a concentração inicial de catecol da água residuária sintética de 910 mg/L em 48 horas. Os dados experimentais da cinética de biodegradação do catecol foram ajustados pelo modelo de Haldane adequadamente, sobre a faixa de concentração de catecol investigada de 36 a 910 mg/L. Os parâmetros cinéticos obtidos do modelo de Haldane foram: µmax = 0,246 h-1, Ks = 16,95 mg/L e Ki = 604,85 mg/L.

  1. Adsorption mechanism and valency of catechol-functionalized hyperbranched polyglycerols

    OpenAIRE

    Stefanie Krysiak; Qiang Wei; Klaus Rischka; Andreas Hartwig; Rainer Haag; Thorsten Hugel

    2016-01-01

    Nature often serves as a model system for developing new adhesives. In aqueous environments, mussel-inspired adhesives are promising candidates. Understanding the mechanism of the extraordinarily strong adhesive bonds of the catechol group will likely aid in the development of adhesives. With this aim, we study the adhesion of catechol-based adhesives to metal oxides on the molecular level using atomic force microscopy (AFM). The comparison of single catechols (dopamine) with multiple catecho...

  2. Reaction pathways in catechol/primary amine mixtures

    OpenAIRE

    Yang, Juan; Saggiomo, Vittorio; Velders, Aldrik H.; Cohen Stuart, Martien; Kamperman, Marleen

    2016-01-01

    Catechol chemistry is used as a crosslinking tool abundantly in both natural organisms (e.g. mussels, sandcastle worms) and synthetic systems to achieve the desired mechanical properties. Despite this abundance and success, the crosslinking chemistry is still poorly understood. In this study, to simplify the system, yet to capture the essential chemistry, model compounds 4-methyl catechol and propylamine are used. The reaction of 4-methyl catechol (2 mM) with propylamine (6 mM) is carried out...

  3. Effects of structural isomerism on solution behaviour of solutes: Apparent molar volumes and isentropic compression of catechol, resorcinal, and hydroquinone in aqueous solution at T = (283.15, 293.15, 298.15, 303.15, and 313.15) K

    Energy Technology Data Exchange (ETDEWEB)

    Bayram, Edip [Department of Chemistry, Akdeniz University, Antalya 07058 (Turkey); Ayranci, Erol, E-mail: eayranci@akdeniz.edu.t [Department of Chemistry, Akdeniz University, Antalya 07058 (Turkey)

    2010-09-15

    Effects of structural isomerism on solution behaviour of dihydroxybenzenes were examined through the determination of volumetric properties such as apparent molar volumes, apparent molar isentropic compressions, and isobaric expansions. The isomers were 1,2-dihydroxybenzene (catechol), 1,3-dihydroxybenzene (resorcinol), and 1,4-dihydroxybenzene (hydroquinone). The volumetric properties were determined from accurate density and speed of sound measurements at T = (283.15, 293.15, 298.15, 303.15, and 313.15) K and at various concentrations. Values at infinite dilution of these parameters were obtained by suitable extrapolation procedures. The results are discussed in terms of hydrophobic, hydrogen bonding, and dipole-dipole interactions between the three isomers and water. Catechol was found to have the strongest hydrophilic and the weakest hydrophobic interactions with water among the three isomers.

  4. Synthesis and Evaluation of Heterocyclic Catechol Mimics as Inhibitors of Catechol-O-methyltransferase (COMT)

    Science.gov (United States)

    2015-01-01

    3-Hydroxy-4-pyridinones and 5-hydroxy-4-pyrimidinones were identified as inhibitors of catechol-O-methyltransferase (COMT) in a high-throughput screen. These heterocyclic catechol mimics exhibit potent inhibition of the enzyme and an improved toxicity profile versus the marketed nitrocatechol inhibitors tolcapone and entacapone. Optimization of the series was aided by X-ray cocrystal structures of the novel inhibitors in complex with COMT and cofactors SAM and Mg2+. The crystal structures suggest a mechanism of inhibition for these heterocyclic inhibitors distinct from previously disclosed COMT inhibitors. PMID:25815153

  5. Catechol Siderophore Transport by Vibrio cholerae.

    Science.gov (United States)

    Wyckoff, Elizabeth E; Allred, Benjamin E; Raymond, Kenneth N; Payne, Shelley M

    2015-09-01

    Siderophores, small iron-binding molecules secreted by many microbial species, capture environmental iron for transport back into the cell. Vibrio cholerae synthesizes and uses the catechol siderophore vibriobactin and also uses siderophores secreted by other species, including enterobactin produced by Escherichia coli. E. coli secretes both canonical cyclic enterobactin and linear enterobactin derivatives likely derived from its cleavage by the enterobactin esterase Fes. We show here that V. cholerae does not use cyclic enterobactin but instead uses its linear derivatives. V. cholerae lacked both a receptor for efficient transport of cyclic enterobactin and enterobactin esterase to promote removal of iron from the ferrisiderophore complex. To further characterize the transport of catechol siderophores, we show that the linear enterobactin derivatives were transported into V. cholerae by either of the catechol siderophore receptors IrgA and VctA, which also transported the synthetic siderophore MECAM [1,3,5-N,N',N″-tris-(2,3-dihydroxybenzoyl)-triaminomethylbenzene]. Vibriobactin is transported via the additional catechol siderophore receptor ViuA, while the Vibrio fluvialis siderophore fluvibactin was transported by all three catechol receptors. ViuB, a putative V. cholerae siderophore-interacting protein (SIP), functionally substituted for the E. coli ferric reductase YqjH, which promotes the release of iron from the siderophore in the bacterial cytoplasm. In V. cholerae, ViuB was required for the use of vibriobactin but was not required for the use of MECAM, fluvibactin, ferrichrome, or the linear derivatives of enterobactin. This suggests the presence of another protein in V. cholerae capable of promoting the release of iron from these siderophores. Vibrio cholerae is a major human pathogen and also serves as a model for the Vibrionaceae, which include other serious human and fish pathogens. The ability of these species to persist and acquire essential

  6. Catechol Siderophore Transport by Vibrio cholerae

    Science.gov (United States)

    Allred, Benjamin E.; Raymond, Kenneth N.; Payne, Shelley M.

    2015-01-01

    ABSTRACT Siderophores, small iron-binding molecules secreted by many microbial species, capture environmental iron for transport back into the cell. Vibrio cholerae synthesizes and uses the catechol siderophore vibriobactin and also uses siderophores secreted by other species, including enterobactin produced by Escherichia coli. E. coli secretes both canonical cyclic enterobactin and linear enterobactin derivatives likely derived from its cleavage by the enterobactin esterase Fes. We show here that V. cholerae does not use cyclic enterobactin but instead uses its linear derivatives. V. cholerae lacked both a receptor for efficient transport of cyclic enterobactin and enterobactin esterase to promote removal of iron from the ferrisiderophore complex. To further characterize the transport of catechol siderophores, we show that the linear enterobactin derivatives were transported into V. cholerae by either of the catechol siderophore receptors IrgA and VctA, which also transported the synthetic siderophore MECAM [1,3,5-N,N′,N″-tris-(2,3-dihydroxybenzoyl)-triaminomethylbenzene]. Vibriobactin is transported via the additional catechol siderophore receptor ViuA, while the Vibrio fluvialis siderophore fluvibactin was transported by all three catechol receptors. ViuB, a putative V. cholerae siderophore-interacting protein (SIP), functionally substituted for the E. coli ferric reductase YqjH, which promotes the release of iron from the siderophore in the bacterial cytoplasm. In V. cholerae, ViuB was required for the use of vibriobactin but was not required for the use of MECAM, fluvibactin, ferrichrome, or the linear derivatives of enterobactin. This suggests the presence of another protein in V. cholerae capable of promoting the release of iron from these siderophores. IMPORTANCE Vibrio cholerae is a major human pathogen and also serves as a model for the Vibrionaceae, which include other serious human and fish pathogens. The ability of these species to persist and

  7. Copper complexes as biomimetic models of catechol oxidase : mechanistic studies

    NARCIS (Netherlands)

    Koval, Iryna A.

    2006-01-01

    The research described in this thesis deals with the synthesis of copper(II) complexes with phenol-based or macrocyclic ligands, which can be regarded as model compounds of the active site of catechol oxidase, and with the mechanism of the catalytic oxidation of catechol mediated by these compounds.

  8. Jack of all trades: Versatile catechol crosslinking mechanisms

    NARCIS (Netherlands)

    Yang, J.; Cohen Stuart, M.A.; Kamperman, M.M.G.

    2014-01-01

    Catechols play an important role in many natural systems. They are known to readily interact with both organic (e.g., amino acids) and inorganic (e.g., metal ions, metal oxides) compounds, thereby providing a powerful system for protein curing. Catechol crosslinked protein networks, such as scleroti

  9. Abiotic oxidation of catechol by soil metal oxides

    Energy Technology Data Exchange (ETDEWEB)

    Colarieti, Maria Letizia [Dipartimento di Ingegneria Chimica, Universita di Napoli Federico II, Naples (Italy); Toscano, Giuseppe [Dipartimento di Ingegneria Chimica, Universita di Napoli Federico II, Naples (Italy)]. E-mail: giuseppe.toscano@unina.it; Ardi, Maria Raffaella [Dipartimento di Ingegneria Chimica, Universita di Napoli Federico II, Naples (Italy); Greco, Guido [Dipartimento di Ingegneria Chimica, Universita di Napoli Federico II, Naples (Italy)

    2006-06-30

    The mechanism of catechol oxidation by soil metal oxides is investigated in a slurry reactor. This abiotic transformation is shown to consist in a three-step process. The first step is a heterogeneous reaction. Catechol undergoes fast, partial oxidation at the expenses of Fe and Mn oxides contained in the soil. In the second step, reduced Fe and Mn are released into the aqueous solution and immediately complexed by catechol. Metal-catecholate complexes are stable at the very low dissolved-oxygen concentration levels attained under nitrogen sparging. The third step is a homogenous reaction. The highly reactive intermediate produced by catechol partial oxidation initiates catechol polymerisation. Under nitrogen sparging, the polymerisation process ends rather rapidly, thus yielding only partial conversion of the phenol and producing low-molecular weight, water-soluble polymers. Further oxidation of the metal-catecholate complexes formed in the second step only occurs under air sparging. Thus, reactive intermediates are formed at much higher concentration levels than those attained when nearly no oxygen is present in solution. The polymerisation proceeds at a much faster rate until, under the experimental conditions adopted, complete catechol conversion is attained and high-molecular-weight, insoluble polymers are produced.

  10. Solvent mediated stabilisation of dissolution at the resorcinol-water interface

    Energy Technology Data Exchange (ETDEWEB)

    Hussain, M.; Sahudin, S. [Faculty of Pharmacy, Universiti Kebangsaan Malaysia, Jalan Raja Muda Abdul Aziz, 50300 Kuala Lumpur (Malaysia)

    2010-02-15

    Experimental evidence suggests dissolution along the polar c-axis of {alpha}-resorcinol in water preferentially occurs at the {l_brace}011{r_brace} surface. In an attempt to understand the mechanism by which solvent influences this process, dissolution at the resorcinol {l_brace}011{r_brace} and {l_brace}011{r_brace} surfaces has been studied using molecular dynamics simulations. Our computations indicate dissolution at the two faces is dependent upon solvent behaviour at the crystal surface, where strong water-crystal interactions serve to stabilise the crystal surface and retard dissolution. (copyright 2010 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  11. EXPERIMENTAL INVESTIGATION ON CHROMIUM(VI REMOVAL FROM AQUEOUS SOLUTION USING ACTIVATED CARBON RESORCINOL FORMALDEHYDE XEROGELS

    Directory of Open Access Journals (Sweden)

    Eghe A. Oyedoh

    2016-10-01

    Full Text Available The adsorption of chromium(VI metal ion in aqueous solutions by activated carbon resorcinol formaldehyde xerogels (ACRF was investigated. The results showed that pore structure, surface area and the adsorbent surface chemistry are important factors in the control of the adsorption of chromium(VI metal ions. The isotherm parameters were obtained from plots of the isotherms and from the application of Langmuir and Freundlich Isotherms. Based on regression analysis, the Langmuir isotherm model was the best fit. The maximum adsorption capacity of ACRF for chromium (VI was 241.9 mg/g. The pseudo-second-order kinetic model was the best fit to the experimental data for the adsorption of chromium metal ions by activated carbon resorcinol formaldehyde xerogels. The thermodynamics of Cr(VI ions adsorption onto ACRF was a spontaneous and endothermic process.

  12. Chemical derivatization to enhance chemical/oxidative stability of resorcinol-formaldehyde resin

    Energy Technology Data Exchange (ETDEWEB)

    Hubler, T. [Pacific Northwest National Laboratory, Richland, WA (United States)

    1996-10-01

    The purpose of this work is to develop modified resorcinol-formaldehyde (R-F) resin with enhanced chemical/oxidative stability in conditions typically encountered in the remediation of radioactive waste tanks. R-F resin is a regenerable organic ion-exchanger developed at Savannah River Technology Center that is being considered for use in the selective removal of radioactive cesium from alkaline waste tank supernates at both the Hanford and Savannah River sites.

  13. Inorganic layered double hydroxides as a 4-hexyl resorcinol delivery system for topical applications

    CSIR Research Space (South Africa)

    Mosangi, Damodar

    2016-08-01

    Full Text Available inhibitors to control pigmentation byRSC Adv., 2016, 6, 77709–77716 | 77709 Fig. 1 Chemical structure of 4-hexyl resorcinol. RSC Advances Paperaffecting the transcription and activity of pigmentary enzymes are peroxidase, tyrosinase, tyrosinase...-related protein-1 (Tyrp-1), tyrosinase-related protein-2 (Tyrp-2), methimazole, ellagic acid and hydroquinone.34–36 Among the different skin lightening agents, hydroquinone has been the most frequently used in numerous even tone formulations for more than 5...

  14. Lawps ion exchange column gravity drain of spherical resorcinol formaldehyde resin

    Energy Technology Data Exchange (ETDEWEB)

    Duignan, M. R. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Herman, D. T. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Restivo, M. L. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Burket, P. R. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2016-01-28

    Experiments at several different scales were performed to understand the removal of spherical resorcinol formaldehyde (sRF) ion exchange resin using a gravity drain system with a valve located above the resin screen in the ion exchange column (IXC). This is being considered as part of the design for the Low Activity Waste Pretreatment System (LAWPS) to be constructed at the DOE Hanford Site.

  15. Adsorption mechanism and valency of catechol-functionalized hyperbranched polyglycerols

    Directory of Open Access Journals (Sweden)

    Stefanie Krysiak

    2015-05-01

    Full Text Available Nature often serves as a model system for developing new adhesives. In aqueous environments, mussel-inspired adhesives are promising candidates. Understanding the mechanism of the extraordinarily strong adhesive bonds of the catechol group will likely aid in the development of adhesives. With this aim, we study the adhesion of catechol-based adhesives to metal oxides on the molecular level using atomic force microscopy (AFM. The comparison of single catechols (dopamine with multiple catechols on hyperbranched polyglycerols (hPG at various pH and dwell times allowed us to further increase our understanding. In particular, we were able to elucidate how to achieve strong bonds of different valency. It was concluded that hyperbranched polyglycerols with added catechol end groups are promising candidates for durable surface coatings.

  16. Adsorption mechanism and valency of catechol-functionalized hyperbranched polyglycerols.

    Science.gov (United States)

    Krysiak, Stefanie; Wei, Qiang; Rischka, Klaus; Hartwig, Andreas; Haag, Rainer; Hugel, Thorsten

    2015-01-01

    Nature often serves as a model system for developing new adhesives. In aqueous environments, mussel-inspired adhesives are promising candidates. Understanding the mechanism of the extraordinarily strong adhesive bonds of the catechol group will likely aid in the development of adhesives. With this aim, we study the adhesion of catechol-based adhesives to metal oxides on the molecular level using atomic force microscopy (AFM). The comparison of single catechols (dopamine) with multiple catechols on hyperbranched polyglycerols (hPG) at various pH and dwell times allowed us to further increase our understanding. In particular, we were able to elucidate how to achieve strong bonds of different valency. It was concluded that hyperbranched polyglycerols with added catechol end groups are promising candidates for durable surface coatings.

  17. Chemical derivatization to enhance chemical/oxidative stability of resorcinol-formaldehyde resin

    Energy Technology Data Exchange (ETDEWEB)

    Hubler, T.L. [Pacific Northwest National Lab., Richland, WA (United States)

    1997-10-01

    The goal of this task is to develop modified resorcinol-formaldehyde (R-F) resin to improve the chemical/oxidative stability of the resin. R-F resin is a regenerable organic ion-exchange resin that is selective for cesium ion in highly alkaline, high ionic-strength solutions. R-F resin tends to undergo chemical degradation, reducing its ability to remove cesium ion from waste solutions; the mechanistic details of these decomposition reactions are currently unknown. The approach used for this task is chemical modification of the resin structure, particularly the resorcinol ring unit of the polymer resin. This approach is based on prior characterization studies conducted at Pacific Northwest National Laboratory (PNNL) that indicated the facile chemical degradation of the resin is oxidation of the resorcinol ring to the para-quinone structure, with subsequent loss of ion-exchange sites for cesium ion. R-F resin represents an important alternative to current radiocesium remediation technology for tank wastes at both the Hanford and Savannah River sites, particularly if regenerable resins are needed.

  18. Heterogeneous cracking of catechol under partially oxidative conditions

    Energy Technology Data Exchange (ETDEWEB)

    Eun-Jae Shin; Mohammad R. Hajaligol; Firooz Rasouli [Philip Morris USA, Richmond, VA (United States). Research Center

    2004-08-01

    Heterogeneous cracking of catechol over the temperature range of 350-650{sup o}C and under partially oxidative conditions was studied using nano-particle iron oxide. We employed a flow tube reactor set-up for heterogeneous cracking, a molecular beam mass spectrometer for the real time sampling and measurement of cracking products, and factor analysis to deconvolute the complex chemistry. The effects on conversion and products distribution of varying process parameters such as catechol feed rate, oxygen concentration, and temperature were considered. Thermal decomposition of catechol begins at above 500{sup o}C. In the presence of the iron oxide, however, catechol significantly decomposes at temperatures as low as 350{sup o}C. The formation of carbon dioxide and water was promoted at the lower catechol feed rates. Higher catechol feed rates suppressed the conversion and enhanced the formation of single ring aromatic products, especially the formation of an aromatic ketone, indanone (m/z 132, C{sub 9}H{sub 8}O), through gas-phase secondary reactions. Increasing oxygen concentration up to 21%, however, completed the cracking of catechol with increasing formation of carbon dioxide and water even at 350{sup o}C for a high catechol feed rate. The iron oxide was deactivated after being exposed to the vapor of catechol at lower temperatures (between 350 and 400{sup o}C). However, it retained its activity at temperatures above 450{sup o}C. High-resolution transmission electron microscopy was used to characterize the iron oxide nano-particles at various reaction conditions. 42 refs., 9 figs.

  19. Bioinspired catecholic copolymers for antifouling surface coatings.

    Science.gov (United States)

    Cho, Joon Hee; Shanmuganathan, Kadhiravan; Ellison, Christopher J

    2013-05-01

    We report here a synthetic approach to prepare poly(methyl methacrylate)-polydopamine diblock (PMMA-PDA) and triblock (PDA-PMMA-PDA) copolymers combining mussel-inspired catecholic oxidative chemistry and atom transfer radical polymerization (ATRP). These copolymers display very good solubility in a range of organic solvents and also a broad band photo absorbance that increases with increasing PDA content in the copolymer. Spin-cast thin films of the copolymer were stable in water and showed a sharp reduction (by up to 50%) in protein adsorption compared to those of neat PMMA. Also the peak decomposition temperature of the copolymers was up to 43°C higher than neat PMMA. The enhanced solvent processability, thermal stability and low protein adsorption characteristics of this copolymer makes it attractive for variety of applications including antifouling coatings on large surfaces such as ship hulls, buoys, and wave energy converters.

  20. Degradation of recalcitrant compounds by catechol-driven Fenton reaction

    Energy Technology Data Exchange (ETDEWEB)

    Rodriguez, J.; Contreras, D.; Oviedo, C.; Freer, J.; Baeza, J. [Renewable Resources Lab., Univ. de Concepcion, Concepcion (Chile)

    2003-07-01

    Dihydroxybenzenes are able to reduce Fe(III) and promote fenton reaction. The Catechol/Fe(III)/H{sub 2}O{sub 2} system has been successfully used to degrade different compounds, being in all cases more efficient than Fe(II)-Fenton reaction. In this paper the possibilities for using the catechol-driven fenton reaction to degrade recalcitrant compounds such as Fe(III)-EDTA complex and veratryl alcohol are reviewed. (orig.)

  1. Application of electrosynthesized poly(aniline-co-p-aminophenol) as a catechol sensor

    Energy Technology Data Exchange (ETDEWEB)

    Chen Chuanxiang [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210093 (China); Department of Chemistry, School of Materials Science and Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003 (China)], E-mail: cxchenyz@yahoo.com.cn; Sun Cheng [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210093 (China)], E-mail: envidean@nju.edu.cn; Gao Yuhua [Department of Chemistry, School of Materials Science and Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003 (China)

    2009-03-30

    Poly(aniline-co-p-aminophenol) (copolymer) film was used as a sensor to determine the presence of catechol, taking advantage of the ability of the film to effectively catalyze the oxidation of catechol. The copolymer served as an electron transfer mediator between the electrode surface and catechol in the solution. The response current of the catechol sensor depended on the applied potential, pH and temperature at a given concentration of catechol. At optimum conditions, the catechol sensor displayed an excellent electrocatalytic response to the detection of catechol in a concentration range from 5 to 500 {mu}M with a detection limit of 0.8 {mu}M. The effects of selected organic compounds on the response of the catechol sensor were studied. Together, these findings show that the catechol sensor exhibits a better selectivity towards interfering species and a better operational and storage stability.

  2. Simultaneous Quantification of Dexpanthenol and Resorcinol from Hair Care Formulation Using Liquid Chromatography: Method Development and Validation

    Directory of Open Access Journals (Sweden)

    Amit Kumar De

    2016-01-01

    Full Text Available The current study presents the simultaneous quantification of dexpanthenol and resorcinol from marketed hair care formulation. Dexpanthenol is often present as an active ingredient in personal care products for its beautifying and invigorating properties and restorative and smoothing properties. On the other hand resorcinol is mainly prescribed for the treatment of seborrheic dermatitis of scalp. The toxic side effects of resorcinol limit its use in dermatological preparations. Therefore an accurate quantification technique for the simultaneous estimation of these two components can be helpful for the formulation industries for the accurate analysis of their product quality. In the current study a high performance liquid chromatographic technique has been developed using a C18 column and a mobile phase consisting of phosphate buffer of pH = 2.8 following a gradient elution. The mobile phase flow rate was 0.6 mL per minute and the detection wavelength was 210 nm for dexpanthenol and 280 nm for resorcinol. The linearity study was carried out using five solutions having concentrations ranging between 10.34 μg·mL−1 and 82.69 μg·mL−1 (r2=0.999 for resorcinol and 10.44 μg·mL−1 and 83.50 μg·mL−1 (r2=0.998 for dexpanthenol. The method has been validated as per ICH Q2(R1 guidelines. The ease of single step sample preparation, accuracy, and precision (intraday and interday study presents the method suitable for the simultaneous quantification of dexpanthenol and resorcinol from any personal care product and dermatological preparations containing these two ingredients.

  3. Chemisorption of catechol on gibbsite, boehmite, and noncrystalline alumina surfaces

    Energy Technology Data Exchange (ETDEWEB)

    McBride, M.B.; Wesselink, L.G.

    1988-06-01

    The mechanism of bonding of catechol and related phenolic compounds on aluminum oxides was elucidated from sorption behavior in the presence of competing adsorbates and the nature of the infrared spectra of the surface-bound molecules. The surfaces demonstrated a high degree of selectivity toward catechol, adsorbing the molecule in the presence of a large excess of chloride. Phosphate competed effectively with catechol for sorption sites while acetate did not. Dispersive and Fourier transform infrared spectroscopy verified that catechol bound on the aluminum oxide surfaces was chemically perturbed in much the same manner as catechol chelated by Al/sup 3 +/, suggesting that the dominant sorption process involved the formation of a 1:1 bidentate complex with surface Al. The mechanisms of bonding was similar for all the aluminum oxides, but the dominant crystal surfaces of the crystalline oxides were unreactive toward catechol, and adsorption was attributed to -AlOH groups situated on edge faces. As a result, the noncrystalline oxide was more reactive per unit of surface area than the crystalline minerals boehmite and gibbsite.

  4. Induction of apoptosis on human hepatocarcinoma cell lines by an alkyl resorcinol isolated from Lithraea molleoides

    Institute of Scientific and Technical Information of China (English)

    Luciana Barbini; Paula Lopez; Julieta Ruffa; Virginia Martino; Graciela Ferraro; Rodolfo Campos; Lucia Cavallaro

    2006-01-01

    AIM: To study the mechanism of cytotoxicity of a new active 5-alkyl resorcinol [1, 3-dihydroxy-5- (tridec-4', 7'-dienyl) benzene] isolated from Lithraea molleoides leaves on liver tumor cells.METHODS: Human hepatocarcinoma cell lines (HepG2and Hep3B) in culture were treated with inhibitory concentrations, 50% of the compound, for 24 h. The induction of apoptosis was detected in treated cells by analysis of DNA fragmentation, DNA content, and acridine orange and propidium iodide staining.RESULTS: After 24 h of 5-alkyl resorcinol treatment,both cell lines showed: (1) the typical morphological alterations of apoptosis; (2) DNA fragmentation, detected by laddering and appearance of a subG0 population by flow cytometry; and (3) condensed and fragmented nuclei by acridine orange-propidium iodide staining.CONCLUSION: Based on the results, this compound exerts its cytotoxic effect in both hepatocellular cell lines through apoptotic cell death. For Hep3B, cells with mutated p53 and Fas, apoptosis would proceed by p53-or Fas-independent pathways.

  5. Induction of apoptosis on human hepatocarcinoma cell lines by an alkyl resorcinol isolated from Lithraea molleoides

    Science.gov (United States)

    Barbini, Luciana; Lopez, Paula; Ruffa, Julieta; Martino, Virginia; Ferraro, Graciela; Campos, Rodolfo; Cavallaro, Lucia

    2006-01-01

    AIM: To study the mechanism of cytotoxicity of a new active 5-alkyl resorcinol [1, 3-dihydroxy-5- (tridec-4’, 7’-dienyl) benzene] isolated from Lithraea molleoides leaves on liver tumor cells. METHODS: Human hepatocarcinoma cell lines (HepG2 and Hep3B) in culture were treated with inhibitory concentrations, 50% of the compound, for 24 h. The induction of apoptosis was detected in treated cells by analysis of DNA fragmentation, DNA content, and acridine orange and propidium iodide staining. RESULTS: After 24 h of 5-alkyl resorcinol treatment, both cell lines showed: (1) the typical morphological alterations of apoptosis; (2) DNA fragmentation, detected by laddering and appearance of a subG0 population by flow cytometry; and (3) condensed and fragmented nuclei by acridine orange-propidium iodide staining. CONCLUSION: Based on the results, this compound exerts its cytotoxic effect in both hepatocellular cell lines through apoptotic cell death. For Hep3B, cells with mutated p53 and Fas, apoptosis would proceed by p53- or Fas-independent pathways. PMID:17009393

  6. Concentrating cesium-137 from seawater using resorcinol-formaldehyde resin for radioecological monitoring

    Energy Technology Data Exchange (ETDEWEB)

    Egorin, Andrei; Tokar, Eduard; Tutov, Mikhail; Avramenko, Valentin [Institute of Chemistry FEBRAS, Vladivostok (Russian Federation); Far Eastern Federal Univ., Vladivostok (Russian Federation); Palamarchuk, Marina; Marinin, Dmitry [Institute of Chemistry FEBRAS, Vladivostok (Russian Federation)

    2017-04-01

    A method of preconcentrating cesium-137 from seawater using a resorcinol-formaldehyde resin, which enables one to optimize the ecological monitoring procedure, has been suggested. Studies of sorption of cesium-137 from seawater by resorcinol-formaldehyde resin have been performed, and it has been demonstrated that the cation exchanger is characterized by high selectivity with respect to cesium-137. It was found that the selectivity depended on the temperature of resin solidification and the seawater pH value. The maximal value of the cesium-137 distribution coefficient is equal to 4.1-4.5 x 10{sup 3} cm{sup 3} g{sup -1}. Under dynamic conditions, the ion-exchange resin capacity is 310-910 bed volumes depending on the seawater pH, whereas the efficiency of cesium removal exceeds 95%. The removal of more than 95% of cesium-137 has been attained using 1-3 M solutions of nitric acid: here, the eluate volume was 8-8.4 bed volumes. Application of 3 M solution of nitric acid results in resin degradation with the release of gaseous products.

  7. Cytotoxic effects of catechols to glial and neuronal cells

    Directory of Open Access Journals (Sweden)

    Ramon Santos El-Bachá

    2015-04-01

    Full Text Available Catechols are compounds that autoxidises under physiological conditions leading to the formation of reactive oxygen species (ROS, semiquinones, and quinones. These molecules can be formed in organisms because of the metabolism of exogenous aromatic substances, such as benzene. However, there are several important endogenous catechols, which have physiological functions, such as catecholamines. Furthermore, several pharmacological agents are catechols, such as apomorphine, or can be metabolised to generate these compounds. In this presentation we will show that apomorphine can unspecifically bind to proteins during its autoxidation, a phenomenon that is inhibited by thiols. Brain endothelial cells and glial cells express xenobiotic-metabolising enzymes as components of the metabolic blood-brain barrier in an attempt to protect the central nervous system against drugs. Since UDP-glucuronosyltransferases (EC 2.4.1.17 are among these enzymes, we investigated the ability of brain microsomes to conjugate catechols with glucuronate. Despite the fact that 1-naphtol could be glucuronidated in the presence of brain cortex microsomes, the same was not observed for most of catechols that were tested. Therefore, this is not the main mechanism used to protect the brain against them. Indeed, catechols may inhibit other xenobiotic-metabolising enzymes. We showed that apomorphine inhibited the cytochrome P450-dependent dealkylation activity. The production of ROS and reactive quinones, as well as their effects on protein functions, seems to be involved in the cytotoxicity of catechols. Glial cells are more resistant than neuronal cells. Apomorphine was more toxic to rat neurons than to rat C6 glioma cells. 1,2-Dihydroxybenzene (catechol killed human GL-15 cells with an EC50 of 230 uM after 72 h, a effect that was significantly inhibited by superoxide dismutase (EC 1.15.1.1. Another mechanism that we found to be involved in catechol cytotoxicity is the inhibition

  8. Wet air oxidation of resorcinol as a model treatment for refractory organics in wastewaters from the wood processing industry.

    Science.gov (United States)

    Weber, Bernd; Chavez, Alma; Morales-Mejia, Julio; Eichenauer, Sabrina; Stadlbauer, Ernst A; Almanza, Rafael

    2015-09-15

    Wastewater treatment systems are important tools to enhance sustainability in terms of reducing environmental impact and complying with sanitary requirements. This work addresses the wet air oxidation (WAO) process for pre-treatment of phenolic wastewater effluents. The aim was to increase biodegradability prior to a subsequent anaerobic stage. In WAO laboratory experiments using a micro-autoclave, the model compound resorcinol was degraded under different oxygen availability regims within the temperature range 150 °C-270 °C. The activation energy was determined to be 51.5 kJ/mol. Analysis of the products revealed that after 3 h of reaction at 230 °C, 97.5% degradation of resorcinol was achieved. At 250 °C and the same reaction time complete removal of resorcinol was observed. In this case the total organic carbon content was reduced down to 29%, from 118.0 mg/L down to 34.4 mg/L. Under these process conditions, the pollutant was only partially mineralized and the ratio of the biological oxygen demand relative to the chemical oxygen demand, which is 0.07 for resorcinol, was increased to a value exceeding 0.5. The main by-product acetic acid, which is a preferred compound for methanogenic bacteria, was found to account for 33% of the total organic carbon.

  9. Surface grafting of resorcinol onto polyethylene film%PE膜表面接枝间苯二酚

    Institute of Scientific and Technical Information of China (English)

    程珏; 郑义; 杨万泰

    2006-01-01

    Low density polyethylene film surface-grafted resorcinol was prepared by a sequential process.Firstly, acrylic acid was grafted to the surface of low density polyethylene by UV photografting.Secondly, the carboxylic groups in poly(acrylic acid) chains were transferred to acyl chloride groups by the reaction of carboxylic groups with thionyl chloride.The stability of acyl chloride groups in several solvents(alcohol, water, acetone, aqueous NaOH and in N2 atmosphere) was investigated, and N2 atmosphere and acetone were appropriate media to protect acyl chloride groups from side reaction.Finally, resorcinol monomer reacted with acyl chloride to append to the poly(acrylic acid)chains at room temperature.FT-IR-ATR was used to characterize the change of carbonyl groups during each step of the grafting process.Furthermore, by the experimental data of gravimetric analysis the grafted resorcinol monomer on the surface of low density polyethylene film was verified to have undergone condensation with acetone further in the resorcinol/acetone solution at 56℃, which might be a useful feature for synthesizing a thermoplastic/thermosetting composition.

  10. Some properties of active and latent catechol oxidase of mushroom

    Directory of Open Access Journals (Sweden)

    Janusz Czapski

    2013-12-01

    Full Text Available Latent form of mushroom catechol oxidase was activated by O,1% sodium dodecyl sulfate (SDS. Catalytic power of the latent form, calculated from the kinetic parameters was 1,8 times higher than that of active one. Salicyl hydroxamic acid (SHAM appeared as a powerful inhibitor for both active and latent forms of catechol oxidase. However, in the range of 150-250 μM SHAM the inhibitory effect for active catechol oxidase was significantly higher than that for the latent one. Non-competitive and irreversible characteristics of inhibition of latent and active catechol oxidase was calculated from kinetic data. Electrophoretic analysis followed by scanning of the gels was used. The spots' absorbance was determined from a computer image of the isoenzyme band patterns. It allowed us to estimate gels quantitatively. Presence of one additional clearly defined slow moving isoform of SDS-activated catechol oxidase, differed in the respect of 3 bands for the active and 4 bands for the total.

  11. Catechol-Based Hydrogel for Chemical Information Processing

    Directory of Open Access Journals (Sweden)

    Eunkyoung Kim

    2017-07-01

    Full Text Available Catechols offer diverse properties and are used in biology to perform various functions that range from adhesion (e.g., mussel proteins to neurotransmission (e.g., dopamine, and mimicking the capabilities of biological catechols have yielded important new materials (e.g., polydopamine. It is well known that catechols are also redox-active and we have observed that biomimetic catechol-modified chitosan films are redox-active and possess interesting molecular electronic properties. In particular, these films can accept, store and donate electrons, and thus offer redox-capacitor capabilities. We are enlisting these capabilities to bridge communication between biology and electronics. Specifically, we are investigating an interactive redox-probing approach to access redox-based chemical information and convert this information into an electrical modality that facilitates analysis by methods from signal processing. In this review, we describe the broad vision and then cite recent examples in which the catechol–chitosan redox-capacitor can assist in accessing and understanding chemical information. Further, this redox-capacitor can be coupled with synthetic biology to enhance the power of chemical information processing. Potentially, the progress with this biomimetic catechol–chitosan film may even help in understanding how biology uses the redox properties of catechols for redox signaling.

  12. Inactivation of urease by catechol: Kinetics and structure.

    Science.gov (United States)

    Mazzei, Luca; Cianci, Michele; Musiani, Francesco; Lente, Gábor; Palombo, Marta; Ciurli, Stefano

    2017-01-01

    Urease is a Ni(II)-containing enzyme that catalyzes the hydrolysis of urea to yield ammonia and carbamate at a rate 10(15) times higher than the uncatalyzed reaction. Urease is a virulence factor of several human pathogens, in addition to decreasing the efficiency of soil organic nitrogen fertilization. Therefore, efficient urease inhibitors are actively sought. In this study, we describe a molecular characterization of the interaction between urease from Sporosarcina pasteurii (SPU) and Canavalia ensiformis (jack bean, JBU) with catechol, a model polyphenol. In particular, catechol irreversibly inactivates both SPU and JBU with a complex radical-based autocatalytic multistep mechanism. The crystal structure of the SPU-catechol complex, determined at 1.50Å resolution, reveals the structural details of the enzyme inhibition.

  13. Nanosheet Graphene Composite Carbon Aerogels from Resorcinol-Formaldehyde via an Adsorption-Assembly Polymerization Method .

    Science.gov (United States)

    Qiu, Jielong; Zhang, Shuting; Mai, Jiawen; Wu, Fangjun; Liu, Wei

    2015-12-01

    An adsorption-assembly sol-gel polymerization between graphene oxide (GO) sheets and resorcinol-formaldehyde aqueous solution was investigated as a method to form graphene composite carbon aerogels (GCAs) with cross-linked nanosheet structure and a surface area as high as 489 m2/g. By adjusting the amount of GO and the catalyst of hexamethylenetetramine (HMTA) in the precursor mixture, aerogels with little drying shrinkage under ambient pressure condition could be obtained. Benefiting from the attendance of graphene oxide, the obtained GCAs showed a regular nanosheets structure with countless nano-size particles on the sheet surface, which is quite different from the conventional carbon aerogels. The electrochemical performance of the GCAs were evaluated, they displayed small internal resistance and outstanding electrochemical specific capacitance (131 F/g), as well as a stable cycle performance (no capacitance loss after 5000 cycles).

  14. Study on efficient removal of clopyralid from water using resorcinol-formaldehyde carbon cryogel

    Directory of Open Access Journals (Sweden)

    Momčilović Milan Z.

    2014-01-01

    Full Text Available Resorcinol-formaldehyde carbon cryogel has been prepared, characterized and used for the removal of commonly used herbicide clopyralid from the aqueous solutions under varying experimental conditions. Carbon has shown a relatively high specific surface area, significant mesoporosity and an amorphous structure. A set of the following isotherm models has been used to interpret the equilibrium data: Langmuir, Freundlich, Temkin, Dubinin-Radushkevich, Jovanović, Hurkins-Jura, and Helsey model. Several models have fitted well although the calculated values for qmax poorly correlate with the data obtained experimentally. The kinetic models of the pseudo-first and pseudo-second-order, the models of Elovich, Bangham and the intraparticle diffusion model have been used for fitting the kinetic data. The rate of the process is fast in the beginning while adsorption equilibrium is attained not until 24 hours. Adsorption was found to be pH dependent and favored in acidic solutions.

  15. An investigation of the radiolytic stability of a resorcinol-formaldehyde ion exchange resin

    Energy Technology Data Exchange (ETDEWEB)

    Crawford, C.L.; Bibler, N.E.

    1994-01-31

    Developing and demonstrating waste separations technologies are the principal objectives of the Underground Storage Tank -Integrated Demonstration (UST-ID) Program carried out by Pacific Northwest Laboratories (PNL) at the DOE Hanford site. One planned separation technique utilizes ion exchange for removal of cesium and strontium from high-level liquid supernates. A resorcinol-formaldehyde resin, which is a polycondensation-type cation exchange resin for cesium removal, has been developed at the Savannah River Technology Center (SRTC) and has demonstrated superlative performance in testing at SRS, Oak Ridge and PNL. Advantages of this resin relative to other media for cesium removal are its high capacity for cesium and its compatibility with the high pH and aluminum and sodium concentrations of both Hanford and SRS high-level liquid wastes.

  16. Evaluations of Mechanisms for Pu Uptake and Retention within Spherical Resorcinol-Formaldehyde Resin Columns

    Energy Technology Data Exchange (ETDEWEB)

    Delegard, Calvin H. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Levitskaia, Tatiana G. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Fiskum, Sandra K. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2016-09-15

    The unexpected uptake and retention of plutonium (Pu) onto columns containing spherical resorcinol-formaldehyde (sRF) resin during ion exchange testing of Cs (Cs) removal from alkaline tank waste was observed in experiments at both the Pacific Northwest National Laboratory (PNNL) and the Savannah River National Laboratory (SRNL). These observations have raised concern regarding the criticality safety of the Cs removal unit operation within the low-activity waste pretreatment system (LAWPS). Accordingly, studies have been initiated at Washington River Protection Solutions (WRPS), who manages the operations of the Hanford Site tank farms, including the LAWPS, PNNL, and elsewhere to investigate these findings. As part of these efforts, PNNL has prepared the present report to summarize the laboratory testing observations, evaluate these phenomena in light of published and unpublished technical information, and outline future laboratory testing, as deemed appropriate based on the literature studies, with the goal to elucidate the mechanisms for the observed Pu uptake and retention.

  17. Cesium Isotherm Testing with Spherical Resorcinol-Formaldehyde Resin at High Sodium Concentrations

    Energy Technology Data Exchange (ETDEWEB)

    Russell, Renee L. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Fiskum, Sandra K. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Smoot, Margaret R. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Rinehart, Donald E. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2016-04-01

    Washington River Protection Solutions (WRPS) is developing a Low-Activity Waste Pretreatment System (LAWPS) to provide low-activity waste (LAW) directly to the Hanford Tank Waste Treatment and Immobilization Plant (WTP) Low-Activity Waste Facility for immobilization. The pretreatment that will be conducted on tank waste supernate at the LAWPS facility entails filtration to remove entrained solids and cesium (Cs) ion exchange to remove Cs from the product sent to the WTP. Currently, spherical resorcinol-formaldehyde (sRF) resin (Microbeads AS, Skedsmokorset, Norway) is the Cs ion exchange resin of choice. Most work on Cs ion exchange efficacy in Hanford tank waste has been conducted at nominally 5 M sodium (Na). WRPS is examining the possibility of processing supernatant at high Na concentrations—up to 8 M Na—to maximize processing efficiency through the LAWPS. Minimal Cs ion exchange work has been conducted at 6 M and 8 M Na concentrations..

  18. Reactive oxygen species production by catechol stabilized copper nanoparticles

    Science.gov (United States)

    Chen, Cheng; Ahmed, Ishtiaq; Fruk, Ljiljana

    2013-11-01

    Stable Cu nanoparticles (NPs) prepared using catechol containing dopamine-based linkers could generate reactive oxygen species (ROS) that can activate peroxidase enzymes and catalyze the degradation of fluorescent dye pollutants.Stable Cu nanoparticles (NPs) prepared using catechol containing dopamine-based linkers could generate reactive oxygen species (ROS) that can activate peroxidase enzymes and catalyze the degradation of fluorescent dye pollutants. Electronic supplementary information (ESI) available: Details of the synthesis of dopamine linkers and Cu NPs, peroxidase activity tests, H2O2 calibration and degradation tests for resorufin, RB and MB. See DOI: 10.1039/c3nr03563h

  19. Comparative study on pore structures of mesoporous ZSM-5 from resorcinol-formaldehyde aerogel and carbon aerogel templating.

    Science.gov (United States)

    Tao, Yousheng; Hattori, Yoshiyuki; Matumoto, Akihiko; Kanoh, Hirofumi; Kaneko, Katsumi

    2005-01-13

    Resorcinol-formaldehyde aerogels and carbon aerogels of different mesoporosities have been used as templates for preparing bimodal zeolites of mesopores. Samples were thoroughly characterized with X-ray diffraction, field emission scanning electron microscopy, thermogravimetric analysis, X-ray photoelectron spectroscopy, N(2) adsorption at 77 K, as well as FT-IR spectroscopy and (29)Si nuclear magnetic resonance spectroscopy. The mesoporous ZSM-5 zeolites have additional mesopores of 9-25 nm in widths and 0.07-0.2 cm(3)/g in volumes, besides their perfect inherent micropores. Experimental results show the mesoporous systems of the finally obtained zeolites can be influenced by proper preparation of resorcinol-formaldehyde aerogels and carbon aerogels through solution chemistry. Consequently, zeolites of tunable mesoporosities can be prepared with this unique methodology.

  20. Preparation of alpha-bisabolol and phenylethyl resorcinol/TiO2 hybrid composites for potential applications in cosmetics.

    Science.gov (United States)

    Leong, H J; Jang, I; Hyun, K-S; Jung, S-K; Hong, G-H; Jeong, H-A; Oh, S-G

    2016-10-01

    Bifunctional alpha-bisabolol and phenylethyl resorcinol/TiO2 hybrids were prepared to apply in cosmetic fields, particularly in anti-ageing and hyperpigmentation treatment. The synergistic effect of combined antioxidant and UV filtering properties was achieved through functionalization of TiO2 particles with skin-lightening materials such as alpha-bisabolol and phenylethyl resorcinol. TiO2 microspheres with a diameter of about 1 μm were synthesized through surfactant-assisted sol-gel method for use as supporting materials in the formation of hybrid composites. Carboxylation treatment was performed for surface modification of the TiO2 surface with carboxyl groups as chemical binders. Esterification reaction between carboxyl groups of carboxylated TiO2 and hydroxyl groups of alpha-bisabolol or phenylethyl resorcinol was performed. The hybrids were characterized using various techniques such as FE-SEM, DLS, EDS, ATR-FTIR, XPS and TGA. For application of prepared TiO2 composites in the field of cosmetics, the anti-radicular antioxidant abilities were evaluated using ABTS and DPPH colorimetric antioxidant assay. Organic/inorganic hybrid composites were successfully formed using esterification reaction between the carboxyl groups at TiO2 surface and the hydroxyl groups of the skin-lightening materials. The results demonstrate that both functionalized microspheres show scavenging ability towards the ABTS(•) and DPPH(•) radicals. Specifically, the phenylethyl resorcinol/TiO2 composites exhibited the highest antioxidant ability among the prepared samples owing to the presence of phenolic groups to scavenge free radicals. Using this strategy, it could be possible to prepare not only inorganic UV filter but also hybrid organic/inorganic materials with multifunctions and advantages which would be in a great demand for cosmetic applications. © 2016 Society of Cosmetic Scientists and the Société Française de Cosmétologie.

  1. PREPARATION AND CHARACTERIZATION OF ORGANIC AEROGELS BY THE LIGNIN - RESORCINOL - FORMALDEHYDE COPOLYMER

    Directory of Open Access Journals (Sweden)

    Feng Chen

    2011-04-01

    Full Text Available Lignin can be used as a cheap natural raw material to prepare organic aerogels based upon gelation and supercritical drying in ethanol. The aerogels were prepared from a mixture of the raw materials with lignin (L, resorcinol (R, and formaldehyde (F, followed by a reaction catalyzed by NaOH(C. The effect of the preparation conditions, such as the LRF concentration, the mass ratio of LR to NaOH (LR/C, the mole ratio of LR to F (LR/F, and the gelation temperature, on the gelation ability and the bulk density were studied. The results showed that the density of LRF aerogels increased with increasing reactant concentration and catalyst content. The microstructure of the porous carbon aerogels was investigated by SEM and TEM. The specific surface area and pore size distribution of LRF and RF aerogels were studied by nitrogen adsorption-desorption analysis. The pore width of LRF aerogels ranged from 1 nm to 100 nm. Most of the pores were about 50 nm wide, as is typical for mesoporous materials.

  2. Fire Safety Tests for Spherical Resorcinol Formaldehyde Resin: Data Summary Report

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Dong-Sang; Peterson, Reid A.; Schweiger, Michael J.

    2012-07-30

    A draft safety evaluation of the scenario for spherical resorcinol-formaldehyde (SRF) resin fire inside the ion exchange column was performed by the Hanford Tank Waste Treatment and Immobilization Plant (WTP) Fire Safety organization. The result of this draft evaluation suggested a potential change of the fire safety classification for the Cesium Ion Exchange Process System (CXP) emergency elution vessels, equipment, and piping, which may be overly bounding based on the fire performance data from the manufacturer of the ion exchange resin selected for use at the WTP. To resolve this question, the fire properties of the SRF resin were measured by Southwest Research Institute (SwRI), following the American Society for Testing and Materials (ASTM) standard procedures, through a subcontract managed by Pacific Northwest National Laboratory (PNNL). For some tests, the ASTM standard procedures were not entirely appropriate or practical for the SRF resin material, so the procedures were modified and deviations from the ASTM standard procedures were noted. This report summarizes the results of fire safety tests performed and reported by SwRI. The efforts by PNNL were limited to summarizing the test results provided by SwRI into one consolidated data report. All as-received SwRI reports are attached to this report in the Appendix. Where applicable, the precision and bias of each test method, as given by each ASTM standard procedure, are included and compared with the SwRI test results of the SRF resin.

  3. Effect of Fiber Treatment and Fiber Loading on Mechanical Properties of Luffa-Resorcinol Composites

    Directory of Open Access Journals (Sweden)

    Chhatrapati Parida

    2015-01-01

    Full Text Available Tensile and compressive behaviour of resorcinol-formaldehyde (RF matrix and its composites reinforced with fibers of Luffa cylindrica (LC have been studied. LC fibers were subjected to chemical treatments such as alkali activation by NaOH followed by bleaching and acid hydrolysis in order to improve fiber-matrix adhesion. Both treated and untreated LC fibers are modified with calcium phosphate. The presence of hydroxy apatite, a polymorph of calcium phosphate and a major constituent of vertebrate bone and teeth, was confirmed from XRD peak of treated LC fiber. XRD analysis of the treated LC fiber has confirmed the crystalline nature of the chemically treated LC fiber by its crystallinity index. The effects of fiber loading of chemically treated and untreated LC fiber on ultimate stress, yield strength, breaking stress, and modulus of the composites were analyzed. The tensile and compressive modulus of the composites were increased with incorporation of both treated and untreated LC fibers into the RF matrix. The modulus of composites with treated LC fiber was enhanced compared to that of the untreated fiber composites. Furthermore the values of ultimate stress, yield stress, and breaking stress were increased with the incorporation of treated LC fiber in the composites.

  4. Gelation mechanism of resorcinol-formaldehyde gels investigated by dynamic light scattering.

    Science.gov (United States)

    Taylor, Stewart J; Haw, Mark D; Sefcik, Jan; Fletcher, Ashleigh J

    2014-09-02

    Xerogels and porous materials for specific applications such as catalyst supports, CO2 capture, pollutant adsorption, and selective membrane design require fine control of pore structure, which in turn requires improved understanding of the chemistry and physics of growth, aggregation, and gelation processes governing nanostructure formation in these materials. We used time-resolved dynamic light scattering to study the formation of resorcinol-formaldehyde gels through a sol-gel process in the presence of Group I metal carbonates. We showed that an underlying nanoscale phase transition (independent of carbonate concentration or metal type) controls the size of primary clusters during the preaggregation phase; while the amount of carbonate determines the number concentration of clusters and, hence, the size to which clusters grow before filling space to form the gel. This novel physical insight, based on a close relationship between cluster size at the onset of gelation and average pore size in the final xerogel results in a well-defined master curve, directly linking final gel properties to process conditions, facilitating the rational design of porous gels with properties specifically tuned for particular applications. Interestingly, although results for lithium, sodium, and potassium carbonate fall on the same master curve, cesium carbonate gels have significantly larger average pore size and cluster size at gelation, providing an extended range of tunable pore size for further adsorption applications.

  5. Spectrophotometric Determination of Gallium(III with 4-(2-Pyridylazo-resorcinol and Nitron

    Directory of Open Access Journals (Sweden)

    Petya Vassileva Racheva

    2015-07-01

    Full Text Available The formation and liquid-liquid extraction of ion-association complex between gallium(III − 4-(2-pyridylazo-resorcinol (PAR – 1,4-diphenyl-3-(phenylamino-1H-1,2,4-triazole (nitron, Nt, water and chloroform were studied. The optimum conditions for gallium(III extraction as an ion-association complex, (NtH+[Ga3+(PAR2]-, were found: pH, concentration of the reagents and shaking time. The following key constants were calculated: constant of extraction (logKex = 6.28 ± 0.07, constant of association (logβ = 4.98 ± 0.05, constant of distribution (logKD = 1.30 ± 0.02 and recovery factor (R / % = 95.17 ± 0.02. Beerʼs law is obeyed for Ga(III concentration up to 0.8 μg cm-3 with apparent molar absorptivity of (10.3 ± 0.4×104 dm-3 mol-1 cm-1 at λmax = 510 nm. Some additional characteristics, such as limit of detection (LOD = 0.072 μg cm-3, limit of quantification (LOQ = 0.24 μg cm-3 and Sandellʼs sensitivity (SS = 0.000675 ng cm-2 were estimated as well.

  6. Ion Exchange Modeling Of Cesium Removal From Hanford Waste Using Spherical Resorcinol-Formaldehyde Resin

    Energy Technology Data Exchange (ETDEWEB)

    Aleman, S. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Hamm, L. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Smith, F. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2007-06-27

    This report discusses the expected performance of spherical Resorcinol-Formaldehyde (RF) ion exchange resin for the removal of cesium from alkaline Hanford radioactive waste. Predictions of full scale column performance in a carousel mode are made for the Hot Commissioning, Envelope B, and Subsequent Operations waste compositions under nominal operating conditions and for perturbations from the nominal. Only the loading phase of the process cycle is addressed in this report. Pertinent bench-scale column tests, kinetic experiments, and batch equilibrium experiments are used to estimate model parameters and to benchmark the ion-exchange model. The methodology and application presented in this report reflect the expected behavior of spherical RF resin manufactured at the intermediate-scale (i.e., approximately 100 gallon batch size; batch 5E-370/641). It is generally believed that scale-up to production-scale in resin manufacturing will result in similarly behaving resin batches whose chemical selectivity is unaffected while total capacity per gram of resin may vary some. As such, the full-scale facility predictions provided within this report should provide reasonable estimates of production-scale column performance.

  7. Fire Safety Tests for Cesium-Loaded Spherical Resorcinol Formaldehyde Resin: Data Summary Report

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Dong-Sang; Schweiger, Michael J.; Peterson, Reid A.

    2012-09-01

    A draft safety evaluation of the scenario for spherical resorcinol formaldehyde (SRF) resin fire inside the ion exchange column was performed by the Hanford Tank Waste Treatment and Immobilization Plant (WTP) Fire Safety organization. The result of this draft evaluation suggested a potential change of the fire safety classification for the Cesium Ion Exchange Process System (CXP) emergency elution vessels, equipment, and piping. To resolve this question, the fire properties of the SRF resin were measured by Southwest Research Institute (SwRI) through a subcontract managed by Pacific Northwest National Laboratory (PNNL). The results of initial fire safety tests on the SRF resin were documented in a previous report (WTP-RPT-218). The present report summarizes the results of additional tests performed by SwRI on the cesium-loaded SRF resin. The efforts by PNNL were limited to summarizing the test results provided by SwRI into one consolidated data report. The as-received SwRI report is attached to this report in the Appendix A. Where applicable, the precision and bias of each test method, as given by each American Society for Testing and Materials (ASTM) standard procedure, are included and compared with the SwRI test results of the cesium-loaded SRF resin.

  8. Equation-of-State Measurements of Resorcinol Formaldehyde Foam Using Imaging X-Ray Thomson Spectrometer

    Science.gov (United States)

    Belancourt, Patrick; Theobald, W.; Keiter, P. A.; Collins, T. J. B.; Bonino, M. J.; Kozlowski, P.; Drake, R. P.

    2015-11-01

    Understanding the equation of state of materials under shocked conditions is important for laboratory astrophysics and high-energy-density physics experiments. This talk will focus on experiments dedicated to developing a platform for measuring the equation of state of shocked foams on OMEGA EP. The foam used in the development of this platform is resorcinol formaldehyde foam with an initial density of 0.34 g/cc. One OMEGA EP beam drives a shock into the foam, while the remaining three beams irradiate a nickel foil to create the x-ray backlighter. The primary diagnostic for this platform, the imaging x-ray Thomson spectrometer (IXTS), spectrally resolves the scattered x-ray beam while imaging in one spatial dimension. The IXTS is ideally suited to measure plasma conditions upstream, downstream and at the shock front in the foam. Preliminary results from these experiments will be shown. This material is based upon work supported by the Department of Energy National Nuclear Security Administration under Award Number DE-NA0001944, the NNSA-DS and SC-OFES Joint Program in High-Energy-Density Laboratory Plasmas DE-NA0001840, and by the National Laser User Facility Program DE-NA0000850.

  9. Adsorption of catechol from aqueous solution by aminated hypercrosslinked polymers

    Institute of Scientific and Technical Information of China (English)

    SUN Yue; LI Xiao-tao; XU Chao; CHEN Jin-long; LI Ai-min; ZHANG Quan-xing

    2005-01-01

    Adsorption of catechol from aqueous solution with the hypercrosslinked polymeric adsorbent NDA-100 and its derivatives AH-1,AH-2 and AH-3 aminated by dimethylamine, the commercial resin Amberlite XAD-4 and weakly basic anion exchanger resin D301 was compared. It was found that the aminated hypercrosslinked resins had the highest adsorption capacities among the tested polymers. The empirical Freundlich equation was successfully employed to describe the adsorption process. Specific surface area and micropore structure of the adsorbent, in company with tertiary amino groups on matrix affected the adsorption performance towards catechol. In addition,thermodynamic study was carried out to interpret the adsorption mechanism. Kinetic study testified that the tertiary amino groups on the polymer matrix could decrease the adsorption rate and increase the adsorption apparent activation energy.

  10. A catechol biosensor based on electrospun carbon nanofibers

    Directory of Open Access Journals (Sweden)

    Dawei Li

    2014-03-01

    Full Text Available Carbon nanofibers (CNFs were prepared by combining electrospinning with a high-temperature carbonization technique. And a polyphenol biosensor was fabricated by blending the obtained CNFs with laccase and Nafion. Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR and field emission scanning electron microscope (FE-SEM were, respectively, employed to investigate the structures and morphologies of the CNFs and of the mixtures. Cyclic voltammetry and chronoamperometry were employed to study the electrocatalysis of the catechol biosensor. The results indicated that the sensitivity of the biosensor was 41 µA·mM−1, the detection limit was 0.63 µM, the linear range was 1–1310 µM and the response time was within 2 seconds, which excelled most other laccase-based biosensor reported. Furthermore, the biosensor showed good repeatability, reproducibility, stability and tolerance to interferences. This novel biosensor also demonstrated its promising application in detecting catechol in real water samples.

  11. A catechol biosensor based on electrospun carbon nanofibers

    Science.gov (United States)

    Li, Dawei; Pang, Zengyuan; Chen, Xiaodong; Luo, Lei; Cai, Yibing

    2014-01-01

    Summary Carbon nanofibers (CNFs) were prepared by combining electrospinning with a high-temperature carbonization technique. And a polyphenol biosensor was fabricated by blending the obtained CNFs with laccase and Nafion. Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR) and field emission scanning electron microscope (FE-SEM) were, respectively, employed to investigate the structures and morphologies of the CNFs and of the mixtures. Cyclic voltammetry and chronoamperometry were employed to study the electrocatalysis of the catechol biosensor. The results indicated that the sensitivity of the biosensor was 41 µA·mM−1, the detection limit was 0.63 µM, the linear range was 1–1310 µM and the response time was within 2 seconds, which excelled most other laccase-based biosensor reported. Furthermore, the biosensor showed good repeatability, reproducibility, stability and tolerance to interferences. This novel biosensor also demonstrated its promising application in detecting catechol in real water samples. PMID:24778958

  12. Computational Study on the Stacking Interaction in Catechol Complexes

    Science.gov (United States)

    Estévez, Laura; Otero, Nicolás; Mosquera, Ricardo A.

    2009-09-01

    The stability and electron density topology of catechol complexes (dimers and tetramer) were studied using the MPW1B95 functional. The QTAIM analysis shows that both dimers (face to face and C-H/π one) display a different electronic origin. The formation of the former is accompanied by a significant change in the values of atomic electron dipole and quadrupole components, flattening the most diffuse part of the electron density distribution toward the molecular plane. A small electron population transfer is observed between catechol monomers connected by C-H/π interactions, whose QTAIM characterization does not differ from that of a weak hydrogen bond. Cooperative effects in the tetramer on binding energies are small and negligible for bond properties and charge transfer. Nevertheless, they are significant on atomic electron populations.

  13. The role of DNA methylation in catechol-enhanced erythroid differentiation of K562 cells

    Energy Technology Data Exchange (ETDEWEB)

    Li, Xiao-Fei; Wu, Xiao-Rong; Xue, Ming; Wang, Yan; Wang, Jie; Li, Yang; Suriguga,; Zhang, Guang-Yao; Yi, Zong-Chun, E-mail: yizc@buaa.edu.cn

    2012-11-15

    Catechol is one of phenolic metabolites of benzene in vivo. Catechol is also widely used in pharmaceutical and chemical industries. In addition, fruits, vegetables and cigarette smoke also contain catechol. Our precious study showed that several benzene metabolites (phenol, hydroquinone, and 1,2,4-benzenetriol) inhibited erythroid differentiation of K562 cells. In present study, the effect of catechol on erythroid differentiation of K562 cells was investigated. Moreover, to address the role of DNA methylation in catechol-induced effect on erythroid differentiation in K562 cells, methylation levels of erythroid-specific genes were analyzed by Quantitative MassARRAY methylation analysis platform. Benzidine staining showed that exposure to catechol enhanced hemin-induced hemoglobin accumulation in K562 cells in concentration- and time-dependent manners. The mRNA expression of erythroid specific genes, including α-globin, β-globin, γ-globin, erythroid 5-aminolevulinate synthase, erythroid porphobilinogen deaminase, and transcription factor GATA-1 genes, showed a significant concentration-dependent increase in catechol-treated K562 cells. The exposure to catechol caused a decrease in DNA methylation levels at a few CpG sites in some erythroid specific genes including α-globin, β-globin and erythroid porphobilinogen deaminase genes. These results indicated that catechol improved erythroid differentiation potency of K562 cells at least partly via up-regulating transcription of some erythroid related genes, and suggested that inhibition of DNA methylation might be involved in up-regulated expression of some erythroid related genes. -- Highlights: ► Catechol enhanced hemin-induced hemoglobin accumulation. ► Exposure to catechol resulted in up-regulated expression of erythroid genes. ► Catechol reduced methylation levels at some CpG sites in erythroid genes.

  14. Biological degradation of catechol in wastewater using the sequencing continuous-inflow reactor (SCR).

    Science.gov (United States)

    Aghapour, Ali Ahmad; Moussavi, Gholamreza; Yaghmaeian, Kamyar

    2013-05-24

    Catechol is used in many industries. It can be removed from wastewater by various methods but biological processes are the most superior and commonly used technology. The SCR is a modified form of SBR used to degrade catechol. The objective of this study was to investigate the performance of SCR for biodegradation and mineralization of catechol under various inlet concentrations (630-1500 mg/L) and hydraulic retention times (HRT) (18-9 h). This study used a bench scale SCR setup to test catechol degradation. The acclimation time of biomass for catechol at degradation at 630 mg/L was 41 d. The SCR operating cycle time was 6 h and the consecutive times taken for aerating, settling and decanting were 4, 1.5 and 0.5 h, respectively. This study investigated the effects of inlet catechol concentration (630-1560 mg/L) and HRT (18-9 h). The average catechol removal efficiencies in steady-state conditions of 630, 930, 12954 and 1559 mg/L of catechol were 98.5%, 98.5%, 98.2% and 96.9% in terms catechol and 97.8%, 97.7%, 96.4% and 94.3% for COD, respectively. SCR with acclimated biomasses could effectively remove the catechol and the corresponding COD from wastewater with concentrations of up to 1560, at the loading rate of 5.38 kg COD/m3.d and at a HRT of up to 13 h. The HRT was determined as an important variable affecting catechol removal from wastewater. Reducing the HRT to below 13 h led to reduced removal of catechol and COD.

  15. Immobilization of amphiphilic polycations by catechol functionality for antimicrobial coatings.

    Science.gov (United States)

    Han, Hua; Wu, Jianfeng; Avery, Christopher W; Mizutani, Masato; Jiang, Xiaoming; Kamigaito, Masami; Chen, Zhan; Xi, Chuanwu; Kuroda, Kenichi

    2011-04-05

    A new strategy for preparing antimicrobial surfaces by a simple dip-coating procedure is reported. Amphiphilic polycations with different mole ratios of monomers containing dodecyl quaternary ammonium, methoxyethyl, and catechol groups were synthesized by free-radical polymerization. The polymer coatings were prepared by immersing glass slides into a polymer solution and subsequent drying and heating. The quaternary ammonium side chains endow the coatings with potent antibacterial activity, the methoxyethyl side chains enable tuning the hydrophobic/hydrophilic balance, and the catachol groups promote immobilization of the polymers into films. The polymer-coated surfaces displayed bactericidal activity against Escherichia coli and Staphylococcus aureus in a dynamic contact assay and prevented the accumulation of viable E. coli, S. aureus, and Acinetobacter baumannii for up to 96 h. Atomic force microscopy (AFM) images of coating surfaces indicated that the surfaces exhibit virtually the same smoothness for all polymers except the most hydrophobic. The hydrophobic polymer without methoxyethyl side chains showed clear structuring into polymer domains, causing high surface roughness. Sum-frequency generation (SFG) vibrational spectroscopy characterization of the surface structures demonstrated that the dodecyl chains are predominantly localized at the surface-air interface of the coatings. SFG also showed that the phenyl groups of the catechols are oriented on the substrate surface. These results support our hypothesis that the adhesive or cross-linking functionality of catechol groups discourages polymer leaching, allowing the tuning of the amphiphilic balance by incorporating hydrophilic components into the polymer chains to gain potent biocidal activity.

  16. Aerosol formation yields from the reaction of catechol with ozone

    Science.gov (United States)

    Coeur-Tourneur, Cécile; Tomas, Alexandre; Guilloteau, Angélique; Henry, Françoise; Ledoux, Frédéric; Visez, Nicolas; Riffault, Véronique; Wenger, John C.; Bedjanian, Yuri

    The formation of secondary organic aerosol from the gas-phase reaction of catechol (1,2-dihydroxybenzene) with ozone has been studied in two smog chambers. Aerosol production was monitored using a scanning mobility particle sizer and loss of the precursor was determined by gas chromatography and infrared spectroscopy, whilst ozone concentrations were measured using a UV photometric analyzer. The overall organic aerosol yield ( Y) was determined as the ratio of the suspended aerosol mass corrected for wall losses ( Mo) to the total reacted catechol concentrations, assuming a particle density of 1.4 g cm -3. Analysis of the data clearly shows that Y is a strong function of Mo and that secondary organic aerosol formation can be expressed by a one-product gas-particle partitioning absorption model. The aerosol formation is affected by the initial catechol concentration, which leads to aerosol yields ranging from 17% to 86%. The results of this work are compared to similar studies reported in the literature.

  17. Fluorescence quenching method for the determination of catechol with gold nanoparticles and tyrosinase hybrid system

    Institute of Scientific and Technical Information of China (English)

    Martin; M.F.Choi

    2010-01-01

    The determination method of catechol by fluorescence quenching was developed.The assay was based on the combination of the unique property of gold nanoparticles with tyrosinase enzymatic reaction.In the presence of tyrosinase,the fluorescence of gold nanoparticles was quenched by catechol which can be employed to detect catechol.Under the optimal conditions,a linear range 5.0×10~(-7)-1.0×10~(-3) mol L~(-1) and a detection limit 1.0×10~(-7) mol L~(-1) of catechol were obtained.o-Quinone intermediate produ...

  18. Defining the Catechol-Cation Synergy for Enhanced Wet Adhesion to Mineral Surfaces.

    Science.gov (United States)

    Rapp, Michael V; Maier, Greg P; Dobbs, Howard A; Higdon, Nicholas J; Waite, J Herbert; Butler, Alison; Israelachvili, Jacob N

    2016-07-27

    Mussel foot proteins (Mfps) exhibit remarkably adaptive adhesion and bridging between polar surfaces in aqueous solution despite the strong hydration barriers at the solid-liquid interface. Recently, catechols and amines-two functionalities that account for >50 mol % of the amino acid side chains in surface-priming Mfps-were shown to cooperatively displace the interfacial hydration and mediate robust adhesion between mineral surfaces. Here we demonstrate that (1) synergy between catecholic and guanidinium side chains similarly promotes adhesion, (2) increasing the ratio of cationic amines to catechols in a molecule reduces adhesion, and (3) the catechol-cation synergy is greatest when both functionalities are present within the same molecule.

  19. Identification of Catechol as a New Marker for Detecting Propolis Adulteration

    Directory of Open Access Journals (Sweden)

    Shuai Huang

    2014-07-01

    Full Text Available Adulteration of propolis with poplar extract is a serious issue in the bee products market. The aim of this study was to identify marker compounds in adulterated propolis, and examine the transformation of chemical components from poplar buds to propolis. The chemical profiles of poplar extracts and propolis were compared, and a new marker compound, catechol, was isolated and identified from the extracts of poplar buds. The polyphenol oxidase, catechol oxidase, responsible for catalyzing oxidation of catechol was detected in poplar buds and propolis. The results indicate catechol can be used as a marker to detect propolis adulterated with poplar extract.

  20. Relative Abundance and the Relationships between Aniline,Phenol and Catechol Degraders in Fresh Water

    Institute of Scientific and Technical Information of China (English)

    MasaoNasu; NevilGOONEWARDENA; 等

    1993-01-01

    Relative abundance and relationships between aniline,phenol and catechol degraders were investigated in unpolluted and polluted fresh waters in Osaka prefectur,Japan,Phenol and catechol degraders were found more frequently compared to aniline degraders.The results indicate that these degraders were more abundant in polluted waters than in unpolluted waters.Aniline degraders isolated from the Ina River water showed a higher capability of degrading catechol than phenol.Analysis on sequence homology among these three kinds of degraders indicated a possible relationship between aniline degraders and certain strains of both catechol and phenol degraders.

  1. Hair dyes resorcinol and lawsone reduce production of melanin in melanoma cells by tyrosinase activity inhibition and decreasing tyrosinase and microphthalmia-associated transcription factor (MITF) expression.

    Science.gov (United States)

    Lee, Shu-Mei; Chen, Yi-Shyan; Lin, Chih-Chien; Chen, Kuan-Hung

    2015-01-09

    Hair coloring products are one of the most important cosmetics for modern people; there are three major types of hair dyes, including the temporary, semi-permanent and permanent hair dyes. The selected hair dyes (such as ammonium persulfate, sodium persulfate, resorcinol and lawsone) are the important components for hair coloring products. Therefore, we analyzed the effects of these compounds on melanogenesis in B16-F10 melanoma cells. The results proved that hair dyes resorcinol and lawsone can reduce the production of melanin. The results also confirmed that resorcinol and lawsone inhibit mushroom and cellular tyrosinase activities in vitro. Resorcinol and lawsone can also downregulate the protein levels of tyrosinase and microphthalmia-associated transcription factor (MITF) in B16-F10 cells. Thus, we suggest that frequent use of hair dyes may have the risk of reducing natural melanin production in hair follicles. Moreover, resorcinol and lawsone may also be used as hypopigmenting agents to food, agricultural and cosmetic industry in the future.

  2. Hair Dyes Resorcinol and Lawsone Reduce Production of Melanin in Melanoma Cells by Tyrosinase Activity Inhibition and Decreasing Tyrosinase and Microphthalmia-Associated Transcription Factor (MITF Expression

    Directory of Open Access Journals (Sweden)

    Shu-Mei Lee

    2015-01-01

    Full Text Available Hair coloring products are one of the most important cosmetics for modern people; there are three major types of hair dyes, including the temporary, semi-permanent and permanent hair dyes. The selected hair dyes (such as ammonium persulfate, sodium persulfate, resorcinol and lawsone are the important components for hair coloring products. Therefore, we analyzed the effects of these compounds on melanogenesis in B16-F10 melanoma cells. The results proved that hair dyes resorcinol and lawsone can reduce the production of melanin. The results also confirmed that resorcinol and lawsone inhibit mushroom and cellular tyrosinase activities in vitro. Resorcinol and lawsone can also downregulate the protein levels of tyrosinase and microphthalmia-associated transcription factor (MITF in B16-F10 cells. Thus, we suggest that frequent use of hair dyes may have the risk of reducing natural melanin production in hair follicles. Moreover, resorcinol and lawsone may also be used as hypopigmenting agents to food, agricultural and cosmetic industry in the future.

  3. Enzymatic activity of catechol 1,2-dioxygenase and catechol 2,3-dioxygenase produced by Gordonia polyisoprenivorans

    Directory of Open Access Journals (Sweden)

    Andréa Scaramal Silva

    2012-01-01

    Full Text Available This study aimed to evaluate the environmental conditions for enzyme activity of catechol 1,2-dioxygenase (C1,2O and catechol 2,3-dioxygenase (C2,3O produced by Gordonia polyisoprenivorans in cell-free and immobilized extracts. The optimum conditions of pH, temperature, time course and effect of ions for enzyme activity were determined. Peak activity of C1,2O occurred at pH 8.0. The isolate exhibited the highest activity of C2,3O at pH 7.0 and 8.0 for the cell-free extract and immobilized extract, respectively. This isolate exhibited important characteristics such as broad range of pH, temperature and time course for enzyme activity.

  4. PILOT-SCALE HYDRAULIC TESTING OF RESORCINOL FORMALDEHYDE ION EXCHANGE RESIN

    Energy Technology Data Exchange (ETDEWEB)

    Adamson, D.

    2009-05-28

    Savannah River National Laboratory (SRNL) performed pilot-scale hydraulic/chemical testing of spherical resorcinol formaldehyde (RF) ion exchange (IX) resin for the River Protection Project-Hanford Tank Waste Treatment & Immobilization Plant (WTP) Project. The RF resin hydraulic cycle testing was conducted in two pilot-scale IX columns, 1/4 and 1/2 scale. A total of twenty-three hydraulic/chemical cycles were successfully completed on the spherical RF resin. Sixteen of these cycles were completed in the 24-inch IX Column (1/2 scale column). Hydraulic testing showed that the permeability of the RF resin remained essentially constant, with no observed trend in the reduction of the permeability as the number of cycles increased. The permeability during the pilot-scale testing was 3 times better than the design requirements of the WTP full-scale IX system. The RF resin bed showed no tendency to form fissures or pack more densely as the number of cycles increased. Particle size measurements of the RF resin showed no indication of particle size change (for a given chemical) with cycles and essentially no fines formation. The permeability of the resin bed was uniform with respect to changes in bed depth. Upflow Regeneration and Simulant Introduction in the IX columns revealed another RF resin benefit; negligible radial pressures to the column walls from the swelling of resin beads. The hydraulic and chemical performance of the spherical RF resin during cycle testing was found to be superior to all other tested IX resins. The pilot-scale testing indicates that the RF resin is durable and should hold up to many hydraulic cycles in actual radioactive Cesium (Cs) separation.

  5. Storage and Aging Effects on Spherical Resorcinol-Formaldehyde Resin Ion Exchange Performance

    Energy Technology Data Exchange (ETDEWEB)

    Fiskum, Sandra K.; Arm, Stuart T.; Edwards, Matthew K.; Steele, Marilyn J.; Thomas, Kathie K.

    2007-09-10

    Bechtel National, Inc. (BNI) is evaluating the alternate Cs ion exchanger, spherical resorcinol-formaldehyde (RF), for use in the River Protection Project-Waste Treatment Plant (RPP-WTP).( ) Previous test activities with spherical RF indicate that it has adequate capacity, selectivity, and kinetics to perform in the plant according to the flowsheet needs. It appears to have better elution and hydraulic properties than the existing alternatives: ground-gel RF and SuperLig® 644 (SL 644).( ) To date, the spherical RF performance testing has been conducted on freshly manufactured resin (within ~2 months of manufacture). The ion exchange resins will be manufactured and shipped to the WTP up to 1 year before being used in the plant. Changes in the resin properties during storage could reduce the capacity of the resin to remove Cs from low-activity waste solutions. Active sites on organic SL-644 resin have been shown to degrade during storage (Arm et al. 2004). Additional testing was needed to study the effects of storage conditions and aging on spherical RF ion exchange performance. Variables that could have a significant impact on ion exchange resins during storage include storage temperature, medium, and time. Battelle—Pacific Northwest Division (PNWD) was contracted to test the effects of various storage conditions on spherical RF resin. Data obtained from the testing will be used by the WTP operations to provide direction for suitable storage conditions and manage the spherical RF resin stock. Storage test conditions included wet and dry resin configurations under nitrogen at three temperatures. Work was initially conducted under contract number 24590-101-TSA-W000-00004 satisfying the needs defined in Appendix C of the Research and Technology Plan( ) TSS A-219 to evaluate the impact of storage conditions on RF resin performance. In February 2007, the contract mechanism was switched to Pacific Northwest National Laboratory (PNNL) Operating Contract DE-AC05-76RL

  6. Mixture Design Approach on the Physical Properties of Lignin-Resorcinol-Formaldehyde Xerogels

    Directory of Open Access Journals (Sweden)

    Chris D. Castro

    2015-01-01

    Full Text Available Organic xerogels were functionalized by incorporating sugarcane bagasse lignin from soda pulping black liquor, not used so far in this materials, with the aim of introducing new functional groups on traditional gels that could improve its adsorptive capacity. Two mixing designs were applied to identify the reactive combinations that allow a well gel formation and to adjust models that predict physical properties. The designs study five components: resorcinol (R, 0.04–0.3, lignin (L, 0.004–0.14, formaldehyde (F, 0.08–0.17, water (W, 0.45–0.8, and NaOH (C, 0.0003–0.0035. The first experimental design was an extreme vertices design and its results showed shrinkage between 4.3 and 59.7 and a bulk density from 0.54 to 1.3; a mass ratio LR/F near 1.5 was required for gel formation. In the second design a D-Optimal was used to achieve better adjusted coefficients and incorporate the largest possible amount of lignin in the gels. Bulk density varies from 0.42 to 0.9, shrinkage varies from 3.42 to 25.35, and specific surface area reaches values of 451.86 m2/g with 13% lignin and 270 m2/g with 27% lignin. High catalyst content improves lignin dissolution and increase shrinkage and bulk density of xerogels and bulk density. Lignin contributes to reducing shrinkage and specific surface area due to his compact and rigid structure.

  7. The effect of catechol O-methylation on radical scavenging characteristics of quercetin and luteolin, a mechanistic insight

    NARCIS (Netherlands)

    Lemanska, K.; Woude, van der H.; Szymusiak, H.; Boersma, M.G.; Gliszczynska-Swiglo, A.; Rietjens, I.M.C.M.; Tyrakowska, B.

    2004-01-01

    The biological effect of flavonoids can be modulated in vivo due to metabolism. The O-methylation of the catechol group in the molecule by catechol O-methyl transferase is one of the important metabolic pathways of flavonoids. In the present study, the consequences of catechol O-methylation for the

  8. Pathways for formation of catechol and 1,2,4-benzenetriol in rabbits

    Energy Technology Data Exchange (ETDEWEB)

    Inoue, Osamu; Seiji, Kazunori (Tohoku Rosai Hospital, Sendai (Japan) Tohoku Univ. School of Medicine, Sendai (Japan)); Ikeda, Masayuki (Tohoku Univ. School of Medicine, Sendai (Japan))

    1989-08-01

    Benzene, an established human leukemogen, was once widely used as an industrial solvent and is currently an important material for organic synthesis. Its metabolism in man and animals has also been studied extensively, and phenolic compounds were identified as major metabolites in urine after benzene exposure. One point yet to be elucidated is the pathway for formation of catechol (or 1,2-benzenediol). Early studies suggested that catechol will be formed via phenol whereas a later study failed to identify catechol in the urine of men and rabbits after oral administration methods of {sup 14}C-phenol. Sensitive HPLC methods have been recently developed in our laboratory to measure urinary phenolic metabolites and t,t-muconic acid. The methods were applied to show that phenol is not a precursor of catechol in rabbits. Evidence is also presented that 1,2,4-benzenetriol is formed only from quinol (1,4-benzenediol) and not from catechol.

  9. Synthesis of tripodal catecholates and their immobilization on zinc oxide nanoparticles

    Directory of Open Access Journals (Sweden)

    Franziska Klitsche

    2015-05-01

    Full Text Available A common approach to generate tailored materials and nanoparticles (NPs is the formation of molecular monolayers by chemisorption of bifunctional anchor molecules. This approach depends critically on the choice of a suitable anchor group. Recently, bifunctional catecholates, inspired by mussel-adhesive proteins (MAPs and bacterial siderophores, have received considerable interest as anchor groups for biomedically relevant metal surfaces and nanoparticles. We report here the synthesis of new tripodal catecholates as multivalent anchor molecules for immobilization on metal surfaces and nanoparticles. The tripodal catecholates have been conjugated to various effector molecules such as PEG, a sulfobetaine and an adamantyl group. The potential of these conjugates has been demonstrated with the immobilization of tripodal catecholates on ZnO NPs. The results confirmed a high loading of tripodal PEG-catecholates on the particles and the formation of stable PEG layers in aqueous solution.

  10. Synthesis of a series of aromatic benziporphyrins and heteroanalogues via tripyrrane-like intermediates derived from resorcinol and 2-methylresorcinol.

    Science.gov (United States)

    Lash, Timothy D; Miyake, Kae; Xu, Linlin; Ferrence, Gregory M

    2011-08-05

    Tripyrrane analogues were prepared by reacting resorcinol or 2-methylresorcinol with 2 equiv of an acetoxymethylpyrrole in the presence of p-toluenesulfonic acid and calcium chloride. Following removal of the benzyl ester protective groups, the resorcinol-derived benzitripyrrane was reacted with a pyrrole dialdehyde to give an aromatic hydroxyoxybenziporphyrin. However, furan and thiophene dialdehydes gave highly insoluble products that could not be fully characterized. The methylresorcinol-derived tripyrrane analogue reacted with pyrrole, furan, thiophene, and selenophene dialdehydes to give unstable porphyrinoids that were further oxidized with [bis(trifluoroacetoxy)iodo]benzene to give stable benziporphyrin derivatives. These oxidized benziporphyrins showed strongly diatropic properties by proton NMR spectroscopy where the differences in chemical shifts (Δδ) were >18 ppm in some cases. The selenophene-derived system was further characterized by X-ray crystallography, and these results showed that one of the pyrrole subunits in this crowded structure was tilted by 21° relative to the mean macrocyclic plane. The tripyrrolic system reacted with silver(I) acetate to give the corresponding silver(III) organometallic complex. Regioselective alkylation with methyl or ethyl iodide and potassium carbonate gave diastereomeric mixtures of N-alkyl derivatives, and the N-ethyl substitution products showed highly diastereotopic characteristics.

  11. Photophysical properties of catechol axially substituted tetra-α-(pentyloxy) titanium (IV) phthalocyanine

    Science.gov (United States)

    Yu, Xinxin; Lin, Ting; Lv, Huafei; Pan, Sujuan; Wu, Shijun; Zeng, Di; Jiang, Yufeng; Wang, Yuhua; Yang, Hongqin; Huang, Yide; Peng, Yiru

    2016-10-01

    Metal phthalocyanines (MPcs) have been found to be a promising photosensitizers for photodynamic therapy (PDT) of cancers and non-cancer diseases. Nevertheless, phthalocyanines are substantially limited in clinical applications owing to their poor solubility, aggregation and insufficient selectivity for cancer cells. Catechol is an important pharmaceutical intermediate, playing important in vivo biological activity in medicine. Using catechol (pyrocatechin) as axial ligands, utilizing of the pharmaceutical effect of catechins, could improve the bioavailability, and achieve synergistic therapeutic effect in PDT. To address these issues, a novel catechol axially substituted tetra-α-(pentyloxy) titanium(IV) (TiPc(OC5H11)4-Catechol) was synthesized. The structure of TiPc(OC5H11)4-Catechol was characterized by elemental analysis, IR, 1HNMR and MS methods. The photophysical properties of TiPc(OC5H11)4 and TiPc(OC5H11)4-Catechol have been studied by UV/Vis and steady-state fluorescence spectra. After being axially substituted with catechin groups, no obviously intensity and position of maximum wavelength in Q-band of TiPc(OC5H11)4 and TiPc(OC5H11)4-Catechol were observed. The fluorescence intensity of TiPc(OC5H11)4 was stronger than that of TiPc(OC5H11)4-Catechol, but the fluorescence lifetime of TiPc(OC5H11)4-Catechol was longer than that of TiPc(OC5H11)4. TiPc(OC5H11)4-Catechol may be considered as a promising photosensitizer for PDT.

  12. EVALUATION OF POTENTIAL ELUANTS FOR NON-ACID ELUTION OF CESIUM FROM RESORCINOL-FORMALDEHYDE RESIN

    Energy Technology Data Exchange (ETDEWEB)

    Adu-Wusu, K.; Pennebaker, F.

    2010-12-22

    Small-column ion exchange (SCIX) units installed in high-level waste tanks to remove Cs-137 from highly alkaline salt solutions are among the waste treatment plans in the DOE-complex. Spherical Resorcinol-Formaldehyde (sRF) is the ion exchange resin selected for use in the Hanford Waste Treatment and Immobilization Plant (WTP). It is also the primary ion exchange material under consideration for SCIX at the Hanford site. The elution step of the multi-step ion exchange process is typically done with 0.5 M nitric acid. An acid eluant is a potential hazard in the event of a spill, leak, etc. because the high-level waste tanks are made of carbon steel. Corrosion and associated structural damage may ensue. A study has been conducted to explore non-acid elution as an alternative. Batch contact sorption equilibrium screening tests have been conducted with 36 potential non-acid eluants. The sorption tests involve equilibrating each cesium-containing eluant solution with the sRF resin for 48 hours at 25 C in a shaker oven. In the sorption tests, an eluant is deemed to have a high cesium elution potential if it minimizes cesium sorption onto the sRF resin. The top candidates (based on lowest cesium sorption distribution coefficients) include ammonium carbonate, ammonium carbonate/ammonium hydroxide, ammonium bicarbonate, rubidium carbonate, ammonium acetate, ammonium acetate/ammonium hydroxide, ammonium bicarbonate/ammonium hydroxide, calcium chloride, and magnesium chloride. A select few of the top candidate eluants from the screening tests were subjected to actual sorption (loading) and elution tests to confirm their elution ability. The actual sorption (loading) and elution tests mimicked the typical sRF-cesium ion exchange process (i.e., sorption or loading, caustic wash, water rinse, and elution) via batch contact sorption and quasi column caustic wash/water rinse/elution. The eluants tested included ammonium carbonate, ammonium acetate, calcium acetate, magnesium

  13. Hypnotizability and Catechol-O-Methyltransferase (COMT polymorphysms in Italians

    Directory of Open Access Journals (Sweden)

    Silvano ePresciuttini

    2014-01-01

    Full Text Available Higher brain dopamine content depending on lower activity of Catechol-O-Methyltransferase (COMT in subjects with high hypnotisability scores (highs has been considered responsible for their attentional characteristics. However, the results of the previous genetic studies on association between hypnotisability and the Catechol-O-Methyltransferase (COMT single nucleotide polymorphism (SNP rs4680 (Val158Met were inconsistent. Here, we used a selective genotyping approach to re-evaluate the association between hypnotisability and COMT in the context of a two-SNP haplotype analysis, considering not only the Val158Met polymorphism, but also the closely located rs4818 SNP. An Italian sample of 53 highs, 49 low hypnotizable subjects (lows and 57 controls, were genotyped for a segment of 805 bp of the COMT gene, including Val158Met and the closely located rs4818 SNP. Our selective genotyping approach had 97.1% power to detect the previously reported strongest association at the significance level of 5%. We found no evidence of association at the SNP, haplotype and diplotype levels. Thus, our results challenge the dopamine-based theory of hypnosis and indirectly support recent neuropsychological and neurophysiological findings reporting the lack of any association between hypnotisability and focused attention abilities.

  14. Bis(imino)pyridine (BIMP) Fe(II) catalyses one-pot green condensation of resorcinol, malononitrile, aromatic aldehydes and cyclohexanone

    Indian Academy of Sciences (India)

    Saman Damavandi; Reza Sandaroos

    2012-03-01

    A novel, efficient and green approach for the synthesis of pyranopyridine derivatives through one-pot, four-component reaction of resorcinol, malononitrile, aromatic aldehydes and cyclohexanone using bis(imino)pyridine (BIMP) Fe(II) catalyst under solvent-free and ultrasonic irradiation is described.

  15. Solution of Azelaic Acid (20%), Resorcinol (10%) and Phytic Acid (6%) Versus Glycolic Acid (50%) Peeling Agent in the Treatment of Female Patients with Facial Melasma.

    Science.gov (United States)

    Faghihi, Gita; Taheri, Azam; Shahmoradi, Zabihollah; Nilforoushzadeh, Mohammad Ali

    2017-01-01

    Melasma, a common acquired disorder of hyperpigmentation, especially in women, is often resistant to therapy. This study was aimed to evaluate the efficacy and safety of azelaic acid, resorcinol and phytic acid solution in chemical peeling of melasma in comparison to 50% glycolic acid. This clinical trial was performed, on 42 female patients with bilateral melasma. Severity of melasma was assessed by melasma area and severity index (MASI). Combination of (20% azelaic acid + 10% resorcinol + 6% phytic acid) was used as a new peeling agent on the right side of the face and 50% glycolic acid on the left side every 2 weeks for 6 times. Follow-up was carried out for 3 months after the last session. Any decrease in MASI score and unwanted complications following peeling were evaluated and compared during the trial. Patients showed marked improvement as calculated with MASI score before and after treatment in both sides of the face. The efficacy of combination formula (azelaic acid, resorcinol and phytic acid) was similar to glycolic acid, but with fewer complications. There was no statistically difference in improvement between two groups (P > 0.05). However, the patient's discomfort following procedures was significantly lower with azelaic acid, resorcinol and phytic compared with the glycolic acid peels (P glycolic acid peel.

  16. INFLUÊNCIA DO CATALISADOR EM SOLUÇÕES POLIMÉRICAS PARA O PREPARO DE GÉIS ORGÂNICOS DE RESORCINOL-FORMALDEÍDO

    Directory of Open Access Journals (Sweden)

    Thalita S. Taiariol

    2015-11-01

    Full Text Available Resorcinol-formaldehyde (RF organic gels have been extensively used to produce carbon aerogels. The organic gel synthesis parameters greatly affect the structure of the resulting aerogel. In this study, the influence of the catalyst quantity on the polymeric solution sol-gel process was investigated. Sodium carbonate was used as a basic catalyst. RF gels were synthesized with a resorcinol to formaldehyde molar ratio of 0.5, a resorcinol to catalyst (R/C molar ratio equal to 50 or 300, and a resorcinol to solvent ratio of 0.1 g mL-1. The sol-gel process was evaluated in situ by Fourier transform infrared spectroscopy using a universal attenuated total reflectance sensor and measurements of the kinematic viscosity. The techniques showed the evolution of the sol-gel process, and the results showed that the lower catalyst quantity induced a higher gel point, with a lower viscosity at the gel point. Differential scanning calorimetry was used to investigate the thermal behavior of the RF dried gel, and results showed that the exothermic event related to the curing process was shifted to higher temperatures for solutions containing higher R/C ratios.

  17. Mussel-mimetic self-healing polyaspartamide derivative gel via boron-catechol interactions

    Directory of Open Access Journals (Sweden)

    B. Wang

    2015-09-01

    Full Text Available The catechol group from catechol of 3,4-dihydroxyphenethylamine (DOP, dopamine has the ability to interact with metal ions to form non-covalent bonds in polymer chains. In this study, a novel kind of mussel-inspired copolymer, dopamine-conjugated poly(hydroxyethyl aspartamide, polyAspAm(DOP/EA, was synthesized and its interaction with boric acid (H3BO3 to form a cross-linked gel via boron-catechol coordinative binding was investigated. The copolymer was designed to contain a pH responsive adhesive catechol group, which reversibly underwent gelation through the metalcatechol binding, as proved by UV-Vis spectroscopy. When the pH is increased from acidic conditions to a specified pH (pH > 9, the B(OH3 is considered to have a functionality of two to bind catechols, leading to bis-complexes. In addition, the reversibility of the boron-catechol bonds provides self-healing characteristics to the polyAspAm gels. The rheological results showed that boron-catechol coordination could lead to quick and full recovery after the fracture of a gel specimen. This novel pH-responsive and self-healing gel system has potential in various applications including smart hydrogels, medical adhesives, and sealants.

  18. Alkylation of Catechol with tert-Butyl Alcohol Catalyzed by Mesoporous Acidic Montmorillonite Heterostructure Catalysts

    Institute of Scientific and Technical Information of China (English)

    周春晖; 葛忠华; 李小年; 童东绅; 李庆伟; 郭红强

    2004-01-01

    The liquid phase alkylation of catechol with tert-butyl alcohol to produce 4-tert-butyl catechol (4-TBC) was carried out over MCM-41, HZSM-5, H-exchanged montmorillonite and novel acidic porous montmorillonite heterostructures (PMHs). Upon all catalysts tested, 4-TBC is the main product and 3-tert-butyl catechol (3-TBC) and 3,5-di-tert-butyl catechol are the side products. The synthetic PMHs showed higher conversion of catechol and better selectivity to 4-TBC compared to other solid acid catalysts tested. Over the PMHs derived from H-exchanged montmorillonite through template extraction processes, the suitable reaction temperature is ca 410 K, the ratio of catechol to tert-butyl alcohol is 1:2. Increasing the amount of catalyst (lower weight hourly space velocity) can improve the conversion of catechol and influence the selectivity slightly. The reasonable reaction time is ca 8 h.The type and strength of acidity of H-montmorillonite and PMH were determined by pyridine adsorption FT-IR and ammonia temperature-programmed desorption techniques. The medium and strong acid sites are conducive to producing 4-TBC and the weak acid sites to facilitating the 3-TBC formation. The differences between the PMHs from calcination and those fi'om extraction are attributed to proton migration and acidity change in the gallery surface.

  19. Joining Two Natural Motifs: Catechol-Containing Poly(phosphoester)s.

    Science.gov (United States)

    Becker, Greta; Ackermann, Lisa-Maria; Schechtel, Eugen; Klapper, Markus; Tremel, Wolfgang; Wurm, Frederik R

    2017-02-14

    Numerous catechol-containing polymers, including biodegradable polymers, are currently heavily discussed for modern biomaterials. However, there is no report combining poly(phosphoester)s (PPEs) with catechols. Adhesive PPEs have been prepared via acyclic diene metathesis polymerization. A novel acetal-protected catechol phosphate monomer was homo- and copolymerized with phosphoester comonomers with molecular weights up to 42000 g/mol. Quantitative release of the catechols was achieved by careful hydrolysis of the acetal groups without backbone degradation. Degradation of the PPEs under basic conditions revealed complete and statistical degradation of the phosphotri- to phosphodiesters. In addition, a phosphodiester monomer with an adhesive P-OH group and no protective group chemistry was used to compare the binding to metal oxides with the multicatechol-PPEs. All PPEs can stabilize magnetite particles (NPs) in polar solvents, for example, methanol, due to the binding of the phosphoester groups in the backbone to the particles. ITC measurements reveal that multicatechol PPEs exhibit a higher binding affinity to magnetite NPs compared to PPEs bearing phosphodi- or phosphotriesters as repeating units. In addition, the catechol-containing PPEs were used to generate organo- and hydrogels by oxidative cross-linking, due to cohesive properties of catechol groups. This unique combination of two natural adhesive motives, catechols and phosphates, will allow the design of novel future gels for tissue engineering applications or novel degradable adhesives.

  20. On the synthesis and structure of resorcinol-formaldehyde polymeric networks – Precursors to 3D-carbon macroassemblies

    Energy Technology Data Exchange (ETDEWEB)

    Lewicki, James P.; Fox, Christina A.; Worsley, Marcus A.

    2015-07-01

    With the new impetus towards the development of hierarchical graphene and CNT macro-assemblies for application in fields such as advanced energy storage, catalysis and electronics; there is much renewed interest in organic carbon-based sol–gel processes as a synthetically convenient and versatile means of forming three dimensional, covalently bonded organic/inorganic networks. Such matrices can act as highly effective precursors, scaffolds or molecular ‘glues’ for the assembly of a wide variety of functional carbon macro-assemblies. However, despite the utility and broad use of organic sol–gel processes – such as the ubiquitous resorcinol-formaldehyde (RF) reaction, there are details of the reaction chemistries of these important sol–gel processes that remain poorly understood at present. It is therefore both timely and necessary to examine these reactions in more detail using modern analytical techniques in order to gain a more rigorous understanding of the mechanisms by which these organic networks form. The goal of such studies is to obtain improved and rational control over the organic network structure, in order to better direct and tailor the architecture of the final inorganic carbon matrix. In this study we have investigated in detail, the mechanism of the organic sol–gel network forming reaction of resorcinol and formaldehyde from a structural and kinetic standpoint, by using a combination of real-time high field solution state nuclear magnetic resonance (NMR), low field NMR relaxometry and differential scanning calorimetry (DSC). These investigations have allowed us to track the network formation processes in real-time, gain both detailed structural information on the mechanisms of the RF sol–gel process and a quantitative assessment of the kinetics of the global network formation process. It has been shown that the mechanism, by which the RF organic network forms, proceeds via an initial exothermic step correlated to the formation of a

  1. EVALUATION OF POTENTIAL ELUANTS FOR NON-ACID ELUTION OF CESIUM FROM SPHERICAL RESORCINOL-FORMALDEHYDE RESIN

    Energy Technology Data Exchange (ETDEWEB)

    Adu-Wusu, K.; Nash, C.; Pennebaker, F.

    2011-10-23

    Ion Exchange column loading and elution of cesium from spherical resorcinol-formaldehyde resin have been conducted for two potential non-acid eluants -(NH{sub 4}){sub 2}CO{sub 3} and CH{sub 3}COONH{sub 4}. The results revealed encouraging cesium elution performance. 100% elution was achieved in at most 22 hours ({approx}28 bed volumes) of elution. Elution performance was fairly high at 6 hours ({approx}8 bed volumes) of elution for some of the eluants and also practically comparable to the benchmark acid eluant (HNO{sub 3}). Hence, it is quite possible 100% percent elution will be closer to the 6th hour than the 22nd hour. Elution is generally enhanced by increasing the concentration and pH of the eluants, and combining the eluants.

  2. An improved assay with 4-(2-thiazolylazo)-resorcinol for non-esterified fatty acids in biological fluids.

    Science.gov (United States)

    Bergmann, S R; Carlson, E; Dannen, E; Sobel, B E

    1980-05-21

    A simple and rapid colorimetric assay for non-esterified fatty acids (NEFA) was developed employing extraction of samples with 0.1 mol/l glycine (pH 2.7) and methoxyethanol : butyl ether, and formation of a copper-fatty acid soap detected with 4-(2-thiazolylazo)-resorcinol. The method developed is sensitive enough to detect as little as 11 nmol/0.25 ml sample. Results are not affected by marked molar excesses of phospholipids, cholesterol, cholesterol esters, triglycerides, bilirubin, or lactate. Recovery of palmitate in the extract averages 94.2 +/- 3.2% (S.D.) and other long chain fatty acids are recovered equally. The copper-NEFA-indicator complex formed is stable. Extracted samples can be stored for as long as 2 weeks without appreciable changes in measured NEFA content. The method developed is suitable for both manual and semi-automated procedures for determining NEFA content in biological fluids.

  3. Identification of catechols as histone-lysine demethylase inhibitors

    DEFF Research Database (Denmark)

    Nielsen, Anders L; Kristensen, Line H; Stephansen, Karen B

    2012-01-01

    Identification of inhibitors of histone-lysine demethylase (HDM) enzymes is important because of their involvement in the development of cancer. An ELISA-based assay was developed for identification of inhibitors of the HDM KDM4C in a natural products library. Based on one of the hits with affinity...... in the low µM range (1, a catechol), a subset of structurally related compounds was selected and tested against a panel of HDMs. In this subset, two inhibitors (2 and 10) had comparable affinities towards KDM4C and KDM6A but no effect on PHF8. One inhibitor restored H3K9me3 levels in KDM4C transfected U2-OS...

  4. Zn-edta degradation by catechol-driven fenton reaction

    Directory of Open Access Journals (Sweden)

    Claudia Oviedo

    2012-01-01

    Full Text Available Zn-EDTA degradabilty by catechol-driven Fenton reaction was studied. Response surface methodology central composite design was employed to maximize this complex degradation. Theoretical speciation calculations were in good agreement with the experimental results. Fenton and Fenton type treatments are typically thought to be applicable only in the highly acidic range, representing a major operational constraint. Interestingly, at optimized concentrations, this CAT-driven Fenton reaction at pH 5.5 achieved 100% Zn-EDTA degradation; 60% COD and 17% TOC removals, using tiny amounts of CAT (50 µM, Fe(III (445 µM and H2O2 (20 mM with no evident ferric sludge.

  5. Quinone Reductase 2 Is a Catechol Quinone Reductase

    Energy Technology Data Exchange (ETDEWEB)

    Fu, Yue; Buryanovskyy, Leonid; Zhang, Zhongtao (NYMEDCO)

    2008-09-05

    The functions of quinone reductase 2 have eluded researchers for decades even though a genetic polymorphism is associated with various neurological disorders. Employing enzymatic studies using adrenochrome as a substrate, we show that quinone reductase 2 is specific for the reduction of adrenochrome, whereas quinone reductase 1 shows no activity. We also solved the crystal structure of quinone reductase 2 in complexes with dopamine and adrenochrome, two compounds that are structurally related to catecholamine quinones. Detailed structural analyses delineate the mechanism of quinone reductase 2 specificity toward catechol quinones in comparison with quinone reductase 1; a side-chain rotational difference between quinone reductase 1 and quinone reductase 2 of a single residue, phenylalanine 106, determines the specificity of enzymatic activities. These results infer functional differences between two homologous enzymes and indicate that quinone reductase 2 could play important roles in the regulation of catecholamine oxidation processes that may be involved in the etiology of Parkinson disease.

  6. Kinetic Study of the Oxidation of Catechols in the Presence of N-Methylaniline

    Directory of Open Access Journals (Sweden)

    Lida Khalafi

    2013-01-01

    Full Text Available The reactions of electrochemically generated o-quinones from oxidation of catechol and 4-methylcatechol as Michael acceptors with N-methylaniline as nucleophile have been studied using cyclic voltammetry. Voltammetric responses show that oxidation of catechols is followed by Michael addition of N-methylaniline. The reaction products are believed to be diphenylamine derivatives of catechols that undergo electron transfer at more negative potentials than the catechols. The observed homogeneous rate constants for Michael addition were estimated by digital simulation and show that the reactivity of 4-methyluinone is considerably less than o-quinone. The oxidation potentials of the desired products drastically depend on the solution pH and their structures.

  7. β-cyclodextrin-cobalt ferrite nanocomposite as enhanced sensing platform for catechol determination.

    Science.gov (United States)

    Han, Jin-Tu; Huang, Ke-Jing; Li, Jing; Liu, Yan-Ming; Yu, Meng

    2012-10-01

    An electrochemical sensor based on β-cyclodextrin-cobalt ferrite nanocomposite was developed for the sensitive detection of catechol (CT). To construct the base of the sensor, a novel composite was initially fabricated and used as the substrate material by combining cobalt ferrite nanocomposite and β-cyclodextrin via a simple sonication-induced assembly. Due to the high catechol-loading capacity on the electrode surface and the upstanding electric conductivity of cobalt ferrite nanocomposite, the electrochemical response of the fabricated sensor was greatly enhanced and displayed excellent analytical performance for catechol detection from 1 to 200 μM with a low detection limit of 0.12 μM (S/N=3). Moreover, the developed electrochemical sensor exhibited good selectivity and acceptable reproducibility and could be used for the detection of catechol in water samples. Copyright © 2012 Elsevier B.V. All rights reserved.

  8. BIOLOGICAL ADHESIVES. Adaptive synergy between catechol and lysine promotes wet adhesion by surface salt displacement.

    Science.gov (United States)

    Maier, Greg P; Rapp, Michael V; Waite, J Herbert; Israelachvili, Jacob N; Butler, Alison

    2015-08-01

    In physiological fluids and seawater, adhesion of synthetic polymers to solid surfaces is severely limited by high salt, pH, and hydration, yet these conditions have not deterred the evolution of effective adhesion by mussels. Mussel foot proteins provide insights about adhesive adaptations: Notably, the abundance and proximity of catecholic Dopa (3,4-dihydroxyphenylalanine) and lysine residues hint at a synergistic interplay in adhesion. Certain siderophores—bacterial iron chelators—consist of paired catechol and lysine functionalities, thereby providing a convenient experimental platform to explore molecular synergies in bioadhesion. These siderophores and synthetic analogs exhibit robust adhesion energies (E(ad) ≥-15 millijoules per square meter) to mica in saline pH 3.5 to 7.5 and resist oxidation. The adjacent catechol-lysine placement provides a "one-two punch," whereby lysine evicts hydrated cations from the mineral surface, allowing catechol binding to underlying oxides.

  9. Protein-responsive assemblies from catechol-metal ion supramolecular coordination.

    Science.gov (United States)

    Yuan, C; Chen, J; Yu, S; Chang, Y; Mao, J; Xu, Y; Luo, W; Zeng, B; Dai, L

    2015-03-21

    Supramolecular self-assembly driven by catechol-metal ion coordination has gained great success in the fabrication of functional materials including adhesives, capsules, coatings and hydrogels. However, this route has encountered a great challenge in the construction of nanoarchitectures in the absence of removable templates, because of the uncontrollable crosslinking of catechol-metal ion coordination. Herein, we show that a supramolecular approach, combining both catechol-metal ion coordination and polymer self-assembly together, can organize polymers into hybrid nanoassemblies ranging from solid particles, homogeneous vesicles to Janus vesicles. Without the introduction of a specific binding ligand or complicated molecular design, these assemblies can totally disassemble in response to proteins. UV/vis absorption, fluorescence quenching and recovery investigations have confirmed that proteins can seize metal ions from the hybrid nanoassemblies, thus causing the degradation of catechol-metal ion coordination networks.

  10. Metal salts of alkyl catechol dithiophosphoric acids and oil compositions containing the salts

    Energy Technology Data Exchange (ETDEWEB)

    Yamaguchi, E.S.; Liston, T.V.

    1988-03-08

    Metal salts of alkyl catechol esters of dithiophosphoric acid suitable as additives in oil compositions are disclosed in this patent. Oil compositions containing the salts of such esters show improved extreme pressure/anti-wear and anit-oxidant properties.

  11. Thermally stable drilling fluid additive comprised of a copolymer of catechol-based monomer

    Energy Technology Data Exchange (ETDEWEB)

    Patel, A.D.

    1986-06-17

    A water soluble polymer is described having thermal stability and exhibiting utility as an aqueous drilling fluid additive comprising: (a) a major portion of a catechol based monomer; (b) a minor portion of a dicarboxylic acid monomer.

  12. A novel palygorskite-modified carbon paste amperometric sensor for catechol determination

    Energy Technology Data Exchange (ETDEWEB)

    Kong Yong [School of Chemistry and Chemical Engineering, Changzhou University, No. 1 Gehu Road, Changzhou 213164, Jiangsu Province (China); Key Lab of Analytical Chemistry for Life Science, Ministry of Education, Nanjing University, Nanjing 210093 (China); Chen Xiaohui; Wang Wenchang [School of Chemistry and Chemical Engineering, Changzhou University, No. 1 Gehu Road, Changzhou 213164, Jiangsu Province (China); Chen Zhidong, E-mail: czd_chen@yahoo.com.cn [School of Chemistry and Chemical Engineering, Changzhou University, No. 1 Gehu Road, Changzhou 213164, Jiangsu Province (China)

    2011-03-04

    A palygorskite-modified carbon paste electrode (CPE) was constructed using graphite powder mixed with palygorskite particles. Compared with the unmodified CPE, the resulting palygorskite-modified CPE remarkably increases the peak currents of catechol, and greatly lowers the peak potential separation. Therefore, the palygorskite exhibits catalytic activity to catechol and significantly improves the determining sensitivity. The electrocatalytic activity of palygorskite is attributed to its high adsorption capability and the -OH groups on its surface, which plays an important role in the electron transfer between the modified CPE and the catechol in the solution. The sensor shows a linear response range between 5 and 100 {mu}M catechol with a correlation coefficient of 0.998. The detection limit was calculated as 0.57 {mu}M (s/n = 3).

  13. Biotransformation of benzene and toluene to catechols by phenol hydroxylase from Arthrobacter sp. W1.

    Science.gov (United States)

    Ma, Fang; Shi, Sheng-Nan; Sun, Tie-Heng; Li, Ang; Zhou, Ji-Ti; Qu, Yuan-Yuan

    2013-06-01

    Phenol hydroxylase gene engineered microorganism (PHIND) was used to synthesize catechols from benzene and toluene by successive hydroxylation reaction. HPLC-MS and (1)H NMR analysis proved that the products of biotransformation were the corresponding catechols via the intermediate production of phenols. It was indicated that the main products of toluene oxidation were o-cresol and p-cresol. 3-Methylcatechol was the predominant product for m-cresol biotransformation. Formation rate of catechol (25 μM/min/g cell dry weight) was 1.43-fold higher than that of methylcatechols. It was suggested that phenol hydroxylase could be successfully used to transform both benzene and toluene to catechols by successive hydroxylation.

  14. Dynamic adsorption of catechol at the goethite/aqueous solution interface: a molecular-scale study.

    Science.gov (United States)

    Yang, Yanli; Yan, Wei; Jing, Chuanyong

    2012-10-16

    Insights from molecular-level mechanisms of catechol adsorption on goethite can further our understanding of the fate and transport of hydroxyaromatic compounds in the environment. The motivation for our study is to explore the dynamic adsorption process of catechol at the goethite/aqueous interface on the molecular scale. Multiple complementary techniques including macroscopic adsorption experiments, flow-cell ATR-FTIR measurement, 2D IR correlation analysis, and quantum chemical calculations were used to study the adsorption mechanisms. Our results show that the adsorption of catechol was elevated at high pH but was not affected by ionic strength because of the formation of inner-sphere complexes. Catechol adsorbed on goethite in mononuclear monodentate and binuclear bidentate configurations in the pH range of 5 to 9. Partial mononuclear monodentate structures could be converted to binuclear bidentate complexes under basic conditions and with increasing surface coverage.

  15. Lycopene and beta-carotene ameliorate catechol estrogen-mediated DNA damage

    OpenAIRE

    2005-01-01

    The consumption of fruits and vegetables is associated with a reduced risk of various ailments, including cancer and cardiovascular diseases. Carotenoids, such as lycopene and beta-carotene, are natural constituents of edible plants and may protect against disease. In this study, the influence of lycopene and beta-carotene on DNA damage caused by catechol-estrogens in vitro is examined. One possible mechanism by which catechol estrogens such as 4-hydroxyestradiol (4-OHE2) and 2-hydroxyestradi...

  16. Removing Dissolved Silica from Waste Water with Catechol and Active Carbon

    Energy Technology Data Exchange (ETDEWEB)

    Sasan, Koroush [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Nanoscale Sciences Dept.; Brady, Patrick [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Advanced Nuclear Energy Program; Krumhansl, James L. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Geosciences Dept.; Nenoff, Tina M. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Physical Chemical and Nano Sciences Center

    2017-01-01

    Fresh water scarcity is going to be a global great challenge in the near future because of the increasing population. Our water resources are limited and, hence, water treatment and recycling methods are the only alternatives for fresh water procurement in the upcoming decades. Water treatment and recycling methods serve to remove harmful or problematic constituents from ground, surface and waste waters prior to its consumption, industrial supply, or other uses. Scale formation in industrial and domestic installations is still an important problem during water treatment. In water treatment, silica scaling is a real and constant concern for plant operations. The focus of this study is on the viability of using a combination of catechol and active carbon to remove dissolved silica from concentrated cooling tower water (CCTW). Various analytical methods, such as ICP-MS and UV-vis, were used to understand the structure-property relationship between the material and the silica removal results. UV-Vis indicates that catechol can react with silica ions and form a silica-catecholate complex. The speciation calculation of catechol and silica shows that catechol and silica bind in the pH range of 8 – 10; there is no evidence of linkage between them in neutral and acidic pHs. The silica removal results indicate that using ~4g/L of catechol and 10g/L active carbon removes up to 50% of the dissolved silica from the CCTW.

  17. A Novel Mechanism for Adenylyl Cyclase Inhibition from the Crystal Structure of its Complex with Catechol Estrogen

    Energy Technology Data Exchange (ETDEWEB)

    Steegborn,C.; Litvin, T.; Hess, K.; Capper, A.; Taussig, R.; Buck, J.; Levin, L.; Wu, H.

    2005-01-01

    Catechol estrogens are steroid metabolites that elicit physiological responses through binding to a variety of cellular targets. We show here that catechol estrogens directly inhibit soluble adenylyl cyclases and the abundant trans-membrane adenylyl cyclases. Catechol estrogen inhibition is non-competitive with respect to the substrate ATP, and we solved the crystal structure of a catechol estrogen bound to a soluble adenylyl cyclase from Spirulina platensis in complex with a substrate analog. The catechol estrogen is bound to a newly identified, conserved hydrophobic patch near the active center but distinct from the ATP-binding cleft. Inhibitor binding leads to a chelating interaction between the catechol estrogen hydroxyl groups and the catalytic magnesium ion, distorting the active site and trapping the enzyme substrate complex in a non-productive conformation. This novel inhibition mechanism likely applies to other adenylyl cyclase inhibitors, and the identified ligand-binding site has important implications for the development of specific adenylyl cyclase inhibitors.

  18. Synthesis of Disperse Dyes from Pyridone and Resorcinol Coupled to Diazotized 2-Amino-4-chloro-5-formylthiazole and Application to Polyester

    Directory of Open Access Journals (Sweden)

    Yusuf Y. Lams

    2014-01-01

    Full Text Available The aim of this study was to synthesize disperse dyes in the derivative of 2-amino-4-chloro-5-formylthiazole by conventional diazotization and couplings with pyridone and resorcinol. The dyes were characterized by visible absorption spectroscopy, IR spectral studies, and 1H and 13C NMR. The pyridone and resorcinol substituted dyes exhausted well with good depth on 100% polyester fabrics with a shade of brown and purple colours, respectively. The heteroatom and the intrinsic conjugation in the thiazole structure results in high bathochromic shifts and lead to brightness of shades. The dyed fabrics showed very good to excellent wash fastness and moderate to good light and perspiration fastness properties.

  19. Heterogeneous Reactions of Surface-Adsorbed Catechol: A Comparison of Tropospheric Aerosol Surrogates

    Science.gov (United States)

    Hinrichs, R. Z.; Woodill, L. A.

    2009-12-01

    Surface-adsorbed organics can alter the chemistry of tropospheric solid-air interfaces, such as aerosol and ground level surfaces, thereby impacting photochemical cycles and altering aerosol properties. The nature of the surface can also influence the chemistry of the surface-adsorbed organic. We employed diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) to monitor the adsorption of gaseous catechol on several tropospheric aerosol surrogates and to investigate the subsequent reactivity of adsorbed-catechol with nitrogen dioxide and, in separate preliminary experiments, ozone. Graphite, kaolinite, and sodium halide (NaF, NaCl, NaBr) powders served as carbonaceous, mineral and sea salt aerosol surrogates, respectively. Broad OH stretching bands for adsorbed catechol shifted to lower wavenumber with peak frequencies following the trend NaBr > NaCl > NaF ≈ kaolinite, consistent with the increasing basicity of the halide anions and basic Brønsted sites on kaolinite. The dark heterogeneous reaction of NO2 with NaCl-adsorbed catechol at relative humidity (RH) 4-nitrocatechol and oxidation forming 1,2-benzoquinone and the ring cleavage product muconic acid, with product yields of 88%, 8%, and 4%, respectively. 4-Nitrocatechol was the dominant product for catechol adsorbed on NaF and kaolinite, while NaBr-adsorbed catechol produced less 4-nitrocatechol and more 1,2-benzoquinone and muconic acid. For all three sodium halides, the reactions of NO2 with adsorbed catechol were orders of magnitude faster than between NO2 and each NaX substrate. 4-Nitrocatechol rates and product yields were consistent with the relative ability of each substrate to enhance the deprotonated nature of adsorbed-catechol. Increasing the relative humidity caused the rate of each product channel to decrease and also altered the product branching ratios. Most notably, 1,2-benzoquinone formation decreased significantly even at 13% RH. The dramatic reactivity of surface

  20. Characterization of catechol 2,3-dioxygenase from Planococcus sp. strain S5 induced by high phenol concentration.

    Science.gov (United States)

    Hupert-Kocurek, Katarzyna; Guzik, Urszula; Wojcieszyńska, Danuta

    2012-01-01

    This study aimed at characterization of a new catechol 2,3-dioxygenase isolated from a Gram-positive bacterium able to utilize phenol as the sole carbon and energy source. Planococcus sp. strain S5 grown on 1 or 2 mM phenol showed activity of both a catechol 1,2- and catechol 2,3-dioxygenase while at a higher concentrations of phenol only catechol 2,3-dioxygenase activity was observed. The enzyme was optimally active at 60°C and pH 8.0. Kinetic studies showed that the K(m) and V(max) of the enzyme were 42.70 µM and 329.96 mU, respectively. The catechol 2,3-dioxygenase showed the following relative meta-cleavage activities for various catechols tested: catechol (100%), 3-methylcatechol (13.67%), 4-methylcatechol (106.33%) and 4-chlorocatechol (203.80%). The high reactivity of this enzyme towards 4-chlorocatechol is different from that observed for other catechol 2,3-dioxygenases. Nucleotide sequencing and homology search revealed that the gene encoding the S5 catechol 2,3-dioxygenase shared the greatest homology with the known genes encoding isoenzymes from Gram-negative Pseudomonas strains.

  1. 1, 4-Pyrone Effects on O-H Bond Dissociation Energies of Catechols in Flavonoids: A Density Functional Theory Study

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Through B3LYP/6-31G** calculations, the 1, 4-pyrone effects on O-H bond dissociation energies (BDEs) of catechols in rings A or B of flavonoids were investigated. For the catechol in ring A, although 1, 4-pyrone enlarged the conjugation system, its electron-withdrawing property increased the O-H BDE 3 ( 4.184 kJ/mol compared with that of catechol. However, for the catechol in ring B, 1, 4-pyrone was poorly conjugated with the moiety, and therefore, had little effect on the O-H BDE.

  2. 间苯二酚催化加氢反应产物的分析及精制%Analysis and Purification of Hydrogenation Products of Resorcinol

    Institute of Scientific and Technical Information of China (English)

    李杏花; 魏作君; 刘迎新; 孟令富

    2011-01-01

    1,3-cyclohexanedione (CHD) has generally been industrially produced from the hydrogenation of resorcinol (RES). In this paper, the analysis and purification of the resorcinol hydrogenation products were studied by GC-MS. A gas chromatography method was established to quantitatively analyze the resorcinol and 1,3-cyclohexanedione. The stability of resorcinol and 1,3-cyclohexanedione in several organic solvents were studied by GC-MS, the results show that the acetonitrile is the most favorable solvent for the extraction and post processing. Then the acetonitrile was used as recrystalization solvent for 1,3-cyclohexanedione and a higher purity was obtained.%间苯二酚催化加氢法是目前生产l,3-环己二酮的主流方法.今采用气相色谱-质谱法对间苯二酚催化加氢反应产物的分析及精制进行研究,建立了间苯二酚及1,3-环己二酮的气相色谱定量分析方法.通过气相色谱-质谱法对该体系在有机溶剂中的稳定性研究表明,丙酮、乙醇和乙酸乙酯均不适合作为该反应体系后处理的溶剂,而乙腈符合选择的要求.用乙腈对反应产物进行重结晶,得到了高纯度的1,3-环己二酮产品.

  3. Sol-Gel Synthesis of Carbon Xerogel-ZnO Composite for Detection of Catechol

    OpenAIRE

    2016-01-01

    Carbon xerogel-zinc oxide (CXZnO) composites were synthesized by a simple method of sol-gel condensation polymerization of formaldehyde and resorcinol solution containing zinc salt followed by drying and thermal treatment. ZnO nanoparticles were observed to be evenly dispersed on the surfaces of the carbon xerogel microspheres. The as-prepared CXZnO composites were mixed with laccase (Lac) and Nafion to obtain a mixture solution, which was further modified on an electrode surface to construct...

  4. Hypnotizability and Catechol-O-Methyltransferase (COMT) polymorphysms in Italians

    Science.gov (United States)

    Presciuttini, Silvano; Gialluisi, Alessandro; Barbuti, Serena; Curcio, Michele; Scatena, Fabrizio; Carli, Giancarlo; Santarcangelo, Enrica L.

    2014-01-01

    Higher brain dopamine content depending on lower activity of Catechol-O-Methyltransferase (COMT) in subjects with high hypnotizability scores (highs) has been considered responsible for their attentional characteristics. However, the results of the previous genetic studies on association between hypnotizability and the COMT single nucleotide polymorphism (SNP) rs4680 (Val158Met) were inconsistent. Here, we used a selective genotyping approach to re-evaluate the association between hypnotizability and COMT in the context of a two-SNP haplotype analysis, considering not only the Val158Met polymorphism, but also the closely located rs4818 SNP. An Italian sample of 53 highs, 49 low hypnotizable subjects (lows), and 57 controls, were genotyped for a segment of 805 bp of the COMT gene, including Val158Met and the closely located rs4818 SNP. Our selective genotyping approach had 97.1% power to detect the previously reported strongest association at the significance level of 5%. We found no evidence of association at the SNP, haplotype, and diplotype levels. Thus, our results challenge the dopamine-based theory of hypnosis and indirectly support recent neuropsychological and neurophysiological findings reporting the lack of any association between hypnotizability and focused attention abilities. PMID:24431998

  5. Inhibition of human catechol-O-methyltransferase (COMT)-mediated O-methylation of catechol estrogens by major polyphenolic components present in coffee.

    Science.gov (United States)

    Zhu, Bao Ting; Wang, Pan; Nagai, Mime; Wen, Yujing; Bai, Hyoung-Woo

    2009-01-01

    In the present study, we investigated the inhibitory effect of three catechol-containing coffee polyphenols, chlorogenic acid, caffeic acid and caffeic acid phenethyl ester (CAPE), on the O-methylation of 2- and 4-hydroxyestradiol (2-OH-E(2) and 4-OH-E(2), respectively) catalyzed by the cytosolic catechol-O-methyltransferase (COMT) isolated from human liver and placenta. When human liver COMT was used as the enzyme, chlorogenic acid and caffeic acid each inhibited the O-methylation of 2-OH-E(2) in a concentration-dependent manner, with IC(50) values of 1.3-1.4 and 6.3-12.5 microM, respectively, and they also inhibited the O-methylation of 4-OH-E(2), with IC(50) values of 0.7-0.8 and 1.3-3.1 microM, respectively. Similar inhibition pattern was seen with human placental COMT preparation. CAPE had a comparable effect as caffeic acid for inhibiting the O-methylation of 2-OH-E(2), but it exerted a weaker inhibition of the O-methylation of 4-OH-E(2). Enzyme kinetic analyses showed that chlorogenic acid and caffeic acid inhibited the human liver and placental COMT-mediated O-methylation of catechol estrogens with a mixed mechanism of inhibition (competitive plus noncompetitive). Computational molecular modeling analysis showed that chlorogenic acid and caffeic acid can bind to human soluble COMT at the active site in a similar manner as the catechol estrogen substrates. Moreover, the binding energy values of these two coffee polyphenols are lower than that of catechol estrogens, which means that coffee polyphenols have higher binding affinity for the enzyme than the natural substrates. This computational finding agreed perfectly with our biochemical data.

  6. Catechol-O-methyltransferase gene polymorphism and vulvar pain in women with vulvodynia.

    Science.gov (United States)

    Patanwala, Insiyyah Y; Lamvu, Georgine; Ledger, William J; Witzeman, Kathryn; Marvel, Richard; Rapkin, Andrea; Bongiovanni, Ann Marie; Feranec, Jessica; Witkin, Steven S

    2017-04-01

    The underlying causes of vulvar pain in women with vulvodynia remain poorly understood. Catechol-O-methyltransferase, an enzyme that metabolizes catecholamines, is a neuromodulator that is involved with perception and sensitivity to pain. The catechol-O-methyltransferase gene is polymorphic, and a single nucleotide polymorphism is associated with low activity and heightened pain sensitivity. The variant allele that encodes this polymorphism commonly is called the "L allele" because of its low enzyme activity as opposed to the normal H (high activity) allele. The methionine-containing catechol-O-methyltransferase protein coded by the L allele results in elevated catecholamine levels, reduced inactivation of the dopaminergic and adrenergic systems, and increased sensitivity to pain. This polymorphism not only may decrease the pain threshold in response to acute pain but also may facilitate the development of chronic pain. Therefore, the objective of our study was to assess whether a variation in the catechol-O-methyltransferase genotype is involved in increased pain sensitivity in women with vulvodynia. We conducted a prospective cohort study. Buccal swabs were collected from 167 white women with vulvodynia and 107 control subjects; the DNA was tested for a single nucleotide polymorphism at position 158 (rs4680) in the catechol-O-methyltransferase gene. Women with vulvodynia had a marginally increased, yet not significant, prevalence of the catechol-O-methyltransferase genotype that is associated with high activity of the coded protein: 32.9% in the women with vulvodynia, as opposed to 21.5% in the control subjects (odds ratio, 1.80; 95% confidence interval, 1.02-3.15). Subgrouping the cases based on pain frequency revealed that the elevated occurrence of this catechol-O-methyltransferase genotype was present in 40.6% of the subset of women who experienced pain only with sexual intercourse vs only 21.5% of control subjects (odds ratio, 2.50; 95% confidence interval

  7. Simultaneous determination of hydroquinone and catechol at gold nanoparticles mesoporous silica modified carbon paste electrode.

    Science.gov (United States)

    Tashkhourian, J; Daneshi, M; Nami-Ana, F; Behbahani, M; Bagheri, A

    2016-11-15

    A new electrochemical sensor based on gold nanoparticles mesoporous silica modified carbon paste electrode (AuNPs-MPS) was developed for simultaneous determination of hydroquinone and catechol. Morphology and structure of the AuNPs-MPS were characterized by transmission electron microscopy, X-ray diffraction and Fourier transform infrared spectroscopy. The electrochemical behavior of hydroquinone and catechol were investigated using square wave voltammetry and the results indicate that the electrochemical responses are improved significantly at the modified electrode. The observed oxidative peaks separation of about 120mV made possible the simultaneous determination of hydroquinone and catechol in their binary-mixture. Under the optimized condition, a linear dynamic range of 10.0μM-1.0mM range for hydroquinone with the detection limit of 1.2μM and from 30.0μM-1.0mM for catechol with the detection limit of 1.1μM were obtained. The applicability of the method was demonstrated by the recovery studies of hydroquinone and catechol in spiked tap water samples.

  8. Electrocatalytic Efficiency Analysis of Catechol Molecules for NADH Oxidation during Nanoparticle Collision.

    Science.gov (United States)

    Zhao, Li-Jun; Qian, Ruo-Can; Ma, Wei; Tian, He; Long, Yi-Tao

    2016-09-06

    Electrocatalysis of molecules is a hot research topic in biological and energy-related chemistry. Here, we develop a new system to study the electrocatalytic efficiency of a single catechol molecule for NADH oxidation by single functionalized nanoparticle collision at ultramicroelectrodes (UMEs). The proposed system is composed of gold nanoparticles (AuNPs) functionalized with catechol molecules and a carbon-fiber ultramicroelectrode. In the absence of NADH, when a functionalized AuNP collides with an UME at a suitable voltage, a small current spike is generated due to the oxidation of catechol molecules modified on the surface of AuNP. In the presence of NADH, the current spike is significantly amplified by the combined effects of the oxidation and electrocatalysis for NADH of catechol molecules. By analyzing the variations of the average peak charges and durations without or with NADH, we calculate that around five thousands NADH molecules could be catalyzed per second by a single catechol molecule, suggesting the successful establishment of this novel catalytic system. Thus, the proposed strategy could be used as a promising platform for research of other molecular electrocatalytic systems.

  9. Investigation on the Electrochemical Polymerization of Catechol by Means of Rotating Ring—disk Electrode

    Institute of Scientific and Technical Information of China (English)

    孔泳; 穆绍林

    2003-01-01

    The electrolysis of catechol was studied in the pH values of 1 to 10. The results from the rotating ring-disk electrode (RRDE) experiments show that at low pH values,the electrochemical polymerization of catechol was performed by one step,and at higher pH values,the electrochemical polymerization of catechol was carried out by two steps,i.e.oxidation of catechol and followed by polymerization.The intermediates generated at the disk were detected at the ring electrode in the ring potential region of -0.2 to 0 V(vs.Ag/AgCl).One of reasons for the decrease in the ratio of ir to id with increasing the ring potential is caused by formation of positively charged intermediates at the disk electrode.This ratio increases with increasing the rotation rate of the RRDE,which indicates that the intermediates are not stable.A shielding effect during polymerization of catechol was observed when the ring potential was set at 0.1 V (vs.Ag/AgCl).The electron spin resonance(ESR) of polycatechol show that polycatechol possesses unpaired electrons.The images of polycatechol films synthesized at differentconditions are described.

  10. Surface Complexation at the TiO(2) (anatase)/Aqueous Solution Interface: Chemisorption of Catechol.

    Science.gov (United States)

    Rodríguez; Blesa; Regazzoni

    1996-01-15

    Catechol adsorbs at the TiO(2) (anatase)/aqueous solution interface forming inner-sphere surface complexes. The UV-visible differential reflectance spectrum of surface titanium-catecholate complexes presents a band centered at 420 nm which corresponds to the ligand to metal charge transfer transition within the surface complexes. At pH values below pK(a1), the surface excess of catechol is almost insensitive toward pH and presents a Langmuirian dependence with the concentration of uncomplexed catechol. The ratio Gamma(max):N(S) (N(S) being the measured density of available OH surface groups) indicates a prevailing 1 to 2 ligand exchange adsorption stoichiometry. In the range pH >/= pK(a1), the catechol surface excess decreases markedly with increasing pH. Formation of 1 to 1 surface complexes produces an excess of negative surface charge that is revealed by the shift of the iep to lower pH values. The reported data, which are supplemented with information on the charging behavior of TiO(2) suspended in indifferent electrolyte solutions, are interpreted in terms of the multi-site surface complexation model. In this model, two types of surface OH groups are considered: identical withTiOH(1/3-) and identical withOH(1/3+). Although both surface groups undergo protonation-deprotonation reactions, only identical withTiOH(1/3-) are prone to chemisorption.

  11. Immobilization of complexes of some heavy metals with a 2-(4-pyridylazo)-resorcinol 'PAR' on Algerian hydrothermal clay

    Science.gov (United States)

    Bendjeffal, H.; Guerfi, K.; Bouhedja, Y.; Rebbani, N.

    2009-11-01

    The immobilization of the complexes of some heavy metals such as Co(II) and Ni(II) with a 2-(4-pyridylazo)-resorcinol 'PAR' from aqueous solution is studied using a natural and activated kaolin of Hameme Edbegh-Guelma (East of Algeria). The sorption of these metals complexes on kaolin from aqueous medium through the process of adsorption is studied under a set of variables such as concentration of metal complex, amount of kaolin, time and temperature of interaction. The suitability of the adsorbent was tested by fitting the adsorption data with Langmuir and Freundlich isotherms. The sorption of these complexes conformed to linear form of Langmuir adsorption equation. Langmuir qm constants for each metal complex were found as 0.391-0.493 mg/g (NiII-PAR2), 0.129-0.168 mg/g (CoII-PAR2) at 30 ∘C, respectively also, kinetic and thermodynamic parameters such as enthalpy (ΔH), free energy (ΔG) and entropy (ΔS) were calculated and these values show that adsorption of Co(II) and Ni(II) complex on kaolin was an exothermic.

  12. One-pot synthesis of interpenetrating inorganic/organic networks of CuO/resorcinol-formaldehyde aerogels: nanostructured energetic materials.

    Science.gov (United States)

    Leventis, Nicholas; Chandrasekaran, Naveen; Sadekar, Anand G; Sotiriou-Leventis, Chariklia; Lu, Hongbing

    2009-04-01

    For many applications ranging from catalysis to sensors to energetic materials, it is desirable to produce intimate mixtures of nanoparticles. For instance, to improve the reaction rates of energetic materials, the oxidizing agent and the fuel need to be mixed as intimately as possible, ideally at the nanoscopic level. In this context, the acidity of a hydrated CuCl(2) solution reacting toward a network of CuO nanoparticles (a good oxidant) is used to induce one-pot cogelation of a nanostructured network of a resorcinol-formaldehyde resin (RF, the fuel). The resulting wet gels are dried to aerogels, and upon pyrolysis under Ar, the interpenetrating CuO/RF network undergoes a smelting reaction toward metallic Cu. Upon ignition in the open air, pure RF aerogels do not burn, while CuO/RF composites, even with substoichiometric CuO, sustain combustion, burning completely leaving only a solid residue of CuO whose role then has been that of a redox mediator through the smelting reaction.

  13. Removal and Recovery of Some From Simulated Nuclear Waste Radionuclides Using Amberlite XAD-16-Pyridylazo Resorcinol (AXAD-PR) Composite

    Science.gov (United States)

    Akçağlar, Sevil

    2016-04-01

    In this study, Amberlite XAD-16-Pyridylazo resorcinol composite (AXAD-PR) were developed under laboratory conditions to detect the removals and recoveries of U(IV) and Am(III) from simulated nuclear wastes by adsorption and desorption processes. The effects of contacting time (5, 15, 25 and 200 min), of AXAD-PR concentrations (5, 25, 50 and 100 mg/l), of temperatures (15, 30 and 45°C), increasing U(IV) and Am(III) concentrations (1, 5, 10, 15, 20, 30 and 40) and pH levels (acidic, basic and neutral conditions) on the removals and recoveries of U(IV) and Am(III) radionuclides were investigated. The data obtained showed that the maximum adsorption yields of U(IV) and Am(III) were found to be 96% and 95%, respectively, after 25 min using 25 mg/l AXAD-PR at 30°C at an acidic pH of 5. The adsorption kinetic of radionuclides to AXAD-PR isotherm was in accordance with Langmuir. The AXAD-PR can be reused and can be used again. The regeneration of the composite is possible and can be attained a desorption efficiency of 99% using 0.4 M HNO3 acid solution from 25 mg/l prepared AXAD-PR.

  14. Enhancement by catechols of hydroxyl-radical formation in the presence of ferric ions and hydrogen peroxide.

    Science.gov (United States)

    Iwahashi, H; Morishita, H; Ishii, T; Sugata, R; Kido, R

    1989-03-01

    The effect of caffeic acid, a kind of catechol, on the Fenton reaction was examined by using the ESR spin trapping technique. Caffeic acid enhanced the formation of hydroxyl radicals in the reaction mixture, which contained caffeic acid, hydrogen peroxide, ferric chloride, EDTA, and potassium phosphate buffer. Chlorogenic acid, which is an ester of caffeic acid with quinic acid, also stimulated the formation of the hydroxyl radicals. Quinic acid did not stimulate the reaction, suggesting that the catechol moiety in chlorogenic acid is essential to the enhancement of the hydroxyl-radical formation. Indeed, other catechols and related compounds such as pyrocatechol, gallic acid, dopamine, and noradrenaline effectively stimulated the formation of the hydroxyl radicals. The above results confirm the idea that the catechol moiety is essential to the enhancement. Ferulic acid, 4-hydroxy-3-methoxybenzoic acid, and salicylic acid had no effect on the formation of the hydroxyl radicals. The results indicate that the enhancement by the catechols of the formation of hydroxyl radicals is diminished if a methyl ester is formed at the position of the hydroxyl group of the catechol. In the absence of iron chelators such as EDTA, DETAPAC, desferrioxamine, citrate, and ADP, formation of hydroxyl radicals was not detected, suggesting that chelators are essential to the reaction. The enhancement of the formation of hydroxyl radicals is presumably due to the reduction of ferric ions by the catechols. Thus, the catechols may exert deleterious effects on biological systems if chelators such as EDTA, DETAPAC, desferrioxamine, citrate, and ADP are present.

  15. A natural small molecule, catechol, induces c-Myc degradation by directly targeting ERK2 in lung cancer

    Science.gov (United States)

    Lim, Do Young; Shin, Seung Ho; Lee, Mee-Hyun; Malakhova, Margarita; Kurinov, Igor; Wu, Qiong; Xu, Jinglong; Jiang, Yanan; Dong, Ziming; Liu, Kangdong; Lee, Kun Yeong; Bae, Ki Beom; Choi, Bu Young; Deng, Yibin; Bode, Ann; Dong, Zigang

    2016-01-01

    Various carcinogens induce EGFR/RAS/MAPK signaling, which is critical in the development of lung cancer. In particular, constitutive activation of extracellular signal-regulated kinase 2 (ERK2) is observed in many lung cancer patients, and therefore developing compounds capable of targeting ERK2 in lung carcinogenesis could be beneficial. We examined the therapeutic effect of catechol in lung cancer treatment. Catechol suppressed anchorage-independent growth of murine KP2 and human H460 lung cancer cell lines in a dose-dependent manner. Catechol inhibited ERK2 kinase activity in vitro, and its direct binding to the ERK2 active site was confirmed by X-ray crystallography. Phosphorylation of c-Myc, a substrate of ERK2, was decreased in catechol-treated lung cancer cells and resulted in reduced protein stability and subsequent down-regulation of total c-Myc. Treatment with catechol induced G1 phase arrest in lung cancer cells and decreased protein expression related to G1-S progression. In addition, we showed that catechol inhibited the growth of both allograft and xenograft lung cancer tumors in vivo. In summary, catechol exerted inhibitory effects on the ERK2/c-Myc signaling axis to reduce lung cancer tumor growth in vitro and in vivo, including a preclinical patient-derived xenograft (PDX) model. These findings suggest that catechol, a natural small molecule, possesses potential as a novel therapeutic agent against lung carcinogenesis in future clinical approaches. PMID:27167001

  16. A natural small molecule, catechol, induces c-Myc degradation by directly targeting ERK2 in lung cancer.

    Science.gov (United States)

    Lim, Do Young; Shin, Seung Ho; Lee, Mee-Hyun; Malakhova, Margarita; Kurinov, Igor; Wu, Qiong; Xu, Jinglong; Jiang, Yanan; Dong, Ziming; Liu, Kangdong; Lee, Kun Yeong; Bae, Ki Beom; Choi, Bu Young; Deng, Yibin; Bode, Ann; Dong, Zigang

    2016-06-07

    Various carcinogens induce EGFR/RAS/MAPK signaling, which is critical in the development of lung cancer. In particular, constitutive activation of extracellular signal-regulated kinase 2 (ERK2) is observed in many lung cancer patients, and therefore developing compounds capable of targeting ERK2 in lung carcinogenesis could be beneficial. We examined the therapeutic effect of catechol in lung cancer treatment. Catechol suppressed anchorage-independent growth of murine KP2 and human H460 lung cancer cell lines in a dose-dependent manner. Catechol inhibited ERK2 kinase activity in vitro, and its direct binding to the ERK2 active site was confirmed by X-ray crystallography. Phosphorylation of c-Myc, a substrate of ERK2, was decreased in catechol-treated lung cancer cells and resulted in reduced protein stability and subsequent down-regulation of total c-Myc. Treatment with catechol induced G1 phase arrest in lung cancer cells and decreased protein expression related to G1-S progression. In addition, we showed that catechol inhibited the growth of both allograft and xenograft lung cancer tumors in vivo. In summary, catechol exerted inhibitory effects on the ERK2/c-Myc signaling axis to reduce lung cancer tumor growth in vitro and in vivo, including a preclinical patient-derived xenograft (PDX) model. These findings suggest that catechol, a natural small molecule, possesses potential as a novel therapeutic agent against lung carcinogenesis in future clinical approaches.

  17. Multimodal underwater adsorption of oxide nanoparticles on catechol-based polymer nanosheets

    Science.gov (United States)

    Yamamoto, Shunsuke; Uchiyama, Shun; Miyashita, Tokuji; Mitsuishi, Masaya

    2016-03-01

    Multimodal underwater adsorption behaviour of catechol units was demonstrated by examining the adsorption of different oxide nanoparticles on nanoscale-integrated polymer nanosheets. Catechol-based polymer nanosheets were fabricated using the Langmuir-Blodgett (LB) technique with random copolymers (p(DDA/DMA)s) of N-dodecylacrylamide (DDA) and dopamine methacrylamide (DMA). The p(DDA/DMA) nanosheets were immersed into water dispersions of SiO2, Al2O3, and WO3 nanoparticles (NPs) respectively. The results show that the adsorption properties can be altered by varying the NP type: SiO2 NP adsorption was observed only below pH = 6, at which the o-quinone form in p(DDA/DMA) nanosheets transforms into the catechol form or vice versa. However, their transition point for Al2O3 NP adsorption was found at approximately pH 10, at which the surface potential of Al2O3 NPs changes the charge polarity, indicating that the electrostatic interaction is predominant. For WO3 NPs, adsorption was observed when citric acid, which modifies the surface of WO3 NPs by complex formation, was used as a pH-controlling agent, but no adsorption was found for hydrochloric acid used as a pH controlling agent. FT-IR measurements proved that miniscule amounts of water molecules were trapped in p(DDA/DMA) nanosheets and that they acquired hydrogen bonding network formations, which might assist nanoparticle adsorption underwater and make the catechol units adjustable. The results indicate that the nanoscale spatial arrangements of catechol units in films are crucially important for the application of multimodal adsorption of oxide nanoparticles on catechol-based polymer materials.Multimodal underwater adsorption behaviour of catechol units was demonstrated by examining the adsorption of different oxide nanoparticles on nanoscale-integrated polymer nanosheets. Catechol-based polymer nanosheets were fabricated using the Langmuir-Blodgett (LB) technique with random copolymers (p(DDA/DMA)s) of N

  18. Purification and spectroscopic studies on catechol oxidase from lemon balm (Melissa officinalis).

    Science.gov (United States)

    Rompel, Annette; Büldt-Karentzopoulos, Klaudia; Molitor, Christian; Krebs, Bernt

    2012-09-01

    A catechol oxidase from lemon balm (Melissa officinalis) moCO which only catalyzes the oxidation of catechols to quinones without hydroxylating tyrosine was purified. The molecular mass of the M. officinalis enzyme of 39,370 Da was obtained by MALDI mass spectrometry and the isoelectric point was determined to be 3.4. Addition of 2 eq. H(2)O(2) to the enzyme leads to oxy catechol oxidase. In the UV/Vis spectrum two new absorption bands occur at 343 nm (ε=8510 M(-1)cm(-1)) and 580 nm (ε=580 M(-1)cm(-1)) due to O(2)(2-)Cu (II) charge transfer transitions in accordance with the oxy forms of other type 3 copper proteins. The N-terminal sequence has been determined by Edman degradation to NPVQAPELDKCGTAT, exhibiting a proline at the second and sixth position conserved in other polyphenol oxidases. Copyright © 2012 Elsevier Ltd. All rights reserved.

  19. Catechol derivatives as fluorescent chemosensors for wide-range pH detection.

    Science.gov (United States)

    Evangelio, Emilia; Hernando, Jordi; Imaz, Inhar; Bardají, Gisela G; Alibés, Ramon; Busqué, Félix; Ruiz-Molina, Daniel

    2008-01-01

    The synthesis and characterization of a new family of catechol derivatives designed to behave as fluorescent chemosensors for wide-range pH detection has been described. These compounds were prepared by covalently coupling a catechol unit with other aromatic rings, thus obtaining pi-delocalized systems with both pH-responsive groups and fluorescent behavior. In the case of a pyridine-catechol derivative, this leads to up to three different protonation states with distinct optical properties in organic media, as corroborated by density functional theory calculations. By applying dual-wavelength detection techniques, this compound shows complementary "off-on-off" and "on-off-on" emission profiles upon pH variation, a behavior that can be exploited to perform acidity detection over a broad pH range.

  20. A DFT Study on Intramolecular Hydrogen Bond in Substituted Catechols and Their Radicals

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    Density functional theory (DFT) at B3LYP/6-31G(d,p) level was employed to calculate intramolecular hydrogen bond enthalpies (HIHB), O-H charge differences, O-H bond lengths and bond orders for various substituted catechols and their radicals generated after H-abstraction. It was found that although the charge difference between hydrogen-bonded H and O played a role in determining HIHB, HIHB was mainly governed by the hydrogen bond length. As the oxygen-centered radical has great tendency to form a chemical bond with the H atom, hydrogen bond lengths in catecholic radicals are systematically shorter than those in catechols. Hence, the HIHB for the former are higher than those for the latter.

  1. Direction-dependent intermolecular interactions: catechol on TiO2(110)-1×1

    Science.gov (United States)

    Li, Shao-Chun; Diebold, Ulrike

    2009-08-01

    The adsorption of a submonolayer of catechol (C6H6O2) on the rutile TiO2(110)-1×1 surface has been investigated by Scanning Tunneling Microscopy (STM). The catechol molecules are preferentially adsorbed on the surface 5-fold coordinated Ti4+ sites, and occupy two neighboring lattice Ti sites. No preference for adsorption at surface step edges is observed at room temperature. A statistical analysis of intermolecular distances demonstrates that the interaction between the molecules strongly depends on the surface crystallographic direction: catechol molecules exhibit attractive interaction along [1-1 0], while they repel each other along the [001] direction. The attractive interaction is proposed to be caused by the coupling of π bonding electrons and the repulsive interaction is possibly mediated by substrate.

  2. Effect of β-cyclodextrin on intra and intermolecular Michael addition of some catechol derivatives

    Science.gov (United States)

    Khalafi, Lida; Rafiee, Mohammad; Fathi, Sahar

    2014-01-01

    The oxidation reactions of catechol, dopamine and epinephrine have been studied in the absence and presence of N-methylaniline by UV-Vis. Spectrophotometry. A variety of reaction pathways (inter and intramolecular reactions) that followed by this oxidation have been observed depending on the nature of catechol derivatives. The observed homogeneous rate constants of the reactions were estimated by fitting the absorption time profiles for each reaction. The effect of β-cyclodextrin and its inclusion complex has also been studied on the chosen reactions. The formation constants of the complexes of catechol, dopamine and epinephrine with β-cyclodextrin as well as the rate constants of the reactions of free and complexed forms have been obtained by fitting the absorption-time spectra to a proposed kinetic-equilibrium model.

  3. Remarkably enhanced adhesion of coherently aligned catechol-terminated molecules on ultraclean ultraflat gold nanoplates

    Science.gov (United States)

    Lee, Miyeon; Park, Changjun; Lee, Hyoban; Kim, Hongki; Kim, Sang Youl; In, Insik; Kim, Bongsoo

    2016-11-01

    We report the characterization and formation of catechol-terminated molecules immobilized on gold nanoplates (Au NPLs) using N-(3,4-dihydroxyphenethyl)-2-mercaptoacetamide (Cat-EAA-SH). Single-crystalline Au NPLs, synthesized using a one-step chemical vapor transport method, have ultraclean and ultraflat surfaces that make Cat-EAA-SH molecules aligned into a well-ordered network of a large-scale. Topographic study of the catechol-terminated molecules on Au NPLs using atomic force microscopy showed more orderly orientation and higher density, leading to significantly higher adhesion as observed from local force-distance curves than those on other Au surfaces. These coherently aligned catechol-terminated molecules on the atomically smooth gold surface led to significanty more reproducible and thus more physico-chemically meaningful measurements than was possible before by employing rough gold surfaces.

  4. Structure and kinetics of formation of catechol complexes of ferric soybean lipoxygenase-1

    Energy Technology Data Exchange (ETDEWEB)

    Nelson, M.J.; Brennan, B.A.; Chase, D.B. [E.I. du Pont de Nemours & Co., Wilmington, DE (United States)]|[Haverford College, PA (United States)] [and others

    1995-11-21

    Ferric soybean lipoxygenase forms stable complexes with 4-substituted catechols. The structure of the complex between the enzyme and 3,4-dihydroxybenzonitrile has been studied by resonance Raman, electron paramagnetic resonance, visible, and X-ray spectroscopies. It is a bidentate iron-catecholate complex with at least one water ligand. The kinetics of formation of complexes between lipoxygenase and 3,4-dihydroxybenzonitrile and 3,4-dihydroxyacetophenone have been studied by stopped-flow spectroscopy. The data are consistent with two kinetically distinct, reversible steps. The pH dependence of the first step suggests that the substrate for the reaction is the catechol monoanion. When these results are combined, plausible mechanisms for the complexation reaction are suggested. 51 refs., 12 figs., 2 tabs.

  5. Copper-Aβ Peptides and Oxidation of Catecholic Substrates: Reactivity and Endogenous Peptide Damage.

    Science.gov (United States)

    Pirota, Valentina; Dell'Acqua, Simone; Monzani, Enrico; Nicolis, Stefania; Casella, Luigi

    2016-11-14

    The oxidative reactivity of copper complexes with Aβ peptides 1-16 and 1-28 (Aβ16 and Aβ28) against dopamine and related catechols under physiological conditions has been investigated in parallel with the competitive oxidative modification undergone by the peptides. It was found that both Aβ16 and Aβ28 markedly increase the oxidative reactivity of copper(II) towards the catechol compounds, up to a molar ratio of about 4:1 of peptide/copper(II). Copper redox cycling during the catalytic activity induces the competitive modification of the peptide at selected amino acid residues. The main modifications consist of oxidation of His13/14 to 2-oxohistidine and Phe19/20 to ortho-tyrosine, and the formation of a covalent His6-catechol adduct. Competition by the endogenous peptide is rather efficient, as approximately one peptide molecule is oxidized every 10 molecules of 4-methylcatechol.

  6. A process optimization for bio-catalytic production of substituted catechols (3-nitrocatechol and 3-methylcatechol

    Directory of Open Access Journals (Sweden)

    Tiwary Bhupendra N

    2010-06-01

    Full Text Available Abstract Background Substituted catechols are important precursors for large-scale synthesis of pharmaceuticals and other industrial products. Most of the reported chemical synthesis methods are expensive and insufficient at industrial level. However, biological processes for production of substituted catechols could be highly selective and suitable for industrial purposes. Results We have optimized a process for bio-catalytic production of 3-substituted catechols viz. 3-nitrocatechol (3-NC and 3-methylcatechol (3-MC at pilot scale. Amongst the screened strains, two strains viz. Pseudomonas putida strain (F1 and recombinant Escherichia coli expression clone (pDTG602 harboring first two genes of toluene degradation pathway were found to accumulate 3-NC and 3-MC respectively. Various parameters such as amount of nutrients, pH, temperature, substrate concentration, aeration, inoculums size, culture volume, toxicity of substrate and product, down stream extraction, single step and two-step biotransformation were optimized at laboratory scale to obtain high yields of 3-substituted catechols. Subsequently, pilot scale studies were performed in 2.5 liter bioreactor. The rate of product accumulation at pilot scale significantly increased up to ~90-95% with time and high yields of 3-NC (10 mM and 3-MC (12 mM were obtained. Conclusion The biocatalytic production of 3-substituted catechols viz. 3-NC and 3-MC depend on some crucial parameters to obtain maximum yields of the product at pilot scale. The process optimized for production of 3-substituted catechols by using the organisms P. putida (F1 and recombinant E. coli expression clone (pDTG602 may be useful for industrial application.

  7. Plasma Activation of Integrated Carbon Nanotube Electrodes for Electrochemical Detection of Catechol

    Institute of Scientific and Technical Information of China (English)

    WANG Shenggao; WANG Tao; LI Yanqiong; ZHAO Xiujian; HAN Jianjun; WANG Jianhua

    2007-01-01

    In this study,integrated multi-wall carbon nanotube (MWCNT) electrodes were prepared in the holes of glass directly by microwave plasma chemical vapour deposition (MWPCVD).The electrochemical behaviour of catechol at the integrated MWCNT electrodes was investigated.The oxygen plasma treated CNT electrodes had better electrochemical performance for the analysis of catechol than that of as-synthesized CNT electrodes.Both the as-synthesized CNTs and plasma treated CNTs were characterized by TEM(transmission electron microscopy,XPS(X-ray photoelectron spectroscopy) and Raman spectroscopy.The results revealed that the oxygen plasma activation is an effective method to enhance the electrochemical properties of CNT electrodes.

  8. Catechol versus bisphosphonate ligand exchange at the surface of iron oxide nanoparticles: towards multi-functionalization

    Science.gov (United States)

    Guénin, Erwann; Lalatonne, Yoann; Bolley, Julie; Milosevic, Irena; Platas-Iglesias, Carlos; Motte, Laurence

    2014-11-01

    We report an investigation of the ligand exchange at the surface of iron oxide nanoparticles in water. For this purpose we compared two strong chelating agents on the iron oxide surface containing catechol and bisphosphonate moieties. Interactions between the coating agents (catechol/bisphosphonate) and the nanoparticle's surface were studied by FTIR and DFT calculations. Ligand exchange experiments were performed using sonication and the exchange yield was characterized by FTIR and EDX. This methodology allowed introducing bisphosphonates with various functionalities (alkyne or biotin) permitting multi-functionalization.

  9. Intramolecular interactions in ortho-methoxyalkylphenylboronic acids and their catechol esters

    Science.gov (United States)

    Adamczyk-Woźniak, Agnieszka; Borys, Krzysztof M.; Czerwińska, Karolina; Gierczyk, Błażej; Jakubczyk, Michał; Madura, Izabela D.; Sporzyński, Andrzej; Tomecka, Ewelina

    2013-12-01

    Catechol esters of ortho-methoxyalkylphenylboronic acids have been synthesized and characterized by 17O NMR spectroscopy. The results were compared with the data for the parent acids. The influence of intramolecular and intermolecular hydrogen bonds on the properties of the boronic acids has been discussed. The 17O NMR data for the boronic esters proved that there are no O → B interactions in the investigated compounds. This fact is connected with weak Lewis acidity of the parent acids and their low sugars' receptors activity. Crystal structure of ortho-methoxyphenylboronic acid catechol ester was determined.

  10. Synthesis, molecular structure and magnetic properties of a rhenium(IV) compound with catechol

    Science.gov (United States)

    Cuevas, A.; Geis, L.; Pintos, V.; Chiozzone, R.; Sanchíz, J.; Hummert, M.; Schumann, H.; Kremer, C.

    2009-03-01

    A novel Re(IV) complex containing catechol as ligand has been prepared and characterized. The crystal structure of (HNEt 3)(NBu 4)[ReCl 4(cat)]·H 2cat was determined. The rhenium ion presents a distorted octahedral geometry, being bonded to a bidentate catecholate group and four chloride anions. The magnetic properties of the complex were studied, a /2 D/ (the energy gap between ±3/2 and ±1/2 Kramers doublets) value of 190(10) cm -1. This is the largest /2 D/ value reported for Re(IV) up to now.

  11. DEVELOPMENT OF AN APPROACH TO MODELING LOADING AND ELUTION OF SPHERICAL RESORCINOL FORMALDEHYDE ION-EXCHANGE RESIN

    Energy Technology Data Exchange (ETDEWEB)

    Aleman, S.; Hamm, L.; Smith, F.

    2011-10-03

    The current strategy for removal of cesium from the Hanford waste stream is ion-exchange using spherical Resorcinol-Formaldehyde (sRF) resin. The original resin of choice was granular SuperLig 644 resin and during testing of this resin several operational issues were identified. For example, the granular material had a high angle of internal friction resulting in fragmentation of resin particles along its edges during cycling and adverse hydraulic performance. Efforts to replace SuperLig 644 were undertaken and one candidate was the granular Resorcinol-Formaldehyde (RF) resin where experience with this cation exchanger dates back to the late 1940's. To minimize hydraulic concerns a spherical version of RF was developed and several different chemically produced batches were created. The 5E-370/641 batch of sRF was selected and for the last decade numerous studies have been performed (e.g., batch contact tests, column loading and elution tests). The Waste Treatment Plant (WTP) flowsheet shows that the aqueous phase waste stream will have a wide range of ionic concentrations (e.g., during the loading step 0-3 M free OH, 5+ M Na, 0-1 M K, 0-3 M NO{sub 3}). Several steps are required in the ion-exchange process to achieve the required Cs separation factors: loading, displacement, washing, elution, and regeneration. The sRF resin will be operated over a wide range in pH (i.e., pH of 12-14 during the loading step and pH of 0.01-1 during the elution step). During some of these steps very high levels of counter-ions and co-ions will be present within the aqueous phase. Alternative process feeds are under consideration as well (e.g., sodium levels as high as 8 M and column operation up to 45 C during loading, reduced and recycled HNO{sub 3} during elution). In order to model the performance of sRF resin through an entire ion-exchange cycle, a more robust isotherm model is required. To achieve this more robust isotherm model requires knowledge of the numbers and kinds of

  12. Development and validation of an ultraviolet-visible spectrophotometric method for determination of phenylethyl resorcinol in new topical nanoemulsions.

    Science.gov (United States)

    Hong, L; Han, D; Li, M-X; Zhang, P; Liu, C-G

    2017-06-01

    To develop a rapid, simple and efficient ultraviolet-visible (UV-vis) spectrophotometric method for the quantification of phenylethyl resorcinol (PR), a potent skin-lightening agent, incorporated into new topical nanoemulsions, and to validate this method according to International Commission for Harmonization (ICH) guidelines. UV-vis spectrophotometric method for quantification of PR in new topical nanoemulsions was developed and validated in terms of specificity, linearity, sensitivity, precision and accuracy. The method was applied to determine PR content (extraction recoveries) in the nanoemulsions and entrapment efficiencies. The calibration curve for PR was linear in the range of 10-60 μg mL(-1) , with a determination coefficient (r(2) ) which is higher than 0.999. The limit of detection (LOD) and limit of quantitation (LOQ) were 1.55 and 4.69 μg mL(-1) , respectively. The method was shown to be specific, precise [intraday, interday and reproducibility levels relative standard deviation < 3%] and accurate (between 91.90 ± 1.28% and 104.73 ± 0.60%). The extraction recoveries of PR in nanoemulsions were 97.07%, 96.64% and 103.54% at concentrations of 3, 6 and 9 mg mL(-1) , respectively. The entrapment efficiencies were nearly 100%, which agrees with the oil core location of PR in nanoemulsions. This developed method was confirmed to be rapid, simple, cost-effective, specific, precise, accurate and suitable for determination of PR content in nanoemulsions and entrapment efficiencies. © 2016 Society of Cosmetic Scientists and the Société Française de Cosmétologie.

  13. Development of a nanostructured lipid carrier formulation for increasing photo-stability and water solubility of Phenylethyl Resorcinol

    Science.gov (United States)

    Fan, Hengfeng; Liu, Guoqing; Huang, Yiqing; Li, Yan; Xia, Qiang

    2014-01-01

    The Phenylethyl Resorcinol loaded nanostructured lipid carrier (PR-NLC) was developed by hot high-pressure homogenization method. The freshly prepared PR-NLC showed a spherical morphology under transmission electron microscope, and the particle size was 218.3 ± 9.2 nm. The value of the zeta potential of PR-NLC decreased from -30.2 ± 1.9 mV to -64.9 ± 1.3 mV when the dilution times reach 10. The loading amount of PR encapsulated in NLC was 2.94 ± 0.03%, and the average entrapment efficiencies of PR-NLC determinated by size exclusion chromatography and ultrafiltration were 90.2 ± 0.6% and 98.3 ± 0.3%. Lyophilization was proved feasible for the storage of NLC dispersion. Fourier transform infrared spectra (FTIR) was exploited to investigate the possible drug-lipid complex formation. Advancements in water solubility of PR were demonstrated by NLC using a contact angle measurement. The hemolysis percentage of the NLC was less than 1.3% in a certain range of concentration. In 90 days' storage, 88.6 ± 2.8% of PR remained unchanged in PR-NLC under natural daylight. In vitro release studies revealed a sustained drug release, and in vitro penetration studies showed an increase of retention amount of PR in the skin, when applying PR-NLC. Therefore, the NLC might be a potential delivery vehicle in cosmetic dermal products.

  14. Development of a nanostructured lipid carrier formulation for increasing photo-stability and water solubility of Phenylethyl Resorcinol

    Energy Technology Data Exchange (ETDEWEB)

    Fan, Hengfeng; Liu, Guoqing; Huang, Yiqing; Li, Yan; Xia, Qiang, E-mail: xiaq@seu.edu.cn

    2014-01-01

    The Phenylethyl Resorcinol loaded nanostructured lipid carrier (PR-NLC) was developed by hot high-pressure homogenization method. The freshly prepared PR-NLC showed a spherical morphology under transmission electron microscope, and the particle size was 218.3 ± 9.2 nm. The value of the zeta potential of PR-NLC decreased from −30.2 ± 1.9 mV to −64.9 ± 1.3 mV when the dilution times reach 10. The loading amount of PR encapsulated in NLC was 2.94 ± 0.03%, and the average entrapment efficiencies of PR-NLC determinated by size exclusion chromatography and ultrafiltration were 90.2 ± 0.6% and 98.3 ± 0.3%. Lyophilization was proved feasible for the storage of NLC dispersion. Fourier transform infrared spectra (FTIR) was exploited to investigate the possible drug–lipid complex formation. Advancements in water solubility of PR were demonstrated by NLC using a contact angle measurement. The hemolysis percentage of the NLC was less than 1.3% in a certain range of concentration. In 90 days’ storage, 88.6 ± 2.8% of PR remained unchanged in PR-NLC under natural daylight. In vitro release studies revealed a sustained drug release, and in vitro penetration studies showed an increase of retention amount of PR in the skin, when applying PR-NLC. Therefore, the NLC might be a potential delivery vehicle in cosmetic dermal products.

  15. I(+1) transfer from diiodomalonic acid to malonic acid and a complete inhibition of the CO and CO2 evolution in the Briggs-Rauscher reaction by resorcinol.

    Science.gov (United States)

    Onel, Lavinia; Bourceanu, Gelu; Wittmann, Maria; Noszticzius, Zoltán; Szabó, Gabriella

    2008-11-20

    A recent report on an intense CO 2 and CO evolution in the Briggs-Rauscher (BR) reaction revealed that iodination of malonic acid (MA) is not the only important organic reaction in the classical BR oscillator. To disclose the source of the gas evolution, iodomalonic (IMA) and diiodomalonic (I2MA) acids were prepared by iodinating MA with nascent iodine in a semibatch reactor. The nascent iodine was generated by an iodide inflow into the reactor, which contained a mixture of MA and acidic iodate. Some CO2 and a minor CO production was observed during these iodinations. It was found that in an aqueous acidic medium the produced I2MA is not stable but decomposes slowly to diiodoacetic acid and CO2. The first-order rate constant of the I 2MA decarboxylation at 20 degrees C was found to be k1 = 9 x 10(-5) s(-1), which is rather close to the rate constant of the analogous decarboxylation of dibromomalonic acid under similar conditions (7 x 10(-5)s(-1)). From the rate of the CO2 evolution, the I2MA concentration can be calculated in a MA-IMA-I2MA mixture as only I2MA decarboxylates spontaneously but MA and IMA are stable. Following CO2 evolution rates, it was proven that I2MA can react with MA in the reversible reaction I2MA + MA 2 IMA. The equilibrium constant of this reaction was calculated as K = 380 together with the rate constants of the forward k 2 = 6.2 x 10 (-2) M (-1)s(-1) and backward k-2 = 1.6 x 10(-4) M(-1)s(-1) reactions. The probable mechanism of the reaction is I(+1) transfer from I2MA to MA. The presence of I(+1) in a I2MA solution is demonstrated by its reduction with ascorbic acid. To estimate the fraction of CO2 coming from the decarboxylation of I2MA in an oscillatory BR reaction, the oscillations were inhibited by resorcinol. Unexpectedly, all CO2 and CO evolution was interrupted for more than one hour after injecting a small amount of resorcinol (10(-5) M initial concentration in the reactor). Finally, some implications of the newly found I(+1

  16. Correlation between Bonding Geometry and Band Gap States at Organic -- inorganic interfaces: Catechol on Rutile TiO2 (110)

    Science.gov (United States)

    Diebold, Ulrike; Li, Shao-Chun; Wang, Jian-Guo; Jacobson, Peter; Gong, Xue-Qing; Selloni, Annabella

    2009-03-01

    Adsorbate-induced band gap states in semiconductors are of particular interest due to the potential of increased light absorption and photoreactivity. A combined theoretical (DFT) and experimental (STM, photoemission) study of the molecular-scale factors involved in the formation of gap states in TiO2 is presented. Using the organic catechol on rutile TiO2(110) as a model system it is found that the bonding geometry strongly affects the molecular electronic structure. At saturation catechol forms an ordered 4 x 1 overlayer. This structure is attributed to catechol adsorbed on rows of surface Ti atoms with the molecular plane tilted from the surface normal by about ±27 in an alternating fashion. In the lowest-energy structure one of the two terminal OH groups at each catechol dissociates and the O binds to a surface Ti atom in a monodentate configuration, while the other OH group forms a H-bond to the next catechol neighbor. Through proton exchange with the surface this structure transforms into one where both OH groups dissociate and the catechol is bound to two surface Ti in a bidentate configuration. Only bidendate catechol introduces states in the band gap of TiO2.

  17. Cloning, expression, and characterization of catechol 1,2-dioxygenase from a phenol-degrading Candida tropicalis JH8 strain.

    Science.gov (United States)

    Long, Yan; Yang, Sheng; Xie, Zhixiong; Cheng, Li

    2016-10-02

    The sequence cato encoding catechol 1,2-dioxygenase from Candida tropicalis JH8 was cloned, sequenced, and expressed in Escherichia coli. The sequence cato contained an ORF of 858 bp encoding a polypeptide of 285 amino acid residues. The recombinant catechol 1,2-dioxygenase exists as a homodimer structure with a subunit molecular mass of 32 KD. Recombinant catechol 1,2-dioxygenase was unstable below pH 5.0 and stable from pH 7.0 to 9.0; its optimum pH was at 7.5. The optimum temperature for the enzyme was 30°C, and it possessed a thermophilic activity within a broad temperature range. Under the optimal conditions with catechol as substrate, the Km and Vmax of recombinant catechol 1,2-dioxygenase were 9.2 µM and 0.987 µM/min, respectively. This is the first article presenting cloning and expressing in E. coli of catechol 1,2-dioxygenase from C. tropicalis and characterization of the recombinant catechol 1,2-dioxygenase.

  18. Organic impurity profiling of 3,4-methylenedioxymethamphetamine (MDMA) synthesised from catechol.

    Science.gov (United States)

    Heather, Erin; Shimmon, Ronald; McDonagh, Andrew M

    2015-03-01

    This work examines the organic impurity profile of 3,4-methylenedioxymethamphetamine (MDMA) that has been synthesised from catechol (1,2-dihydroxybenzene), a common chemical reagent available in industrial quantities. The synthesis of MDMA from catechol proceeded via the common MDMA precursor safrole. Methylenation of catechol yielded 1,3-benzodioxole, which was brominated and then reacted with magnesium allyl bromide to form safrole. Eight organic impurities were identified in the synthetic safrole. Safrole was then converted to 3,4-methylenedioxyphenyl-2-propanone (MDP2P) using two synthetic methods: Wacker oxidation (Route 1) and an isomerisation/peracid oxidation/acid dehydration method (Route 2). MDMA was then synthesised by reductive amination of MDP2P. Thirteen organic impurities were identified in MDMA synthesised via Route 1 and eleven organic impurities were identified in MDMA synthesised via Route 2. Overall, organic impurities in MDMA prepared from catechol indicated that synthetic safrole was used in the synthesis. The impurities also indicated which of the two synthetic routes was utilised.

  19. Xylem occlusion in Bouvardia flowers : evidence for a role of peroxidase and catechol oxidase

    NARCIS (Netherlands)

    Vaslier, N.; Doorn, van W.G.

    2003-01-01

    During vase life, Bouvardia flowers show rapid leaf wilting, especially if they are stored dry prior to placement in water. Wilting is due to a blockage in the basal stem end. We investigated the possible role of peroxidase and catechol oxidase in the blockage in cv. van Zijverden flowers, which wer

  20. Chloridazon-catechol dioxygenases, a distinct group of meta-cleaving enzymes.

    Science.gov (United States)

    Schmitt, S; Müller, R; Wegst, W; Lingens, F

    1984-02-01

    We previously described a new meta-cleaving enzyme, termed chloridazon-catechol dioxygenase. The present paper describes the comparison of this enzyme with the meta-cleaving enzymes of eighteen strains of soil bacteria isolated with various aromatic compounds. Four of these strains were isolated with the herbicide chloridazon, six with the analgeticum aminopyrine and one with the analgeticum antipyrine as sole carbon source. These strains all belonged to a new type of bacteria, called Phenylobacteria. The seven other strains were isolated with aromatic compounds such as toluene, 3-phenylpropionate, benzoate, papaverine and 4-chlorobenzoate, and belonged to various species including Pseudomonas, Acinetobacter and Nocardia. In double diffusion experiments with antibodies, prepared against chloridazon-catechol dioxygenase, extracts from the eleven strains of Phenylobacteria gave a cross reaction, whereas the extracts of the seven other strains showed no reaction. The enzymes of the eleven positive strains showed the same characteristic kinetic behaviour as the previously described enzyme. In contrast to catechol 2, 3-dioxygenase they needed the addition of exogenous Fe2+ ions for activity. On ion-exchange chromatography they emerged at the same buffer concentration as chloridazon-catechol dioxygenase. In polyacrylamide electrophoresis they migrated identically. The linkage map derived from the activities of the various enzymes with 10 different substrates revealed an identity of more than 80% for these eleven enzymes. So the meta-cleaving enzymes of the Phenylobacteria seem to form a distinct group among the non-heme iron-containing dioxygenases.

  1. Catechol-O-methyltransferase gene methylation and substance use in adolescents : the TRAILS study

    NARCIS (Netherlands)

    van der Knaap, L. J.; Schaefer, J. M.; Franken, I. H. A.; Verhulst, F. C.; van Oort, F. V. A.; Riese, H.

    2014-01-01

    Substance use often starts in adolescence and poses a major problem for society and individual health. The dopamine system plays a role in substance use, and catechol-O-methyltransferase (COMT) is an important enzyme that degrades dopamine. The Val(108/158)Met polymorphism modulates COMT activity an

  2. Reaction Pathways in Catechol/Primary Amine Mixtures: A Window on Crosslinking Chemistry

    Science.gov (United States)

    Yang, Juan; Saggiomo, Vittorio; Velders, Aldrik H.; Cohen Stuart, Martien A.; Kamperman, Marleen

    2016-01-01

    Catechol chemistry is used as a crosslinking tool abundantly in both natural organisms (e.g. mussels, sandcastle worms) and synthetic systems to achieve the desired mechanical properties. Despite this abundance and success, the crosslinking chemistry is still poorly understood. In this study, to simplify the system, yet to capture the essential chemistry, model compounds 4-methyl catechol and propylamine are used. The reaction of 4-methyl catechol (2 mM) with propylamine (6 mM) is carried out in the presence of NaIO4 (2 mM) in 10 mM Na2CO3 aqueous solution. A variety of spectroscopic/spectrometric and chromatographic methods such as 1H NMR, LC-MS, and UV-VIS are used to track the reaction and identify the products/intermediates. It is found that the crosslinking chemistry of a catechol and an amine is both fast and complicated. Within five minutes, more than 60 products are formed. These products encompass 19 different masses ranging from molecular weight of 179 to 704. By combining time-dependent data, it is inferred that the dominant reaction pathways: the majority is formed via aryloxyl-phenol coupling and Michael-type addition, whereas a small fraction of products is formed via Schiff base reactions. PMID:27930671

  3. Chromium(VI) reduction by catechol(amine)s results in DNA cleavage in vitro

    DEFF Research Database (Denmark)

    Pattison, D I; Davies, Michael Jonathan; Levina, A;

    2001-01-01

    ) or 4-tert-butylcatechol (5) do not damage DNA. The Cr(VI)/catechol(amine) reactions have been studied at low added H(2)O(2) concentrations, which lead to enhanced DNA cleavage with 1 and induce DNA cleavage with 4. The Cr(V) and organic intermediates generated by the reactions of Cr(VI) with 1 or 4...

  4. Oxidation of Catechol using Titanium Silicate (TS-1 Catalyst: Modeling and Optimization

    Directory of Open Access Journals (Sweden)

    Sonali Sengupta

    2013-12-01

    Full Text Available The oxidation of catechol was studied in an eco-friendly process with commercial titanium silicate-1 (TS-1 catalyst and hydrogen peroxide as oxidant in absence of all mass transfer effects. The process was opti-mized by Box-Behnken design in terms of three independent process variables such as reaction tempera-ture, moles of hydrogen peroxide per mole of catechol and catalyst amount whose optimum values of the process variables were found to be 60 °C, 13.2 and 1.24 g respectively for maximum conversion of 75.8 %. The effects of different process parameters such as mole ratio of hydrogen peroxide to catechol, catalyst par-ticle size, catalyst amount, temperature and reaction time were studied. A pseudo first order kinetic model was fitted with the experimental rate data. The apparent activation energy for the reaction was found to be 11.37 kJ/mole.  © 2013 BCREC UNDIP. All rights reservedReceived: 22nd April 2013; Revised: 25th October 2013; Accepted: 1st November 2013[How to Cite: Sengupta, S., Ghosal, D., Basu, J.K. (2013. Oxidation of Catechol using Titanium Silicate (TS-1 Catalyst: Modeling and Optimization. Bulletin of Chemical Reaction Engineering & Catalysis, 8 (2: 167-177. (doi:10.9767/bcrec.8.2.4759.167-177][Permalink/DOI: http://dx.doi.org/10.9767/bcrec.8.2.4759.167-177

  5. Degradation of catechol by ionizing radiation, ozone and the combined process ozone-electron-beam

    Energy Technology Data Exchange (ETDEWEB)

    Kubesch, K. E-mail: sonja.solar@univie.ac.at; Zona, R.; Solar, S.; Gehringer, P

    2005-03-01

    The influence of oxygen on the radiation-induced degradation of catechol (5x10{sup -4} mol dm{sup -3}, 55 mg dm{sup -3}) in distilled water was studied by gamma-radiolysis in the presence of air (A) and using air saturation (AS) during irradiation. Under AS conditions a complete decomposition of catechol as well as of the trihydroxybenzene products was obtained by a dose of 6 kGy, without air saturation all phenolic compounds were still present at 10 kGy. Using AS, at 12 kGy the total organic carbon (TOC) was reduced by 63%, without air saturation by 17.5%. Detoxification was only obtained in AS solutions. In the presence of the natural matrix of the local tap water no trihydroxybenzene products were formed and for total decomposition of catechol in AS solutions 9 kGy were required. The comparison of the effectiveness of an electron beam (EB), an ozone (O{sub 3}) and a combined EB/O{sub 3} process showed, that by EB/O{sub 3} the extent of catechol degradation corresponded to the sum of the decay with EB and with ozone, whereas for the chemical oxygen demand and TOC reduction a synergistic effect was evident.

  6. Preserving the adhesion of catechol-conjugated hydrogels by thiourea-quinone coupling.

    Science.gov (United States)

    Xu, Yang J; Wei, Kongchang; Zhao, Pengchao; Feng, Qian; Choi, Chun Kit K; Bian, Liming

    2016-11-15

    Mussel adhesion has inspired the development of catechol-based adhesive polymers. However, conventional strategies require basic pH conditions and lead to the loss of adhesion. To solve the problem, we report the first attempt to use thiourea-functionalized polymers for preserving hydrogel adhesion. We believe that this simple thiourea-quinone coupling chemistry is instrumental to synthetic adhesive materials.

  7. Catechol-Bisphosphonate Conjugates:New Potential Chelating Agents for Metal Intoxication Therapy

    Institute of Scientific and Technical Information of China (English)

    Guang Yu XU; Chun Hao YANG; Bo LIU; Xi Han WU; Yu Yuan XIE

    2004-01-01

    In a quest for better chelating therapy drugs for the treatment of intoxication by Fe, Al, or actinides, two new series of mixed catechol-bisphosphonate through amide linkage were synthesized.Benzyl group was used as protecting group to avoid the breakage of amide by acid hydrolysis or imcomplete reaction in silylation-dealkylation using bromotrimethylsilane.

  8. Association of Catechol-O-Methyltransferase (COMT) Polymorphism and Academic Achievement in a Chinese Cohort

    Science.gov (United States)

    Yeh, Ting-Kuang; Chang, Chun-Yen; Hu, Chung-Yi; Yeh, Ting-Chi; Lin, Ming-Yeh

    2009-01-01

    Catechol-O-methyltransferase (COMT) is a methylation enzyme that catalyzes the degradation pathway and inactivation of dopamine. It is accepted widely as being involved in the modulation of dopaminergic physiology and prefrontal cortex (PFC) function. The COMT Val158Met polymorphism is associated with variation in COMT activity. COMT 158Met allele…

  9. Catechol-O-methyltransferase: a method for autoradiographic visualization of isozymes in cellogel

    Energy Technology Data Exchange (ETDEWEB)

    Brahe, C.; Crosti, N.; Meera Khan, P.; Serra, A.

    1984-02-01

    An electrophoretic procedure for separating the molecular forms of catechol-O-methyltransferase in cellulose acetate gel is described; the zones of enzyme activity were revealed by autoradiography. The electrophoretic patterns of the enzyme in several tissues and cell lines derived from four different species are presented.

  10. Revealing the role of catechol moieties in the interactions between peptides and inorganic surfaces.

    Science.gov (United States)

    Das, Priyadip; Reches, Meital

    2016-08-18

    Catechol (1,2-dihydroxy benzene) moieties are being widely used today in new adhesive technologies. Understanding their mechanism of action is therefore of high importance for developing their applications in materials science. This paper describes a single-molecule study of the interactions between catechol-related amino acid residues and a well-defined titanium dioxide (TiO2) surface. It is the first quantified measurement of the adhesion of these residues with a well-defined TiO2 surface. Single-molecule force spectroscopy measurements with AFM determined the role of different substitutions of the catechol moiety on the aromatic ring in the adhesion to the surface. These results shed light on the nature of interactions between these residues and inorganic metal oxide surfaces. This information is important for the design and fabrication of catechol-based materials such as hydrogels, coatings, and composites. Specifically, the interaction with TiO2 is important for the development of solar cells.

  11. Synthesis, characterization and self-assembly of Co3+ complexes appended with phenol and catechol groups

    Indian Academy of Sciences (India)

    Afsar Ali; Deepak Bansal; Rajeev Gupt

    2014-09-01

    This work presents the syntheses, characterization and hydrogen bonding based self-assembly of Co3+ complexes of pyridine-amide based bidentate ligands containing appended phenol and catechol groups. Placement of multiple hydrogen bond donors (phenolic OH and amidic NH groups) and acceptors (Oamide groups) in these molecules results in interesting self-assembled architectures.

  12. Free radical scavenging potency of quercetin catecholic colonic metabolites: Thermodynamics of 2H(+)/2e(-) processes.

    Science.gov (United States)

    Amić, Ana; Lučić, Bono; Stepanić, Višnja; Marković, Zoran; Marković, Svetlana; Dimitrić Marković, Jasmina M; Amić, Dragan

    2017-03-01

    Reaction energetics of the double (2H(+)/2e(-)), i.e., the first 1H(+)/1e(-) (catechol→ phenoxyl radical) and the second 1H(+)/1e(-) (phenoxyl radical→ quinone) free radical scavenging mechanisms of quercetin and its six colonic catecholic metabolites (caffeic acid, hydrocaffeic acid, homoprotocatechuic acid, protocatechuic acid, 4-methylcatechol, and catechol) were computationally studied using density functional theory, with the aim to estimate the antiradical potency of these molecules. We found that second hydrogen atom transfer (HAT) and second sequential proton loss electron transfer (SPLET) mechanisms are less energy demanding than the first ones indicating 2H(+)/2e(-) processes as inherent to catechol moiety. The Gibbs free energy change for reactions of inactivation of selected free radicals indicate that catecholic colonic metabolites constitute an efficient group of more potent scavengers than quercetin itself, able to deactivate various free radicals, under different biological conditions. They could be responsible for the health benefits associated with regular intake of flavonoid-rich diet.

  13. Iron(III) complexes of certain tetradentate phenolate ligands as functional models for catechol dioxygenases

    Indian Academy of Sciences (India)

    Mallayan Palaniandavar; Marappan Velusamy; Ramasamy Mayilmurugan

    2006-11-01

    Catechol 1,2-dioxygenase (CTD) and protocatechuate 3,4-dioxygenase (PCD) are bacterial non-heme iron enzymes, which catalyse the oxidative cleavage of catechols to cis, cis-muconic acids with the incorporation of molecular oxygen via a mechanism involving a high-spin ferric centre. The iron(III) complexes of tripodal phenolate ligands containing N3O and N2O2 donor sets represent the metal binding region of the iron proteins. In our laboratory iron(III) complexes of mono- and bisphenolate ligands have been studied successfully as structural and functional models for the intradiol-cleaving catechol dioxygenase enzymes. The single crystal X-ray crystal structures of four of the complexes have been determined. One of the bis-phenolato complexes contains a FeN2O2Cl chromophore with a novel trigonal bipyramidal coordination geometry. The Fe-O-C bond angle of 136.1° observed for one of the iron(III) complex of a monophenolate ligand is very similar to that in the enzymes. The importance of the nearby sterically demanding coordinated -NMe2 group has been established and implies similar stereochemical constraints from the other ligated amino acid moieties in the 3,4-PCD enzymes, the enzyme activity of which is traced to the difference in the equatorial and axial Fe-O(tyrosinate) bonds (Fe-O-C, 133, 148°). The nature of heterocyclic rings of the ligands and the methyl substituents on them regulate the electronic spectral features, FeIII/FeII redox potentials and catechol cleavage activity of the complexes. Upon interacting with catecholate anions, two catecholate to iron(III) charge transfer bands appear and the low energy band is similar to that of catechol dioxygenase-substrate complex. Four of the complexes catalyze the oxidative cleavage of H2DBC by molecular oxygen to yield intradiol cleavage products. Remarkably, the more basic N-methylimidazole ring in one of the complexes facilitates the rate-determining productreleasing phase of the catalytic reaction. The present

  14. Growth of Actinobacillus pleuropneumoniae is promoted by exogenous hydroxamate and catechol siderophores.

    Science.gov (United States)

    Diarra, M S; Dolence, J A; Dolence, E K; Darwish, I; Miller, M J; Malouin, F; Jacques, M

    1996-03-01

    Siderophores bind ferric ions and are involved in receptor-specific iron transport into bacteria. Six types of siderophores were tested against strains representing the 12 different serotypes of Actinobacillus pleuropneumoniae. Ferrichrome and bis-catechol-based siderophores showed strong growth-promoting activities for A. pleuropneumoniae in a disk diffusion assay. Most strains of A. pleuropneumoniae tested were able to use ferrichrome (21 of 22 or 95%), ferrichrome A (20 of 22 or 90%), and lysine-based bis-catechol (20 of 22 or 90%), while growth of 36% (8 of 22) was promoted by a synthetic hydroxamate, N5-acetyl-N5-hydroxy-L-ornithine tripeptide. A. pleuropneumoniae serotype 1 (strain FMV 87-682) and serotype 5 (strain 2245) exhibited a distinct yellow halo around colonies on Chrome Azurol S agar plates, suggesting that both strains can produce an iron chelator (siderophore) in response to iron stress. The siderophore was found to be neither a phenolate nor a hydroxamate by the chemical tests of Arnow and Csaky, respectively. This is the first report demonstrating the production of an iron chelator and the use of exogenous siderophores by A. pleuropneumoniae. A spermidine-based bis-catechol siderophore conjugated to a carbacephalosporin was shown to inhibit growth of A. pleuropneumoniae. A siderophore-antibiotic-resistant strain was isolated and shown to have lost the ability to use ferrichrome, synthetic hydroxamate, or catechol-based siderophores when grown under conditions of iron restriction. This observation indicated that a common iron uptake pathway, or a common intermediate, for hydroxamate- and catechol-based siderophores may exist in A. pleuropneumoniae.

  15. Reactivity and selectivity differences between catecholate and catechothiolate Ru complexes. Implications regarding design of stereoselective olefin metathesis catalysts.

    Science.gov (United States)

    Khan, R Kashif M; Torker, Sebastian; Hoveyda, Amir H

    2014-10-15

    The origins of the unexpected finding that Ru catechothiolate complexes, in contrast to catecholate derivatives, promote exceptional Z-selective olefin metathesis reactions are elucidated. We show that species containing a catechothiolate ligand, unlike catecholates, preserve their structural integrity under commonly used reaction conditions. DFT calculations indicate that, whereas alkene coordination is the stereochemistry-determining step with catecholate complexes, it is through the metallacyclobutane formation that the identity of the major isomer is determined with catechothiolate systems. The present findings suggest that previous models for Z selectivity, largely based on steric differences, should be altered to incorporate electronic factors as well.

  16. The role of the interaction between oxygen and catechol in the pitting corrosion of steel in alkaline sulfide solutions

    Energy Technology Data Exchange (ETDEWEB)

    Kannan, S.; Kelly, R.G. [Univ. of Virginia, Charlottesville, VA (United States)

    1995-12-01

    Black liquor corrosivity is shown to depend on the interaction of the chemical species present. Specifically, an interaction between oxygen and 1,2-dihydroxybenzene compounds (catechols) in alkaline sulfide solutions leads to a distinct increase in the severity of the attack. This increased corrosivity is explained in terms of the oxidation of catechol leading to increased open circuit potentials for steel. The importance of the ratio of sulfide concentration to hydroxyl concentration in the initiation of pitting is stressed. The possible role of catechol in stabilizing metastable pits is also discussed.

  17. Adsorption Properties of Ionic Species on Cross-linked Chitosans Modified with Catechol and Salicylic Acid Moieties

    OpenAIRE

    Oshita, Koji; Takayanagi, Toshio; Oshima, Mitsuko; Motomizu, Shoji

    2008-01-01

    Catechol-type chitosan resin and salicylic acid-type chitosan resin were easily synthesized for use in estimating the adsorption behavior of 34 elements at pH 1 - 7 in aquatic media. The catechol-type chitosan resin could adsorb Cu(II) at pH 3 - 7, In(III) at pH 4 - 6, Pb(II) and lanthanoids at pH 5 - 7, and U(VI) at pH 4 - 7 more effectively than the salicylic acid-type chitosan resin and the cross-linked chitosan resin (base material). Adsorption ability was in the order: catechol-type chit...

  18. Synthesis, characterization, thermal behavior, and DNA-cleaving studies of cyano-bridged nickel(II)-copper(II) complexes of 4-(pyridin-2-ylazenyl)resorcinol.

    Science.gov (United States)

    Karipcin, Fatma; Ozmen, Ismail; Cülü, Burcin; Celikoğlu, Umut

    2011-10-01

    We present here the syntheses of a mononuclear Cu(II) complex and two polynuclear Cu(II)-Ni(II) complexes of the azenyl ligand, 4-(pyridin-2-ylazenyl)resorcinol (HL; 1). The reaction of HL (1) and copper(II) perchlorate with KCN gave a mononuclear complex [CuL(CN)] (4). Using 4, one pentanuclear complex, [{CuL(NC)}(4) Ni](ClO(4))(2) (5) and one trinuclear complex, [{CuL(CN)}(2) NiL]ClO(4) (6), were prepared and characterized by elemental analyses, magnetic susceptibility, molar conductance, IR, and thermal analysis. Stoichiometric and spectral results of the mononuclear Cu(II) complex indicated that the metal/ligand/CN ratio was 1 : 1 : 1, and the ligand behaved as a tridentate ligand forming neutral metal chelates through the pyridinyl and azenyl N-, and resorcinol O-atom. The interaction between the compounds (the ligand 1, its Ni(II) and Cu(II) complexes without CN, i.e., 2 and 3, and its complexes with CN, 4-6) and DNA has also been investigated by agarose gel electrophoresis. The pentanuclear Cu(4) Ni complex (5) with H(2) O(2) as a co-oxidant exhibited the strongest DNA-cleaving activity.

  19. Study of transport properties and conduction mechanism of pure and composite resorcinol formaldehyde aerogel doped with Co-ferrite

    Energy Technology Data Exchange (ETDEWEB)

    Attia, S.M., E-mail: saidattia2004@yahoo.com [Physics Department, Faculty of Science, Kafrelsheikh University, Kafr El-Sheikh (Egypt); Physics Department, College of Applied Sciences, Umm Al-Qura University, PB 7296, Makkah 21955 (Saudi Arabia); Sharshar, T. [Physics Department, Faculty of Science, Kafrelsheikh University, Kafr El-Sheikh (Egypt); Physics Department, Faculty of Science, Taif University, Taif, 888 Hawiya (Saudi Arabia); Abd-Elwahed, A.R. [Physics Department, Faculty of Science, Kafrelsheikh University, Kafr El-Sheikh (Egypt); Tawfik, A. [Physics Department, Faculty of Science, Tanta University, Tanta (Egypt)

    2013-08-20

    Highlights: • A novel composite RF aerogels with Co-ferrite were prepared by sol–gel process. • RF aerogels exhibit a semiconducting behavior. • The dielectric constant of RF aerogel is very low (4 times as that of air) and can be controlled by adding Co-ferrite. • Large overlapping polaron (OLP) was found to be the preferred conduction mechanism in these materials. -- Abstract: A series of resorcinol formaldehyde aerogels (RF aerogels) composite with nanoparticles of CoFe{sub 2}O{sub 4} have been prepared by sol–gel method. Four samples of pure RF aerogels were prepared at different concentrations of Na{sub 2}CO{sub 3} as catalyst (0.02, 0.025, 0.03, and 0.04 wt.%) and four samples of composite RF aerogels were prepared at different concentration of doped CoFe{sub 2}O{sub 4} (0.075, 0.1, 0.125, and 0.15 wt.%; Na{sub 2}CO{sub 3} concentration = 0.03 wt.%). DC electrical conductivity as a function of temperature was studied in the temperature range 25 °C–200 °C for all samples. AC electrical conductivity and dielectric properties were determined using RLC Bridge in the frequency range 100 Hz–1 MHz at different temperature (25–200 °C). The pore size of the samples was determined using positron annihilation lifetime spectroscopy (PALS). RF aerogels are found to exhibit a semiconducting behavior and characterized by two transition temperatures T{sub 1} and T{sub 2}. Also σ{sub DC} increases with increase of Co-ferrite contents. Pure RF aerogels posses a very low dielectric constant, where the lowest value of ε′ is ∼4 times as that of air. ε′ decreases with increase of frequency, and increases with increase of temperature. Large overlapping polaron (OLP) is found to be the preferred conduction mechanism in these materials. The results of PALS show that there are two types of pore size in these samples; the first ranges from 1.9 to 2.5 nm, while the second ranges from 3.2 to 5.3 nm.

  20. Regulation of aromatics biodegradation by rhl quorum sensing system through induction of catechol meta-cleavage pathway.

    Science.gov (United States)

    Yong, Yang-Chun; Zhong, Jian-Jiang

    2013-05-01

    The mechanism for quorum sensing (QS) regulation on aromatics degradation was investigated. Deletion of rhl QS system resulted in a significant decrease in aromatics biodegradation as well as the activity of catechol 2,3-dioxygenase (C23O, key enzyme for catechol meta-cleavage pathway) in Pseudomonas aeruginosa CGMCC1.860. Interestingly, this repression could be relieved by N-butyryl homoserine lactone (the signaling molecule of rhl QS system) addition. In accordance, the transcription level of nahH (the gene encoding C23O) and nahR (transcriptional activator) also responded to rhl perturbation in a similar way. The results indicated that rhl QS system positively controlled the catechol meta-cleavage pathway, and hence improved aromatics biodegradation. It suggested manipulation of QS system could be a promising strategy to tune the catechol cleavage pathway and to control aromatics biodegradation.

  1. C{sub 24}H{sub 14} polycyclic aromatic hydrocarbons from the pyrolysis of catechol

    Energy Technology Data Exchange (ETDEWEB)

    Thomas, S.; Wornat, M.J. [Louisiana State University, Baton Rouge, LA (United States). Dept. of Chemical Engineering

    2008-07-01

    Polycyclic aromatic hydrocarbons (PAH) of the C{sub 24}H{sub 14} isomer class, some of which are potent mutagens and carcinogens, are produced during the burning of solid fuels. For a clearer understanding of the formation of PAH, pyrolysis experiments have been performed in an isothermal laminar-flow reactor with the model fuel catechol (ortho-dihydroxybenzene) - a phenol-type compound representative of structural entities in complex solid fuels like coal, wood, and biomass. The catechol pyrolysis experiments are conducted at 1000{sup o}C and at a residence time of 0.3 s. The pyrolysis products are analysed by high-pressure liquid chromatography with ultraviolet-visible absorbance detection and mass spectrometric detection. Product analysis reveals that the C{sub 24}H{sub 14} PAH products of catechol pyrolysis belong to three structural classes: perylene benzologues, fluoranthene benzologues and pyrene benzologues. The 12 C{sub 24}H{sub 14} PAH identified in the present study are: benzo(b)perylene, naphtho(1,2-b)fluoranthene, naphtho(1,2-k)fluoranthene, dibenzo(b,k)fluoranthene, naphtho(2,3-b)fluoranthene, naphtho(2,3-k)fluoranthene, naphtho(1,2-e)pyrene, naphtho(2,3-e)pyrene, naphtho(1,2-a)pyrene, dibenzo(a,e)pyrene, dibenzo(e, l)pyrene, and dibenzo(a,h)pyrene. In addition to these, our earlier identifications of naphtho(2,1-a)pyrene, naphtho(2,3-a)pyrene, and dibenzo(a,i)pyrene among the products of catechol pyrolysis bring the total number of C{sub 24}H{sub 14} PAH identified as products of catechol pyrolysis to 15. Of these 15, 12 have been reported to be mutagens and 6 have been reported to be carcinogens. The UV spectra establishing the identities of the 15 C{sub 24}H{sub 14} catechol pyrolysis products are presented.

  2. Evolution of CO{sub 2} during birnessite-induced oxidation of {sup 14}C-labeled catechol

    Energy Technology Data Exchange (ETDEWEB)

    Majcher, E.H.; Chorover, J.; Bollag, J.M.; Huang, P.M.

    2000-02-01

    Phenolic compounds undergo several transformation processes in soil and water (i.e., partial degradation, mineralization, and polymerization), many of which have been attributed primarily to biological activity. Results from previous work indicate that naturally occurring Mn oxides are also capable of oxidizing phenolic compounds. In the present study, {sup 14}C-labeled catechol was reacted with birnessite (manganese oxide) in aqueous suspension of pH 4. The mass of catechol-derived c in solid, solution, and gas phases was quantified as a function of time. Between 5 and 16% of the total catechol C was liberated as CO{sub 2} from oxidation and abiotic ring cleavage under various conditions. Most of the {sup 14}C (55--83%) was incorporated into the solid phase in the form of stable organic reaction products whereas solution phase {sup 14}C concentrations increased from 16 to 39% with a doubling of total catechol added. Polymerization and CO{sub 2} evolution appear to be competitive pathways in the transformation of catechol since their relative importance was strongly dependent on initial birnessite-catechol reaction conditions. Solid phase Fourier transform infrared (FTIR) spectra are consistent with the presence of phenolic, quinone, and aromatic ring cleavage products. Carbon dioxide release appears to be limited by availability of reactive birnessite surface sites and it is diminished in the presence of polymerized reaction products.

  3. Development of catechol 2,3-dioxygenase-specific primers for monitoring bioremediation by competitive quantitative PCR

    Energy Technology Data Exchange (ETDEWEB)

    Mesarch, M.B.; Nakatsu, C.H.; Nies, L.

    2000-02-01

    Benzene, toluene, xylenes, phenol, naphthalene, and biphenyl are among a group of compounds that have at least one reported pathway for biodegradation involving catechol 2,3-dioxygenase enzymes. Thus, detection of the corresponding catechol 2,3-dioxygenase genes can serve as a basis for identifying and quantifying bacteria that have these catabolic abilities. Primes that can successfully amplify a 238-bp catechol 2,3-dioxygenase gene fragment from eight different bacteria are described. The identities of the amplicons were confirmed by hybridization with a 238-bp catechol 2,3-dioxygenase probe. The detection limit was 10{sup 2} to 10{sup 3} gene copies, which was lowered to 10{sup 0} to 10{sup 1} gene copies of hybridization. Using the dioxygenase-specific primers, an increase in catechol 2,3-dioxygenase genes was detected in petroleum-amended soils. The dioxygenase genes were enumerated by competitive quantitative PCR and a 163-bp competitor that was amplified using the same primers. Target and competitor sequences had identical amplification kinetics. Potential PCR inhibitors that could coextract with DNA, nonamplifying DNA, soil factors (humics), and soil pollutants (toluene) did not impact enumeration. Therefore, this technique can be used to accurately and reproducibly quantify catechol 2,3-dioxygenase genes in complex environments such as petroleum-contaminated soil. Direct, non-cultivation-based molecular techniques for detecting and enumerating microbial pollutant-biodegrading genes in environmental samples are powerful tools for monitoring bioremediation and developing field evidence in support of natural attenuation.

  4. pH-dependent cross-linking of catechols through oxidation via Fe(3+) and potential implications for mussel adhesion.

    Science.gov (United States)

    Fullenkamp, Dominic E; Barrett, Devin G; Miller, Dusty R; Kurutz, Josh W; Messersmith, Phillip B

    2014-01-01

    The mussel byssus is a remarkable attachment structure that is formed by injection molding and rapid in-situ hardening of concentrated solutions of proteins enriched in the catecholic amino acid 3,4-dihydroxy-L-phenylalanine (DOPA). Fe(3+), found in high concentrations in the byssus, has been speculated to participate in redox reactions with DOPA that lead to protein polymerization, however direct evidence to support this hypothesis has been lacking. Using small molecule catechols, DOPA-containing peptides, and native mussel foot proteins, we report the first direct observation of catechol oxidation and polymerization accompanied by reduction of Fe(3+) to Fe(2+). In the case of the small molecule catechol, we identified two dominant dimer species and characterized their connectivities by nuclear magnetic resonance (NMR), with the C6-C6 and C5-C6 linked species as the major and minor products, respectively. For the DOPA-containing peptide, we studied the pH dependence of the reaction and demonstrated that catechol polymerization occurs readily at low pH, but is increasingly diminished in favor of metal-catechol coordination interactions at higher pH. Finally, we demonstrate that Fe(3+) can induce cross-links in native byssal mussel proteins mefp-1 and mcfp-1 at acidic pH. Based on these findings, we discuss the potential implications to the chemistry of mussel adhesion.

  5. New Hybrid Properties of TiO2 Nanoparticles Surface Modified With Catecholate Type Ligands

    Science.gov (United States)

    Janković, Ivana A.; Šaponjić, Zoran V.; Džunuzović, Enis S.; Nedeljković, Jovan M.

    2010-01-01

    Surface modification of nanocrystalline TiO2 particles (45 Å) with bidentate benzene derivatives (catechol, pyrogallol, and gallic acid) was found to alter optical properties of nanoparticles. The formation of the inner-sphere charge-transfer complexes results in a red shift of the semiconductor absorption compared to unmodified nanocrystallites. The binding structures were investigated by using FTIR spectroscopy. The investigated ligands have the optimal geometry for chelating surface Ti atoms, resulting in ring coordination complexes (catecholate type of binuclear bidentate binding-bridging) thus restoring in six-coordinated octahedral geometry of surface Ti atoms. From the Benesi-Hildebrand plot, the stability constants at pH 2 of the order 103 M-1 have been determined.

  6. Robust Alginate-Catechol@Polydopamine Free-Standing Membranes Obtained from the Water/Air Interface.

    Science.gov (United States)

    Ponzio, Florian; Le Houerou, Vincent; Zafeiratos, Spyridon; Gauthier, Christian; Garnier, Tony; Jierry, Loic; Ball, Vincent

    2017-03-07

    The formation of polydopamine composite membranes at the water/air interface using different chemical strategies is reported. The use of either small molecules (urea, pyrocatechol) or polymers paves the way to understand which kind of compounds can be used for the formation of PDA-composite free-standing membranes produced at the water/air interface. On the basis of these screening results, we have found that alginate grafted with catechol groups allows the formation of robust free-standing films with asymmetric composition, stimuli-responsiveness, and self-healing properties. The stickiness of these membranes depends on the relative humidity, and its adhesion behavior on PDMS was characterized using the JKR method. Thus, alginate-catechol polydopamine films appear as a new class of PDA composites, mechanically robust through covalent cross-linking and based on fully biocompatible constituting partners. These results open the door to potential applications in the biomedical field.

  7. Crystal structure of thermostable catechol 2,3-dioxygenase determined by multiwavelength anomalous dispersion method

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The selenomethionyl derivative of the thermostable catechol 2,3-dioxygenase (SeMet-TC23O) is expressed,purified and crystallized. By using multiwave length anomalous dispersion (MAD) phasing techniques, the crystal structure of TC23O at 0.3 nm resolutions is determined.TC23O is a homotetramer. Each monomer is composed of N-terminal and C-terminal domains (residues 1~153 and 153~319, respectively). The two domains are proximately symmetric by a non-crystallographic axis. Each domain contains two characteristic motifs which are found in almost all of extradial dioxygenases.Kevwords: multiwavelength anomalous dispersion (MAD), X-ray diffraction, thermostable catechol 2,3-dioxygenase, crystal structure,synchrotron light source.

  8. Clean and Green Synthesis of New Benzothiazole Derivatives via Electrochemical Oxidation of Catechol Derivatives

    Directory of Open Access Journals (Sweden)

    Mansour Arab Chamjangali

    2016-06-01

    Full Text Available Electrochemical oxidation of the catechols 1a and 1b is studied in the presence of 6-methyl-2-thouracil (3b and 6-propyl-2-thiouracil (3a as nucleophiles in a phosphate buffer (0.15 mol L−1, pH = 6.8/DMF (95:5 solution using cyclic voltammetry and controlled-potential coulometry. The results obtained indicate that the quinones derived from the catechols participate in 1,4-Michael-addition reactions with the nucleophiles to form the corresponding new benzothiazole compounds. In this work, we derive a variety of products with good yields using controlled potential at graphite electrodes in an undivided cell. This work is licensed under a Creative Commons Attribution 4.0 International License.

  9. Catechol Removal from Aqueous Media Using Laccase Immobilized in Different Macro- and Microreactor Systems.

    Science.gov (United States)

    Tušek, Ana Jurinjak; Šalić, Anita; Zelić, Bruno

    2017-01-23

    Laccase belongs to the group of enzymes that are capable to catalyze the oxidation of phenols. Since the water is only by-product in laccase-catalyzed phenol oxidations, it is ideally "green" enzyme with many possible applications in different industrial processes. To make the oxidation process more sustainable in terms of biocatalyst consumption, immobilization of the enzyme is implemented in to the processes. Additionally, when developing a process, choice of a reactor type plays a significant role in the total outcome.In this study, the use of immobilized laccase from Trametes versicolor for biocatalytic catechol oxidation was explored. Two different methods of immobilization were performed and compared using five different reactor types. In order to compare different systems used for catechol oxidation, biocatalyst turnover number and turnover frequency were calculated. With low consumption of the enzyme and good efficiency, obtained results go in favor of microreactors with enzyme covalently immobilized on the microchannel surface.

  10. Characterization of catechol 1,2-dioxygenase from cell extracts of Sphingomonas xenophaga QYY

    Institute of Scientific and Technical Information of China (English)

    GOU Min; QU YuanYuan; ZHOU JiTi; LI Ang; M.Salah Uddin

    2009-01-01

    Sphingomonas xenophaga QYY, capable of growing significantly on more than ten kinds of aromatic compounds as sole carbon source, was used to study characterization of catechol 1,2-dioxygenase (C120) in cell extracts. Characterization of the crude C120 showed that the maximum activity was obtained at 40-70℃ and pH 7.8-8.8. Metal ions had different influences on the activity of crude C120. It was suggested that strain QYY possessed an inducible and ferric-dependent C120. Kinetic studies showed that the value of Vmax and Km was 0.25 μmol catechol/L/mg protein/min and 52.85 μmol/L, respectively. In addition, the partial purification of C120 was achieved by a HiTrap Q Sepharose column chromatography.

  11. Crystallization and preliminary X-ray diffraction studies of a catechol-O-methyltransferase/inhibitor complex

    Energy Technology Data Exchange (ETDEWEB)

    Rodrigues, M. L. [Instituto de Tecnologia Química e Biológica (ITQB), Universidade Nova de Lisboa, Av. República, Apt. 127, 2781-901 Oeiras (Portugal); Bonifácio, M. J.; Soares-da-Silva, P. [Department of Research and Development, BIAL, 4785 S. Mamede do Coronado (Portugal); Carrondo, M. A.; Archer, M., E-mail: archer@itqb.unl.pt [Instituto de Tecnologia Química e Biológica (ITQB), Universidade Nova de Lisboa, Av. República, Apt. 127, 2781-901 Oeiras (Portugal)

    2005-01-01

    Catechol-O-methyltransferase has been co-crystallized with a novel inhibitor, which has potential therapeutic application in the Parkinson’s disease therapy. Inhibitors of the enzyme catechol-O-methyltransferase (COMT) are used as co-adjuvants in the therapy of Parkinson’s disease. A recombinant form of the soluble cytosolic COMT from rat has been co-crystallized with a new potent inhibitor, BIA 8-176 [(3,4-dihydroxy-2-nitrophenyl)phenylmethanone], by the vapour-diffusion method using PEG 6K as precipitant. Crystals diffract to 1.6 Å resolution on a synchrotron-radiation source and belong to the monoclinic space group P2{sub 1}, with unit-cell parameters a = 52.77, b = 79.63, c = 61.54 Å, β = 91.14°.

  12. Characterization of catechol 1,2-dioxygenase from cell extracts of Sphingomonas xenophaga QYY

    Institute of Scientific and Technical Information of China (English)

    M.Salah; Uddin

    2009-01-01

    Sphingomonas xenophaga QYY, capable of growing significantly on more than ten kinds of aromatic compounds as sole carbon source, was used to study characterization of catechol 1,2-dioxygenase (C12O) in cell extracts. Characterization of the crude C12O showed that the maximum activity was obtained at 40-70℃ and pH 7.8-8.8. Metal ions had different influences on the activity of crude C12O. It was suggested that strain QYY possessed an inducible and ferric-dependent C12O. Kinetic studies showed that the value of Vmax and Km was 0.25 μmol catechol/L/mg protein/min and 52.85 μmol/L, respectively. In addition, the partial purification of C12O was achieved by a HiTrap Q Sepharose column chromatography.

  13. Polymeric Framboidal Nanoparticles Loaded with a Carbon Monoxide Donor via Phenylboronic Acid-Catechol Complexation.

    Science.gov (United States)

    van der Vlies, André J; Inubushi, Ryosuke; Uyama, Hiroshi; Hasegawa, Urara

    2016-06-15

    Carbon monoxide (CO) is an essential gaseous signaling molecule in the human body. Toward the controlled delivery of CO to the target tissues or cells, nanomaterial-based CO donors have attracted growing attention. Here, we present CO-releasing polymeric nanoparticles (CONPs) prepared by simple mixing of phenylboronic acid-containing framboidal nanoparticles with the catechol-bearing CO-donor Ru(CO)3Cl(L-DOPA) via phenylboronic acid-catechol complexation. The CONPs release CO in response to cysteine and suppress the production of the pro-inflammatory mediators interleukin 6 (IL-6) and nitric oxide (NO) in lipopolysaccharide (LPS)-stimulated murine macrophages. This CONP platform may show promise in therapeutic applications of CO.

  14. High-Temperature Hydrogen Storage of Multiple Molecules: Theoretical Insights from Metalated Catechols.

    Science.gov (United States)

    Tsivion, Ehud; Veccham, Srimukh Prasad; Head-Gordon, Martin

    2017-01-18

    Insertion of open metal sites (OMS) into metal-organic frameworks (MOFs) is a promising strategy for preparation of physical adsorbents that enable H2 storage at room temperature. Density functional theory (DFT) calculations are reported on a promising paradigm for adsorption of multiple hydrogen molecules to a single OMS attached to an MOF linker via a catechol or thiocatechol. The interactions between adsorbed H2 and the OMS are characterized with special attention to their degrees of freedom and thermal properties. By combining the present calculations with experimental data, some of these materials are predicted to have usable capacities close to the Department of Energy (DOE) 2020 target of 40 gr L(-1) marking them as important synthetic targets. Surprisingly, calculations suggest that a Ca-catechol OMS retains the ability to bind up to two hydrogens even in the presence of residual solvent. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. The Role of Catechol-O-Methyltransferase (COMT Gene in the Etiopathogenesis of Schizophrenia

    Directory of Open Access Journals (Sweden)

    Ceren Acar

    2014-09-01

    Full Text Available Genetic factors in the risk of developing schizophrenia is of great importance. With the help of the advances in the field of genetics in recent years by using linkage analysis several genes have been identified that may be a risk factor in schizophrenia. Several association studies have been performed in many different populations on the candidate susceptibility genes that were defined in previous studies. However, these studies give controversial results in different countries with different populations, and there are problems in obtaining replicable results. In this review we aimed to focus on the genetic basis of schizophrenia and the relationship between schizophrenia and catechol-O-methyltransferase (COMT gene. COMT encodes an enzyme molecule which has an important function in dopamine pathways. It has great importance in catecholamine metabolism and pharmacology and genetic mechanism of catechol metabolism variations and their clinical consequences. COMT transfers the methyl group from S-adenosyl-methionine to the hydroxyl group of catechol nucleus (such as dopamine, norepinephrine or catechol estrogen. Genetic variations found in COMT gene are associated with a broad spectrum of clinical phenotype including psychiatric disorders or estrogen related cancers. Several groups have performed studies on the relationship between schizophrenia and COMT. The most commonly studied polymorphism in COMT gene is rs4680 and it causes a valine methionine conversion at codon 158. The association studies on this polymorphism in different populations gave both positive and negative results. Schizoprenia is a complex disease caused by the interaction of environmental and genetic factors, while interpreting the genetic data, this fact and the possibility of the presence of different gene products should be taken into account. [Psikiyatride Guncel Yaklasimlar - Current Approaches in Psychiatry 2014; 6(3.000: 217-226

  16. Growth of Actinobacillus pleuropneumoniae is promoted by exogenous hydroxamate and catechol siderophores.

    OpenAIRE

    Diarra, M. S.; Dolence, J A; Dolence, E K; Darwish, I; Miller, M.J.; Malouin, F; Jacques, M.

    1996-01-01

    Siderophores bind ferric ions and are involved in receptor-specific iron transport into bacteria. Six types of siderophores were tested against strains representing the 12 different serotypes of Actinobacillus pleuropneumoniae. Ferrichrome and bis-catechol-based siderophores showed strong growth-promoting activities for A. pleuropneumoniae in a disk diffusion assay. Most strains of A. pleuropneumoniae tested were able to use ferrichrome (21 of 22 or 95%), ferrichrome A (20 of 22 or 90%), and ...

  17. Synthesis of 4-O-Methylcedrusin. Selective Protection of Catechols with Diphenyl Carbonate

    OpenAIRE

    Roger Dommisse; Jonckers, Tim H M; Guy L. F. Lemière; Dyck, Stefaan M. O. Van

    2000-01-01

    4-O-Methylcedrusin, a minor component in ‘sangre de drago’, has been synthesized using a strategy of successive protection and deprotection reactions under very mild conditions. The key step of this synthesis is a selective protection of a catechol group as a cyclic carbonate in the presence of an isolated phenol group.

  18. Carrier-microencapsulation using Si-catechol complex for suppressing pyrite floatability

    Energy Technology Data Exchange (ETDEWEB)

    Jha, R.K.T.; Satur, J.; Hiroyoshi, N.; Ito, M.; Tsunekawa, M. [Hokkaido University, Hokkaido (Japan). Graduate School of Engineering

    2008-11-15

    Pyrite (FeS{sub 2}) is a common sulfide mineral associated with valuable metal minerals and coal, and it is rejected as a gangue mineral using physical separation techniques such as froth flotation and discharged into tailing pond. In the flotation, pyrite is frequently entrapped in the froth due to its hydrophobic nature. Formation of acid mine drainage due to the air-oxidation of pyrite in the tailing pond is also a serious problem. The authors have proposed carrier-microencapsulation (CME) as a method for suppressing both the floatability and oxidation of pyrite. In this method, pyrite is coated with a thin layer of metal oxide or hydroxide using catechol solution as a carrier combined with metal ions. The layer converts the pyrite surface from hydrophobic to hydrophilic and acts as a protective coating against oxidation. The present study demonstrates the effect of CME using Si-catechol complex to suppress the pyrite floatability: The bubble pick-up experiments showed that attachment of pyrite particles to air bubble is suppressed by the CME treatment at pH 4-10, Si-catechol complex concentration over 0.5 mol m{sup -3} and treatment time within 2 min. The Hallimond tube flotation experiments showed that the pyrite floatability is suppressed by the CME treatment even in the presence of typical flotation collectors such as kerosene and xanthate. SEM-EDX analysis confirmed that Si present on the pyrite surface treated by Si-catechol complex, implying that SiO{sub 2} or SiOH{sub 4} layer formed by the CME treatment convert the pyrite surface hydrophobic to hydrophilic.

  19. Lubricating oil compositions containing overbased calcium sulfonates and metal salts of alkyl catechol dithiophosphoric acid

    Energy Technology Data Exchange (ETDEWEB)

    Yamaguchi, E.S.; Cerrito, E.; Liston, T.V.

    1987-05-26

    This patent describes a lubricating oil composition containing an overbased calcium hydrocarbyl sulfonate. The improvement wherein the lubricating oil composition additionally comprises an effective amount to reduce wear of a metal salt of an alkyl catechol dithiophosphoric acid ester of the formula: wherein R is alkyl containing 10 to 18 carbon atoms, or mixtures thereof, M is an alkali or alkaline earth metal or transition metal and n corresponds to the valence of the metal M.

  20. Synthesis of 4-O-Methylcedrusin. Selective Protection of Catechols with Diphenyl Carbonate

    Directory of Open Access Journals (Sweden)

    Roger Dommisse

    2000-02-01

    Full Text Available 4-O-Methylcedrusin, a minor component in ‘sangre de drago’, has been synthesized using a strategy of successive protection and deprotection reactions under very mild conditions. The key step of this synthesis is a selective protection of a catechol group as a cyclic carbonate in the presence of an isolated phenol group.

  1. Extraction of metals from metal ion-catechol-quaternary base systems.

    Science.gov (United States)

    Vrchlabský, M; Sommer, L

    1968-09-01

    Methods are given for the extraction of iron(III), molybdenum(VI), titanium(IV), niobium(V), vanadium(IV), uranium(VI) and tungsten(VI) as ternary complexes with catechol and a quaternary cation such as n-butyltriphenylphosphonium, n-propyltriphenylphosphonium, tetraphenylarsonium, cetylpyridinium, cetyltrimethylammonium and 2,3,5-triphenyltetrazolium, the solvent being chloroform. By use of masking agents and pH control, some of these elements can be separated from each other by this means.

  2. Dinuclear copper complexes with imidazole derivative ligands: a theoretical study related to catechol oxidase activity.

    Science.gov (United States)

    Martínez, Ana; Membrillo, Ingrid; Ugalde-Saldívar, Victor M; Gasque, Laura

    2012-07-19

    Catechol oxidase is a very important and interesting metalloprotein. In spite of the efforts to understand the reaction mechanism of this protein, there are important questions that remain unanswered concerning the catalytic mechanism of this enzyme. In this article, dinuclear copper compounds are used as biomimetic models of catechol oxidase to study plausible reaction paths. These dinuclear copper(II) complexes have distant metal centers (of 7.5 Å approximately) and superior catalytic activity to that of many dicopper complexes with shorter Cu-Cu distances. One mononuclear copper(II) complex is also analyzed in this investigation in order to see the influence of the two metal centers in the catalytic activity. Density functional theory calculations were performed to obtain optimized structures, vertical ionization energies, vertical electron affinities, the electrodonating power (ω(-)), the electroaccepting power (ω(+)) and the energy difference of several reaction paths. The K(M) experimental results that were previously reported compare well with the electroaccepting power (ω(+)) of the copper compounds that are included in this article, indicating that this index is useful for the interpretation of the electron transfer capacity and therefore the catalytic activity. The catechol moiety coordinates to only one Cu ion, but two metal atoms are needed in order to have a good electron acceptor capacity of the biomimetic models.

  3. Versatile tuning of supramolecular hydrogels through metal complexation of oxidation-resistant catechol-inspired ligands.

    Science.gov (United States)

    Menyo, Matthew S; Hawker, Craig J; Waite, J Herbert

    2013-11-21

    The mussel byssal cuticle employs DOPA-Fe(3+) complexation to provide strong, yet reversible crosslinking. Synthetic constructs employing this design motif based on catechol units are plagued by oxidation-driven degradation of the catechol units and the requirement for highly alkaline pH conditions leading to decreased performance and loss of supramolecular properties. Herein, a platform based on a 4-arm poly(ethylene glycol) hydrogel system is used to explore the utility of DOPA analogues such as the parent catechol and derivatives, 4-nitrocatechol (nCat) and 3-hydroxy-4-pyridinonone (HOPO), as structural crosslinking agents upon complexation with metal ions. HOPO moieties are found to hold particular promise, as robust gelation with Fe(3+) occurs at physiological pH and is found to be largely resistant to oxidative degradation. Gelation is also shown to be triggered by other biorelevant metal ions such as Al(3+), Ga(3+) and Cu(2+) which allows for tuning of the release and dissolution profiles with potential application as injectable delivery systems.

  4. Vapour-phase O-methylation of Catechol with Methanol on Ti-containing Phosphate Catalysts

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    Ti-containing phosphate(Ti-P-O) catalysts with different molar ratios of P to Ti(0-2.0) were synthesized and characterized by XRD, N2-adsorption/desorption, IR and temperature-programmed desorption(TPD) methods. The catalytic properties of Ti-P-O samples in the vapor-phase O-methylation of catechol with methanol were also studied. The catechol conversion increases with the increase of the molar ratio of P to Ti in a range of 0-0.33, while a further increase in the P content leads to a decrease of the catalytic activity. Meanwhile, the selectivities of the catalysts to the main product(guaiacol) increase gradually with the increase of the molar ratio of P to Ti. The presence of relatively strong Lewis acidic and/or basic sites in the P-free catalyst should be responsible for the formation of C-alkylation products. The weak acid-base characteristics of the catalysts are favourable for the mono-O-methylation of catechol. In comparison with the Lewis acidic sites, the Br(o)nsted acidic sites on the catalysts are more active for the title reaction.

  5. Secondary Organic Aerosol formation from the gas-phase reaction of catechol with ozone

    Science.gov (United States)

    Coeur-Tourneur, C.; Tomas, A.; Guilloteau, A.; Henry, F.; Ledoux, F.; Visez, N.; Riffault, V.; Wenger, J. C.; Bedjanian, Y.; Foulon, V.

    2009-04-01

    The formation of secondary organic aerosol from the gas-phase reaction of catechol (1,2-dihydroxybenzene) with ozone has been studied in two smog chambers (at the LPCA in France and at the CRAC in Ireland). Aerosol production was monitored using a scanning mobility particle sizer. The overall organic aerosol yield (Y) was determined as the ratio of the suspended aerosol mass corrected for wall losses (Mo) to the total reacted catechol concentrations, assuming a particle density of 1.4 g cm-3. Analysis of the data clearly shows that Y is a strong function of Mo and that secondary organic aerosol formation can be expressed by a one-product gas/particle partitioning absorption model. The aerosol formation is affected by the initial catechol concentration, which leads to aerosol yields ranging from 17% to 86%. The aerosol yields determined in the LPCA and CRAC smog chambers were comparable and were also in accordance with those determined in a previous study performed in EUPHORE (EUropean PHOto REactor, Spain).

  6. Serotonin-Induced Hypersensitivity via Inhibition of Catechol O-Methyltransferase Activity

    Directory of Open Access Journals (Sweden)

    Tsao Douglas

    2012-04-01

    Full Text Available Abstract The subcutaneous and systemic injection of serotonin reduces cutaneous and visceral pain thresholds and increases responses to noxious stimuli. Different subtypes of 5-hydroxytryptamine (5-HT receptors are suggested to be associated with different types of pain responses. Here we show that serotonin also inhibits catechol O-methyltransferase (COMT, an enzyme that contributes to modultion the perception of pain, via non-competitive binding to the site bound by catechol substrates with a binding affinity comparable to the binding affinity of catechol itself (Ki = 44 μM. Using computational modeling, biochemical tests and cellular assays we show that serotonin actively competes with the methyl donor S-adenosyl-L-methionine (SAM within the catalytic site. Binding of serotonin to the catalytic site inhibits the access of SAM, thus preventing methylation of COMT substrates. The results of in vivo animal studies show that serotonin-induced pain hypersensitivity in mice is reduced by either SAM pretreatment or by the combined administration of selective antagonists for β2- and β3-adrenergic receptors, which have been previously shown to mediate COMT-dependent pain signaling. Our results suggest that inhibition of COMT via serotonin binding contributes to pain hypersensitivity, providing additional strategies for the treatment of clinical pain conditions.

  7. Effect of Metal Ions on the Formation of Trichloronitromethane during Chlorination of Catechol and Nitrite.

    Science.gov (United States)

    Gan, Guojuan; Mei, Rongwu; Qiu, Lin; Hong, Huachang; Wang, Qingjun; Mazumder, Asit; Wu, Shikai; Pan, Xiangliang; Liang, Yan

    2016-11-01

    Catechol, nitrite, and dissolved metals are ubiquitous in source drinking water. Catechol and nitrite have been identified as precursors for halonitromethanes (HNMs), but the effect of metal ions on HNM formation during chlorination remains unclear. The main objective of this study was to investigate the effect of metal ions (Fe, Ti, Al) on the formation of trichloronitromethane (TCNM) (the most representative HNM species in disinfected water) on chlorinating catechol and nitrite. Trichloronitromethane was extracted by methyl tert-butyl ether and detected by gas chromatography. The results show that metal ions promoted the formation of TCNM and that the enhancement efficiency followed the order of Fe > Ti > Al. Trichloronitromethane formation increased greatly within 2 h, and a basic condition (pH 8-9) favored TCNM formation more than acidic or neutral conditions. The conjoint effect of the metal-ion mixtures was shown to be similar to that of the single metal ion having the highest promoting effect on TCNM formation. Our results strongly suggest that metal ions play a significant role in enhancing TCNM formation.

  8. Computational studies of catechol and water interactions with titanium oxide nanoparticles.

    Energy Technology Data Exchange (ETDEWEB)

    Redfern, P. C.; Zapol, P.; Curtiss, L. A.; Rajh, T.; Thurnauer, M.

    2003-10-16

    The interaction of catechol and water with titanium oxide nanoparticles was investigated using ab initio molecular orbital theory and density functional theory. Hydrogen-terminated TiO{sub 2} clusters were used to model the surface of anatase nanoparticles. The calculations indicate that catechol reacts with a Ti{double_bond}O defect site on the surface to form a bidentate structure that is favored over dissociative or molecular adsorption on the (101) anatase surface. The dissociative adsorption of catechol at the defect site leads to a much larger red shift in the TiO{sub 2} excitation energy than molecular adsorption on the (101) anatase surface on the basis of ZINDO/S calculations. This is consistent with recent experimental results on small (<2 nm) titania nanoparticles. The calculations on water adsorption indicate that it can also add to the Ti{double_bond}O double bond site. However, molecular adsorption of water on the (101) anatase surface is more favorable.

  9. Cloning and expression of a novel catechol-O-methyltransferase in common marmosets.

    Science.gov (United States)

    Uehara, Shotaro; Uno, Yasuhiro; Inoue, Takashi; Sasaki, Erika; Yamazaki, Hiroshi

    2017-02-04

    Catechol-O-methyltransferase (COMT) catalyzes the O-methylation of endogenous catechol amines and estrogens and exogenous catechol-type of drugs. A Parkinson's disease model of common marmoset (Callithrix jacchus) has been widely used in preclinical studies to evaluate inhibitory potential of new drug candidates on marmoset COMT. Despite COMT inhibitors could potentiate the pharmacological action of levodopa on Parkinson's disease in animal models, marmoset COMT cDNA has not yet been identified and characterized. In this study, a cDNA highly homologous to human COMT was cloned from marmoset livers. This cDNA encoded 268 amino acids containing a transmembrane region and critical amino acid residues for catalytic function. The amino acid sequences of marmoset COMT shared high sequence identity (90%) with human COMT. COMT mRNA was expressed in all five tissues tested, including brain, lung, liver, kidney and small intestine, and was more abundant in marmoset liver and kidney. Membrane-bound COMT was immunochemically detected in livers and kidneys, whereas soluble COMT was detected in livers, similar to humans. These results indicated that the molecular characteristics of marmoset COMT were generally similar to the human ortholog.

  10. Polyaniline/polysulfone composite film electrode for simultaneous determination of hydroquinone and catechol

    Energy Technology Data Exchange (ETDEWEB)

    Feng Xiaojuan, E-mail: fengxiaojuan820@yahoo.cn [Chemistry Department of HeXi University, Zhangye 734000 (China); Shi Yanlong [Chemistry Department of HeXi University, Zhangye 734000 (China); Hu Zhongai [Key Laboratory of Polymer, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070 (China)

    2011-12-15

    Highlights: Black-Right-Pointing-Pointer We prepared a composite film which has bi-layers with asymmetric microstructure and relatively rich porosity which provides larger surface area for electrochemical reaction. Black-Right-Pointing-Pointer The outer polysulfone layer is propitious for the organic molecules to enrich on the composite film, which brings great enhancement in electron transfer kinetics. Black-Right-Pointing-Pointer The composite film electrode can be used to detect qualitatively or quantitatively hydroquinone and catechol in the single solute or mixed systems. - Abstract: Polyaniline (PAN)/polysulfone (PSF) composite film electrodes were successfully prepared by electropolymerization using cyclic votammetry technique. The composite film electrodes show a great enhancement in electron transfer kinetics, and the separation between oxidation and reduction peaks ({Delta}E{sub p}) decreases from 200 to 35 mV for hydroquinone (H{sub 2}Q) and from 275 to 42 mV for catechol (CC) at bare Pt and composite film electrodes respectively. In their mixed systems, the redox peak of H{sub 2}Q and two pairs of redox peaks of CC on this composite film electrode could be obviously distinguished which indicates the composite film electrodes have excellent electrocatalytic activity and reversibility towards the oxidation of two diphenols (hydroquinone and catechol). The linear relationships between the peak current and concentration are observed for single solute and mixed systems within the certain concentration range, implying that the composite film electrodes have potential application in the qualitative or quantitative analysis of diphenol.

  11. Less is more: reduced catechol production permits Pseudomonas putida F1 to grow on styrene.

    Science.gov (United States)

    George, Kevin W; Hay, Anthony

    2012-11-01

    Pseudomonas putida F1 is unable to grow on styrene due to the accumulation of 3-vinylcatechol, a toxic metabolite that is produced through the toluene degradation (tod) pathway and causes catechol-2,3-dioxygenase (C23O) inactivation. In this study, we characterized a spontaneous F1 mutant, designated SF1, which acquired the ability to grow on styrene and did not accumulate 3-vinylcatechol. Whereas adaptation to new aromatic substrates has typically been shown to involve increased C23O activity or the acquisition of resistance to C23O inactivation, SF1 retained wild-type C23O activity. Surprisingly, SF1 grew more slowly on toluene, its native substrate, and exhibited reduced toluene dioxygenase (TDO) activity (approximately 50 % of that of F1), the enzyme responsible for ring hydroxylation and subsequent production of 3-vinylcatechol. DNA sequence analysis of the tod operon of SF1 revealed a single base pair mutation in todA (C479T), a gene encoding the reductase component of TDO. Replacement of the wild-type todA allele in F1 with todA(C479T) reduced TDO activity to SF1 levels, obviated vinylcatechol accumulation, and conferred the ability to grow on styrene. This novel 'less is more' strategy - reduced catechol production as a means to expand growth substrate range - sheds light on an alternative approach for managing catechol toxicity during the metabolism of aromatic compounds.

  12. Magnetic catechol-chitosan with bioinspired adhesive surface: preparation and immobilization of ω-transaminase.

    Directory of Open Access Journals (Sweden)

    Kefeng Ni

    Full Text Available The magnetic chitosan nanocomposites have been studied intensively and been used practically in various biomedical and biological applications including enzyme immobilization. However, the loading capacity and the remained activity of immobilized enzyme based on existing approaches are not satisfied. Simpler and more effective immobilization strategies are needed. Here we report a simple catechol modified protocol for preparing a novel catechol-chitosan (CCS-iron oxide nanoparticles (IONPs composites carrying adhesive moieties with strong surface affinity. The ω-transaminase (ω-TA was immobilized onto this magnetic composite via nucleophilic reactions between catechol and ω-TA. Under optimal conditions, 87.5% of the available ω-TA was immobilized on the composite, yielding an enzyme loading capacity as high as 681.7 mg/g. Furthermore, the valuation of enzyme activity showed that ω-TA immobilized on CCS-IONPs displayed enhanced pH and thermal stability compared to free enzyme. Importantly, the immobilized ω-TA retained more than 50% of its initial activity after 15 repeated reaction cycles using magnetic separation and 61.5% of its initial activity after storage at 4°C in phosphate buffered saline (PBS for 15 days. The results suggested that such adhesive magnetic composites may provide an improved platform technology for bio-macromolecules immobilized.

  13. Effects of the co-carcinogen catechol on benzo(a)pyrene metabolism and DNA adduct formation in mouse skin

    Energy Technology Data Exchange (ETDEWEB)

    Melikian, A.A.; Leszczynska, J.M.; Hecht, S.S.; Hoffmann, D.

    1986-01-01

    We have studied the effects of the co-carcinogen catechol (1,2-dihydroxybenzene) on the metabolic activation of (/sup 3/H) benzo(a)pyrene (BaP) in mouse skin, in vivo and on the binding of BaP metabolites to DNA and protein at intervals from 0.5-24 h. Upon topical application of 0.015 mg (/sup 3/H)BaP and 0.25 or 0.5 mg catechol per mouse, catechol had little effect on the total amount of (/sup 3/H)BaP metabolized in mouse skin, but it affected the relative proportions of (/sup 3/H)BaP metabolites. Catechol (0.5 mg/mouse) decreased the proportion of water-soluble (/sup 3/H)BaP metabolites, ethyl acetate-soluble polar metabolites and quinones, but doubled the levels of unconjugated 3-hydroxy-BaP at all measured intervals after treatment. Catechol also caused a small increase in the levels of trans-7,8-dihydroxy-7,8-dihydroBaP and trans-9,10-dihydroxy-9,10-dihydroBaP 0.5 h after treatment. Two hours after treatment, the levels of these metabolites subsided to those of the controls. Catechol did not affect the levels of glutathione conjugates of BaP. However, it caused a decrease in glucuronide and sulphate conjugate formation from BaP. Catechol caused an approximately 2-fold increase in the formation of anti-7,8-dihydroxy-9,10-epoxy-7,8,9,10-tetrahydroBaP (BPDE) DNA adducts and elevated the ratio of anti-syn-BPDE-DNA adducts 1.6 to 2.9-fold. Catechol treatment increased the radioactivity associated with epidermal proteins after (/sup 3/H)BaP application. Because catechol increased levels of 3-hydroxyBaP, we considered the possibility that 3-hydroxyBaP might enhance the tumor initiating activities of BaP or BPDE in mouse skin; a bioassay demonstrated that this was not the case. The results of this study indicate that one important effect of catechol related to its co-carcinogenicity is its ability to enhance formation of anti-BPDE-DNA adducts in mouse skin.

  14. A direct spectrophotometric method for the simultaneous determination of zinc and cobalt in metalloproteins using 4-(2-pyridylazo)resorcinol.

    Science.gov (United States)

    Säbel, Crystal E; Shepherd, Jeffrey L; Siemann, Stefan

    2009-08-01

    An assay involving the direct and simultaneous determination of low micromolar concentrations (1-10 microM) of both zinc and cobalt ions suitable for metal content analyses of metalloproteins is described. The procedure exploits differences in the visible absorption spectra of the chromophoric chelator 4-(2-pyridylazo)resorcinol (PAR) resulting from its complexation to Zn2+ and/or Co2+ ions and is based on the fit of experimental spectra to a linear addition of Beer-Lambert law. The method eliminates the need for separating or masking one of the metal ions prior to their quantification and could prove to be particularly useful in studies on Co2+-substituted zinc proteins.

  15. Complex Formation in a Liquid-Liquid Extraction System Containing Co(II), 4-(2-Thiazolylazo)resorcinol and Monotetrazolium Salt.

    Science.gov (United States)

    Divarova, Vidka; Stojnova, Kirila; Racheva, Petya; Lekova, Vanya

    2016-01-01

    The ion-associated complex formed between anionic chelate of Co(II)-4-(2-Thiazolylazo)resorcinol (TAR) with the monotetrazolium cation of 2-(4-Iodophenyl)-3-(4-nitrophenyl)-5-phenyl-2H-tetrazolium chloride (INT) in the liquid-liquid extraction system Co(II)-TAR-INT-H(2)O-CHCl(3) was studied by the spectrophotometric method. The optimum extraction conditions of Co(II) were found. The extraction equilibria were studied. The equilibrium constants, the recovery factor and some analytical characteristics were calculated. The validity of Beer's law was checked. The molar ratio of the components in the ternary ion-associated complex Co(II)-TAR-INT was determined. The general formula of the complex was suggested. The effect of various foreign ions and reagents on the process of complex formation in the liquid-liquid extraction system was studied.

  16. Polymer-supported sulfonated catechol and linear catechol amide ligands and their use in selective metal ion removal and recovery from aqueous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Fish, Richard H. (Berkeley, CA)

    1997-01-01

    The present invention concerns the synthesis of several biomimetically important polymer-supported, sulfonated catechol (PS-CATS), sulfonated bis-catechol linear amide (PS-2-6-LICAMS) and sulfonated 3,3-linear tris-catechol amide (PS-3,3-LICAMS) ligands, which chemically bond to modified 6% crosslinked macroporous polystyrene-divinylbenzene beads (PS-DVB). These polymers are useful for the for selective removal and recovery of environmentally and economically important metal ions from aqueous solution, as a function of pH. The Fe.sup.3+ ion selectivity shown for PS-CATS, PS-2-6-LICAMS, and PS-3,3-LICAMS polymer beads in competition with a similar concentration of Cu.sup.2+, Zn.sup.2+, Mn.sup.2+, Ni.sup.2+,Mg.sup.2+, Al.sup.3+, and Cr.sup.3+ ions at pH 1-3. Further, the metal ion selectivity is changed at higher pH values in the absence of Fe.sup.3+ (for example, Hg.sup.2+ at pH 3). The rates of selective removal and recovery of the trivalent metal ions, e.g. Fe.sup.3+ Al.sup.3+ ion etc. with the PS-CATS, PS-2-6-LICAMS, and PS-3,3-LICAMS polymer beads use determined are useful as well as equilibrium selectivity coefficient (K.sub.m) values for all metal competition studies. The chelate effect for the predisposed octahedral PS-3,3-LICAMS polymer pendant ligand is the reason that this ligand has a more pronounced selectivity for Fe.sup.3+ ion in comparison to the PS-CATS polymer beads. The predisposed square planar PS-2-6-Mn.sup.2+, Ni.sup.2+, and Mg.sup.2+, than either PS-CATS or PS-3,3-LICAMS. However, Fe.sup.3+ ion still dominates in competition with other divalent and trivalent metal ions. In the absence of Fe.sup.3+, the polymer ligand is selective for Al.sup.3+, Cu.sup.2+ or Hg.sup.2+. The changing of the cavity size from two CH.sub.2 groups to six CH.sub.2 groups in the PS-2-6-LICAMS polymer pendant ligand series does not effect the order of metal ion selectivity.

  17. Polymer-supported sulfonated catechol and linear catechol amide ligands and their use in selective metal ion removal and recovery from aqueous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Fish, R.H.

    1997-04-22

    The present invention concerns the synthesis of several biomimetically important polymer-supported, sulfonated catechol (PS-CATS), sulfonated bis-catechol linear amide (PS-2-6-LICAMS) and sulfonated 3,3-linear tris-catechol amide (PS-3,3-LICAMS) ligands, which chemically bond to modified 6% crosslinked macroporous polystyrene-divinylbenzene beads (PS-DVB). These polymers are useful for the for selective removal and recovery of environmentally and economically important metal ions from aqueous solution, as a function of pH. The Fe{sup 3+} ion selectivity shown for PS-CATS, PS-2-6-LICAMS, and PS-3,3-LICAMS polymer beads in competition with a similar concentration of Cu{sup 2+}, Zn{sup 2+}, Mn{sup 2+}, Ni{sup 2+}, Mg{sup 2+}, Al{sup 3+}, and Cr{sup 3+} ions at pH 1--3. Further, the metal ion selectivity is changed at higher pH values in the absence of Fe{sup 3+} (for example, Hg{sup 2+} at pH 3). The rates of selective removal and recovery of the trivalent metal ions, e.g. Fe{sup 3+}, Al{sup 3+} ion etc. with the PS-CATS, PS-2-6-LICAMS, and PS-3,3-LICAMS polymer beads use determined are useful as well as equilibrium selectivity coefficient (K{sub m}) values for all metal competition studies. The chelate effect for the predisposed octahedral PS-3,3-LICAMS polymer pendant ligand is the reason that this ligand has a more pronounced selectivity for Fe{sup 3+} ion in comparison to the PS-CATS polymer beads. The predisposed square planar PS-2-6-Mn{sup 2+}, Ni{sup 2+}, and Mg{sup 2+}, than either PS-CATS or PS-3,3-LICAMS. However, Fe{sup 3+} ion still dominates in competition with other divalent and trivalent metal ions. In the absence of Fe{sup 3+}, the polymer ligand is selective for Al{sup 3+}, Cu{sup 2+} or Hg{sup 2+}. The changing of the cavity size from two CH{sub 2} groups to six CH{sub 2} groups in the PS-2-6-LICAMS polymer pendant ligand series does not effect the order of metal ion selectivity. 9 figs.

  18. Polymer-supported sulfonated catechol and linear catechol amide ligands and their use in selective metal ion removal recovery from aqueous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Fish, R.H.

    1998-11-10

    The present invention concerns the synthesis of several biomimetically important polymer-supported, sulfonated catechol (PS-CATS), sulfonated bis-catechol linear amide (PS-2-6-LICAMS) and sulfonated 3,3-linear tris-catechol amide (PS-3,3-LICAMS) ligands, which chemically bond to modified 6% crosslinked macroporous polystyrene-divinylbenzene beads (PS-DVB). These polymers are useful for the for selective removal and recovery of environmentally and economically important metal ions from aqueous solution, as a function of pH. The Fe{sup 3+} ion selectivity shown for PS-CATS, PS-2-6-LICAMS, and PS-3,3-LICAMS polymer beads in competition with a similar concentration of Cu{sup 2+}, Zn{sup 2+}, Mn{sup 2+}, Ni{sup 2+}, Mg{sup 2+}, Al{sup 3+}, and Cr{sup 3+} ions at pH 1--3. Further, the metal ion selectivity is changed at higher pH values in the absence of Fe{sup 3+} (for example, Hg{sup 2+} at pH 3). The rates of selective removal and recovery of the trivalent metal ions, e.g. Fe{sup 3+}, Al{sup 3+} ion etc. with the PS-CATS, PS-2-6-LICAMS, and PS-3,3-LICAMS polymer beads used determined are useful as well as equilibrium selectivity coefficient (K{sub m}) values for all metal competition studies. The chelate effect for the predisposed octahedral PS-3,3-LICAMS polymer pendant ligand is the reason that this ligand has a more pronounced selectivity for Fe{sup 3+} ion in comparison to the PS-CATS polymer beads. The predisposed square planar PS-2,6-LICAMS series of polymer pendant ligands are more selective to divalent metal ions Cu{sup 2+}, Zn{sup 2+}, Mn{sup 2+}, Ni{sup 2+}, and Mg{sup 2+}, than either PS-CATS or PS-3,3-LICAMS. However, Fe{sup 3+} ion still dominates in competition with other divalent and trivalent metal ions. In the absence of Fe{sup 3+}, the polymer ligand is selective for Al{sup 3+}, Cu{sup 2+} or Hg{sup 2+}. The changing of the cavity size from two CH{sub 2} groups to six CH{sub 2} groups in the PS-2-6-LICAMS polymer pendant ligand series does not effect

  19. Polymer-supported sulfonated catechol and linear catechol amide ligands and their use in selective metal ion removal recovery from aqueous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Fish, Richard H. (Berkeley, CA)

    1998-01-01

    The present invention concerns the synthesis of several biomimetically important polymer-supported, sulfonated catechol (PS-CATS), sulfonated bis-catechol linear amide (PS-2-6-LICAMS) and sulfonated 3,3-linear tris-catechol amide (PS-3,3-LICAMS) ligands, which chemically bond to modified 6% crosslinked macroporous polystyrene-divinylbenzene beads (PS-DVB). These polymers are useful for the for selective removal and recovery of environmentally and economically important metal ions from aqueous solution, as a function of pH. The Fe.sup.3+ ion selectivity shown for PS-CATS, PS-2-6-LICAMS, and PS-3,3-LICAMS polymer beads in competition with a similar concentration of Cu.sup.2+, Zn.sup.2+, Mn.sup.2+, Ni.sup.2+, Mg.sup.2+, Al.sup.3+, and Cr.sup.3+ ions at pH 1-3. Further, the metal ion selectivity is changed at higher pH values in the absence of Fe.sup.3+ (for example, Hg.sup.2+ at pH 3). The rates of selective removal and recovery of the trivalent metal ions, e.g. Fe.sup.3+ Al.sup.3+ ion etc. with the PS-CATS, PS-2-6-LICAMS, and PS-3,3-LICAMS polymer beads used determined are useful as well as equilibrium selectivity coefficient (K.sub.m) values for all metal competition studies. The chelate effect for the predisposed octahedral PS-3,3-LICAMS polymer pendant ligand is the reason that this ligand has a more pronounced selectivity for Fe.sup.3+ ion in comparison to the PS-CATS polymer beads. The predisposed square planar PS-2,6-LICAMS series of polymer pendant ligands are more selective to divalent metal ions Cu.sup.2+, Zn.sup.2+, Mn.sup.2+, Ni.sup.2+, and Mg.sup.2+, than either PS-CATS or PS-3,3-LICAMS. However, Fe.sup.3+ ion still dominates in competition with other divalent and trivalent metal ions. In the absence of Fe.sup.3+, the polymer ligand is selective for Al.sup.3+, Cu.sup.2+ or Hg.sup.2+. The changing of the cavity size from two CH.sub.2 groups to six CH.sub.2 groups in the PS-2-6-LICAMS polymer pendant ligand series does not effect the order of metal ion

  20. Catechol-Functionalized Synthetic Polymer as a Dental Adhesive to Contaminated Dentin Surface for a Composite Restoration.

    Science.gov (United States)

    Lee, Sang-Bae; González-Cabezas, Carlos; Kim, Kwang-Mahn; Kim, Kyoung-Nam; Kuroda, Kenichi

    2015-08-10

    This study reports a synthetic polymer functionalized with catechol groups as dental adhesives. We hypothesize that a catechol-functionalized polymer functions as a dental adhesive for wet dentin surfaces, potentially eliminating the complications associated with saliva contamination. We prepared a random copolymer containing catechol and methoxyethyl groups in the side chains. The mechanical and adhesive properties of the polymer to dentin surface in the presence of water and salivary components were determined. It was found that the new polymer combined with an Fe(3+) additive improved bond strength of a commercial dental adhesive to artificial saliva contaminated dentin surface as compared to a control sample without the polymer. Histological analysis of the bonding structures showed no leakage pattern, probably due to the formation of Fe-catechol complexes, which reinforce the bonding structures. Cytotoxicity test showed that the polymers did not inhibit human gingival fibroblast cells proliferation. Results from this study suggest a potential to reduce failure of dental restorations due to saliva contamination using catechol-functionalized polymers as dental adhesives.

  1. Kinetic study on electrochemical oxidation of catechols in the presence of cycloheptylamine and aniline: Experiments and digital simulation

    Indian Academy of Sciences (India)

    DAVOOD NEMATOLLAHI; FATEMEH GHASEMI; SADEGH KHAZALPOUR; FAHIMEH VARMAGHANI

    2016-12-01

    Oxidative coupling reaction of some catechols has been studied by cyclic voltammetry at the glassy carbon electrode in different experimental conditions. The electrogenerated o-banzoquinone participates in a coupling reaction with anionic and dianionic forms of catechol. Based on EC mechanism, the observed homogenous rate constants of the coupling reaction of catechols were estimated by analyzing the cyclic voltammetric responses using the simulation software DIGIELCH. This paper deals with reaction of o-benzoquinones derived by the oxidation of catechol (CAT), 3-methylcatechol (3-MC), 3-methoxycatechol(3-MOC) and 3,4-dihydroxybenzoic acid (3,4-DHBA) with cycloheptylamine (a primary aliphatic amine) and aniline (a primary aromatic amine) as nucleophiles to gain mechanistic insight. The outcome indicates participation of o-benzoquinone in the Michael addition reaction with the studied primary amines. The best fit of theexperimental and simulated results was obtained for ECE mechanism. The calculated/estimated homogeneous rate constants (kobs) for Michael addition reaction were found to vary in the order CAT>3-MC>3-MOC>3,4- DHBA and CAT>3,4-DHBA>3-MC>3-MOC for cycloheptylamine and aniline, respectively. These data are in agreement with the trend of electronic properties (electron-donating/-withdrawing) of the substitutions on the catechol ring.

  2. Catechol-Functionalized Synthetic Polymer as a Dental Adhesive to Contaminated Dentin Surface for a Composite Restoration

    Science.gov (United States)

    2015-01-01

    This study reports a synthetic polymer functionalized with catechol groups as dental adhesives. We hypothesize that a catechol-functionalized polymer functions as a dental adhesive for wet dentin surfaces, potentially eliminating the complications associated with saliva contamination. We prepared a random copolymer containing catechol and methoxyethyl groups in the side chains. The mechanical and adhesive properties of the polymer to dentin surface in the presence of water and salivary components were determined. It was found that the new polymer combined with an Fe3+ additive improved bond strength of a commercial dental adhesive to artificial saliva contaminated dentin surface as compared to a control sample without the polymer. Histological analysis of the bonding structures showed no leakage pattern, probably due to the formation of Fe–catechol complexes, which reinforce the bonding structures. Cytotoxicity test showed that the polymers did not inhibit human gingival fibroblast cells proliferation. Results from this study suggest a potential to reduce failure of dental restorations due to saliva contamination using catechol-functionalized polymers as dental adhesives. PMID:26176305

  3. Crystallization and preliminary crystallographic analysis of the catechol 2,3-dioxygenase PheB from Bacillus stearothermophilus BR219

    Energy Technology Data Exchange (ETDEWEB)

    Sugimoto, Keisuke; Matsufuzi, Kazuki; Ohnuma, Hiroaki [Department of Material Chemistry, Asahikawa National College of Technology, 2-2-1-6 Shunko-dai, Asahikawa, Hokkaido 071-8142 (Japan); Senda, Miki [Japan Biological Information Research Center (JBIRC), Japan Biological Informatics Consortium (JBIC), 2-42 Aomi, Koto-ku, Tokyo 135-0064 (Japan); Fukuda, Masao [Department of Bioengineering, Nagaoka University of Technology, Nagaoka, Niigata 940-2188 (Japan); Senda, Toshiya, E-mail: tsenda@jbirc.aist.go.jp [Biological Information Research Center (BIRC), National Institute of Advanced Industrial Science and Technology (AIST), 2-42 Aomi, Koto-ku, Tokyo (Japan); Department of Material Chemistry, Asahikawa National College of Technology, 2-2-1-6 Shunko-dai, Asahikawa, Hokkaido 071-8142 (Japan)

    2006-02-01

    PheB, an extradiol-cleaving catecholic dioxygenase, was crystallized by the hanging-drop vapour-diffusion method using PEG 4000 as a precipitant. The crystal belongs to the orthorhombic system, space group P2{sub 1}2{sub 1}2{sub 1}, and diffracts to 2.3 Å resolution. Class II extradiol-cleaving catecholic dioxygenase, a key enzyme of aromatic compound degradation in bacteria, cleaves the aromatic ring of catechol by adding two O atoms. PheB is one of the class II extradiol-cleaving catecholic dioxygenases and shows a high substrate specificity for catechol derivatives, which have one aromatic ring. In order to reveal the mechanism of the substrate specificity of PheB, PheB has been crystallized by the hanging-drop vapour-diffusion method using PEG 4000 as a precipitant. The space group of the obtained crystal was P2{sub 1}2{sub 1}2{sub 1}, with unit-cell parameters a = 65.5, b = 119.2, c = 158.7 Å. The crystal diffracted to 2.3 Å resolution.

  4. Electro-catalytic Oxidation of Catechol at Poly(1-amino-9,10-anthraquinone)-SDS Composite Film.

    Science.gov (United States)

    Nikoofard, Hossein; Solbi, Malihe

    2016-12-01

    An electro-chemically active composite film containing the environmentally friendly surfactant sodium dodecyl sulfate (SDS) and poly(1-amino-9,10-anthraquinone) (PAAQ) is used as an electron transfer mediator in the electro-chemical oxidation of catechol. Compared with the bare platinum (Pt) electrode, the Pt/PAAQ-SDS modified electrode remarkably lowers the anodic peak potential of catechol, and increases the peak currents. The results obtained indicate that the activation energy for the electro-chemical oxidation of catechol at the polymer film is low (7.05 kJ mol-1). The influence of the operational conditions on the response current of the catechol sensor is also investigated. Studying the surface morphology of the modified electrode reveals a more porous structure for it due to the incorporation of the anionic surfactant on the PAAQ film. The modified electrode displays a linear response in the concentration range of 0.01-8.0 mM for catechol. A lower detection limit was obtained to be 2.60 μM. The ability of the modified electrode is also examined for the electro-chemical detection of hydroquinone (HQ) with simplicity.

  5. Kinetic and mechanism of atmospheric degradation of three volatile organics compounds: acetone, phenol and catechol; Cinetique et mecanisme de degradation atmospherique de trois composes organiques volatils: l'acetone, le phenol et le catechol

    Energy Technology Data Exchange (ETDEWEB)

    Turpin, E.

    2004-12-01

    In this thesis, atmospheric degradation of three VOC (volatile organic compound), acetone, phenol and catechol, has been studied. These compounds are renowned to be some of main compounds in the atmosphere because the relative importance of their primary emissions (biogenic, gas fumes,...) and secondary emissions (VOCs oxidation). This work has been realised in two laboratories using two complementary devices. These instruments are the fast flow tube with LIF (laser induce fluorescence) and a smog Teflon chamber with gas-phase chromatography with FTIR, FID, MS. The both use of these techniques enable to determine the main pathway of the acetone oxidation with OH radical. The smog chamber's studies of the phenol and catechol reactions with OH radical enable to determine some relative rate constants and mechanisms. It's the first mechanism proposition for the catechol + OH radical reaction. These obtained results have been used to mention the atmospheric impact of these compounds. (author)

  6. Mechanochemical transformation of an organic ligand on mineral surfaces: The efficiency of birnessite in catechol degradation

    Energy Technology Data Exchange (ETDEWEB)

    Di Leo, Paola, E-mail: pdileo@imaa.cnr.it [Consiglio Nazionale delle Ricerche - Istituto di Metodologie per l' Analisi Ambientale, C.da S. Loja, Zona Industriale, 85050 Tito Scalo (PZ) (Italy); Pizzigallo, Maria Donata Rosa [Dipartimento di Biologia e Chimica Agroforestale e Ambientale, Universita di Bari Aldo Moro, Via Amendola 165/a, 70126 Bari (Italy); Ancona, Valeria [Consiglio Nazionale delle Ricerche - Istituto di Ricerca sulle Acque, Via F. De Blasio 5, 70132 Bari (Italy); Di Benedetto, Francesco [Dipartimento di Chimica, Universita di Firenze, Via della Lastruccia, 3, 50019 Sesto Fiorentino (Italy); Mesto, Ernesto; Schingaro, Emanuela; Ventruti, Gennaro [Dipartimento di Scienze della Terra e Geoambientali, Universita di Bari Aldo Moro, Via Orabona, 4, 70125 Bari (Italy)

    2012-01-30

    Graphical abstract: . The efficiency of mechanochemical treatments in degrading CAT molecules in presence of the highly reactive phyllomanganate birnessite, and without using organic solvents, has been demonstrated in the present study. Integrating information from different techniques on solid let it possible to get a comprehensive picture of the most reliable reaction mechanism of degradation of CAT molecules onto KBi surfaces, thus allowing the individuation of specific sites in the synthesized oxides on which catechol molecules were preferentially adsorbed, and thus degraded. The degradation mechanism mainly occurs via a redox reaction. It implies the formation of a surface bidentate inner-sphere complex between the phenolic group of the organic molecules and the Mn(IV) from the birnessite structure. Structural changes occur on the MnO{sub 6} layers of birnessite as due to the mechanically induced surface reactions: reduction of Mn(IV), consequent formation of Mn(III) and new vacancies, and free Mn{sup 2+} ions production. The extent of the mechanochemical degradation of CAT onto birnessite surfaces is higher. This is a consequence of the two phenolic groups of catechol that easily reacts. Highlights: Black-Right-Pointing-Pointer A basic insight at molecular scale of the mechanically induced transformations of CAT onto birnessite is obtained. Black-Right-Pointing-Pointer The abiotic degradative mechanisms of CAT onto birnessite is provided. Black-Right-Pointing-Pointer The mechanically induced degradation of CAT mainly occurs via a redox reaction. Black-Right-Pointing-Pointer Mechanochemistry improves the efficiency of birnessite to degrade CAT. Black-Right-Pointing-Pointer The mechanochemical technique offer potentials in remediating contaminated sites. - Abstract: The aim of this work is to investigate the efficiency of the phyllomanganate birnessite in degrading catechol after mechanochemical treatments. A synthesized birnessite and the organic molecule were

  7. Biomimetic PEG-catecholates for stabile antifouling coatings on metal surfaces: applications on TiO2 and stainless steel.

    Science.gov (United States)

    Khalil, Faiza; Franzmann, Elisa; Ramcke, Julian; Dakischew, Olga; Lips, Katrin S; Reinhardt, Alexander; Heisig, Peter; Maison, Wolfgang

    2014-05-01

    Trimeric catecholates have been designed for the stable immobilization of effector molecules on metal surfaces. The design of these catecholates followed a biomimetic approach and was inspired by natural multivalent metal binders, such as mussel adhesion proteins (MAPs) and siderophores. Three catecholates have been conjugated to central scaffolds based on adamantyl or trisalkylmethyl core structures. The resulting triscatecholates have been immobilized on TiO2 and stainless steel. In a proof of concept study we have demonstrated the high stability of the resulting nanolayers at neutral and slightly acidic pH. Furthermore, polyethylene glycol (PEG) conjugates of our triscatecholates have been synthesized and were immobilized on TiO2 and stainless steel. The PEG coated surfaces showed excellent antifouling properties upon exposure to human blood and bacteria as demonstrated by fluorescence microscopy, ellipsometry and a bacterial assay with Staphylococcus epidermidis. In addition, our PEG-triscatecholates showed no cytotoxicity against bone-marrow stem cells on TiO2.

  8. Facile fabrication of gold nanoparticle on zein ultrafine fibers and their application for catechol biosensor

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Xiaodong; Li, Dawei; Li, Guohui; Luo, Lei; Ullah, Naseeb; Wei, Qufu, E-mail: qfwei@jiangnan.edu.cn; Huang, Fenglin, E-mail: flhuang@jiangnan.edu.cn

    2015-02-15

    Graphical abstract: (A) Formation mechanism of A-CZNF and (B) reaction principle and formation mechanism of A-CZUF biosensor. - Highlights: • We utilized the hydrophobic protein nanofibers to fabricate a laccase-based biosensor for the first time. • The composite containing gold nanoparticles was prepared by combining electrospinning and one-step reduction method, which is a novel nanomaterial. • It is noticeable that the laccase biosensor showed a high electrochemical response and electrochemical activity toward catechol. • The novel biosensor will offer a simple, convenient and high efficient method for detecting polyphenolic compounds in environment. - Abstract: A novel laccase biosensor based on a new composite of laccase–gold nanoparticles (Au NPs)-crosslinked zein ultrafine fibers (CZUF) has been fabricated for catechol determination in real solution samples. Firstly, crosslinked zein ultrafine fibers containing gold nanoparticles (A-CZUF) were prepared by combining electrospinning and one-step reduction method using poly(ethyleneimine) (PEI) as reducing and crosslinking agent. A smooth morphology and relative average distribution of A-CZUF were depicted by scanning electron microscope (SEM) and transmission electron microscopy (TEM). The Fourier transform infrared spectroscopy (FT-IR) analysis indicated that PEI molecules attached to the surface of the zein ultrafine fibers via the reaction of functional groups between PEI and glyoxal. The results obtained from ultraviolet visible spectroscopy (UV–vis spectroscopy), X-ray diffraction (XRD) and thermal gravimetric analysis (TGA) for A-CZUF confirmed the existence of Au NPS coated on the surface of CZUF. Square wave voltammetry (SWV) and cyclic voltammetry (CV) were used to detect the electrochemical performance of the proposed biosensor. The results demonstrated that this biosensor possessed a high sensitive detection to catechol, which was attributed to the direct electron transfer (DET

  9. pH Responsive and Oxidation Resistant Wet Adhesive based on Reversible Catechol-Boronate Complexation.

    Science.gov (United States)

    Narkar, Ameya R; Barker, Brett; Clisch, Matthew; Jiang, Jingfeng; Lee, Bruce P

    2016-08-09

    A smart adhesive capable of binding to a wetted surface was prepared by copolymerizing dopamine methacrylamide (DMA) and 3-acrylamido phenylboronic acid (AAPBA). pH was used to control the oxidation state and the adhesive property of the catechol side chain of DMA and to trigger the catechol-boronate complexation. FTIR spectroscopy confirmed the formation of the complex at pH 9, which was not present at pH 3. The formation of the catechol-boronate complex increased the cross-linking density of the adhesive network. Most notably, the loss modulus values of the adhesive were more than an order of magnitude higher for adhesive incubated at pH 9 when compared to those measured at pH 3. This drastic increase in the viscous dissipation property is attributed to the introduction of reversible complexation into the adhesive network. Based on the Johnson Kendall Roberts (JKR) contact mechanics test, adhesive containing both DMA and AAPBA demonstrated strong interfacial binding properties (work of adhesion (Wadh) = 2000 mJ/m(2)) to borosilicate glass wetted with an acidic solution (pH 3). When the pH was increased to 9, Wadh values (180 mJ/m(2)) decreased by more than an order of magnitude. During successive contact cycles, the adhesive demonstrated the capability to transition reversibly between its adhesive and nonadhesive states with changing pH. Adhesive containing only DMA responded slowly to repeated changes in pH and became progressively oxidized without the protection of boronic acid. Although adhesive containing only AAPBA also demonstrated strong wet adhesion (Wadh ∼ 500 mJ/m(2)), its adhesive properties were not pH responsive. Both DMA and AAPBA are required to fabricate a smart adhesive with tunable and reversible adhesive properties.

  10. Catechol-O-Methyltransferase and 3,4-(±)-Methylenedioxymethamphetamine Toxicity

    Science.gov (United States)

    Herndon, Joseph M.; Cholanians, Aram B.; Lizarraga, Lucina E.; Lau, Serrine S.; Monks, Terrence J.

    2014-01-01

    Metabolism of 3,4-(±)-methylenedioxymethamphetamine (MDMA) is necessary to elicit its neurotoxic effects. Perturbations in phase I and phase II hepatic enzymes can alter the neurotoxic profile of systemically administered MDMA. In particular, catechol-O-methyltransferase (COMT) plays a critical role in determining the fraction of MDMA that is converted to potentially neurotoxic metabolites. Thus, cytochrome P450 mediated demethylenation of MDMA, or its N-demethylated metabolite, 3,4-(±)-methylenedioxyamphetamine, give rise to the catechols, N-methyl-α-methyldopamine and α-methyldopamine, respectively. Methylation of these catechols by COMT limits their oxidation and conjugation to glutathione, a process that ultimately gives rise to neurotoxic metabolites. We therefore determined the effects of modulating COMT, a critical enzyme involved in determining the fraction of MDMA that is converted to potentially neurotoxic metabolites, on MDMA-induced toxicity. Pharmacological inhibition of COMT in the rat potentiated MDMA-induced serotonin deficits and exacerbated the acute MDMA-induced hyperthermic response. Using a genetic mouse model of COMT deficiency, in which mice lack a functional COMT gene, such mice displayed greater reductions in dopamine concentrations relative to their wild-type (WT) counterparts. Neither WT nor COMT deficient mice were susceptible to MDMA-induced decreases in serotonin concentrations. Interestingly, mice devoid of COMT were far more susceptible to the acute hyperthermic effects of MDMA, exhibiting greater increases in body temperature that ultimately resulted in death. Our findings support the view that COMT plays a pivotal role in determining the toxic response to MDMA. PMID:24591155

  11. Phorbol myristate acetate and catechol as skin cocarcinogens in SENCAR mice

    Energy Technology Data Exchange (ETDEWEB)

    Van Duuren, B.L.; Melchionne, S.; Seidman, I.

    1986-09-01

    The enhancement of the carcinogenicity of benzo(a) pyrene (B(a)P) and ..beta..-propiolactone (BPL) by the mouse skin cocarcinogens phorbol myristate acetate (PMA) and catechol were examined in female SENCAR mice, 30 per group. The carcinogen and cocarcinogen were applied simultaneously, three times weekly for 490-560 days. B(a)P and BPL were used at constant doses of 5 and 50 ..mu..g, respectively, in all experiments. PMA was used at three doses, 2.5, 1.0, and 0.5 ..mu..g per application, and catechol was used at one dose, 2 mg per application. Control groups included animals that received carcinogen only, cocarcinogen only, acetone only, and no treatment. The carcinogenicity of B(a)P and BPL were enhanced by the cocarcinogens, particularly in terms of tumor multiplicity. For both carcinogens, the most marked cocarcinogenic effects were observed at the lowest dose of PMA used (0.5 ..mu..g per application). This observation applied for days to first tumor, animals with tumors, tumor multiplicity, and incidence of malignant skin tumors. Catechol applied alone did not induce any tumors; with PMA alone there were significant incidences of benign and malignant tumors, e.g., at a dose of only 0.5 ..mu..g per application, 15 of 30 animals had 28 tumors, 5 of which were squamous carcinomas. In two-stage carcinogenesis experiments with 7,12-dimethylbenz(a)anthracene (DMBA) as initiator and PMA as promoter, SENCAR mice showed a greater susceptibility to tumor induction when compared to ICR/Ha mice used in earlier work. This susceptibility was most notable in terms of rate of tumor appearance and tumor multiplicity.

  12. Correlation of electronic transitions and redox potentials measured for pyrocatechol, resorcinol, hydroquinone, pyrogallol, and gallic acid with results of semi-empirical molecular orbital computations A useful interpretation tool

    Science.gov (United States)

    Carter, Melvin Keith

    2007-04-01

    Cyclic voltammogram (CV) electrochemical measurements for pyrocatechol, resorcinol, hydroquinone, pyrogallol, and gallic acid in strong alkaline solution produced observable oxidation-reduction potentials for each hydroxy group present except for resorcinol. UV absorption spectra were also observed for the diluted solutions. Semi-empirical molecular orbital computations were conducted for these molecules of C2 v point group symmetry to determine the character and energies to aid interpretation of the experimental results. CV oxidation removed a π-electron by a radiationless π-π* transition followed by an electron shift from a negative oxygen to the positive aromatic π-system indicated by an observable σ-π* transition. Simple semi-empirical computations correlated with measured excited electronic states during electron transfer.

  13. Synthesis and optimization of N-heterocyclic pyridinones as catechol-O-methyltransferase (COMT) inhibitors.

    Science.gov (United States)

    Zhao, Zhijian; Harrison, Scott T; Schubert, Jeffrey W; Sanders, John M; Polsky-Fisher, Stacey; Zhang, Nanyan Rena; McLoughlin, Debra; Gibson, Christopher R; Robinson, Ronald G; Sachs, Nancy A; Kandebo, Monika; Yao, Lihang; Smith, Sean M; Hutson, Pete H; Wolkenberg, Scott E; Barrow, James C

    2016-06-15

    A series of N-heterocyclic pyridinone catechol-O-methyltransferase (COMT) inhibitors were synthesized. Physicochemical properties, including ligand lipophilic efficiency (LLE) and clogP, were used to guide compound design and attempt to improve inhibitor pharmacokinetics. Incorporation of heterocyclic central rings provided improvements in physicochemical parameters but did not significantly reduce in vitro or in vivo clearance. Nevertheless, compound 11 was identified as a potent inhibitor with sufficient in vivo exposure to significantly affect the dopamine metabolites homovanillic acid (HVA) and dihydroxyphenylacetic acid (DOPAC), and indicate central COMT inhibition.

  14. Application of p-toluidine in chromogenic detection of catechol and protocatechuate, diphenolic intermediates in catabolism of aromatic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Parke, D. (Yale Univ., New Haven, CT (United States))

    1992-08-01

    In the presence of p-toluidine and iron, protocatechuate and catechols yield color. Inclusion of p-toluidine in media facilities the screening of microbial strains for alterations affecting aromatic catabolism. Such strains include mutants affected in the expression of oxygenases and Escherichia coli colonies carrying cloned or subcloned aromatic catabolic genes which encode enzymes giving rise to protocatechuate or catechol. The diphenolic detection system can also be applied to the creation of vectors relying on insertion of cloned DNA into one of the latter marker genes.

  15. A new synthetic resorcinolic lipid 3-heptyl-3,4,6-trimethoxy-3H-isobenzofuran-1-one: evaluation of toxicology and ability to potentiate the mutagenic and apoptotic effects of cyclophosphamide.

    Science.gov (United States)

    Navarro, Stephanie Dynczuki; Beatriz, Adilson; Meza, Alisson; Pesarini, João Renato; Gomes, Roberto da Silva; Karaziack, Caroline Bilhar; Cunha-Laura, Andréa Luiza; Monreal, Antônio Carlos Duenhas; Romão, Wanderson; Lacerda Júnior, Valdemar; Mauro, Mariana de Oliveira; Oliveira, Rodrigo Juliano

    2014-03-21

    Resorcinolic lipids have important biological actions, including anti-carcinogenic activity. Therefore, we evaluated the mutagenic, genotoxic, immunomodulatory and apoptotic potential and the biochemical and histopathological changes caused by the synthetic resorcinolic lipid 3-Heptyl-3,4,6-trimethoxy-3H-isobenzofuran-1-one, (AMS35AA; 10, 20 and 40 mg/kg) alone or in combination with cyclophosphamide (100 mg/kg) in Swiss mice. The results indicated that AMS35AA is not genotoxic or mutagenic and does not alter liver or kidney histology. However, the compound does cause an increase (p mutagenic damage (although the compound had anti-genotoxic activity), splenic phagocytosis, neutropenia and glutamic-oxaloacetic transaminase and creatinine levels (even in the absence of histological damage) and induced liver and kidney apoptosis. We conclude that this resorcinolic lipid may be an important chemotherapy adjuvant that can potentiate mutagenic damage and increase apoptosis caused by cyclophosphamide without causing adverse effects. In addition, the immunomodulatory activity of the compound should be noted, which counters reductions in lymphocyte number, a primary side effect of cyclophosphamide in cancer therapy.

  16. Bio-inspired multifunctional catecholic assembly for photo-programmable biointerface.

    Science.gov (United States)

    Huang, Chun-Jen; Wang, Lin-Chuan

    2015-10-01

    This article reports a novel multifunctional mussel-inspired zwitterionic catecholic assembly to form a photoresponsive biointerface. The assembly is the combination of the antifouling sulfobetaine and photocleavable o-nitrophenyl moieties into a molecule, becoming sulfobetaine nitrodopamine (SB-nDA). We demonstrated the formation of a compact thin SB-nDA film on TiO₂ by using the pH transition approach. The film thickness, surface wettability and elemental composition were characterized using ellipsometry, contact angle goniometer, atomic force microscopy and X-ray photoelectron spectroscopy, respectively. The SB-nDA thin films can effectively resist adhesion of both Gram-positive Staphylococcus epidermidis and Gram-negative Pseudomonas aeruginosa by more than 95% relative to bare TiO₂. Quartz crystal microbalance with dissipation (QCM-D) sensor was employed for protein fouling tests, showing the comparable antifouling property of SB-nDA with thiol- or silane-based surface ligands. More importantly, the spatiotemporal control over the bioinertness by UV irradiation has been studied with bacterial and protein adsorption. Therefore, the catecholic chemistry can be used for programmable tailoring of interfacial properties, permitting potential application in light-guided targeting for nanomedicine. Copyright © 2015 Elsevier B.V. All rights reserved.

  17. Electrochemical Investigation of Catechol at Poly(niacinamide Modified Carbon Paste Electrode: A Voltammetric Study

    Directory of Open Access Journals (Sweden)

    A. B. Teradale

    2016-01-01

    Full Text Available A polymeric thin film modified electrode, that is, poly(niacinamide modified carbon paste electrode (MCPE, was developed for the electrochemical determination of catechol (CC by using cyclic voltammetric technique. Compared to bare carbon paste electrode (BCPE, the poly(niacinamide MCPE shows good electrocatalytic activity towards the oxidation of catechol in phosphate buffer solution (PBS of physiological pH 7.4. All experimental parameters were optimized. Poly(niacinamide modified carbon paste electrode gave a linear response between concentration of CC and its anodic peak current in the range within 20.6–229.0 μM. The limit of detection (3S/M and limit of quantification (10S/M were 1.497 μM and 4.99 μM, respectively. From the study of scan rate variation, the electrode process was found to be adsorption-controlled. The involvement of protons and electrons in the oxidation of CC was found to be equal. The probable electropolymerisation mechanism of niacinamide was proposed. Finally, this method can be used in development of a sensor for sensitive determination of CC.

  18. Single micelle force microscopy reveals the coordination interaction between catechol and Fe33+

    Science.gov (United States)

    Li, Yiran; Cao, Yi; Wang, Wei

    Metal coordination bonds are widely found in natural adhesive, load-bearing, and protective materials, which are thought to be responsible for their high strength and toughness. However, it remains unknown how the metal-ligand complexes could give rise to such superb mechanical properties. Here, combining single molecule force spectroscopy and quantum calculation, we study the mechanical properties of individual catechol-Fe3 + complexes, the key elements accounting for the high toughness and extensibility of byssal threads of marine mussels. We find that catechol-Fe3 + complexes possess a unique combination of mechanical features, including high mechanical stability, fast reformation kinetics, and stoichiometry-dependent mechanics. Therefore, they can serve as sacrificial bonds to efficiently dissipate energy in the material, quickly recover the mechanical properties when load is released, and be responsive to environmental conditions. Our study provides the mechanistic understanding of the coordination bond-mediated mechanical properties of biogenetic materials, and could guide future rational design and regulation of the mechanical properties of synthetic materials.

  19. Human catechol-O-methyltransferase: Cloning and expression of the membrane-associated form

    Energy Technology Data Exchange (ETDEWEB)

    Bertocci, B.; Miggiano, V.; Da Prada, M.; Dembic, Z.; Lahm, H.W.; Malherbe, P. (F. Hoffmann-La Roche Ltd., Basel (Switzerland))

    1991-02-15

    A cDNA clone for human catechol-O-methyltransferase was isolated from a human hepatoma cell line (Hep G2) cDNA library by hybridization screening with a porcine cDNA probe. The cDNA clone was sequenced and found to have an insert of 1226 nucleotides. The deduced primary structure of hCOMT is composed of 271 amino acid residues with the predicted molecular mass of 30 kDa. At its N terminus it has a hydrophobic segment of 21 amino acid residues that may be responsible for insertion of hCOMT into the endoplasmic reticulum membrane. The primary structure of hCOMT exhibits high homology to the porcine partial cDNA sequence (93%). The deduced amino acid sequence contains two tryptic peptide sequences (T-22, T-33) found in porcine liver catechol-O-methyltransferase (CEMT). The coding region of hCOMT cDNA was placed under the control of the cytomegalovirus promoter to transfect human kidney 293 cells. The recombinant hCOMT was shown by immunoblot analysis to be mainly associated with the membrane fraction. RNA blot analysis revealed one COMT mRNA transcript of 1.4 kilobases in Hep G2 poly(A){sup +} RNA.

  20. Facile fabrication of gold nanoparticle on zein ultrafine fibers and their application for catechol biosensor

    Science.gov (United States)

    Chen, Xiaodong; Li, Dawei; Li, Guohui; Luo, Lei; Ullah, Naseeb; Wei, Qufu; Huang, Fenglin

    2015-02-01

    A novel laccase biosensor based on a new composite of laccase-gold nanoparticles (Au NPs)-crosslinked zein ultrafine fibers (CZUF) has been fabricated for catechol determination in real solution samples. Firstly, crosslinked zein ultrafine fibers containing gold nanoparticles (A-CZUF) were prepared by combining electrospinning and one-step reduction method using poly(ethyleneimine) (PEI) as reducing and crosslinking agent. A smooth morphology and relative average distribution of A-CZUF were depicted by scanning electron microscope (SEM) and transmission electron microscopy (TEM). The Fourier transform infrared spectroscopy (FT-IR) analysis indicated that PEI molecules attached to the surface of the zein ultrafine fibers via the reaction of functional groups between PEI and glyoxal. The results obtained from ultraviolet visible spectroscopy (UV-vis spectroscopy), X-ray diffraction (XRD) and thermal gravimetric analysis (TGA) for A-CZUF confirmed the existence of Au NPS coated on the surface of CZUF. Square wave voltammetry (SWV) and cyclic voltammetry (CV) were used to detect the electrochemical performance of the proposed biosensor. The results demonstrated that this biosensor possessed a high sensitive detection to catechol, which was attributed to the direct electron transfer (DET) facilitated by Au NPs and high catalytic ability obtained from laccase. In addition, the proposed biosensor exhibited good reproducibility, stability and selectivity.

  1. Suicide inactivation of catechol 2,3-dioxygenase from Pseudomonas putida mt-2 by 3-halocatechols

    Energy Technology Data Exchange (ETDEWEB)

    Bartels, I.; Knackmuss, H.J.; Reineke, W.

    1984-03-01

    The inactivation of catechol 2,3-dioxygenase from Pseudomonas putida mt-2 by 3-chloro- and 3-fluorocatechol and the iron-chelating agent Tiron (catechol-3,5-disulfonate) was studied. Whereas inactivation by Tiron is an oxygen-independent and mostly reversible process, inactivation by the 3-halocatechols was only observed in the presence of oxygen and was largely irreversible. The rate constants for inactivation (K/sub 2/) were 1.62 x 10/sup -3/ sec/sup -1/ for 3-chlorocatechol and 2.38 x 10/sup -3/ sec/sup -1/ for 3-fluorocatechol. The inhibitor constants (K/sub i/) were 23 ..mu..M for 3-chlorocatechol and 17 ..mu..M for 3-fluorocatechol. The kinetic data for 3-fluorocatechol could only be obtained in the presence of 2-mercaptoethanol. Besides inactivated enzyme, some 2-hydroxyhexa-2,4-dienoic acid as the actual suicide product of meta-cleavage. A side product of 3-fluorocatechol cleavage is a yellow compound with the spectral characteristics of a 2-hydroxy-6-oxohexa-2,4-dienoci acid indicating 1,6-cleavage. Rates of inactivation by 3-fluorocatechol were reduced in the presence of superoxide dismutase, catalase, formate, and mannitol, which implies that superoxide anion, hydrogen peroxide, and hydroxyl radical exhibit additional inactivation. 64 references.

  2. Coordination chemistry of microbial iron transport compounds. IX. Stability constants for catechol models of enterobactin

    Energy Technology Data Exchange (ETDEWEB)

    Avdeef, A.; Sofen, S.R.; Bregante, T.L.; Raymond, K.N.

    1978-08-16

    The stability constants of ferric complexes with several substituted catechol (1,2-dihydroxybenzene) ligands in aqueous solutions of low ionic strength have been determined at 27/sup 0/C in the pH range 2 to 11. Enterobactin, the principal siderophore of enteric bacteria, is a tricatechol and, from the formation constants reported here, is estimated to have a formation constant with ferric ion which is greater than 10/sup 45/. The stepwise formation constants, K/sub n/, of the catechol ligands reported here are defined as (ML/sub n/)/(ML/sub n-1/)(L), in units of L mol/sup -1/, where (L) is the concentration of the deprotonated catechol ligand. The constants were determined from potentiometric and spectroscopic data and were refined on pH values by weighted least squares. Qualitative examination of electron spin resonance spectra of the systems indicated some oxidation of the ligand by ferric ions at pH values as high as 4. The ligands studied included catechol (cat) (log K/sub 1/ = 20.01, log K/sub 2/ = 14.69, log K/sub 3/ = 9.01); 4,5-dihydroxy-m-benzenedisulfonate (Tiron) (log K/sub 2/ = 15.12, log K/sub 3/ = 10.10); 4-nitrocatechol (ncat) (log K/sub 1/ = 17.08, log K/sub 2/ = 13.43, log K/sub 3/ = 9.51); 3,4-dihydroxyphenylacetic acid (dhpa) (log K/sub 1/ = 20.1, log K/sub 2/ = 14.9, log K/sub 3/ = 9.0); and 2,3-dihydroxybenzoic acid (dhba) (log K/sub 1/ = 20.5). The acid dissociation constants, K/sub a/s, were determined also. For the catechol protons these follow: cat (pK/sub a/sub 1// = 9.22, pK/sub a/sub 2// = 13.0); Tiron (pK/sub a/sub 1// = 7.70, pK/sub a/sub 2// = 12.63); ncat (pK/sub a/sub 1// = 6.65, pK/sub a/sub 2// = 10.80); dhpa (pK/sub a/sub 1// = 9.49, pK/sub a/sub 2// = 13.7); and dhba (pK/sub a/sub 1// = 10.06, pK/sub a/sub 2// = 13.1). In addition, carboxylate substituents of dhpa and dhba have pK/sub a/s of 4.17 and 2.70, respectively.In solution, exchange is slow between these two types of coordination following changes in pH. 2 tables, 11

  3. ADSORCIÓN DE RESORCINOL DESDE SOLUCIÓN ACUOSA SOBRE CARBÓN ACTIVADO. RELACIÓN ISOTERMAS DE ADSORCIÓN Y ENTALPÍA DE INMERSIÓN

    Directory of Open Access Journals (Sweden)

    Diego Blanco

    2009-04-01

    Full Text Available Se estudia la adsorción de resorcinol, sobre carbones activados modificados, obtenidos a partir de un carbón activado comercial CarbochemTM –PS30, CAG, por medio de tratamiento químico con HNO3 7M, CAO y tratamiento térmico bajo flujo de H2, CAR; se analiza la influencia del pH de la solución, la reducción y oxidación de la superficie del carbón y se determina la entalpía de inmersión de los carbones activados en soluciones acuosas de resorcinol.La interacción sólido-solución se caracteriza por el análisis de las isotermas de adsorción a 298 K a los pHs de 7, 9 y 11 con el propósito de evaluar el sistema sobre y por debajo del valor de las pKa del resorcinol. La capacidad de adsorción de los carbones aumenta al disminuir el pH de la solución. La cantidad retenida aumenta en el carbón reducido al pH de máxima adsorción y disminuye en el carbón oxidado. Los resultados experimentales de las isotermas de adsorción se ajustaron a los modelos de Freundlich y Langmuir, obteniendo valores para el parámetro Qmáx del modelo de Langmuir en el CAG de 179, 156 y 44 mgg-1, para valores de pH de 7, 9 y 11 respectivamente. En el caso de los carbones modificados se obtienen valores de 233, 179 y 164 mgg-1, para el CAR, CAG y CAO a pH 7 respectivamente. Como tendencia general la adsorción de resorcinol aumenta en el siguiente orden CAR > CAG > CAO Similares conclusiones se obtienen de las entalpías de inmersión, cuyos valores se incrementan con la cantidad de soluto retenido. En el caso del CAG se obtienen entalpías de inmersión entre 25,8 a 40,9 Jg-1 para soluciones acuosas de resorcinol en un rango de 20 a 1500 mgL-1.

  4. Structural features of resorcinol-formaldehyde resin chars and interfacial behavior of water co-adsorbed with low-molecular weight organics

    Science.gov (United States)

    Gun'ko, Vladimir M.; Bogatyrov, Viktor M.; Turov, Vladimir V.; Leboda, Roman; Skubiszewska-Zięba, Jadwiga; Urubkov, Iliya V.

    2013-10-01

    Products of resorcinol-formaldehyde resin carbonization (chars) are characterized by different morphology (particle shape and sizes) and texture (specific surface area, pore volume and pore size distribution) depending on water content during resin polymerization. At a low amount of water (Cw = 37.8 wt.%) during synthesis resulting in strongly cross-linked polymers, carbonization gives nonporous particles. An increase in the water content to 62.7 wt.% results in a nano/mesoporous char, but if Cw = 73.3 wt.%, a char is purely nanoporous. Despite these textural differences, the Raman spectra of all the chars are similar because of the similarity in the structure of their carbon sheets with a significant contribution of sp3 C atoms. However, the difference in the spatial organization of the carbon sheet stacks in the particles results in the significant differences in the textural and morphological characteristics and in the adsorption properties of chars with respect to water, methane, benzene, hydrogen, methylene chloride, and dimethylsulfoxide.

  5. Role of 2-hexyl, 5-propyl resorcinol production by Pseudomonas chlororaphis PCL1606 in the multitrophic interactions in the avocado rhizosphere during the biocontrol process.

    Science.gov (United States)

    Calderón, Claudia E; de Vicente, Antonio; Cazorla, Francisco M

    2014-07-01

    Different bacterial traits can contribute to the biocontrol of soilborne phytopathogenic fungus. Among others, (1) antagonism, (2) competition for nutrients and niches, (3) induction of systemic resistance of the plants and (4) predation and parasitism are the most studied. Pseudomonas chlororaphis PCL1606 is an antagonistic rhizobacterium that produces the antifungal metabolite 2-hexyl, 5-propyl resorcinol (HPR). This bacterium can biologically control the avocado white root rot caused by Rosellinia necatrix. Confocal laser scanning microscopy of the avocado rhizosphere revealed that this biocontrol bacterium and the fungal pathogen compete for the same niche and presumably also for root exudate nutrients. The use of derivative mutants in the geners related to HPR biosynthesis (dar genes) revealed that the lack of HPR production by P. chlororaphis PCL1606 negatively influences the bacterial colonisation of the avocado root surface. Microscopical analysis showed that P. chlororaphis PCL1606 closely interacts and colonises the fungal hyphae, which may represent a novel biocontrol mechanism in this pseudomonad. Additionally, the presence of HPR-producing biocontrol bacteria negatively affects the ability of the fungi to infect the avocado root. HPR production negatively affects hyphal growth, leading to alterations in the R. necatrix physiology visible under microscopy, including the curling, vacuolisation and branching of hyphae, which presumably affects the colonisation and infection abilities of the fungus. This study provides the first report of multitrophic interactions in the avocado rhizosphere, advancing our understanding of the role of HPR production in those interactions.

  6. Correlation between bonding geometry and band gap states at organic-inorganic interfaces: catechol on rutile TiO2(110).

    Science.gov (United States)

    Li, Shao-Chun; Wang, Jian-guo; Jacobson, Peter; Gong, X-Q; Selloni, Annabella; Diebold, Ulrike

    2009-01-28

    Adsorbate-induced band gap states in semiconductors are of particular interest due to the potential of increased light absorption and photoreactivity. A combined theoretical and experimental (STM, photoemission) study of the molecular-scale factors involved in the formation of gap states in TiO(2) is presented. Using the organic catechol on rutile TiO(2)(110) as a model system, it is found that the bonding geometry strongly affects the molecular electronic structure. At saturation catechol forms an ordered 4 x 1 overlayer. This structure is attributed to catechol adsorbed on rows of surface Ti atoms with the molecular plane tilted from the surface normal in an alternating fashion. In the computed lowest-energy structure, one of the two terminal OH groups at each catechol dissociates and the O binds to a surface Ti atom in a monodentate configuration, whereas the other OH group forms an H-bond to the next catechol neighbor. Through proton exchange with the surface, this structure can easily transform into one where both OH groups dissociate and the catechol is bound to two surface Ti in a bidentate configuration. Only bidendate catechol introduces states in the band gap of TiO(2).

  7. Correlation between bonding geometry and band gap states at organic-inorganic interfaces: catechol on rutile TiO{sub 2}(110)

    Energy Technology Data Exchange (ETDEWEB)

    Selloni, Annabella; Wang, Jian-Guo; Gong, Xue-Qing [Department of Chemistry, Princeton University, Princeton, NJ (United States); Li, Shao-Chun; Jacobson, Peter; Diebold, Ulrike [Department of Physics, Tulane University, New Orleans, LA (United States)

    2009-07-01

    Adsorbate-induced band gap states in semiconductors are of particular interest due to the potential of increased light absorption and photoreactivity. A combined theoretical and experimental (STM, photoemission) study of the molecular-scale factors involved in the formation of gap states in TiO{sub 2} is presented. Using the organic catechol on rutile TiO{sub 2}(110) as a model system it is found that the bonding geometry strongly affects the molecular electronic structure. At saturation catechol forms an ordered 4x1 overlayer. This structure is attributed to catechol adsorbed on rows of surface Ti atoms with the molecular plane tilted from the surface normal in an alternating fashion. In the computed lowest-energy structure one of the two terminal OH groups at each catechol dissociates and the O binds to a surface Ti atom in a monodentate configuration, while the other OH group forms a H-bond to the next catechol neighbor. Through proton exchange with the surface this structure can easily transform into one where both OH groups dissociate and the catechol is bound to two surface Ti in a bidentate configuration. Only bidendate catechol introduces states in the band gap of TiO{sub 2}.

  8. Synthesis of Catechol Ethylether from Catechol and Ethanol Over Potasssium Loaded Active Carbon Catalyst%活性炭负载乙酸钾催化邻苯二酚和乙醇合成邻羟基苯乙醚

    Institute of Scientific and Technical Information of China (English)

    施志昆; 陈飞; 李倩; 朱天琦; 张丹凤; 方星星

    2012-01-01

    以活性碳为载体,以乙酸钾为活性组分的固体碱催化剂对邻苯二酚与乙醇气固相催化合成邻羟基苯乙醚的过程,考察了乙酸钾负载量对催化剂活性的影响以及反应条件对该反应的影响。结果表明随乙酸钾负载量的增加催化剂的碱性先增加后减小,乙酸钾负载量为15%质量分数的催化剂对该反应有最好的催化性能,当反应温度为433 K,邻苯二酚和乙醇摩尔比为10时,反应时间为150 min较适宜。在此条件下,邻苯二酚的转化率和邻羟基苯乙醚的选择性分别为99%和97%。%Synthesis of catechol ethylether by ethylation of catechol with ethanol is carried out over potassium acetate.Results show that the catalyst of 15 wt % potassium acetate loaded on active carbon exhibites the highest catalytic activity.Under the reaction conditions as follows: 433K and 1∶5 of molar ratio of ethanol to catechol,150 min of reaction time,the conversion rate of catechol and seletivity of catechol ethylether can both 99.5 % and 97.8 %.

  9. Altering substrate specificity of catechol 2,3-dioxygenase from Planococcus sp. strain S5 by random mutagenesis.

    Science.gov (United States)

    Hupert-Kocurek, Katarzyna; Wojcieszyńska, Danuta; Guzik, Urszula

    2014-01-01

    c23o gene, encoding catechol 2,3-dioxygenase from Planococcus sp. strain S5 was randomly mutagenized to generate variant forms of the enzyme with higher degradation activity. Additionally, the effect of introduced mutations on the enzyme structure was analyzed based on the putative 3D models the wild-type and mutant enzymes. C23OB58 and C23OB81 mutant proteins with amino acid substitutions in close proximity to the enzyme surface or at the interface and in the vicinity of the enzyme active site respectively showed the lowest activity towards all catecholic substrates. The relative activity of C23OC61 mutant towards para-substituted catechols was 20-30% lower of the wild-type enzyme. In this mutant all changes: F191I, C268R, Y272H, V280A and Y293D were located within the conserved regions of C-terminal domain. From these F191I seems to have significant implications for enzyme activity. The highest activity towards different catechols was found for mutant C23OB65. R296Q mutation improved the activity of C23O especially against 4-chlorocatechol. The relative activity of above-mentioned mutant detected against this substrate was almost 6-fold higher than the wild-type enzyme. These results should facilitate future engineering of the enzyme for bioremediation.

  10. Cloning and mutagenesis of catechol 2,3-dioxygenase gene from the gram-positive Planococcus sp. strain S5.

    Science.gov (United States)

    Hupert-Kocurek, Katarzyna; Stawicka, Agnieszka; Wojcieszyńska, Danuta; Guzik, Urszula

    2013-01-01

    In this study, the catechol 2,3-dioxygenase gene that encodes a 307- amino-acid protein was cloned from Planococcus sp. S5. The protein was identified to be a member of the superfamily I, subfamily 2A of extradiol dioxygenases. In order to study residues and regions affecting the enzyme's catalytic parameters, the c23o gene was randomly mutated by error-prone PCR. The wild-type enzyme and mutants containing substitutions within either the C-terminal or both domains were functionally produced in Escherichia coli and their activity towards catechol was characterized. The C23OB65 mutant with R296Q substitution showed significant tolerance to acidic pH with an optimum at pH 5.0. In addition, it showed activity more than 1.5 as high as that of the wild type enzyme and its Km was 2.5 times lower. It also showed altered sensitivity to substrate inhibition. The results indicate that residue at position 296 plays a role in determining pH dependence of the enzyme and its activity. Lower activity toward catechol was shown for mutants C23OB58 and C23OB81. Despite lower activity, these mutants showed higher affinity to catechol and were more sensitive to substrate concentration than nonmutated enzyme.

  11. Bio-inspired catechol chemistry: a new way to develop a re-moldable and injectable coacervate hydrogel.

    Science.gov (United States)

    Oh, Yeon Jeong; Cho, Il Hwan; Lee, Haeshin; Park, Ki-Jung; Lee, Hyukjin; Park, Sung Young

    2012-12-18

    A new way is demonstrated to develop a bio-inspired coacervate hydrogel by following catechol chemistry showing injectable and re-moldable physical properties. The formed coacervate shows potential long-term stability under water. Depending on pH, formation of the coacervate has been verified which is confirmed by XPS and zeta potential measurements.

  12. Mesoporous carbon nitride based biosensor for highly sensitive and selective analysis of phenol and catechol in compost bioremediation.

    Science.gov (United States)

    Zhou, Yaoyu; Tang, Lin; Zeng, Guangming; Chen, Jun; Cai, Ye; Zhang, Yi; Yang, Guide; Liu, Yuanyuan; Zhang, Chen; Tang, Wangwang

    2014-11-15

    Herein, we reported here a promising biosensor by taking advantage of the unique ordered mesoporous carbon nitride material (MCN) to convert the recognition information into a detectable signal with enzyme firstly, which could realize the sensitive, especially, selective detection of catechol and phenol in compost bioremediation samples. The mechanism including the MCN based on electrochemical, biosensor assembly, enzyme immobilization, and enzyme kinetics (elucidating the lower detection limit, different linear range and sensitivity) was discussed in detail. Under optimal conditions, GCE/MCN/Tyr biosensor was evaluated by chronoamperometry measurements and the reduction current of phenol and catechol was proportional to their concentration in the range of 5.00 × 10(-8)-9.50 × 10(-6)M and 5.00 × 10(-8)-1.25 × 10(-5)M with a correlation coefficient of 0.9991 and 0.9881, respectively. The detection limits of catechol and phenol were 10.24 nM and 15.00 nM (S/N=3), respectively. Besides, the data obtained from interference experiments indicated that the biosensor had good specificity. All the results showed that this material is suitable for load enzyme and applied to the biosensor due to the proposed biosensor exhibited improved analytical performances in terms of the detection limit and specificity, provided a powerful tool for rapid, sensitive, especially, selective monitoring of catechol and phenol simultaneously. Moreover, the obtained results may open the way to other MCN-enzyme applications in the environmental field.

  13. Laccase Immobilized on a PAN/Adsorbents Composite Nanofibrous Membrane for Catechol Treatment by a Biocatalysis/Adsorption Process

    Directory of Open Access Journals (Sweden)

    Qingqing Wang

    2014-03-01

    Full Text Available The treatment of catechol via biocatalysis and adsorption with a commercial laccase immobilized on polyacrylonitrile/montmorillonite/graphene oxide (PAN/MMT/GO composite nanofibers was evaluated with a homemade nanofibrous membrane reactor. The properties in this process of the immobilized laccase on PAN, PAN/MMT as well as PAN/MMT/GO with different weight ratios of MMT and GO were investigated. These membranes were successfully applied for removal of catechol from an aqueous solution. Scanning electron microscope images revealed different morphologies of the enzyme aggregates on different supports. After incorporation of MMT or MMT/GO, the optimum pH showed an alkaline shift to 4, compared to 3.5 for laccase immobilized on pure PAN nanofibers. The optimum temperature was at 55 °C for all the immobilized enzymes. Besides, the addition of GO improved the operational stability and storage stability. A 39% ± 2.23% chemical oxygen demand (COD removal from the catechol aqueous solution was achieved. Experimental results suggested that laccase, PAN, adsorbent nanoparticles (MMT/GO can be combined together for catechol treatment in industrial applications.

  14. Systemic catechol-O-methyl transferase inhibition enables the D1 agonist radiotracer R-[11C]SKF 82957

    DEFF Research Database (Denmark)

    Palner, Mikael; McCormick, Patrick; Parkes, Jun

    2010-01-01

    R-[(11)C]-SKF 82957 is a high-affinity and potent dopamine D(1) receptor agonist radioligand, which gives rise to a brain-penetrant lipophilic metabolite. In this study, we demonstrate that systemic administration of catechol-O-methyl transferase (COMT) inhibitors blocks this metabolic pathway, f...

  15. RATE AND CAPACITY OF HEPATIC MICROSOMAL RING HYDROXYLATION OF PHENOL TO HYDROQUINONE AND CATECHOL IN RAINBOW TROUT

    Science.gov (United States)

    Rainbow trout (Oncorhynchus mykiss) liver microsomes were used to study the rate of ring-hydroxylation of phenol PH) by directly measuring the production of hydroquinone (HQ), the primary metabolite, and catechol (CAT), a secondary metabolite. An HPLC method with integrated ultra...

  16. Current understanding of the interplay between catechol-O-methyltransferase genetic variants, sleep, brain development and cognitive performance in schizophrenia

    NARCIS (Netherlands)

    Tucci, Valter; Lassi, Glenda; Kas, Martien J

    2012-01-01

    Abnormal sleep is an endophenotype of schizophrenia. Here we provide an overview of the genetic mechanisms that link specific sleep physiological processes to schizophrenia-related cognitive defects. In particular, we will review the possible relationships between catechol-O-methyltransferase (COMT)

  17. VISCOSITY AND BINDER COMPOSITION EFFECTS ON TYROSINASE-BASED CARBON PASTE ELECTRODE FOR DETECTION OF PHENOL AND CATECHOL

    Science.gov (United States)

    The systematic study of the effect of binder viscosity on the sensitivity of a tyrosinase-based carbon paste electrode (CPE) biosensor for phenol and catechol is reported. Silicon oil binders with similar (polydimethylsiloxane) chemical composition were used to represent a wid...

  18. Activity of a Carboxyl-Terminal Truncated Form of Catechol 2,3-Dioxygenase from Planococcus sp. S5

    Directory of Open Access Journals (Sweden)

    Katarzyna Hupert-Kocurek

    2014-01-01

    Full Text Available Catechol 2,3-dioxygenases (C23Os, E.C.1.13.12.2 are two domain enzymes that catalyze degradation of monoaromatic hydrocarbons. The catalytically active C-domain of all known C23Os comprises ferrous ion ligands as well as residues forming active site pocket. The aim of this work was to examine and discuss the effect of nonsense mutation at position 289 on the activity of catechol 2,3-dioxygenase from Planococcus strain. Although the mutant C23O showed the same optimal temperature for activity as the wild-type protein (35°C, it exhibited activity slightly more tolerant to alkaline pH. Mutant enzyme exhibited also higher affinity to catechol as a substrate. Its Km (66.17 µM was approximately 30% lower than that of wild-type enzyme. Interestingly, removal of the C-terminal residues resulted in 1.5- to 1.8-fold (P<0.05 increase in the activity of C23OB61 against 4-methylcatechol and 4-chlorocatechol, respectively, while towards catechol the activity of the protein dropped to about 80% of that of the wild-type enzyme. The results obtained may facilitate the engineering of the C23O for application in the bioremediation of polluted areas.

  19. A smartphone-based colorimetric reader coupled with a remote server for rapid on-site catechols analysis.

    Science.gov (United States)

    Wang, Yun; Li, Yuanyuan; Bao, Xu; Han, Juan; Xia, Jinchen; Tian, Xiaoyu; Ni, Liang

    2016-11-01

    The search of a practical method to analyze cis-diol-containing compounds outside laboratory settings remains a substantial scientific challenge. Herein, a smartphone-based colorimetric reader was coupled with a remote server for rapid on-site analysis of catechols. A smallest-scale 2×2 colorimetric sensor array composed of pH indicators and phenylboronic acid was configured. The array was able to distinguish 13 catechols at 6 serial concentrations, through simultaneous treatment via principal component analysis, hierarchical cluster analysis, and linear discriminant analysis. After both the discriminatory power of the array and the prediction ability of the partial least squares quantitative models were proved to be predominant, the smartphone was coupled to the remote server. All the ΔRGB data were uploaded to the remote server wherein linear discriminant analysis and partial least squares processing modules were established to provide qualitative discrimination and quantitative calculation, respectively, of the analytes in real time. The applicability of this novel method to a real-life scenario was confirmed by the on-site analysis of various catechols from a water sample of the Yangtze River; the feedback result in the smartphone showed the method was able to identify the catechols with 100% accuracy and predict the concentrations to within 0.706-2.240 standard deviation.

  20. Laccase immobilized on a PAN/adsorbents composite nanofibrous membrane for catechol treatment by a biocatalysis/adsorption process.

    Science.gov (United States)

    Wang, Qingqing; Cui, Jing; Li, Guohui; Zhang, Jinning; Li, Dawei; Huang, Fenglin; Wei, Qufu

    2014-03-19

    The treatment of catechol via biocatalysis and adsorption with a commercial laccase immobilized on polyacrylonitrile/montmorillonite/graphene oxide (PAN/MMT/GO) composite nanofibers was evaluated with a homemade nanofibrous membrane reactor. The properties in this process of the immobilized laccase on PAN, PAN/MMT as well as PAN/MMT/GO with different weight ratios of MMT and GO were investigated. These membranes were successfully applied for removal of catechol from an aqueous solution. Scanning electron microscope images revealed different morphologies of the enzyme aggregates on different supports. After incorporation of MMT or MMT/GO, the optimum pH showed an alkaline shift to 4, compared to 3.5 for laccase immobilized on pure PAN nanofibers. The optimum temperature was at 55 °C for all the immobilized enzymes. Besides, the addition of GO improved the operational stability and storage stability. A 39% ± 2.23% chemical oxygen demand (COD) removal from the catechol aqueous solution was achieved. Experimental results suggested that laccase, PAN, adsorbent nanoparticles (MMT/GO) can be combined together for catechol treatment in industrial applications.

  1. Comparison between the removal of phenol and catechol by modified montmorillonite with two novel hydroxyl-containing Gemini surfactants

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Yuening; Gao, Manglai, E-mail: mlgao@cup.edu.cn; Gu, Zheng; Luo, Zhongxin; Ye, Yage; Lu, Laifu

    2014-02-01

    Highlights: • Organo-clays were prepared by two novel hydroxyl-containing Gemini surfactants. • The kinetics and thermodynamics of the novel organo-clays were studied. • The hydroxyl group of organo-clays can increase the adsorption capacity. • BHHP-Mt was proved to be a high-efficiency adsorbent to remove phenols. - Abstract: Na-montmorillonites were modified with two novel hydroxyl-containing Gemini surfactants, 1,3-bis(hexadecyldimethylammonio)-2-hydroxypropane dichloride (BHHP) and 1,3-bis(octyldimethylammonio)-2-hydroxypropane dichloride (BOHP), via ion-exchange reaction in this study. The modified samples were characterized by X-ray diffraction (XRD) and Fourier Transform Infrared (FT-IR) spectroscopy. Phenol and catechol were removed from aqueous solution by these two kinds of organo-montmorillonites in a batch system. Important parameters have been investigated, which affect the adsorption efficiency, such as the amount of modifier, temperature, pH and contact time. The adsorption kinetics of phenol and catechol were discussed using pseudo-first-order, pseudo-second-order and intra-particle diffusion model. It indicated that the experimental data fitted very well with the pseudo-second-order kinetic model, and the equilibrium adsorption data was proved in good agreement with the Langmuir isotherm. The result also showed the adsorption capacity of catechol was higher than that of phenol in the same conditions, which might result from the extra hydroxyl in the structure of catechol. Thermodynamic quantities such as Gibbs free energy (ΔG°), the enthalpy (ΔH°), and the entropy change of sorption (ΔS°) were also determined. These parameters suggested the adsorption of phenol was a spontaneous and exothermic process, while the sorption of catechol was endothermic.

  2. Antiplatelet Effect of Catechol Is Related to Inhibition of Cyclooxygenase, Reactive Oxygen Species, ERK/p38 Signaling and Thromboxane A2 Production

    Science.gov (United States)

    Wang, Tong-Mei; Lin, Bor-Ru; Yeung, Sin-Yuet; Yeh, Chien-Yang; Cheng, Ru-Hsiu; Jeng, Jiiang-Huei

    2014-01-01

    Catechol (benzenediol) is present in plant-derived products, such as vegetables, fruits, coffee, tea, wine, areca nut and cigarette smoke. Because platelet dysfunction is a risk factor of cardiovascular diseases, including stroke, atherosclerosis and myocardial infarction, the purpose of this study was to evaluate the anti-platelet and anti-inflammatory effect of catechol and its mechanisms. The effects of catechol on cyclooxygenase (COX) activity, arachidonic acid (AA)-induced aggregation, thromboxane B2 (TXB2) production, lactate dehydrogenase (LDH) release, reactive oxygen species (ROS) production and extracellular signal-regulated kinase (ERK)/p38 phosphorylation were determined in rabbit platelets. In addition, its effect on IL-1β-induced prostaglandin E2 (PGE2) production by fibroblasts was determined. The ex vivo effect of catechol on platelet aggregation was also measured. Catechol (5-25 µM) suppressed AA-induced platelet aggregation and inhibited TXB2 production at concentrations of 0.5–5 µM; however, it showed little cytotoxicity and did not alter U46619-induced platelet aggregation. Catechol (10–50 µM) suppressed COX-1 activity by 29–44% and COX-2 activity by 29–50%. It also inhibited IL-1β-induced PGE2 production, but not COX-2 expression of fibroblasts. Moreover, catechol (1–10 µM) attenuated AA-induced ROS production in platelets and phorbol myristate acetate (PMA)-induced ROS production in human polymorphonuclear leukocytes. Exposure of platelets to catechol decreased AA-induced ERK and p38 phosphorylation. Finally, intravenous administration of catechol (2.5–5 µmole/mouse) attenuated ex vivo AA-induced platelet aggregation. These results suggest that catechol exhibited anti-platelet and anti-inflammatory effects, which were mediated by inhibition of COX, ROS and TXA2 production as well as ERK/p38 phosphorylation. The anti-platelet effect of catechol was confirmed by ex vivo analysis. Exposure to catechol may affect platelet

  3. Antiplatelet effect of catechol is related to inhibition of cyclooxygenase, reactive oxygen species, ERK/p38 signaling and thromboxane A2 production.

    Directory of Open Access Journals (Sweden)

    Mei-Chi Chang

    Full Text Available Catechol (benzenediol is present in plant-derived products, such as vegetables, fruits, coffee, tea, wine, areca nut and cigarette smoke. Because platelet dysfunction is a risk factor of cardiovascular diseases, including stroke, atherosclerosis and myocardial infarction, the purpose of this study was to evaluate the anti-platelet and anti-inflammatory effect of catechol and its mechanisms. The effects of catechol on cyclooxygenase (COX activity, arachidonic acid (AA-induced aggregation, thromboxane B2 (TXB2 production, lactate dehydrogenase (LDH release, reactive oxygen species (ROS production and extracellular signal-regulated kinase (ERK/p38 phosphorylation were determined in rabbit platelets. In addition, its effect on IL-1β-induced prostaglandin E2 (PGE2 production by fibroblasts was determined. The ex vivo effect of catechol on platelet aggregation was also measured. Catechol (5-25 µM suppressed AA-induced platelet aggregation and inhibited TXB2 production at concentrations of 0.5-5 µM; however, it showed little cytotoxicity and did not alter U46619-induced platelet aggregation. Catechol (10-50 µM suppressed COX-1 activity by 29-44% and COX-2 activity by 29-50%. It also inhibited IL-1β-induced PGE2 production, but not COX-2 expression of fibroblasts. Moreover, catechol (1-10 µM attenuated AA-induced ROS production in platelets and phorbol myristate acetate (PMA-induced ROS production in human polymorphonuclear leukocytes. Exposure of platelets to catechol decreased AA-induced ERK and p38 phosphorylation. Finally, intravenous administration of catechol (2.5-5 µmole/mouse attenuated ex vivo AA-induced platelet aggregation. These results suggest that catechol exhibited anti-platelet and anti-inflammatory effects, which were mediated by inhibition of COX, ROS and TXA2 production as well as ERK/p38 phosphorylation. The anti-platelet effect of catechol was confirmed by ex vivo analysis. Exposure to catechol may affect platelet function

  4. Crystal structures of human 108V and 108M catechol O-methyltransferase

    Energy Technology Data Exchange (ETDEWEB)

    Rutherford, K.; Le Trong, I.; Stenkamp, R.E.; Parson, W.W. (UWASH)

    2008-08-01

    Catechol O-methyltransferase (COMT) plays important roles in the metabolism of catecholamine neurotransmitters and catechol estrogens. The development of COMT inhibitors for use in the treatment of Parkinson's disease has been aided by crystallographic structures of the rat enzyme. However, the human and rat proteins have significantly different substrate specificities. Additionally, human COMT contains a common valine-methionine polymorphism at position 108. The methionine protein is less stable than the valine polymorph, resulting in decreased enzyme activity and protein levels in vivo. Here we describe the crystal structures of the 108V and 108M variants of the soluble form of human COMT bound with S-adenosylmethionine (SAM) and a substrate analog, 3,5-dinitrocatechol. The polymorphic residue 108 is located in the {alpha}5-{beta}3 loop, buried in a hydrophobic pocket {approx}16 {angstrom} from the SAM-binding site. The 108V and 108M structures are very similar overall [RMSD of C{sup {alpha}} atoms between two structures (C{sup {alpha}} RMSD) = 0.2 {angstrom}], and the active-site residues are superposable, in accord with the observation that SAM stabilizes 108M COMT. However, the methionine side chain is packed more tightly within the polymorphic site and, consequently, interacts more closely with residues A22 ({alpha}2) and R78 ({alpha}4) than does valine. These interactions of the larger methionine result in a 0.7-{angstrom} displacement in the backbone structure near residue 108, which propagates along {alpha}1 and {alpha}5 toward the SAM-binding site. Although the overall secondary structures of the human and rat proteins are very similar (C{sup {alpha}} RMSD = 0.4 {angstrom}), several nonconserved residues are present in the SAM-(I89M, I91M, C95Y) and catechol- (C173V, R201M, E202K) binding sites. The human protein also contains three additional solvent-exposed cysteine residues (C95, C173, C188) that may contribute to intermolecular disulfide bond

  5. Emergence of hydrogen bonds from molecular dynamics simulation of substituted N-phenylthiourea-catechol oxidase complex.

    Science.gov (United States)

    Park, Kyung-Lae

    2017-01-01

    A series of N-phenylthiourea derivatives was built starting from the X-ray structure in the molecular mechanics framework and the interaction profile in the complex with the catechol oxidase was traced using molecular dynamics simulation. The results showed that the geometry and interactions between ligand and receptor were highly related to the position of the substituted side chains of phenyl moiety. At the end of molecular dynamics run, a concentrated multicenter hydrogen bond was created between the substituted ligand and receptor. The conformation of the ligand itself were also restricted in the receptor pocket. Furthermore, the simulation time of 50 ns were found to be long enough to explore the relevant conformational space and the stationary behavior of the molecular dynamic could be observed.

  6. New catechol derivatives of safrole and their antiproliferative activity towards breast cancer cells.

    Science.gov (United States)

    Madrid Villegas, Alejandro; Espinoza Catalán, Luis; Montenegro Venegas, Iván; Villena García, Joan; Carrasco Altamirano, Héctor

    2011-06-03

    Catechols were synthesized from safrole. Nine derivatives were prepared and assessed for antiproliferative effects using different human cell lines. The in vitro growth inhibition assay was based on the sulphorhodamine dye to quantify cell viability. The derivatives 4-allylbenzene-1,2-diol (3), 4 4-[3-(acetyloxy)propyl]-1,2-phenylene diacetate (6) and 4-[3-(acetyloxy)propyl]-5-nitro-1,2-phenylene diacetate (10) showed higher cytotoxicity than the parent compound 2 in tests performed on two breast cancer cell lines (MCF-7 and MDA-MB-231). The IC₅₀ values of 40.2 ± 6.9 μM, 5.9 ± 0.8 μM and 33.8 ± 4.9 μM, respectively, were obtained without toxicity towards dermal human fibroblast (DHF cells).

  7. Catechol-O-Methyltransferase gene val158met polymorphism and depressive symptoms during early childhood

    Science.gov (United States)

    Sheikh, Haroon I.; Kryski, Katie R.; Smith, Heather J.; Dougherty, Lea R.; Klein, Daniel N.; Bufferd, Sara J.; Singh, Shiva M.; Hayden, Elizabeth P.

    2017-01-01

    Catechol-O-Methyltransferase (COMT) is a critical regulator of catecholamine levels in the brain. A functional polymorphism of the COMT gene, val158met, has been linked to internalizing symptoms (i.e., depression and anxiety) in adolescents and adults. We extended this research by investigating whether the val158met polymorphism was associated with childhood symptoms of depression and anxiety in two independent samples of young children (Ns = 476 and 409). In both samples, preschool-aged children were genotyped for the COMT val158met polymorphism. Symptoms of psychopathology were assessed via parent interviews and primary caregiver reports. In both samples, children homozygous for the val allele had higher levels of depressive symptoms compared to children with at least one copy of the met allele. Our findings extend previous research in older participants by showing links between the COMT val158met polymorphism and internalizing symptoms in early childhood. PMID:23475824

  8. The catechol-O-methyltransferase gene (COMT) and cognitive function from childhood through adolescence.

    Science.gov (United States)

    Gaysina, Darya; Xu, Man K; Barnett, Jennifer H; Croudace, Tim J; Wong, Andrew; Richards, Marcus; Jones, Peter B

    2013-02-01

    Genetic variation in the catechol-O-methyltransferase gene (COMT) can influence cognitive function, and this effect may depend on developmental stage. Using a large representative British birth cohort, we investigated the effect of COMT on cognitive function (verbal and non-verbal) at ages 8 and 15 years taking into account the possible modifying effect of pubertal stage. Five functional COMT polymorphisms, rs6269, rs4818, rs4680, rs737865 and rs165599 were analysed. Associations between COMT polymorphisms and cognition were tested using regression and latent variable structural equation modelling (SEM). Before correction for multiple testing, COMT rs737865 showed association with reading comprehension, verbal ability and global cognition at age 15 years in pubescent boys only. Although there was some evidence for age- and sex-specific effects of the COMT rs737865 none remained significant after correction for multiple testing. Further studies are necessary in order to make firmer conclusions.

  9. New Catechol Derivatives of Safrole and Their Antiproliferative Activity towards Breast Cancer Cells

    Directory of Open Access Journals (Sweden)

    Héctor Carrasco Altamirano

    2011-06-01

    Full Text Available Catechols were synthesized from safrole. Nine derivatives were prepared and assessed for antiproliferative effects using different human cell lines. The in vitro growth inhibition assay was based on the sulphorhodamine dye to quantify cell viability. The derivatives 4-allylbenzene-1,2-diol (3, 4 4-[3-(acetyloxypropyl]-1,2-phenylene diacetate (6 and 4-[3-(acetyloxypropyl]-5-nitro-1,2-phenylene diacetate (10 showed higher cytotoxicity than the parent compound 2 in tests performed on two breast cancer cell lines (MCF-7 and MDA-MB-231. The IC50 values of 40.2 ± 6.9 μM, 5.9 ± 0.8 μM and 33.8 ± 4.9 μM, respectively, were obtained without toxicity towards dermal human fibroblast (DHF cells.

  10. A model for recombination in Type II dye-sensitized solar cells: Catechol-thiophene dyes

    Science.gov (United States)

    Manzhos, Sergei; Segawa, Hiroshi; Yamashita, Koichi

    2011-03-01

    Recombination in dye-sensitized solar cells with direct injection is cast as internal conversion in the dye-Ti(OH) 2 complex. For catechol-thiophene dyes with 1, 2, or 3 thiophene units, the complex reproduces the previously observed dye-to-semiconductor bands. We compare the decomposition of the internal conversion rate by vibrational mode and predict a trend in recombination with the extension of conjugation, which offers an explanation for the trend in DSSC efficiency. We employ a simple model for the vibrational factors and show that they are only important in the presence of vibrational modes with ℏω⩽kT and strong electronic factors, as is the case here.

  11. Catechol-derivatized poly(vinyl alcohol) as a coating molecule for magnetic nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    Burnand, David [Adolphe Merkle Institute, University of Fribourg, Route de l' Ancienne Papéterie CP209, 1723 Marly 1 (Switzerland); Chemistry Department, University of Fribourg, Chemin du Musée 9, 1700 Fribourg (Switzerland); Monnier, Christophe A.; Redjem, Anthony [Adolphe Merkle Institute, University of Fribourg, Route de l' Ancienne Papéterie CP209, 1723 Marly 1 (Switzerland); Schaefer, Mark [Chemistry Department, University of Fribourg, Chemin du Musée 9, 1700 Fribourg (Switzerland); Rothen-Rutishauser, Barbara [Adolphe Merkle Institute, University of Fribourg, Route de l' Ancienne Papéterie CP209, 1723 Marly 1 (Switzerland); Kilbinger, Andreas, E-mail: andreas.kilbinger@unifr.ch [Chemistry Department, University of Fribourg, Chemin du Musée 9, 1700 Fribourg (Switzerland); Petri-Fink, Alke, E-mail: alke.fink@unifr.ch [Adolphe Merkle Institute, University of Fribourg, Route de l' Ancienne Papéterie CP209, 1723 Marly 1 (Switzerland); Chemistry Department, University of Fribourg, Chemin du Musée 9, 1700 Fribourg (Switzerland)

    2015-04-15

    Surface functionalization of superparamagnetic iron oxide nanoparticles (SPIONs) remains indispensable in promoting colloidal stability and biocompatibility. We propose a well-defined and characterized synthesis of a new catechol-functionalized RAFT (reversible addition–fragmentation chain transfer) poly(vinyl alcohol) polymer, which can be anchored onto hydrophobic SPIONs via a one-pot emulsion ligand exchange process. Both single and clustered nanoparticles are obtained and can be separated from each other. As clustered SPIONs are receiving increasing attention, this new macroligand might be of considerable interest for both basic and applied sciences. - Highlights: • We prepared well-defined polymer coated magnetic nanoparticles. • We used polyvinyl alcohol (PVA) as an alternative to commonly used plyethylene glycol (PEG). • We strongly anchored the polymer on the magnetic nanoparticles' surfaces. • We developed a one-pot emulsion ligand exchange process. • We obtained single coated particles and well defined magnetic clusters, which we successfully separated.

  12. Seawater-Assisted Self-Healing of Catechol Polymers via Hydrogen Bonding and Coordination Interactions.

    Science.gov (United States)

    Li, Jincai; Ejima, Hirotaka; Yoshie, Naoko

    2016-07-27

    It is highly desirable to prevent crack formation in polymeric materials at an early stage and to extend their lifespan, particularly when repairs to these materials would be difficult for humans. Here, we designed and synthesized catechol-functionalized polymers that can self-heal in seawater through hydrogen bonding and coordination. These bioinspired acrylate polymers are originally viscous materials, but after coordination with environmentally safe, common metal cations in seawater, namely, Ca(2+) and Mg(2+), the mechanical properties of the polymers were greatly enhanced from viscous to tough, hard materials. Reduced swelling in seawater compared with deionized water owing to the higher osmotic pressure resulted in greater toughness (∼5 MPa) and self-healing efficiencies (∼80%).

  13. A two-electron shell game: Intermediates of the extradiol-cleaving catechol dioxygenases

    Science.gov (United States)

    Fielding, Andrew J.

    2014-01-01

    Extradiol catechol ring-cleaving dioxygenases function by binding both the organic substrate and O2 at a divalent metal center in the active site. They have proven to be a particularly versatile group of enzymes with which to study the O2 activation process. Here, recent studies of homoprotocatechuate 2,3-dioxygenase (HPCD) are summarized with the objective of showing how Nature can utilize the enzyme structure and the properties of the metal and the substrate to select among many possible chemical paths to achieve both specificity and efficiency. Possible intermediates in the mechanism have been trapped by swapping active site metals, introducing active site amino acid substituted variants, and using substrates with different electron donating capacities. While each of these intermediates could form part of a viable reaction pathway, kinetic measurements significantly limit the likely candidates. Structural, kinetic, spectroscopic and computational analysis of the various intermediates shed light on how catalytic efficiency can be achieved. PMID:24615282

  14. Production, purification and chemical characterization of the catecholate siderophore from potent probiotic strains of Bacillus spp.

    Science.gov (United States)

    Patel, Anil K; Deshattiwar, Maroti K; Chaudhari, Bhushan L; Chincholkar, Sudhir B

    2009-01-01

    The aim of the present study was to characterize the probiotic qualities of Bacillus isolates and study their siderophore prior to possible siderophoregenic probiotic application for iron nutrition in animals and humans. Bacillus strains were selectively isolated from dairy waste and mango pulp waste. Best two siderophore positive isolates, JHT3 and DET6 showed high homology with Bacillus megaterium (98%) and B. subtilis (99%), respectively, using partial 16S-rRNA sequencing and biochemical characterization. These isolates produced catecholate type of siderophore under iron stressed conditions and were screened for probiotic properties as per WHO and FAO guidelines. Spores of these strains showed excellent tolerance in partially simulated gastrointestinal tract conditions and exhibited antimicrobial activity against organisms such as Staphylococcus aureus, Micrococcus flavus and Escherichia coli. Importantly, these isolates were susceptible to the most of the antibiotics tested, in conflict that they would not donate resistance determinants if administered in the form of probiotic preparations.

  15. Low enzymatic activity haplotypes of the human catechol-O-methyltransferase gene: enrichment for marker SNPs.

    Directory of Open Access Journals (Sweden)

    Andrea G Nackley

    Full Text Available Catechol-O-methyltransferase (COMT is an enzyme that plays a key role in the modulation of catechol-dependent functions such as cognition, cardiovascular function, and pain processing. Three common haplotypes of the human COMT gene, divergent in two synonymous and one nonsynonymous (val(158met position, designated as low (LPS, average (APS, and high pain sensitive (HPS, are associated with experimental pain sensitivity and risk of developing chronic musculoskeletal pain conditions. APS and HPS haplotypes produce significant functional effects, coding for 3- and 20-fold reductions in COMT enzymatic activity, respectively. In the present study, we investigated whether additional minor single nucleotide polymorphisms (SNPs, accruing in 1 to 5% of the population, situated in the COMT transcript region contribute to haplotype-dependent enzymatic activity. Computer analysis of COMT ESTs showed that one synonymous minor SNP (rs769224 is linked to the APS haplotype and three minor SNPs (two synonymous: rs6267, rs740602 and one nonsynonymous: rs8192488 are linked to the HPS haplotype. Results from in silico and in vitro experiments revealed that inclusion of allelic variants of these minor SNPs in APS or HPS haplotypes did not modify COMT function at the level of mRNA folding, RNA transcription, protein translation, or enzymatic activity. These data suggest that neutral variants are carried with APS and HPS haplotypes, while the high activity LPS haplotype displays less linked variation. Thus, both minor synonymous and nonsynonymous SNPs in the coding region are markers of functional APS and HPS haplotypes rather than independent contributors to COMT activity.

  16. Energy level alignment of catechol molecular orbitals on ZnO(1 1 2-bar 0) and TiO{sub 2}(1 1 0) surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Rangan, Sylvie, E-mail: rangan@physics.rutgers.edu [Department of Physics and Astronomy and Laboratory for Surface Modification, Rutgers University, 136 Frelinghuysen Road, Piscataway, NJ 08854 (United States); Theisen, Jean-Patrick; Bersch, Eric; Bartynski, R.A. [Department of Physics and Astronomy and Laboratory for Surface Modification, Rutgers University, 136 Frelinghuysen Road, Piscataway, NJ 08854 (United States)

    2010-05-15

    The occupied and unoccupied electronic structure of catechol adsorbed onto two single crystal surfaces, rutile TiO{sub 2}(1 1 0) and wurtzite ZnO(1 1 2-bar 0), have been investigated using UV-photoemission and inverse photoemission spectroscopies (UPS and IPS) in an ultra-high vacuum environment. To aid in assignment of the spectral features, model metal-bound catechol structures were calculated using a DFT approach. From these measurements, the energy alignment of the catechol-related states with respect to the substrates band edges is directly determined and is in good agreement with a direct injection process of the photoexcited electron into the substrate conduction band, resulting in the characteristic absorption properties of adsorbed catechol.

  17. Energy level alignment of catechol molecular orbitals on ZnO(1 1 2¯ 0) and TiO 2(1 1 0) surfaces

    Science.gov (United States)

    Rangan, Sylvie; Theisen, Jean-Patrick; Bersch, Eric; Bartynski, R. A.

    2010-05-01

    The occupied and unoccupied electronic structure of catechol adsorbed onto two single crystal surfaces, rutile TiO 2(1 1 0) and wurtzite ZnO(1 1 2¯ 0), have been investigated using UV-photoemission and inverse photoemission spectroscopies (UPS and IPS) in an ultra-high vacuum environment. To aid in assignment of the spectral features, model metal-bound catechol structures were calculated using a DFT approach. From these measurements, the energy alignment of the catechol-related states with respect to the substrates band edges is directly determined and is in good agreement with a direct injection process of the photoexcited electron into the substrate conduction band, resulting in the characteristic absorption properties of adsorbed catechol.

  18. Molar absorption coefficients and stability constants of metal complexes of 4-(2-pyridylazo)resorcinol (PAR): Revisiting common chelating probe for the study of metalloproteins.

    Science.gov (United States)

    Kocyła, Anna; Pomorski, Adam; Krężel, Artur

    2015-11-01

    4-(2-Pyridylazo)resorcinol (PAR) is one of the most popular chromogenic chelator used in the determination of the concentrations of various metal ions from the d, p and f blocks and their affinities for metal ion-binding biomolecules. The most important characteristics of such a sensor are the molar absorption coefficient and the metal-ligand complex dissociation constant. However, it must be remembered that these values are dependent on the specific experimental conditions (e.g. pH, solvent components, and reactant ratios). If one uses these values to process data obtained in different conditions, the final result can be under- or overestimated. We aimed to establish the spectral properties and the stability of PAR and its complexes accurately with Zn(2+), Cd(2+), Hg(2+), Co(2+), Ni(2+), Cu(2+), Mn(2+) and Pb(2+) at a multiple pH values. The obtained results account for the presence of different species of metal-PAR complexes in the physiological pH range of 5 to 8 and have been frequently neglected in previous studies. The effective molar absorption coefficient at 492 nm for the ZnHx(PAR)2 complex at pH7.4 in buffered water solution is 71,500 M(-1) cm(-1), and the dissociation constant of the complex in these conditions is 7.08×10(-13) M(2). To confirm these values and estimate the range of the dissociation constants of zinc-binding biomolecules that can be measured using PAR, we performed several titrations of zinc finger peptides and zinc chelators. Taken together, our results provide the updated parameters that are applicable to any experiment conducted using inexpensive and commercially available PAR.

  19. The Role of Human Aldo-Keto Reductases in the Metabolic Activation and Detoxication of Polycyclic Aromatic Hydrocarbons: Interconversion of PAH Catechols and PAH o-Quinones

    OpenAIRE

    Li eZhang; Yi eJin; Meng eHuang; Penning, Trevor M.

    2012-01-01

    Polycyclic aromatic hydrocarbons (PAH) are ubiquitous environmental pollutants. They are procarcinogens requiring metabolic activation to elicit their deleterious effects. Aldo-keto reductases (AKR) catalyze the oxidation of proximate carcinogenic PAH trans-dihydrodiols to yield electrophilic and redox-active PAH o-quinones. AKRs are also found to be capable of reducing PAH o-quinones to form PAH catechols. The interconversion of o-quinones and catechols results in the redox-cycling of PAH o-...

  20. New route to the mixed valence semiquinone-catecholate based mononuclear FeIII and catecholate based dinuclear MnIII complexes: first experimental evidence of valence tautomerism in an iron complex.

    Science.gov (United States)

    Shaikh, Nizamuddin; Goswami, Sanchita; Panja, Anangamohan; Wang, Xin-Yi; Gao, Song; Butcher, Ray J; Banerjee, Pradyot

    2004-09-20

    The semiquinone-catecholate based mixed valence complex, [FeIII(bispicen)(Cl4Cat)(Cl4SQ)] x DMF (1), and catecholate based (H2bispictn)[Mn2III(Cl4Cat)4(DMF)2] (2) (bispicen = N,N'-bis(2-pyridylmethyl)-1,2-ethanediamine, bispictn = N,N'-bis(2-pyridylmethyl)-1,3-propanediamine, Cl4Cat = tetrachlorocatecholate dianion, and Cl4SQ = tetrachlorosemiquinone radical anion) were synthesized directly utilizing a facile route. Both the complexes have been characterized by single crystal X-ray diffraction study. The electronic structures have been elucidated by UV-vis-NIR absorption spectroscopy, cyclic voltammetry, EPR, and magnetic properties. The structural as well as spectroscopic features support the mixed valence tetrachlorosemiquinone-tetrachlorocatecholate charge distribution in 1. The ligand based mixed valence state was further confirmed by the presence of an intervalence charge transfer (IVCT) band in the 1900 nm region both in solution and in the solid. The intramolecular electron transfer, a phenomenon known as valence tautomerism (VT), has been followed by electronic absorption spectroscopy. For 1, the isomeric form [FeIII(bispicen)(Cl4Cat)(Cl4SQ)] is favored at low temperature, while at an elevated temperature, the [FeII(bispicen)(Cl4SQ)2] redox isomer dominates. Infrared as well as UV-vis-NIR spectral characterization for 2 suggest that the MnIII(Cat)2- moiety is admixed with its mixed valence semiquinone-catecholate isomer MnII(SQ)(Cat)-, and the electronic absorption spectrum is dominated by the mixed charged species. The origin of the intervalence charge transfer band in the 1900 nm range is associated with the mixed valence form, MnII(Cl4Cat)(Cl4SQ)-. The observation of VT in complex 1 is the first example where a mixed valence semiquinone-catecholate iron(III) complex undergoes intramolecular electron transfer similar to manganese and cobalt complexes.

  1. Suppression of electrochemical decomposition of propylene carbonate (PC) on a graphite anode in PC base electrolyte with catechol carbonate; Catechol carbonate tenka denkaieki deno graphite fukyokujo ni okeru propylene carbonate no bunseki yokusei

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Congxiao; Nakamura, H. [Saga Univ. (Japan). Faculty of Science and Engineering; Noguchi, H.; Yoshio, M.; Yoshitake, H. [Ube Industries Ltd. (Japan)

    1998-03-05

    In this study, 0.5-2.0 wt.% of catechol carbonates were added to a 1MLiPF6/propylene carbonate (PC) - diethyl carbonate (DEC) electrolyte, and this addition could suppress the decomposition of PC on MCMB6-28 (graphitized meso-phase carbon manufactured by the Osaka, Gas Co., Ltd.). The catechol carbonate-added electrolyte proved effective in suppressing the decomposition of PC even on graphite, such as NG-7 (manufactured by the Kansai Netsu Kagaku Co, Ltd.), natural graphite produced in China and natural graphite produced in Madagascar. It is highly possible that catechol carbonates act as radical scavengers. It could be ascertained that, when this electrolyte was used for a LiCoO2/MCMB6-28 lithium ion secondary battery, the capacity was substantially the same as the calculated one, and a PC-based electrolyte can be used for a lithium ion secondary battery using a negative electrode of graphite. 13 refs., 10 figs., 2 tabs.

  2. Enhancement of fill factor in air-processed inverted organic solar cells using self-assembled monolayer of fullerene catechol

    Science.gov (United States)

    Jeon, Il; Ogumi, Keisuke; Nakagawa, Takafumi; Matsuo, Yutaka

    2016-08-01

    [60]Fullerene catechol self-assembled monolayers were prepared and applied to inverted organic solar cells by an immersion method, and their energy conversion properties were measured. By introducing fullerenes at the surface, we improved the hole-blocking capability of electron-transporting metal oxide, as shown by the fill factor enhancement. The fullerene catechol-treated TiO x -containing device gave a power conversion efficiency (PCE) of 2.81% with a fill factor of 0.56 while the non treated device gave a PCE of 2.46% with a fill factor of 0.49. The solar cell efficiency improved by 13% compared with the non treated reference device.

  3. A novel amperometric catechol biosensor based on α-Fe2O3 nanocrystals-modified carbon paste electrode.

    Science.gov (United States)

    Sarika, C; Shivakumar, M S; Shivakumara, C; Krishnamurthy, G; Narasimha Murthy, B; Lekshmi, I C

    2017-05-01

    In this work, we designed an amperometric catechol biosensor based on α-Fe2O3 nanocrystals (NCs) incorporated carbon-paste electrode. Laccase enzyme is then assembled onto the modified electrode surface to form a nanobiocomposite enhancing the electron transfer reactions at the enzyme's active metal centers for catechol oxidation. The biosensor gave good sensitivity with a linear detection response in the range of 8-800 μM with limit of detection 4.28 μM. We successfully employed the sensor for real water sample analysis. The results illustrate that the metal oxide NCs have enormous potential in the construction of biosensors for sensitive determination of phenol derivatives.

  4. A highly sensitive electrochemical biosensor for catechol using conducting polymer reduced graphene oxide-metal oxide enzyme modified electrode.

    Science.gov (United States)

    Sethuraman, V; Muthuraja, P; Anandha Raj, J; Manisankar, P

    2016-10-15

    The fabrication, characterization and analytical performances were investigated for a catechol biosensor, based on the PEDOT-rGO-Fe2O3-PPO composite modified glassy carbon (GC) electrode. The graphene oxide (GO) doped conducting polymer poly (3,4-ethylenedioxythiophene) (PEDOT) was prepared through electrochemical polymerization by potential cycling. Reduction of PEDOT-GO was carried out by amperometric method. Fe2O3 nanoparticles were synthesized in ethanol by hydrothermal method. The mixture of Fe2O3, PPO and glutaraldehyde was casted on the PEDOT-rGO electrode. The surface morphology of the modified electrodes was studied by FE-SEM and AFM. Cyclic voltammetric studies of catechol on the enzyme modified electrode revealed higher reduction peak current. Determination of catechol was carried out successfully by Differential Pulse Voltammetry (DPV) technique. The fabricated biosensor investigated shows a maximum current response at pH 6.5. The catechol biosensor exhibited wide sensing linear range from 4×10(-8) to 6.20×10(-5)M, lower detection limit of 7×10(-9)M, current maxima (Imax) of 92.55µA and Michaelis-Menten (Km) constant of 30.48µM. The activation energy (Ea) of enzyme electrode is 35.93KJmol(-1) at 50°C. There is no interference from d-glucose and l-glutamic acid, ascorbic acid and o-nitrophenol. The PEDOT-rGO-Fe2O3-PPO biosensor was stable for at least 75 days when stored in a buffer at about 4°C.

  5. In Situ Synthesis of Antimicrobial Silver Nanoparticles within Antifouling Zwitterionic Hydrogels by Catecholic Redox Chemistry for Wound Healing Application.

    Science.gov (United States)

    GhavamiNejad, Amin; Park, Chan Hee; Kim, Cheol Sang

    2016-03-14

    A multifunctional hydrogel that combines the dual functionality of both antifouling and antimicrobial capacities holds great potential for many bioapplications. Many approaches and different materials have been employed to synthesize such a material. However, a systematic study, including in vitro and in vivo evaluation, on such a material as wound dressings is highly scarce at present. Herein, we report on a new strategy that uses catecholic chemistry to synthesize antimicrobial silver nanoparticles impregnated into antifouling zwitterionic hydrogels. For this purpose, hydrophobic dopamine methacrylamide monomer (DMA) was mixed in an aqueous solution of sodium tetraborate decahydrate and DMA monomer became soluble after increasing pH to 9 due to the complexation between catechol groups and boron. Then, cross-linking polymerization of zwitterionic monomer was carried out with the solution of the protected dopamine monomer to produce a new hydrogel. When this new hydrogel comes in contact with a silver nitrate solution, silver nanoparticles (AgNPs) are formed in its structure as a result of the redox property of the catechol groups and in the absence of any other external reducing agent. The results obtained from TEM and XRD measurements indicate that AgNPs with diameters of around 20 nm had formed within the networks. FESEM images confirmed that the silver nanoparticles were homogeneously incorporated throughout the hydrogel network, and FTIR spectroscopy demonstrated that the catechol moiety in the polymeric backbone of the hydrogel is responsible for the reduction of silver ions into the AgNPs. Finally, the in vitro and in vivo experiments suggest that these mussel-inspired, antifouling, antibacterial hydrogels have great potential for use in wound healing applications.

  6. Electrocatalytic oxidation of dihydronicotineamide adenine dinucleotide on gold electrode modified with catechol-terminated alkanethiol self-assembly

    Energy Technology Data Exchange (ETDEWEB)

    Nakano, Koji [Department of Applied Chemistry, Faculty of Engineering, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-0395 (Japan)], E-mail: kojitcm@mbox.nc.kyushu-u.ac.jp; Ohkubo, Kimihiko; Taira, Hiroaki [Department of Applied Chemistry, Faculty of Engineering, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-0395 (Japan); Takagi, Makoto [Fukuoka Women' s University, 1-1-1, Kasumigaoka, Higashi-ku, Fukuoka 813-8529 (Japan); Imato, Toshihiko [Department of Applied Chemistry, Faculty of Engineering, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-0395 (Japan)

    2008-06-30

    Synthesis of a mercaptoundecaneamide derivative having a terminus of catechol is described. FT-IR spectroscopic characterization showed that the new molecular entry simply undergoes molecular self-assembly on Au substrate surfaces promoting intra- and intermolecular hydrogen bonds to form well-packed monolayers. Cyclic voltammetric (CV) measurements on the monolayer-modified Au electrode revealed that the surface adlayer possesses specific electrochemical activity due to the reversible catechol/o-quinone redox reaction having characteristics of a surface process and also pH-dependence in its formal potential (59 mV per pH). Detailed analysis of CVs gave fundamental electrochemical parameters including the electroactive surface coverage (0.20-0.24 nmol cm{sup -2}), the transfer coefficients (0.24 in oxidation and 0.81 in reduction), and also the electron transfer rate constant (1.10-2.76 s{sup -1}). These data were almost consistent to those seen in literature. We have also found that the catechol monolayer modified electrode exhibits an electrocatalytic function in NADH oxidation. That is, the faradaic current appeared reinforcingly at around the same potential where catechol function is oxidized in the monolayer and increased with an increase in the NADH concentration from 1 to 5 mM, and then reached to a plateau indicating a catalyzed reaction pathway. Detailed analyses revealed that the present system could be characterized by its weak stability of the intermediate compound formed and prompt reaction rate compared with the previously reported chemically modified electrode (CME) systems. We think this type of achievement should be important for the basics of biosensors that rely on dehydrogenase enzymes.

  7. Construction of mussel-inspired coating via the direct reaction of catechol and polyethyleneimine for efficient heparin immobilization

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Yujie [School of Material Science and Engineering, Southwest Jiaotong University, Chengdu 610031 (China); The Institute of Biomaterials and Surface Engineering, Southwest Jiaotong University, Chengdu 610031 (China); Luo, Rifang, E-mail: lrifang@126.com [School of Material Science and Engineering, Southwest Jiaotong University, Chengdu 610031 (China); The Institute of Biomaterials and Surface Engineering, Southwest Jiaotong University, Chengdu 610031 (China); Shen, Fangyu; Tang, Linlin [School of Material Science and Engineering, Southwest Jiaotong University, Chengdu 610031 (China); The Institute of Biomaterials and Surface Engineering, Southwest Jiaotong University, Chengdu 610031 (China); Wang, Jin, E-mail: jinxxwang@263.net [School of Material Science and Engineering, Southwest Jiaotong University, Chengdu 610031 (China); The Institute of Biomaterials and Surface Engineering, Southwest Jiaotong University, Chengdu 610031 (China); Huang, Nan [School of Material Science and Engineering, Southwest Jiaotong University, Chengdu 610031 (China); The Institute of Biomaterials and Surface Engineering, Southwest Jiaotong University, Chengdu 610031 (China)

    2015-02-15

    Highlights: • Catechol (CA) and PEI copolymerization was a mimetic and dopamine-like coating method. • CA/PEI film provided amine groups and was effective in heparin immobilization. • CA/PEI coating could inhibit smooth muscle cell proliferation. • CA/PEI coating did not show any significant cytotoxicity to endothelial cell. - Abstract: Dopamine could self-polymerize to form the coating on various substrates and the co-existence of catechols and amines was crucial in performing such polymerization process. In this work, a mimetic approach of coating formation was carried out based on the co-polymerization of catechol (CA) and polyethyleneimine (PEI). Mussel-inspired CA/PEI coating was deposited on 316L stainless steel (SS). Fourier transform infrared spectra (FTIR) and X-ray photoelectron spectroscopy (XPS) demonstrated the successful coating formation. QCM measurement showed good affinity of heparin immobilization on CA/PEI coating surface ascribed to the amine groups. Herein, vascular cell-material interactions like endothelial cells (ECs) and smooth muscle cells (SMCs) were also investigated. Interestingly, CA/PEI and heparin modified coatings presented no cytotoxicity to ECs, however to a certain extent, decreased SMCs proliferation. Moreover, heparin-binding surface presented significant anti-platelet adhesion and activation properties. These results effectively suggested that the mussel-inspired CA/PEI coating might be promising when served as a platform for biomolecule immobilization.

  8. Application of a Novel Semiconductor Catalyst, CT, in Degradation of Aromatic Pollutants in Wastewater: Phenol and Catechol

    Directory of Open Access Journals (Sweden)

    Xiao Chen

    2014-01-01

    Full Text Available Water-soluble phenol and phenolic compounds were generally removed via advanced oxidation processes. A novel semiconductor catalyst, CT, was the first-time employed in the present study to degrade phenol and catechol. The phenolic compounds (initial concentration of 88 mg L−1 were completely mineralized by the CT catalytic nanoparticles (1% within 15 days, under acidic condition and with the presence of mild UV radiation (15 w, the emitted wavelength is 254 nm and the light intensity <26 μw/cm2. Under the same reaction condition, 1% TiO2 (mixture of rutile and anatase, nanopowder, <100 nm and H2O2 had lower removal efficiency (phenol: <42%; catechol: <60%, whereas the control (without addition of catalysts/H2O2 only showed <12% removal. The processes of phenol/catechol removal by CT followed pseudo-zero-order kinetics. The aromatic structures absorbed the UV energy and passed to an excited state, which the CT worked on. The pollutants were adsorbed on the CT’s surface and oxidized via charge-transfer and hydroxyl radical generation by CT. Given low initial concentrations, a circumstance encountered in wastewater polishing, the current set-up should be an efficient and less energy- and chemical-consumptive treatment method.

  9. Browning inhibition mechanisms by cysteine, ascorbic acid and citric acid, and identifying PPO-catechol-cysteine reaction products.

    Science.gov (United States)

    Ali, Hussein M; El-Gizawy, Ahmed M; El-Bassiouny, Rawia E I; Saleh, Mahmoud A

    2015-06-01

    The titled compounds were examined as PPO inhibitors and antibrowning agents; their various mechanisms were investigated and discussed. All compounds reduced significantly both the browning process and PPO activity. Browning index gave strong correlation with PPO activity (r(2) = 0.96, n = 19) indicating that the browning process is mainly enzymatic. Ascorbic acid could reduce the formed quinone instantly to the original substrate (catechol) at high concentration (>1.5 %) while at lower concentrations acted as competitive inhibitor (KI = 0.256 ± 0.067 mM). Cysteine, at higher concentrations (≥1.0 %), reacted with the resulted quinone to give a colorless products while at the low concentrations, cysteine worked as competitive inhibitor (KI = 1.113 ± 0.176 mM). Citric acid acted only as PPO non-competitive inhibitor with KI = 2.074 ± 0.363 mM. The products of PPO-catechole-cysteine reaction could be separation and identification by LC-ESI-MS. Results indicated that the product of the enzymatic oxidation of catechol, quinone, undergoes two successive nucleophilic attacks by cysteine thiol group. Cysteine was condensed with the resulted mono and dithiocatechols to form peptide side chains.

  10. Syntheses, characterization, and anti-cancer activities of pyridine-amide based compounds containing appended phenol or catechol groups

    Indian Academy of Sciences (India)

    Afsar Ali; Deepak Bansal; Nagendra K Kaushik; Neha Kaushik; Neha Kaushik; Eun Ha Choi; Rajeev Gupta

    2014-07-01

    Several pyridine-amide compounds appended with phenol/catechol groups are synthesized. These compounds consist of protected or deprotected phenol/catechol groups and offer pyridine, amide, and phenol/catechol functional groups. All compounds have been well-characterized by various spectroscopic methods, elemental analysis, thermal studies, and crystallography. The biological activities of all compounds were investigated while a few compounds significantly decreased the metabolic viability, growth and clonogenicity of T98G cells in dose dependent manner. Accumulation of ROS was observed in T98G cells, which displayed a compromised redox status as evident from increased cellular Caspase 3/7 activity and formation of micronuclei. The in silico pharmacokinetic studies suggest that all compounds have good bioavailability, water solubility and other drug-like parameters. A few compounds were identified as the lead molecules for future investigation due to their: (a) high activity against T98G brain, H-460 lung, and SNU-80 thyroid cancer cells; (b) low cytotoxicity in non-malignant HEK and MRC-5 cells; (c) low toxic risks based on in silico evaluation; (d) good theoretical oral bioavailability according to Lipinski ‘rule of five’ pharmacokinetic parameters; and (e) better drug-likeness and drug-score values.

  11. Optical Absorption Spectra and Excitons of Dye-Substrate Interfaces: Catechol on TiO2(110).

    Science.gov (United States)

    Mowbray, Duncan John; Migani, Annapaola

    2016-06-14

    Optimizing the photovoltaic efficiency of dye-sensitized solar cells (DSSC) based on staggered gap heterojunctions requires a detailed understanding of sub-band gap transitions in the visible from the dye directly to the substrate's conduction band (CB) (type-II DSSCs). Here, we calculate the optical absorption spectra and spatial distribution of bright excitons in the visible region for a prototypical DSSC, catechol on rutile TiO2(110), as a function of coverage and deprotonation of the OH anchoring groups. This is accomplished by solving the Bethe-Salpeter equation (BSE) based on hybrid range-separated exchange and correlation functional (HSE06) density functional theory (DFT) calculations. Such a treatment is necessary to accurately describe the interfacial level alignment and the weakly bound charge transfer transitions that are the dominant absorption mechanism in type-II DSSCs. Our HSE06 BSE spectra agree semiquantitatively with spectra measured for catechol on anatase TiO2 nanoparticles. Our results suggest deprotonation of catechol's OH anchoring groups, while being nearly isoenergetic at high coverages, shifts the onset of the absorption spectra to lower energies, with a concomitant increase in photovoltaic efficiency. Further, the most relevant bright excitons in the visible region are rather intense charge transfer transitions with the electron and hole spatially separated in both the [110] and [001] directions. Such detailed information on the absorption spectra and excitons is only accessible via periodic models of the combined dye-substrate interface.

  12. Amperometric catechol biosensor based on laccase immobilized on nitrogen-doped ordered mesoporous carbon (N-OMC)/PVA matrix

    Science.gov (United States)

    Guo, Meiqing; Wang, Hefeng; Huang, Di; Han, Zhijun; Li, Qiang; Wang, Xiaojun; Chen, Jing

    2014-06-01

    A functionalized nitrogen-containing ordered mesoporous carbon (N-OMC), which shows good electrical properties, was synthesized by the carbonization of polyaniline inside a SBA-15 mesoporous silica template. Based on this, through entrapping laccase onto the N-OMC/polyvinyl alcohol (PVA) film a facilely fabricated amperometric biosensor was developed. Laccase from Trametes versicolor was assembled on a composite film of a N-OMC/PVA modified Au electrode and the electrochemical behavior was investigated. The results indicated that the N-OMC modified electrode exhibits electrical properties towards catechol. The optimum experimental conditions of a biosensor for the detection of catechol were studied in detail. Under the optimal conditions, the sensitivity of the biosensor was 0.29 A*M-1 with a detection limit of 0.31 μM and a linear detection range from 0.39 μM to 8.98 μM for catechol. The calibration curve followed the Michaelis-Menten kinetics and the apparent Michaelis-Menten \\left( K_{M}^{app} \\right) was 6.28 μM. This work demonstrated that the N-OMC/PVA composite provides a suitable support for laccase immobilization and the construction of a biosensor.

  13. Hydroxyapatite-based sorbents: elaboration, characterization and application for the removal of catechol from the aqueous phase.

    Science.gov (United States)

    Sebei, Haroun; Minh, Doan Pham; Lyczko, Nathalie; Sharrock, Patrick; Nzihou, Ange

    2016-12-26

    Hydroxyapatite (HAP) is highly considered as good sorbent for the removal of metals from the aqueous phase. However, soluble metals co-exist with organic pollutants in wastewaters. But little work has been devoted to investigate the reactivity of HAP for the removal of organic compounds. The main objective of this work is to study the reactivity of HAP-based sorbents for the removal of catechol as a model organic pollutant from an aqueous solution. Thus, HAP sorbents were firstly synthesized using calcium carbonate and potassium dihydrogen phosphate under moderate conditions (25-80°C, atmospheric pressure). A zinc-doped HAP was also used as sorbent, which was obtained from the contact of HAP with an aqueous solution of zinc nitrate. All the sorbents were characterized by different standard physico-chemical techniques. The sorption of catechol was carried out in a batch reactor under stirring at room temperature and pressure. Zinc-doped HAP sorbent was found to be more reactive than non-doped HAP sorbents for the fixation of catechol. The highest sorption capacity was of 15 mg of C per gram of zinc-doped HAP sorbent. The results obtained suggest the reaction scheme of HAP sorbents with metals and organic pollutants when HAP sorbents were used for the treatment of complex wastewaters.

  14. An Optical Biosensor based on Immobilization of Laccase and MBTH in Stacked Films for the Detection of Catechol.

    Directory of Open Access Journals (Sweden)

    Hamidah Sidek

    2007-10-01

    Full Text Available The fabrication of an optical biosensor by using stacked films where 3-methyl-2-benzothiazolinone hydrazone (MBTH was immobilized in a hybrid nafion/sol-gelsilicate film and laccase in a chitosan film for the detection of phenolic compounds wasdescribed. Quinone and/or phenoxy radical product from the enzymatic oxidation ofphenolic compounds was allowed to couple with MBTH to form a colored azo-dye productfor spectrophometric detection. The biosensor demonstrated a linear response to catecholconcentration range of 0.5-8.0 mM with detection limit of 0.33 mM and response time of10 min. The reproducibility of the fabricated biosensor was good with RSD value of 5.3 %(n = 8 and stable for at least 2 months. The use of the hybrid materials of nafion/sol-gelsilicate to immobilize laccase has altered the selectivity of the enzyme to various phenoliccompounds such as catechol, guaicol, o-cresol and m-cresol when compared to the non-immobilized enzyme. When immobilized in this hybrid film, the biosensor response onlyto catechol and not other phenolic compounds investigated. Immobilization in this hybridmaterial has enable the biosensor to be more selective to catechol compared with the non-immobilized enzyme. This shows that by a careful selection of different immobilizationmatrices, the selectivity of an enzyme can be modified to yield a biosensor with goodselectivity towards certain targeted analytes.

  15. Diazonium modification of porous graphitic carbon with catechol and amide groups for hydrophilic interaction and attenuated reversed phase liquid chromatography.

    Science.gov (United States)

    Iverson, Chad D; Zhang, Ya; Lucy, Charles A

    2015-11-27

    Porous graphitic carbon (PGC) is an increasingly popular and attractive phase for HPLC on account of its chemical and thermal stability, and its unique separation mechanism. However, native PGC is strongly hydrophobic and in some instances excessively retentive. As part of our effort to build a library of hydrophilic covalently modified PGC phases, we functionalized PGC with catechol and amide groups by means of aryl diazonium chemistry to produce two new phases. Successful grafting was confirmed by X-ray photoelectron spectroscopy (XPS). Under HILIC conditions, the Catechol-PGC showed up to 5-fold increased retention relative to unmodified PGC and selectivity that differed from four other HILIC phases. Under reversed phase conditions, the Amide-PGC reduced the retentivity of PGC by almost 90%. The chromatographic performance of Catechol-PGC and Amide-PGC is demonstrated by separations of nucleobases, nucleosides, phenols, alkaline pharmaceuticals, and performance enhancing stimulants. These compounds had retention factors (k) ranging from 0.5 to 13.

  16. Organic impurity profiling of methylone and intermediate compounds synthesized from catechol.

    Science.gov (United States)

    Heather, Erin; Bortz, Adam; Shimmon, Ronald; McDonagh, Andrew M

    2016-11-25

    This work examined the synthesis and organic impurity profile of methylone prepared from catechol. The primary aim of this work was to determine whether the synthetic pathway used to prepare 3,4-methylenedioxypropiophenone could be ascertained through analysis of the synthesized methylone. The secondary aim was the structural elucidation and origin determination of the organic impurities detected in methylone and the intermediate compounds. The organic impurities present in the reaction products were identified using GC-MS and NMR spectroscopy. Six organic impurities were detected in 1,3-benzodioxole and identified as the 1,3-benzodioxole dimer, 1,3-benzodioxole trimer, [1,3] dioxolo[4,5-b]oxanthrene, 4,4'-, 4,5'-, and 5,5'-methylenebis-1,3-benzodioxole. Six organic impurities were detected in 3,4-methylenedioxypropiophenone and identified as (2-hydroxyphenyl) propanoate, [2-(chloromethoxy) phenyl] propanoate, (2-propanoyloxyphenyl)propanoate, 5-[1-(1,3-benzodioxol-5-yl)prop-1-enyl]-1,3-benzodioxole, (5E)- and (5Z)-7-(1,3-benzodioxol-5-yl)-5-ethylidene-6-methyl-cyclopenta[f][1,3]benzodioxole). Exploratory synthetic experiments were also conducted to unambiguously identify the organic impurities detected in 3,4-methylenedioxypropiophenone. Two organic impurities were detected in 5-bromo-3,4-methylenedioxypropiophenone and identified as [2-(chloromethoxy)phenyl] propanoate and 3,4-methylenedioxypropiophenone. Five organic impurities were detected in methylone and identified as 3,4-methylenedioxypropiophenone, 1-(1,3-benzodioxol-5-yl)-N-methyl-propan-1-imine, 1-(1,3-benzodioxol-5-yl)-2-methylimino-propan-1-one, 1-(1,3-benzodioxol-5-yl)-N1,N2-dimethyl-propane-1,2-diimine and butylated hydroxytoluene. The origin of these organic impurities was also ascertained, providing valuable insight into the chemical profiles of methylone and the intermediate compounds. However, neither the catechol precursor nor the 1,3-benzodioxole intermediate could be identified based on the

  17. Role of hydrogen-bonding and photoinduced electron transfer (PET) on the interaction of resorcinol based acridinedione dyes with Bovine Serum Albumin (BSA) in water

    Energy Technology Data Exchange (ETDEWEB)

    Kumaran, Rajendran, E-mail: kumaranwau@rediffmail.com [Department of Chemistry, Dwaraka Doss Goverdhan Doss, Vaishnav College (Autonomous), 833, Gokul Bagh, E.V.R. Periyar Road, Arumbakkam, Chennai 600106, Tamil Nadu (India); Vanjinathan, Mahalingam [Department of Chemistry, Dwaraka Doss Goverdhan Doss, Vaishnav College (Autonomous), 833, Gokul Bagh, E.V.R. Periyar Road, Arumbakkam, Chennai 600106, Tamil Nadu (India); Ramamurthy, Perumal [National Centre for Ultrafast Processes, University of Madras, Taramani Campus Chennai 600113, Tamil Nadu (India)

    2015-08-15

    Resorcinol based acridinedione (ADDR) dyes are a class of laser dyes and have structural similarity with purine derivatives, nicotinamide adenine dinucleotide (NADH) analogs. These dyes are classified into photoinduced electron transfer (PET) and non-photoinduced electron transfer dyes, and the photophysical properties of family of these dyes exhibiting PET behavior are entirely different from that of non-PET dyes. The PET process in ADDR dyes is governed by the solvent polarity such that an ADDR dye exhibits PET process through space in an aprotic solvent like acetonitrile and does not exhibit the same in protic solvents like water and methanol. A comparison on the fluorescence emission, lifetime and nature of interaction of various ADDR dyes with a large globular protein like Bovine Serum Albumin (BSA) was carried out in aqueous solution. The interaction of PET based ADDR dyes with BSA in water is found to be largely hydrophobic, but hydrogen-bonding interaction of BSA with dye molecule influences the fluorescence emission of the dye and shifts the emission towards red region. Fluorescence spectral studies reveal that the excited state properties of PET based ADDR dyes are largely influenced by the addition of BSA. The microenvironment around the dye results in significant change in the fluorescence lifetime and emission. Fluorescence enhancement with a red shift in the emission results after the addition of BSA to ADDR dyes containing free amino hydrogen in the 10th position of basic acridinedione dye. The amino hydrogen (N–H) in the 10th position of ADDR dye is replaced by methyl group (N–CH{sub 3}), a significant decrease in the fluorescence intensity with no apparent shift in the emission maximum was observed after the addition of BSA. The nature of interaction between ADDR dyes with BSA is hydrogen-bonding and the dye remains unbound even at the highest concentration of BSA. Circular Dichroism (CD) studies show that the addition of dye to BSA results in

  18. Polycyclic aromatic hydrocarbons from the pyrolysis of catechol (ortho-dihydroxybenzene), a model fuel representative of entities in tobacco, coal, and lignin

    Energy Technology Data Exchange (ETDEWEB)

    Wornat, M.J.; Ledesma, E.B.; Marsh, N.D. [Princeton University, Princeton, NJ (United States). Dept. of Mechanical and Aerospace Engineering

    2001-10-09

    In order to better understand the formation of polycyclic aromatic hydrocarbons (PAH) from complex fuels, we have performed pyrolysis experiments in a laminar-flow reactor, using the model fuel catechol (Ortho-dihydroxybenzene), a phenol-type compound representative of structural entities in tobacco, coal and wood. Employing high pressure liquid chromatography with diode-array ultraviolet-visible (UV) detection, we have unequivocally identified 59 individual species among the condensed-phase products of catechol pyrolysis at a temperature of 1000{degree}C and a residence time of 0.4 s. Also identified are two oxygen-containing compounds that are produced only at pyrolysis temperatures lower than 900{degree}C. Of the total 61 species, fifty have never before been identified as pyrolysis products of any pure phenol type compound. Two of the catechol pyrolysis products, 5-ethynylacenaphthylene and 3-ethynylphenanthrene, have never before been identified as products of any fuel. Ranging in size from one to eight fused aromatic rings, the catechol pyrolysis products comprise several compound classes: bi-aryls, indene benzologues, benzenoid PAH, alkylated aromatics, fluoranthene benzologues, cyclopenta-fused PAH, ethynyl-substituted aromatics, polyacetylenes, and oxygen-containing aromatics. The catechol pyrolysis products bear remarkable compositional similarity to the products of bituminous coal volatiles pyrolyzed at the same temperature - demonstrating the relevance of these catechol model compound experiments to the study of complex fuels such as coal, wood and tobacco. The UV spectra, establishing compound identity, are presented for several of the identified catechol product components. 70 refs., 13 figs., 6 tabs.

  19. Characterization of NF-kB-mediated inhibition of catechol-O-methyltransferase

    Directory of Open Access Journals (Sweden)

    Conrad Matthew

    2009-03-01

    Full Text Available Abstract Background Catechol-O-methyltransferase (COMT, an enzyme that metabolizes catecholamines, has recently been implicated in the modulation of pain. Specifically, low COMT activity is associated with heightened pain perception and development of musculoskeletal pain in humans as well as increased experimental pain sensitivity in rodents. Results We report that the proinflammatory cytokine tumor necrosis factor α (TNFα downregulates COMT mRNA and protein in astrocytes. Examination of the distal COMT promoter (P2-COMT reveals a putative binding site for nuclear factor κB (NF-κB, the pivotal regulator of inflammation and the target of TNFα. Cell culture assays and functional deletion analyses of the cloned P2-COMT promoter demonstrate that TNFα inhibits P2-COMT activity in astrocytes by inducing NF-κB complex recruitment to the specific κB binding site. Conclusion Collectively, our findings provide the first evidence for NF-κB-mediated inhibition of COMT expression in the central nervous system, suggesting that COMT contributes to the pathogenesis of inflammatory pain states.

  20. Catechol-O-methyltransferase val158met polymorphism predicts placebo effect in irritable bowel syndrome.

    Directory of Open Access Journals (Sweden)

    Kathryn T Hall

    Full Text Available Identifying patients who are potential placebo responders has major implications for clinical practice and trial design. Catechol-O-methyltransferase (COMT, an important enzyme in dopamine catabolism plays a key role in processes associated with the placebo effect such as reward, pain, memory and learning. We hypothesized that the COMT functional val158met polymorphism, was a predictor of placebo effects and tested our hypothesis in a subset of 104 patients from a previously reported randomized controlled trial in irritable bowel syndrome (IBS. The three treatment arms from this study were: no-treatment ("waitlist", placebo treatment alone ("limited" and, placebo treatment "augmented" with a supportive patient-health care provider interaction. The primary outcome measure was change from baseline in IBS-Symptom Severity Scale (IBS-SSS after three weeks of treatment. In a regression model, the number of methionine alleles in COMT val158met was linearly related to placebo response as measured by changes in IBS-SSS (p = .035. The strongest placebo response occurred in met/met homozygotes treated in the augmented placebo arm. A smaller met/met associated effect was observed with limited placebo treatment and there was no effect in the waitlist control. These data support our hypothesis that the COMT val158met polymorphism is a potential biomarker of placebo response.

  1. Catechol-O-methyltransferase val158met polymorphism predicts placebo effect in irritable bowel syndrome.

    Science.gov (United States)

    Hall, Kathryn T; Lembo, Anthony J; Kirsch, Irving; Ziogas, Dimitrios C; Douaiher, Jeffrey; Jensen, Karin B; Conboy, Lisa A; Kelley, John M; Kokkotou, Efi; Kaptchuk, Ted J

    2012-01-01

    Identifying patients who are potential placebo responders has major implications for clinical practice and trial design. Catechol-O-methyltransferase (COMT), an important enzyme in dopamine catabolism plays a key role in processes associated with the placebo effect such as reward, pain, memory and learning. We hypothesized that the COMT functional val158met polymorphism, was a predictor of placebo effects and tested our hypothesis in a subset of 104 patients from a previously reported randomized controlled trial in irritable bowel syndrome (IBS). The three treatment arms from this study were: no-treatment ("waitlist"), placebo treatment alone ("limited") and, placebo treatment "augmented" with a supportive patient-health care provider interaction. The primary outcome measure was change from baseline in IBS-Symptom Severity Scale (IBS-SSS) after three weeks of treatment. In a regression model, the number of methionine alleles in COMT val158met was linearly related to placebo response as measured by changes in IBS-SSS (p = .035). The strongest placebo response occurred in met/met homozygotes treated in the augmented placebo arm. A smaller met/met associated effect was observed with limited placebo treatment and there was no effect in the waitlist control. These data support our hypothesis that the COMT val158met polymorphism is a potential biomarker of placebo response.

  2. Isolation and characterization of an anticancer catechol compound from Semecarpus anacardium.

    Science.gov (United States)

    Nair, P K Raveedran; Melnick, Steven J; Wnuk, Stanislaw F; Rapp, Magdalena; Escalon, Enrique; Ramachandran, Cheppail

    2009-04-21

    The fruits and seeds of Semecarpus anacardium are used widely for the treatment of human cancers and other diseases in the Ayurvedic and Sidda systems of medicine in India. The principal aim of this investigation was to isolate and characterize the anticancer compound from the kernel of Semecarpus anacardium nut. The bioactivity-tailored isolation and detailed chemical characterization were used to identify the active compound. Cytotoxicity, apoptosis, cell cycle arrest as well as synergism between the identified anticancer compound and doxorubicin in human tumor cell lines were analyzed. GC/MS, IR, proton NMR, carbon NMR and collisionally induced dissociation (CID) spectra analysis showed that the isolated active compound is 3-(8'(Z),11'(Z)-pentadecadienyl) catechol (SA-3C). SA-3C is cytotoxic to tumor cell lines with IC(50) values lower than doxorubicin and even multidrug resistant tumor cell lines were equally sensitive to SA-3C. SA-3C induced apoptosis in human leukemia cell lines in a dose-dependent manner and showed synergistic cytotoxicity with doxorubicin. The cell cycle arrest induced by SA-3C at S- and G(2)/M-phases correlated with inhibition of checkpoint kinases. SA-3C isolated from the kernel of Semecarpus anacardium can be developed as an important anticancer agent for single agent and/or multiagent cancer therapy.

  3. The synthesis, structure and activity evaluation of pyrogallol and catechol derivatives as Helicobacter pylori urease inhibitors.

    Science.gov (United States)

    Xiao, Zhu-Ping; Ma, Tao-Wu; Fu, Wei-Chang; Peng, Xiao-Chun; Zhang, Ai-Hua; Zhu, Hai-Liang

    2010-11-01

    Some pyrogallol and catechol derivatives were synthesized, and their urease inhibitory activity was evaluated by using acetohydroxamic acid (AHA), a well known Helicobacter pylori urease inhibitor, as positive control. The assay results indicate that many compounds have showed potential inhibitory activity against H. pylori urease. 4-(4-Hydroxyphenethyl)phen-1,2-diol (2a) was found to be the most potent urease inhibitor with IC(50)s of 1.5±0.2 μM for extracted fraction and 4.2±0.3 μM for intact cell, at least 10 times and 20 times lower than those of AHA (IC(50) of 17.2±0.9 μM, 100.6±13 μM), respectively. This finding indicate that 2a would be a potential urease inhibitor deserves further research. Molecular dockings of 2a into H. pylori urease active site were performed for understanding the good activity observed.

  4. Catechol-O-Methyltransferase val158met Polymorphism Predicts Placebo Effect in Irritable Bowel Syndrome

    Science.gov (United States)

    Hall, Kathryn T.; Lembo, Anthony J.; Kirsch, Irving; Ziogas, Dimitrios C.; Douaiher, Jeffrey; Jensen, Karin B.; Conboy, Lisa A.; Kelley, John M.; Kokkotou, Efi; Kaptchuk, Ted J.

    2012-01-01

    Identifying patients who are potential placebo responders has major implications for clinical practice and trial design. Catechol-O-methyltransferase (COMT), an important enzyme in dopamine catabolism plays a key role in processes associated with the placebo effect such as reward, pain, memory and learning. We hypothesized that the COMT functional val158met polymorphism, was a predictor of placebo effects and tested our hypothesis in a subset of 104 patients from a previously reported randomized controlled trial in irritable bowel syndrome (IBS). The three treatment arms from this study were: no-treatment (“waitlist”), placebo treatment alone (“limited”) and, placebo treatment “augmented” with a supportive patient-health care provider interaction. The primary outcome measure was change from baseline in IBS-Symptom Severity Scale (IBS-SSS) after three weeks of treatment. In a regression model, the number of methionine alleles in COMT val158met was linearly related to placebo response as measured by changes in IBS-SSS (p = .035). The strongest placebo response occurred in met/met homozygotes treated in the augmented placebo arm. A smaller met/met associated effect was observed with limited placebo treatment and there was no effect in the waitlist control. These data support our hypothesis that the COMT val158met polymorphism is a potential biomarker of placebo response. PMID:23110189

  5. Schistosome and liver fluke derived catechol-estrogens and helminth associated cancers

    Directory of Open Access Journals (Sweden)

    José M Correia da Costa

    2014-12-01

    Full Text Available Infection with helminth parasites remains a persistent public health problem in developing countries. Three of these pathogens, the liver flukes Clonorchis sinensis, Opisthorchis viverrini and the blood fluke Schistosoma haematobium, are of particular concern due to their classification as Group 1 carcinogens: infection with these worms is carcinogenic. Using liquid chromatography-mass spectrometry (LC-MS/MS approaches, we identified steroid hormone like (e.g. oxysterol-like, catechol estrogen quinone-like, etc. metabolites and related DNA-adducts, apparently of parasite origin, in developmental stages including eggs of S. haematobium, in urine of people with urogenital schistosomiasis, and in the adult stage of Opisthorchis viverrini. Since these kinds of sterol derivatives are metabolized to active quinones that can modify DNA, which in other contexts can lead to breast and other cancers, helminth parasite associated sterols might induce tumor-like phenotypes in the target cells susceptible to helminth parasite associated cancers, i.e. urothelial cells of the bladder in the case of urogenital schistosomiasis and the bile duct epithelia or cholangiocytes, in the case of O. viverrini and C. sinensis. Indeed we postulate that helminth induced cancers originate from parasite estrogen-host epithelial/urothelial cell chromosomal DNA adducts, and here we review recent findings that support this conjecture.

  6. Analysis of oxidative stress status, catalase and catechol-O-methyltransferase polymorphisms in Egyptian vitiligo patients.

    Directory of Open Access Journals (Sweden)

    Dina A Mehaney

    Full Text Available Vitiligo is the most common depigmentation disorder of the skin. Oxidative stress is implicated as one of the probable events involved in vitiligo pathogenesis possibly contributing to melanocyte destruction. Evidence indicates that certain genes including those involved in oxidative stress and melanin synthesis are crucial for development of vitiligo. This study evaluates the oxidative stress status, the role of catalase (CAT and catechol-O-Methyltransferase (COMT gene polymorphisms in the etiology of generalized vitiligo in Egyptians. Total antioxidant capacity (TAC and malondialdehyde (MDA levels as well as CAT exon 9 T/C and COMT 158 G/A polymorphisms were determined in 89 patients and 90 age and sex-matched controls. Our results showed significantly lower TAC along with higher MDA levels in vitiligo patients compared with controls. Meanwhile, genotype and allele distributions of CAT and COMT polymorphisms in cases were not significantly different from those of controls. Moreover, we found no association between both polymorphisms and vitiligo susceptibility. In conclusion, the enhanced oxidative stress with the lack of association between CAT and COMT polymorphisms and susceptibility to vitiligo in our patients suggest that mutations in other genes related to the oxidative pathway might contribute to the etiology of generalized vitiligo in Egyptian population.

  7. Genetic influences on insight problem solving: the role of catechol-O-methyltransferase (COMT) gene polymorphisms.

    Science.gov (United States)

    Jiang, Weili; Shang, Siyuan; Su, Yanjie

    2015-01-01

    People may experience an "aha" moment, when suddenly realizing a solution of a puzzling problem. This experience is called insight problem solving. Several findings suggest that catecholamine-related genes may contribute to insight problem solving, among which the catechol-O-methyltransferase (COMT) gene is the most promising candidate. The current study examined 753 healthy individuals to determine the associations between 7 candidate single nucleotide polymorphisms on the COMT gene and insight problem-solving performance, while considering gender differences. The results showed that individuals carrying A allele of rs4680 or T allele of rs4633 scored significantly higher on insight problem-solving tasks, and the COMT gene rs5993883 combined with gender interacted with correct solutions of insight problems, specifically showing that this gene only influenced insight problem-solving performance in males. This study presents the first investigation of the genetic impact on insight problem solving and provides evidence that highlights the role that the COMT gene plays in insight problem solving.

  8. Catechol-O-methyltransferase val158met Polymorphism Interacts with Sex to Affect Face Recognition Ability

    Science.gov (United States)

    Lamb, Yvette N.; McKay, Nicole S.; Singh, Shrimal S.; Waldie, Karen E.; Kirk, Ian J.

    2016-01-01

    The catechol-O-methyltransferase (COMT) val158met polymorphism affects the breakdown of synaptic dopamine. Consequently, this polymorphism has been associated with a variety of neurophysiological and behavioral outcomes. Some of the effects have been found to be sex-specific and it appears estrogen may act to down-regulate the activity of the COMT enzyme. The dopaminergic system has been implicated in face recognition, a form of cognition for which a female advantage has typically been reported. This study aimed to investigate potential joint effects of sex and COMT genotype on face recognition. A sample of 142 university students was genotyped and assessed using the Faces I subtest of the Wechsler Memory Scale – Third Edition (WMS-III). A significant two-way interaction between sex and COMT genotype on face recognition performance was found. Of the male participants, COMT val homozygotes and heterozygotes had significantly lower scores than met homozygotes. Scores did not differ between genotypes for female participants. While male val homozygotes had significantly lower scores than female val homozygotes, no sex differences were observed in the heterozygotes and met homozygotes. This study contributes to the accumulating literature documenting sex-specific effects of the COMT polymorphism by demonstrating a COMT-sex interaction for face recognition, and is consistent with a role for dopamine in face recognition. PMID:27445927

  9. Cell-Adhesive Bioinspired and Catechol-Based Multilayer Freestanding Membranes for Bone Tissue Engineering

    Directory of Open Access Journals (Sweden)

    Maria P. Sousa

    2017-10-01

    Full Text Available Mussels are marine organisms that have been mimicked due to their exceptional adhesive properties to all kind of surfaces, including rocks, under wet conditions. The proteins present on the mussel’s foot contain 3,4-dihydroxy-l-alanine (DOPA, an amino acid from the catechol family that has been reported by their adhesive character. Therefore, we synthesized a mussel-inspired conjugated polymer, modifying the backbone of hyaluronic acid with dopamine by carbodiimide chemistry. Ultraviolet–visible (UV–Vis spectroscopy and nuclear magnetic resonance (NMR techniques confirmed the success of this modification. Different techniques have been reported to produce two-dimensional (2D or three-dimensional (3D systems capable to support cells and tissue regeneration; among others, multilayer systems allow the construction of hierarchical structures from nano- to macroscales. In this study, the layer-by-layer (LbL technique was used to produce freestanding multilayer membranes made uniquely of chitosan and dopamine-modified hyaluronic acid (HA-DN. The electrostatic interactions were found to be the main forces involved in the film construction. The surface morphology, chemistry, and mechanical properties of the freestanding membranes were characterized, confirming the enhancement of the adhesive properties in the presence of HA-DN. The MC3T3-E1 cell line was cultured on the surface of the membranes, demonstrating the potential of these freestanding multilayer systems to be used for bone tissue engineering.

  10. Electrochemical preparation of activated graphene oxide for the simultaneous determination of hydroquinone and catechol.

    Science.gov (United States)

    Velmurugan, Murugan; Karikalan, Natarajan; Chen, Shen-Ming; Cheng, Yi-Hui; Karuppiah, Chelladurai

    2017-03-31

    This paper describes the electrochemical preparation of highly electrochemically active and conductive activated graphene oxide (aGO). Afterwards, the electrochemical properties of aGO was studied towards the simultaneous determination of hydroquinone (HQ) and catechol (CC). This aGO is prepared by the electrochemical activation of GO by various potential treatments. The resultant aGOs are examined by various physical and electrochemical characterizations. The high potential activation (1.4 to -1.5) process results a highly active GO (aGO1), which manifest a good electrochemical behavior towards the determination of HQ and CC. This aGO1 modified screen printed carbon electrode (SPCE) was furnished the sensitive detection of HQ and CC with linear concentration range from 1 to 312μM and 1 to 350μM. The aGO1 modified SPCE shows the lowest detection limit of 0.27μM and 0.182μM for the HQ and CC, respectively. The aGO1 modified SPCE reveals an excellent selectivity towards the determination of HQ and CC in the presence of 100 fold of potential interferents. Moreover, the fabricated disposable aGO1/SPCE sensor was demonstrated the determination of HQ and CC in tap water and industrial waste water.

  11. Antiproliferative and Antiestrogenic Activities of Bonediol an Alkyl Catechol from Bonellia macrocarpa

    Directory of Open Access Journals (Sweden)

    Rosa Moo-Puc

    2015-01-01

    Full Text Available The purpose of this study was to investigate antiproliferative activity of bonediol, an alkyl catechol isolated from the Mayan medicinal plant Bonellia macrocarpa. Bonediol was assessed for growth inhibition of androgen-sensitive (LNCaP, androgen-insensitive (PC-3, and metastatic androgen-insensitive (PC-3M human prostate tumor cells; toxicity on normal cell line (HEK 293 was also evaluated. Hedgehog pathway was evaluated and competitive 3H-estradiol ligand binding assay was performed. Additionally, antioxidant activity on Nrf2-ARE pathway was evaluated. Bonediol induced a growth inhibition on prostate cancer cell lines (IC50 from 8.5 to 20.6 µM. Interestingly, bonediol binds to both estrogen receptors (ERα (2.5 µM and ERβ (2.1 µM and displaces the native ligand E2 (17β-estradiol. No significant activity was found in the Hedgehog pathway. Additionally, activity of bonediol on Nrf2-ARE pathway suggested that bonediol could induce oxidative stress and activation of detoxification enzymes at 1 µM (3.8-fold. We propose that the compound bonediol may serve as a potential chemopreventive treatment with therapeutic potential against prostate cancer.

  12. Laccase Biosensor Based on Electrospun Copper/Carbon Composite Nanofibers for Catechol Detection

    Directory of Open Access Journals (Sweden)

    Jiapeng Fu

    2014-02-01

    Full Text Available The study compared the biosensing properties of laccase biosensors based on carbon nanofibers (CNFs and copper/carbon composite nanofibers (Cu/CNFs. The two kinds of nanofibers were prepared by electrospinning and carbonization under the same conditions. Scanning electron microscopy (SEM, X-ray diffraction (XRD and Raman spectroscopy were employed to investigate the morphologies and structures of CNFs and Cu/CNFs. The amperometric results indicated that the Cu/CNFs/laccase(Lac/Nafion/glass carbon electrode (GCE possessed reliable analytical performance for the detection of catechol. The sensitivity of the Cu/CNFs/Lac/Nafion/GCE reached 33.1 μA/mM, larger than that of CNFs/Lac/Nafion/GCE. Meanwhile, Cu/CNFs/Lac/Nafion/GCE had a wider linear range from 9.95 × 10−6 to 9.76 × 10−3 M and a lower detection limit of 1.18 μM than CNFs/Lac/Nafion/GCE. Moreover, it exhibited a good repeatability, reproducibility, selectivity and long-term stability, revealing that electrospun Cu/CNFs have great potential in biosensing.

  13. Structural mechanism of S-adenosyl methionine binding to catechol O-methyltransferase.

    Directory of Open Access Journals (Sweden)

    Douglas Tsao

    Full Text Available Methyltransferases possess a homologous domain that requires both a divalent metal cation and S-adenosyl-L-methionine (SAM to catalyze its reactions. The kinetics of several methyltransferases has been well characterized; however, the details regarding their structural mechanisms have remained unclear to date. Using catechol O-methyltransferase (COMT as a model, we perform discrete molecular dynamics and computational docking simulations to elucidate the initial stages of cofactor binding. We find that COMT binds SAM via an induced-fit mechanism, where SAM adopts a different docking pose in the absence of metal and substrate in comparison to the holoenzyme. Flexible modeling of the active site side-chains is essential for observing the lowest energy state in the apoenzyme; rigid docking tools are unable to recapitulate the pose unless the appropriate side-chain conformations are given a priori. From our docking results, we hypothesize that the metal reorients SAM in a conformation suitable for donating its methyl substituent to the recipient ligand. The proposed mechanism enables a general understanding of how divalent metal cations contribute to methyltransferase function.

  14. Is catechol-o-methyltransferase gene polymorphism a risk factor in the development of premenstrual syndrome?

    Science.gov (United States)

    Deveci, Esma Ozturk; Selek, Salih; Camuzcuoglu, Aysun; Hilali, Nese Gul; Camuzcuoglu, Hakan; Erdal, Mehmet Emin; Vural, Mehmet

    2014-01-01

    Objective The objective of this study was to investigate whether there was a correlation between catechol-o-methyltransferase (COMT) gene polymorphism, which is believed to play a role in the etiology of psychotic disorders, and premenstrual syndrome (PMS). Methods Fifty-three women with regular menstrual cycles, aged between 18 and 46 years and diagnosed with PMS according to the American Congress of Obstetrics and Gynecology criteria were included in this study as the study group, and 53 healthy women having no health problems were selected as the controls. Venous blood was collected from all patients included in the study and kept at -18℃ prior to analysis. Results There was no significant difference between the groups in terms of demographic features such as age, body mass index, number of pregnancies, parity, and number of children. No statistically significant difference was observed in terms of COMT gene polymorphism (p=0.61) between women in the PMS and the control groups. However, a significant difference was found between arthralgia, which is an indicator of PMS, and low-enzyme activity COMT gene (Met/Met) polymorphism (p=0.04). Conclusion These results suggested that there was no significant relationship between PMS and COMT gene polymorphism. Since we could not find a direct correlation between the COMT gene polymorphism and PMS, further studies including alternative neurotransmitter pathways are needed to find an effective treatment for this disease. PMID:25045629

  15. Colloidal stability of iron oxide nanocrystals coated with a PEG-based tetra-catechol surfactant

    Science.gov (United States)

    Mondini, Sara; Drago, Carmelo; Ferretti, Anna M.; Puglisi, Alessandra; Ponti, Alessandro

    2013-03-01

    Long-term colloidal stability of magnetic iron oxide nanoparticles (NPs) is an important goal that has not yet been fully achieved. To make an advance in our understanding of the colloidal stability of iron oxide NPs in aqueous media, we prepared NPs comprising a monodisperse (13 nm) iron oxide core coated with a PEG-based (PEG: polyethyleneglycol) surfactant. This consists of a methoxy-terminated PEG chain (MW = 5000 Da) bearing four catechol groups via a diethylenetriamine linker. The surfactant was grafted onto the nanocrystals by ligand exchange monitored by infrared spectroscopy. The colloidal stability of these nanoparticles was probed by monitoring the time evolution of the Z-average intensity-weighted radius Rh and volume-weighted size distribution Pv obtained from analysis of dynamic light scattering data. The nanoparticles showed no sign of aggregation for four months in deionized water at room temperature and also when subjected to thermal cycling between 25 and 75 °C. In 0.01 M PBS (phosphate buffered saline), aggregation (if any) is slow and partial; after 66 h, about 50% of NPs have not aggregated. Aggregation is more effective in 0.15 M NH4AcO buffer, where isolated particles are not observed after 66 h, and especially in acidic NH4AcO/AcOH buffer, where aggregation is complete within 1 h and precipitation is observed. The differing stability of the NPs in the above aqueous media is closely related to their ζ potential.

  16. Effects of Catechol O-Methyl Transferase Inhibition on Anti-Inflammatory Activity of Luteolin Metabolites.

    Science.gov (United States)

    Ha, Sang Keun; Lee, Jin-Ah; Cho, Eun Jung; Choi, Inwook

    2017-02-01

    Although luteolin is known to have potent anti-inflammatory activities, much less information has been provided on such activities of its hepatic metabolites. Luteolin was subjected to hepatic metabolism in HepG2 cells either without or with catechol O-methyl transferase (COMT) inhibitor. To identify hepatic metabolites of luteolin without (luteolin metabolites, LMs) or with COMT inhibitor (LMs+CI), metabolites were treated by β-glucuronidase and sulfatase, and found that they were composed of glucuronide and sulfate conjugates of diosmetin in LMs or these conjugates of luteolin in LMs+CI. LMs and LMs+CI were examined for their anti-inflammatory activities on LPS stimulated Raw 264.7 cells. Expression of iNOS and production of nitric oxide and pro-inflammatory cytokines such as TNF-α, IL-1β, and IL-6 were suppressed more effectively by the treatment with LMs+CI than LMs. Our data provide a new insight on possible improvement in functional properties of luteolin on target cells by modifying their metabolic pathway in hepatocytes.

  17. Catechol-O-Methyltransferase Val158Met Polymorphism Is Associated with Somatosensory Amplification and Nocebo Responses

    Science.gov (United States)

    Benson, Sven; Engler, Harald; Engler, Andrea; Hinney, Anke; Rief, Winfried; Witzke, Oliver; Schedlowski, Manfred

    2014-01-01

    A large number of unwanted adverse events and symptoms reported by patients in clinical trials are not caused by the drug provided, since most of adverse events also occur in corresponding placebo groups. These nocebo effects also play a major role in drug discontinuation in clinical practice, negatively affecting treatment efficacy as well as patient adherence and compliance. Experimental and clinical data document a large interindividual variability in nocebo responses, however, data on psychological, biological or genetic predictors of nocebo responses are lacking. Thus, with an established paradigm of behaviorally conditioned immunosuppressive effects we analyzed possible genetic predictors for nocebo responses. We focused on the genetic polymorphisms in the catechol-O-methyltransferase (COMT) gene (Val158Met) and analyzed drug specific and general side effects before and after immunosuppressive medication and subsequent placebo intake in 62 healthy male subjects. Significantly more drug-specific as well as general side effects were reported from homozygous carriers of the Val158 variant during medication as well as placebo treatment compared to the other genotype groups. Val158/Val158 carriers also had significantly higher scores in the somatosensory amplification scale (SSAS) and the BMQ (beliefs about medicine questionnaire). Together these data demonstrate potential genetic and psychological variables predicting nocebo responses after drug and placebo intake, which might be utilized to minimize nocebo effects in clinical trials and medical practice. PMID:25222607

  18. Synthesis, Characterization, and Preliminary Investigation of Cell Interaction of Magnetic Nanoparticles with Catechol-Containing Shells

    Science.gov (United States)

    Wagner, Kerstin; Seemann, Thomas; Wyrwa, Ralf; Clement, Joachim H.; Müller, Robert; Nietzsche, Sandor; Schnabelrauch, Matthias

    2010-12-01

    Superparamagnetic iron oxide cores were synthesized by co-precipitation of Fe(II) and Fe(III) salts and subsequently stabilized by coating with different catechols (levodopa, dopamine, hydrocaffeic acid, dopamine-containing carboxymethyl dextran) known to act as high-affinity, bidentate ligands for Fe(III). The prepared stable magnetic fluids were characterized with regard to their chemical composition (content of iron and shell material, Fe(II)/Fe(III) ratio) and their physical properties (size, surface charge, magnetic parameters). The nanoparticles showed no or only slight cytotoxic effects within 1 and 4 days of incubation with 3T3 fibroblast cells. Preliminary experiments were performed to study the interaction of the prepared nanoparticles with human MCF-7 breast cancer cells and leukocytes. An intense interaction of the MCF-7 cells with these particles was found whereas the leukocytes showed a lower tendency of interaction. Based on these finding, the novel magnetic nanoparticles possess the potential for use in depletion of tumor cells from peripheral blood.

  19. Genetic variation in catechol-O-methyltransferase modifies effects of clonidine treatment in chronic fatigue syndrome.

    Science.gov (United States)

    Hall, K T; Kossowsky, J; Oberlander, T F; Kaptchuk, T J; Saul, J P; Wyller, V B; Fagermoen, E; Sulheim, D; Gjerstad, J; Winger, A; Mukamal, K J

    2016-10-01

    Clonidine, an α2-adrenergic receptor agonist, decreases circulating norepinephrine and epinephrine, attenuating sympathetic activity. Although catechol-O-methyltransferase (COMT) metabolizes catecholamines, main effectors of sympathetic function, COMT genetic variation effects on clonidine treatment are unknown. Chronic fatigue syndrome (CFS) is hypothesized to result in part from dysregulated sympathetic function. A candidate gene analysis of COMT rs4680 effects on clinical outcomes in the Norwegian Study of Chronic Fatigue Syndrome in Adolescents: Pathophysiology and Intervention Trial (NorCAPITAL), a randomized double-blinded clonidine versus placebo trial, was conducted (N=104). Patients homozygous for rs4680 high-activity allele randomized to clonidine took 2500 fewer steps compared with placebo (Pinteraction=0.04). There were no differences between clonidine and placebo among patients with COMT low-activity alleles. Similar gene-drug interactions were observed for sleep (Pinteraction=0.003) and quality of life (Pinteraction=0.018). Detrimental effects of clonidine in the subset of CFS patients homozygous for COMT high-activity allele warrant investigation of potential clonidine-COMT interaction effects in other conditions.

  20. Polymorphism of the catechol-O-methyltransferase gene in Han Chinese patients with psoriasis vulgaris

    Directory of Open Access Journals (Sweden)

    Lin Gao

    2009-01-01

    Full Text Available Psoriasis vulgaris is defined by a series of linked cellular changes in the skin: hyperplasia of epidermal keratinocytes, vascular hyperplasia and ectasia, and infiltration of T lymphocytes, neutrophils and other types of leukocytes in the affected skin. Catechol-O-methyltransferase ( COMT 158 polymorphism can reduce the activity of the COMT enzyme that may trigger defective differentiation of keratinocytes in psoriasis. Immunocytes can degrade and inactivate catecholamines via monamine oxidase (MAO and COMT in the cells. We hypothesized that the COMT-158 G > A polymorphism was associated with the risk of psoriasis vulgaris in Han Chinese people. In a hospital-based case-control study, 524 patients with psoriasis vulgaris and 549 psoriasis-free controls were studied. COMT-158 G > A polymorphism was genotyped using the PCR sequence-specific primer (PCR-SSP technique. We found no statistically significant association between the COMT-158 allele A and the risk of psoriasis vulgaris (p = 0.739 adjusted OR = 1.03; 95% CI = 0.81-1.31. This suggests that the COMT-158 G > A polymorphism may not contribute to the etiology of psoriasis vulgaris in the Han Chinese population.

  1. Catechol-O-methyltransferase promoter hypomethylation is associated with the risk of coronary heart disease.

    Science.gov (United States)

    Zhong, Jinyan; Chen, Xiaoying; Wu, Nan; Shen, Caijie; Cui, Hanbin; Du, Weiping; Zhang, Zhaoxia; Feng, Mingjun; Liu, Junsong; Lin, Shaoyi; Zhang, Lulu; Wang, Jian; Chen, Xiaomin; Duan, Shiwei

    2016-11-01

    Catechol-O-methyltransferase (COMT) gene variation is known to be associated with the risk of acute coronary events. The purpose of the present study was to investigate the contribution of COMT promoter methylation towards the risk of coronary heart disease (CHD). COMT methylation was evaluated in 48 CHD cases and 48 well-matched non-CHD controls using bisulfite pyrosequencing technology. The results demonstrated that CHD cases had a significantly lower level of methylation at COMT CpG3 sites compared with the controls (33.77±5.71 vs. 36.42±5.00%; P=0.018). Further analysis, according to gender, showed that CpG3 methylation was associated with CHD in males (P=0.038) but not in females (P=0.253), suggesting that there is a gender disparity in the association between COMT methylation and CHD. In conclusion, it was determined that COMT CpG3 hypomethylation is associated with an increased risk of CHD in males.

  2. Revisiting catechol derivatives as robust chromogenic hydrogen donors working in alkaline media for peroxidase mimetics.

    Science.gov (United States)

    Drozd, Marcin; Pietrzak, Mariusz; Pytlos, Jakub; Malinowska, Elżbieta

    2016-12-15

    Colloidal noble metal-based nanoparticles are able to catalyze oxidation of chromogenic substrates by H2O2, similarly to peroxidases, even in basic media. However, lack of robust chromogens, which work in high pH impedes their real applications. Herein we demonstrate the applicability of selected catechol derivatives: bromopyrogallol red (BPR) and pyrogallol (PG) as chromogenic substrates for peroxidase-like activity assays, which are capable of working over wide range of pH, covering also basic values. Hyperbranched polyglycidol-stabilized gold nanoparticles (HBPG@AuNPs) were used as model enzyme mimetics. Efficiency of several methods of improving stability of substrates in alkaline media by means of selective suppression of their autoxidation by molecular oxygen was evaluated. In a framework of presented studies the impact of borate anion, applied as complexing agent for PG and BPR, on their stability and reactivity towards oxidation mediated by catalytic AuNPs was investigated. The key role of high concentration of hydrogen peroxide in elimination of non-catalytic oxidation of PG and improvement of optical properties of BPR in alkaline media containing borate was underlined. Described methods of peroxidase-like activity characterization with the use of BPR and PG can become universal tools for characterization of nanozymes, which gain various applications, among others, they are used as catalytic labels in bioassays and biosensors.

  3. Genetic influences on insight problem solving: The role of catechol-o-methyltransferase (COMT gene polymorphisms

    Directory of Open Access Journals (Sweden)

    Weili eJiang

    2015-10-01

    Full Text Available People may experience an aha moment, when suddenly realizing a solution of a puzzling problem. This experience is called insight problem solving. Several findings suggest that catecholamine-related genes may contribute to insight problem solving, among which the catechol-o-methyltransferase (COMT gene is the most promising candidate. The current study examined 753 healthy individuals to determine the associations between 7 candidate single nucleotide polymorphisms on the COMT gene and insight problem-solving performance, while considering gender differences. The results showed that individuals carrying A allele of rs4680 or T allele of rs4633 scored significantly higher on insight problem-solving tasks, and the COMT gene rs5993883 combined with gender interacted with correct solutions of insight problems, specifically showing that this gene only influenced insight problem-solving performance in males. This study presents the first investigation of the genetic impact on insight problem solving and provides evidence that highlights the role that the COMT gene plays in insight problem solving.

  4. Hyaluronan/Tannic Acid Nanoparticles Via Catechol/Boronate Complexation as a Smart Antibacterial System.

    Science.gov (United States)

    Montanari, Elita; Gennari, Arianna; Pelliccia, Maria; Gourmel, Charlotte; Lallana, Enrique; Matricardi, Pietro; McBain, Andrew J; Tirelli, Nicola

    2016-12-01

    Nanoparticles based on hyaluronic acid (HA) are designed to deliver tannic acid (TA) as an antimicrobial agent. The presence of HA makes these particles potentially useful to target bacteria that colonize cells presenting HA membrane receptors (e.g. CD44), such as macrophages. HA bearing 3-aminophenyl boronic acid groups (HA-APBA) is reacted with TA, yielding nanoparticles with a size that decreases with decreasing HA molecular weight (e.g. 200 nm for 44 kDa, 400 nm for 737 kDa). The boronate esters make the nanoparticles stable at physiological pH, but their hydrolysis in an acidic environment (pH = 5) leads to swelling/solubilization, therefore potentially allowing TA release in endosomal compartments. We have assessed the nanoparticle toxicity profile (on RAW 264.7 macrophages) and their antimicrobial activity (on E. coli and on both methicillin-sensitive and -resistant S. aureus). The antibacterial effect of HA-APBA/TA nanoparticles was significantly higher than that of TA alone, and has very similar activity to TA coformulated with a reducing agent (ascorbic acid), which indicates both the nanoparticles to protect TA catechols from oxidation, and the effective release of TA after nanoparticle internalization. Therefore, there is potential for these nanoparticles to be used in stable, effective, and potentially targetable nanoparticle-based antimicrobial formulations.

  5. Development of fed-batch profiles for efficient biosynthesis of catechol-O-methyltransferase

    Directory of Open Access Journals (Sweden)

    G.M. Espírito Santo

    2014-09-01

    Full Text Available Catechol-O-methyltransferase (COMT, EC 2.1.1.6 plays a crucial role in dopamine metabolism which has intimately linked this enzyme to some neurodegenerative diseases, such as Parkinson's disease. In recent years, in the attempt of developing new therapeutic strategies for Parkinson's disease, there has been a growing interest in the search for effective COMT inhibitors. In order to do so, large amounts of COMT in an active form are needed, and the best way to achieve this is by up-scaling its production through biotechnological processes. In this work, a fed-batch process for the biosynthesis of the soluble isoform of COMT in Escherichia coli is proposed. This final process was selected through the evaluation of the effect of different dissolved oxygen concentrations, carbon and nitrogen source concentrations and feeding profiles on enzymatic production and cell viability, while controlling various parameters (pH, temperature, starting time of the feeding and induction phases and carbon source concentration during the process. After several batch and fed-batch experiments, a final specific COMT activity of 442.34 nmol/h/mg with approximately 80% of viable cells at the end of the fermentation were achieved. Overall, the results described herein provide a great improvement on hSCOMT production in recombinant bacteria and provide a new and viable option for the use of a fed-batch fermentation with a constant feeding profile to the large scale production of this enzyme.

  6. Catechol-O-methyltransferase, a new target for pancreatic cancer therapy

    Science.gov (United States)

    Wu, Wenming; Wu, Qiao; Hong, Xiafei; Zhou, Li; Zhang, Jie; You, Lei; Wang, Wenze; Wu, Huanwen; Dai, Hongmei; Zhao, Yupei

    2015-01-01

    Catechol-O-methyltransferase (COMT) is an important molecule in different types of cancers. Its biological effect and therapeutic significance, however, rarely been investigated fully in pancreatic cancer. Immunohistologically, high COMT expression was significantly correlated with the longer overall survival of patients (P < 0.05), indicating its protective nature. The effects of COMT on cell growth, apoptosis, and invasion were evaluated using overexpression and silencing methods. In detail, we carried out experiments using one stably transduced and two transiently transfected pancreatic cancer cell lines in vitro, and one stably transduced cell line in vivo mice xenograft models. In vitro experiments showed that COMT inhibited cell proliferation, enhanced gemcitabine-induced apoptosis, and inhibited cell invasion in stably transduced and transiently transfected cell lines by regulating the PI3K/Akt pathway, p53, and E-cadherin. The COMT overexpressed and silenced cell lines showed significantly inhibited and enhanced growth capacities in in vivo xenograft models, respectively. In conclusion, COMT suppressed pancreatic cancer and its high expression predicted longer survival time. The interaction of COMT with the PI3K/Akt pathway makes it a potential target for therapy. PMID:25711924

  7. Laccase Biosensor Based on Electrospun Copper/Carbon Composite Nanofibers for Catechol Detection

    Science.gov (United States)

    Fu, Jiapeng; Qiao, Hui; Li, Dawei; Luo, Lei; Chen, Ke; Wei, Qufu

    2014-01-01

    The study compared the biosensing properties of laccase biosensors based on carbon nanofibers (CNFs) and copper/carbon composite nanofibers (Cu/CNFs). The two kinds of nanofibers were prepared by electrospinning and carbonization under the same conditions. Scanning electron microscopy (SEM), X-ray diffraction (XRD) and Raman spectroscopy were employed to investigate the morphologies and structures of CNFs and Cu/CNFs. The amperometric results indicated that the Cu/CNFs/laccase(Lac)/Nafion/glass carbon electrode (GCE) possessed reliable analytical performance for the detection of catechol. The sensitivity of the Cu/CNFs/Lac/Nafion/GCE reached 33.1 μA/mM, larger than that of CNFs/Lac/Nafion/GCE. Meanwhile, Cu/CNFs/Lac/Nafion/GCE had a wider linear range from 9.95 × 10−6 to 9.76 × 10−3 M and a lower detection limit of 1.18 μM than CNFs/Lac/Nafion/GCE. Moreover, it exhibited a good repeatability, reproducibility, selectivity and long-term stability, revealing that electrospun Cu/CNFs have great potential in biosensing. PMID:24561403

  8. Catechol-O-methyltransferase Val158Met polymorphism is associated with somatosensory amplification and nocebo responses.

    Directory of Open Access Journals (Sweden)

    Laura Wendt

    Full Text Available A large number of unwanted adverse events and symptoms reported by patients in clinical trials are not caused by the drug provided, since most of adverse events also occur in corresponding placebo groups. These nocebo effects also play a major role in drug discontinuation in clinical practice, negatively affecting treatment efficacy as well as patient adherence and compliance. Experimental and clinical data document a large interindividual variability in nocebo responses, however, data on psychological, biological or genetic predictors of nocebo responses are lacking. Thus, with an established paradigm of behaviorally conditioned immunosuppressive effects we analyzed possible genetic predictors for nocebo responses. We focused on the genetic polymorphisms in the catechol-O-methyltransferase (COMT gene (Val158Met and analyzed drug specific and general side effects before and after immunosuppressive medication and subsequent placebo intake in 62 healthy male subjects. Significantly more drug-specific as well as general side effects were reported from homozygous carriers of the Val158 variant during medication as well as placebo treatment compared to the other genotype groups. Val158/Val158 carriers also had significantly higher scores in the somatosensory amplification scale (SSAS and the BMQ (beliefs about medicine questionnaire. Together these data demonstrate potential genetic and psychological variables predicting nocebo responses after drug and placebo intake, which might be utilized to minimize nocebo effects in clinical trials and medical practice.

  9. Catechol-O-methyltransferase (COMT) gene modulates private self-consciousness and self-flexibility.

    Science.gov (United States)

    Wang, Bei; Ru, Wenzhao; Yang, Xing; Yang, Lu; Fang, Pengpeng; Zhu, Xu; Shen, Guomin; Gao, Xiaocai; Gong, Pingyuan

    2016-08-01

    Dopamine levels in the brain influence human consciousness. Inspired by the role of Catechol-O-methyltransferase (COMT) in inactivating dopamine in the brain, we investigated to what extent COMT could modulate individual's self-consciousness dispositions and self-consistency by genotyping the COMT Val158Met (rs4680) polymorphism and measuring self-consciousness and self-consistency and congruence in a college student population. The results indicated that COMT Val158Met polymorphism significantly modulated the private self-consciousness. The individuals with Val/Val genotype, corresponding to lower dopamine levels in the brain, were more likely to be aware of their feelings and beliefs. The results also indicated that this polymorphism modulated one's self-flexibility. The individuals with Val/Val genotype showed higher levels of stereotype in self-concept compared with those with Met/Met genotype. These findings suggest that COMT is a predictor of the individual differences in self-consciousness and self-flexibility.

  10. Catechol-O-methyltransferase val(158)met Polymorphism Interacts with Sex to Affect Face Recognition Ability.

    Science.gov (United States)

    Lamb, Yvette N; McKay, Nicole S; Singh, Shrimal S; Waldie, Karen E; Kirk, Ian J

    2016-01-01

    The catechol-O-methyltransferase (COMT) val158met polymorphism affects the breakdown of synaptic dopamine. Consequently, this polymorphism has been associated with a variety of neurophysiological and behavioral outcomes. Some of the effects have been found to be sex-specific and it appears estrogen may act to down-regulate the activity of the COMT enzyme. The dopaminergic system has been implicated in face recognition, a form of cognition for which a female advantage has typically been reported. This study aimed to investigate potential joint effects of sex and COMT genotype on face recognition. A sample of 142 university students was genotyped and assessed using the Faces I subtest of the Wechsler Memory Scale - Third Edition (WMS-III). A significant two-way interaction between sex and COMT genotype on face recognition performance was found. Of the male participants, COMT val homozygotes and heterozygotes had significantly lower scores than met homozygotes. Scores did not differ between genotypes for female participants. While male val homozygotes had significantly lower scores than female val homozygotes, no sex differences were observed in the heterozygotes and met homozygotes. This study contributes to the accumulating literature documenting sex-specific effects of the COMT polymorphism by demonstrating a COMT-sex interaction for face recognition, and is consistent with a role for dopamine in face recognition.

  11. STUDY ON THE COPOLYMERIC COATING OF TERPENE-CATECHOL WITH RAW LACQUER(Ⅰ)--Synthesis of terpene-catechol functional resin and its separation from terpene resin%萜烯邻苯二酚树脂-生漆共聚涂料研究(Ⅰ)--萜烯-邻苯二酚功能基树脂的分离提纯

    Institute of Scientific and Technical Information of China (English)

    雷福厚; 蓝虹云; 姚兴东; 蒙晓波; 安鑫南

    2005-01-01

    以萜烯树脂和邻苯二酚为原料,合成了萜烯-邻苯二酚树脂.采用柱层析法分离萜烯树脂和萜烯-邻苯二酚树脂,分别采用中性氧化铝和强碱性阴离子交换树脂作固定相,汽油、乙醇、NaOH-乙醇溶液作洗脱剂对萜烯树脂和萜烯-邻苯二酚树脂进行分离提纯.通过对洗脱液进行紫外光谱分析,表明用中性氧化铝作固定相,分别用汽油、乙醇和NaOH-乙醇溶液洗脱,能较好地分离萜烯树脂和萜烯-邻苯二酚树脂.%Synthesis of terpene-catechol resin from terpene resin and catechol was reported in this paper.Results showed that terpene-catechol resin could be synthesized directly with the proposed method.The synthesized terpene-catechol resin could be separated from terpene resin and catechol on neutral alumina column with petroleum,absolute ethanol and 5% NaOH-ethanol solution as eluates.Anion exchange resin was not suitable for the separation as stationary phase due to the strong adsorption toward catechol.The chemicals of eluates were measured by UV and IR.Terpene-catechol resin can be used for preparing copolymeric coating from terpene-catechol resin with raw lacquer.

  12. THE RELATION OF CHEMICAL STRUCTURE IN CATECHOL COMPOUNDS AND DERIVATIVES TO POISON IVY HYPERSENSITIVENESS IN MAN AS SHOWN BY THE PATCH TEST.

    Science.gov (United States)

    Keil, H; Wasserman, D; Dawson, C R

    1944-10-01

    1. Additional evidence is presented in support of the view which postulates a close chemical and biologic relation between the active ingredients in poison ivy and Japan lac. 2. Biologic evidence, based on the use of the patch test in man, is presented in support of the view that the active ingredient in poison ivy is a catechol derivative with a long, unsaturated side-chain in the 3-position. 3. Of the catechol compounds and derivatives studied, group reactions in patients sensitive to poison ivy leaves or extract were exhibited by the following compounds: 3-pentadecyl catechol (100 per cent of 21 cases), 4-pentadecyl catechol (38 per cent of 21 cases), "urushiol" dimethyl ether (33 per cent of 33 cases), 3-pentadecenyl-1'-veratrole (21 per cent of 14 cases), 3-methyl catechol (14 per cent of 21 cases), and hydrourushiol dimethyl ether (10 per cent of 20 cases). It has been found that 3-geranyl catechol shows a practically constant group reactivity in persons sensitive to poison ivy. 4. The uniformly positive group reaction to 3-pentadecyl catechol is notable since this substance possesses a saturated side-chain, whereas the active ingredient in poison ivy is known to have an unsaturated side-chain. 5. The group reactivity was not restricted to the 3-position, for in some instances 4-pentadecyl catechol also gave group reactions which, however, were less intense and less frequent than those shown by 3-pentadecyl catechol. This indicates that in some cases a long side-chain in the 4 position may be effective in producing group specific reactions. 6. Only an occasional person showed sensitiveness to 3-methyl catechol (short side-chain), and in one instance the group reactivity appeared to be specific for the 3-position. 7. The position of the side-chain in the catechol configuration has some bearing on the degree and incidence of group reactions in persons hypersensitive to poison ivy. 8. Evidence is presented to indicate that the introduction of double bonds in the

  13. Metabolism of (/sup 3/H)noradrenaline in different compartments of rat brain with respect to the role of catechol-O-methyltransferase

    Energy Technology Data Exchange (ETDEWEB)

    Koester, G.; Goede, E.; Breuer, H.

    1984-03-01

    Rats were pretreated with either reserpine or desmethylimipramine, either alone or in combination with tropolone. At either 10 min or 1 h after the intraventricular injection of (/sup 3/H)noradrenaline, in several brain regions the complete metabolic patterns were determined: normetanephrine; the glycol metabolites (methylated and nonmethylated) and their sulfate conjugates; and the acidic metabolites (methylated and non-methylated). A reserpine-induced increase in the turnover of (/sup 3/H)noradrenaline caused a transient increase of the catechol glycol followed by elevated levels of the two glycol sulfates. The stimulated (/sup 3/H)noradrenaline turnover if achieved by desmethylimipramine caused a transient increase of normetanephrine and initially lowered values of catechol glycols (both free and sulfated), which were followed by elevated levels. Drug-pretreated rats compensated for the inhibition of catechol-O-methyl-transferase by tropolone in different ways: Reserpine caused an early increase of the catechol glycol beyond the measurements in other treatment groups, whereas desmethylimipramine increased the nonmethylated carboxylic acid and glycol sulfates rather slowly to levels beyond those of other groups. The results support the existence of two compartments with a fast metabolism (an intraneuronal monoamine oxidase compartment and an extraneuronal catechol-O-methyltransferase compartment). In addition, there seems to exist another extra-neuronal space with a slow, monoamine oxidase-dependent noradrenaline turnover.

  14. Catechol estrogen formation and metabolism in brain tissue: comparison of tritium release from different positions in ring A of the steroid

    Energy Technology Data Exchange (ETDEWEB)

    Jellinck, P.H.; Hahn, E.F.; Norton, B.I.; Fishman, J.

    1984-11-01

    Catechol estrogens labeled with /sup 3/H at different positions in rings A and B of the steroid were synthesized by chemical or enzymatic methods, and their oxidative transformation by male rat brain microsomes was followed by the transfer of /sup 3/H into /sup 3/H/sub 2/O. This reaction was shown to occur more readily with the catechol estrogens than with the parent steroid and was also influenced by the position of the radiolabel. Tritium was displaced less readily from C-1 than from C-2 or C-4 of the aromatic ring. Spermine, which is known to increase cytochrome P-450-mediated hydroxylation reactions, had no effect on the release of /sup 3/H from ring A of either estradiol or 2-hydroxyestradiol with rat brain microsomes in contrast to liver. Glutathione and other thiols were able to cause a rapid loss of /sup 3/H from labeled catechol estrogens, even in the absence of tissue, but in double label experiments with (4-/sup 3/H)- and (4-/sup 14/C)2-hydroxyestradiol, the isotope ratio in the recovered catechol estrogen was unchanged. The results illustrate some of the problems in determining accurately the metabolism of estrogens by measuring /sup 3/H/sub 2/O formation when aromatic hydroxylation is involved and also highlight the possible interaction of the catechol estrogens with cellular nucleophiles such as glutathione.

  15. Polymer pendant ligand chemistry. 3. A biomimetic approach to selective metal ion removal and recovery from aqueous solution with polymer-supported sulfonated catechol and linear catechol amide ligands

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Song-Ping; Li, Wei; Franz, K.J.; Albright, R.L.; Fish, R.H. [Univ. of California, Berkeley, CA (United States)

    1995-05-24

    The design of organic ligands to selectively remove and recover metal ions from aqueous solution is a new and important area of environmental inorganic chemistry. One approach to designing organic ligands for these purposes is to use biological systems as examples for selective metal ion complexation. Thus, the authors report results on the synthesis of several biomimetically important polymer-supported, sulfonated catechol (PS-CATS), sulfonated bis(catechol) linear amide (PS-2-6-LICAMS), and sulfonated 3.3-linear tris(catechol) amide (PS-3,3-LICAMS) ligands that are chemically bonded to modified 6% cross-linked macroporous polystyrene-divinylbenzene beads (PS-DVB) for selective removal and recovery of environmentally and economically important metal ions from aqueous solution, as a function of pH. The Fe{sup 3+} ion selectivity was dramatically shown for PS-CATS, PS-2-6-LICAMS and PS-3,3-LICAMS polymer beads in competition with a similar concentration of Cu{sup 2+}, Zn{sup 2+}, Mn{sup 2+}, Ni{sup 2+}, Mg{sup 2+}, Al{sup 3+}, and Cr{sup 3+} ions at pH 1-3, while metal ion selectivity could be changed at higher pH values in the absence of Fe{sup 3+} (for example, Hg{sup 2+} at pH 3). Rates of removal and recovery of the Fe{sup 3+} ion with the PS-CATS, PS-2-6LICAMS and PS-3,3-LICAMS polymer beads were also studied as well as relative equilibrium selectivity coefficient (K{sub m}) values for all metal competition studies.

  16. The Role of Human Aldo-Keto Reductases in the Metabolic Activation and Detoxication of Polycyclic Aromatic Hydrocarbons: Interconversion of PAH Catechols and PAH o-Quinones.

    Science.gov (United States)

    Zhang, Li; Jin, Yi; Huang, Meng; Penning, Trevor M

    2012-01-01

    Polycyclic aromatic hydrocarbons (PAH) are ubiquitous environmental pollutants. They are procarcinogens requiring metabolic activation to elicit their deleterious effects. Aldo-keto reductases (AKR) catalyze the oxidation of proximate carcinogenic PAH trans-dihydrodiols to yield electrophilic and redox-active PAH o-quinones. AKRs are also found to be capable of reducing PAH o-quinones to form PAH catechols. The interconversion of o-quinones and catechols results in the redox-cycling of PAH o-quinones to give rise to the generation of reactive oxygen species and subsequent oxidative DNA damage. On the other hand, PAH catechols can be intercepted through phase II metabolism by which PAH o-quinones could be detoxified and eliminated. The aim of the present review is to summarize the role of human AKRs in the metabolic activation/detoxication of PAH and the relevance of phase II conjugation reactions to human lung carcinogenesis.

  17. Catechol as an efficient anchoring group for attachment of ruthenium-poly-pyridine photo-sensitizers to solar cells based on nanocrystalline TiO{sub 2} films

    Energy Technology Data Exchange (ETDEWEB)

    Rice, C.R.; Ward, M.D. [Bristol Univ., School of Chemistry (United Kingdom); Nazeeruddin, M.K.; Gratzel, M. [Institute of Physical Chemistry, Institute of Technology, Lab. for Photonics and Interfaces, Lausanne (Switzerland). Swiss Federal

    2000-09-01

    The Ru(II)-poly-pyridyl complexes [Ru(H{sub 2}L)(terpy)][PF{sub 6}]{sub 2} (1) and [Bu{sub 4}N] [Ru(H{sub 2}L)(NCS){sub 3}] (2) (H{sub 2}L = 4'-(3,4-4-di-hydroxy-phenyl)-2,2': 6',2''-ter-pyridine), in which H{sub 2}L is coordinated as a ter-pyridyl fragment with a catechol site pendant from the C4' position, adhere effectively to nanocrystalline TiO{sub 2} (anatase) surfaces via the pendant catechol group; incident photon-to-current conversion efficiency values of up to 50% were obtained in their photocurrent action spectra, suggesting that the catechol unit may be a convenient and effective anchoring group for attaching dyes to TiO{sub 2}-based photovoltaic cells. (authors)

  18. Electroceramics from source materials via molecular intermediates; BaTiO sub 3 from TiO sub 2 via (Ti(catecholate) sub 3 ) sup 2 minus

    Energy Technology Data Exchange (ETDEWEB)

    Davies, J.A.; Dutremez, S. (Toledo Univ., OH (USA). Dept. of Chemistry)

    1990-05-01

    Rutile or anatase may be depolymerized and complexed by sequential treatment with H{sub 2}SO{sub 4}/(NH{sub 4}){sub 2}SO{sub 4}, H{sub 2}O, and catechol/NH{sub 4}OH to produce the intermediate (NH{sub 4}){sub 2}(Ti(catecholate){sub 3}) {center dot} 2H{sub 2}O. Treatment with Ba(OH){sub 2} {center dot} 8H{sub 2}O leads to an acid-base reaction generating Ba(Ti(catecholate){sub 3}) {center dot} 3H{sub 2}O, in which the Ba:Ti ratio is held at 1:1 at the molecular level. Calcination produces BaTiO{sub 3} powder.

  19. A Novel Catechol-O-Methyltransferase Variant Associated with Human Disc Degeneration

    Science.gov (United States)

    Gruber, Helen E.; Sha, Wei; Brouwer, Cory R.; Steuerwald, Nury; Hoelscher, Gretchen L.; Hanley, Edward N. Jr.

    2014-01-01

    Background: Disc degeneration and its associated low back pain are a major health care concern causing disability with a prominent role in this country's medical, social and economic structure. Low back pain is devastating and influences the quality of life for millions. Low back pain lifetime prevalence approximates 80% with an estimated direct cost burden of $86 billion per year. Back pain patients incur higher costs, greater health care utilization, and greater work loss than patients without back pain. Methods: Research was performed following approval of our Institutional Review Board. DNA was isolated, processed and amplified using routine techniques. Amplified DNA was hybridized to Affymetrix Genome-Wide Human SNP Arrays. Quality control and genotyping analysis were performed using Affymetrix Genotyping Console. The Birdseed v2 algorithm was used for genotyping analysis. 2589 SNPs were selected a priori to enter statistical analysis using lotistic regression in SAS. Results: Our objective was to search for novel single nucleotide polymorphisms (SNPs) associated with disc degeneration. Four SNPs were found to have a significant relationship to disc degeneration; three are novel. Rs165656, a new SNP found to be associated with disc degeneration, was in catechol-O-methyltransferase (COMT), a gene with well-recognized pain involvement, especially in female subjects (p=0.01). Analysis confirmed the previously association between COMT SNP rs4633 and disc degeneration. We also report two novel disc degeneration-related SNPs (rs2095019 and rs470859) located in intergenic regions upstream to thrombospondin 2. Conclusions: Findings contribute to the challenging field of disc degeneration and pain, and are important in light of the high clinical relevance of low back pain and the need for improved understanding of its fundamental basis. PMID:24904231

  20. Genetic Polymorphisms of Catechol-O-Methyltransferase Modify the Neurobehavioral Effects of Mercury in Children

    Science.gov (United States)

    Woods, James S.; Heyer, Nicholas J.; Russo, Joan E.; Martin, Michael D.; Pillai, Pradeep B.; Bammler, Theodor K.; Farin, Federico M.

    2014-01-01

    Mercury (Hg) is neurotoxic and children may be particularly susceptible to this effect. A current major challenge is identification of children who may be uniquely susceptible to Hg toxicity because of genetic disposition. This study examined the hypothesis that genetic variants of catechol-O-methyltransferase (COMT) that are reported to alter neurobehavioral functions that are also affected by Hg in adults might modify the adverse neurobehavioral effects of Hg exposure in children. Five hundred and seven children, 8–12 yr of age at baseline, participated in a clinical trial to evaluate the neurobehavioral effects of Hg from dental amalgam tooth fillings. Subjects were evaluated at baseline and at seven subsequent annual intervals for neurobehavioral performance and urinary Hg levels. Following the clinical trial, genotyping assays were performed for single-nucleotide polymorphisms (SNPs) of COMT rs4680, rs4633, rs4818, and rs6269 on biological samples provided by 330 of the trial participants. Regression-modeling strategies were employed to evaluate associations between allelic status, Hg exposure, and neurobehavioral test outcomes. Similar analysis was performed using haplotypes of COMT SNPs. Among girls, few interactions for Hg exposure and COMT variants were found. In contrast, among boys, numerous gene–Hg interactions were observed between individual COMT SNPs, as well as with a common COMT haplotype affecting multiple domains of neurobehavioral function. These findings suggest increased susceptibility to the adverse neurobehavioral effects of Hg among children with common genetic variants of COMT, and may have important implications for strategies aimed at protecting children from the potential health risks associated with Hg exposure. PMID:24593143

  1. How metal substitution affects the enzymatic activity of catechol-o-methyltransferase.

    Directory of Open Access Journals (Sweden)

    Manuel Sparta

    Full Text Available Catechol-O-methyltransferase (COMT degrades catecholamines, such as dopamine and epinephrine, by methylating them in the presence of a divalent metal cation (usually Mg(II, and S-adenosyl-L-methionine. The enzymatic activity of COMT is known to be vitally dependent on the nature of the bound metal: replacement of Mg(II with Ca(II leads to a complete deactivation of COMT; Fe(II is slightly less than potent Mg(II, and Fe(III is again an inhibitor. Considering the fairly modest role that the metal plays in the catalyzed reaction, this dependence is puzzling, and to date remains an enigma. Using a quantum mechanical / molecular mechanical dynamics method for extensive sampling of protein structure, and first principle quantum mechanical calculations for the subsequent mechanistic study, we explicate the effect of metal substitution on the rate determining step in the catalytic cycle of COMT, the methyl transfer. In full accord with experimental data, Mg(II bound to COMT is the most potent of the studied cations and it is closely followed by Fe(II, whereas Fe(III is unable to promote catalysis. In the case of Ca(II, a repacking of the protein binding site is observed, leading to a significant increase in the activation barrier and higher energy of reaction. Importantly, the origin of the effect of metal substitution is different for different metals: for Fe(III it is the electronic effect, whereas in the case of Ca(II it is instead the effect of suboptimal protein structure.

  2. Determination of catechin in green tea using a catechol oxidase biomimetic sensor

    Energy Technology Data Exchange (ETDEWEB)

    Fernandes, Suellen C.; Osorio, Renata El-Hage M. de Barros; Anjos, Ademir dos; Neves, Ademir; Micke, Gustavo Amadeu; Vieira, Iolanda C. [Universidade Federal de Santa Catarina (UFSC), Florianopolis, SC (Brazil). Dept. de Quimica]. E-mail: iolanda@qmc.ufsc.br

    2008-07-01

    A catechol oxidase biomimetic sensor, based on a novel copper(II) complex, was developed for the determination of catechin in green tea and the results were compared with those obtained by capillary electrophoresis. The dinuclear copper(II) complex, [Cu{sub 2}(HL)({mu}-CH{sub 3}COO)](ClO{sub 4}), containing the ligand N,N-[bis-(2-pyridylmethyl)]-N',N'-[(2-hydroxybenzyl)(2-hydroxy-3,5-di-tert - butylbenzyl)]-1,3-propanediamine-2-ol (H{sub 3}L), was synthesized and characterized by IR, {sup 1}H NMR and elemental analysis. The best conditions for the optimization of the biomimetic sensor were established by square wave voltammetry. The best performance for this sensor was obtained in 75:15:10% (m/m/m) of the graphite powder:nujol:copper(II) complex, 0.05 mol L{sup -1} phosphate buffer solution (pH 7.5) and frequency, pulse amplitude, scan increment at 30 Hz, 80 mV, 3.3 mV, respectively. The analytical curve was linear in the concentration range 4.95 x 10{sup -6} to 3.27 x 10{sup -5} mol L{sup -1} (r = 0.9993) with a detection limit of 2.8 x 10{sup -7} mol L{sup -1}. This biomimetic sensor demonstrated long-term stability (9 months; 800 determinations) and reproducibility with a relative standard deviation of 3.5%. The recovery of catechin from green tea samples ranged from 93.8 to 106.9% and the determination, compared with that obtained using capillary electrophoresis, was found to be acceptable at the 95% confidence level. (author)

  3. Catechol-O-methyltransferase Val158Met polymorphism influences prefrontal executive function in early Parkinson's disease.

    Science.gov (United States)

    Zhang, Youwen; Feng, Shujun; Nie, Kun; Zhao, Xin; Gan, Rong; Wang, Limin; Zhao, Jiehao; Tang, Hongmei; Gao, Liang; Zhu, Ruiming; Wang, Lijuan; Zhang, Yuhu

    2016-10-15

    The catechol-O-methyltransferase (COMT) Val158Met polymorphism has been proposed to be associated with increased risk of Parkinson's disease (PD) and have a specific impact on dopamine-mediated prefrontal executive function in an inverted-U curve manner. We explored the influence of this genetic polymorphism on prefrontal executive function in a well-established Chinese cohort of early PD patients with no current or past history of motor fluctuations or dyskinesias. Cognitive functions were assessed in 250 patients with early PD using Wechsler Adult Intelligence Scale-Chinese Revision (WAIS-RC) and Wechsler Memory Scale-Chinese Revision (WMS-RC). These patients and 300 healthy controls were subsequently genotyped for the COMT gene Val158Met polymorphism. We employed analysis of covariance (ANCOVA) and a stratified analysis to determine the associations between the COMT Val158Met genotype and cognitive functions. The COMT Val158Met allele frequency and genotype distributions showed no statistically significant differences between PD patients and controls. However, patients with met/met genotype performed significantly worse on WAIS-RC similarities, a measure of executive function, compared to individuals with val/val genotype. Subsequent ANCOVA analysis revealed that COMT genotype interacted with sex and daily levodopa equivalent dose (LED) to influence executive function. Further stratified analysis showed that the lower-activity COMT met/met genotype has a detrimental effect on executive function among women. Our results demonstrate that COMT Val158Met polymorphism is probably not associated with increased risk of PD, but has an effect on prefrontal executive function interacting with gender and dopaminergic medication. Copyright © 2016. Published by Elsevier B.V.

  4. Influence of catechol-O-methyltransferase (COMT) gene polymorphisms in pain sensibility of Brazilian fibromialgia patients.

    Science.gov (United States)

    Barbosa, Flávia Regina; Matsuda, Josie Budag; Mazucato, Mendelson; de Castro França, Suzelei; Zingaretti, Sônia Marli; da Silva, Lucienir Maria; Martinez-Rossi, Nilce Maria; Júnior, Milton Faria; Marins, Mozart; Fachin, Ana Lúcia

    2012-02-01

    Fibromyalgia syndrome (FS) is a rheumatic syndrome affecting to 2-3% of individuals of productive age, mainly women. Neuroendocrine and genetic factors may play a significant role in development of the disease which is characterized by diffuse chronic pain and presence of tender points. Several studies have suggested an association between FS, especially pain sensitivity, and polymorphism of the catechol-O-methyltransferase (COMT) gene. The aim of the present study was to characterize the SNPs rs4680 and rs4818 of the COMT gene and assess its influence in pain sensitivity of patients with fibromyalgia screened by the Fibromyalgia Impact Questionnaire (FIQ). DNA was extracted from peripheral blood of 112 patients with fibromyalgia and 110 healthy individuals and was used as template in PCR for amplification of a 185-bp fragment of the COMT gene. The amplified fragment was sequenced for analyses of the SNPs rs4680 and rs4818. The frequency of mutant genotype AA of SNP rs6860 was 77.67% in patients with FS and 28.18% for the control group. For the SNP rs4818, the frequency of mutant genotype CC was 73.21 and 39.09% for patients with FS and controls, respectively. Moreover, the FIQ score was higher in patients with the homozygous mutant genotype for SNPs rs4680 (87.92 points) and rs4818 (86.14 points). These results suggest that SNPs rs4680 and rs4818 of the COMT gene may be associated with fibromyalgia and pain sensitivity in FS Brazilian patients.

  5. Catechol O-methyltransferase and monoamine oxidase A genotypes, and plasma catecholamine metabolites in bipolar and schizophrenic patients.

    Science.gov (United States)

    Zumárraga, Mercedes; Dávila, Ricardo; Basterreche, Nieves; Arrue, Aurora; Goienetxea, Biotza; Zamalloa, María I; Erkoreka, Leire; Bustamante, Sonia; Inchausti, Lucía; González-Torres, Miguel A; Guimón, José

    2010-01-01

    Metabolites of dopamine and norepinephrine measured in the plasma have long been associated with symptomatic severity and response to treatment in schizophrenic, bipolar and other psychiatric patients. Plasma concentrations of catecholamine metabolites are genetically regulated. The genes encoding enzymes that are involved in the synthesis and degradation of these monoamines are candidate targets for this genetic regulation. We have studied the relationship between the Val158Met polymorphism in catechol O-methyltransferase gene, variable tandem repeat polymorphisms in the monoamine oxidase A gene promoter, and plasma concentrations of 3-methoxy-4-hydroxyphenylglycol, 3,4-dihydroxyphenylacetic acid and homovanillic acid in healthy control subjects as well as in untreated schizophrenic and bipolar patients. We found that the Val158Met substitution in catechol O-methyltransferase gene influences the plasma concentrations of homovanillic and 3,4-dihydroxyphenylacetic acids. Although higher concentrations of plasma homovanillic acid were found in the high-activity ValVal genotype, this mutation did not affect the plasma concentration of 3-methoxy-4-hydroxyphenylglycol. 3,4-dihydroxyphenylacetic acid concentrations were higher in the low-activity MetMet genotype. Interestingly, plasma values 3-methoxy-4-hydroxyphenylglycol were greater in schizophrenic patients and in bipolar patients than in healthy controls. Our results are compatible with the previously reported effect of the Val158Met polymorphism on catechol O-methyltransferase enzymatic activity. Thus, our results suggest that this polymorphism, alone or associated with other polymorphisms, could have an important role in the genetic control of monoamine concentration and its metabolites.

  6. The effects of oxygen on the yields of the thermal decomposition products of catechol under pyrolysis and fuel-rich oxidation conditions

    Energy Technology Data Exchange (ETDEWEB)

    Shiju Thomas; Elmer B. Ledesma; Mary J. Wornat [Louisiana State University, Baton Rouge, LA (United States). Department of Chemical Engineering

    2007-11-15

    In order to investigate the effects of oxygen on the distribution of thermal decomposition products from complex solid fuels, pyrolysis and fuel-rich oxidation experiments have been performed in an isothermal laminar-flow reactor, using the model fuel catechol (ortho-dihydroxybenzene), a phenol-type compound representative of structural entities in coal, wood, and biomass. The gas-phase catechol pyrolysis experiments are conducted at a residence time of 0.3 s, over a temperature range of 500-1000{sup o}C, and at oxygen ratios ranging from 0 (pure pyrolysis) to 0.92 (near stoichiometric oxidation). The pyrolysis products are analyzed by nondispersive infrared analysis and by gas chromatography with flame-ionization and mass spectrometric detection. In addition to an abundance of polycyclic aromatic hydrocarbons, catechol pyrolysis and fuel-rich oxidation produce a range of C1-C5 light hydrocarbons as well as single-ring aromatics. Quantification of the products reveals that the major products are CO, acetylene, 1,3-butadiene, phenol, benzene, vinylacetylene, ethylene, methane, cyclopentadiene, styrene, and phenylacetylene; minor products are ethane, propyne, propadiene, propylene and toluene. Under oxidative conditions, CO{sub 2} is also produced. At temperatures {lt}850{sup o}C, increases in oxygen concentration bring about increases in catechol conversion and yields of C1-C5 and single-ring aromatic products in accordance with increased rates of pyrolytic reactions, due to the enhanced free-radical pool. At temperatures {gt}850{sup o}C, catechol conversion is complete, and increases in oxygen bring about drastic decreases in the yields of virtually all hydrocarbon products, as oxidative destruction reactions dominate. Reactions responsible for the formation of the C1-C5 and single-ring aromatic products from catechol, under pyrolytic and oxidative conditions, are discussed. 74 refs., 22 figs., 1 tab.

  7. Inhibition of DNA methylation by caffeic acid and chlorogenic acid, two common catechol-containing coffee polyphenols.

    Science.gov (United States)

    Lee, Won Jun; Zhu, Bao Ting

    2006-02-01

    We studied the modulating effects of caffeic acid and chlorogenic acid (two common coffee polyphenols) on the in vitro methylation of synthetic DNA substrates and also on the methylation status of the promoter region of a representative gene in two human cancer cells lines. Under conditions that were suitable for the in vitro enzymatic methylation of DNA and dietary catechols, we found that the presence of caffeic acid or chlorogenic acid inhibited in a concentration-dependent manner the DNA methylation catalyzed by prokaryotic M.SssI DNA methyltransferase (DNMT) and human DNMT1. The IC50 values of caffeic acid and chlorogenic acid were 3.0 and 0.75 microM, respectively, for the inhibition of M.SssI DNMT-mediated DNA methylation, and were 2.3 and 0.9 microM, respectively, for the inhibition of human DNMT1-mediated DNA methylation. The maximal in vitro inhibition of DNA methylation was approximately 80% when the highest concentration (20 microM) of caffeic acid or chlorogenic acid was tested. Kinetic analyses showed that DNA methylation catalyzed by M.SssI DNMT or human DNMT1 followed the Michaelis-Menten curve patterns. The presence of caffeic acid or chlorogenic acid inhibited DNA methylation predominantly through a non-competitive mechanism, and this inhibition was largely due to the increased formation of S-adenosyl-L-homocysteine (SAH, a potent inhibitor of DNA methylation), resulting from the catechol-O-methyltransferase (COMT)-mediated O-methylation of these dietary catechols. Using cultured MCF-7 and MAD-MB-231 human breast cancer cells, we also demonstrated that treatment of these cells with caffeic acid or chlorogenic acid partially inhibited the methylation of the promoter region of the RARbeta gene. The findings of our present study provide a general mechanistic basis for the notion that a variety of dietary catechols can function as inhibitors of DNA methylation through increased formation of SAH during the COMT-mediated O-methylation of these dietary

  8. Preparation of Cu@Cu₂O Nanocatalysts by Reduction of HKUST-1 for Oxidation Reaction of Catechol.

    Science.gov (United States)

    Jang, Seongwan; Yoon, Chohye; Lee, Jae Myung; Park, Sungkyun; Park, Kang Hyun

    2016-11-02

    HKUST-1, a copper-based metal organic framework (MOF), has been investigated as a catalyst in various reactions. However, the HKUST-1 shows low catalytic activity in the oxidation of catechol. Therefore, we synthesized Fe₃O₄@HKUST-1 by layer-by layer assembly strategy and Cu@Cu₂O by reduction of HKUST-1 for enhancement of catalytic activity. Cu@Cu₂O nanoparticles exhibited highly effective catalytic activity in oxidation of 3,5-di-tert-butylcatechol. Through this method, MOF can maintain the original core-shell structure and be used in various other reactions with enhanced catalytic activity.

  9. A novel non-heme iron-containing dioxygenase. Chloridazon-catechol dioxygenase from Phenylobacterium immobilis DSM 1986.

    Science.gov (United States)

    Müller, R; Schmitt, S; Lingens, F

    1982-07-01

    Previously we purified an enzyme from Phenylobacterium immobilis DSM 1986, which cleaves the catechol derivative of the herbicide Chloridazon [5-amino-4-chloro-2-phenyl-3 (2H)-pyridazinone] in the meta position. The enzyme, which could be crystallized, proved in Ouchterlony double-diffusion tests to consist of a single protein species. No cross-reaction was observed with other meta-cleaving enzymes. Its light absorption spectrum showed a maximum at 279 nm (epsilon = 310 mM -1 cm -1), shoulders at 289 nm and 275 nm and a very weak band at around 430 nm (epsilon = 1.14 mM -1 cm -1). The amino acid analysis showed a slight excess of acidic amino acids, in agreement with the pl of 4.5. Surprisingly the enzyme per se is completely inactive, although it contains one non-dialysable iron atom per submit. It has to be activated by preincubation with ferrous ions or ascorbate. The enzyme activated this way is autoxidizable and returns to its non-activated state in the presence of oxygen. During the reaction with the substrate, this inactivation seems to be enhanced about 100 times. Since this kind of activation and inactivation is not observed in other meta-cleaving enzymes, this enzyme seems to represent a new type of a non-heme iron dioxygenase. We tentatively propose the name Chloridazon-catechol dioxygenase for this enzyme.

  10. Development of an HTRF Assay for the Detection and Characterization of Inhibitors of Catechol-O-Methyltransferase.

    Science.gov (United States)

    Kimos, Martha; Burton, Maggi; Urbain, David; Caudron, Didier; Martini, Murielle; Famelart, Michel; Gillard, Michel; Barrow, James; Wood, Martyn

    2016-06-01

    Catechol-O-methyltransferase (COMT) plays an important role in the deactivation of catecholamine neurotransmitters and hormones. Inhibitors of COMT, such as tolcapone and entacapone, are used clinically in the treatment of Parkinson's disease. Discovery of novel inhibitors has been hampered by a lack of suitable assays for high-throughput screening (HTS). Although assays using esculetin have been developed, these are affected by fluorescence, a common property of catechol-type compounds. We have therefore evaluated a new homogenous time-resolved fluorescence (HTRF)-based assay from CisBio (Codolet, France), which measures the production of S-adenosyl-L-homocysteine (SAH). The assay has been run in both HTS and medium-throughput screening (MTS) modes. The assay was established using membranes expressing human membrane-bound COMT and was optimized for protein and time to give an acceptable signal window, good potency for tolcapone, and a high degree of translation between data in fluorescence ratio and data in terms of [SAH] produced. pIC50 values for the hits from the HTS mode were determined in the MTS mode. The assay also proved suitable for kinetic studies such as Km,app determination.

  11. Molecular-level spectroscopic investigations of the complexation and photodegradation of catechol to/by iron(III)

    Science.gov (United States)

    Al-Abadleh, Hind; Tofan-Lazar, Julia; Situm, Arthur; Slikboer, Samantha

    2014-05-01

    Surface water plays a crucial role in facilitating or inhibiting surface reactions in atmospheric aerosols. Little is known about the role of surface water in the complexation of organic molecules to transition metals in multicomponent aerosol systems. We will show results from real time diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) experiments for the in situ complexation of catechol to Fe(III) and its photosensitized degradation under dry and humid conditions. Catechol was chosen as a simple model for humic-like substances (HULIS) in aerosols and aged polyaromatic hydrocarbons (PAH). It has also been detected in secondary organic aerosols (SOA) formed from the reaction of hydroxyl radicals with benzene. Given the importance of the iron content in aerosols and its biogeochemistry, our studies were conducted using FeCl3. For comparison, these surface-sensitive studies were complemented with bulk aqueous ATR-FTIR, UV-vis, and HPLC measurements for structural, quantitative and qualitative information about complexes in the bulk, and potential degradation products. The implications of our studies on understanding interfacial and condensed phase chemistry relevant to multicomponent aerosols, water thin islands on buildings, and ocean surfaces containing transition metals will be discussed.

  12. Catechol functionalized aminopropyl silica gel: synthesis, characterization and preconcentrative separation of uranium(VI) from thorium(IV)

    Energy Technology Data Exchange (ETDEWEB)

    Metilda, P.; Mary Gladis, J.; Prasada Rao, T.P. [Regional Research Lab. (CSIR), Trivandrum (India)

    2005-07-01

    A novel solid phase extractant is prepared by chemically immobilizing catechol with diazotized aminopropyl silica gel. The resulting catechol functionalized silica gel (CASG) was characterized by FTIR, and microanalysis and was used for selective enrichment of uranium(VI) from other inorganic ions. The optimum pH range for maximum sorption of uranium(VI) and thorium(IV) was found to be in the range 3.5-6.0. The above actinides were eluted with 10 cm{sup 3} of 1.0 mol dm{sup -3} HCl and determined by using an Arsenazo III spectrophotometric procedure. The calibration graph was rectilinear over the uranium(VI) concentration in the range 2-100 {mu}g dm{sup -3} with a relative standard deviation of 2.15% (for 25 {mu}g of uranium(VI) present in 1.0 dm{sup 3} of sample). The validation of the developed preconcentration procedure was carried out by analyzing marine sediment (MESS-3, NRC, Canada) and soil (IAEA soil-7, Austria) reference materials. The developed preconcentration method enables a simple instruments like a spectrophotometer gave comparable values of uranium(VI) to that of standard inductively coupled plasma-mass spectrometric values during the analysis of real soil and sediment samples. (orig.)

  13. The catechol-O-methyltransferase inhibitory potential of Z-vallesiachotamine by in silicoand in vitro approaches

    Directory of Open Access Journals (Sweden)

    Carolina dos Santos Passos

    2015-08-01

    Full Text Available AbstractZ-Vallesiachotamine is a monoterpene indole alkaloid that has a β-N-acrylate group in its structure. This class of compounds has already been described in different Psychotriaspecies. Our research group observed that E/Z-vallesiachotamine exhibits a multifunctional feature, being able to inhibit targets related to neurodegeneration, such as monoamine oxidase A, sirtuins 1 and 2, and butyrylcholinesterase enzymes. Aiming at better characterizing the multifunctional profile of this compound, its effect on cathecol-O-methyltransferase activity was investigated. The cathecol-O-methyltransferase activity was evaluated in vitro by a fluorescence-based method, using S-(5′-adenosyl-l-methionine as methyl donor and aesculetin as substrate. The assay optimization was performed varying the concentrations of methyl donor (S-(5′-adenosyl-l-methionine and enzyme. It was observed that the highest concentrations of both factors (2.25 U of the enzyme and 100 µM of S-(5′-adenosyl-l-methionine afforded the more reproducible results. The in vitro assay demonstrated that Z-vallesiachotamine was able to inhibit the cathecol-O-methyltransferase activity with an IC50 close to 200 µM. Molecular docking studies indicated that Z-vallesiachotamine can bind the catechol pocket of catechol-O-methyltransferase enzyme. The present work demonstrated for the first time the inhibitory properties of Z-vallesiachotamine on cathecol-O-methyltransferase enzyme, affording additional evidence regarding its multifunctional effects in targets related to neurodegenerative diseases.

  14. Removal of Cu(II) from aqueous solution using synthetic poly(catechol-diethylenetriamine-p-phenylenediamine) particles.

    Science.gov (United States)

    Liu, Qiang; Liu, Qinze; Ruan, Zining; Chang, Xiaoqing; Yao, Jinshui

    2016-07-01

    A novel poly(catechol-diethylenetriamine-pphenylenediamine)(PCEA) adsorbent was synthesized in methanol, with chelating groups supplied by catechol and diethylenetriamine, which showed a strong removal performance and efficient adsorption toward Cu(II) ions in aqueous solution. The adsorbent was characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA). Besides, factors such as adsorbent dosage, pH, initial ionic and metal concentrations, contact time, and temperature on the adsorption of Cu(II) were studied. The data revealed that the adsorption followed a pseudo-second order kinetic model and the adsorption rate was influenced by the intra-particle diffusion. Furthermore, the adsorption process followed the Langmuir isotherm model, and the maximum adsorption capacity (Qm) was 44.2mg/g at 298K in simulated wastewater. The value of ΔG (kJ/mol) and ΔH (kJ/mol) also demonstrated that the adsorption process was spontaneous and endothermic. Studies revealed that PCEA particles were powerful and stable for the removal of Cu(II) in water, and it could be directly applied to the Cu(II)-contaminated water.

  15. Site-specific covalent modifications of human insulin by catechol estrogens: Reactivity and induced structural and functional changes

    Science.gov (United States)

    Ku, Ming-Chun; Fang, Chieh-Ming; Cheng, Juei-Tang; Liang, Huei-Chen; Wang, Tzu-Fan; Wu, Chih-Hsing; Chen, Chiao-Chen; Tai, Jung-Hsiang; Chen, Shu-Hui

    2016-06-01

    Proteins, covalently modified by catechol estrogens (CEs), were identified recently from the blood serum of diabetic patients and referred to as estrogenized proteins. Estrogenization of circulating insulin may occur and affect its molecular functioning. Here, the chemical reactivity of CEs towards specific amino acid residues of proteins and the structural and functional changes induced by the estrogenization of insulin were studied using cyclic voltammetry, liquid chromatography-mass spectrometry, circular dichroism spectroscopy, molecular modeling, and bioassays. Our results indicate that CEs, namely, 2- and 4-hydroxyl estrogens, were thermodynamically and kinetically more reactive than the catechol moiety. Upon co-incubation, intact insulin formed a substantial number of adducts with one or multiple CEs via covalent conjugation at its Cys 7 in the A or B chain, as well as at His10 or Lys29 in the B chain. Such conjugation was coupled with the cleavage of inter-chain disulfide linkages. Estrogenization on these sites may block the receptor-binding pockets of insulin. Insulin signaling and glucose uptake levels were lower in MCF-7 cells treated with modified insulin than in cells treated with native insulin. Taken together, our findings demonstrate that insulin molecules are susceptible to active estrogenization, and that such modification may alter the action of insulin.

  16. Polymorphisms in Catechol-O-methyltransferase Modify Treatment Effects of Aspirin on Risk of Cardiovascular Disease

    Science.gov (United States)

    Hall, Kathryn T.; Nelson, Christopher P.; Davis, Roger B.; Buring, Julie E.; Kirsch, Irving; Mittleman, Murray A.; Loscalzo, Joseph; Samani, Nilesh J.; Ridker, Paul M; Kaptchuk, Ted J.; Chasman, Daniel I.

    2014-01-01

    Objective Catechol-O-methyltransferase (COMT), a key enzyme in catecholamine metabolism, is implicated in cardiovascular, sympathetic, and endocrine pathways. This study aimed to confirm preliminary association of COMT genetic variation with incident cardiovascular disease (CVD). It further aimed to evaluate whether aspirin, a commonly used CVD prevention agent, modified the potential association of COMT with incident CVD. Approach and Results We examined COMT polymorphism rs4680 (MAF=0.47), encoding a non-synonymous methionine (met)-to-valine (val) substitution, in the Women's Genome Health Study (WGHS), a large population-based cohort of women with randomized allocation to aspirin or vitamin E compared with placebo and 10 years follow-up. Rs4680 effects were confirmed with COMT polymorphism rs4818 and also examined in CARDIoGRAM/C4D, consortia for genome-wide association studies of coronary artery disease. Among WGHS women allocated to placebo (135 events/N=5811), the rs4680 val allele was protective against incident CVD relative to the met, (HR[95%CI]=0.66[0.51-0.84], p=0.0007); an association also observed in CARDIoGRAM and C4D (combined p=2.4×10-5). In the WGHS, the rs4680 association was abolished by randomized allocation to aspirin, such that val/val women experienced higher CVD rates with aspirin allocation compared to placebo (HR[95%CI]=1.85[1.05-3.25], p=0.033) while met/met women experienced lower rates (HR[95%CI]=0.60[0.39-0.93], p=0.023). Allocation to vitamin E also conferred higher but non-significant CVD rates on val/val (HR[95%CI]=1.50 [0.83-2.70], p=0.180) compared with significantly lower rates on met/met (HR[95%CI]=0.53[0.34-0.84], p=0.006) women. Rs4818 results were similar. Conclusions Common COMT polymorphisms were associated with incident CVD, and this association was modified by randomized allocation to aspirin or vitamin E. Replication of these findings is required. PMID:25035343

  17. Autoxidation-product-initiated dioxygenases: vanadium-based, record catalytic lifetime catechol dioxygenase catalysis.

    Science.gov (United States)

    Yin, Cindy-Xing; Sasaki, Yoh; Finke, Richard G

    2005-11-14

    In recent work, it was shown that V-containing polyoxometalates such as (n-Bu4N)7SiW9V3O40 or (n-Bu4N)9P2W15V3O62, as well as eight other V-containing precatalysts tested, evolve to a high activity, long catalytic lifetime (> or = 30,000-100,000 total turnovers) 3,5-di-tert-butylcatechol dioxygenase, in which Pierpont's complex [VO(DBSQ)(DTBC)]2 (where DBSQ is 3,5-di-tert-butylsemiquinone and DTBC is the 3,5-di-tert-butylcatecholate dianion) was identified as a common catalyst or catalyst resting state (Yin, C.-X.; Finke, R. G. Vanadium-Based, Extended Catalytic Lifetime Catechol Dioxygenases: Evidence For a Common Catalyst. J. Am. Chem. Soc. 2005, 127 (25), 9003-9013). Herein, those findings are followed up by studies aimed at answering the following questions about this record catalytic lifetime 3,5-di-tert-butylcatechol dioxygenase catalyst: (i) What is the key to how V leaches from, for example, seemingly robust V-containing polyoxometalate precatalysts? (ii) What is the key to the sigmoidal, apparently autocatalytic kinetics observed? (iii) What can be learned about the underlying reactions that form [VO(DBSQ)(DTBC)]2? (iv) Finally, do the answers to (i-iii) lead to any broader insights or concepts? Key findings from the present work include the fact that the reaction involves a novel, autoxidation-product-induced dioxygenase, that is, one in which the undesired autoxidation of the 3,5-di-tert-butylcatechol substrate to the corresponding benzoquinone and H2O2 turns on the desired dioxygenase catalysis via a V-leaching process which eventually yields Pierpont's complex, [VO(DBSQ)(DTBC)]2. Plausible reactions en route to [VO(DBSQ)(DTBC)]2 consistent with the kinetic data, the role of H2O2, and the relevant literature are provided. The results provide a prototype example of the little observed but likely more general concept of an autoxidation-product-initiated reaction. The results also provide considerable simplification of, and insight into, the previously

  18. Bioavailability of phenanthrene in the presence of birnessite-mediated catechol polymers.

    Science.gov (United States)

    Russo, Fabio; Rao, Maria A; Gianfreda, Liliana

    2005-07-01

    Polycyclic aromatic hydrocarbons (PAHs) are widespread environmental contaminants and contribute to the pollution of aquatic and terrestrial environments. In soil, their fate may be affected by interactions with the soil biological community and soil colloids. This study was conducted to investigate the fate of phenanthrene (Phe), selected as a representative PAH, in simplified model systems, which simulate processes naturally occurring in soil. Phe was interacted with catechol (Cat), an orthodiphenol, and common intermediate in the microbial degradation of PAHs, and birnessite (Bir), an abiotic strong oxidative catalyst abundant in soil. Two experimental conditions were investigated: Cat (5 mM)+Bir (1 mg ml(-1))+Phe (0.05 mg ml(-1)) mixed at the same time and incubated for 24 h at 25 degrees C (Cat-Bir-Phe) and Cat+Bir incubated for 24 h at 25 degrees C before Phe addition and then incubated for a further 24 h (Cat-Bir+Phe). After incubation, the systems were analysed for residual Cat and Phe, supplied with a selected Phe-degrading mixed bacterial culture, and then the microbial degradation of Phe and the growth of cells were monitored. Complex phenomena simultaneously occurred. Cat was completely removed after a 24-h incubation with Bir, and no interference by Phe in the Bir-mediated transformation of Cat was observed. Elemental analysis and UV-Vis and Fourier transfer infrared spectra showed that Cat transformation by Bir produced soluble and insoluble polymeric aggregates involving Phe. The hydrocarbon also interacted with the surfaces of Bir either previously coated (Cat-Bir+Phe sample) or not by Cat polymers. When a Phe-degrading bacterial culture was added to the systems after Bir-mediated Cat polymerisation, a different behaviour was observed in terms of Phe consumption and bacterial growth, thus suggesting differentiated availability of Phe to the microbial cells. The hydrocarbon was completely transformed in the presence of Bir and/or Bir covered by Cat

  19. Genotype status of the dopamine-related catechol-O-methyltransferase (COMT) gene corresponds with desirability of “unhealthy” foods

    NARCIS (Netherlands)

    Wallace, D.L.; Aarts, E.; d'Oleire Uquillas, F.; Dang, L.C.; Greer, S.M.; Jagust, W.J.; D'Esposito, M.

    2015-01-01

    The role of dopamine is extensively documented in weight regulation and food intake in both animal models and humans. Yet the role of dopamine has not been well studied in individual differences for food desirability. Genotype status of the dopamine-related catechol-O-methyltransferase (COMT) gene h

  20. The catechol-O-methyltransferase (COMT) Val158Met genotype modulates working memory-related dorsolateral prefrontal response and performance in bipolar disorder

    DEFF Research Database (Denmark)

    Miskowiak, K W; Kjaerstad, H L; Støttrup, M M

    2017-01-01

    OBJECTIVES: Cognitive dysfunction affects a substantial proportion of patients with bipolar disorder (BD), and genetic-imaging paradigms may aid in the elucidation of mechanisms implicated in this symptomatic domain. The Val allele of the functional Val158Met polymorphism of the catechol-O-methyl...

  1. Biochar, activated carbon, and carbon nanotubes have different effects on fate of (14)C-catechol and microbial community in soil.

    Science.gov (United States)

    Shan, Jun; Ji, Rong; Yu, Yongjie; Xie, Zubin; Yan, Xiaoyuan

    2015-10-30

    This study investigated the effects of biochar, activated carbon (AC)-, and single-walled and multi-walled carbon nanotubes (SWCNTs and MWCNTs) in various concentrations (0, 0.2, 20, and 2,000 mg/kg dry soil) on the fate of (14)C-catechol and microbial community in soil. The results showed that biochar had no effect on the mineralization of (14)C-catechol, whereas AC at all amendment rates and SWCNTs at 2,000 mg/kg significantly reduced mineralization. Particularly, MWCNTs at 0.2 mg/kg significantly stimulated mineralization compared with the control soil. The inhibitory effects of AC and SWCNTs on the mineralization were attributed to the inhibited soil microbial activities and the shifts in microbial communities, as suggested by the reduced microbial biomass C and the separated phylogenetic distance. In contrast, the stimulatory effects of MWCNTs on the mineralization were attributed to the selective stimulation of specific catechol-degraders by MWCNTs at 0.2 mg/kg. Only MWCNTs amendments and AC at 2,000 mg/kg significantly changed the distribution of (14)C residues within the fractions of humic substances. Our findings suggest biochar, AC, SWCNTs and MWCNTs have different effects on the fate of (14)C-catechol and microbial community in soil.

  2. Biochar, activated carbon, and carbon nanotubes have different effects on fate of 14C-catechol and microbial community in soil

    Science.gov (United States)

    Shan, Jun; Ji, Rong; Yu, Yongjie; Xie, Zubin; Yan, Xiaoyuan

    2015-10-01

    This study investigated the effects of biochar, activated carbon (AC)-, and single-walled and multi-walled carbon nanotubes (SWCNTs and MWCNTs) in various concentrations (0, 0.2, 20, and 2,000 mg/kg dry soil) on the fate of 14C-catechol and microbial community in soil. The results showed that biochar had no effect on the mineralization of 14C-catechol, whereas AC at all amendment rates and SWCNTs at 2,000 mg/kg significantly reduced mineralization. Particularly, MWCNTs at 0.2 mg/kg significantly stimulated mineralization compared with the control soil. The inhibitory effects of AC and SWCNTs on the mineralization were attributed to the inhibited soil microbial activities and the shifts in microbial communities, as suggested by the reduced microbial biomass C and the separated phylogenetic distance. In contrast, the stimulatory effects of MWCNTs on the mineralization were attributed to the selective stimulation of specific catechol-degraders by MWCNTs at 0.2 mg/kg. Only MWCNTs amendments and AC at 2,000 mg/kg significantly changed the distribution of 14C residues within the fractions of humic substances. Our findings suggest biochar, AC, SWCNTs and MWCNTs have different effects on the fate of 14C-catechol and microbial community in soil.

  3. Isolation of Alcaligenes sp strain L6 at low oxygen concentrations and degradation of 3-chlorobenzoate via a pathway not involving (chloro)catechols

    NARCIS (Netherlands)

    Krooneman, J; Wieringa, EBA; Moore, ERB; Gerritse, J; Prins, RA; Gottschal, JC

    1996-01-01

    Isolations of 3-chlorobenzoate (3CBA)-degrading aerobic bacteria under reduced O-2, partial pressures yielded organisms which metabolized 3CBA via the gentisate or the protocatechuate pathway rather than via the catechol route. The 3CBA metabolism of one of these isolates, L6, which,vas identified a

  4. Catechol-O-Methyltransferase "Val[superscript 158]Met" Genotype, Parenting Practices and Adolescent Alcohol Use: Testing the Differential Susceptibility Hypothesis

    Science.gov (United States)

    Laucht, Manfred; Blomeyer, Dorothea; Buchmann, Arlette F.; Treutlein, Jens; Schmidt, Martin H.; Esser, Gunter; Jennen-Steinmetz, Christine; Rietschel, Marcella; Zimmermann, Ulrich S.; Banaschewski, Tobias

    2012-01-01

    Background: Recently, first evidence has been reported for a gene-parenting interaction (G x E) with regard to adolescent alcohol use. The present investigation set out to extend this research using the catechol-O-methyltransferase ("COMT") "Val[superscript 158]Met" polymorphism as a genetic susceptibility factor. Moreover, the current study…

  5. Conversion of 3-chlorocatechol by various catechol 2,3-dioxygenases and sequence analysis of the chlorocatechol dioxygenase region of Pseudomonas putida GJ31

    NARCIS (Netherlands)

    Mars, Astrid E.; Kingma, Jaap; Kaschabek, Stefan R.; Reineke, Walter; Janssen, Dick B.

    1999-01-01

    Pseudomonas putida GJ31 contains an unusual catechol 2,3-dioxygenase that converts 3-chlorocatechol and 3-methylcatechol, which enables the organism to use both chloroaromatics and methylaromatics for growth, A 3.1-kb region of genomic DNA of strain GJ31 containing the gene for this chlorocatechol 2

  6. Catechol degradation on hematite/silica-gas interface as affected by gas composition and the formation of environmentally persistent free radicals

    Science.gov (United States)

    Li, Hao; Guo, Huiying; Pan, Bo; Liao, Shaohua; Zhang, Di; Yang, Xikun; Min, Chungang; Xing, Baoshan

    2016-04-01

    Environmentally persistent free radicals (EPFRs) formed on a solid particle surface have received increasing attention because of their toxic effects. However, organic chemical fate regulated by EPFRs has rarely been investigated, and this information may provide the missing link in understanding their environmental behavior. Previous studies have suggested that the reduction of transition metals is involved in EPFRs formation. We thus hypothesize that an oxidative environment may inhibit EPFRs formation in particle-gas interface, which will consequently release free radicals and accelerate organic chemical degradation. Our result indicates that a 1% hematite coating on a silica surface inhibited catechol degradation in N2, especially at low catechol loadings on solid particles (SCT). However, under an O2 environment, catechol degradation decreased when SCT was 1 μg/mg. Stable organic free radicals were observed in the N2 system with g factors in the 2.0035-2.0050 range, suggesting the dominance of oxygen-centered free radicals. The introduction of O2 into the catechol degradation system substantially decreased the free radical signals and decreased the Fe(II) content. These results were observed in both dark and light irradiation systems, indicating the ubiquitous presence of EPFRs in regulating the fate of organic chemicals.

  7. Catechol degradation on hematite/silica-gas interface as affected by gas composition and the formation of environmentally persistent free radicals.

    Science.gov (United States)

    Li, Hao; Guo, Huiying; Pan, Bo; Liao, Shaohua; Zhang, Di; Yang, Xikun; Min, Chungang; Xing, Baoshan

    2016-04-15

    Environmentally persistent free radicals (EPFRs) formed on a solid particle surface have received increasing attention because of their toxic effects. However, organic chemical fate regulated by EPFRs has rarely been investigated, and this information may provide the missing link in understanding their environmental behavior. Previous studies have suggested that the reduction of transition metals is involved in EPFRs formation. We thus hypothesize that an oxidative environment may inhibit EPFRs formation in particle-gas interface, which will consequently release free radicals and accelerate organic chemical degradation. Our result indicates that a 1% hematite coating on a silica surface inhibited catechol degradation in N2, especially at low catechol loadings on solid particles (SCT). However, under an O2 environment, catechol degradation decreased when SCT was 1 μg/mg. Stable organic free radicals were observed in the N2 system with g factors in the 2.0035-2.0050 range, suggesting the dominance of oxygen-centered free radicals. The introduction of O2 into the catechol degradation system substantially decreased the free radical signals and decreased the Fe(II) content. These results were observed in both dark and light irradiation systems, indicating the ubiquitous presence of EPFRs in regulating the fate of organic chemicals.

  8. Catechol siderophores repress the pyochelin pathway and activate the enterobactin pathway in Pseudomonas aeruginosa: an opportunity for siderophore-antibiotic conjugates development.

    Science.gov (United States)

    Gasser, Véronique; Baco, Etienne; Cunrath, Olivier; August, Pamela Saint; Perraud, Quentin; Zill, Nicolas; Schleberger, Christian; Schmidt, Alexander; Paulen, Aurélie; Bumann, Dirk; Mislin, Gaëtan L A; Schalk, Isabelle J

    2016-03-01

    Previous studies have suggested that antibiotic vectorization by siderophores (iron chelators produced by bacteria) considerably increases the efficacy of such drugs. The siderophore serves as a vector: when the pathogen tries to take up iron via the siderophore, it also takes up the antibiotic. Catecholates are among the most common iron-chelating compounds used in synthetic siderophore-antibiotic conjugates. Using reverse transcription polymerase chain reaction and proteomic approaches, we showed that the presence of catecholate compounds in the medium of Pseudomonas aeruginosa led to strong activation of the transcription and expression of the outer membrane transporter PfeA, the ferri-enterobactin importer. Iron-55 uptake assays on bacteria with and without PfeA expression confirmed that catechol compounds imported iron into P. aeruginosa cells via PfeA. Uptake rates were between 0.3 × 10(3) and 2 × 10(3) Fe atoms/bacterium/min according to the used catechol siderophore in iron-restricted medium, and remained as high as 0.8 × 10(3) Fe atoms/bacterium/min for enterobactin, even in iron-rich medium. Reverse transcription polymerase chain reaction and proteomic approaches showed that in parallel to this switching on of PfeA expression, a repression of the expression of pyochelin (PCH) pathway genes (PCH being one of the two siderophores produced by P. aeruginosa for iron acquisition) was observed.

  9. The effects of oxygen on the yields of polycyclic aromatic hydrocarbons formed during the pyrolysis and fuel-rich oxidation of catechol

    Energy Technology Data Exchange (ETDEWEB)

    Shiju Thomas; Mary J. Wornat [Louisiana State University, Baton Rouge, LA (United States). Department of Chemical Engineering

    2008-05-15

    To better understand the effects of oxygen on the formation and destruction of polycyclic aromatic hydrocarbons (PAH) during the burning of complex solid fuels, we have performed pyrolysis and fuel-rich oxidation experiments in an isothermal laminar-flow reactor, using the model fuel catechol (ortho-dihydroxybenzene), a phenol-type compound representative of structural entities in coal, wood, and biomass. The catechol pyrolysis experiments are conducted at a fixed residence time of 0.3 s, at nine temperatures spanning the range of 500-1000{sup o}C, and under varying oxygen ratios ranging from 0 (pure pyrolysis) to 0.92 (near stoichiometric oxidation). The PAH products, ranging in size from two to nine fused aromatic rings, have been analyzed by gas chromatography with flame-ionization and mass spectrometric detection, and by high-pressure liquid chromatography with diode-array ultraviolet-visible absorbance detection. The quantified PAH products fall into six structural classes. A comparison of product yields from pyrolysis and fuel-rich oxidation of catechol reveals that at temperatures {lt}800{sup o}C, where only two-ring PAH are produced in significant quantities, increases in oxygen concentration bring about increases in yields of the two-ring aromatics indene and naphthalene. At temperatures {gt}800{sup o}C, increases in oxygen concentration bring about dramatic decreases in the yields of all PAH products, due to oxidative destruction reactions. The smaller-ring-number PAH are produced in higher abundance under all conditions studied, and the oxygen-induced decreases in the yields of PAH are increasingly more pronounced as the PAH ring number is increased. These observations fully support our finding from catechol pyrolysis in the absence of oxygen: that PAH formation and growth occur by successive ring-buildup reactions involving the C1-C5 and single-ring aromatic products of catechol's thermal decomposition. 51 refs., 26 figs., 1 tab.

  10. Association of catechol-o-methyl transferase gene polymorphism with prostate cancer and benign prostatic hyperplasia

    Directory of Open Access Journals (Sweden)

    mir davood omrani

    2009-08-01

    Full Text Available

    • BACKGROUND: A single nucleotide variation within  atechol-o-methyl transferase (COMT gene may alter the COMT enzyme activity level. Polymorphism of Val158Met in the COMT gene has been related to malignancy. In this regard, a study was carried out to find a possible association between the COMT gene polymorphism in patients with sporadic prostate cancer (PCa and benign prostatic hyperplasia (BPH.
    • METHODS: All types of COMT158 Val/Met polymorphism were carried out using ASO-PCR method in 41 patients with prostate cancer, 193 patients with benign prostatic hyperplasia and 107 healthy male individuals.
    • RESULTS: The results of this study showed that the frequency of low producer allele A at codon 158 of the  OMT gene is significantly different in BPH group compared to normal male control group (OR, 95% CI, p value 1.95: 1.46, 2.44, 0.021, respectively. However no significant difference was noticed when the comparison was made between prostate cancer group and normal male control group and also between BPH and PCa groups.
    • CONCLUSIONS: Decreased level of catechol-o-methyl transferase gene

    • Extraction of catechol violet, chrome azurol S and eriochrome cyanine R with chloroform solutions of liquid anion-exchangers.

      Science.gov (United States)

      Przeszlakowski, S; Wydra, H

      1984-06-01

      The extraction of Catechol Violet, Chrome Azurol S and Eriochrome Cyanine R with chloroform solutions of tri-n-octylamine (TOA), TOA hydrochloride and Aliquat 336 has been investigated. From the extraction isotherms, absorption spectra of the organic phases and dependence of the extraction coefficients on extractant concentration, it was found that the singly-charged anions HL(-) are extracted preferentially, but acidic groups other than sulphonate can also form ion-pairs with alkylammonium cations at higher pH values of the aqueous phase, and at high acidity these dyes can be extracted other than by an anion-exchange reaction. The three dyes (especially Eriochrome Cyanine R and Chrome Azurol S) were strongly extracted with the liquid anion-exchanger used and Aliquat 336 was a better extractant than TOA or TOA hydrochloride. The absorption spectra for the organic phases containing Chrome Azurol S and Eriochrome Cyanine R depended on the extractant used.

    • Catechol conjugation with hemolymph proteins and their incorporation into the cuticle of the American cockroach, Periplaneta americana

      Energy Technology Data Exchange (ETDEWEB)

      Bailey, W.D.; Kimbrough, T.D.; Mills, R.R. [Department of Biology, Virginia Commonwealth University, Richmond, VA 23284-2012 (United States)

      1999-01-01

      Newly ecdysed American cockroaches, Periplaneta americana (six to last instar)were injected with radioactive dopamine. In addition, the reinjection of radiolabeled protein of any size resulted in the incorporation of the label into the newly sclerotized cuticle. Hemolymph proteins were synthesized in vivo using [{sup 14}C]leucine and subsequently double labeled in vivo with [{sup 3}H]dopamine. After sclerotization (7 h post-ecdysis) the cuticle was extirpated, hydrolyzed and counted. An identical ratio of {sup 14}C to {sup 3}H was found in cuticle extracts as in the double-labeled hemolymph proteins, suggesting that the phenol-bound protein was incorporated in the cuticle unchanged. It appears that the catechol bound to the proteins exists as a {beta}-glucoside. (Copyright (c) 1999 Elsevier Science B.V., Amsterdam. All rights reserved.)

    • Electroless deposition of Au nanoparticles on reduced graphene oxide/polyimide film for electrochemical detection of hydroquinone and catechol

      Science.gov (United States)

      Shen, Xuan; Xia, Xiaohong; Du, Yongling; Wang, Chunming

      2017-09-01

      An electrochemical sensor for determination of hydroquinone (HQ) and catechol (CC) was developed using Au nanoparticles (AuNPs) fabricated on reduced graphene oxide/polyimide (PI/RGO) film by electroless deposition. The electrochemical behaviors of HQ and CC at PI/RGO-AuNPs electrode were investigated by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). Under the optimized condition, the current responses at PI/RGO-AuNPs electrode were linear over ranges from 1 to 654 mol/L for HQ and from 2 to 1289 mol/L for CC, with the detection limits of 0.09 and 0.2 mol/L, respectively. The proposed electrode exhibited good reproducibility, stability and selectivity. In addition, the proposed electrode was successfully applied in the determination of HQ and CC in tap water and the Yellow River samples.

    • Association between polymorphisms of the dopamine receptor D2 and catechol-o-methyl transferase genes and cognitive function.

      Science.gov (United States)

      Bolton, Jennifer L; Marioni, Riccardo E; Deary, Ian J; Harris, Sarah E; Stewart, Marlene C; Murray, Gordon D; Fowkes, F Gerry R; Price, Jackie F

      2010-09-01

      The dopaminergic neurotransmitter system of the brain is involved in working memory and other cognitive functions. Studies suggest an important role for dopamine synthesis and uptake in modulation of human cognitive processes. We studied the association between polymorphisms in the catechol-o-methyl transferase (COMT) and dopamine receptor D2 (DRD2) genes and general cognitive ability in a secondary analysis of 2091 men and women, aged 55-80 years living in Scotland. General cognitive ability 'g' was derived from five cognitive tests of different domains. COMT was not associated with cognitive ability in this population. The DRD2 C:C genotype of rs6277 was associated with decreased general cognitive ability 'g' (p = 0.003), and DRD2 rs1800497 heterozygotes had lowest mean general cognitive ability 'g' (p = 0.007). There was an indication of a potential interaction between the DRD2 SNPs.

    • STUDY OF CATECHOL SIDEROPHORE FROM A NEWLY ISOLATED Azotobacter sp. SUP-III FOR ITS ANTIMICROBIAL PROPERTY

      Directory of Open Access Journals (Sweden)

      Shirishkumar Supanekar

      2013-12-01

      Full Text Available In present study, the isolate SUP III showed maximum siderophore production in Burk’s medium with maximum 43% decolorization of CAS reagent in liquid CAS assay. Optimum yield of siderophore was obtained at pH 7.2. The culture was identified as Azotobacter sp. based on 16S rRNA gene sequencing and phylogenetic studies using MEGA 4. The siderophore extraction and purification was achieved using XAD2 column. Colorimetric reactions prove that purified siderophore is of catecholate type. Fourier – transform infrared (FTIR analysis showed peaks at 3402 cm-1, 1652 cm-1, 1032 cm-1, and 1112 cm-1 which supported the colorimetric results. Antimicrobial activity of the purified siderophore showed significant zones of inhibition for some pathogens. This type of study has not been previously reported in this area.

    • Synthesis of [{sup 18}F]RO41-0960, a potent catechol-O-methyltransferase inhibitor, for PET studies

      Energy Technology Data Exchange (ETDEWEB)

      Ding, Y.-S.; Sugano, Y.; Koomen, J.; Aggarwal, D. [Brookhaven National Lab., Upton, NY (United States). Dept. of Chemistry

      1997-04-01

      Ro41-0960 (3,4-dihydroxy-5-nitro-2`-fluorobenzophenone) is a potent, fluorine containing COMT inhibitor. In order to map catechol-O-methyltransferase (COMT) in vivo with PET, no-carrier-added [{sup 18}F]Ro41-0960 was synthesized by the nucleophilic aromatic substitution of [{sup 18}F]fluoride for 2`-nitro on 3,4-dimethoxy-5,2`-dimethoxy-5,2`-dinitrobenzophenone, followed by hydrolysis with HBr. During the course of this study it was found that [{sup 18}F]fluoromethane ([{sup 18}F]CH{sub 3}F) was generated as the side product of nucleophilic aromatic substitution reaction. Various precursors with different hydroxyl protecting groups were then investigated for the effects on this side reaction. (Author).

    • Theoretical study of the Pb(II)-catechol system in dilute aqueous solution: Complex structure and metal coordination sphere determination

      Science.gov (United States)

      Lapouge, Christine; Cornard, Jean-Paul

      2010-04-01

      We investigated the unknown interaction of Pb(II) with catechol ligand in diluted aqueous solution by electronic spectroscopies combined with quantum chemical calculations. The aim of this work is the determination of the complete structure of the complex formed and particularly the metal coordination sphere. Three successive steps have been necessary to reach this goal: (i) the comparison of the experimental electronic absorption spectrum with theoretical spectra calculated from various hypothetical structures, (ii) complexation reaction pathways calculations in vacuum and with taking into account the solvent effects and finally (iii) the fluorescence emission wavelength calculations. All these investigations led to identify a monodentate complex with the monodeprotonated ligand, in which the Pb atom presents a coordination number of five. The formula of the complex is [Pb(Hcat)(HO)4]mono+.

    • Synthesis and characterization of chromium(III) Schiff base complexes: Antimicrobial activity and its electrocatalytic sensing ability of catechol

      Science.gov (United States)

      Praveen Kumar, S.; Suresh, R.; Giribabu, K.; Manigandan, R.; Munusamy, S.; Muthamizh, S.; Narayanan, V.

      2015-03-01

      A series of acyclic Schiff base chromium(III) complexes were synthesized with the aid of microwave irradiation method. The complexes were characterized on the basis of elemental analysis, spectral analysis such as UV-Visible, Fourier transform infrared (FT-IR), nuclear magnetic resonance (NMR), electron paramagnetic resonance (EPR) spectroscopies and electrospray ionization (ESI) mass spectrometry. Electrochemical analysis of the complexes indicates the presence of chromium ion in +3 oxidation state. Cr (III) ion is stabilized by the tetradentate Schiff base ligand through its nitrogen and phenolic oxygen. From the spectral studies it is understood that the synthesized chromium(III) complexes exhibits octahedral geometry. Antimicrobial activity of chromium complexes was investigated towards the Gram positive and Gram negative bacteria. In the present work, an attempt was made to fabricate a new kind of modified electrode based on chromium Schiff base complexes for the detection of catechol at nanomolar level.

    • Properties of catechol 1,2-dioxygenase in the cell free extract and immobilized extract of Mycobacterium fortuitum

      Directory of Open Access Journals (Sweden)

      A.S. Silva

      2013-01-01

      Full Text Available Polycyclic aromatic hydrocarbons (PAH are carcinogenic compounds which contaminate water and soil, and the enzymes can be used for bioremediation of these environments. This study aimed to evaluate some environmental conditions that affect the production and activity of the catechol 1,2-dioxygenase (C12O by Mycobacterium fortuitum in the cell free and immobilized extract in sodium alginate. The bacterium was grown in mineral medium and LB broth containing 250 mg L-1 of anthracene (PAH. The optimum conditions of pH (4.0-9.0, temperature (5-70 ºC, reaction time (10-90 min and the effect of ions in the enzyme activity were determined. The Mycobacterium cultivated in LB shown higher growth and the C12O activity was two-fold higher to that in the mineral medium. To both extracts the highest enzyme activity was at pH 8.0, however, the immobilized extract promoted the increase in the C12O activity in a pH range between 4.0 and 8.5. The immobilized extract increased the enzymatic activity time and showed the highest C12O activity at 45 ºC, 20 ºC higher than the greatest temperature in the cell free extract. The enzyme activity in both extracts was stimulated by Fe3+, Hg2+ and Mn2+ and inhibited by NH4+ and Cu2+, but the immobilization protected the enzyme against the deleterious effects of K+ and Mg2+ in tested concentrations. The catechol 1,2-dioxygenase of Mycobacterium fortuitum in the immobilized extract has greater stability to the variations of pH, temperature and reaction time, and show higher activity in presence of ions, comparing to the cell free extract.

    • Association of Catechol-O-methyltransferase polymorphism Val158Met and mammographic density: A meta-analysis.

      Science.gov (United States)

      Kallionpää, Roope A; Uusitalo, Elina; Peltonen, Juha

      2017-08-15

      The Val158Met polymorphism in catechol-O-methyltransferase (COMT) enzyme reduces the methylation of catechol estrogens, which may affect mammographic density. High mammographic density is a known risk factor of breast cancer. Our aim was to perform meta-analysis of the effect of COMT Val158Met polymorphism on mammographic density. Original studies reporting data on mammographic density, stratified by the presence of COMT Val158Met polymorphism, were identified and combined using genetic models Met/Val vs. Val/Val, Met/Met vs. Val/Val, Val/Met+Met/Met vs. Val/Val (dominant model) and Met/Met vs. Val/Met+Val/Val (recessive model). Subgroup analyses by breast cancer status, menopausal status and use of hormone replacement therapy (HRT) were also performed. Eight studies were included in the meta-analysis. The overall effect in percent mammographic density was -1.41 (CI -2.86 to 0.05; P=0.06) in the recessive model. Exclusion of breast cancer patients increased the effect size to -1.93 (CI -3.49 to -0.37; P=0.02). The results suggested opposite effect of COMT Val158Met for postmenopausal users of HRT versus premenopausal women or postmenopausal non-users of HRT. COMT Val158Met polymorphism may be associated with mammographic density at least in healthy women. Menopausal status and HRT should be taken into account in future studies to avoid masking of the underlying effects. Copyright © 2017 Elsevier B.V. All rights reserved.

  1. Purification and Characterization of Catechol 1,2-Dioxygenase from Acinetobacter sp. Y64 Strain and Escherichia coli Transformants.

    Science.gov (United States)

    Lin, J; Milase, R N

    2015-12-01

    This study intends to purify and characterize catechol 1,2-dioxygenase (C1,2O) of phenol-degrading Acinetobacter sp. Y64 and of E. coli transformant. Acinetobacter sp. Y64 was capable of degrading 1000 mg/L of phenol within 14 ± 2 h at 30 °C, 160 rpm and pH of 7. One C1,2O of 36 kDa was purified using ammonium sulphate precipitation and Hitrap QFF column chromatograph with 49% recovery and a 10.6-fold increase in purity. Purified Y64 C1,2O had temperature and pH optimum at 37 °C and pH 7.7 respectively with the Michaelis constant of 17.53 µM and the maximal velocity of 1.95 U/mg, respectively. The presence of Fe(3+) or Fe(2+) enhanced the activity of Y64 C1,2O while other compounds such as Ca(2+), and EDTA had an inhibitory effect. 80% of C1,2O activity remained using 4-nitrocatechol as substrate while 2% remained using 3-methylcatechol compared with that using catechol. Y64 catA gene encoding C1,2O was amplified using PCR cloned into pET22b vector and expressed in Escherichia coli BL21 DE3 (pLysS) after transformation. Purified and cloned Y64 C1,2O show no significant differences in the biochemical properties. The phylogenetic tree based on the protein sequences indicates that these C1,2Os possess a common ancestry.

  2. Inhibition of human catechol-O-methyltransferase-mediated dopamine O-methylation by daphnetin and its Phase II metabolites.

    Science.gov (United States)

    Liang, Si-Cheng; Ge, Guang-Bo; Xia, Yang-Liu; Pei-Pei, Dong; Ping, Wang; Qi, Xiao-Yi; Cai-Xia, Tu; Ling, Yang

    2016-07-20

    1. Finding and developing inhibitors of catechol-O-methyltransferase (COMT) from natural products is highly recommended. Daphnetin, a naturally occurring catechol from the family thymelaeaceae, has a chemical structure similar to several potent COMT inhibitors reported previously. Here the potential of daphnetin and its Phase II metabolites as inhibitors of COMT was investigated with human liver cytosol (HLC). 2. Daphnetin and its methylated metabolite (8-O-methyldaphnetin) were found to inhibit COMT-mediated dopamine O-methylation in a dose-dependent manner. The IC50 values for daphnetin (0.51∼0.53 μM) and 8-O-methyldaphnetin (22.5∼24.3 μM) were little affected by changes in HLC concentrations. Further kinetic analysis showed the differences in inhibition type and parameters (Ki) between daphnetin (competitive, 0.37 μM) and 8-O-methyldaphnetin (noncompetitive, 25.7 μM). Other metabolites, including glucuronidated and sulfated species, showed negligible inhibition against COMT. By using in vitro-in vivo extrapolation (IV-IVE), a 24.3-fold increase in the exposure of the COMT substrates was predicted when they are co-administrated with daphnetin. 3. With high COMT-inhibiting activity, daphnetin could serve as a lead compound for the design and development of new COMT inhibitors. Also, much attention should be paid to the clinical impact of combination of daphnetin and herbal preparations containing daphnetin with the drugs primarily cleared by COMT.

  3. Biological degradation of 4-chlorobenzoic acid by a PCB-metabolizing bacterium through a pathway not involving (chloro)catechol.

    Science.gov (United States)

    Adebusoye, Sunday A

    2017-02-01

    Cupriavidus sp. strain SK-3, previously isolated on polychlorinated biphenyl mixtures, was found to aerobically utilize a wide spectrum of substituted aromatic compounds including 4-fluoro-, 4-chloro- and 4-bromobenzoic acids as a sole carbon and energy source. Other chlorobenzoic acid (CBA) congeners such as 2-, 3-, 2,3-, 2,5-, 3,4- and 3,5-CBA were all rapidly transformed to respective chlorocatechols (CCs). Under aerobic conditions, strain SK-3 grew readily on 4-CBA to a maximum concentration of 5 mM above which growth became impaired and yielded no biomass. Growth lagged significantly at concentrations above 3 mM, however chloride elimination was stoichiometric and generally mirrored growth and substrate consumption in all incubations. Experiments with resting cells, cell-free extracts and analysis of metabolite pools suggest that 4-CBA was metabolized in a reaction exclusively involving an initial hydrolytic dehalogenation yielding 4-hydroxybenzoic acid, which was then hydroxylated to protocatechuic acid (PCA) and subsequently metabolized via the β-ketoadipate pathway. When strain SK-3 was grown on 4-CBA, there was gratuitous induction of the catechol-1,2-dioxygenase and gentisate-1,2-dioxygenase pathways, even if both were not involved in the metabolism of the acid. While activities of the modified ortho- and meta-cleavage pathways were not detectable in all extracts, activity of PCA-3,4-dioxygenase was over ten-times higher than those of catechol-1,2- and gentisate-1,2-dioxygenases. Therefore, the only reason other congeners were not utilized for growth was the accumulation of CCs, suggesting a narrow spectrum of the activity of enzymes downstream of benzoate-1,2-dioxygenase, which exhibited affinity for a number of substituted analogs, and that the metabolic bottlenecks are either CCs or catabolites of the modified ortho-cleavage metabolic route.

  4. Quantitative Determination of α-Arbutin, β-Arbutin, Kojic Acid, Nicotinamide, Hydroquinone, Resorcinol, 4-Methoxyphenol, 4-Ethoxyphenol, and Ascorbic Acid from Skin Whitening Products by HPLC-UV.

    Science.gov (United States)

    Wang, Yan-Hong; Avonto, Cristina; Avula, Bharathi; Wang, Mei; Rua, Diego; Khan, Ikhlas A

    2015-01-01

    An HPLC-UV method was developed for the quantitative analysis of nine skin whitening agents in a single injection. These compounds are α-arbutin, β-arbutin, kojic acid, nicotinamide, resorcinol, ascorbic acid, hydroquinone, 4-methoxyphenol, and 4-ethoxyphenol. The separation was achieved on a reversed-phase C18 column within 30 min. The mobile phase was composed of water and methanol, both containing 0.1% acetic acid (v/v). The stability of the analytes was evaluated at different pH values between 2.3 and 7.6, and the extraction procedure was validated for different types of skin whitening product matrixes, which included two creams, a soap bar, and a capsule. The best solvent system for sample preparation was 20 mM NaH2PO4 containing 10% methanol at pH 2.3. The analytical method was validated for accuracy, precision, LOD, and LOQ. The developed HPLC-UV method was applied for the quantitation of the nine analytes in 59 skin whitening products including creams, lotions, sera, foams, gels, mask sheets, soap bars, tablets, and capsules.

  5. Determinação espectrofotométrica indireta de capsaicinoides em pimentas Capsicum a partir da reação com o complexo de Co(II com 4-(2-piridilazo resorcinol

    Directory of Open Access Journals (Sweden)

    Patrícia Tonon de Souza

    2014-01-01

    Full Text Available Capsaicinoids (CAPS are substances responsible for pungency in Capsicum. It is important to quantify these types of compounds owing to their broad application in food, pharmaceuticals, cosmetics and chemical weapons. In this work, we developed an indirect spectrophotometric method based on the colorimetric reaction between CAPS, Co(II 3.10×10-5 mol L-1 and 4-(2-pyridylazo resorcinol (PAR 6.23×10-5 and, in cachaça:water 92:8v/v solutions, for quantification of total CAPS in Capsicum peppers. The product of the reaction is CoPAR2CAPS2 and its absorption in aquo-ethanolic solution at 510 nm is proportional to the total CAPS concentration from 0.60 to 17.94 mg L-1. The values of limit of detection and limit of quantification were 0.0004 and 0.001 mg of CAPS/g of pepper, respectively, with 4% relative standard deviation. The developed method yielded similar results to those obtained from high performance liquid chromatography, with 95% of confidence.

  6. Simultaneous preconcentration of copper, zinc, cadmium, and nickel in water samples by cloud point extraction using 4-(2-pyridylazo)-resorcinol and their determination by inductively coupled plasma optic emission spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Edson Luiz, E-mail: edsonqmc@hotmail.com [Centro de Energia Nuclear na Agricultura, Universidade de Sao Paulo, Av. Centenario, 303, CP 96, 13416-000 Piracicaba, SP (Brazil); Santos Roldan, Paulo dos [Universidade Federal de Alagoas, Campus A.C. Simoes, Av. Lourival Melo Mota, Tabuleiro do Martins, CEP: 57072-970 AL (Brazil); Gine, Maria Fernanda [Centro de Energia Nuclear na Agricultura, Universidade de Sao Paulo, Av. Centenario, 303, CP 96, 13416-000 Piracicaba, SP (Brazil)

    2009-11-15

    A procedure for simultaneous separation/preconcentration of copper, zinc, cadmium, and nickel in water samples, based on cloud point extraction (CPE) as a prior step to their determination by inductively coupled plasma optic emission spectrometry (ICP-OES), has been developed. The analytes reacted with 4-(2-pyridylazo)-resorcinol (PAR) at pH 5 to form hydrophobic chelates, which were separated and preconcentrated in a surfactant-rich phase of octylphenoxypolyethoxyethanol (Triton X-114). The parameters affecting the extraction efficiency of the proposed method, such as sample pH, complexing agent concentration, buffer amount, surfactant concentration, temperature, kinetics of complexation reaction, and incubation time were optimized and their respective values were 5, 0.6 mmol L{sup -1}, 0.3 mL, 0.15% (w/v), 50 deg. C, 40 min, and 10 min for 15 mL of preconcentrated solution. The method presented precision (R.S.D.) between 1.3% and 2.6% (n = 9). The concentration factors with and without dilution of the surfactant-rich phase for the analytes ranged from 9.4 to 10.1 and from 94.0 to 100.1, respectively. The limits of detection (L.O.D.) obtained for copper, zinc, cadmium, and nickel were 1.2, 1.1, 1.0, and 6.3 {mu}g L{sup -1}, respectively. The accuracy of the procedure was evaluated through recovery experiments on aqueous samples.

  7. Simultaneous preconcentration of copper, zinc, cadmium, and nickel in water samples by cloud point extraction using 4-(2-pyridylazo)-resorcinol and their determination by inductively coupled plasma optic emission spectrometry.

    Science.gov (United States)

    Silva, Edson Luiz; Roldan, Paulo dos Santos; Giné, Maria Fernanda

    2009-11-15

    A procedure for simultaneous separation/preconcentration of copper, zinc, cadmium, and nickel in water samples, based on cloud point extraction (CPE) as a prior step to their determination by inductively coupled plasma optic emission spectrometry (ICP-OES), has been developed. The analytes reacted with 4-(2-pyridylazo)-resorcinol (PAR) at pH 5 to form hydrophobic chelates, which were separated and preconcentrated in a surfactant-rich phase of octylphenoxypolyethoxyethanol (Triton X-114). The parameters affecting the extraction efficiency of the proposed method, such as sample pH, complexing agent concentration, buffer amount, surfactant concentration, temperature, kinetics of complexation reaction, and incubation time were optimized and their respective values were 5, 0.6 mmol L(-1), 0.3 mL, 0.15% (w/v), 50 degrees C, 40 min, and 10 min for 15 mL of preconcentrated solution. The method presented precision (R.S.D.) between 1.3% and 2.6% (n=9). The concentration factors with and without dilution of the surfactant-rich phase for the analytes ranged from 9.4 to 10.1 and from 94.0 to 100.1, respectively. The limits of detection (L.O.D.) obtained for copper, zinc, cadmium, and nickel were 1.2, 1.1, 1.0, and 6.3 microg L(-1), respectively. The accuracy of the procedure was evaluated through recovery experiments on aqueous samples.

  8. Simultaneous preconcentration of vanadium(V/IV) species with palmitoyl quinolin-8-ol bonded to amberlite XAD 2 and their separate spectrophotometric determination with 4-(2-pyridylazo)-resorcinol using CDTA as masking agent

    Energy Technology Data Exchange (ETDEWEB)

    Filik, Hayati; Berker, Kadriye Isil; Balkis, Nuray; Apak, Resat

    2004-08-02

    This paper reports the simultaneous preconcentration and separation of trace amounts of V species in synthetic solutions and seawater with palmitoyl quinolin-8-ol bonded amberlite XAD 2 copolymer resin column prior to simultaneous speciation analysis. Both V(IV) and V(V) species could be sorbed and preconcentrated by the resin. Both vanadium species were quantitatively eluted together from the resin column using HCl as stripping agent and used for speciation studies. For the speciation analysis of eluted V species, the selected route involved spectrophotometric determination of total vanadium with 4-(2-pyridylazo)-resorcinol (PAR) and vanadate estimation by masking vanadyl with 1,2 cyclohexanediaminetetraacetic acid (CDTA). The preconcentrated V species were assayed spectrophotometrically with PAR at 542 nm, and the results were compared with those of FAAS. The detection limits of V(V) with spectrophotometry and FAAS were 1.6 and 0.9 {mu}g l{sup -1}, respectively. The optimal experimental parameters such as pH, sample flow rate, desorption flow rate, redox behaviour of V(IV) and V(V) in resin and volume of eluent and sample were investigated. The values obtained for the preconcentration factor by the two methods were nearly consistent, and were in the range 150-fold. Analysis of certified reference material (IAEA-405) by the proposed method showed good agreement with the certified value. The established procedure was employed for preconcentrating the vanadium species from artificial and real seawater.

  9. Solid-phase extraction and preconcentration of copper in mineral waters with 4-(2-pyridyl-azo) resorcinol-loaded amberlite XAD-7 and flame atomic absorption spectrometry.

    Science.gov (United States)

    Ince, Muharrem; Kaplan, Olcay; Yaman, Mehmet

    2008-11-01

    A simple, sensitive, accurate, and selective method for determination of ultratrace levels of copper is modified. The method is based on preconcentration of copper on the 4-(2-pyridyl-azo) resorcinol-loaded amberlite XAD-7 (non-ionic copoly[styrene-acrylic compound]) at pH 5.0 to 6.5 for contact time as low as 45 minutes. The adsorbed copper was eluted with concentrated nitric acid and measured by flame atomic absorption spectrometry. Recoveries of up to 90% were achieved. The optimized preconcentration method was applied to copper determination in various water samples. The detection limit was found to be 0.09 ng mL(-1). The relative standard deviation was found to be 9% using 300 mL of 5.0 ng mL(-1) for 10 replicate preconcentration procedures. Copper concentrations in the studied water samples were found to be in the ranges of 0.4 to 18.0 ng mL(-1).

  10. Mechanistic study of electrochemical oxidation of catechols in the presence of 4-hydroxy-1-methyl-2(1H)-quinolone

    Energy Technology Data Exchange (ETDEWEB)

    Fakhari, Ali Reza [Department of Chemistry, Faculty of Science, University of Shahid Beheshti, Tehran 19835389 (Iran, Islamic Republic of)]. E-mail: a-zavareh@sbu.ac.ir; Nematollahi, Davood [Department of Chemistry, Faculty of Science, University of Bu-Ali-Sina, Hamadan (Iran, Islamic Republic of); Moghaddam, Abdolmajid Bayandori [Department of Chemistry, Faculty of Science, University of Shahid Beheshti, Tehran 19835389 (Iran, Islamic Republic of)

    2005-09-20

    Electrochemical oxidation of catechols (1a-1c) has been studied in the presence of 4-hydroxy-1-methyl-2(1H)-quinolone (3) as a nucleophile in aqueous solution using cyclic voltammetry and controlled-potential coulometry. The results indicate that the quinones derived from catechols (1a-1c) participate in Michael addition reactions with 3 to form the corresponding benzofuran (or isochromeno[4,3-c]quinoline) derivatives (6a-6c). The electrochemical synthesis of (6a-6c) has been successfully performed in an undivided cell in good yield and purity. The oxidation mechanism was deduced from voltammetric data and by coulometry at controlled-potential. The products have been characterized after purification by IR, {sup 1}H NMR, {sup 13}C NMR and MS.

  11. Observation of UV-induced Auger features in catechol adsorbed on anatase TiO{sub 2} (101) single crystal surface

    Energy Technology Data Exchange (ETDEWEB)

    Thomas, Andrew G. [School of Physics and Astronomy and Photon Science Institute, University of Manchester, Oxford Road, Manchester M13 9PL (United Kingdom); Syres, Karen L. [School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD (United Kingdom)

    2012-04-23

    We have investigated the electronic structure of catechol adsorbed on the anatase TiO{sub 2} (101) surface under illumination with ultraviolet (UV) light (4.75 eV) using resonant photoemission spectroscopy. UV illumination results in the appearance of a strong Ti MVV (M refers to photoionization of 3p level and VV the Auger decay process via the valence levels) feature at a kinetic energy of 26.2 eV. This is attributed to the creation of localised states following catechol to Ti-3d excitation by the UV source. A sharp resonance attributed to excitation from Ti 3p states into these localised states is observed in constant final state spectra.

  12. Formation of environmentally persistent free radicals as the mechanism for reduced catechol degradation on hematite-silica surface under UV irradiation.

    Science.gov (United States)

    Li, Hao; Pan, Bo; Liao, Shaohua; Zhang, Di; Xing, Baoshan

    2014-05-01

    Iron is rich in soils, and is recently reported to form stable complexes with organic free radicals, generating environmentally persistent free radicals (EPFRs). The observation may challenge the common viewpoint that iron is an effective catalyst to facilitate the degradation of various organic chemicals. But no study was specifically designed to investigate the possible inhibited degradation of organic chemicals because of the formation of EPFRs in dry environment. We observed that catechol degradation under UV irradiation was decreased over 20% in silica particles coated with 1% hematite in comparison to uncoated silica particles. Stabilized semiquinone or quinine and phenol radicals were involved in HMT-silica system. EPFR formation was thus the reason for the reduced catechol degradation on HMT-silica surface under UV irradiation at ambient temperature. EPFRs should be incorporated in the studies of organic contaminants geochemical behavior, and will be a new input in their environmental fate modeling.

  13. Protective Role of Maternal P.VAL158MET Catechol-O-methyltransferase Polymorphism against Early-Onset Preeclampsia and its Complications

    Directory of Open Access Journals (Sweden)

    Krnjeta Tijana

    2016-09-01

    Full Text Available Background: Up until now there have been contradictory data about the association between p.Val158Met catechol-O-methyltransferase (COMT polymorphism and risk of preeclampsia (PE. The goal of this study was to assess the potential correlation between p.Val158Met COMT polymorphism and risk of early-onset PE, risk of a severe form of early-onset PE, as well as risk of small-for-gestationalage (SGA complicating PE.

  14. 苯酚双氧水氧化法制邻、对苯二酚%CATECHOL AND HYDROQUINONE FROM HYDROXYLATION OF PHENOL BY HYDROGEN PEROXIDE

    Institute of Scientific and Technical Information of China (English)

    崔咪芬; 乔旭

    2001-01-01

    For the preparation of catechol and hydroquinone from catalytic hydroxylation of phenol by lower concentration aqueous hydrogen peroxide. In the experiment, aqueous phenol solution was added to the reactor in batch to hydrogen peroxide drop by drop. Effects of different molar ratio of phenol and hydrogen peroxide、initial concentration of phenol、reactive temperature etc. on conversion of phenol and selectivity of catechol and hydroquinone were investigated. Under the suitable conditions, the mixture gave 40% conversion of phenol and 90% selectivity of catechol and hydroquinone. The molar ratio of catechol and hydroquinone was 1.6~1.8.%对苯酚、双氧水合成邻、对苯二酚的反应体系,采用苯酚溶液一次性加入反应器、双氧水连续滴加的半间歇操作方式,研究了苯酚与双氧水的摩尔配比、苯酚初浓度、双氧水滴加速率、反应温度等因素对苯酚转化率和邻、对苯二酚选择性的影响。在适宜的工艺条件下,苯酚的转化率可达到40%左右,苯二酚的总选择性可达到90%左右,邻/对比为1.6~1.8。

  15. Cytoprotective Effect of Caffeic Acid Phenethyl Ester (CAPE) and Catechol Ring-Fluorinated CAPE Derivatives Against Menadione-Induced Oxidative Stress in Human Endothelial Cells

    Science.gov (United States)

    2006-03-31

    chlorogenic acid , and rosmari- nic acid did not display any cytoprotective effect in this assay at 15 lM (data not shown). Within the same pas- sage of HUVEC...Cytoprotective effect of caffeic acid phenethyl ester (CAPE) and catechol ring-fluorinated CAPE derivatives against menadione-induced oxidative...accepted 13 March 2006 Available online 31 March 2006 Abstract—Caffeic acid phenethyl ester (CAPE), a natural polyphenolic compound with many

  16. [Preparation of OMC-Au/L-Lysine/Au modified glassy carbon electrode and the study on its detection response to hydroquinone and catechol].

    Science.gov (United States)

    Zhou, Yao-Yu; Tang, Lin; Li, Zhen; Liu, Yuan-Yuan; Yang, Gui-De; Wu, Meng-Shi; Lei, Xiao-Xia; Zheng, Guang-Ming

    2013-03-01

    Ordered mesoporous carbon-Au nanoparticles (OMC-Au) nanocomposites were synthesized by a one-step chemical reduction route, and an OMC-Au/L-Lysine/Au composite film-modified glassy carbon electrode (GCE) was constructed. The microstructure of OMC and OMC-Au/L-Lysine/Au composite films were characterized by SEM, and the preparation process of OMC-Au/L-Lysine/Au modified glassy carbon electrode was investigated using cyclic voltammetry and electrochemical impedance spectroscopy. The electrocatalytic oxidation of hydroquinone and catechol on the modified electrode was discussed by differential pulse voltammetry in this study, and a sensor for separate determination of hydroquinone and catechol based on OMC-Au/L-Lysine/Au modified glassy carbon electrode was developed. Under the optimal conditions, the cathodic peak current was linearly related to hydroquinone concentration over ranges from 1.0 x 10(-6) mol x L(-1) to 8.0 x 10(-4) mol x L(-1) with a detection limit of 3.0 x 10(-7) mol x L(-1), and linearly related to catechol concentration from 1.0 x 10(-7) mol x L(-1) to 8.0 x 10(-5) mol x L(-1) with a detection limit of 8.0 x 10(-7) mol x L(-1).

  17. The Use of Screen-Printed Electrodes in a Proof of Concept Electrochemical Estimation of Homocysteine and Glutathione in the Presence of Cysteine Using Catechol

    Directory of Open Access Journals (Sweden)

    Patricia T. Lee

    2014-06-01

    Full Text Available Screen printed electrodes were employed in a proof of concept determination of homocysteine and glutathione using electrochemically oxidized catechol via a 1,4-Michael addition reaction in the absence and presence of cysteine, and each other. Using cyclic voltammetry, the Michael reaction introduces a new adduct peak which is analytically useful in detecting thiols. The proposed procedure relies on the different rates of reaction of glutathione and homocysteine with oxidized catechol so that at fast voltage scan rates only homocysteine is detected in cyclic voltammetry. At slower scan rates, both glutathione and homocysteine are detected. The combination of the two sets of data provides quantification for homocysteine and glutathione. The presence of cysteine is shown not to interfere provided sufficient high concentrations of catechol are used. Calibration curves were determined for each homocysteine and glutathione detection; where the sensitivities are 0.019 µA·µM−1 and 0.0019 µA·µM−1 and limit of detections are ca. 1.2 µM and 0.11 µM for homocysteine and glutathione, respectively, within the linear range. This work presents results with potential and beneficial use in re-useable and/or disposable point-of-use sensors for biological and medical applications.

  18. The effect of substituents on the surface modification of anatase nanoparticles with catecholate-type ligands: a combined DFT and experimental study.

    Science.gov (United States)

    Savić, Tatjana D; Čomor, Mirjana I; Nedeljković, Jovan M; Veljković, Dušan Ž; Zarić, Snežana D; Rakić, Vesna M; Janković, Ivana A

    2014-10-14

    The surface modification of nanocrystalline TiO2 particles (45 Å) with catecholate-type ligands having different electron donating/electron withdrawing substituent groups, specifically 3-methylcatechol, 4-methylcatechol, 3-methoxycatechol, 3,4-dihydroxybenzaldehyde and 4-nitrocatechol, was found to alter the optical properties of nanoparticles in a similar way to catechol. The formation of the inner-sphere charge-transfer (CT) complexes results in a red shift of the semiconductor absorption compared to unmodified nanocrystallites and a reduction of the effective band gap, being slightly less pronounced in the case of electron withdrawing substituents. The investigated ligands have the optimal geometry for binding to surface Ti atoms, resulting in ring coordination complexes of the catecholate type (binuclear bidentate binding-bridging) thus restoring six-coordinated octahedral geometry of surface Ti atoms. From the absorption measurements (Benesi-Hildebrand plot), the stability constants in methanol/water = 90/10 solutions at pH 2 in the order of 10(3) M(-1) have been determined. The binding structures were investigated by using FTIR spectroscopy. Thermal stability of CT-complexes was investigated by using TG/DSC/MS analysis. Quantum chemical calculations on model systems using density functional theory (DFT) were performed to obtain the vibrational frequencies of charge transfer complexes, and the calculated values were compared with the experimental data.

  19. Speciation analysis of aluminium(III) in natural waters and biological fluids by complexing with various catechols followed by differential pulse voltammetry detection.

    Science.gov (United States)

    Liu, Jian; Bi, Shuping; Yang, Li; Gu, Xiaodong; Ma, Pengju; Gan, Ning; Wang, Xianlong; Long, Xiufeng; Zhang, Fuping

    2002-12-01

    The biological effects of aluminium have received much attention in recent years. Speciation of Al is of basic relevance as it concerns its reactivity and bioavailability. A differential pulse voltammetry (DPV) procedure is proposed for speciation analysis of Al(III) in natural waters and biological fluids using six catechols (L-dopa, dopamine, epinephrine, norepinephrine, caffeic acid and o-benzenediol) as electroactive ligands. The decrease of the DPV anodic peak current for each catechol ligand is linear with the increase of Al concentration. This speciation analysis idea is based on the measurement of the complexation capacity, namely, different affinities of Al(III) for catechols and organic ligands under two pH conditions. The labile monomeric Al fraction (mainly inorganic aluminium) is determined at pH 4.6, while the total monomeric Al fraction is determined at pH 8.5. The principle for Al(III) speciation analysis by an electrochemical method is discussed. This sensitive and simple fractionation method is successfully applied to the speciation analysis of Al in natural waters and the results agree well with those of Driscoll's method. The speciation analysis of Al in biological fluids is also explored and the results are compared with those obtained by ultrafiltration and dialysis. Compared with other speciation protocols the electrochemical method possesses some remarkable advantages: rapidity, high sensitivity, cheap instrumentation and a simple operation procedure.

  20. Regiospecific attack of nitrogen and sulfur nucleophiles on quinones derived from poison oak/ivy catechols (urushiols) and analogues as models for urushiol-protein conjugate formation.

    Science.gov (United States)

    Liberato, D J; Byers, V S; Dennick, R G; Castagnoli, N

    1981-01-01

    Attempts to characterize potential biologically important covalent interactions between electrophilic quinones derived from catechols present in poison oak/ivy (urushiol) and biomacromolecules have led to the analysis of model reactions involving sulfur and amino nucleophiles with 3-heptadecylbenzoquinone. Characterization of the reaction products indicates that this quinone undergoes regiospecific attack by (S)-N-acetylcysteine at C-6 and by 1-aminopentane at C-5. The red solid obtained with 1-aminopentane proved to be 3-heptadecyl-5-(pentylamino)-1,2-benzoquinone. Analogous aminobenzoquinones were obtained with the quinones derived from the 4- and 6-methyl analogues of 3-pentadecylcatechol. All three adducts absorbed visible light at different wavelengths. When the starting catechols were incubated with human serum albumin almost identical chromophores were formed. These results establish that cathechols responsible for the production of the poison oak/ivy contact dermatitis in humans undergo a sequence of reactions in the presence of human serum albumin that lead to covalent attachment of the catechols to the protein via carbon-nitrogen bonds. Estimations of the extent of this binding indicate that, at least with human serum albumin, the reaction is quantitative.

  1. Effect of cobalt doping level of ferrites in enhancing sensitivity of analytical performances of carbon paste electrode for simultaneous determination of catechol and hydroquinone.

    Science.gov (United States)

    Lakić, Mladen; Vukadinović, Aleksandar; Kalcher, Kurt; Nikolić, Aleksandar S; Stanković, Dalibor M

    2016-12-01

    This work presents the simultaneous determination of catechol (CC) and hydroquinone (HQ), employing a modified carbon paste electrode (CPE) with ferrite nanomaterial. Ferrite nanomaterial was doped with different amount of cobalt and this was investigated toward simultaneous oxidation of CC and HQ. It was shown that this modification strongly increases electrochemical characteristics of the CPE. Also, electrocatalytic activity of such materials strongly depends on the level of substituted Co in the ferrite nanoparticles. The modified electrodes, labeled as CoFerrite/CPE, showed two pairs of well-defined redox peaks for the electrochemical processes of catechol and hydroquinone. Involving of ferrite material in the structure of CPE, cause increase in the potentials differences between redox couples of the investigated compounds, accompanied with increases in peaks currents. Several important parameters were optimized and calibration curves, with limits of detection (LOD) of 0.15 and 0.3µM for catechol and hydroquinone, respectively, were constructed by employing amperometric detection. Effect of possible interfering compounds was also studied, and proposed method was successfully applied for CC and HQ quantification in real samples.

  2. Substrate-dependent aromatic ring fission of catechol and 2-aminophenol with O2 catalyzed by a nonheme iron complex of a tripodal N4 ligand.

    Science.gov (United States)

    Lakshman, Triloke Ranjan; Chatterjee, Sayanti; Chakraborty, Biswarup; Paine, Tapan Kanti

    2016-06-07

    The catalytic reactivity of an iron(ii) complex [(TPA)Fe(II)(CH3CN)2](2+) (1) (TPA = tris(2-pyridylmethyl)amine) towards oxygenative aromatic C-C bond cleavage of catechol and 2-aminophenol is presented. Complex 1 exhibits catalytic and regioselective C-C bond cleavage of 3,5-di-tert-butylcatechol (H2DBC) to form intradiol products, whereas it catalyzes extradiol-type C-C bond cleavage of 2-amino-4,6-di-tert-butylphenol (H2AP). The catalytic reactions are found to be pH-dependent and the complex exhibits maximum turnovers at pH 5 in acetonitrile-phthalate buffer. An iron(iii)-catecholate complex [(TPA)Fe(III)(DBC)](+) (2) is formed in the ring cleavage of catechol. In the extradiol-type cleavage of H2AP, an iron(iii)-2-iminobenzosemiquinonate complex [(TPA)Fe(III)(ISQ)](2+) (3) (ISQ = 4,6-di-tert-butyl-2-iminobenzosemiquinonate radical anion) is observed in the reaction pathway. This work shows the importance of the nature of 'redox non-innocent' substrates in governing the mode of ring fission reactivity.

  3. The Use of Screen-Printed Electrodes in a Proof of Concept Electrochemical Estimation of Homocysteine and Glutathione in the Presence of Cysteine Using Catechol

    Science.gov (United States)

    Lee, Patricia T.; Lowinsohn, Denise; Compton, Richard G.

    2014-01-01

    Screen printed electrodes were employed in a proof of concept determination of homocysteine and glutathione using electrochemically oxidized catechol via a 1,4-Michael addition reaction in the absence and presence of cysteine, and each other. Using cyclic voltammetry, the Michael reaction introduces a new adduct peak which is analytically useful in detecting thiols. The proposed procedure relies on the different rates of reaction of glutathione and homocysteine with oxidized catechol so that at fast voltage scan rates only homocysteine is detected in cyclic voltammetry. At slower scan rates, both glutathione and homocysteine are detected. The combination of the two sets of data provides quantification for homocysteine and glutathione. The presence of cysteine is shown not to interfere provided sufficient high concentrations of catechol are used. Calibration curves were determined for each homocysteine and glutathione detection; where the sensitivities are 0.019 μA·μM−1 and 0.0019 μA·μM−1 and limit of detections are ca. 1.2 μM and 0.11 μM for homocysteine and glutathione, respectively, within the linear range. This work presents results with potential and beneficial use in re-useable and/or disposable point-of-use sensors for biological and medical applications. PMID:24926695

  4. Generation of membrane-bound catechol-O-methyl transferase deficient mice with disctinct sex dependent behavioral phenotype.

    Science.gov (United States)

    Tammimaki, A; Aonurm-Helm, A; Zhang, F P; Poutanen, M; Duran-Torres, G; Garcia-Horsman, A; Mannisto, P T

    2016-12-01

    Catechol-O-methyltransferase (COMT) has two isoforms: soluble (S-COMT), which resides in the cytoplasm, and membrane-bound (MB-MT), anchored to intracellular membranes. COMT is involved in the O-methylation of L-DOPA, dopamine and other catechols. The exact role of MB-COMT is still mostly unclear. We wanted to create a novel genetically modified mouse model that specifically lacks MB-COMT activity and to study their behavioral phenotype. MB-COMT knock-in mutant mice were generated by introducing two point mutations in exon 2 of the Comt gene (ATGCTG->GAGCTC disabling the function of the P2 promoter and allowing only the P1-regulated S-COMT transcription. The first mutation changes methionine to glutamic acid whereas the second one does not affect coding. The expression of the two COMT isoforms, total COMT activity in several areas of the brain and peripheral tissues and extracellular dopamine concentrations after L-DOPA (10 mg/kg) and carbidopa (30 mg/kg) subcutaneous administration were assessed. A battery of behavioral tests was performed to compare MB-COMT deficient mice and their wild type littermates of both sexes. MB-COMT deficient mice were seemingly normal, bred usually and had unaltered COMT activity in the brain and periphery despite a complete lack of the MB-COMT protein. MB-COMT deficient male mice showed higher extracellular dopamine levels than their wild-type littermates in the striatum, but not in the mPFC. In addition, the MB-COMT deficient male mice exhibited a distinct endophenotype characterized by schizophrenia-related behaviors like aggressive behavior and reduced prepulse inhibition. They also had prolonged immobility in the tail suspension test. Both sexes were sensitized to acute pain and had normal motor activity but disturbed short-term memory. Hence the behavioral phenotype was not limited to schizophrenia-related endophenotype and some behavioural findings were not sex-dependent. Our findings indicate that MB-COMT is critical for

  5. 流动注射-Luminol/Tween20化学发光体系测定邻苯二酚%Determination of catechol with flow injection-luminol/Tween 20 chemiluminescence system

    Institute of Scientific and Technical Information of China (English)

    谢建新; 伍贤学

    2013-01-01

    基于邻苯二酚对luminol-Tween 20化学发光体系的强烈的抑制作用,建立了一种简单、灵敏的luminol-Tween 20化学发光体系测定邻苯二酚的新方法.在最佳实验条件下,方法的检出限为5.0 ×l0-10mo1/L,线性范围为1.0 × 10-9mol/L~1.0×10-2mol/L,对5.0×10-8mol/L邻苯二酚进行平行测定11次,其RSD为4.1%.该方法可应用于自来水样中邻苯二酚的测定.%A simple and sensitive flow injection-chemiluminescence (CL) system of luminol-Tween 20 for the direct determination of catechol was developed.Proposed method was based on the strongly inhibition effect of catechol on the CL intensity of luminol-Tween 20 system.Under the optimial conditions,catechol was determined.The detection limit of the method is 5.0 × 10-10mol/L for catechol,the linear range for catechol is 1.0 × 10-9mol/L ~ 1.0 × 10-7mol/L.The relative standard deviation is 4.1% for 5.0 × 10-8mol/L catechol in 11 repeated measurements.The method was successfully applied to the detection of catechol in tap water samples.

  6. Catechol-o-methyltransferase gene polymorphism modifies the effect of coffee intake on incidence of acute coronary events.

    Directory of Open Access Journals (Sweden)

    Pertti Happonen

    Full Text Available BACKGROUND: The role of coffee intake as a risk factor for coronary heart disease (CHD has been debated for decades. We examined whether the relationship between coffee intake and incidence of CHD events is dependent on the metabolism of circulating catecholamines, as determined by functional polymorphism of the catechol-O-methyltransferase (COMT gene. METHODOLOGY/PRINCIPAL FINDINGS: In a cohort of 773 men who were 42 to 60 years old and free of symptomatic CHD at baseline in 1984-89, 78 participants experienced an acute coronary event during an average follow-up of 13 years. In logistic regression adjusting for age, smoking, family history of CHD, vitamin C deficiency, blood pressure, plasma cholesterol concentration, and diabetes, the odds ratio (90% confidence interval comparing heavy coffee drinkers with the low activity COMT genotype with those with the high activity or heterozygotic genotypes was 3.2 (1.2-8.4. Urinary adrenaline excretion increased with increasing coffee intake, being over two-fold in heavy drinkers compared with nondrinkers (p = 0.008 for trend. CONCLUSIONS/SIGNIFICANCE: Heavy coffee consumption increases the incidence of acute coronary events in men with low but not high COMT activity. Further studies are required to determine to which extent circulating catecholamines mediate the relationship between coffee intake and CHD.

  7. A novel prokaryotic expression system for biosynthesis of recombinant human membrane-bound catechol-O-methyltransferase.

    Science.gov (United States)

    Pedro, A Q; Bonifácio, M J; Queiroz, J A; Maia, C J; Passarinha, L A

    2011-11-10

    Membrane proteins constitute 20-30% of all proteins encoded by the genome of various organisms. While large amounts of purified proteins are required for pharmaceutical and crystallization attempts, there is an unmet need for the development of novel heterologous membrane protein overexpression systems. Specifically, we tested the application of Brevibacillus choshinensis cells for the biosynthesis of human membrane bound catechol-O-methyltransferase (hMBCOMT). In terms of the upstream stage moderate to high expression was obtained for complex media formulation with a value near 45 nmol/h/mg for hMBCOMT specific activity achieved at 20 h culture with 37°C and 250 rpm. Subsequently, the efficiency for reconstitution of hMBCOMT is markedly null in the presence of ionic detergents, such as sodium dodecyl sulphate (SDS). In general, for non-ionic and zwiterionic detergents, until a detergent critic micellar concentration (CMC) of 1.0 mM, hMBCOMT shows more biological activity at lower detergent concentrations while for detergent CMC higher than 1 mM, higher detergent concentrations seem to be ideal for hMBCOMT solubilization. Indeed, from the detergents tested, the non-ionic digitonin at 0.5% (w/v) appears to be the most suitable for hMBCOMT solubilization. Copyright © 2011 Elsevier B.V. All rights reserved.

  8. Association between the catechol-o-methyltransferase val158met polymorphism with susceptibility and severity of carpal tunnel syndrome

    Directory of Open Access Journals (Sweden)

    Erkol İnal E

    2015-12-01

    Full Text Available Carpal tunnel syndrome (CTS is the most common entrapment neuropathy of the upper extremity. In this study, we aimed to clarify the relationships between the catechol-O-methyltransferase (COMT gene Val158Met (rs4680 polymorphism and development, functional and clinical status of CTS. Ninety-five women with electro diagnostically confirmed CTS and 95 healthy controls were enrolled in the study. The functional and clinical status of the patients was measured by the Turkish version of the Boston Questionnaire and intensity of pain related to the past 2 weeks was evaluated on a visual analog scale (VAS. The Val158Met polymorphism was determined using the polymerase chain reaction-restriction fragment length polymorphism (PCR-RFLP, method. We divided patients according to the genotypes of the Val158Met polymorphism as Val/Val, Val/Met and Met/Met. There were not any significant differences in terms of Val158Met polymorphisms between patients and healthy controls (p >0.05. We also did not find any relationships between the Val158Met polymorphism and CTS (p >0.05. In conclusion, although we did not find any relationships between CTS and the Val158Met polymorphism, we could not generalize this result to the general population. Future studies are warranted to conclude precise associations.

  9. Iron binding efficiency of polyphenols: Comparison of effect of ascorbic acid and ethylenediaminetetraacetic acid on catechol and galloyl groups.

    Science.gov (United States)

    Tamilmani, Poonkodi; Pandey, Mohan Chandra

    2016-04-15

    Dietary polyphenols are markedly studied for their antioxidant activity. They also have a negative impact on nutrition whereby they interfere with iron absorption. Common dietary polyphenols include: catechins, flavonols, flavanols, flavones, anthocyanins, proanthocyanidins and phenolic acids. Ascorbic acid (AA) and Ethylenediaminetetraacetic acid (EDTA) are commonly used to counter act this reaction and increase iron bioavailability. This study was aimed at determining the effect of AA and EDTA on the catechol or galloyl iron binding ability of pure phenolics, coffee and tea. Phenolic concentrations of 40, 80, 610, 240, 320, 400, 520 and 900 μg/ml were tested against six levels of AA and EDTA. These effects were studied in detail using Multivariate Analysis of Variance (MANOVA) with the hypothesis that there would be one or more mean differences between the ratio of enhancer and the different concentrations of samples tested. AA was found to be more efficient than EDTA in a way that lesser quantity is required for completely overcoming negative iron binding effects of polyphenols and similar samples.

  10. Genetic contribution of catechol-O-methyltransferase polymorphism (Val158Met) in children with chronic tension-type headache.

    Science.gov (United States)

    Fernández-de-las-Peñas, César; Ambite-Quesada, Silvia; Rivas-Martínez, Inés; Ortega-Santiago, Ricardo; de-la-Llave-Rincón, Ana Isabel; Fernández-Mayoralas, Daniel M; Pareja, Juan A

    2011-10-01

    Our aim was to investigate the relationship between Val158Met polymorphisms, headache, and pressure hypersensitivity in children with chronic tension-type headache (CTTH). A case-control study with blinded assessor was conducted. Seventy children with CTTH associated with pericranial tenderness and 70 healthy children participated. After amplifying Val158Met polymorphism by polymerase chain reactions, we assessed genotype frequencies and allele distributions. We classified children according to their Val158Met polymorphism: Val/Val, Val/Met, Met/Met. Pressure pain thresholds (PPT) were bilaterally assessed over the temporalis, upper trapezius, second metacarpal, and tibialis anterior muscles. The distribution of Val158Met genotypes was not significantly different (p = 0.335), between children with CTTH and healthy children, and between boys and girls (p = 0.872). Children with CTTH with the Met/Met genotype showed a longer headache history compared with those with Met/Val (p = 0.001) or Val/Val (p = 0.002) genotype. Children with CTTH with Met/Met genotype showed lower PPT over upper trapezius and temporalis muscles than children with CTTH with Met/Val or Val/Val genotype (p < 0.01). The Val158Met catechol-O-methyltransferase (COMT) polymorphism does not appear to be involved in predisposition to suffer from CTTH in children; nevertheless, this genetic factor may be involved in the phenotypic expression, as pressure hypersensitivity was greater in those CTTH children with the Met/Met genotype.

  11. The effect of GSM and TETRA mobile handset signals on blood pressure, catechol levels and heart rate variability.

    Science.gov (United States)

    Barker, Anthony T; Jackson, Peter R; Parry, Helen; Coulton, Leslie A; Cook, Greg G; Wood, Steven M

    2007-09-01

    An acute rise in blood pressure has been reported in normal volunteers during exposure to signals from a mobile phone handset. To investigate this finding further we carried out a double blind study in 120 healthy volunteers (43 men, 77 women) in whom we measured mean arterial pressure (MAP) during each of six exposure sessions. At each session subjects were exposed to one of six different radio frequency signals simulating both GSM and TETRA handsets in different transmission modes. Blood catechols before and after exposure, heart rate variability during exposure, and post exposure 24 h ambulatory blood pressure were also studied. Despite having the power to detect changes in MAP of less than 1 mmHg none of our measurements showed any effect which we could attribute to radio frequency exposure. We found a single statistically significant decrease of 0.7 mmHg (95% CI 0.3-1.2 mmHg, P = .04) with exposure to GSM handsets in sham mode. This may be due to a slight increase in operating temperature of the handsets when in this mode. Hence our results have not confirmed the original findings of an acute rise in blood pressure due to exposure to mobile phone handset signals. In light of this negative finding from a large study, coupled with two smaller GSM studies which have also proved negative, we are of the view that further studies of acute changes in blood pressure due to GSM and TETRA handsets are not required.

  12. Catechol-O-methyltransferase (COMT Genotype Affects Age-Related Changes in Plasticity in Working Memory: A Pilot Study

    Directory of Open Access Journals (Sweden)

    Stephan Heinzel

    2014-01-01

    Full Text Available Objectives. Recent work suggests that a genetic variation associated with increased dopamine metabolism in the prefrontal cortex (catechol-O-methyltransferase Val158Met; COMT amplifies age-related changes in working memory performance. Research on younger adults indicates that the influence of dopamine-related genetic polymorphisms on working memory performance increases when testing the cognitive limits through training. To date, this has not been studied in older adults. Method. Here we investigate the effect of COMT genotype on plasticity in working memory in a sample of 14 younger (aged 24–30 years and 25 older (aged 60–75 years healthy adults. Participants underwent adaptive training in the n-back working memory task over 12 sessions under increasing difficulty conditions. Results. Both younger and older adults exhibited sizeable behavioral plasticity through training (P<.001, which was larger in younger as compared to older adults (P<.001. Age-related differences were qualified by an interaction with COMT genotype (P<.001, and this interaction was due to decreased behavioral plasticity in older adults carrying the Val/Val genotype, while there was no effect of genotype in younger adults. Discussion. Our findings indicate that age-related changes in plasticity in working memory are critically affected by genetic variation in prefrontal dopamine metabolism.

  13. Association between cerebrospinal fluid dopamine concentrations and catechol-O-methyltransferase gene polymorphisms in forensic autopsy cases of methamphetamine abusers.

    Science.gov (United States)

    Matsusue, Aya; Ishikawa, Takaki; Michiue, Tomomi; Waters, Brian; Hara, Kenji; Kashiwagi, Masayuki; Takayama, Mio; Ikematsu, Natsuki; Kubo, Shin-Ichi

    2017-01-01

    Methamphetamine (MA) is an illicit psychostimulant that stimulates the release of catecholamines from sympathetic nerve terminals and is widely abused worldwide. Since catechol-O-methyltransferase (COMT) metabolizes catecholamines and mediates adrenergic, noradrenergic, and dopaminergic signaling responses, we investigated the effects of the COMT polymorphisms rs4633 and rs4680 on cerebrospinal fluid (CSF) catecholamine concentrations in autopsies of subjects who died of drug intoxication. 28 MA abusers and 22 fatal psychotropic drug intoxication cases were evaluated. No correlations were identified between rs4633 or rs4680 polymorphisms and CSF concentrations of adrenaline (Adr), noradrenaline (Nad), or dopamine (DA) in fatal psychotropic cases. However, among MA abusers, DA concentrations in the CSF were significantly higher in those with the T allele (CT and TT) of rs4633 than in CC genotype carriers (p=0.004). Moreover, among MA abusers, DA concentrations were significantly higher in those with the A allele (GA and AA) of rs4680 than in GG genotype carriers (p=0.017). In subsequent haplotype analyses of MA abusers, a strong correlation was identified between two COMT haplotypes and CSF DA concentrations (p=0.002). However, the CSF concentrations of Adr and Nad were not associated with COMT genotypes or haplotypes. The present results indicate that rs4633 and rs4680 polymorphisms influence CSF DA concentrations and MA toxicity in MA abusers.

  14. Catechol-O-Methyltransferase (COMT Val108/158 Met polymorphism does not modulate executive function in children with ADHD

    Directory of Open Access Journals (Sweden)

    Stepanian Marina

    2004-12-01

    Full Text Available Abstract Background An association has been observed between the catechol-O-methyltransferase (COMT gene, the predominant means of catecholamine catabolism within the prefrontal cortex (PFC, and neuropsychological task performance in healthy and schizophrenic adults. Since several of the cognitive functions typically deficient in children with Attention Deficit Hyperactivity Disorder (ADHD are mediated by prefrontal dopamine (DA mechanisms, we investigated the relationship between a functional polymorphism of the COMT gene and neuropsychological task performance in these children. Methods The Val108/158 Met polymorphism of the COMT gene was genotyped in 118 children with ADHD (DSM-IV. The Wisconsin Card Sorting Test (WCST, Tower of London (TOL, and Self-Ordered Pointing Task (SOPT were employed to evaluate executive functions. Neuropsychological task performance was compared across genotype groups using analysis of variance. Results ADHD children with the Val/Val, Val/Met and Met/Met genotypes were similar with regard to demographic and clinical characteristics. No genotype effects were observed for WCST standardized perseverative error scores [F2,97 = 0.67; p > 0.05], TOL standardized scores [F2,99 = 0.97; p > 0.05], and SOPT error scores [F2,108 = 0.62; p > 0.05]. Conclusions Contrary to the observed association between WCST performance and the Val108/158 Met polymorphism of the COMT gene in both healthy and schizophrenic adults, this polymorphism does not appear to modulate executive functions in children with ADHD.

  15. Graphene-like carbon nanosheets as a new electrode material for electrochemical determination of hydroquinone and catechol.

    Science.gov (United States)

    Jiang, Hongmei; Wang, Shuqin; Deng, Wenfang; Zhang, Youming; Tan, Yueming; Xie, Qingji; Ma, Ming

    2017-03-01

    We report here graphene-like carbon nanosheets (GCN) as a new electrode material for the electrochemical determination of hydroquinone (HQ) and catechol (CC). The GCN were prepared from maltose using ammonia chloride as a blowing agent and cobalt nitrate as a graphitization catalyst precursor. The as-prepared GCN material shows high graphitization degree, abundant porosity, and large specific surface area. Two well-separated anodic peaks for HQ and CC are obtained at GCN modified glassy carbon electrode (GCE) with a peak-to-peak separation of 118mV. The redox peak currents of HQ and CC at GCN/GCE were much higher than those at bare GCE and reduced graphene oxide modified GCE. For differential pulse voltammetric detection of HQ and CC, the GCN/GCE shows linear response ranges of 1×10(-7) ̶ 3×10(-5)M for HQ and 5×10(-7) ̶ 5×10(-5)M for CC, with detection limits of 2×10(-8)M for HQ, and 5×10(-8) M for CC. Satisfactory recoveries were achieved for the determination of HQ and CC in real water samples.

  16. Association between the Catechol O-methyltransferase (COMT Val158met polymorphism and different dimensions of impulsivity.

    Directory of Open Access Journals (Sweden)

    Leandro Fernandes Malloy-Diniz

    Full Text Available BACKGROUND: Impulsivity is a multidimensional construct which has been associated with dopaminergic neurotransmission. Nonetheless, until this moment, few studies addressed the relationship between different types of impulsivity and the single nucleotide polymorphism caused by a substitution of valine (val with methionine (met in the 158 codon of the Catechol-o-Methyltransferase gene (COMT-val158met. The present study aimed to investigate the association between val158met COMT polymorphism and impulsive behavior measured by two neuropsychological tests. METHODOLOGY/PRINCIPAL FINDINGS: We administered two neuropsychological tests, a Continuous Performance Task and the Iowa Gambling Task were applied to 195 healthy participants to characterize their levels of motor, attentional and non-planning impulsivity. Then, subjects were grouped by genotype, and their scores on impulsivity measures were compared. There were no significant differences between group scores on attentional and motor impulsivity. Those participants who were homozygous for the met allele performed worse in the Iowa Gambling Task than val/val and val/met subjects. CONCLUSIONS/SIGNIFICANCE: Our results suggest that met allele of val158met COMT polymorphism is associated with poor performance in decision-making/cognitive impulsivity task. The results reinforce the hypothesis that val and met alleles of the val158met polymorphism show functional dissociation and are related to different prefrontal processes.

  17. One pot electrochemical synthesis of poly(melamine) entrapped gold nanoparticles composite for sensitive and low level detection of catechol.

    Science.gov (United States)

    Palanisamy, Selvakumar; Ramaraj, Sayee Kannan; Chen, Shen-Ming; Chiu, Te-Wei; Velusamy, Vijayalakshmi; Yang, Thomas C K; Chen, Tse-Wei; Selvam, Sonadevi

    2016-12-29

    A simple and cost effective synthesis of nanomaterials with advanced physical and chemical properties have received much attention to the researchers, and is of interest to the researchers from different disciplines. In the present work, we report a simple and one pot electrochemical synthesis of poly(melamine) entrapped gold nanoparticles (PM-AuNPs) composite. The PM-AuNPs composite was prepared by a single step electrochemical method, wherein the AuNPs and PM were simultaneously fabricated on the electrode surface. The as-prepared materials were characterized by various physicochemical methods. The PM-AuNPs composite modified electrode was used as an electrocatalyst for oxidation of catechol (CC) due to its well-defined redox behavior and enhanced electro-oxidation ability towards CC than other modified electrodes. Under optimized conditions, the differential pulse voltammetry (DPV) was used for the determination of CC. The DPV response of CC was linear over the concentration ranging from 0.5 to 175.5μM with a detection limit of 0.011μM. The PM-AuNPs composite modified electrode exhibits the high selectivity in the presence of range of potentially interfering compounds including dihydroxybenzene isomers. The sensor shows excellent practicality in CC containing water samples, which reveals the potential ability of PM-AuNPs composite modified electrode towards the determination of CC in real samples.

  18. Catechol-O-methyltransferase (COMT) Genotype Affects Age-Related Changes in Plasticity in Working Memory: A Pilot Study

    Science.gov (United States)

    Riemer, Thomas G.; Schulte, Stefanie; Onken, Johanna; Heinz, Andreas; Rapp, Michael A.

    2014-01-01

    Objectives. Recent work suggests that a genetic variation associated with increased dopamine metabolism in the prefrontal cortex (catechol-O-methyltransferase Val158Met; COMT) amplifies age-related changes in working memory performance. Research on younger adults indicates that the influence of dopamine-related genetic polymorphisms on working memory performance increases when testing the cognitive limits through training. To date, this has not been studied in older adults. Method. Here we investigate the effect of COMT genotype on plasticity in working memory in a sample of 14 younger (aged 24–30 years) and 25 older (aged 60–75 years) healthy adults. Participants underwent adaptive training in the n-back working memory task over 12 sessions under increasing difficulty conditions. Results. Both younger and older adults exhibited sizeable behavioral plasticity through training (P < .001), which was larger in younger as compared to older adults (P < .001). Age-related differences were qualified by an interaction with COMT genotype (P < .001), and this interaction was due to decreased behavioral plasticity in older adults carrying the Val/Val genotype, while there was no effect of genotype in younger adults. Discussion. Our findings indicate that age-related changes in plasticity in working memory are critically affected by genetic variation in prefrontal dopamine metabolism. PMID:24772423

  19. How Large Should the QM Region Be in QM/MM Calculations? The Case of Catechol O-Methyltransferase.

    Science.gov (United States)

    Kulik, Heather J; Zhang, Jianyu; Klinman, Judith P; Martínez, Todd J

    2016-11-10

    Hybrid quantum mechanical-molecular mechanical (QM/MM) simulations are widely used in studies of enzymatic catalysis. Until recently, it has been cost prohibitive to determine the asymptotic limit of key energetic and structural properties with respect to increasingly large QM regions. Leveraging recent advances in electronic structure efficiency and accuracy, we investigate catalytic properties in catechol O-methyltransferase, a prototypical methyltransferase critical to human health. Using QM regions ranging in size from reactants-only (64 atoms) to nearly one-third of the entire protein (940 atoms), we show that properties such as the activation energy approach within chemical accuracy of the large-QM asymptotic limits rather slowly, requiring approximately 500-600 atoms if the QM residues are chosen simply by distance from the substrate. This slow approach to asymptotic limit is due to charge transfer from protein residues to the reacting substrates. Our large QM/MM calculations enable identification of charge separation for fragments in the transition state as a key component of enzymatic methyl transfer rate enhancement. We introduce charge shift analysis that reveals the minimum number of protein residues (approximately 11-16 residues or 200-300 atoms for COMT) needed for quantitative agreement with large-QM simulations. The identified residues are not those that would be typically selected using criteria such as chemical intuition or proximity. These results provide a recipe for a more careful determination of QM region sizes in future QM/MM studies of enzymes.

  20. Association between the Catechol-O-Methyltransferase (COMT) Val158Met Polymorphism and Manual Aiming Control in Healthy Subjects

    Science.gov (United States)

    Lage, Guilherme M.; Miranda, Débora M.; Romano-Silva, Marco A.; Campos, Simone B.; Albuquerque, Maicon R.; Corrêa, Humberto; Malloy-Diniz, Leandro F.

    2014-01-01

    Background Prefrontal dopamine is catabolized by the catechol-O-methyltransferase (COMT) enzyme. Current evidence suggests that the val/met single nucleotide polymorphism in the COMT gene can predict the efficiency of executive cognition in humans. Individuals carrying the val allele perform more poorly because less synaptic dopamine is available. Methodology/Principal Findings We investigated the influence of the COMT polymorphism on motor performance in a task that requires different executive functions. We administered a manual aiming motor task that was performed under four different conditions of execution by 111 healthy participants. Participants were grouped according to genotype (met/met, met/val, val/val), and the motor performance among groups was compared. Overall, the results indicate that met/met carriers presented lower levels of peak velocity during the movement trajectory than the val carriers, but met/met carriers displayed higher accuracy than the val carriers. Conclusions/Significance This study found a significant association between the COMT polymorphism and manual aiming control. Few studies have investigated the genetics of motor control, and these findings indicate that individual differences in motor control require further investigation using genetic studies. PMID:24956262

  1. Expression, Purification and Activity Assay of the Recombinant Protein of Catechol-O-Methyltransferase from Chinese White Shrimp (Fenneropenaeus chinensis

    Directory of Open Access Journals (Sweden)

    Dian-Xiang Li

    2010-01-01

    Full Text Available Problem statement: We have previously cloned a gene of Chinese white shrimp Catechol O-Methyltransferase (designated Fc-COMT and characterized the gene expression pattern. In this study, expression and purification as well as activity assay of the recombinant Fc-COMT was further conducted. Approach: Using pET-30a (+ as a prokaryotic expression vector, the recombinant Fc- COMT was expressed in the supernatant of Escherichia coli lysate and easily purified by His-Bind resin chromatography. SDS-PAGE analysis showed that the molecular mass of recombinant Fc-COMT was approximately 30,000 Da, in good agreement with the software-predicted molecular weight. The enzymatic activity of recombinant Fc-COMT was tested using Dihydroxybenzoic Acid (DHBAc as a substrate. Results: The methyl products of DHBAc, Vanillic Acid (VA and Isovanillic Acid (IVA, were detected in the enzymatic reaction mixture with recombinant Fc-COMT by High Performance Liquid Chromatography-Mass Spectrometry (HPLC-MS. Conclusion: The recombinant Fc-COMT has catalytic activity of transferring methyl group from S-Adenosyl-L-Methionine (SAM to the 3’ hydroxyl or 4’ hydroxyl group of benzyl ring of DHBAc.

  2. Catechol-O-methyltransferase Val158met Polymorphism Interacts With Early Experience to Predict Executive Functions in Early Childhood

    Science.gov (United States)

    Blair, Clancy; Sulik, Michael; Willoughby, Michael; Mills-Koonce, Roger; Petrill, Stephen; Bartlett, Christopher; Greenberg, Mark

    2017-01-01

    Numerous studies demonstrate that the Methionine variant of the catechol-O-methyltransferase Val158Met polymorphism, which confers less efficient catabolism of catecholamines, is associated with increased focal activation of prefrontal cortex (PFC) and higher levels of executive function abilities. By and large, however, studies of COMT Val158Met have been conducted with adult samples and do not account for the context in which development is occurring. Effects of early adversity on stress response physiology and the inverted U shape relating catecholamine levels to neural activity in PFC indicate the need to take into account early experience when considering relations between genes such as COMT and executive cognitive ability. Consistent with this neurobiology, we find in a prospective longitudinal sample of children and families (N=1292) that COMT Val158Met interacts with early experience to predict executive function abilities in early childhood. Specifically, the Valine variant of the COMT Val158Met polymorphism, which confers more rather than less efficient catabolism of catecholamines is associated with higher executive function abilities at child ages 48 and 60 months and with faster growth of executive function for children experiencing early adversity, as indexed by cumulative risk factors in the home at child ages 7, 15, 24, and 36 months. Findings indicate the importance of the early environment for the relation between catecholamine genes and developmental outcomes and demonstrate that the genetic moderation of environmental risk is detectable in early childhood. PMID:26251232

  3. Association study between the rs165599 catechol-O-methyltransferase genetic polymorphism and schizophrenia in a Brazilian sample

    Directory of Open Access Journals (Sweden)

    Quirino Cordeiro

    2012-12-01

    Full Text Available Schizophrenia is a severe psychiatric disorder with frequent recurrent psychotic relapses and progressive functional impairment. It results from a poorly understood gene-environment interaction. The gene encoding catechol-O-methyltransferase (COMT is a likely candidate for schizophrenia. Its rs165599 (A/G polymorphism has been shown to be associated with alteration of COMT gene expression. Therefore, the present study aimed to investigate a possible association between schizophrenia and this polymorphism. The distribution of the alleles and genotypes of this polymorphism was investigated in a Brazilian sample of 245 patients and 834 controls. The genotypic frequencies were in Hardy-Weinberg equilibrium and no statistically significant differences were found between cases and controls when analyzed according to gender or schizophrenia subtypes. There was also no difference in homozygosis between cases and controls. Thus, in the sample studied, there was no evidence of any association between schizophrenia and rs165599 (A/G polymorphism in the non-coding region 3' of the COMT gene.

  4. Self-healable mussel-mimetic nanocomposite hydrogel based on catechol-containing polyaspartamide and graphene oxide.

    Science.gov (United States)

    Wang, Bo; Jeon, Young Sil; Park, Ho Seok; Kim, Ji-Heung

    2016-12-01

    Stimuli-responsive and self-healing materials have a wide range of potential uses, and some significant research has focused on cross-linking of hydrogel materials by means of reversible coordination bonding. The resulting materials, however, tend to have poor mechanical properties with pronounced weakness and brittleness. In this work, we present a novel mussel-inspired graphene oxide(GO)-containing hydrogel based on modified polyaspartamide with γ-amino butyric acid (GABA), 3.4-dihydroxyphenethylamine (DOPA), and ethanolamine (EA), termed PolyAspAm(GABA/DOPA/EA). Here both GO nanosheets and boric acid (H3BO3) act as cross-linkers, interacting with polar functional groups of the PolyAspAm(GABA/DOPA/EA). Compared to PolyAspAm(GABA/DOPA/EA)/B(3+) gel without GO, the same containing 5wt% of GO yielded a 10-fold increase in both the storage and loss moduli, as well as 134% and 104% increases in the tensile and compressive strengths, respectively. In addition, the GO-containing polyaspartamide hydrogel exhibited rapid and autonomous self-healing property. Two types of bonding, boron-catechol coordination and strong hydrogen bonding interactions between PolyAspAm side chains and GO nanosheets, would impart the enhanced mechanical strength and good reversible gelation behavior upon pH stimulation to the hydrogel, making this biocompatible hydrogel a promising soft matter for biomedical applications.

  5. The catechol-O-methyltransferase inhibitor, tolcapone, increases the bioavailability of unmethylated (−)-epigallocatechin-3-gallate in mice*

    Science.gov (United States)

    Forester, Sarah C.; Lambert, Joshua D.

    2015-01-01

    (−)-Epigallocatechin-3-gallate (EGCG), has been shown to inhibit cancer in vivo. EGCG, however, is rapidly methylated by catechol-O-methyl transferase (COMT), which reduces its cancer preventive efficacy. Tolcapone (TOL), is a clinically-used COMT inhibitor. Here, we examined the effect of TOL on the bioavailability of EGCG in male CF-1 mice. Plasma and tissue levels of EGCG and its methyl metabolites were determined following intragastric administration of EGCG (100 mg/kg), TOL (30 mg/kg), or the combination. In mice treated with EGCG, unmethylated plasma EGCG accounted for 63.4 % of the total. Co-administration of TOL increased this fraction to 87.9 %. In the urine, unmethylated EGCG accounted for 29.2 % of the total, whereas treatment with EGCG plus TOL increased this to 81.8 %. Similar effects were observed in the major organs examined. TOL effectively inhibited the methylation of EGCG in vivo. Future studies should examine the cancer preventive effects of the combination. PMID:26213577

  6. Race Moderates the Association of Catechol-O-methyltransferase Genotype and Posttraumatic Stress Disorder in Preschool Children

    Science.gov (United States)

    Humphreys, Kathryn L.; Scheeringa, Michael S.

    2014-01-01

    Abstract Objective: The present study sought to replicate previous findings of an association between the Catechol-O-methyltransferase (COMT) val158met polymorphism with posttraumatic stress disorder (PTSD) and symptomatology in a novel age group, preschool children. Methods: COMT genotype was determined in a sample of 171 3–6-year-old trauma-exposed children. PTSD was assessed with a semistructured interview. Accounting for sex, trauma type, and age, genotype was examined in relation to categorical and continuous measures of PTSD both controlling for race and within the two largest racial categories (African American [AA] and European American [EA]). Results: Race significantly moderated the association between genotype and PTSD. Specifically, the genotype associated with increased PTSD symptoms in one racial group had the opposite association in the other racial group. For AA children the met/met genotype was associated with more PTSD symptoms. However, for EA children, val allele carriers had more PTSD symptoms. Whereas every AA child with the met/met genotype met criteria for PTSD, none of the EA children with the met/met genotype did. This genetic association with COMT genotype, in both races but in opposite directions, was most associated with increased arousal symptoms. Conclusions: These findings replicate previous findings in participants of African descent, highlight the moderating effect of race on the association between COMT genotype and PTSD, and provide direct evidence that consideration of population stratification within gene-by-environment studies is valuable to prevent false negative findings. PMID:25329975

  7. Iron Oxide Surface Chemistry: The Effect of Chemical Structure on Binding in Benzoic Acid and Catechol Derivatives.

    Science.gov (United States)

    Korpany, Katalin V; Majewski, Dorothy D; Chiu, Cindy T; Cross, Shoronia N; Blum, Amy Szuchmacher

    2017-02-18

    Excellent performance of functionalized iron oxide nanoparticles in nanomaterial and biomedical applications often relies on achieving attachment of ligands to the iron oxide surface both in sufficient number and with proper orientation. Towards this end, we determine relationships between ligand chemical structure and surface binding on magnetic iron oxide nanoparticles for a series of related benzoic acid and catechol derivatives. Ligand exchange was used to introduce the model ligands, and the resulting nanoparticles were characterized by FTIR-ATR, transmission electron microscopy (TEM), and nanoparticle solubility behavior. An in-depth analysis of ligand electronic effects and reaction conditions reveals that the nature of ligand binding does not solely depend on the presence of functional groups known to bind to iron oxide nanoparticles. The structure of the resulting ligand-surface complex was primarily influenced by the relative positioning of hydroxyl and carboxylic acid groups within the ligand as well as whether or not HCl(aq) was added to the ligand exchange reaction. Overall, this study will help guide future ligand design and ligand exchange strategies towards realizing truly custom-built iron oxide nanoparticles.

  8. Metabolic Disposition of Luteolin Is Mediated by the Interplay of UDP-Glucuronosyltransferases and Catechol-O-Methyltransferases in Rats.

    Science.gov (United States)

    Wang, Liping; Chen, Qingwei; Zhu, Lijun; Li, Qiang; Zeng, Xuejun; Lu, Linlin; Hu, Ming; Wang, Xinchun; Liu, Zhongqiu

    2017-03-01

    Luteolin partially exerts its biologic effects via its metabolites catalyzed by UDP-glucuronosyltransferases (UGTs) and catechol-O-methyltransferases (COMTs). However, the interplay of UGTs and COMTs in mediating luteolin disposition has not been well clarified. In this study, we investigated the glucuronidation and methylation pathways of luteolin mediated by the interplay of UGTs and COMTs in vivo and in vitro. A total of nine luteolin metabolites was detected in rat plasma and bile by liquid chromatography-tandem mass spectrometry, namely, three glucuronides, two methylated metabolites, and four methylated glucuronides. Luteolin-3'-glucuronide (Lut-3'-G) exhibited the highest systemic exposure among these metabolites. Kinetics studies in rat liver S9 fractions suggested two pathways, as follows: 1) Luteolin was glucuronidated to luteolin-7-glucuronide, luteolin-4'-glucuronide, and Lut-3'-G by UGTs, and then Lut-7-G was methylated to chrysoeriol-7-glucuronide and diosmetin-7-glucuronide by COMTs. 2) Alternatively, luteolin was methylated to chrysoeriol and diosmetin by COMTs, and then chrysoeriol and diosmetin were glucuronidated by UGTs to their respective glucuronides. The methylation rate of luteolin was significantly increased by the absence of glucuronidation, whereas the glucuronidation rate was increased by the absence of methylation, but to a lesser extent. In conclusion, two pathways mediated by the interplay of UGTs and COMTs are probably involved in the metabolic disposition of luteolin. The glucuronidation and methylation of luteolin compensate for each other, although glucuronidation is the predominant pathway.

  9. Impedance spectroscopy study of a catechol-modified activated carbon electrode as active material in electrochemical capacitor

    Science.gov (United States)

    Cougnon, C.; Lebègue, E.; Pognon, G.

    2015-01-01

    Modified activated carbon (Norit S-50) electrodes with electrochemical double layer (EDL) capacitance and redox capacitance contributions to the electric charge storage were tested in 1 M H2SO4 to quantify the benefit and the limitation of the surface redox reactions on the electrochemical performances of the resulting pseudo-capacitive materials. The electrochemical performances of an electrochemically anodized carbon electrode and a catechol-modified carbon electrode, which make use both EDL capacitance of the porous structure of the carbon and redox capacitance, were compared to the performances obtained for the pristine carbon. Nitrogen gas adsorption measurements have been used for studying the impact of the grafting on the BET surface area, pore size distribution, pore volume and average pore diameter. The electrochemical behavior of carbon materials was studied by cyclic voltammetry and electrochemical impedance spectroscopy (EIS). The EIS data were discussed by using a complex capacitance model that allows defining the characteristic time constant, the global capacitance and the frequency at which the maximum charge stored is reached. The EIS measurements were achieved at different dc potential values where a redox activity occurs and the evolution of the capacitance and the capacitive relaxation time with the electrode potential are presented. Realistic galvanostatic charge/discharge measurements performed at different current rates corroborate the results obtained by impedance.

  10. Membrane-bound catechol-O-methyl transferase in cortical neurons and glial cells is intracellularly oriented

    Directory of Open Access Journals (Sweden)

    Björn H Schott

    2010-10-01

    Full Text Available Catechol-O-methyl transferase (COMT is involved in the inactivation of dopamine in brain regions in which the dopamine transporter (DAT1 is sparsely expressed. The membrane-bound isoform of COMT (MB-COMT is the predominantly expressed form in the mammalian central nervous system (CNS. It has been a matter of debate whether in neural cells of the CNS the enzymatic domain of MB-COMT is oriented towards the cytoplasmic or the extracellular compartment. Here we used live immunocytochemistry on cultured neocortical neurons and glial cells to investigate the expression and membrane orientation of native COMT and of transfected MB-COMT fused to green fluorescent protein (GFP. After live staining, COMT immunoreactivity was reliably detected in both neurons and glial cells after permeabilization, but not on unpermeabilized cells. Similarly, autofluorescence of COMT-GFP fusion protein and antibody fluorescence showed overlap only in permeabilized neurons. Our data provide converging evidence for an intracellular membrane orientation of MB-COMT in neurons and glial cells, suggesting the presence of a DAT1-independent postsynaptic uptake mechanism for dopamine, prior to its degradation via COMT.

  11. 1,2-环己二醇气相催化脱氢制备邻苯二酚的研究%Synthesis of Catechol by Gaseous Catalytic Dehydrogenation of 1,2-Cyclohexanediol

    Institute of Scientific and Technical Information of China (English)

    熊前政; 刘智凌; 陈明; 李玉明; 廖文文; 任伟

    2001-01-01

    探讨了由1,2-环己二醇气相催化脱氢制备邻苯二酚的工艺过程,采用Pd/活性炭为催化剂,在催化剂负荷为0.3 g环己二醇/(g催化剂*h),反应温度300 ℃条件下,环己二醇转化率>90%,邻苯二酚选择性>85%。产物采用溶剂萃取,产品含量w(邻苯二酚)≥99%。%The process of catechol synthesis by gaseous catalytic dehydrogenation of 1,2-cyclohexanediol was researched.Convervion of 1,2-cyclohexandiol and selectivity for catechol were over 90% and 85% respectively.Purity of catechol was over 99% by solvent extraction.

  12. The Role of Human Aldo-Keto Reductases (AKRs in the Metabolic Activation and Detoxication of Polycyclic Aromatic Hydrocarbons: Interconversion of PAH-catechols and PAH o-Quinones

    Directory of Open Access Journals (Sweden)

    Li eZhang

    2012-11-01

    Full Text Available Polycyclic aromatic hydrocarbons (PAH are ubiquitous environmental pollutants. They are procarcinogens requiring metabolic activation to elicit their deleterious effects. Aldo-keto reductases (AKR catalyze the oxidation of proximate carcinogenic PAH trans-dihydrodiols to yield electrophilic and redox-active PAH o-quiniones. AKRs are also found to be capable of reducing PAH o-quinones to form PAH catechols. The interconversion of o-quinones and catechols results in the redox cycling of PAH o-quinones to give rise to the generation of reactive oxygen species and subsequent oxidative DNA damage. On the other hand, PAH catechols can be intercepted through phase II metabolism by which PAH o-quinones could be detoxified and eliminated. The aim of the present review is to summarize the role of human AKRs in the metabolic activation/detoxication of PAH and the relevance of phase II conjugation reactions to human lung carcinogenesis.

  13. Association between catechol-O-methyltrasferase Val108/158Met genotype and prefrontal hemodynamic response in schizophrenia.

    Directory of Open Access Journals (Sweden)

    Ryu Takizawa

    Full Text Available BACKGROUND: "Imaging genetics" studies have shown that brain function by neuroimaging is a sensitive intermediate phenotype that bridges the gap between genes and psychiatric conditions. Although the evidence of association between functional val108/158met polymorphism of the catechol-O-methyltransferase gene (COMT and increasing risk for developing schizophrenia from genetic association studies remains to be elucidated, one of the most topical findings from imaging genetics studies is the association between COMT genotype and prefrontal function in schizophrenia. The next important step in the translational approach is to establish a useful neuroimaging tool in clinical settings that is sensitive to COMT variation, so that the clinician could use the index to predict clinical response such as improvement in cognitive dysfunction by medication. Here, we investigated spatiotemporal characteristics of the association between prefrontal hemodynamic activation and the COMT genotype using a noninvasive neuroimaging technique, near-infrared spectroscopy (NIRS. METHODOLOGY/PRINCIPAL FINDINGS: Study participants included 45 patients with schizophrenia and 60 healthy controls matched for age and gender. Signals that are assumed to reflect regional cerebral blood volume were monitored over prefrontal regions from 52-channel NIRS and compared between two COMT genotype subgroups (Met carriers and Val/Val individuals matched for age, gender, premorbid IQ, and task performance. The [oxy-Hb] increase in the Met carriers during the verbal fluency task was significantly greater than that in the Val/Val individuals in the frontopolar prefrontal cortex of patients with schizophrenia, although neither medication nor clinical symptoms differed significantly between the two subgroups. These differences were not found to be significant in healthy controls. CONCLUSIONS/SIGNIFICANCE: These data suggest that the prefrontal NIRS signals can noninvasively detect the impact

  14. A catechol-like phenolic ligand-functionalized hydrothermal carbon: One-pot synthesis, characterization and sorption behavior toward uranium

    Energy Technology Data Exchange (ETDEWEB)

    Li, Bo; Ma, Lijian; Tian, Yin; Yang, Xiaodan; Li, Juan; Bai, Chiyao; Yang, Xiaoyu; Zhang, Shuang; Li, Shoujian, E-mail: sjli000616@scu.edu.cn; Jin, Yongdong, E-mail: jinyongdong@scu.edu.cn

    2014-04-01

    Highlights: • A new catechol-like ligand-functionalized hydrothermal carbon sorbent is synthesized. • A combination of bayberry tannin and glyoxal is firstly used as starting materials. • Simple, economically viable and environment-friendly synthesis method. • The sorbent exhibits high sorption capacity and distinct selectivity for uranium. - Abstract: We proposed a new approach for preparing an efficient uranium-selective solid phase extractant (HTC-btg) by choosing bayberry tannin as the main building block and especially glyoxal as crosslinking agent via a simple, economic, and green one-pot hydrothermal synthesis. The results of characterization and analysis show that after addition of glyoxal into only bayberry tannin-based hydrothermal reaction system, the as-synthesized HTC-btg displayed higher thermal stability, larger specific surface area and more than doubled surface phenolic hydroxyl groups. The sorption behavior of the sorbents toward uranium under various conditions was investigated in detail and the results indicated that the process is fast, endothermic, spontaneous, and pseudo-second-order chemisorption. The U(VI) sorption capacity reached up to 307.3 mg g{sup −1} under the current experimental conditions. The selective sorption in a specially designed multi-ion solution containing 12 co-existing cations over the range of pH 1.0–4.5 shown that the amount of uranium sorbed accounts for about 53% of the total sorption amount at pH 4.5 and distinctively about 85%, unreported so far to our knowledge, at pH 2.0. Finally, a possible mechanism involving interaction between uranyl ions and phenolic hydroxyl groups on HTC-btg was proposed.

  15. Affect-modulated startle: interactive influence of catechol-O-methyltransferase Val158Met genotype and childhood trauma.

    Science.gov (United States)

    Klauke, Benedikt; Winter, Bernward; Gajewska, Agnes; Zwanzger, Peter; Reif, Andreas; Herrmann, Martin J; Dlugos, Andrea; Warrings, Bodo; Jacob, Christian; Mühlberger, Andreas; Arolt, Volker; Pauli, Paul; Deckert, Jürgen; Domschke, Katharina

    2012-01-01

    The etiology of emotion-related disorders such as anxiety or affective disorders is considered to be complex with an interaction of biological and environmental factors. Particular evidence has accumulated for alterations in the dopaminergic and noradrenergic system--partly conferred by catechol-O-methyltransferase (COMT) gene variation--for the adenosinergic system as well as for early life trauma to constitute risk factors for those conditions. Applying a multi-level approach, in a sample of 95 healthy adults, we investigated effects of the functional COMT Val158Met polymorphism, caffeine as an adenosine A2A receptor antagonist (300 mg in a placebo-controlled intervention design) and childhood maltreatment (CTQ) as well as their interaction on the affect-modulated startle response as a neurobiologically founded defensive reflex potentially related to fear- and distress-related disorders. COMT val/val genotype significantly increased startle magnitude in response to unpleasant stimuli, while met/met homozygotes showed a blunted startle response to aversive pictures. Furthermore, significant gene-environment interaction of COMT Val158Met genotype with CTQ was discerned with more maltreatment being associated with higher startle potentiation in val/val subjects but not in met carriers. No main effect of or interaction effects with caffeine were observed. Results indicate a main as well as a GxE effect of the COMT Val158Met variant and childhood maltreatment on the affect-modulated startle reflex, supporting a complex pathogenetic model of the affect-modulated startle reflex as a basic neurobiological defensive reflex potentially related to anxiety and affective disorders.

  16. The catechol-O-methyltransferase (COMT val158met polymorphism affects brain responses to repeated painful stimuli.

    Directory of Open Access Journals (Sweden)

    Marco L Loggia

    Full Text Available Despite the explosion of interest in the genetic underpinnings of individual differences in pain sensitivity, conflicting findings have emerged for most of the identified "pain genes". Perhaps the prime example of this inconsistency is represented by catechol-O-methyltransferase (COMT, as its substantial association to pain sensitivity has been reported in various studies, but rejected in several others. In line with findings from behavioral studies, we hypothesized that the effect of COMT on pain processing would become apparent only when the pain system was adequately challenged (i.e., after repeated pain stimulation. In the present study, we used functional Magnetic Resonance Imaging (fMRI to investigate the brain response to heat pain stimuli in 54 subjects genotyped for the common COMT val158met polymorphism (val/val = n 22, val/met = n 20, met/met = n 12. Met/met subjects exhibited stronger pain-related fMRI signals than val/val in several brain structures, including the periaqueductal gray matter, lingual gyrus, cerebellum, hippocampal formation and precuneus. These effects were observed only for high intensity pain stimuli after repeated administration. In spite of our relatively small sample size, our results suggest that COMT appears to affect pain processing. Our data demonstrate that the effect of COMT on pain processing can be detected in presence of 1 a sufficiently robust challenge to the pain system to detect a genotype effect, and/or 2 the recruitment of pain-dampening compensatory mechanisms by the putatively more pain sensitive met homozygotes. These findings may help explain the inconsistencies in reported findings of the impact of COMT in pain regulation.

  17. The relationship between childhood abuse and dissociation. Is it influenced by catechol-O-methyltransferase (COMT) activity?

    Science.gov (United States)

    Savitz, Jonathan B; van der Merwe, Lize; Newman, Timothy K; Solms, Mark; Stein, Dan J; Ramesar, Rajkumar S

    2008-03-01

    Dissociation is a failure of perceptual, memorial and emotional integration that is associated with a variety of psychiatric disorders. Dissociative processes are usually attributed to the sequelae of childhood trauma although there are data to suggest that genetic influences are also important. Bipolar disorder (BD), a condition with a strong genetic basis, has also been associated with early psychological trauma. Since childhood trauma is a risk factor for both BD and dissociation, we tested for potential gene-childhood abuse interactions on dissociation in a pilot sample of BD probands and their affected and unaffected relatives (n=178). Dissociation was measured with the Dissociative Experiences Scale (DES II) and childhood maltreatment with the Childhood Trauma Questionnaire (CTQ). The BD and recurrent unipolar depression (MDE-R) groups showed higher levels of self-reported abuse and dissociation than their unaffected relatives. The low-activity Met allele of the Val66Met polymorphism of the brain-derived neurotrophic factor (BDNF) gene was associated with lower levels of self-reported dissociation. Further, the functional catechol-O-methyltransferase (COMT) Val158Met polymorphism interacted significantly with total CTQ abuse scores to impact perceived dissociation. The Val/Val genotype was associated with increasing levels of dissociation in participants exposed to higher levels of childhood trauma. The opposite was observed in people with Met/Met genotypes who displayed decreased dissociation with increasing self-reported childhood trauma. The current findings support the involvement of the COMT Val158Met polymorphism in mediating the relationship between trauma and psychopathology.

  18. The influence of the Val158Met catechol-O-methyltransferase polymorphism on the personality traits of bipolar patients.

    Directory of Open Access Journals (Sweden)

    Wendy Dávila

    Full Text Available INTRODUCTION: Certain personality traits and genetic polymorphisms are contributing factors to bipolar disorder and its symptomatology, and in turn, this syndrome influences personality. The aim of the present study is to compare the personality traits of euthymic bipolar patients with healthy controls and to investigate the effect of the catechol-O-methyltransferase (COMT Val158Met genotype on those traits. We recruited thirty seven bipolar I patients in euthymic state following a manic episode and thirty healthy controls and evaluated their personality by means of the Cloninger's Temperament and Character Inventory (version TCI-R-140. We assessed the influence of the polymorphism Val158Met in the COMT gene on the personality of these patients. The patients scored higher than controls in harm avoidance (61.3±12.5 vs. 55.3±8.1 and self-transcendence (45.3±12.8 vs. 32.7±8.2 and scored lower than controls in self-directedness (68.8±13.3 vs. 79.3±8.1, cooperativeness (77.1±9.1 vs. 83.9±6.5 and persistence (60.4±15.1 vs. 67.1±8.9. The novelty seeking dimension associates with the Val158Met COMT genotype; patients with the low catabolic activity genotype, Met/Met, show a higher score than those with the high catabolic activity genotype, Val/Val. CONCLUSIONS: Suffering from bipolar disorder could have an impact on personality. A greater value in harm avoidance may be a genetic marker for a vulnerability to the development of a psychiatric disorder, but not bipolar disorder particularly, while a low value in persistence may characterize affective disorders or a subgroup of bipolar patients. The association between novelty seeking scores and COMT genotype may be linked with the role dopamine plays in the brain's reward circuits.

  19. Catechol-o-methyltransferase expression and 2-methoxyestradiol affect microtubule dynamics and modify steroid receptor signaling in leiomyoma cells.

    Directory of Open Access Journals (Sweden)

    Salama A Salama

    Full Text Available CONTEXT: Development of optimal medicinal treatments of uterine leiomyomas represents a significant challenge. 2-Methoxyestradiol (2ME is an endogenous estrogen metabolite formed by sequential action of CYP450s and catechol-O-methyltransferase (COMT. Our previous study demonstrated that 2ME is a potent antiproliferative, proapoptotic, antiangiogenic, and collagen synthesis inhibitor in human leiomyomas cells (huLM. OBJECTIVES: Our objectives were to investigate whether COMT expression, by the virtue of 2ME formation, affects the growth of huLM, and to explore the cellular and molecular mechanisms whereby COMT expression or treatment with 2ME affect these cells. RESULTS: Our data demonstrated that E(2-induced proliferation was less pronounced in cells over-expressing COMT or treated with 2ME (500 nM. This effect on cell proliferation was associated with microtubules stabilization and diminution of estrogen receptor alpha (ERalpha and progesterone receptor (PR transcriptional activities, due to shifts in their subcellular localization and sequestration in the cytoplasm. In addition, COMT over expression or treatment with 2ME reduced the expression of hypoxia-inducible factor -1alpha (HIF-1 alpha and the basal level as well as TNF-alpha-induced aromatase (CYP19 expression. CONCLUSIONS: COMT over expression or treatment with 2ME stabilize microtubules, ameliorates E(2-induced proliferation, inhibits ERalpha and PR signaling, and reduces HIF-1 alpha and CYP19 expression in human uterine leiomyoma cells. Thus, microtubules are a candidate target for treatment of uterine leiomyomas. In addition, the naturally occurring microtubule-targeting agent 2ME represents a potential new therapeutic for uterine leiomyomas.

  20. Catechol-O-methyltransferase Val158Met polymorphism modulates gray matter volume and functional connectivity of the default mode network.

    Directory of Open Access Journals (Sweden)

    Tian Tian

    Full Text Available The effect of catechol-O-methyltransferase (COMT Val158Met polymorphism on brain structure and function has been previously investigated separately and regionally; this prevents us from obtaining a full picture of the effect of this gene variant. Additionally, gender difference must not be overlooked because estrogen exerts an interfering effect on COMT activity. We examined 323 young healthy Chinese Han subjects and analyzed the gray matter volume (GMV differences between Val/Val individuals and Met carriers in a voxel-wise manner throughout the whole brain. We were interested in genotype effects and genotype × gender interactions. We then extracted these brain regions with GMV differences as seeds to compute resting-state functional connectivity (rsFC with the rest of the brain; we also tested the genotypic differences and gender interactions in the rsFCs. Val/Val individuals showed decreased GMV in the posterior cingulate cortex (PCC compared with Met carriers; decreased GMV in the medial superior frontal gyrus (mSFG was found only in male Val/Val subjects. The rsFC analysis revealed that both the PCC and mSFG were functionally correlated with brain regions of the default mode network (DMN. Both of these regions showed decreased rsFCs with different parts of the frontopolar cortex of the DMN in Val/Val individuals than Met carriers. Our findings suggest that the COMT Val158Met polymorphism modulates both the structure and functional connectivity within the DMN and that gender interactions should be considered in studies of the effect of this genetic variant, especially those involving prefrontal morphology.

  1. Catechol-O-methyltransferase Val158Met polymorphism on the relationship between white matter hyperintensity and cognition in healthy people.

    Directory of Open Access Journals (Sweden)

    Mu-En Liu

    Full Text Available BACKGROUND: White matter lesions can be easily observed on T2-weighted MR images, and are termed white matter hyperintensities (WMH. Their presence may be correlated with cognitive impairment; however, the relationship between regional WMH volume and catechol-O-methyltransferase (COMT Val158Met polymorphism in healthy populations remains unclear. METHODS: We recruited 315 ethnic Chinese adults with a mean age of 54.9 ± 21.8 years (range: 21-89 y to examine the genetic effect of COMT on regional WMH and the manner in which they interact to affect cognitive function in a healthy adult population. Cognitive tests, structural MRI scans, and genotyping of COMT were conducted for each participant. RESULTS: Negative correlations between the Digit Span Forward (DSF score and frontal WMH volumes (r = -.123, P = .032, uncorrected were noted. For the genetic effect of COMT, no significant difference in cognitive performance was observed among 3 genotypic groups. However, differences in WMH volumes over the subcortical region (P = .016, uncorrected, whole brain (P = .047, uncorrected, and a trend over the frontal region (P = .050, uncorrected were observed among 3 COMT genotypic groups. Met homozygotes and Met/Val heterozygotes exhibited larger WMH volumes in these brain regions than the Val homozygotes. Furthermore, a correlation between the DSF and regional WMH volume was observed only in Met homozygotes. The effect size (cohen's f revealed a small effect. CONCLUSIONS: The results indicate that COMT might modulate WMH volumes and the effects of WMH on cognition.

  2. Modulation of catechol estrogen synthesis by rat liver microsomes: effects of treatment with growth hormone or testosterone

    Energy Technology Data Exchange (ETDEWEB)

    Quail, J.A.; Jellinck, P.H.

    1987-09-01

    The ability of GH from various mammalian species, administered to normal mature male rats by constant infusion, to decrease the hepatic 2-hydroxylation of estradiol (E2) to female levels, as measured by the release of /sup 3/H/sub 2/O from (2-3H)E2, was determined. Rat and human GH (hGH) showed the highest activity while ovine GH was inactive. PRL (0.6 IU/h X kg) administered together with hGH (0.02 IU/h X kg) did not antagonize the feminizing action of GH. Infusion of hGH into male rats decreased the affinity of estradiol 2-hydroxylase for its steroid substrate and altered the linear Lineweaver-Burk plot towards a nonlinear hyperbolic plot characteristic of the female. The apparent Michaelis-Menten constant (Km) for the reaction was 1.69 microM for males and 2.75 microM for testosterone-treated ovariectomized females. An equal mixture of liver microsomes from male and female rats gave kinetic values similar to those observed with males alone. Neonatal imprinting with androgen did not alter the magnitude of the response of female rats to treatment with testosterone and/or GH at maturity and the androgen effect could only be shown in ovariectomized animals. The results with rats of different endocrine status were corroborated by the kinetic data and by the pattern of metabolites obtained with (4-/sup 14/C)E2 when examined by TLC and autoradiography. The hormonal control of estradiol 2-hydroxylase, the key enzyme in catechol estrogen formation, and the contribution of sex-specific multiple forms of the enzyme to this reaction are discussed.

  3. Electrochemical behavior of polypyrrol/AuNP composites deposited by different electrochemical methods: sensing properties towards catechol

    Science.gov (United States)

    García-Hernández, Celia; Medina-Plaza, Cristina; Martín-Pedrosa, Fernando; Blanco, Yolanda; de Saja, José Antonio

    2015-01-01

    Summary Two different methods were used to obtain polypyrrole/AuNP (Ppy/AuNP) composites. One through the electrooxidation of the pyrrole monomer in the presence of colloidal gold nanoparticles, referred to as trapping method (T), and the second one by electrodeposition of both components from one solution containing the monomer and a gold salt, referred to as cogeneration method (C). In both cases, electrodeposition was carried out through galvanostatic and potentiostatic methods and using platinum (Pt) or stainless steel (SS) as substrates. Scanning electron microscopy (SEM) demonstrated that in all cases gold nanoparticles of similar size were uniformly dispersed in the Ppy matrix. The amount of AuNPs incorporated in the Ppy films was higher when electropolymerization was carried out by chronopotentiometry (CP). Besides, cogeneration method allowed for the incorporation of a higher number of AuNPs than trapping. Impedance experiments demonstrated that the insertion of AuNPs increased the conductivity. As an electrochemical sensor, the Ppy/AuNp deposited on platinum exhibited a strong electrocatalytic activity towards the oxidation of catechol. The effect was higher in films obtained by CP than in films obtained by chronoamperometry (CA). The influence of the method used to introduce the AuNPs (trapping or cogeneration) was not so important. The limits of detection (LOD) were in the range from 10−5 to 10−6 mol/L. LODs attained using films deposited on platinum were lower due to a synergy between AuNPs and platinum that facilitates the electron transfer, improving the electrocatalytic properties. Such synergistic effects are not so pronounced on stainless steel, but acceptable LOD are attained with lower price sensors. PMID:26665076

  4. Electrochemical behavior of polypyrrol/AuNP composites deposited by different electrochemical methods: sensing properties towards catechol

    Directory of Open Access Journals (Sweden)

    Celia García-Hernández

    2015-10-01

    Full Text Available Two different methods were used to obtain polypyrrole/AuNP (Ppy/AuNP composites. One through the electrooxidation of the pyrrole monomer in the presence of colloidal gold nanoparticles, referred to as trapping method (T, and the second one by electrodeposition of both components from one solution containing the monomer and a gold salt, referred to as cogeneration method (C. In both cases, electrodeposition was carried out through galvanostatic and potentiostatic methods and using platinum (Pt or stainless steel (SS as substrates. Scanning electron microscopy (SEM demonstrated that in all cases gold nanoparticles of similar size were uniformly dispersed in the Ppy matrix. The amount of AuNPs incorporated in the Ppy films was higher when electropolymerization was carried out by chronopotentiometry (CP. Besides, cogeneration method allowed for the incorporation of a higher number of AuNPs than trapping. Impedance experiments demonstrated that the insertion of AuNPs increased the conductivity. As an electrochemical sensor, the Ppy/AuNp deposited on platinum exhibited a strong electrocatalytic activity towards the oxidation of catechol. The effect was higher in films obtained by CP than in films obtained by chronoamperometry (CA. The influence of the method used to introduce the AuNPs (trapping or cogeneration was not so important. The limits of detection (LOD were in the range from 10−5 to 10−6 mol/L. LODs attained using films deposited on platinum were lower due to a synergy between AuNPs and platinum that facilitates the electron transfer, improving the electrocatalytic properties. Such synergistic effects are not so pronounced on stainless steel, but acceptable LOD are attained with lower price sensors.

  5. Catechol-O-Methyltransferase Val158Met Polymorphism on the Relationship between White Matter Hyperintensity and Cognition in Healthy People

    Science.gov (United States)

    Liu, Mu-En; Huang, Chu-Chung; Yang, Albert C.; Tu, Pei-Chi; Yeh, Heng-Liang; Hong, Chen-Jee; Liou, Ying-Jay; Chen, Jin-Fan; Chou, Kun-Hsien; Lin, Ching-Po; Tsai, Shih-Jen

    2014-01-01

    Background White matter lesions can be easily observed on T2-weighted MR images, and are termed white matter hyperintensities (WMH). Their presence may be correlated with cognitive impairment; however, the relationship between regional WMH volume and catechol-O-methyltransferase (COMT) Val158Met polymorphism in healthy populations remains unclear. Methods We recruited 315 ethnic Chinese adults with a mean age of 54.9±21.8 years (range: 21–89 y) to examine the genetic effect of COMT on regional WMH and the manner in which they interact to affect cognitive function in a healthy adult population. Cognitive tests, structural MRI scans, and genotyping of COMT were conducted for each participant. Results Negative correlations between the Digit Span Forward (DSF) score and frontal WMH volumes (r = −.123, P = .032, uncorrected) were noted. For the genetic effect of COMT, no significant difference in cognitive performance was observed among 3 genotypic groups. However, differences in WMH volumes over the subcortical region (P = .016, uncorrected), whole brain (P = .047, uncorrected), and a trend over the frontal region (P = .050, uncorrected) were observed among 3 COMT genotypic groups. Met homozygotes and Met/Val heterozygotes exhibited larger WMH volumes in these brain regions than the Val homozygotes. Furthermore, a correlation between the DSF and regional WMH volume was observed only in Met homozygotes. The effect size (cohen’s f) revealed a small effect. Conclusions The results indicate that COMT might modulate WMH volumes and the effects of WMH on cognition. PMID:24551149

  6. Affect-modulated startle: interactive influence of catechol-O-methyltransferase Val158Met genotype and childhood trauma.

    Directory of Open Access Journals (Sweden)

    Benedikt Klauke

    Full Text Available The etiology of emotion-related disorders such as anxiety or affective disorders is considered to be complex with an interaction of biological and environmental factors. Particular evidence has accumulated for alterations in the dopaminergic and noradrenergic system--partly conferred by catechol-O-methyltransferase (COMT gene variation--for the adenosinergic system as well as for early life trauma to constitute risk factors for those conditions. Applying a multi-level approach, in a sample of 95 healthy adults, we investigated effects of the functional COMT Val158Met polymorphism, caffeine as an adenosine A2A receptor antagonist (300 mg in a placebo-controlled intervention design and childhood maltreatment (CTQ as well as their interaction on the affect-modulated startle response as a neurobiologically founded defensive reflex potentially related to fear- and distress-related disorders. COMT val/val genotype significantly increased startle magnitude in response to unpleasant stimuli, while met/met homozygotes showed a blunted startle response to aversive pictures. Furthermore, significant gene-environment interaction of COMT Val158Met genotype with CTQ was discerned with more maltreatment being associated with higher startle potentiation in val/val subjects but not in met carriers. No main effect of or interaction effects with caffeine were observed. Results indicate a main as well as a GxE effect of the COMT Val158Met variant and childhood maltreatment on the affect-modulated startle reflex, supporting a complex pathogenetic model of the affect-modulated startle reflex as a basic neurobiological defensive reflex potentially related to anxiety and affective disorders.

  7. Genetic variation in the Catechol-O-Methyltransferase (COMT gene and morphine requirements in cancer patients with pain

    Directory of Open Access Journals (Sweden)

    Kaasa Stein

    2008-12-01

    Full Text Available Abstract Background Genetic variation contributes to differences in pain sensitivity and response to different analgesics. Catecholamines are involved in the modulation of pain and are partly metabolized by the catechol-O-methyltransferase (COMT enzyme. Genetic variability in the COMT gene may therefore contribute to differences in pain sensitivity and response to analgesics. It is shown that a polymorphism in the COMT gene, Rs4680 (Val158Met, influence pain sensitivity in human experimental pain and the efficacy for morphine in cancer pain treatment. In this study we wanted to investigate if variability in other regions in the COMT gene also contributes to interindividual variability in morphine efficacy. Results We genotyped 11 single nucleotide polymorphisms (SNPs throughout the COMT gene, and constructed haplotypes from these 11 SNPs, which were in Hardy-Weinberg equilibrium. We compared both genotypes and haplotypes against pharmacological, demographical and patient symptoms measurements in a Caucasian cancer patient cohort (n = 197 receiving oral morphine treatment for cancer pain. There were two frequent haplotypes (34.5% and 17.8% in our cohort. Multivariate analyses showed that patients carrying the most frequent haplotype (34.5% needed lower morphine doses than patients not carrying the haplotype, with a reduction factor of 0.71 (p = 0.005. On the allele level, carriers of alleles for six of the SNPs show weak associations in respect to morphine dose and the alleles associated with the lowest morphine doses constitute part of the most frequent haplotype. Conclusion This study suggests that genetic variability in the COMT gene influence the efficacy of morphine in cancer patients with pain, and that increased understanding of this variability is reached by expanding from analyses of single SNPs to haplotype construction and analyses.

  8. Catechol-O-methyltransferase val158met genotype determines effect of reboxetine on emotional memory in healthy male volunteers

    Science.gov (United States)

    Gibbs, Ayana A.; Bautista, Carla E.; Mowlem, Florence D.; Naudts, Kris H.; Duka, Dora T.

    2014-01-01

    Background Catechol-O-methyltransferase (COMT) metabolizes catecholamines in the prefrontal cortex (PFC). A common polymorphism in the COMT gene (COMT val158met) has pleiotropic effects on cognitive and emotional processing. The met allele has been associated with enhanced cognitive processing but impaired emotional processing relative to the val allele. Methods We genotyped healthy, white men in relation to the COMT val158met polymorphism. They were given a single 4 mg dose of the selective noradrenaline reuptake inhibitor (NRI) reboxetine or placebo in a randomized, double-blind between-subjects model and then completed an emotional memory task 2 hours later. Results We included 75 men in the study; 41 received reboxetine and 34 received placebo. In the placebo group, met/met carriers did not demonstrate the usual memory advantage for emotional stimuli that was observed in val carriers. Reboxetine restored this emotional enhancement of memory in met/met carriers, but had no significant effect in val carriers. Limitations We studied only men, thus limiting the generalizability of our findings. We also relied on self-reported responses to screening questions to establish healthy volunteer status, and in spite of the double-blind design, participants were significantly better than chance at identifying their intervention allocation. Conclusion Emotional memory is impaired in healthy met homozygotes and selectively improved in this group by reboxetine. This has potential translational implications for the use of reboxetine, which is currently licensed as an antidepressant in several countries, and edivoxetine, a new selective NRI currently in development. PMID:24467942

  9. Sexually dimorphic effects of catechol-O-methyltransferase (COMT inhibition on dopamine metabolism in multiple brain regions.

    Directory of Open Access Journals (Sweden)

    Linda M Laatikainen

    Full Text Available The catechol-O-methyltransferase (COMT enzyme metabolises catecholamines. COMT inhibitors are licensed for the adjunctive treatment of Parkinson's disease and are attractive therapeutic candidates for other neuropsychiatric conditions. COMT regulates dopamine levels in the prefrontal cortex (PFC but plays a lesser role in the striatum. However, its significance in other brain regions is largely unknown, despite its links with a broad range of behavioural phenotypes hinting at more widespread effects. Here, we investigated the effect of acute systemic administration of the brain-penetrant COMT inhibitor tolcapone on tissue levels of dopamine, noradrenaline, and the dopamine metabolites 3,4-dihydroxyphenylacetic acid (DOPAC and homovanillic acid (HVA. We examined PFC, striatum, hippocampus and cerebellum in the rat. We studied both males and females, given sexual dimorphisms in several aspects of COMT's function. Compared with vehicle, tolcapone significantly increased dopamine levels in the ventral hippocampus, but did not affect dopamine in other regions, nor noradrenaline in any region investigated. Tolcapone increased DOPAC and/or decreased HVA in all brain regions studied. Notably, several of the changes in DOPAC and HVA, particularly those in PFC, were more prominent in females than males. These data demonstrate that COMT alters ventral hippocampal dopamine levels, as well as regulating dopamine metabolism in all brain regions studied. They demonstrate that COMT is of significance beyond the PFC, consistent with its links with a broad range of behavioural phenotypes. Furthermore, they suggest that the impact of tolcapone may be greater in females than males, a finding which may be of clinical significance in terms of the efficacy and dosing of COMT inhibitors.

  10. A self-assembled complex with a titanium(IV) catecholate core as a potential bimodal contrast agent.

    Science.gov (United States)

    Dehaen, Geert; Eliseeva, Svetlana V; Kimpe, Kristof; Laurent, Sophie; Vander Elst, Luce; Muller, Robert N; Dehaen, Wim; Binnemans, Koen; Parac-Vogt, Tatjana N

    2012-01-01

    A ditopic chelating ligand (H(6)4) that bears catechol and diethylenetriamine-N,N,N',N'',N''-pentaacetate (DTPA) has been designed and shown to specifically bind lanthanide(III) ions at the DTPA core ([Ln(H(2)4)(H(2)O)](-)) and further self-assemble with titanium(IV), thereby giving rise to the formation of a supramolecular metallostar complex with a lanthanide(III)-to-titanium(IV) ratio of 3:1, [(Ln4)(3)Ti(H(2)O)(3)](5-) (Ln=La, Eu, Gd). The efficacy of the metallostar complex as a potential bimodal optical/magnetic resonance imaging (MRI) agent has been evaluated. Nuclear magnetic relaxation dispersion (NMRD) measurements for the [(Gd4)(3)Ti(H(2)O)(3)](5-) complex have demonstrated an enhanced r(1) relaxivity that corresponds to 36.9 s(-1) mM(-1) per metallostar molecule at 20 MHz and 310 K, which is a result of a decreased tumbling rate. The ability of the complex to bind to human serum albumin (HSA) was also examined by relaxometric measurements. In addition, upon UV irradiation the [(Gd4)(3)Ti(H(2)O)(3)](5-) complex exhibits broad-band green emission in the range 400-750 nm with a maximum at 490 nm. Taking into account the high relaxivity and luminescence properties, the [(Gd4)(3)Ti(H(2)O)(3)](5-) complex is a good lead compound for the development of efficient bimodal contrast agents.

  11. Molybdenum (VI) binded to humic and nitrohumic acid models in aqueous solutions: phthalic, 3- and 4-nitrophthalic acids, catechol and 4-nitrocathecol, part 1

    Energy Technology Data Exchange (ETDEWEB)

    Merce, Ana Lucia R.; Greboge, Cristiane; Mendes, Giovani; Mangrich, Antonio S. [Parana Univ., Curitiba, PR (Brazil). Dept. de Quimica]. E-mail: anamerce@ufpr.br

    2005-02-01

    Many mathematical models have been tested in the literature in the search of how humic acids (HA) from many natural sources complex to metal ions. HA are composed of natural degradation sources of C, N, P and S, bearing hydroxyl and carboxyl aromatic units in their inner structure. The presence of metal ions binded to these basic sites promotes fertility to the soil as well as can hold metal ions to be slowly released as the mineralization of the soil occurs. Nitrohumic substances are a laboratory artifact with higher N content then humic acids with an electron withdrawing group - NO{sub 2}. However they still bear the main HA constituent chemical groups such as salicylate, catecholate and phthalate derivatives, all prone to bind to metal ions depending on the chemical conditions of the environment. This work intended to study the complexing behaviour of some HA models having very different Lewis basic binding sites in the presence of molybdenum (VI) ions, in aqueous systems, with varying pH values using some analytical tools. The formation constants of phthalic acid, 3- and 4-nitrophthalic acids, catechol and 4-nitrocatechol with Mo(VI) as well as the speciation of the complex species according to varying pH values were determined. Potentiometric and cyclic voltammetric titrations were employed to calculate the formation constants and to monitor the formation and decomposition of some complexed species. The results showed that although there is complexation between phthalic derived acids and molybdenum, the speciation favours it only until pH 6.0 at the best. On the other hand, salicylic and catechol derived models showed existence of complexation until basic pH values, allowing a compromising complexation pH range when humic and nitrohumic substances are involved. (author)

  12. Recovery of (/sup 3/H)noradrenaline from different metabolic compartments of rat brain with respect to the role of catechol-O-methyltransferase

    Energy Technology Data Exchange (ETDEWEB)

    Koester, G.; Goede, E.; Breuer, H.

    1984-03-01

    Rats were treated with reserpine, desmethyl-imipramine, or carrier, either alone or in combination with tropolone. Either 10 min (t1) or 1 h (t2) after intraventricular injection of (/sup 3/H)noradrenaline, they were decapitated. The total /sup 3/H activity and the recovery of (/sup 3/H)noradrenaline were determined in tissue extracts from various brain regions. Maximum total /sup 3/H activity was measured at t1 in all tropolone-treated rats; the mean sum of these results served as an estimate of the initial tissue concentration of (/sup 3/H)noradrenaline. At t1, 40-50% of the sum of (/sup 3/H)noradrenaline and its metabolites was recovered unchanged in normal rats; reserpine and DMI reduced the recovery to 18-27%. In all groups, the decline of (/sup 3/H)noradrenaline was retarded after t1. Inhibition of catechol-O-methyltransferase by tropolone caused consistently elevated (/sup 3/H)noradrenaline levels, but did not affect the metabolic rate after t1 when compared with similarly pretreated, but tropolone-free rats. Thus, if catechol-O-methyltransferase was inhibited during the injection of (/sup 3/H)noradrenaline, a higher percentage of the amine had been taken up into spaces with a slow noradrenaline turnover. The maximum increase was seen when the neuronal uptake1 was inhibited by desmethylimipramine. This supported the hypothesis that an additional extraneuronal space exists, in addition to the known intraneuronal and extraneuronal compartments, which has a slow noradrenaline turnover. The tropolone effect on the noradrenaline recovery possibly shows that there might be a saturable ''methylating system,'' similar to that described for the periphery, in which catechol-O-methyltransferase is linked to the extraneuronal uptake.

  13. 3-(2-hydroxyphenyl)catechol as substrate for proximal meta ring cleavage in dibenzofuran degradation by Brevibacterium sp. strain DPO 1361

    Energy Technology Data Exchange (ETDEWEB)

    Strubel, V.; Engesser, K.H.; Fischer, P.; Knackmuss, H.J. (Univ. Stuttgart (West Germany))

    1991-03-01

    Dibenzofuran (DBF) has been used in some recent studies as a model compound for investigating the microbial degradation of cyclic biaryl ethers. Public attention has focused on this class of compounds, since it comprises some of the most pernicious and persistent molecules, such as TCDD (2,3,7,8-tetrachlorodibenzo-p-dioxin). For DBF, the most simple cyclic biaryl ether, a novel degradation mechanism involving angular dioxygenation has been described with 3-(2-hydroxyphenyl)catechol (HPC) as a central intermediate. Definite proof for this mechanism is presented in this paper, and the total degradation of DBF by Brevibacterium is described.

  14. Novel, Unifying Mechanism for Mescaline in The Central Nervous System: Electrochemistry, Catechol Redox Metabolite, Receptor, Cell Signaling and Structure Activity Relationships

    Directory of Open Access Journals (Sweden)

    Peter Kovacic

    2009-01-01

    Full Text Available A unifying mechanism for abused drugs has been proposed previously from the standpoint of electron transfer. Mescaline can be accommodated within the theoretical framework based on redox cycling by the catechol metabolite with its quinone counterpart. Electron transfer may play a role in electrical effects involving the nervous system in the brain. This approach is in accord with structure activity relationships involving mescaline, abused drugs, catecholamines and etoposide. Inefficient demethylation is in keeping with the various drug properties, such as requirement for high dosage and slow acting.

  15. Polymer-pendant ligand chemistry. 1. Reactions of organoarsonic acids and arsenic acid with catechol ligands bonded to polystryene-divinylbenzene and regeneration of the ligand site by a simple hydrolysis procedure

    Energy Technology Data Exchange (ETDEWEB)

    Fish, R.H.; Tannous, R.S.

    1985-12-18

    A novel method is reported for reactions of organoarsonic acids and arsenic acid, known to be present in oil shale and its pyrolysis products, with catechol ligands bonded to either 2% or 20% cross-linked methylated polystyrene-divinylbenzene (PS-DVB) resins. A previous study with catechol-bonded ligands on PS-DVB resins dealt with their reactions with metal ions in aqueous solution and showed a selectivity toward Hg/sup 2 +/ ions. As far as we have been able to determine, reactions of this polymer-supported ligand with organometallic compounds or inorganic anions have not been reported. 9 references, 2 figures, 1 table.

  16. 单分散间苯二酚-甲醛气凝胶微球的制备工艺%Preparation of Monodisperse Resorcinol-formaldehyde Aerogel Microspheres

    Institute of Scientific and Technical Information of China (English)

    侯海乾; 王朝阳; 唐永建; 付志兵; 周莹

    2009-01-01

    采用T型微流体注射成型技术,以邻苯二甲酸二丁酯、液体石蜡和司班80为油相,间苯二酚/甲醛(RF)溶液为水相,经过溶胶-凝胶、溶剂交换、超临界干燥等过程制备了单分散RF气凝胶微球,并就制备过程中RF溶液与分散剂油相的选择、预聚时间、流速比、搅拌速率、固化温度等影响因素进行了初步讨论.当RF溶液质量分数为10%,60℃预聚1.5 h,间苯二酚与碳酸钠的物质的量之比为100,邻苯二甲酸二丁酯与液体石蜡的质量比为8:1,流速比控制在8~16,搅拌速率为65~90r/min,固化温度为35℃时,制备得到了RF乳液,其粒径分布系数小于2%.%Based on a novel T-shaped microfluidic device, monodisperse RF aerogel microspheres are prepared by using dibutyl phthalate,atoleine and span 80 as oil phase, RF solution as water phase, and by sol-gel, solvent exchanging and supercritical drying. The factors such as the choice of RF solution and oil, prepolymerization time, the flow rate ratio of oil to water phase, stirring rate and solidification temperature, which affect the process have been preliminarily discussed. When the polymerization reaction occur in the following conditions: RF solution is 10% ,prepolymerization time is 1. 5 hours at 60℃, the molar ratio of resorcinol to sodium carbonate is 100, the mass ratio of dibutyl phthalate to atoleine is 8,the flow rate ratio of oil to water phase is 8-16, stirring rate is 65~90r/min and solidification temperature is 35℃, the experiment has fabricated monodisperse RF aerogel microspheres, whose coefficient of variation (CV value) of all the RF droplets is below 2% .

  17. 4-(2-吡啶偶氮)间苯二酚分光光度法测定酸泥中铌%Determination of niobium in acid sludge by 4- (2-pyridylazo)-resorcinol spectrophotometry

    Institute of Scientific and Technical Information of China (English)

    张光华

    2012-01-01

    The conditions for color reaction of 4-(2-pyridineazo)-resorcinol (PAR) with niobium was investigated, and a method for the determination of niobium in acid sludge (which was expressed as niobium pentoxide) by spectrophotometry was developed. The results showed that in the solution at pH 5. 6-6. 0, a red ternary complex was formed by PAR with the complex anion of niobium tartrate in the presence of beryllium salt and tartaric acid, and its maximum absorption wavelength was 550 nm with apparent molar absorptivity (ε) of 2. 6×104 L · mol-1 · cm-1. Under the optimum experimental conditions, there was a good linear relationship between the niobium pentoxide concentration within the range of 0. 02 to 0. 8 μg/mL and its corresponding absorbance, the correlation coefficient (r) was 0. 998 8 and the detection limit was 0. 004 8 μg/mL. The method was used for the determination of niobium in acid sludge. The results were in accordance with those obtained by chlorosulphophenol S spectrophotometry, and the relative standard deviations were 2. l%-2. 5%.%研究了4-(2-吡啶偶氮)间苯二酚(PAR)与铌的显色条件,建立了测定酸泥中铌(以五氧化二铌来表示)含量的分光光度法.结果表明,在pH5.6~6.0的溶液中,在铍盐和酒石酸存在下,PAR与酒石酸铌的络阴离子形成红色三元络合物.该络合物最大吸收波长为550nm,表观摩尔吸光系数ε=2.6×104 L·mol-1·cm-1,在最佳实验条件下,五氧化二铌的浓度与其对应的吸光度在0.02~0.8 μg/mL范围内呈良好的线性关系,相关系数r=0.998 8,检出限为0.004 8μg/mL.方法用于酸泥中铌的测定,结果与氯代磺酚S光度法一致,相对标准偏差为2.1%~2.5%.

  18. Protective activity of the Uncaria tomentosa extracts on human erythrocytes in oxidative stress induced by 2,4-dichlorophenol (2,4-DCP) and catechol.

    Science.gov (United States)

    Bors, Milena; Bukowska, Bożena; Pilarski, Radosław; Gulewicz, Krzysztof; Oszmiański, Jan; Michałowicz, Jaromir; Koter-Michalak, Maria

    2011-09-01

    The purpose of this study was to evaluate the effect of the ethanolic and aqueous extracts of Uncaria tomentosa on human erythrocytes and additionally the assessment of protective effect of these extracts on hemolysis induction, hemoglobin oxidation, and changes in the level of reactive oxygen species (ROS) and lipid peroxidation, which were provoked by selected xenobiotics, i.e. 2,4-dichlorophenol (2,4-DCP) and catechol. All tested extracts, even at a very high concentration of 500 μg/ml were not toxic to the erythrocytes because they did not cause lipid peroxidation, increase methemoglobin and ROS levels nor provoked hemolysis. The results of this study also revealed protective effect of extracts of U. tomentosa. The extracts studied depleted the extent of hemoglobin oxidation and lipid peroxidation as well as decreased the level of ROS and hemolysis, which was provoked by 2,4-DCP. No protective activity of the extracts against catechol action, which is a precursor of semiquinones in cell was found. A difference in the effect of the extracts studied was observed. Ethanol-based extracts revealed more pronounced ability to inhibit oxidation processes in human erythrocytes. Copyright © 2011 Elsevier Ltd. All rights reserved.

  19. Campylobacter jejuni ferric-enterobactin receptor CfrA is TonB3 dependent and mediates iron acquisition from structurally different catechol siderophores

    Science.gov (United States)

    Naikare, Hemant; Butcher, James; Flint, Annika; Xu, Jide; Raymond, Kenneth N.; Stintzi, Alain

    2013-01-01

    Campylobacter jejuni NCTC11168 does not produce any endogenous siderophores of its own yet requires the CfrA enterobactin transporter for in vivo colonization. In addition, the genome of C. jejuni NCTC11168 contains three distinct TonB energy transduction systems, named TonB1, TonB2, and TonB3, that have not been tested for their role in siderophore uptake or their functional redundancy. We demonstrate that C. jejuni NCTC11168 transports ferric-enterobactin in an energy dependant manner that requires TonB3 for full activity with TonB1 showing partial functional redundancy. Moreover C. jejuni NCTC11168 can utilize a wide variety of structurally different catechol siderophores as sole iron sources during growth. This growth is solely dependent on the CfrA enterobactin transporter and highlights the wide range of substrates that this transporter can recognize. TonB3 is also required for growth on most catechol siderophores. Furthermore, either TonB1 or TonB3 is sufficient for growth on hemin or hemoglobin as a sole iron source demonstrating functional redundancy between TonB1 and TonB3. In vivo colonization assays with isogenic deletion mutants revealed that both TonB1 and TonB3 are required for chick colonization with TonB2 dispensable in this model. These results further highlight the importance of iron transport for efficient C. jejuni colonization. PMID:23702883

  20. The enzymatic activities of brain catechol-O-methyltransferase (COMT) and methionine sulphoxide reductase are correlated in a COMT Val/Met allele-dependent fashion.

    Science.gov (United States)

    Moskovitz, Jackob; Walss-Bass, Consuelo; Cruz, Dianne A; Thompson, Peter M; Hairston, Jenaqua; Bortolato, Marco

    2015-12-01

    The enzyme catechol-O-methyltransferase (COMT) plays a primary role in the metabolism of catecholamine neurotransmitters and is implicated in the modulation of cognitive and emotional responses. The best characterized single nucleotide polymorphism (SNP) of the COMT gene consists of a valine (Val)-to-methionine (Met) substitution at codon 108/158. The Met-containing variant confers a marked reduction in COMT catalytic activity. We recently showed that the activity of recombinant COMT is positively regulated by the enzyme Met sulphoxide reductase (MSR), which counters the oxidation of Met residues of proteins. The current study was designed to assess whether brain COMT activity may be correlated to MSR in an allele-dependent fashion. COMT and MSR activities were measured from post-mortem samples of prefrontal cortices, striata and cerebella of 32 subjects by using catechol and dabsyl-Met sulphoxide as substrates, respectively. Allelic discrimination of COMT Val(108/185) Met SNP was performed using the Taqman 5'nuclease assay. Our studies revealed that, in homozygous carriers of Met, but not Val alleles, the activity of COMT and MSR was significantly correlated throughout all tested brain regions. These results suggest that the reduced enzymatic activity of Met-containing COMT may be secondary to Met sulphoxidation and point to MSR as a key molecular determinant for the modulation of COMT activity. © 2015 British Neuropathological Society.