The influence of conventional heating and microwave irradiation on the resolution of (RS)-sec-butylamine catalyzed by free or immobilized lipases

Energy Technology Data Exchange (ETDEWEB)

Pilissao, Cristiane; Nascimento, Maria da Graca, E-mail: maria.nascimento@ufsc.br [Departamento de Quimica, Universidade Federal de Santa Catarina, Florianopolis,SC (Brazil); Carvalho, Patricia de Oliveira [Curso de Farmacia, Universidade Sao Francisco, Braganca Paulista, SP (Brazil)

2012-09-15

The lipases CAL-B, PSL, PSL-C, PSL-D, and A. niger lipase, free or immobilized in starch (obtained from two types of yam, known in Brazil as 'cara' (Discorea alata L.) and 'inhame' (Colocasia esculenta (L.) Schott) or gelatin films, were used in the acylation of (RS)-sec-butylamine with different acyl donors in various organic solvents applying conventional heating (CH) or microwave (MW) irradiation. In the case of free A. niger lipase, the conversion degrees were three times higher using MW irradiation when compared to conventional heating at 35 deg C. Using free A. niger lipase, the (R)-amide was obtained with a conversion degree of 21%, resulting in ee{sub p}> 99% and E-value (enantioselectivity value) > 200, in 1 min of reaction under MW irradiation. When the A. niger lipase was immobilized in yam starch films, the (R)-amide was obtained in moderate conversions of 8-25% after 3 or 5 min of reaction under MW irradiation, but with higher selectivity (eep > 99% and E > 200) in comparison with the free form (conversion degree of 45%, eep 81% and E value of 18). (author)

Equilibrium and Transport Properties of Primary, Secondary and Tertiary Amines by Molecular Simulation

International Nuclear Information System (INIS)

Orozco, Gustavo A.; Nieto-Draghi, Carlos; Lachet, Veronique; Mackie, Allan D.

2014-01-01

Using molecular simulation techniques such as Monte Carlo (MC) and molecular dynamics (MD), we present several simulation results of thermodynamic and transport properties for primary, secondary and tertiary amines. These calculations are based on a recently proposed force field for amines that follows the Anisotropic United Atom approach (AUA). Different amine molecules have been studied, including n-Butylamine, di-n-Butylamine, tri-n-Butylamine and 1,4-Butanediamine for primary, secondary, tertiary and multi-functional amines respectively. For the transport properties, we have calculated the viscosity coefficients as a function of temperature using the isothermal-isobaric (NPT) ensemble. In the case of the pure components, we have investigated different thermodynamic properties using NVT Gibbs ensemble simulations such as liquid-vapor phase equilibrium diagrams, vaporization enthalpies, vapor pressures, normal boiling points, critical temperatures and critical densities. We have also calculated the excess enthalpies for water-n-Butylamine and n-heptane-n-Butylamine mixtures using Monte Carlo simulations in the NPT ensemble. In addition, we present the calculation of liquid-vapor surface tensions of n-Butylamine using a two-phase NVT simulation as well as the radial distribution functions. Finally, we have investigated the physical Henry constants of nitrous oxide (N 2 O) and nitrogen (N 2 ) in an aqueous solutions of n-Butylamine. In general, we found a good agreement between the available experimental information and our simulation results for all the studied properties, ratifying the predictive capability of the AUA force field for amines. (authors)

Thermometric titrations of amines with nitrosyl perchlorate in acetonitrile solvent.

Science.gov (United States)

Gündüz, T; Kiliç, E; Cakirer, O

1996-05-01

Thirteen aliphatic and four aromatic amines, namely diethylamine, triethylamine, n-propylamine, di-n-propylamine, tri-n-butylamine, isopropylamine, di-isopropylamine, n-butylamine, di-n-butylamine, tri-n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, aniline, N,N-dimethylaniline, 2-nitroaniline and 4-nitroaniline were titrated thermometrically with nitrosyl perchlorate in acetonitrile solvent. All the aliphatic amines gave very well-shaped thermometric titration curves. The calculated recovery values of the amines were very good. In comparison, the aromatic amines, aniline and N,N-dimethylaniline gave rather well-shaped titration curves, but the recovery values were fairly low. 2-Nitro- and 4-nitro anilines gave no thermometric response at all. The heats of reaction of the amines with nitrosyl perchlorate are rather high. However, the average heat of reaction of the aromatic amines is approximately two-thirds that of the average heat of the aliphatic amines. To support this method all the amines were also titrated potentiometrically and very similar results to those obtained with the thermometric method are seen. The nitrosyl ion is a Lewis acid, strong enough to titrate quantitatively aliphatic amines in acetonitrile solvent, but not strong enough to titrate aromatic amines at the required level in the same solvent.

Laboratory study on new particle formation from the reaction OH + SO2: influence of experimental conditions, H2O vapour, NH3 and the amine tert-butylamine on the overall process

Directory of Open Access Journals (Sweden)

J. Curtius

2010-08-01

Full Text Available Nucleation experiments starting from the reaction of OH radicals with SO2 have been performed in the IfT-LFT flow tube under atmospheric conditions at 293±0.5 K for a relative humidity of 13–61%. The presence of different additives (H2, CO, 1,3,5-trimethylbenzene for adjusting the OH radical concentration and resulting OH levels in the range (4–300 ×105 molecule cm−3 did not influence the nucleation process itself. The number of detected particles as well as the threshold H2SO4 concentration needed for nucleation was found to be strongly dependent on the counting efficiency of the used counting devices. High-sensitivity particle counters allowed the measurement of freshly nucleated particles with diameters down to about 1.5 nm. A parameterization of the experimental data was developed using power law equations for H2SO4 and H2O vapour. The exponent for H2SO4 from different measurement series was in the range of 1.7–2.1 being in good agreement with those arising from analysis of nucleation events in the atmosphere. For increasing relative humidity, an increase of the particle number was observed. The exponent for H2O vapour was found to be 3.1 representing an upper limit. Addition of 1.2×1011 molecule cm−3 or 1.2×1012 molecule cm−3 of NH3 (range of atmospheric NH3 peak concentrations revealed that NH3 has a measureable, promoting effect on the nucleation rate under these conditions. The promoting effect was found to be more pronounced for relatively dry conditions, i.e. a rise of the particle number by 1–2 orders of magnitude at RH = 13% and only by a factor of 2–5 at RH = 47% (NH3 addition: 1.2×1012 molecule cm−3. Using the amine tert-butylamine instead of NH3, the enhancing impact of the base for nucleation and particle growth appears to be stronger. Tert-butylamine addition of about 1010 molecule cm−3 at RH = 13% enhances particle formation by about two orders of magnitude, while for NH3 only a small or negligible

Synthesis, characterization, crystal structure and HSA binding of two new N,O,O-donor Schiff-base ligands derived from dihydroxybenzaldehyde and tert-butylamine

Science.gov (United States)

Khosravi, Iman; Hosseini, Farnaz; Khorshidifard, Mahsa; Sahihi, Mehdi; Rudbari, Hadi Amiri

2016-09-01

Two new o-hydroxy Schiff-bases compounds, L1 and L2, were derived from the 1:1 M condensation of 2,3-dihydroxybenzaldehyde and 2,4-dihydroxybenzaldehyde with tert-butylamine and were characterized by elemental analysis, FT-IR, 1H and 13C NMR spectroscopies. The crystal structure of L2 was also determined by single crystal X-ray analysis. The crystal structure of L2 showed that the compound exists as a zwitterionic form in the solid state, with the H atom of the phenol group being transferred to the imine N atom. It adopts an E configuration about the central Cdbnd N double bond. Furthermore, binding of these Schiff base ligands to Human Serum Albumin (HSA) was investigated by fluorescence quenching, absorption spectroscopy, molecular docking and molecular dynamics (MD) simulation methods. The fluorescence emission of HSA was quenched by ligands. Also, suitable models were used to analyze the UV-vis absorption spectroscopy data for titration of HSA solution by various amounts of Schiff bases. The spectroscopic studies revealed that these Schiff bases formed 1:1 complex with HSA. Energy transfer mechanism of quenching was discussed and the values of 3.35 and 1.57 nm as the mean distances between the bound ligands and the HSA were calculated for L1 and L2, respectively. Molecular docking results indicated that the main active binding site for these Schiff bases ligands is in subdomain IB. Moreover, MD simulation results suggested that this Schiff base complex can interact with HSA, with a slight modification of its tertiary structure.

Application of some geometrical and empirical models to excess molar volume for the multi-component mixtures at T = 298.15 K

International Nuclear Information System (INIS)

Iloukhani, H.; Khanlarzadeh, K.

2012-01-01

Highlights: ► Excess molar volume of quartenary mixtures of 1-chlorobutane, 2-chlorobutane, butylamine, and butylacetate was determined. ► The experimental data were correlated by some empirical and semi empirical models. ► A comparison with PFP theory has been successfully applied from binary data. - Abstract: Densities of the quaternary mixture consisting of {1-chlorobutane (1) + 2-chlorobutane (2) + butylamine (3) + butylacetate (4)} and related ternary mixtures of {1-chlorobutane (1) + 2-chlorobutane (2) + butylamine (3)}, {1-chlorobutane (1) + 2-chlorobutane (2) + butylacetate (4)}, {2-chlorobutane (2) + butylamine (3) + butylacetate (4)}, and binary systems of {1-chlorobutane (1) + 2-chlorobutane (2)}, {2-chlorobutane (2) + butylamine (3)}, were measured over the whole range of composition at T = 298.15 K and ambient pressure. Excess molar volumes, V m E , for the mixtures were derived and correlated as a function of mole fraction by using the Redlich–Kister and the Cibulka equations for binary and ternary mixtures, respectively. From the experimental data, partial molar volumes, V m,i and excess partial molar volumes, V m,i E were also calculated for binary systems. The experimental results of the constituted binary mixtures have been used to test the applicability of the Prigogine–Flory–Paterson (PFP) theory. A number of geometrical and empirical equations were also used to verify their ability to predict ternary and quaternary properties from their lower order mixtures. The experimental data were used to evaluate the nature and type of intermolecular interactions in multi-component mixtures.

Halloysite nanotube supported Ag nanoparticles heteroarchitectures as catalysts for polymerization of alkylsilanes to superhydrophobic silanol/siloxane composite microspheres.

Science.gov (United States)

Li, Cuiping; Li, Xueyuan; Duan, Xuelan; Li, Guangjie; Wang, Jiaqiang

2014-12-15

Halloysite nanotube supported Ag nanoparticles heteroarchitectures have been prepared through a very simple electroless plating method. Robust Ag nanocrystals can be reproducibly fabricated by soaking halloysite nanotubes in ethanolic solutions of AgNO3 and butylamine. By simply adjusting the molar ratio of AgNO3 and butylamine, Ag nanoparticles with tunable size and quantity on halloysite nanotube are achieved. It reveals that the Ag nanoparticles are well-dispersed on the surface of halloysite nanotubes. The halloysite nanotube supported Ag nanoparticles heteroarchitectures can serve as active catalysts for the polymerization of an alkylsilane C18H37SiH3 with water to form silanol/siloxane composite microspheres and exhibit interesting superhydrophobicity ascribed to the micro/nanobinary structure. Copyright © 2014 Elsevier Inc. All rights reserved.

Multistage wet lipid extraction from fresh water stressed Neochloris oleoabundans slurry – Experiments and modelling

NARCIS (Netherlands)

Du, Ying; Schuur, Boelo; Kersten, Sascha R.A.; Brilman, D. W.F.(Wim)

2018-01-01

Algae are considered an important renewable feedstock for lipid extraction to produce biofuels. Algae strain Neochloris oleoabundans used in this research can yield a high lipid content under stressed conditions. N-ethyl butylamine (EBA) as a switchable solvent has previously shown outstanding

Relation between separation factor of carbon isotope and chemical reaction of CO2 with amine in nonaqueous solvent

International Nuclear Information System (INIS)

Takeshita, Kenji; Kitamoto, Asashi

1989-01-01

The separation factor for carbon isotope exchange reaction between CO 2 and amine in nonaqueous solvent was related to absorption reaction of CO 2 in a solution. The test solutions were mixtures of primary amine (such as butylamine and tert-butylamine) or secondary amine (such as diethylamine, dipropylamine and dibutylamine) diluted with nonpolar solvent (octane or triethyalmine) or polar solvent (methanol), respectively. The isotope exchange reaction consists of three steps related to chemical reaction of CO 2 in amine and nonaqueous solvent mixture, namely the reaction between CO 2 and carbamic acid, that between CO 2 and amine carbamate, and that between CO 2 and carbamic ion. Above all, the isotope separation factor between CO 2 and carbamic acid had the highest value. The overall separation factor can be higher in amine-nonaqueous solvent mixture where the concentration of carbamic acid becomes higher. (author)

Secondary organic aerosol formation from primary aliphatic amines with NO3 radical

Science.gov (United States)

Malloy, Q. G. J.; Qi, Li; Warren, B.; Cocker, D. R., III; Erupe, M. E.; Silva, P. J.

2009-03-01

Primary aliphatic amines are an important class of nitrogen containing compounds emitted from automobiles, waste treatment facilities and agricultural animal operations. A series of experiments conducted at the UC-Riverside/CE-CERT Environmental Chamber is presented in which oxidation of methylamine, ethylamine, propylamine, and butylamine with O3 and NO3 have been investigated. Very little aerosol formation is observed in the presence of O3 only. However, after addition of NO, and by extension NO3, large aerosol mass yields (~44% for butylamine) are seen. Aerosol generated was determined to be organic in nature due to the small fraction of NO and NO2 in the total signal (tested) as detected by an aerosol mass spectrometer (AMS). We propose a reaction mechanism between carbonyl containing species and the parent amine leading to formation of particulate imine products. These findings can have significant impacts on rural communities with elevated nighttime PM loadings, when significant levels of NO3 exist.

Secondary organic aerosol formation from primary aliphatic amines with NO3 radical

Directory of Open Access Journals (Sweden)

P. J. Silva

2009-03-01

Full Text Available Primary aliphatic amines are an important class of nitrogen containing compounds emitted from automobiles, waste treatment facilities and agricultural animal operations. A series of experiments conducted at the UC-Riverside/CE-CERT Environmental Chamber is presented in which oxidation of methylamine, ethylamine, propylamine, and butylamine with O3 and NO3 have been investigated. Very little aerosol formation is observed in the presence of O3 only. However, after addition of NO, and by extension NO3, large aerosol mass yields (~44% for butylamine are seen. Aerosol generated was determined to be organic in nature due to the small fraction of NO and NO2 in the total signal (<1% for all amines tested as detected by an aerosol mass spectrometer (AMS. We propose a reaction mechanism between carbonyl containing species and the parent amine leading to formation of particulate imine products. These findings can have significant impacts on rural communities with elevated nighttime PM loadings, when significant levels of NO3 exist.

VIBRATIONAL SPECTRA OF t-BUTYL ALCOHOL, t-BUTYLAMINE ...

African Journals Online (AJOL)

a

good stray light rejection. A Spectra-Physics ... the spectrometer. The vial was then spun to enhance the Raman signal and reduce the risk of .... *Abbreviations used: m, medium; s, strong; v, very; w, weak; sh, shoulder; -, not detected due to the ...

Derivatives of 1,3-oxazolidines on the base of diamino-alcohols

International Nuclear Information System (INIS)

Karimov, M.B.; Kimsanov, B.Kh.; Tagaeva, S.E.; Khuseynov, K.B.

2001-01-01

In this article authors investigated the reaction of 1-cyclohexyl amino-3-diethyl amino-2-propanol, 1-butylamine-3-diethyl amino-2-propanol. By authors was determined that reaction of initial diamino-alcohols with furfural passing at molar correlation of reagents 1:1 at temperature 20-22 d ig C at presence dehydrating medium-potash during 36 hours

Curcumin: Synthesis optimization and in silico interaction with cyclin dependent kinase.

Science.gov (United States)

Ahmed, Mahmood; Abdul Qadir, Muhammad; Imtiaz Shafiq, Muhammad; Muddassar, Muhammad; Hameed, Abdul; Nadeem Arshad, Muhammad; Asiri, Abdullah M

2017-09-01

Curcumin is a natural product with enormous biological potential. In this study, curcumin synthesis was revisited using different reaction solvents, a catalyst (n-butylamine) and a water scavenger [(n-BuO)3B], to develop the optimal procedure for its rapid acquisition. During synthesis, solvent choice was found to be an important parameter for better curcumin yield and high purity. In a typical reaction, acetyl acetone was treated with boron trioxide, followed by condensation with vanillin in the presence of tri-n-butyl borate as water scavenger and n-butylamine as catalyst at 80 °C in ethyl acetate to afford curcumin. Moreover, curcumin was also extracted from turmeric powder and spectroscopic properties such as IR, MS, 1H NMR and 13C NMR with synthetic curcumin were established to identify any impurity. The purity of synthetic and extracted curcumin was also checked by TLC and HPLC-DAD. To computationally assess its therapeutic potential against cyclin dependent kinases (CDKs), curcumin was docked in different isoforms of CDKs. It was observed that it did not dock at the active sites of CDK2 and CDK6. However, it could enter into weak interactions with CDK4 protein.

Neighboring Hetero-Atom Assistance of Sacrificial Amines to Hydrogen Evolution Using Pt-Loaded TiO2-Photocatalyst

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Masahide Yasuda

2014-05-01

Full Text Available Photocatalytic H2 evolution was examined using Pt-loaded TiO2-photocatalyst in the presence of amines as sacrificial agents. In the case of amines with all of the carbon attached to the hetero-atom such as 2-aminoethanol, 1,2-diamonoethane, 2-amino-1,3-propanediol, and 3-amino-1,2-propanediol, they were completely decomposed into CO2 and water to quantitatively evolve H2. On the other hand, the amines with both hetero-atoms and one methyl group at the β-positions (neighboring carbons of amino group such as 2-amino-1-propanol and 1,2-diaminopropane were partially decomposed. Also, the photocatalytic H2 evolution using amines without the hetero-atoms at the β-positions such as ethylamine, propylamine, 1-butylamine, 1,3-diaminopropane, 2-propylamine, and 2-butylamine was inefficient. Thus, it was found that the neighboring hetero-atom strongly assisted the degradation of sacrificial amines. Moreover, rate constants for H2 evolution were compared among amines. In conclusion, the neighboring hetero-atom did not affect the rate constants but enhanced the yield of hydrogen evolution.

Demonstration of Regenerable, Large-Scale Ion Exchange System Using WBA Resin in Rialto, CA (Drinking Water Treatment - Pilot Scale)

Science.gov (United States)

2008-08-01

Administration NDBA N-nitrosodi-n-butylamine NDEA N-nitrosodiethylamine NDMA N-nitrosodimethylamine NDPA N-nitrosodi-n-propylamine v ACRONYMS...spectrometry (IC-MS/MS). Nitrosamines were analyzed using EPA Method 521. N-nitrosodimethylamine ( NDMA ) was 2.6 parts per trillion (ppt) with a detection...and metals (Ca, Cu, Fe, Mg, Mn, K, Na , and Zn). Specific methods are listed in Table 5. ** N-nitrosodimethylamine ( NDMA ), N-nitrosodiethylamine

Perchlorate Removal, Destruction and Field Monitoring Demonstration (Groundwater RemediationPilot-Scale)

Science.gov (United States)

2008-08-01

Space Administration NDBA N-nitrosodi-n-butylamine NDEA N-nitrosodiethylamine NDMA N-nitrosodimethylamine NDPA N-nitrosodi-n-propylamine v...spectrometry (IC-MS/MS). Nitrosamines were analyzed using EPA Method 521. N-nitrosodimethylamine ( NDMA ) was 2.6 parts per trillion (ppt) with a...TS/TDS]), and metals (Ca, Cu, Fe, Mg, Mn, K, Na , and Zn). Specific methods are listed in Table 5. ** N-nitrosodimethylamine ( NDMA ), N

40 CFR 117.3 - Determination of reportable quantities.

Science.gov (United States)

2010-07-01

... A 10 (4.54) Lead fluoride A 10 (4.54) Lead iodide A 10 (4.54) Lead nitrate A 10 (4.54) Lead stearate... fluoride X 1 (0.454) Beryllium nitrate X 1 (0.454) Butyl acetate D 5,000 (2,270) Butylamine C 1,000 (454) n... B 100 (45.4) Cupric acetoarsenite X 1 (0.454) Cupric chloride A 10 (4.54) Cupric nitrate B 100 (45.4...

Investigations of (acid+base) equilibria in systems modelling interactions occurring in biomolecules

International Nuclear Information System (INIS)

Kozak, Anna; Czaja, Malgorzata; Chmurzynski, Lech

2006-01-01

By using the potentiometric microtitration method, acidity constants, K a , anionic, K AHA - , and cationic, K BHB + , homoconjugation constants, as well as molecular heteroconjugation, K BHA , constants have been determined in (acid+base) systems formed by the following compounds: acetic acid, phenol, n-butylamine, imidazole, and 4(5)-methylimidazole. These compounds constitute fragments of the side chains of amino acids capable of proton exchange in active sites of enzymes. The (acid+base) equilibria were studied in five polar solvents of different properties, namely in aprotic protophobic acetonitrile, acetone and propylene carbonate, in aprotic protophilic dimethyl sulfoxide and in amphiprotic methanol. The lowest values of the acidity constants of the molecular and cationic acids have been found in aprotic protophobic polar solvents - acetonitrile, propylene carbonate and acetone. Their acid strength have been found to depend on solvent basicity expressed as donor numbers, DN. These media, in particular acetonitrile and acetone, are also favourable for establishing molecular homo- and heteroconjugation equilibria. The most stable homocomplexes are formed in the case of acetic acid (K AHA - values range from 2.26 to 3.56 in these media, being more than an order of magnitude higher than those for the remaining compounds). The magnitudes of lgK BHA reveal that the most stable heterocomplexes are formed by n-butylamine and acetic acid that are characterized by the smallest differences in pK a values

Time-resolved energy transfer from single chloride-terminated nanocrystals to graphene

International Nuclear Information System (INIS)

Ajayi, O. A.; Wong, C. W.; Anderson, N. C.; Wolcott, A.; Owen, J. S.; Cotlet, M.; Petrone, N.; Hone, J.; Gu, T.; Gesuele, F.

2014-01-01

We examine the time-resolved resonance energy transfer of excitons from single n-butyl amine-bound, chloride-terminated nanocrystals to two-dimensional graphene through time-correlated single photon counting. The radiative biexponential lifetime kinetics and blinking statistics of the individual surface-modified nanocrystal elucidate the non-radiative decay channels. Blinking modification as well as a 4× reduction in spontaneous emission were observed with the short chloride and n-butylamine ligands, probing the energy transfer pathways for the development of graphene-nanocrystal nanophotonic devices

Time-resolved energy transfer from single chloride-terminated nanocrystals to graphene

Energy Technology Data Exchange (ETDEWEB)

Ajayi, O. A., E-mail: oaa2114@columbia.edu, E-mail: cww2104@columbia.edu; Wong, C. W., E-mail: oaa2114@columbia.edu, E-mail: cww2104@columbia.edu [Optical Nanostructures Laboratory, Center for Integrated Science and Engineering, Solid-State Science and Engineering, Columbia University, New York, New York 10027 (United States); Department of Mechanical Engineering, Columbia University, New York, New York 10027 (United States); Anderson, N. C.; Wolcott, A.; Owen, J. S. [Department of Chemistry, Columbia University, New York, New York 10027 (United States); Cotlet, M. [Brookhaven National Laboratory, Upton, New York, New York 11973 (United States); Petrone, N.; Hone, J. [Department of Mechanical Engineering, Columbia University, New York, New York 10027 (United States); Gu, T.; Gesuele, F. [Optical Nanostructures Laboratory, Center for Integrated Science and Engineering, Solid-State Science and Engineering, Columbia University, New York, New York 10027 (United States)

2014-04-28

We examine the time-resolved resonance energy transfer of excitons from single n-butyl amine-bound, chloride-terminated nanocrystals to two-dimensional graphene through time-correlated single photon counting. The radiative biexponential lifetime kinetics and blinking statistics of the individual surface-modified nanocrystal elucidate the non-radiative decay channels. Blinking modification as well as a 4× reduction in spontaneous emission were observed with the short chloride and n-butylamine ligands, probing the energy transfer pathways for the development of graphene-nanocrystal nanophotonic devices.

Investigations of (acid+base) equilibria in systems modelling interactions occurring in biomolecules

Energy Technology Data Exchange (ETDEWEB)

Kozak, Anna [Department of General Chemistry, University of Gdansk, Sobieskiego 18, 80-952 Gdansk (Poland); Czaja, Malgorzata [Department of General Chemistry, University of Gdansk, Sobieskiego 18, 80-952 Gdansk (Poland); Chmurzynski, Lech [Department of General Chemistry, University of Gdansk, Sobieskiego 18, 80-952 Gdansk (Poland)]. E-mail: lech@chem.univ.gda.pl

2006-05-15

By using the potentiometric microtitration method, acidity constants, K{sub a}, anionic, K{sub AHA{sup -}}, and cationic, K{sub BHB{sup +}}, homoconjugation constants, as well as molecular heteroconjugation, K{sub BHA}, constants have been determined in (acid+base) systems formed by the following compounds: acetic acid, phenol, n-butylamine, imidazole, and 4(5)-methylimidazole. These compounds constitute fragments of the side chains of amino acids capable of proton exchange in active sites of enzymes. The (acid+base) equilibria were studied in five polar solvents of different properties, namely in aprotic protophobic acetonitrile, acetone and propylene carbonate, in aprotic protophilic dimethyl sulfoxide and in amphiprotic methanol. The lowest values of the acidity constants of the molecular and cationic acids have been found in aprotic protophobic polar solvents - acetonitrile, propylene carbonate and acetone. Their acid strength have been found to depend on solvent basicity expressed as donor numbers, DN. These media, in particular acetonitrile and acetone, are also favourable for establishing molecular homo- and heteroconjugation equilibria. The most stable homocomplexes are formed in the case of acetic acid (K{sub AHA{sup -}} values range from 2.26 to 3.56 in these media, being more than an order of magnitude higher than those for the remaining compounds). The magnitudes of lgK{sub BHA} reveal that the most stable heterocomplexes are formed by n-butylamine and acetic acid that are characterized by the smallest differences in pK{sub a} values.

Impact of the counterion on the solubility and physicochemical properties of salts of carboxylic acid drugs.

Science.gov (United States)

David, S E; Timmins, P; Conway, B R

2012-01-01

Salt formation is a widely used approach to improve the physicochemical and solid state properties of an active pharmaceutical ingredient. In order to better understand the relationships between the active drug, the selected counterion and the resultant salt form, crystalline salts were formed using four different carboxylic acid drugs and a closely related series of amine counterions. Thirty-six related crystalline salts were prepared, characterized and the relationship between solubility and dissolution behaviour and other properties of the salt and the counterion studied. Salts of four model acid drugs, gemfibrozil, flurbiprofen, ibuprofen and etodolac were prepared using the counterions butylamine, hexylamine, octylamine, benzylamine, cyclohexylamine, tert-butylamine, 2-amino-2-methylpropan-1-ol, 2-amino-2-methylpropan-1,3-diol and tris(hydroxymethyl)aminomethane. Salt formation was confirmed, the salts were characterized and their corresponding solubilities determined and rationalized with respect to the counterions' properties. The properties of the salt highly dependent on the nature of the counterion and, although there is considerable variation, some general conclusion can be drawn. For the alkyl amines series, increasing chain length leads to a reduction in solubility across all the acidic drugs studied and a reduction in melting point, thus contradicting simplistic relationships between solubility and melting point. Small, compact counterions consistently produce crystalline salts with high melting point accompanied with a modest improvement in solubility and the nature of hydrogen bonding between the ions has a major impact on the solubility.

CdSe/AsS core-shell quantum dots: preparation and two-photon fluorescence.

Science.gov (United States)

Wang, Junzhong; Lin, Ming; Yan, Yongli; Wang, Zhe; Ho, Paul C; Loh, Kian Ping

2009-08-19

Arsenic(II) sulfide (AsS)-coated CdSe core-shell nanocrystals can be prepared by a cluster-complex deposition approach under mild conditions. At 60 degrees C, growth of an AsS shell onto a CdSe nanocrystal can be realized through the crystallization of a cluster complex of AsS/butylamine in a mixed solvent of isopropanol/chloroform. The new, type I core-shell nanocrystal exhibits markedly enhanced one-photon fluorescence as well two-photon upconversion fluorescence. The nanocrystals can be used for infrared-excited upconversion cellular labeling.

Determination of ascorbic acid by high performance liquid chromatography (H. P. L. C.) using photodiode array detector

International Nuclear Information System (INIS)

Elbashier, E. E.; Greenway, G. M; Townshend, A.

2005-01-01

This paper describes a simple and rapid method for the determination of vitamin C using H. P. L. C. A reversed phase C 1 8 column was used to perform ion pairing chromatography, the ion pairing agent tri-n-butylamine and mobile phase 90:10 phospate buffer (pH 4.5) to methanol. A diode array spectrophotometric detector facilitated method development allowing chromatograms to be obtained for range of wavelengths. A linear calibration curve was obtained in range 0-50 μg/ml with correlation coefficient of 0.999 and detection limit was 1.5 μg/ml and relative standard deviation was 1.8% for ten samples at 10μg/ml.(Author)

Synthesis of trifluoromethyl-substituted pyrazolo[4,3-c]pyridines – sequential versus multicomponent reaction approach

Directory of Open Access Journals (Sweden)

Barbara Palka

2014-07-01

Full Text Available A straightforward synthesis of 6-substituted 1-phenyl-3-trifluoromethyl-1H-pyrazolo[4,3-c]pyridines and the corresponding 5-oxides is presented. Hence, microwave-assisted treatment of 5-chloro-1-phenyl-3-trifluoromethylpyrazole-4-carbaldehyde with various terminal alkynes in the presence of tert-butylamine under Sonogashira-type cross-coupling conditions affords the former title compounds in a one-pot multicomponent procedure. Oximes derived from (intermediate 5-alkynyl-1-phenyl-3-trifluoromethyl-1H-pyrazole-4-carbaldehydes were transformed into the corresponding 1H-pyrazolo[4,3-c]pyridine 5-oxides by silver triflate-catalyzed cyclization. Detailed NMR spectroscopic investigations (1H, 13C, 15N and 19F were undertaken with all obtained products.

Porous Silicates Modified with Zirconium Oxide and Sulfate Ions for Alcohol Dehydration Reactions

Directory of Open Access Journals (Sweden)

Heriberto Esteban Benito

2015-01-01

Full Text Available Porous silicates were synthesized by a nonhydrothermal method, using sodium silicate as a source of silica and cetyltrimethylammonium bromide as a template agent. Catalysts were characterized using thermogravimetric analysis, N2 physisorption, X-ray diffraction, FTIR spectroscopy, pyridine adsorption, potentiometric titration with n-butylamine, scanning electronic microscopy, and transmission electronic microscopy. The surface area of the materials synthesized was greater than 800 m2/g. The introduction of zirconium atoms within the porous silicates increased their acid strength from −42 to 115 mV, while the addition of sulfate ions raised this value to 470 mV. The catalytic activity for the dehydration of alcohols yields conversions of up to 70% for ethanol and 30% for methanol.

Research into aroma changes in irradiated foodstuffs. I.- Studies on Fish

International Nuclear Information System (INIS)

Barrero Pinero, R.; Gasco Sanchez, L.; Valverde Garcia, F.

1972-01-01

Radiolytic formation of volatile compounds have been investigated in fillets of hake, codfish and bonito gamma-irradiated at a dose range of 0.1-5 Mrads. Analytical methods have been developed by gas chromatography of functional group derivatives: carbonyls as 2,4,-dinitrophenyl hydrazones, primary and secondary amines as N-alkyl benzamides, and thiols as 2,4-dinitrophenyl alkyl thioethers. The main results are as follows: increasing with the integral dose of the whole carbonyls, the most significant components being acetaldehyde, propional dehyde and formaldehyde; no significant variations with the integral dose od the traces of ammonia, methylamine, trimethylamine, ethylamine, diethylamine, propylamine, butylamine and pentylamine found in unirradiated samples; and radiolytic formation of methanethiol and dimethyl disulfide. (Author) 98 refs

Research into aroma changes in irradiated foodstuffs. I.- Studies on Fish; Investigacion de Alteraciones de Aroma en alimentos irradiados. I Estudio sobre Pescado

Energy Technology Data Exchange (ETDEWEB)

Barreiro Pinero, R; Gasco Sanchez, L; Valverde Garcia, F

1972-07-01

Radiolytic formation of volatile compounds have been investigated in fillets of hake, codfish and bonito gamma-irradiated at a dose range of 0.1-5 Mrads. Analytical methods have been developed by gas chromatography of functional group derivatives: carbonyls as 2,4,-dinitrophenyl hydrazones, primary and secondary amines as N-alkyl benzamides, and thiols as 2,4-dinitrophenyl alkyl thioethers. The main results are as follows: increasing with the integral dose of the whole carbonyls, the most significant components being acetaldehyde, propional dehyde and formaldehyde; no significant variations with the integral dose od the traces of ammonia, methylamine, trimethylamine, ethylamine, diethylamine, propylamine, butylamine and pentylamine found in unirradiated samples; and radiolytic formation of methanethiol and dimethyl disulfide. (Author) 98 refs.

Highly enhanced vapor sensing of multi-walled carbon nanotube network sensors by n-butylamine functionalization

Czech Academy of Sciences Publication Activity Database

Slobodian, P.; Říha, Pavel; Cavallo, P.; Barbero, C.A.; Cvelbar, U.; Benlikaya, R.; Petras, D.; Sáha, P.

2014-01-01

Roč. 2014, August (2014), Article ID 589627 ISSN 1687-4110 Grant - others:UTB Zlín(CZ) IGA/FT/2014/013; GA MŠk(CZ) ED2.1.00/03.0111; GA MŠk(CZ) 7AMB13AR019 Institutional support: RVO:67985874 Keywords : carbon nanotube (CNT) * multiwall carbon nanotube (MWCNT) * nanotube networks * volatile organic compounds (VOC) Subject RIV: BK - Fluid Dynamics Impact factor: 1.644, year: 2014

NIOSH Manual of Analytical Methods (third edition). Fourth supplement

Energy Technology Data Exchange (ETDEWEB)

1990-08-15

The NIOSH Manual of Analytical Methods, 3rd edition, was updated for the following chemicals: allyl-glycidyl-ether, 2-aminopyridine, aspartame, bromine, chlorine, n-butylamine, n-butyl-glycidyl-ether, carbon-dioxide, carbon-monoxide, chlorinated-camphene, chloroacetaldehyde, p-chlorophenol, crotonaldehyde, 1,1-dimethylhydrazine, dinitro-o-cresol, ethyl-acetate, ethyl-formate, ethylenimine, sodium-fluoride, hydrogen-fluoride, cryolite, sodium-hexafluoroaluminate, formic-acid, hexachlorobutadiene, hydrogen-cyanide, hydrogen-sulfide, isopropyl-acetate, isopropyl-ether, isopropyl-glycidyl-ether, lead, lead-oxide, maleic-anhydride, methyl-acetate, methyl-acrylate, methyl-tert-butyl ether, methyl-cellosolve-acetate, methylcyclohexanol, 4,4'-methylenedianiline, monomethylaniline, monomethylhydrazine, nitric-oxide, p-nitroaniline, phenyl-ether, phenyl-ether-biphenyl mixture, phenyl-glycidyl-ether, phenylhydrazine, phosphine, ronnel, sulfuryl-fluoride, talc, tributyl-phosphate, 1,1,2-trichloro-1,2,2-trifluoroethane, trimellitic-anhydride, triorthocresyl-phosphate, triphenyl-phosphate, and vinyl-acetate.

A comparison of cationic polymerization and esterification for end-point detection in the catalytic thermometric titration of organic bases.

Science.gov (United States)

J Greenhow, E; Viñas, P

1984-08-01

A systematic comparison has been made of two indicator systems for the non-aqueous catalytic thermometric titration of strong and weak organic bases. The indicator reagents, alpha-methylstyrene and mixtures of acetic anhydride and hydroxy compounds, are shown to give results (for 14 representative bases) which do not diner significantly in coefficient of variation or titration error. Calibration graphs for all the samples, in the range 0.01-0.1 meq, are linear, with correlation coefficients of 0.995 or better. Aniline, benzylamine, n-butylamine, morpholine, pyrrole, l-dopa, alpha-methyl-l-dopa, dl-alpha-alanine, dl-leucine and l-cysteine cannot be determined when acetic anhydride is present in the sample solution, but some primary and second amines can. This is explained in terms of rates of acetylation of the amino groups.

Self-Assembled PbSe Nanowire:Perovskite Hybrids

KAUST Repository

Yang, Zhenyu

2015-12-02

© 2015 American Chemical Society. Inorganic semiconductor nanowires are of interest in nano- and microscale photonic and electronic applications. Here we report the formation of PbSe nanowires based on directional quantum dot alignment and fusion regulated by hybrid organic-inorganic perovskite surface ligands. All material synthesis is carried out at mild temperatures. Passivation of PbSe quantum dots was achieved via a new perovskite ligand exchange. Subsequent in situ ammonium/amine substitution by butylamine enables quantum dots to be capped by butylammonium lead iodide, and this further drives the formation of a PbSe nanowire superlattice in a two-dimensional (2D) perovskite matrix. The average spacing between two adjacent nanowires agrees well with the thickness of single atomic layer of 2D perovskite, consistent with the formation of a new self-assembled semiconductor nanowire:perovskite heterocrystal hybrid.

Syntheses of radiolabelled forms of a novel histamine H1 antagonist (SKandF 94944)

International Nuclear Information System (INIS)

Cashyap, M.M.; Mitchell, M.B.; Osborne, D.C.; Saunders, D.

1985-01-01

A novel histamine H 1 antagonist SKandF 93944, 2-[4-(5-bromo-3-methylpyrid-2-yl)butylamino]-5-(6-methylpyrid-3-yl-methyl)-4(3H)-pyrimidone, has been labelled with carbon-14 in two different positions for use in metabolism and pharmacokinetic studies. The four stage synthesis of [pyrimidone-2- 14 C] SKandF 93944 from barium [ 14 C]cyanamide is described. The overall radiochemical yield was 38%. [butylamino-4- 14 C] SKandF 93944 was synthesised in four steps from [ 14 C]methyl iodide. The key steps in this synthesis were alkylation of 2-lithio-3-methyl pyridine with [ 14 C]methyl iodide and the bromination of 4-(3-methyl-2-pyridyl)[4- 14 C]butylamine in a liquid sulphur trioxide/freon mixture. The overall radiochemical yield was 1.6% from [ 14 C]methyl iodide. (author)

Autoinduced catalysis and inverse equilibrium isotope effect in the frustrated Lewis pair catalyzed hydrogenation of imines.

Science.gov (United States)

Tussing, Sebastian; Greb, Lutz; Tamke, Sergej; Schirmer, Birgitta; Muhle-Goll, Claudia; Luy, Burkhard; Paradies, Jan

2015-05-26

The frustrated Lewis pair (FLP)-catalyzed hydrogenation and deuteration of N-benzylidene-tert-butylamine (2) was kinetically investigated by using the three boranes B(C6F5)3 (1), B(2,4,6-F3-C6H2)3 (4), and B(2,6-F2-C6H3)3 (5) and the free activation energies for the H2 activation by FLP were determined. Reactions catalyzed by the weaker Lewis acids 4 and 5 displayed autoinductive catalysis arising from a higher free activation energy (2 kcal mol(-1)) for the H2 activation by the imine compared to the amine. Surprisingly, the imine reduction using D2 proceeded with higher rates. This phenomenon is unprecedented for FLP and resulted from a primary inverse equilibrium isotope effect. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Self-Assembled PbSe Nanowire:Perovskite Hybrids

KAUST Repository

Yang, Zhenyu; Yassitepe, Emre; Voznyy, Oleksandr; Janmohamed, Alyf; Lan, Xinzheng; Levina, Larissa; Comin, Riccardo; Sargent, Edward H.

2015-01-01

© 2015 American Chemical Society. Inorganic semiconductor nanowires are of interest in nano- and microscale photonic and electronic applications. Here we report the formation of PbSe nanowires based on directional quantum dot alignment and fusion regulated by hybrid organic-inorganic perovskite surface ligands. All material synthesis is carried out at mild temperatures. Passivation of PbSe quantum dots was achieved via a new perovskite ligand exchange. Subsequent in situ ammonium/amine substitution by butylamine enables quantum dots to be capped by butylammonium lead iodide, and this further drives the formation of a PbSe nanowire superlattice in a two-dimensional (2D) perovskite matrix. The average spacing between two adjacent nanowires agrees well with the thickness of single atomic layer of 2D perovskite, consistent with the formation of a new self-assembled semiconductor nanowire:perovskite heterocrystal hybrid.

Size control in the synthesis of 1-6 nm gold nanoparticles via solvent-controlled nucleation.

Science.gov (United States)

Song, Jieun; Kim, Dukhan; Lee, Dongil

2011-11-15

We report a facile synthetic route for size-controlled preparation of gold nanoparticles. Nearly monodisperse gold nanoparticles with core diameters of 1-6 nm were obtained by reducing AuP(Phenyl)(3)Cl with tert-butylamine borane in the presence of dodecanethiol in the solvent mixture of benzene and CHCl(3). Mechanism studies have shown that the size control is achieved by the solvent-controlled nucleation in which the nuclei concentration increases with increasing the fraction of CHCl(3), leading to smaller particles. It was also found that, following the solvent-controlled nucleation, particle growth occurs via ligand replacement of PPh(3) on the nuclei by Au(I)thiolate generated by the digestive etching of small particles. This synthetic strategy was successfully demonstrated with other alkanethiols of different chain length with which size-controlled, monodisperse gold nanoparticles were prepared in remarkable yield without requiring any postsynthesis treatments.

Synthesis and Antimicrobial Activities of Some Novel Quinoxalinone Derivatives

Directory of Open Access Journals (Sweden)

Y. A. Ammar

2000-06-01

Full Text Available Condensation of 4-benzoyl-1,2-phenylenediamine with sodium pyruvate in acetic acid furnished two products which were identified as 6-benzoyl and 7-benzoyl-3-methyl-2(1Hquinoxalinones (1a,b. Fusion of 1a with aromatic aldehydes furnished the styryl derivatives 2a-c. Alkylation of 1a,b with dimethyl sulphate or ethyl chloroacetate produced the N-alkyl derivatives 3a,b and 4a,b. Hydrazinolysis of the ester derivative 4a with hydrazine hydrate afforded the hydrazide derivative 5 which underwent condensation with aldehydes to give the corresponding hydrazone derivatives 6a,b. In addition, chlorination of 1a with thionyl chloride afforded the 2-chloro derivative 7 which was subjected to reaction with sodium azide and n-butylamine to yield the corresponding tetrazolo (8 and n-butylamino (9 derivatives, respectively. The structures of the compounds prepared were confirmed by analytical and spectral data. Also, some of the synthesized compounds were screened for antimicrobial activity.

Observation of interstitial molecular hydrogen in clathrate hydrates.

Science.gov (United States)

Grim, R Gary; Barnes, Brian C; Lafond, Patrick G; Kockelmann, Winfred A; Keen, David A; Soper, Alan K; Hiratsuka, Masaki; Yasuoka, Kenji; Koh, Carolyn A; Sum, Amadeu K

2014-09-26

The current knowledge and description of guest molecules within clathrate hydrates only accounts for occupancy within regular polyhedral water cages. Experimental measurements and simulations, examining the tert-butylamine + H2 + H2O hydrate system, now suggest that H2 can also be incorporated within hydrate crystal structures by occupying interstitial sites, that is, locations other than the interior of regular polyhedral water cages. Specifically, H2 is found within the shared heptagonal faces of the large (4(3)5(9)6(2)7(3)) cage and in cavities formed from the disruption of smaller (4(4)5(4)) water cages. The ability of H2 to occupy these interstitial sites and fluctuate position in the crystal lattice demonstrates the dynamic behavior of H2 in solids and reveals new insight into guest-guest and guest-host interactions in clathrate hydrates, with potential implications in increasing overall energy storage properties. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of a new class of fused cyclotetraphosphazene ring systems.

Science.gov (United States)

Beşli, Serap; Mutlu, Ceylan; İbişoğlu, Hanife; Yuksel, Fatma; Allen, Christopher W

2015-01-05

Octachlorocyclotetraphosphazene (1) was reacted with butylamines [n-butyl, i-butyl, sec-butyl, and t-butyl] in a 1:0.8 mol ratio in THF to obtain cyclotetraphosphazenes bearing a P-NH group, N4P4Cl7(NHR) [R = n-butyl (2a), i-butyl (2b), sec-butyl (2c), t-butyl (2d)](2a-d). The cyclotetraphosphazene derivatives 2a, 2b, and 2c were treated with sodium hydride giving rise to a new type of cyclophosphazene compounds (P8N8 ring) consisting of three fused tetramer rings (3a-c). Whereas reaction of sodium hydride with the t-butylaminocyclophosphazene derivative (2d) gave a P-O-P bridged compound (4) presumably as a result of hydrolysis reaction associated with moisture in the solvent. It is likely that the 16-membered cyclooctaphosphazene derivatives (3a-c) are formed by a proton abstraction/chloride ion elimination, intramolecular nucleophilic attack, ring opening and intermolecular condensation processes, respectively.

Biosynthesis of amorphous mesoporous aluminophosphates using yeast cells as templates

International Nuclear Information System (INIS)

Sifontes, Ángela B.; González, Gema; Tovar, Leidy M.; Méndez, Franklin J.; Gomes, Maria E.; Cañizales, Edgar; Niño-Vega, Gustavo; Villalobos, Hector; Brito, Joaquin L.

2013-01-01

Graphical abstract: Display Omitted Highlights: ► Amorphous aluminophosphates can take place using yeast as template. ► A mesoporous material was obtained. ► The specific surface area after calcinations ranged between 176 and 214 m 2 g −1 . -- Abstract: In this study aluminophosphates have been synthesized from aluminum isopropoxide and phosphoric acid solutions using yeast cells as template. The physicochemical characterization was carried out by thermogravimetric analysis; X-ray diffraction; Fourier transform infrared; N 2 adsorption–desorption isotherms; scanning electron microscopy; transmission electron microscopy and potentiometric titration with N-butylamine for determination of: thermal stability; crystalline structure; textural properties; morphology and surface acidity, respectively. The calcined powders consisted of an intimate mixture of amorphous and crystallized AlPO particles with sizes between 23 and 30 nm. The average pore size observed is 13–16 nm and the specific surface area after calcinations (at 650 °C) ranged between 176 and 214 m 2 g −1 .

Sub-10 nm Platinum Nanocrystals with Size and Shape Control: Catalytic Study for Ethylene and Pyrrole Hydrogenation

Energy Technology Data Exchange (ETDEWEB)

Tsung, Chia-Kuang; Kuhn, John N.; Huang, Wenyu; Aliaga, Cesar; Hung, Ling-I; Somorjai, Gabor A.; Yang, Peidong

2009-03-02

Platinum nanocubes and nanopolyhedra with tunable size from 5 to 9 nm were synthesized by controlling the reducing rate of metal precursor ions in a one-pot polyol synthesis. A two-stage process is proposed for the simultaneous control of size and shape. In the first stage, the oxidation state of the metal ion precursors determined the nucleation rate and consequently the number of nuclei. The reaction temperature controlled the shape in the second stage by regulation of the growth kinetics. These well-defined nanocrystals were loaded into MCF-17 mesoporous silica for examination of catalytic properties. Pt loadings and dispersions of the supported catalysts were determined by elemental analysis (ICP-MS) and H2 chemisorption isotherms, respectively. Ethylene hydrogenation rates over the Pt nanocrystals were independent of both size and shape and comparable to Pt single crystals. For pyrrole hydrogenation, the nanocubes enhanced ring-opening ability and thus showed a higher selectivity to n-butylamine as compared to nanopolyhedra.

Coulometric titrations of bases in propylene carbonate and g-butyrolactone using hydroquinone as the depolarizer and a quinhydrone indicator electrode

Directory of Open Access Journals (Sweden)

Z. D. STANIC

2000-08-01

Full Text Available The application of hydroquinone for the coulometric generation of hydrogen ions in propylene carbonate (PC and g-butyrolactone (GBL is described. The current-potential curves recorded for theid sepolarizer, titrated bases, indicator and the solvents used showed that the investigated depolarizer is oxidized at lower potentials than the oxidation potentials of other components in the solution. the hydrogen ions generated by the oxidation of hydroquinone were used for the titration of organic bases (triethylamine, n-butylamine, pyridine, quinoline, aniline, N,N’-diphenylguanidine, piperidine, and 2,2’-bipiridine in PC and GBL with visual (Crystal Violet as indicator and potentiometric end-point detection using a quinhydrone electrode as the indicator electrode. The quinhydrone added to the to be analyzed solution served both as a source of hydrogen ions and, together with the immersed platinum electrode, as a quinhydrone electrode. The relative error of the determination of the bases was about 1 %.

Solution-phase synthesis of nanomaterials at low temperature

Science.gov (United States)

Zhu, Yongchun; Qian, Yitai

2009-01-01

This paper reviews the solution-phase synthesis of nanoparticles via some routes at low temperatures, such as room temperature route, wave-assisted synthesis (γ-irradiation route and sonochemical route), directly heating at low temperatures, and hydrothermal/solvothermal methods. A number of strategies were developed to control the shape, the size, as well as the dispersion of nanostructures. Using diethylamine or n-butylamine as solvent, semiconductor nanorods were yielded. By the hydrothermal treatment of amorphous colloids, Bi2S3 nanorods and Se nanowires were obtained. CdS nanowires were prepared in the presence of polyacrylamide. ZnS nanowires were obtained using liquid crystal. The polymer poly (vinyl acetate) tubule acted as both nanoreactor and template for the CdSe nanowire growth. Assisted by the surfactant of sodium dodecyl benzenesulfonate (SDBS), nickel nanobelts were synthesized. In addition, Ag nanowires, Te nanotubes and ZnO nanorod arrays could be prepared without adding any additives or templates.

A microanalytical method for ammonium and short-chain primary aliphatic amines using precolumn derivatization and capillary liquid chromatography.

Science.gov (United States)

Moliner-Martínez, Y; Herráez-Hernández, R; Campíns-Falcó, P

2007-09-14

A new microscale method is presented for the determination of ammonium and primary short-chain aliphatic amines (methylamine, ethylamine, propylamine, n-butylamine and n-pentylamine) in water. The assay uses precolumn derivatization with the reagent o-phthaldialdehyde (OPA) in combination with the thiol N-acetyl-L-cysteine (NAC), and capillary liquid chromatography with UV detection at 330 nm. The described method is very simple and rapid as no preconcentration of the analytes is necessary, and the volume of sample required is only 0.1 mL. Under the proposed conditions good linearity has been obtained up to a concentration of the analytes of 10.0 mgL(-1), the limits of detection being of 8-50 microgL(-1). No matrix effect was found, and recoveries between 97 and 110% were obtained. The precision of the method was good, and the achieved variation coefficients were below 12%. The reliability of the proposed approach has been tested by analyzing a microsample of fogwater collected from leaf surfaces.

Biosynthesis of amorphous mesoporous aluminophosphates using yeast cells as templates

Energy Technology Data Exchange (ETDEWEB)

Sifontes, Ángela B., E-mail: asifonte@ivic.gob.ve [Centro de Química, Instituto Venezolano de Investigaciones Científicas, Apartado 20632, Caracas 1020-A (Venezuela, Bolivarian Republic of); González, Gema [Centro de Ingeniería de Materiales y Nanotecnología, Instituto Venezolano de Investigaciones Científicas, Apartado 20632, Caracas 1020-A (Venezuela, Bolivarian Republic of); Tovar, Leidy M.; Méndez, Franklin J. [Centro de Química, Instituto Venezolano de Investigaciones Científicas, Apartado 20632, Caracas 1020-A (Venezuela, Bolivarian Republic of); Gomes, Maria E. [Centro de Ingeniería de Materiales y Nanotecnología, Instituto Venezolano de Investigaciones Científicas, Apartado 20632, Caracas 1020-A (Venezuela, Bolivarian Republic of); Cañizales, Edgar [Área de Análisis Químico Inorgánico, PDVSA, INTEVEP, Los Teques 1070-A (Venezuela, Bolivarian Republic of); Niño-Vega, Gustavo; Villalobos, Hector [Centro de Microbiología y Biología Celular, Instituto Venezolano de Investigaciones Científicas, Apartado 20632, Caracas 1020-A (Venezuela, Bolivarian Republic of); Brito, Joaquin L. [Centro de Química, Instituto Venezolano de Investigaciones Científicas, Apartado 20632, Caracas 1020-A (Venezuela, Bolivarian Republic of)

2013-02-15

Graphical abstract: Display Omitted Highlights: ► Amorphous aluminophosphates can take place using yeast as template. ► A mesoporous material was obtained. ► The specific surface area after calcinations ranged between 176 and 214 m{sup 2} g{sup −1}. -- Abstract: In this study aluminophosphates have been synthesized from aluminum isopropoxide and phosphoric acid solutions using yeast cells as template. The physicochemical characterization was carried out by thermogravimetric analysis; X-ray diffraction; Fourier transform infrared; N{sub 2} adsorption–desorption isotherms; scanning electron microscopy; transmission electron microscopy and potentiometric titration with N-butylamine for determination of: thermal stability; crystalline structure; textural properties; morphology and surface acidity, respectively. The calcined powders consisted of an intimate mixture of amorphous and crystallized AlPO particles with sizes between 23 and 30 nm. The average pore size observed is 13–16 nm and the specific surface area after calcinations (at 650 °C) ranged between 176 and 214 m{sup 2} g{sup −1}.

Assessment of surface acidity in mesoporous materials containing aluminum and titanium

Science.gov (United States)

Araújo, Rinaldo S.; Maia, Débora A. S.; Azevedo, Diana C. S.; Cavalcante, Célio L., Jr.; Rodríguez-Castellón, E.; Jimenez-Lopez, A.

2009-04-01

The surface acidity of mesoporous molecular sieves of aluminum and titanium was evaluated using four different techniques: n-butylamine volumetry, cyclohexylamine thermodesorption, temperature-programmed desorption of ammonia and adsorption of pyridine. The nature, strength and concentration of the acid sites were determined and correlated to the results of a probe reaction of anthracene oxidation to 9,10-anthraquinone (in liquid phase). In general, the surface acidity was highly influenced by the nature, location and coordination of the metal species (Al and Ti) in the mesoporous samples. Moderate to strong Brönsted acid sites were identified for the Al-MCM-41 sample in a large temperature range. For mesoporous materials containing Ti, the acidity was represented by a combination of weak to moderate Brönsted and Lewis acid sites. The Ti-HMS sample exhibits a higher acidity of moderate strength together with a well-balanced concentration of Brönsted and Lewis acid sites, which enhanced both conversion and selectivity in the oxidation reaction of anthracene.

MOCVD of hexagonal boron nitride thin films on Si(100) using new single source precursors

CERN Document Server

Boo, J H; Yu, K S; Kim, Y S; Kim, Y S; Park, J T

1999-01-01

We have been carried out the growth of hexagonal boron nitride (h-BN) thin films on Si(100) substrates by low pressure metal-organic chemical vapor deposition (LPMOCVD) method using triethylborane tert-butylamine complex (TEBTBA), Et sub 3 BNH sub 2 ( sup t Bu), and triethylborane isopropylamine complex (TEBIPA), Et sub 3 BNH sub 2 ( sup t Pr) as a new single molecular precursors in the temperature range of 850 approx 1000 .deg. C. polycrystalline, crack-free h-BN film was successfully grown on Si(100) substrate at 850 .deg. C using TEBTBA. This growth temperature is very lower than those in previous reports. Carbon-rich polycrystalline BN was also obtained at 900 .deg. C from TEBIPA. With increasing substrate temperature to 1000 .deg. C, however, BC sub 4 N-like species are strongly formed along with h-BN and the BN films obtained from both TEBTBA and TEBIPA but almost polycrystalline. To our best knowledge, this is the first report of the growth of h-BN films formed with the new single source precursors of ...

Electrochemical characterization of platinum nanoparticles stabilized by amines

International Nuclear Information System (INIS)

Ramirez-Meneses, E.; Dominguez-Crespo, M.A.; Montiel-Palma, V.; Chavez-Herrera, V.H.; Gomez, E.; Hernandez-Tapia, G.

2009-01-01

In this work we present the synthesis by Chaudret approach of Pt nanoparticles stabilized by primary amine (-NH 2 ) compounds. Their electrochemical performance as cathodes in low temperature polymer electrolite fuel cells on the oxygen reduction reaction (ORR) is also presented. Transmission electron microscopy (TEM) images of the samples show Pt nanostructures with particle size varying from 10 to 100 nm depending on the kind of the stabilizer used during the catalyst preparation. In some cases well-dispersed isolated platinum nanoparticles were observed. The activity of the dispersed catalysts (Pt/C) with respect to the ORR was investigated using steady state polarization measurements. The kinetic parameters showed that although no significant differences between the Tafel slopes of the Pt catalysts exist, transfer coefficients and exchange current densities show higher activities when the Pt nanoparticles were stabilized by tert-butylamine (TBA). The performance with respect to the ORR of the Pt/C catalyst on vulcan carbon substrate is active and comparable to that reported in the literature for state-of-art electrocatalysts.

Inhibition study of additives towards the corrosion of ferrous metal in palm biodiesel

International Nuclear Information System (INIS)

Fazal, M.A.; Sazzad, B.S.; Haseeb, A.S.M.A.; Masjuki, H.H.

2016-01-01

Highlights: • TBA doped biodiesel exhibits fairly good corrosion inhibition efficiency. • TBA forms nitrogen-containing layer on metal surface and protects the corrosion. • Materials exposed to TBA doped biodiesel show less surface roughness. - Abstract: Some efforts have already been given by other researchers to characterize the corrosion behavior of different metals in biodiesel. However, there is very limited information on its remedial measure. Therefore, this study investigates the effects of tert-butylamine (TBA), benzotriazole (BTA), butylate-dhydroxytoluene (BHT), and pyrogallol (PY) on the corrosion of cast iron (CI) and low carbon steel (LCS) through an immersion test in palm biodiesel (B100) at 300 K. Result shows that TBA-doped biodiesel exhibits fairly good corrosion-inhibiting properties for materials exposed to B100. Inhibition efficiency of TBA is found to be 86.54% and 86.71% for CI and LCS, respectively which is far better than other tested additives in this study. The high inhibition efficiency could be attributed to the dominant physical adsorption of N-containing compound which creates a protective layer over the metal surface and prevents corrosion.

Physicochemical studies of the carbamate-CO2-solvent system

International Nuclear Information System (INIS)

Prencipe, M.; Ishida, T.

1977-08-01

The formation of carbamate from CO 2 and the various amine solutions has been investigated for the purpose of elucidating the structure of the species generated in the reaction. The amine solutions used were 1 and 2 molar solutions of di-n-butylamine (DNBA) in triethylamine (TEA), pure DNBA and pure TEA. It has been found that the nonaqueous solvent participates in the formation of carbamate in 1 and 2M-DNBA/TEA solutions as a proton acceptor in DNBA-carbamate formation. However, due to the high concentration of the solutions and the basicities of the amines, a significant amount of DNBA which does not form the DNBA-carbamate anion is also found to be participating as a proton acceptor. Pure TEA absorbs only 1 / 60 of the absorption by pure DNBA. The extent of TEA participation in the CO 2 -absorption process other than as a proton acceptor in DNBA-carbamate is negligible. The formation of carbamic acid and zwitterion have been found unlikely. 7 tables, 15 figs

Chapter 19. Design and evaluation of potential 99mTc radiopharmaceuticals based on the Tc-Carbonyl, 4 + 1 mixed ligand chelate system and Tc-nitrido approaches

International Nuclear Information System (INIS)

Giglio, J.; Muslera, A.; Leon, E.; Paolino, A.; Leon, A.; Rey, A.; Incerti, M.; Fernandez, R.; Manta, E.; Brugnini, A.; Chabalgoity, A.

2007-01-01

The aim of the work was to explore the possibilities of the novel labelling strategies in the development of 99m Tc labelled small biomolecules. Different steps required to fulfil this objective were undertaken: organic synthesis of glucose derivatives, optimization of labelling and in vitro and in vivo evaluation of Rd peptides and anne xin 13 derivatives using either the Hyonic bifunctional ligand, the Tc-tricarbonyl, the 4 + 1 mixed ligand or the Tc(V)-nitri do approaches. Glucose-O-hexyl bromide, glucose- O-butylbromide and glucose-O-butylamine were successfully synthesized, opening the possibility of introducing different chelators according to the desired labelling procedure. c(RGDyK) derivatives bearing different chelators were labelled with 99m Tc using novel approaches and evaluated both in vitro and in vivo in order to compare the effect of the chelator and labelling method on the physicochemical and biological behaviour. Annexin 13 peptides were also labelled using the HYNIC and Tc(I)-tricarbonyl approaches. A primary evaluation in normal animals and in a model of cardiac apoptosis is also presented. Cooperation with other participants was crucial to develop this work. (author)

Complex formation reactions of uranyl(VI) with neutral N-donors in dimethyl sulfoxide. Influence of small amounts of water

International Nuclear Information System (INIS)

Cassol, A.; Di Bernardo, P.; Zanonato, P.; Portanova, R.; Tolazzi, M.

1990-01-01

Quantitative information about the existence and thermodynamic stability of uranyl(VI) ion complexes based solely upon nitrogen coordination has been obtained in the solvent dimethyl sulfoxide. Calorimetric, potentiometric, and FT-IR investigations, under controlled anhydrous conditions, show that the uranyl(VI) ion can form both mono and bis chelates with the ethylenediamine ligand and only a mono chelate of rather low stability with propylenediamine. With the monodentate ligand n-butylamine only a very weak metal-ligand interaction has been detected. The stability constants and the enthalpy and entropy changes have been calculated for the identified coordinated species. All data refer to 25.0 degree C and a tetraethylammonium perchlorate medium of ionic strength 0.1 M. All the complexes are enthalpy stabilized whereas the entropy contributions oppose the complex formation. Calorimetric and FT-IR measurements carried out to investigate the effects of small amounts of water present show that a very low water concentration, comparable to that of the coordinating metal ion, can give rise to hydrolysis reactions that may compete with complex formation. This is due to the combined action of different factors that are discussed. 39 refs., 6 figs., 1 tab

Quantification of isocyanates and amines in polyurethane foams and coated products by liquid chromatography–tandem mass spectrometry

Science.gov (United States)

Mutsuga, Motoh; Yamaguchi, Miku; Kawamura, Yoko

2014-01-01

An analytical method for the identification and quantification of 10 different isocyanates and 11 different amines in polyurethane (PUR) foam and PUR-coated products was developed and optimized. Isocyanates were extracted and derivatized with di-n-butylamine, while amines were extracted with methanol. Quantification was subsequently performed by liquid chromatography–tandem mass spectrometry. Using this methodology, residual levels of isocyanates and amines in commercial PUR products were quantified. Although the recoveries of certain isocyanates and amines were low, the main compounds used as monomers in the production of PUR products, and their decomposition species, were clearly identified at quantifiable levels. 2,4-and 2,6-toluenediisocyanate were detected in most PUR foam samples and a pastry bag in the range of 0.02–0.92 mg/kg, with their decomposition compounds, 2,4-and 2,6-toluenediamine, detected in all PUR foam samples in the range of 9.5–59 mg/kg. PUR-coated gloves are manufactured using 4,4′-methylenebisphenyl diisocyanate as the main raw material, and a large amount of this compound, in addition to 4,4′-methylenedianiline and dicyclohexylmethane-4,4′-diamine were found in these samples. PMID:24804074

Characterization of 12-molybdophosphoric acid supported on mesoporous silica MCM-41 and its catalytic performance in the synthesis of hydroquinone diacetate

International Nuclear Information System (INIS)

Ahmed, Awad I.; Samra, S.E.; El-Hakam, S.A.; Khder, A.S.; El-Shenawy, H.Z.; El-Yazeed, W.S. Abo

2013-01-01

12-molybdophosphoric acid (PMA) was supported on mesoporous molecular sieves MCM-41 by impregnation of 12-molybdophosphoric acid followed by calcination. The nanochannels of MCM-41 provide a large surface area for the solid state dispersion of 12-molybdophosphoric acid. The samples have been characterized by N 2 adsorption–desorption at −196 °C, transmission electron microscopy (TEM), powder X-ray diffraction (PXRD), and FT-IR measurements. The acidity and catalytic activity have been, respectively, examined by nonaqueous titration of n-butylamine in acetonitrile and synthesis of hydroquinone diacetate. The results showed that ordered hexagonal pore structure was observed in the synthesized MCM-41. Also the results indicate that PMA are highly dispersed on mesoporous silica MCM-41 spherical nanoparticles while PMA retains its Keggin structure. On the other hand, with increasing the introduced PMA amount, the specific surface area decreases, and the mesoporous ordering of the samples become poor. Both the surface acidity and the catalytic activity sharply increase with the modification of MCM-41 by PMA but decrease by increasing the calcination temperature. The sample with 55 wt% PMA/MCM-41 calcined at 350 °C shows the highest acidity and catalytic activity.

Control of the Intrinsic Sensor Response to Volatile Organic Compounds with Fringing Electric Fields.

Science.gov (United States)

Henning, Alex; Swaminathan, Nandhini; Vaknin, Yonathan; Jurca, Titel; Shimanovich, Klimentiy; Shalev, Gil; Rosenwaks, Yossi

2018-01-26

The ability to control surface-analyte interaction allows tailoring chemical sensor sensitivity to specific target molecules. By adjusting the bias of the shallow p-n junctions in the electrostatically formed nanowire (EFN) chemical sensor, a multiple gate transistor with an exposed top dielectric layer allows tuning of the fringing electric field strength (from 0.5 × 10 7 to 2.5 × 10 7 V/m) above the EFN surface. Herein, we report that the magnitude and distribution of this fringing electric field correlate with the intrinsic sensor response to volatile organic compounds. The local variations of the surface electric field influence the analyte-surface interaction affecting the work function of the sensor surface, assessed by Kelvin probe force microscopy on the nanometer scale. We show that the sensitivity to fixed vapor analyte concentrations can be nullified and even reversed by varying the fringing field strength, and demonstrate selectivity between ethanol and n-butylamine at room temperature using a single transistor without any extrinsic chemical modification of the exposed SiO 2 surface. The results imply an electric-field-controlled analyte reaction with a dielectric surface extremely compelling for sensitivity and selectivity enhancement in chemical sensors.

Dopamine agonist activity of EMD 23,448

International Nuclear Information System (INIS)

Martin, G.E.; Pettibone, D.J.

1985-01-01

EMD 23,448 was examined in tests of dopaminergic function and was found to be an atypical dopamine (DA) agonist. EMD 23,448 was a weak or inactive DA agonist when examined in tests of normal postsynaptic DA receptor function: production of stereotypy in the rat (ED 50 greater than sign 5.0 mg/kg.i.p.); production of emesis in beagles (minimum effective dose = 81μg/kg i.v.); and, enhanced locomotor activity of the mouse (no excitation in doses 3 H]-apomorphine binding to rat striatal membranes (Ki, 205 nM). On the other hand, this indolyl-3-butylamine did activate supersensitive postsynaptic DA receptors. Specifically, it elicited contralateral turning in rats with a unilateral 6-hydroxydopamine lesion of the substantia nigra (ED 50 value = 0.9 mg/kg) and did elicit stereotypy in rats given chronic daily haloperidol treatments. EMD 23,448 also exerted pharmacological effects in tests designed to measure activation of dopamine autoreceptors. It inhibited the γ-butyrolactone-induced increase in striatal dopa levels (ED 50 = 1 mg/kg i.p.) and produced a dose-related fall in the locomotor activity of the mouse. The results are discussed and contrasted with data derived for apomorphine and the putatively selective autoreceptor agonist (+-)-3-PPP. (Author)

Electron spin resonance of spin-trapped radicals of amines and polyamines

International Nuclear Information System (INIS)

Mossoba, M.M.; Rosenthal, Ionel; Riesz, Peter

1982-01-01

The reactions of hydroxyl radicals with methylamine, dimethylamine, trimethylamine, diethylamine, sec-butylamine, ethylene-diamine, 1,3-diaminopropane, putrescine, cadaverine, 1,7-diaminoheptane, ornithine, spermidine, spermine, agmatine, and arcaine in aqueous solutions have been investigated by spin-trapping and esr. Hydroxyl radicals were generated by the uv photolysis of H 2 O 2 and 2-methyl-2-nitrosopropane (MNP) was used as the spin-trap. The effects of ionizing radiation on the same polyamines in the polycrystalline state were also investigated. The free radicals produced by ν-radiolysis of these solids at room temperature in the absence of air were identified by dissolution in aqueous solutions of MNP. The predominant reaction of OH radicals with amines and polyamines below pH 7 was the abstraction of hydrogen atoms from a carbon that is not adjacent to the protonated amino group. For agmatine and arcaine which contain guanidinium groups abstraction occurred from the α-CH. Dimethylamine was oxidized to the dimethylnitroxyl radical by H 2 O 2 in the dark. ν-Radiolysis of polyamines in the polycrystalline state generated radicals due to H-abstraction from either the α-Ch or from a carbon atom in the middle of the alkyl chain. The deamination radical was obtained from ornithine

Electron spin resonance of spin-trapped radicals of amines and polyamines. Hydroxyl radical reactions in aqueous solutions and. gamma. radiolysis in the solid state

Energy Technology Data Exchange (ETDEWEB)

Mossoba, M.M.; Rosenthal, I.; Riesz, P. (National Cancer Inst., Bethesda, MD (USA))

1982-06-15

The reactions of hydroxyl radicals with methylamine, dimethylamine, trimethylamine, diethylamine, sec-butylamine, ethylene-diamine, 1,3-diaminopropane, putrescine, cadaverine, 1,7-diaminoheptane, ornithine, spermidine, spermine, agmatine, and arcaine in aqueous solutions have been investigated by spin-trapping and esr. Hydroxyl radicals were generated by the uv photolysis of H/sub 2/O/sub 2/ and 2-methyl-2-nitrosopropane (MNP) was used as the spin-trap. The effects of ionizing radiation on the same polyamines in the polycrystalline state were also investigated. The free radicals produced by ..gamma..-radiolysis of these solids at room temperature in the absence of air were identified by dissolution in aqueous solutions of MNP. The predominant reaction of OH radicals with amines and polyamines below pH 7 was the abstraction of hydrogen atoms from a carbon that is not adjacent to the protonated amino group. For agmatine and arcaine which contain guanidinium groups abstraction occurred from the ..cap alpha..-CH. Dimethylamine was oxidized to the dimethylnitroxyl radical by H/sub 2/O/sub 2/ in the dark. ..gamma..-Radiolysis of polyamines in the polycrystalline state generated radicals due to H-abstraction from either the ..cap alpha..-Ch or from a carbon atom in the middle of the alkyl chain. The deamination radical was obtained from ornithine.

Field Evaluation of Solvent-Free Sampling with Di-n-butylamine for the Determination of Airborne Monomeric and Oligomeric 1,6-Hexamethylene Diisocyanate

Science.gov (United States)

2014-03-27

ISO Guide 34:2009 and ISO / IEC 17025 :2005) for HDI oligomers. Per the manufacturer, a single ASSETTM sampler may be used for over 8 hours which leads...hexamethylene diisocyanate (HDI). During this study, the Supelco ASSETTM EZ4-NCO Dry Sampler was compared to the Omega Specialty Instrument Company ISO ...detection (HPLC-MS); 2) do ASSETTM and ISO -CHEK® samplers collect equivalent HDI monomer and oligomer concentrations; and 3) what is the relative cost of

Dopamine agonist activity of EMD 23,448

Energy Technology Data Exchange (ETDEWEB)

Martin, G E; Pettibone, D J [Merck Sharp and Dohme Research Laboratories, West Point, Pennsylvania (USA). Dept. of Pharmacology

1985-01-01

EMD 23,448 was examined in tests of dopaminergic function and was found to be an atypical dopamine (DA) agonist. EMD 23,448 was a weak or inactive DA agonist when examined in tests of normal postsynaptic DA receptor function: production of stereotypy in the rat (ED/sub 50/ greater than sign 5.0 mg/kg.i.p.); production of emesis in beagles (minimum effective dose = 81..mu..g/kg i.v.); and, enhanced locomotor activity of the mouse (no excitation in doses <=50 mg/i.p.). Moreover, EMD 23,448 was relatively weak in competing for (/sup 3/H)-apomorphine binding to rat striatal membranes (Ki, 205 nM). On the other hand, this indolyl-3-butylamine did activate supersensitive postsynaptic DA receptors. Specifically, it elicited contralateral turning in rats with a unilateral 6-hydroxydopamine lesion of the substantia nigra (ED/sub 50/ value = 0.9 mg/kg) and did elicit stereotypy in rats given chronic daily haloperidol treatments. EMD 23,448 also exerted pharmacological effects in tests designed to measure activation of dopamine autoreceptors. It inhibited the ..gamma..-butyrolactone-induced increase in striatal dopa levels (ED/sub 50/ = 1 mg/kg i.p.) and produced a dose-related fall in the locomotor activity of the mouse. The results are discussed and contrasted with data derived for apomorphine and the putatively selective autoreceptor agonist (+-)-3-PPP.

Catalytic Mechanism of Nitrile Hydratase Proposed by Time-resolved X-ray Crystallography Using a Novel Substrate, tert-Butylisonitrile*S⃞

Science.gov (United States)

Hashimoto, Koichi; Suzuki, Hiroyuki; Taniguchi, Kayoko; Noguchi, Takumi; Yohda, Masafumi; Odaka, Masafumi

2008-01-01

Nitrile hydratases (NHases) have an unusual iron or cobalt catalytic center with two oxidized cysteine ligands, cysteine-sulfinic acid and cysteine-sulfenic acid, catalyzing the hydration of nitriles to amides. Recently, we found that the NHase of Rhodococcus erythropolis N771 exhibited an additional catalytic activity, converting tert-butylisonitrile (tBuNC) to tert-butylamine. Taking advantage of the slow reactivity of tBuNC and the photoreactivity of nitrosylated NHase, we present the first structural evidence for the catalytic mechanism of NHase with time-resolved x-ray crystallography. By monitoring the reaction with attenuated total reflectance-Fourier transform infrared spectroscopy, the product from the isonitrile carbon was identified as a CO molecule. Crystals of nitrosylated inactive NHase were soaked with tBuNC. The catalytic reaction was initiated by photo-induced denitrosylation and stopped by flash cooling. tBuNC was first trapped at the hydrophobic pocket above the iron center and then coordinated to the iron ion at 120 min. At 440 min, the electron density of tBuNC was significantly altered, and a new electron density was observed near the isonitrile carbon as well as the sulfenate oxygen of αCys114. These results demonstrate that the substrate was coordinated to the iron and then attacked by a solvent molecule activated by αCys114-SOH. PMID:18948265

Hydrogen-transfer and charge-transfer in photochemical and radiation induced reactions. Progress report, November 1, 1975--October 31, 1976

International Nuclear Information System (INIS)

Cohen, S.G.

1976-10-01

The relative importance of light absorption, quenching of triplet, and hydrogen transfer repair has been examined in retardation by mercaptans of photoreduction of aromatic ketones by alcohols. In the reduction of benzophenone by 2-propanol, retardation is efficient and, after correction for the first two effects, is due entirely to hydrogen-transfer repair, as indicated by deuterium labeling. In reduction of acetophenone by α-methylbenzyl alcohol, repair by hydrogen transfer is also operative. In reduction of benzophenone by benzhydrol, retardation is less efficient and is due to quenching, as the ketyl radical does not abstract hydrogen from mercaptan rapidly in competition with coupling. Deuterium isotope effects are discussed in terms of competitive reactions. Photoreduction of benzophenone by 2-butylamine and by triethylamine is retarded by aromatic mercaptans and disulfides. Of the retardation not due to light absorption and triplet quenching by the sulfur compounds, half is due to hydrogen-transfer repair, as indicated by racemization and deuterium labeling. The remainder is attributed to quenching by the sulfur compound of the charge-transfer-complex intermediate. Photoreduction by primary and secondary amines, but not by tertiary amines, is accelerated by aliphatic mercaptans. The acceleration is attributed to catalysis of hydrogen transfer by the mercaptan in the charge-transfer complex. The effect is large in hydrocarbon solvent, less in polar organic solvents and absent in water

Rate constants for some electrophilic reactions of benzyl, benzhydryl, and trityl cations in solution

International Nuclear Information System (INIS)

Ujdak, R.J.; Jones, R.L.; Dorfman, L.M.

1976-01-01

Absolute rate constants have been determined by the pulse radiolysis technique for several electrophilic reactions of the benzyl, the benzhydryl, and the trityl cation in 1,2-dichloroethane solution. The rate constants for the reactions of these carbonium ions with chloride ion, with bromide ion, and with iodide ion are all very nearly the same, namely 6 x 10 10 M -1 s -1 at 24 0 C. The values very likely represent the diffusion controlled limit for the ion combination reactions. The rate constants for the reactions with triethylamine, tri-n-propylamine, and tri-n-butylamine range from 2.0 x 10 9 to 7 x 10 6 M -1 s -1 at 24 0 C. With increasing phenyl substitution, the decreasing trend in the magnitude of the rate constant is consistent with the combined electronic and steric effects. With increasing size of the amine, the decrease in the value of the rate constant seems to indicate that the steric effect predominates. The values of the rate constants for reactions of benzyl and benzhydryl cation with methanol, ethanol, and 2-propanol indicate the following. The rate constant is higher for reaction with the alcohol dimer in solution than with alcohol monomer. The rate constants for reaction with alcohol monomer have values of 1 x 10 8 M -1 s -1 or lower

Rabi like angular splitting in Surface Plasmon Polariton - Exciton interaction in ATR configuration

Science.gov (United States)

Hassan, Heba; Abdallah, T.; Negm, S.; Talaat, H.

2018-05-01

We have studied the coupling of propagating Surface Plasmon Polaritons (SPP) on silver films and excitons in CdS quantum dots (QDs). We employed the Kretschmann-Raether configuration of the attenuated total reflection (ATR) to propagate the SPP on silver film of thickness 47.5 nm at three different wavelengths. The CdS QD have been chemically synthesized with particular size such that its exciton of energy would resonate with SPP. High resolution transmission electron microscopy (HRTEM) and scan tunneling microscopy (STM) were used to measure the corresponding QDs size and confirm its shape. Further confirmation of the size has been performed by the effective mass approximation (EMA) model utilizing the band gap of the prepared QDs. The band gaps have been measured through UV-vis absorption spectra as well as scan tunneling spectroscopy (STS). The coupling has been observed as two branching dips in the ATR spectra indicating Rabi like splitting. To the best of our knowledge, this is the first time that Rabi interaction is directly observed in an ATR angular spectra. This observation is attributed to the use a high resolution angular scan (±0.005°), in addition to the Doppler width of the laser line as well as the energy distribution of the excitons. The effect of three different linker molecules (TOPO, HDA), (Pyridine) and (Tri-butylamine) as surface ligands, on SPP-Exciton interaction has been examined.

Polymer supported synthesis of unsymmetrical n.c.a. selenium-73/75 ethers for the labelling of amino acids

International Nuclear Information System (INIS)

Schmaljohann, J.

1995-09-01

The synthesis of n.c.a. selenium-73/75 labelled methionine and of a selenoalkylation agent have been performed according to a reaction including a primary, polymer supported alkylation step. The selenium-75 was produced through the 75 As(p, n)-process and separated as [ 75 Se]selenium dioxide by thermochromatography. The [ 75 Se]SeO 2 -sublimate was dissolved in hydrochloric acid and reduced with sulfur dioxide to obtain elemental n.c.a. selenium-75, which was extracted into benzene. Reaction of the elemental n.c.a. selenium-75 with polymeric bound triphenylphosphine led to the formation of the corresponding [ 75 Se]triphenylphosphinselenide in a nearly quantitative yield. The asymmetrical [ 75 Se]selenoethers were synthesized in homogeneous phase through the reaction of the [ 75 Se]MeSe - with propylhalides in radiochemical yields up of to 55%. A selenium-75 labelled prosthetic group was synthesized in radiochemical yields of 48% by the reaction of 1-chloro-3-iodopropane with the [ 75 ]selenation reagent [ 75 Se]MeSe - . For labelling amino functions via [ 75 Se]selenoalkylation the [ 75 Se]selenated propyl chloride has to be transfered into the iodide with sodium iodide, which was performed in radiochemical yields of 90%. After the reaction of [ 75 Se]-1-iodo-3-(methylseleno)propane with butylamine or with N α -, O-protected lysine in DMF at 80 C the [ 75 Se]methylselenopropylated products were obtained in radiochemical yields of 95% and 90%, respectively. (orig./SR)

Designing N-halamine based antibacterial surface on polymers: Fabrication, characterization, and biocidal functions

Energy Technology Data Exchange (ETDEWEB)

Chen Yong, E-mail: ychen168@126.com [Department of Applied Chemistry, College of Chemical and Environmental Engineering, Shandong University of Science and Technology, 579 Qianwangang Rd., Huangdao Zone, Qingdao 266510 (China); Han Qiuxia [Department of Biological Engineering, College of Chemical and Environmental Engineering, Shandong University of Science and Technology, Qingdao 266510 (China)

2011-05-01

We demonstrate a valuable method to generate reactive groups on inert polymer surfaces and bond antibacterial agents for biocidal ability. Polystyrene (PS) surfaces were functionalized by spin coating of sub-monolayer and monolayer films of poly(styrene-b-tert-butyl acrylate) (PS-PtBA) block copolymer from solutions in toluene. PS-PtBA self-assembled to a bilayer structure on PS that contains a surface layer of the PtBA blocks ordering at the air-polymer interface and a bottom layer of the PS blocks entangling with the PS substrate. The thickness of PtBA layer could be linearly controlled by the concentration of the spin coating solution and a 2.5 nm saturated monolayer coverage of PtBA was achieved at 0.35% (w/w). Carboxyl groups were generated by exposing the tert-butyl ester groups of PtBA on saturated surface to trifluoroacetic acid (TFA) to bond tert-butylamine via amide bonds that were further chlorinated to N-halamine with NaOCl solution. The density of N-halamine on the chlorinated surface was calculated to be 1.05 x 10{sup -5} mol/m{sup 2} by iodimetric/thiosulfate titration. Presented data showed the N-halamine surface provided powerful antibacterial activities against Staphylococcus aureus and Escherichia coli. Over 50% of the chlorine lost after UVA irradiation could be regained upon rechlorination. This design concept can be virtually applied to any inert polymer by choosing appropriate block copolymers and antibacterial agents to attain desirable biocidal activity.

Survivability and reactivity of glycine and alanine in early oceans: effects of meteorite impacts.

Science.gov (United States)

Umeda, Yuhei; Fukunaga, Nao; Sekine, Toshimori; Furukawa, Yoshihiro; Kakegawa, Takeshi; Kobayashi, Takamichi; Nakazawa, Hiromoto

2016-01-01

Prebiotic oceans might have contained abundant amino acids, and were subjected to meteorite impacts, especially during the late heavy bombardment. It is so far unknown how meteorite impacts affected amino acids in the early oceans. Impact experiments were performed under the conditions where glycine was synthesized from carbon, ammonia, and water, using aqueous solutions containing (13)C-labeled glycine and alanine. Selected amino acids and amines in samples were analyzed with liquid chromatography-mass spectrometry (LC/MS). In particular, the (13)C-labeled reaction products were analyzed to distinguish between run products and contaminants. The results revealed that both amino acids survived partially in the early ocean through meteorite impacts, that part of glycine changed into alanine, and that large amounts of methylamine and ethylamine were formed. Fast decarboxylation was confirmed to occur during such impact processes. Furthermore, the formation of n-butylamine, detected only in the samples recovered from the solutions with additional nitrogen and carbon sources of ammonia and benzene, suggests that chemical reactions to form new biomolecules can proceed through marine impacts. Methylamine and ethylamine from glycine and alanine increased considerably in the presence of hematite rather than olivine under similar impact conditions. These results also suggest that amino acids present in early oceans can contribute further to impact-induced reactions, implying that impact energy plays a potential role in the prebiotic formation of various biomolecules, although the reactions are complicated and depend upon the chemical environments as well.

Shock wave synthesis of amino acids from solutions of ammonium formate and ammonium bicarbonate

Science.gov (United States)

Suzuki, Chizuka; Furukawa, Yoshihiro; Kobayashi, Takamichi; Sekine, Toshimori; Nakazawa, Hiromoto; Kakegawa, Takeshi

2015-07-01

The emergence of life's building blocks, such as amino acids and nucleobases, on the prebiotic Earth was a critical step for the beginning of life. Reduced species with low mass, such as ammonia, amines, or carboxylic acids, are potential precursors for these building blocks of life. These precursors may have been provided to the prebiotic ocean by carbonaceous chondrites and chemical reactions related to meteorite impacts on the early Earth. The impact of extraterrestrial objects on Earth occurred more frequently during this period than at present. Such impacts generated shock waves in the ocean, which have the potential to progress chemical reactions to form the building blocks of life from reduced species. To simulate shock-induced reactions in the prebiotic ocean, we conducted shock-recovery experiments on ammonium bicarbonate solution and ammonium formate solution at impact velocities ranging from 0.51 to 0.92 km/s. In the products from the ammonium formate solution, several amino acids (glycine, alanine, ß-alanine, and sarcosine) and aliphatic amines (methylamine, ethylamine, propylamine, and butylamine) were detected, although yields were less than 0.1 mol % of the formic acid reactant. From the ammonium bicarbonate solution, smaller amounts of glycine, methylamine, ethylamine, and propylamine were formed. The impact velocities used in this study represent minimum cases because natural meteorite impacts typically have higher velocities and longer durations. Our results therefore suggest that shock waves could have been involved in forming life's building blocks in the ocean of prebiotic Earth, and potentially in aquifers of other planets, satellites, and asteroids.

Crystal engineered acid–base complexes with 2D and 3D hydrogen bonding systems using p-hydroxybenzoic acid as the building block

Directory of Open Access Journals (Sweden)

PU SU ZHAO

2010-04-01

Full Text Available p-Hydroxybenzoic acid (p-HOBA was selected as the building block for self-assembly with five bases, i.e., diethylamine, tert-butylamine, cyclohexylamine, imidazole and piperazine, and generation of the corresponding acid–base complexes 1–5. Crystal structure analyses suggest that proton-transfer from the carboxyl hydrogen to the nitrogen atom of the bases can be observed in 1–4, while only in 5 does a solvent water molecule co-exist with p--HOBA and piperazine. With the presence of O–H···O hydrogen bonds in 1–4, the deprotonated p-hydroxybenzoate anions (p-HOBAA– are simply connected each other in a head-to-tail motif to form one-dimensional (1D arrays, which are further extended to distinct two-dimensional (2D (for 1 and 4 and three-dimensional (3D (for 2 and 3 networks via N–H···O interactions. While in 5, neutral acid and base are combined pair-wise by O–H···N and N–H···O bonds to form a 1D tape and then the 1D tapes are sequentially combined by water molecules to create a 3D network. Some interlayer or intralayer C–H···O, C–H···p and p×××p interactions help to stabilize the supramolecular buildings. Melting point determination analyses indicate that the five acid–base complexes are not the ordinary superposition of the reactants and they are more stable than the original reactants.

Airborne thermal degradation products of polyurethene coatings in car repair shops.

Science.gov (United States)

Karlsson, D; Spanne, M; Dalene, M; Skarping, G

2000-10-01

A methodology for workplace air monitoring of aromatic and aliphatic, mono- and polyisocyanates by derivatisation with di-n-butylamine (DBA) is presented. Air sampling was performed using midget impinger flasks containing 10 ml of 0.01 mol l(-1) DBA in toluene and a glass-fibre filter in series after the impinger flask, thereby providing the possibility of collecting and derivatising isocyanates in both the gas and particle phases. Quantification was made by LC-MS, monitoring the molecular ions [MH]+. Air samples taken with this method in car repair shops showed that many different isocyanates are formed during thermal decomposition of polyurethane (PUR) coatings. In addition to isocyanates such as hexamethylene (HDI), isophorone (IPDI), toluene (TDI) and methylenediphenyl diisocyanate (MDI), monoisocyanates such as methyl (MIC), ethyl (EIC), propyl (PIC), butyl (BIC) and phenyl isocyanate (PhI) were found. In many air samples the aliphatic monoisocyanates dominated. During cutting and welding operations, the highest levels of isocyanates were observed. In a single air sample from a welding operation in a car repair shop, the highest concentrations found were: MIC, 290; EIC, 60; PIC, 20; BIC, 9; PhI, 27; HDI, 105; IPDI, 39; MDI, 4; and 2,4-TDI and 2,6-TDI 140 microg m(-3). Monitoring the particle size distribution and concentration during grinding, welding and cutting operations showed that ultrafine particles (< 0.1 microm) were formed at high concentrations. Isocyanates with low volatility were mainly found in the particle phase, but isocyanates with a relatively high volatility such as TDI, were found in both the particle and gas phases.

Monitoring exposure of personnel to volatile nitrosamines in the laboratory environment

Energy Technology Data Exchange (ETDEWEB)

Issenberg, P; Swanson, S E

1980-01-01

A convenient sampling method was developed for collection of volatile nitrosamines from large-volume air samples. Stainless steel tubes containing 0.3 g Tenax GC were employed to collect nitrosamines from 5-30 1 air samples. Nitrosamines were eluted from the sample tubes with diethylether to minimize formation of artifacts which were observed when thermal desorption was employed. Eluates were analysed directly by GC-TEA and nitrosamine identities were confirmed using high-resolution GC-MS with selected ion-monitoring. The detection limit was approximately 0.8 micrograms/m3 (0.3 ppb) for NDMA in 2 ml of diethylether extract. The laboratory operations studied included chemical synthesis, trace analysis, animal treatment, microbial mutagenesis tests and in vitro biochemical procedures. In most cases, nitrosamines were not detected in laboratory air, but levels of 200-800 micrograms/m3 (42 to 180 ppb) of N-nitrosomethyl-tert-butylamine were measured during animal treatment, 0.8-8.6 micrograms/m3 (0.3 to 2.8 ppb) of NDMA during mutagenesis assays, 12-22 micrograms/m3 (4-7 ppb) of NDMA during in vitro metabolism studies and 11 micrograms/m3 (3.6 ppb) of NDMA in a walk-in refrigerator. Appropriate corrective measures reduced all nitrosamine levels to below the detection limit. Hamsters and rats treated with NDAA (80 mg/kg, s.c.) excreted 4.4 and 12.9%, respectively, of the nitrosamine in expired air in 24 hr. This route of excretion may be metabolically significant and should be considered in the safe design of animal treatment and holding facilities.

Identification of N-nitrosamines in treated drinking water using nanoelectrospray ionization high-field asymmetric waveform ion mobility spectrometry with quadrupole time-of-flight mass spectrometry.

Science.gov (United States)

Zhao, Yuan Yuan; Liu, Xin; Boyd, Jessica M; Qin, Feng; Li, Jianjun; Li, Xing-Fang

2009-01-01

We report a nanoelectrospray ionization (nESI) with high-field asymmetric waveform ion mobility spectrometry (FAIMS) and tandem mass spectrometry (MS-MS) method for determination of small molecules of m/z 50 to 200 and its potential application in environmental analysis. Integration of nESI with FAIMS and MS-MS combines the advantages of these three techniques into one method. The nESI provides efficient sample introduction and ionization and allows for collection of multiple data from only microliters of samples. The FAIMS provides rapid separation, reduces or eliminates background interference, and improves the signal-to-noise ratio as much as 10-fold over nESI-MS-MS. The tandem quadrupole time-of-flight MS detection provides accurate mass and mass spectral measurements for structural identification. Characteristics of FAIMS compensation voltage (CV) spectra of seven nitrosamines, N-nitrosodimethylamine (NDMA), N-nitrosomethylethylamine (NMEA), N-nitrosodiethylamine (NDEA), N-nitrosodi-n-propylamine (NDPA), N-nitrosodi-n-butylamine (NDBA), N-nitrosopiperidine (NPip), and N-nitrosopyrrolidine (NPyr), were analyzed. The optimal CV of the nitrosamines (at DV -4000 V) were: -1.6 V, NDBA; 2.6 V, NDPA; 6.6 V, NPip; 8.8 V, NDEA; 13.2 V, NPyr; 14.4 V, NMEA; and 19.4 V, NDMA. Fragmentation patterns of the seven nitrosamines in the nESI-FAIMS-MS-MS were also obtained. The specific CV and MS-MS spectra resulted in positive identification of NPyr and NPip in a treated water sample, demonstrating the potential application of this technique in environmental analysis.

Polymer supported synthesis of unsymmetrical n.c.a. selenium-73/75 ethers for the labelling of amino acids; Polymergestuetzte Synthese von unsymmetrischen n.c.a. [{sup 73,75}Se] Selenoethern zur Markierung von Aminosaeuren

Energy Technology Data Exchange (ETDEWEB)

Schmaljohann, J

1995-09-01

The synthesis of n.c.a. selenium-73/75 labelled methionine and of a selenoalkylation agent have been performed according to a reaction including a primary, polymer supported alkylation step. The selenium-75 was produced through the {sup 75}As(p, n)-process and separated as [{sup 75}Se]selenium dioxide by thermochromatography. The [{sup 75}Se]SeO{sub 2}-sublimate was dissolved in hydrochloric acid and reduced with sulfur dioxide to obtain elemental n.c.a. selenium-75, which was extracted into benzene. Reaction of the elemental n.c.a. selenium-75 with polymeric bound triphenylphosphine led to the formation of the corresponding [{sup 75}Se]triphenylphosphinselenide in a nearly quantitative yield. The asymmetrical [{sup 75}Se]selenoethers were synthesized in homogeneous phase through the reaction of the [{sup 75}Se]MeSe{sup -} with propylhalides in radiochemical yields up of to 55%. A selenium-75 labelled prosthetic group was synthesized in radiochemical yields of 48% by the reaction of 1-chloro-3-iodopropane with the [{sup 75}]selenation reagent [{sup 75}Se]MeSe{sup -}. For labelling amino functions via [{sup 75}Se]selenoalkylation the [{sup 75}Se]selenated propyl chloride has to be transfered into the iodide with sodium iodide, which was performed in radiochemical yields of 90%. After the reaction of [{sup 75}Se]-1-iodo-3-(methylseleno)propane with butylamine or with N{sup {alpha}}-, O-protected lysine in DMF at 80 C the [{sup 75}Se]methylselenopropylated products were obtained in radiochemical yields of 95% and 90%, respectively. (orig./SR)

Synthesis and physico-chemical characterization of CeO2/ZrO2-SO42- mixed oxides

International Nuclear Information System (INIS)

Hernandez E, J. M.; Silva R, R.; Garcia A, R.; Garcia S, L. A.; Handy, B. E.; Cardenas G, G.; Cueto H, A.

2012-01-01

Environmentally friendly solid-acid catalysts CeO 2 /ZrO 2 -SO 4 2- were prepared by the sol gel method varying CeO 2 content (10, 20 and 30 wt %) and using sulfation in situ, maintaining the sulfate ions amount present in the materials at 20 wt %. ZrO 2 and ZrO 2 -SO 4 2- were also prepared for comparison proposes using the same synthesis method. The materials were characterized by X-ray diffraction, nitrogen physisorption, potentiometric titration with n-butylamine, decomposition of 2-propanol and n-pentane isomerization. The specific surface area of ZrO 2 -SO 4 2- was high (160 m 2 /g) compared with the unmodified ZrO 2 (80 m 2 /g), however this area decreased with increasing the CeO 2 content (37-100 m 2 /g). There was no significant effect of CeO 2 on the tetragonal structure of ZrO 2 -SO 4 2- . The variation of acid sites amount runs parallel to the change of specific surface area. The acid sites amount decreased with increasing cerium oxide content. The decomposition of 2-propanol results fundamentally in the formation of dehydration products such as propylene and diisopropyl ether, both involving acid sites. In addition, a good performance during the n-pentane isomerization was observed for these materials. The selectivity towards isopentane reaches 84% when the Pt/CeO 2 /ZrO 2 -SO 4 2- catalyst with the highest CeO 2 content was used. (Author)

Acidity enhancement of niobia by sulfation: An experimental and DFT study

International Nuclear Information System (INIS)

Rocha, Angela S.; Costa, Gustavo C.; Tamiasso-Martinhon, Priscila; Sousa, Célia; Rocha, Alexandre B.

2017-01-01

Acidic solids are used as catalyst at several industrial processes and studies to improve their activities have been developed by different groups. One method well known is sulfating oxide to create new acid sites, but investigations about sulfated niobia are still scarce. This work studied the influence of sulfation on the niobia acidity by using a very simple reaction model, the esterification of acetic acid with ethanol, performed at 60 °C and 1 atm. Niobia and sulfated niobia samples were characterized by N 2 adsorption, X-ray diffraction, FTIR and titration with n-butylamine. To investigate the nature of sulfate groups formed on the surface of niobia, calculations based on the Density Functional Theory (DFT) have been performed for two models: pure niobia with hydroxylated surface and sulfated niobia where one OH − surface group was replaced by a HSO 4 − . The experimental results indicated that the sulfation treatment leads to an increase in the specific surface area, acidity and, consequently, in the activity of niobia, with small changes in the crystal structure of the solid. The presence of sulfate groups was evidenced by FTIR spectra and calculations have indicated HSO 4 − species bounded to the surface. Density Functional Perturbation Theory (DFPT) was also employed to obtain infrared intensities in the region of sulfate vibration bands. - Highlights: • Sulfation treatment has improved the acidity of niobium oxide. • A sulfate group on niobia (T-Nb 2 O 5 ) was proposed using DFT method. • Niobia and sulfated niobia are used for esterification of acetic acid with ethanol.

Cytotoxicity of Diimine Palladium (II) Complexes of Alkyldithiocarbamate Derivatives on Human Lung, Ovary and Liver Cells.

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Aryanpour, Narges; Mansouri-Torshizi, Hassan; Nakhjavan, Maryam; H Shirazi, Farshad

2012-01-01

Three new Complexes of formula [pd(bpy)(R-NH-CSS)] Cl (where bpy is 2/2'- bipyridine, and R-NH-CSS is butylamine, hexylamine- and octyamine-dithiocabamate anion) have been synthesized by University of Sistan and Blachostan. These complexes have been characterized by spectroscopic methods such as ultraviolet-visible, infrared and (1)H-NMR as well as conductivity measurements and chemical analysis. In these complexes, each of the dithiocarbamate ligands coordinates to Pd (II) center as bidentate with two sulfur atoms. We have found a 1:1 electrolyte in water conductivity test for the above mentioned compounds. To measure the biologic activity and potential anticancer efficacy of these compounds, they have been compared with cisplatin and its palladium analogue of [Pd (NH3)2 Cl2] on three different cell lines of human hepatocarcinoma HepG2, human ovarian carcinoma OV2008, and human lung adenocarcinoma A549. Clonogenic assay has shown LD50s in the range of 0.131±0.025 to 0.934 ± 0.194 for these compounds on above cell lines. In comparison, cisplatin has shown LD50s of 0.838 ± 0.074, 2.196 ± 0.220, and 2.799 ± 0.733 on OV2008, HepG2 and A549 cell lines, respectively. As a conclusion, above three new complexes have shown higher cytotoxicities compared to cisplatin on three different human cell lines. Based on biological tests, these compounds may potentially be considered as good anticancer candidates for further pharmacological studies.

H3PW12O40 Encapsulation by Nanoporous Metal Organic Framework HKUST-1: Synthesis, Characterization, Activity and Stability.

Science.gov (United States)

Rafiee, Ezzat; Nobakht, Narges

2016-01-01

Hybrid composite material was obtained through encapsulation of H3PW12O40 (PW) into HKUST-1 (Cu3(BTC)2, BTC = 1,3,5-benzenetricarboxylic acid), in molar composition of 5 Cu(NO3)2 · 3H2O/2.8 BTC/0.3 PW/0.6 CTAB by adding solutions of PW and copper salts to mixture of BTC and surfactant. The catalyst was characterized by various techniques including powder X-ray diffraction (XRD), Fourier transform infrared (FT-IR), scanning electron microscopy (SEM), energy dispersive X-ray (EDX), laser particle size analyzer, Brunauer Emmett-Teller (BET). The acidity of the catalyst was measured by a potentiometric titration with n-butylamine and PW/HKUST-1 presented very strong acidic sites with Ei > 100 mV. This nano catalyst was successfully used for the synthesis of various β-keto enol ethers at 45 °C with 51-98% yield after 5-75 min. The catalyst was easily recycled and reused at least four times without significant loss of its activity (94% yield after forth run). The presence of the PW in PW/HKUST-1 and reused PW/HKUST-1 structure, eliminating any doubt about collapse of the HKUST-1 after catalytic reaction and can be followed by FT-IR, XRD and SEM techniques. Brönsted and Lewis acidity of the PW/HKUST-1 catalyst was distinguished by studying the FT-IR and determined by chemisorption of pyridine. The strength and dispersion of the protons on PW/HKUST-1 was considerably high and active surface protons became more available for reactant.

Acidity enhancement of niobia by sulfation: An experimental and DFT study

Energy Technology Data Exchange (ETDEWEB)

Rocha, Angela S., E-mail: angela.sanches.rocha@gmail.com [Universidade do Estado do Rio de Janeiro, Departamento de Físico-Química, Instituto de Química, Rio de Janeiro (Brazil); Costa, Gustavo C. [Universidade do Estado do Rio de Janeiro, Departamento de Físico-Química, Instituto de Química, Rio de Janeiro (Brazil); Tamiasso-Martinhon, Priscila; Sousa, Célia; Rocha, Alexandre B. [Universidade Federal do Rio de Janeiro, Departamento de Físico-Química, Instituto de Química, Rio de Janeiro (Brazil)

2017-01-15

Acidic solids are used as catalyst at several industrial processes and studies to improve their activities have been developed by different groups. One method well known is sulfating oxide to create new acid sites, but investigations about sulfated niobia are still scarce. This work studied the influence of sulfation on the niobia acidity by using a very simple reaction model, the esterification of acetic acid with ethanol, performed at 60 °C and 1 atm. Niobia and sulfated niobia samples were characterized by N{sub 2} adsorption, X-ray diffraction, FTIR and titration with n-butylamine. To investigate the nature of sulfate groups formed on the surface of niobia, calculations based on the Density Functional Theory (DFT) have been performed for two models: pure niobia with hydroxylated surface and sulfated niobia where one OH{sup −} surface group was replaced by a HSO{sub 4}{sup −}. The experimental results indicated that the sulfation treatment leads to an increase in the specific surface area, acidity and, consequently, in the activity of niobia, with small changes in the crystal structure of the solid. The presence of sulfate groups was evidenced by FTIR spectra and calculations have indicated HSO{sub 4}{sup −} species bounded to the surface. Density Functional Perturbation Theory (DFPT) was also employed to obtain infrared intensities in the region of sulfate vibration bands. - Highlights: • Sulfation treatment has improved the acidity of niobium oxide. • A sulfate group on niobia (T-Nb{sub 2}O{sub 5}) was proposed using DFT method. • Niobia and sulfated niobia are used for esterification of acetic acid with ethanol.

Synthesis and physico-chemical characterization of CeO{sub 2}/ZrO{sub 2}-SO{sub 4}{sup 2-} mixed oxides

Energy Technology Data Exchange (ETDEWEB)

Hernandez E, J. M.; Silva R, R.; Garcia A, R. [Instituto Tecnologico de Ciudad Madero, Div. de Estudios de Posgrado e Investigacion, Juventino Rosas y Jesus Urueta s/n, Col. Los Mangos, 89440 Ciudad Madero, Tamaulipas (Mexico); Garcia S, L. A. [IPN, Centro Interdisciplinario de Investigaciones y de Estudios sobre Medio Ambiente y Desarrollo, 30 de Junio No. 1520, Barrio La Laguna Ticoman, 07340 Mexico D. F. (Mexico); Handy, B. E.; Cardenas G, G. [Universidad Autonoma de San Luis Potosi, CIEP, Facultad de Ciencias Quimicas, Av. Dr. Manuel Nava No. 6, Zona Universitaria, 78210 SLP, San Luis Potosi (Mexico); Cueto H, A. [Universidad Autonoma Metropolitana, Unidad Azcapotzalco, Av. San Pablo No. 180, Col. Reynosa Tamaulipas, 02200 Mexico D. F. (Mexico)

2012-07-01

Environmentally friendly solid-acid catalysts CeO{sub 2}/ZrO{sub 2}-SO{sub 4}{sup 2-} were prepared by the sol gel method varying CeO{sub 2} content (10, 20 and 30 wt %) and using sulfation in situ, maintaining the sulfate ions amount present in the materials at 20 wt %. ZrO{sub 2} and ZrO{sub 2}-SO{sub 4}{sup 2-} were also prepared for comparison proposes using the same synthesis method. The materials were characterized by X-ray diffraction, nitrogen physisorption, potentiometric titration with n-butylamine, decomposition of 2-propanol and n-pentane isomerization. The specific surface area of ZrO{sub 2}-SO{sub 4}{sup 2-} was high (160 m{sup 2}/g) compared with the unmodified ZrO{sub 2} (80 m{sup 2}/g), however this area decreased with increasing the CeO{sub 2} content (37-100 m{sup 2}/g). There was no significant effect of CeO{sub 2} on the tetragonal structure of ZrO{sub 2}-SO{sub 4}{sup 2-}. The variation of acid sites amount runs parallel to the change of specific surface area. The acid sites amount decreased with increasing cerium oxide content. The decomposition of 2-propanol results fundamentally in the formation of dehydration products such as propylene and diisopropyl ether, both involving acid sites. In addition, a good performance during the n-pentane isomerization was observed for these materials. The selectivity towards isopentane reaches 84% when the Pt/CeO{sub 2}/ZrO{sub 2}-SO{sub 4}{sup 2-} catalyst with the highest CeO{sub 2} content was used. (Author)

Investigating the synthesis of ligated metal clusters in solution using a flow reactor and electrospray ionization mass spectrometry.

Science.gov (United States)

Olivares, Astrid; Laskin, Julia; Johnson, Grant E

2014-09-18

The scalable synthesis of ligated subnanometer metal clusters containing an exact number of atoms is of interest due to the highly size-dependent catalytic, electronic, and optical properties of these species. While significant research has been conducted on the batch preparation of clusters through reduction synthesis in solution, the processes of metal complex reduction as well as cluster nucleation, growth, and postreduction etching are still not well understood. Herein, we demonstrate a prototype temperature-controlled flow reactor for qualitatively studying cluster formation in solution at steady-state conditions. Employing this technique, methanol solutions of a chloro(triphenylphosphine)gold precursor, 1,4-bis(diphenylphosphino)butane capping ligand, and borane-tert-butylamine reducing agent were combined in a mixing tee and introduced into a heated capillary with a known length. In this manner, the temperature dependence of the relative abundance of different ionic reactants, intermediates, and products synthesized in real time was characterized qualitatively using online mass spectrometry. A wide distribution of doubly and triply charged cationic gold clusters was observed as well as smaller singly charged organometallic complexes. The results demonstrate that temperature plays a crucial role in determining the relative population of cationic gold clusters and, in general, that higher temperature promotes the formation of doubly charged clusters and singly charged organometallic complexes while reducing the abundance of triply charged species. Moreover, the distribution of clusters observed at elevated temperatures is found to be consistent with that obtained at longer reaction times at room temperature, thereby demonstrating that heating may be used to access cluster distributions characteristic of different stages of batch reduction synthesis in solution.

N-nitrosamine formation by monochloramine, free chlorine, and peracetic acid disinfection with presence of amine precursors in drinking water system.

Science.gov (United States)

West, Danielle M; Wu, Qihua; Donovan, Ariel; Shi, Honglan; Ma, Yinfa; Jiang, Hua; Wang, Jianmin

2016-06-01

In this study, the formation of eight N-nitrosamines, N-nitrosodimethylamine (NDMA), N-nitrosodiethylamine, N-nitrosomethylamine, N-nitrosodi-n-propylamine, N-nitrosodi-n-butylamine, N-Nitrosopiperidine, N-Nitrosopyrrolidine, N-Nitrosomorpholine, were systematically evaluated with respect to seven N-nitrosamine precursors (dimethylamine, trimethylamine, 3-(dimethylaminomethyl)indole, 4-dimethylaminoantipyrine, ethylmethylamine, diethylamine, dipropylamine) and three disinfectants (monochloramine, free chlorine, peracetic acid) under variable dosages, exposure times, and pH in a drinking water system. Without the presence of the seven selected N-nitrosamine precursors N-nitrosamine formation was not observed under any tested condition except very low levels of N-Nitrosopyrrolidine under some conditions. With selected N-nitrosamine precursors present N-nitrosamines formed at different levels under different conditions. The highest N-nitrosamine formation was NDMA with a maximum concentration of 1180 ng/L by monochloramine disinfection with precursors present; much lower levels of N-nitrosamines were formed by free chlorine disinfection; and no detectable level of N-nitrosamines were observed by peracetic acid disinfection except low level of N-Nitrosodi-n-propylamine under some conditions. NDMA formation was not affected by pH while four other N-nitrosamine formations were slightly affected by sample pH tested between 7 and 9, with formation decreasing with increasing pH. Monochloramine exposure time study displayed fast formation of N-nitrosamines, largely formed in four hours of exposure and maximized after seven days. This was a systematic study on the N-nitrosamine formation with the seven major N-nitrosamine precursors presence and absence under different conditions, including peracetic acid disinfection which has not been studied elsewhere. Copyright © 2016 Elsevier Ltd. All rights reserved.

Amines in boreal forest air at SMEAR II station in Finland

Science.gov (United States)

Hemmilä, Marja; Hellén, Heidi; Virkkula, Aki; Makkonen, Ulla; Praplan, Arnaud P.; Kontkanen, Jenni; Ahonen, Lauri; Kulmala, Markku; Hakola, Hannele

2018-05-01

We measured amines in boreal forest air in Finland both in gas and particle phases with 1 h time resolution using an online ion chromatograph (instrument for Measuring AeRosols and Gases in Ambient Air - MARGA) connected to an electrospray ionization quadrupole mass spectrometer (MS). The developed MARGA-MS method was able to separate and detect seven different amines: monomethylamine (MMA), dimethylamine (DMA), trimethylamine (TMA), ethylamine (EA), diethylamine (DEA), propylamine (PA), and butylamine (BA). The detection limits of the method for amines were low (0.2-3.1 ng m-3), the accuracy of IC-MS analysis was 11-37 %, and the precision 10-15 %. The proper measurements in the boreal forest covered about 8 weeks between March and December 2015. The amines were found to be an inhomogeneous group of compounds, showing different seasonal and diurnal variability. Total MMA (MMA(tot)) peaked together with the sum of ammonia and ammonium ions already in March. In March, monthly means for MMA were NH4+ these were 52 ± 16 and 425 ± 371 ng m-3, respectively. Monthly medians in March for MMA(tot), NH3, and NH4+ were 90 %, gas-phase DMA correlated well with 1.1-2 nm particle number concentration (R2 = 0.63) suggesting that it participates in atmospheric clustering. EA concentrations were low all the time. Its July means were < 0.36 and 0.4 ± 0.4 ng m-3 in gas and aerosol phases, respectively, but individual concentration data correlated well with monoterpene concentrations in July. Monthly means of PA and BA were below detection limits at all times.

Production of 13C by chemical exchange reaction between amine carbamate and carbon dioxide in a solvent-carrier system

International Nuclear Information System (INIS)

Ghate, M.R.; Taylor, T.I.

1975-01-01

The chemical exchange reaction between amine carbamate and CO 2 has been investigated for the purpose of using it as a practical method to concentrate 13 C. The effects of solvent, concentration of amines, catalysts, flow rate, and diameter of the column have been studied for a number of amines. Of the solutions studied, di-n-butylamine (DNBA) in triethylamine (TEA) as a solvent proved to be the most favorable for use in the preparation of highly enriched 13 C. The overall separations obtained as a function of the concentration of DNBA using 2.5 cm i.d. x 100 cm column ranged from 2.05 at 1 M to 1.69 at 2.84 M. For 2 M DNBA the maximum separation was 1.94. At this concentration of DNBA the overall separation as a function of flow rate ranged from 1.94 at 0.845 ml/cm 2 -min to 1.31 at 2.9 ml/cm 2 -min. Neither the rate of exchange nor the overall separations were improved by use of catalysts. Increasing the diameter twofold resulted in little or no loss in overall separations. On the basis of the properties of the system and the data obtained with respect to the above variables, design calculations were made for a six-stage tapered cascade. These calculations were based on a flow of 40 ml/min of 2 M DNBA in TEA, giving a maximum transport of 7.1 x 10 -3 mmole/min or a maximum production rate of 130 mg 13 C/day. The cascade was operated for about 5 months during which period gram quantities of 67 percent 13 C were produced

Effect of foamability index of short chain alkyl amines on flotation of quartz

Directory of Open Access Journals (Sweden)

Szczerkowska Sabina

2016-01-01

Full Text Available Amines can be used for flotation of various minerals, especially quartz. The flotation efficiency of quartz depends on the amine type and dose. It was proved that the shorter alkyl amine, higher amine concentration has to be used to recover quartz at the same level. In flotation amines play a role of both collectors and frothers. The ability of a amine to collect particles can be expressed in the form of contact angle, while the foaming properties by different parameters including dynamic foamability index (DFI and critical coalescence concentration (CCC. Determination of DFI and CCC requires advanced techniques and methods. Therefore, in this paper a rapid and facile method for determination of foaming properties of amines and also other surfactants was used. It was based on measuring the initial foam and froth heights in a conventional flotation machine at different concentrations of surfactants. The foam height-concentration curve was described by utilizing an empirical equation which was based on one-adjustable parameter called the foamability index (FI. In this work the foamability index was determined for butylamine (ButNH2, hexylamine (HexNH2 and octylamine (OctNH2 as examples of short chain alkyl amines. The determined foamability indices were 92, 12 and 4 mg/dm3 for ButNH2, HexNH2 and OctNH2, respectively. It was shown that when the flotation results of quartz were presented in the form of recovery versus normalized amine concentration in relation to the foamability index (c/FI, all the experimental data points converged to one curve. It indicates that amines act similarly but at different concentrations expressed as FI. The foamability index seems to be a useful parameter for characterizing any flotation frother.

Biomimetic trapping cocktail to screen reactive metabolites: use of an amino acid and DNA motif mixture as light/heavy isotope pairs differing in mass shift.

Science.gov (United States)

Hosaka, Shuto; Honda, Takuto; Lee, Seon Hwa; Oe, Tomoyuki

2018-06-01

Candidate drugs that can be metabolically transformed into reactive electrophilic products, such as epoxides, quinones, and nitroso compounds, are of special concern because subsequent covalent binding to bio-macromolecules can cause adverse drug reactions, such as allergic reactions, hepatotoxicity, and genotoxicity. Several strategies have been reported for screening reactive metabolites, such as a covalent binding assay with radioisotope-labeled drugs and a trapping method followed by LC-MS/MS analyses. Of these, a trapping method using glutathione is the most common, especially at the early stage of drug development. However, the cysteine of glutathione is not the only nucleophilic site in vivo; lysine, histidine, arginine, and DNA bases are also nucleophilic. Indeed, the glutathione trapping method tends to overlook several types of reactive metabolites, such as aldehydes, acylglucuronides, and nitroso compounds. Here, we introduce an alternate way for screening reactive metabolites as follows: A mixture of the light and heavy isotopes of simplified amino acid motifs and a DNA motif is used as a biomimetic trapping cocktail. This mixture consists of [ 2 H 0 ]/[ 2 H 3 ]-1-methylguanidine (arginine motif, Δ 3 Da), [ 2 H 0 ]/[ 2 H 4 ]-2-mercaptoethanol (cysteine motif, Δ 4 Da), [ 2 H 0 ]/[ 2 H 5 ]-4-methylimidazole (histidine motif, Δ 5 Da), [ 2 H 0 ]/[ 2 H 9 ]-n-butylamine (lysine motif, Δ 9 Da), and [ 13 C 0 , 15 N 0 ]/[ 13 C 1 , 15 N 2 ]-2'-deoxyguanosine (DNA motif, Δ 3 Da). Mass tag triggered data-dependent acquisition is used to find the characteristic doublet peaks, followed by specific identification of the light isotope peak using MS/MS. Forty-two model drugs were examined using an in vitro microsome experiment to validate the strategy. Graphical abstract Biomimetic trapping cocktail to screen reactive metabolites.

TUNGSTOPHOSPHORIC ACID HETEROGENIZED ONTO NH4ZSM5 AS AN EFFICIENT AND RECYCLABLE CATALYST FOR THE PHOTOCATALYTIC DEGRADATION OF DYES

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Candelaria Leal Marchena

2015-05-01

Full Text Available Materials based on tungstophosphoric acid (TPA immobilized on NH4ZSM5 zeolite were prepared by wet impregnation of the zeolite matrix with TPA aqueous solutions. Their concentration was varied in order to obtain TPA contents of 5%, 10%, 20%, and 30% w/w in the solid. The materials were characterized by N2 adsorption-desorption isotherms, XRD, FT-IR, 31P MAS-NMR, TGA-DSC, DRS-UV-Vis, and the acidic behavior was studied by potentiometric titration with n-butylamine. The BET surface area (SBET decreased when the TPA content was raised as a result of zeolite pore blocking. The X-ray diffraction patterns of the solids modified with TPA only presented the characteristic peaks of NH4ZSM5 zeolites, and an additional set of peaks assigned to the presence of (NH43PW12O40. According to the Fourier transform infrared and 31P magic angle spinning-nuclear magnetic resonance spectra, the main species present in the samples was the [PW12O40]3- anion, which was partially transformed into the [P2W21O71]6- anion during the synthesis and drying steps. The thermal stability of the NH4ZSM5TPA materials was similar to that of their parent zeolites. Moreover, the samples with the highest TPA content exhibited band gap energy values similar to those reported for TiO2. The immobilization of TPA on NH4ZSM5 zeolite allowed the obtention of catalysts with high photocatalytic activity in the degradation of methyl orange dye (MO in water, at 25 ºC. These can be reused at least three times without any significant decrease in degree of degradation.

Interplay of charge distribution and conformation in peptides: comparison of theory and experiment.

Science.gov (United States)

Makowska, Joanna; Bagińska, Katarzyna; Kasprzykowski, F; Vila, Jorge A; Jagielska, Anna; Liwo, Adam; Chmurzyński, Lech; Scheraga, Harold A

2005-01-01

We assessed the correlation between charge distribution and conformation of flexible peptides by comparing the theoretically calculated potentiometric-titration curves of two model peptides, Ac-Lys5-NHMe (a model of poly-L-lysine) and Ac-Lys-Ala11-Lys-Gly2-Tyr-NH2 (P1) in water and methanol, with the experimental curves. The calculation procedure consisted of three steps: (i) global conformational search of the peptide under study using the electrostatically driven Monte Carlo (EDMC) method with the empirical conformational energy program for peptides (ECEPP)/3 force field plus the surface-hydration (SRFOPT) or the generalized Born surface area (GBSA) solvation model as well as a molecular dynamics method with the assisted model building and energy refinement (AMBER)99/GBSA force field; (ii) reevaluation of the energy in the pH range considered by using the modified Poisson-Boltzmann approach and taking into account all possible protonation microstates of each conformation, and (iii) calculation of the average degree of protonation of the peptide at a given pH value by Boltzmann averaging over conformations. For Ac-Lys5-NHMe, the computed titration curve agrees qualitatively with the experimental curve of poly-L-lysine in 95% methanol. The experimental titration curves of peptide P1 in water and methanol indicate a remarkable downshift of the first pK(a) value compared to the values for reference compounds (n-butylamine and phenol, respectively), suggesting the presence of a hydrogen bond between the tyrosine hydroxyl oxygen and the H(epsilon) proton of a protonated lysine side chain. The theoretical titration curves agree well with the experimental curves, if conformations with such hydrogen bonds constitute a significant part of the ensemble; otherwise, the theory predicts too small a downward pH shift. Copyright 2005 Wiley Periodicals, Inc

15th International Sunflower Conference Synthesis of new derivatives from vegetable sunflower oil methyl esters via epoxydation and oxirane opening

Directory of Open Access Journals (Sweden)

Pages Xavier

2001-03-01

Full Text Available Recently, epoxides have received increased attention because they are of interest both as end-products and as chemical intermediates; epoxidized oils, mainly High Oleic Sunflower Oil, and their ester derivatives have thus found important applications as plasticizers and additives for polyvinyl chloride (PVC. Epoxidized esters have been produced classically from High Oleic Sunflower Methyl Esters (HOSME using H2O2 and formic acid. The epoxidation reaches 90% on pilot scale (5kg. Epoxidized esters produced from HOSME have respectively hydroxyl values of 0, oxirane values of 5.2/4.5 and iodine values of 1.7/1.5. Cleavage trials of the oxirane group of the epoxidized esters with different reactants have been undertaken in order to produce on pilot scale new derivatives to be characterized and tested in different fields of application (lubrication, detergency and as chemical intermediates. Reaction of Epoxy-HOSME with an excess of oleic acid was conducted under atmospheric pressure without any catalyst and solvent. The oxirane opening leads to complete estolide formation: after neutralization, analytical controls (chemical values, GC and HPLC analysis indicate that the estolides are composed of a mixture of C36 (oleate of methyl hydroxystearate and C54 (di-oleate of methyl dihydroxystearate. Oxirane opening with alcohols (ethanol and octanol was preferentially performed by acid catalysis at 100°C under atmospheric pressure. Analytical controls show the formation of different etheralcohols and secondary products resulting from dehydration, transesterification and dimerization side-reactions. Cleavage reaction of Epoxy-HOSME with a primary amine (butylamine was conducted under pressure, at high temperature (180/200°C. Both transesterification and opening of the oxirane group occur under these conditions. Reaction products are composed of amides formed by transesterification and a mixture of fatty amines/imines obtained by ring opening as established

Photocytotoxic trans-diam(m)ine platinum(IV) diazido complexes more potent than their cis isomers.

Science.gov (United States)

Farrer, Nicola J; Woods, Julie A; Munk, Vivienne P; Mackay, Fiona S; Sadler, Peter J

2010-02-15

The photocytotoxicity of a series of anticancer trans-dihydroxido [Pt(N(3))(2)(OH)(2)(NH(3))(X)] (X = alkyl or aryl amine) platinum(IV) diazido complexes has been examined, and the influence of cis-trans isomerism has been investigated. A series of photoactivatable Pt(IV)-azido complexes has been synthesized: The synthesis, characterization, and photocytotoxicity of six mixed-ligand ammine/amine Pt(IV) diazido complexes, cis,trans,cis-[Pt(N(3))(2)(OH)(2)(NH(3))(X)] where X = propylamine (4c), butylamine (5c), or pentylamine (6c) and aromatic complexes where X = pyridine (7c), 2-methylpyridine (8c), or 3-methylpyridine (9c) are reported. Six all-trans isomers have also been studied where X = methylamine (2t), ethylamine (3t), 2-methylpyridine (8t), 4-methylpyridine (10t), 3-methylpyridine (9t), and 2-bromo-3-methylpyridine (11t). All of the complexes exhibit intense azide-to-Pt(IV) LMCT bands (ca. 290 nm for trans and ca. 260 nm for cis). When irradiated with UVA light (365 nm), the Pt(IV) complexes undergo photoreduction to Pt(II) species, as monitored by UV-vis spectroscopy. The trans isomers of complexes containing aliphatic or aromatic amines were more photocytotoxic than their cis isomers. One of the cis complexes (9c) was nonphotocytotoxic despite undergoing photoreduction. Substitution of NH(3) ligands by MeNH(2) or EtNH(2) results in more potent photocytotoxicity for the all-trans complexes. The complexes were all nontoxic toward human keratinocytes (HaCaT) and A2780 human ovarian cancer cells in the dark, apart from the 3-methylpyridine (9t), 2-bromo-3-methylpyridine (11t), and 4-methylpyridine (10t) derivatives.

Covalent defects restrict supramolecular self-assembly of homopolypeptides: case study of β2-fibrils of poly-L-glutamic acid.

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Aleksandra Fulara

Full Text Available Poly-L-glutamic acid (PLGA often serves as a model in studies on amyloid fibrils and conformational transitions in proteins, and as a precursor for synthetic biomaterials. Aggregation of PLGA chains and formation of amyloid-like fibrils was shown to continue on higher levels of superstructural self-assembly coinciding with the appearance of so-called β2-sheet conformation manifesting in dramatic redshift of infrared amide I' band below 1600 cm(-1. This spectral hallmark has been attributed to network of bifurcated hydrogen bonds coupling C = O and N-D (N-H groups of the main chains to glutamate side chains. However, other authors reported that, under essentially identical conditions, PLGA forms the conventional in terms of infrared characteristics β1-sheet structure (exciton-split amide I' band with peaks at ca. 1616 and 1683 cm(-1. Here we attempt to shed light on this discrepancy by studying the effect of increasing concentration of intentionally induced defects in PLGA on the tendency to form β1/β2-type aggregates using infrared spectroscopy. We have employed carbodiimide-mediated covalent modification of Glu side chains with n-butylamine (NBA, as well as electrostatics-driven inclusion of polylysine chains, as two different ways to trigger structural defects in PLGA. Our study depicts a clear correlation between concentration of defects in PLGA and increasing tendency to depart from the β2-structure toward the one less demanding in terms of chemical uniformity of side chains: β1-structure. The varying predisposition to form β1- or β2-type aggregates assessed by infrared absorption was compared with the degree of morphological order observed in electron microscopy images. Our results are discussed in the context of latent covalent defects in homopolypeptides (especially with side chains capable of hydrogen-bonding that could obscure their actual propensities to adopt different conformations, and limit applications in the field of

Covalent Defects Restrict Supramolecular Self-Assembly of Homopolypeptides: Case Study of β2-Fibrils of Poly-L-Glutamic Acid

Science.gov (United States)

Fulara, Aleksandra; Hernik, Agnieszka; Nieznańska, Hanna; Dzwolak, Wojciech

2014-01-01

Poly-L-glutamic acid (PLGA) often serves as a model in studies on amyloid fibrils and conformational transitions in proteins, and as a precursor for synthetic biomaterials. Aggregation of PLGA chains and formation of amyloid-like fibrils was shown to continue on higher levels of superstructural self-assembly coinciding with the appearance of so-called β2-sheet conformation manifesting in dramatic redshift of infrared amide I′ band below 1600 cm−1. This spectral hallmark has been attributed to network of bifurcated hydrogen bonds coupling C = O and N-D (N-H) groups of the main chains to glutamate side chains. However, other authors reported that, under essentially identical conditions, PLGA forms the conventional in terms of infrared characteristics β1-sheet structure (exciton-split amide I′ band with peaks at ca. 1616 and 1683 cm−1). Here we attempt to shed light on this discrepancy by studying the effect of increasing concentration of intentionally induced defects in PLGA on the tendency to form β1/β2-type aggregates using infrared spectroscopy. We have employed carbodiimide-mediated covalent modification of Glu side chains with n-butylamine (NBA), as well as electrostatics-driven inclusion of polylysine chains, as two different ways to trigger structural defects in PLGA. Our study depicts a clear correlation between concentration of defects in PLGA and increasing tendency to depart from the β2-structure toward the one less demanding in terms of chemical uniformity of side chains: β1-structure. The varying predisposition to form β1- or β2-type aggregates assessed by infrared absorption was compared with the degree of morphological order observed in electron microscopy images. Our results are discussed in the context of latent covalent defects in homopolypeptides (especially with side chains capable of hydrogen-bonding) that could obscure their actual propensities to adopt different conformations, and limit applications in the field of synthetic

Dermal, inhalation, and internal exposure to 1,6-HDI and its oligomers in car body repair shop workers and industrial spray painters.

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Pronk, A; Yu, F; Vlaanderen, J; Tielemans, E; Preller, L; Bobeldijk, I; Deddens, J A; Latza, U; Baur, X; Heederik, D

2006-09-01

To study inhalation and dermal exposure to hexamethylene diisocyanate (HDI) and its oligomers as well as personal protection equipment (PPE) use during task performance in conjunction with urinary hexamethylene diamine (HDA) in car body repair shop workers and industrial spray painters. Personal task based inhalation samples (n = 95) were collected from six car body repair shops and five industrial painting companies using impingers with di-n-butylamine (DBA) in toluene. In parallel, dermal exposure was assessed using nitril rubber gloves. Gloves were submerged into DBA in toluene after sampling. Analysis for HDI and its oligomers was performed by LC-MS/MS. Urine samples were collected from 55 workers (n = 291) and analysed for HDA by GC-MS. Inhalation exposure was strongly associated with tasks during which aerosolisation occurs. Dermal exposure occurred during tasks that involve direct handling of paint. In car body repair shops associations were found between detectable dermal exposure and glove use (odds ratio (OR) 0.22, 95% confidence interval (CI) 0.09 to 0.57) and inhalation exposure level (OR 1.34, 95% CI 0.97 to 1.84 for a 10-fold increase). HDA in urine could be demonstrated in 36% and 10% of car body repair shop workers and industrial painting company workers respectively. In car body repair shops, the frequency of detectable HDA was significantly elevated at the end of the working day (OR 2.13, 95% CI 1.07 to 4.22 for 3-6 pm v 0-8 am). In both branches HDA was detected in urine of approximately 25% of the spray painters. In addition HDA was detected in urine of a large proportion of non-spray painters in car body repair shops. Although (spray) painting with lacquers containing isocyanate hardeners results in the highest external exposures to HDI and oligomers, workers that do not perform paint related tasks may also receive a considerable internal dose.

Dermal, inhalation, and internal exposure to 1,6‐HDI and its oligomers in car body repair shop workers and industrial spray painters

Science.gov (United States)

Pronk, A; Yu, F; Vlaanderen, J; Tielemans, E; Preller, L; Bobeldijk, I; Deddens, J A; Latza, U; Baur, X; Heederik, D

2006-01-01

Objectives To study inhalation and dermal exposure to hexamethylene diisocyanate (HDI) and its oligomers as well as personal protection equipment (PPE) use during task performance in conjunction with urinary hexamethylene diamine (HDA) in car body repair shop workers and industrial spray painters. Methods Personal task based inhalation samples (n = 95) were collected from six car body repair shops and five industrial painting companies using impingers with di‐n‐butylamine (DBA) in toluene. In parallel, dermal exposure was assessed using nitril rubber gloves. Gloves were submerged into DBA in toluene after sampling. Analysis for HDI and its oligomers was performed by LC‐MS/MS. Urine samples were collected from 55 workers (n = 291) and analysed for HDA by GC‐MS. Results Inhalation exposure was strongly associated with tasks during which aerosolisation occurs. Dermal exposure occurred during tasks that involve direct handling of paint. In car body repair shops associations were found between detectable dermal exposure and glove use (odds ratio (OR) 0.22, 95% confidence interval (CI) 0.09 to 0.57) and inhalation exposure level (OR 1.34, 95% CI 0.97 to 1.84 for a 10‐fold increase). HDA in urine could be demonstrated in 36% and 10% of car body repair shop workers and industrial painting company workers respectively. In car body repair shops, the frequency of detectable HDA was significantly elevated at the end of the working day (OR 2.13, 95% CI 1.07 to 4.22 for 3–6 pm v 0–8 am). In both branches HDA was detected in urine of ∼25% of the spray painters. In addition HDA was detected in urine of a large proportion of non‐spray painters in car body repair shops. Conclusion Although (spray) painting with lacquers containing isocyanate hardeners results in the highest external exposures to HDI and oligomers, workers that do not perform paint related tasks may also receive a considerable internal dose. PMID:16728504

Determination of eight nitrosamines in water at the ng L-1 levels by liquid chromatography coupled to atmospheric pressure chemical ionization tandem mass spectrometry

International Nuclear Information System (INIS)

Ripolles, Cristina; Pitarch, Elena; Sancho, Juan V.; Lopez, Francisco J.; Hernandez, Felix

2011-01-01

Highlights: · Eight N-nitrosamines in water by LC(APCI)MS/MS QqQ analysis. · Validation at two levels: 10 ng L -1 (LOQ) and 100 ng L -1 in drinking water. · Developed method applied to different types of water samples. · NDMA was the analyte more frequently detected and at the highest concentration levels. - Abstract: In this work, we have developed a sensitive method for detection and quantification of eight N-nitrosamines, N-nitrosodimethylamine (NDMA), N-nitrosomorpholine (NMor), N-nitrosomethylethylamine (NMEA), N-nitrosopirrolidine (NPyr), N-nitrosodiethylamine (NDEA), N-nitrosopiperidine (NPip), N-nitroso-n-dipropylamine (NDPA) and N-nitrosodi-n-butylamine (NDBA) in drinking water. The method is based on liquid chromatography coupled to tandem mass spectrometry, using atmospheric pressure chemical ionization (APCI) in positive mode with a triple quadrupole analyzer (QqQ). The simultaneous acquisition of two MS/MS transitions in selected reaction monitoring mode (SRM) for each compound, together with the evaluation of their relative intensity, allowed the simultaneous quantification and reliable identification in water at ppt levels. Empirical formula of the product ions selected was confirmed by UHPLC-(Q)TOF MS accurate mass measurements from reference standards. Prior to LC-MS/MS QqQ analysis, a preconcentration step by off-line SPE using coconut charcoal EPA 521 cartridges (by passing 500 mL of water sample) was necessary to improve the sensitivity and to meet regulation requirements. For accurate quantification, two isotope labelled nitrosamines (NDMA-d 6 and NDPA-d 14 ) were added as surrogate internal standards to the samples. The optimized method was validated at two concentration levels (10 and 100 ng L -1 ) in drinking water samples, obtaining satisfactory recoveries (between 90 and 120%) and precision (RSD -1 . The described methodology has been applied to different types of water samples: chlorinated from drinking water and wastewater treatment

Determination of eight nitrosamines in water at the ng L{sup -1} levels by liquid chromatography coupled to atmospheric pressure chemical ionization tandem mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Ripolles, Cristina; Pitarch, Elena; Sancho, Juan V; Lopez, Francisco J [Research Institute for Pesticides and Water, University Jaume I, Avda. Sos Baynat, E-12071 Castellon (Spain); Hernandez, Felix [Research Institute for Pesticides and Water, University Jaume I, Avda. Sos Baynat, E-12071 Castellon (Spain)

2011-09-19

Highlights: {center_dot} Eight N-nitrosamines in water by LC(APCI)MS/MS QqQ analysis. {center_dot} Validation at two levels: 10 ng L{sup -1} (LOQ) and 100 ng L{sup -1} in drinking water. {center_dot} Developed method applied to different types of water samples. {center_dot} NDMA was the analyte more frequently detected and at the highest concentration levels. - Abstract: In this work, we have developed a sensitive method for detection and quantification of eight N-nitrosamines, N-nitrosodimethylamine (NDMA), N-nitrosomorpholine (NMor), N-nitrosomethylethylamine (NMEA), N-nitrosopirrolidine (NPyr), N-nitrosodiethylamine (NDEA), N-nitrosopiperidine (NPip), N-nitroso-n-dipropylamine (NDPA) and N-nitrosodi-n-butylamine (NDBA) in drinking water. The method is based on liquid chromatography coupled to tandem mass spectrometry, using atmospheric pressure chemical ionization (APCI) in positive mode with a triple quadrupole analyzer (QqQ). The simultaneous acquisition of two MS/MS transitions in selected reaction monitoring mode (SRM) for each compound, together with the evaluation of their relative intensity, allowed the simultaneous quantification and reliable identification in water at ppt levels. Empirical formula of the product ions selected was confirmed by UHPLC-(Q)TOF MS accurate mass measurements from reference standards. Prior to LC-MS/MS QqQ analysis, a preconcentration step by off-line SPE using coconut charcoal EPA 521 cartridges (by passing 500 mL of water sample) was necessary to improve the sensitivity and to meet regulation requirements. For accurate quantification, two isotope labelled nitrosamines (NDMA-d{sub 6} and NDPA-d{sub 14}) were added as surrogate internal standards to the samples. The optimized method was validated at two concentration levels (10 and 100 ng L{sup -1}) in drinking water samples, obtaining satisfactory recoveries (between 90 and 120%) and precision (RSD < 20%). Limits of detection were found to be in the range of 1-8 ng L{sup -1

Amine Measurements in Boreal Forest Air

Science.gov (United States)

Hemmilä, Marja; Hellén, Heidi; Makkonen, Ulla; Hakola, Hannele

2015-04-01

Amines are reactive, volatile bases in the air with a general formula of RNH2, R2NH or R3N. Especially small amines can stabilize sulphuric acid clusters and hence affect nucleation. Amines react rapidly with hydroxyl radical (OH˙) thus affecting oxidative capacity of the atmosphere. The amine concentrations are higher in forest air than in urban air (Hellén et al., 2014), but the sources are not known. In order to get more information concerning amine sources, we conducted a measurement campaign in a boreal forest. At SMEAR II station at Hyytiälä, Southern Finland (61°510'N, 24°170'E, 180 m a.s.l.) The measurements cover seven months, from June to December 2014. For sampling and measuring we used MARGA (The instrument for Measuring AeRosols and Gases in Ambient air) which is an on-line ion chromatograph (IC) connected to a sampling system. The IC component of the MARGA system was coupled to an electrospray ionization quadrupole mass spectrometer (MS) to improve sensitivity of amine measurements. This new set-up enabled amine concentration measurements in ambient air both in aerosol and gas phases with a time resolution of only 1 hour. With MARGA-MS we analysed 7 different amines: monomethylamine (MMA), dimethylamine (DMA), trimethylamine (TMA), ethylamine (EA), diethylamine (DEA), propylamine (PA) and butylamine (BA). In preliminary data-analysis we found out, that in June and July most of the measured amines were in gas phase, and particle phase amine concentrations were mostly under detection limits (<1.7 pptv). In June the gaseous amine concentrations were higher than in July. The measured concentrations of gaseous amines followed temperature variation, which could indicate that amines are produced and emitted from the environment or re-emitted from the surfaces as temperature rises after deposition during night-time. All measured amines had similar diurnal variation with maxima during afternoon and minima during night. Results from other months will also

Resonator Sensitivity Optimization in Magnetic Resonance and the Development of a Magic Angle Spinning Probe for the NMR Study of Rare Spin Nuclei on Catalytic Surfaces.

Science.gov (United States)

Doty, Francis David

The sensitivity of an arbitrary resonator for the detection of a magnetic resonance signal is derived from basic energy considerations, and is shown to be dependent on V(,s)/t(,90)P(' 1/2). The radiation damping time constant is shown to be inversely dependent on the rf filling factor. Several resonators are analyzed in detail. The optimum solenoid is shown to have a length of about 1.5 times the diameter. The multilayer solenoid and the capacitively shortened slotted line resonator are shown to have advantages for samples with high dielectric losses. The capacitively shortened slotted line resonator is shown to substantially reduce acoustic ringing problems. Efficient methods are discussed for double and triple tuning these resonators. A slotted cylindrical resonator is described which gives higher sensitivity and faster response time than conventional cavities for very small samples at X-band ESR frequencies. Double tuned circuits using lumped elements are shown to be generally more efficient than those using transmission lines in generating rf fields. The optimum inductance ratio of the two coils in a ('13)C, ('1)H CP experiment is about 3. The high speed cylindrical sample spinner is analyzed in terms of compressible fluid dynamics, resonant modes, and structural analysis to arrive at optimum air bearing and spinner design recommendations. The optimum radial clearance is shown to depend on the 1/3 power of the rotor diameter. The required air bearing hole diameter has a square root dependence on the rotor diameter. Air pockets are shown to increase the resonant frequencies. Relevant data for a number of high strength insulators including hard ceramics are tabulated, and limiting speeds are calculated. CP MAS experiments on a 5% monolayer of n-butylamine absorbed on (gamma)-alumina reveal six lines. By comparison with the liquid phase spectrum it was determined that at least two types of chemically different surface species were present and that surface

Reactivity of cosmetic UV filters towards skin proteins: model studies with Boc-lysine, Boc-Gly-Phe-Gly-Lys-OH, BSA and gelatin.

Science.gov (United States)

Stiefel, C; Schwack, W

2014-12-01

Organic UV filters are used as active ingredients in most sunscreens and also in a variety of daily care products. Their good (photo) stability is of special interest to guarantee protective function and to prevent interactions with the human skin. Due to the mostly electrophilic character of the UV filters, reactions with nucleophilic protein moieties like lysine side chains are conceivable. Prior studies showed that the UV filters octocrylene (OCR), butyl methoxydibenzoylmethane (BM-DBM), ethylhexyl salicylate (EHS), ethylhexyl methoxycinnamate (EHMC), benzophenone-3 (BP-3), ethylhexyl triazone (EHT) and dibenzoylmethane (DBM) were able to covalently bind to an HPTLC amino phase and the amino acid models ethanolamine and butylamine after slightly heating and/or radiation. Boc-protected lysine, the tetrapeptide Boc-Gly-Phe-Gly-Lys-OH, bovine serum albumin (BSA) and porcine gelatin were used as more complex models to determine the reactivity of the mentioned UV filters towards skin proteins under thermal or UV irradiation conditions. After gentle heating at 37°C, benzophenone imines were identified as reaction products of BP-3 and OCR with Boc-lysine and the tetrapeptide, whereas DBM and BM-DBM yielded enamines. For EHMC, a Michael-type reaction occurred, which resulted in addition of Boc-lysine or the tetrapeptide to the conjugated double bond. Ester aminolysis of EHS and EHT mainly afforded the corresponding amides. Reactions of the UV filters with BSA changed the UV spectrum of BSA, generally associated with an increase of the absorption strength in the UVA or UVB range. For all protein models, the UV filters showed an increasing reactivity in the order EHT < EHMC < EHS < BP-3 < OCR < DBM < BM-DBM. Especially the UV absorbers BM-DBM, OCR and BP-3, which are seen as common allergens or photoallergens, showed a high reactivity towards the different skin protein models. As the formation of protein adducts is recognized as important key element in the induction of

High-Performance Supercapacitor of Functionalized Carbon Fiber Paper with High Surface Ionic and Bulk Electronic Conductivity: Effect of Organic Functional Groups

International Nuclear Information System (INIS)

Suktha, Phansiri; Chiochan, Poramane; Iamprasertkun, Pawin; Wutthiprom, Juthaporn; Phattharasupakun, Nutthaphon; Suksomboon, Montakan; Kaewsongpol, Tanon; Sirisinudomkit, Pichamon; Pettong, Tanut; Sawangphruk, Montree

2015-01-01

Highlights: • A supercapacitor of organic functionalized carbon fiber paper (f-CFP) exhibits high areal and volumetric capacitances. • The performance of the supercapacitor depends on the organic functional group on the surface of the f-CFP. • Hydroxyl and carboxylic groups modified on the surface of f-CFP have higher pseudocapacitive property than amide and amine functional groups. • The f-CFP exhibits high surface ionic and bulk electrical conductivities. - Abstract: Although carbon fiber paper (CFP) or nonwovens are widely used as a non-corrosive and conductive substrate or current collector in batteries and supercapacitors as well as a gas diffusion layer in proton exchange membrane fuel cells, the CFP cannot store charges due to its poor ionic conductivity and its hydrophobic surface. In this work, the chemically functionalized CFP (f-CFP) consisting of hydroxyl and carboxylic groups on its surface was produced by an oxidation reaction of CFP in a mixed concentrated acid solution of H 2 SO 4 :HNO 3 (3:1 v/v) at 60 °C for 1 h. Other amide and amine groups modified CFP were also synthesized for comparison using a dehydration reaction of carboxylic modified CFP with ethylenediamine and n-butylamine. Interestingly, it was found that hydroxyl and carboxylic groups modified CFP behave as a pseudocapacitor electrode, which can store charges via the surface redox reaction in addition to electrochemical double layer capacitance. The aqueous-based supercapacitor of f-CFP has high areal, volumetric, and specific energy (49.0 μW.h/cm 2 , 1960 mW.h/L, and 5.2 W.h/Kg) and power (3.0 mW/cm 2 , 120 W/L, and 326.2 W/Kg) based on the total geometrical surface area and volume as well as the total weight of positive and negative electrodes. High charge capacity of the f-CFP stems from high ionic charge and pseudocapacitive behavior due to hydroxyl and carboxylic groups on its surface and high bulk electronic conductivity (2.03 mS/cm) due to 1D carbon fiber paper. The

Synthesis and physical-chemical properties of functional derivatives of 3-benzyl-8-propylxanthinyl-7-acetic acid

Directory of Open Access Journals (Sweden)

E. K. Mikhal’chenko

2017-08-01

with butylamine, benzylamine, p-methylbenzylamine or p-fluorobenzylamine. It should be noted that we conducted reaction without solvent in the medium of amine and reagents were not reflux but heated at 80 оС. The structures of all obtained compounds were proved by the elemental analysis, IR- and 1H NMR-spectroscopy. Conclusions. Obtained results of our work can be used for further search of biological active compounds among functional derivatives of xanthinyl-7-alkanyl acids xanthines; organic synthesis; IR-spectroscopy; NMR-spectroscopy

In-situ Studies of the Reactions of Bifunctional and Heterocyclic Molecules over Noble Metal Single Crystal and Nanoparticle Catalysts Studied with Kinetics and Sum-Frequency Generation Vibrational Spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Kliewer, Christopher J. [Univ. of California, Berkeley, CA (United States)

2009-06-30

Sum frequency generation surface vibrational spectroscopy (SFG-VS) in combination with gas chromatography (GC) was used in-situ to monitor surface bound reaction intermediates and reaction selectivities for the hydrogenation reactions of pyrrole, furan, pyridine, acrolein, crotonaldehyde, and prenal over Pt(111), Pt(100), Rh(111), and platinum nanoparticles under Torr reactant pressures and temperatures of 300K to 450K. The focus of this work is the correlation between the SFG-VS observed surface bound reaction intermediates and adsorption modes with the reaction selectivity, and how this is affected by catalyst structure and temperature. Pyrrole hydrogenation was investigated over Pt(111) and Rh(111) single crystals at Torr pressures. It was found that pyrrole adsorbs to Pt(111) perpendicularly by cleaving the N-H bond and binding through the nitrogen. However, over Rh(111) pyrrole adsorbs in a tilted geometry binding through the {pi}-aromatic orbitals. A surface-bound pyrroline reaction intermediate was detected over both surfaces with SFG-VS. It was found that the ring-cracking product butylamine is a reaction poison over both surfaces studied. Furan hydrogenation was studied over Pt(111), Pt(100), 10 nm cubic platinum nanoparticles and 1 nm platinum nanoparticles. The product distribution was observed to be highly structure sensitive and the acquired SFG-VS spectra reflected this sensitivity. Pt(100) exhibited more ring-cracking to form butanol than Pt(111), while the nanoparticles yielded higher selectivities for the partially saturated ring dihydrofuran. Pyridine hydrogenation was investigated over Pt(111) and Pt(100). The α-pyridyl surface adsorption mode was observed with SFG-VS over both surfaces. 1,4-dihydropyridine was seen as a surface intermediate over Pt(100) but not Pt(111). Upon heating the surfaces to 350K, the adsorbed pyridine changes to a flat-lying adsorption mode. No evidence was found for the pyridinium cation. The hydrogenation of the �

Determination of The Anti-Fungal Effort of Morganella Morganii and Determination of Its Chemical Composition by Means of Gas Chromatography Method - Mass Spectrometry Gas Chromatography-Mass Spectrometry

Directory of Open Access Journals (Sweden)

Sabreen Abdul Amir Kamal Al – Khafaji

2018-03-01

Full Text Available The analysis of bioactive was done by used gas chromatography-mass spectroscopy(GC-MS method then antifungal and antimicrobial activity for methanolic extract was measured in the lab. The analysis of  Morganella morganii  by GC-MS revealed the existence of the Tricyclo, 3-Methoxybenzaldehyde semicarbazone , undecan-1-amine, carboxaldehyde , 1-methyl-,oxime ,(Z-(+, 4-(2,5-Dihydro-3-methoxyphenyl butylamine , Paromomycin , 1,5,5-Trimethyl-6-methylene-cyclohexene, 9-Borabicyclo[3.31], Benzenemethanol , nonane , 9-mercapto-2-(2-aminopropoxy-3-methyl, Acetamide , N-(6-acetylaminobenzothiazol-2-yl-2-(adamantan, rin-6-carboxylic acid , N-(2,5-Dicyano-3,4-dihydro-2H-pyrrol-2-yl- acetamide, 3,10-Dioxatricyclo4-(2,5-Dihydro-3-methoxyphenylbutylamine, [4.3.1.0(2,4] phenylmethyl ester, 3,7-Diazabicyclo dec-7-ene, 3-Cyclohex-3-enyl-propionic acid, Eicosanoic acid  [3.3.1] 9,9-dimethyl-, nonane ,Dithiocarbamate , dl-Homocysteine, 2-(2-Furylpyridine, S-methyl-,N-(2-methyl-3-oxobutyl-, 1,7-Dioxa-10-thia-4,13-diazacyclopentadeca-5,9,12-trione, 5,7-Dodecadiyn-1,12-diol, 1-(β-d-Arabinofuranosyl-4-O-difluoromethyluracil, Uric acid, Pyrrolo[1.2-a]pyrazine-1,4-dione , hexahydro-,12-Methyl-oxa-cyclododecan-2-one, Phthalic acid , butyl undecyl ester, 9,12,15-Octadecatrienoic acid , 2,3-bis(acetyloxypropyl ester, , methyl ester, 12-Dimethylamino-10-oxododecanoic acid , 1,2,4-Trioxolane-2-octanoic acid 5-octyl-, Octahydrochromen-2-one, L-Aspartic acid, N-glycyl-,2H-Oxecin-2-one , 3,4,7,8,91,10-hexahydro-4-hydroxy-10-meth, Thiazolo[4,5-d]pyrimidine-5,7(4H,6H-dione , 3,6,12-Trimethyl-1,4,7,10,13,16-hexaaza-cyclooctadecane, 2-lodohiistidine, 2-amino-4-(2-ph,Dec-9-en-6-oxo-1-ylamide,2,5-Piperazinedione,3,6-bis(2-ethylpropyl-, 9-Octadecenamide , (Z-, 3',8,8'-Trimethoxy-3-piperidyl-2,2'-binaphthalene-1,1',4,4'-tetra . Citrullus colocynthis (Crude was very highly active (6.39±0.27 mm anti-fungal activity of Morganella morganii showed that unstable compounds ( volatile were