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Sample records for benzylamines

  1. Kinetics and mechanism of the oxidation of substituted benzylamines by cetyltrimethylammonium permanganate

    Indian Academy of Sciences (India)

    Raghvendra Shukla; Pradeep K Sharma; László Kótai; Kalyan K Banerji

    2003-04-01

    Oxidation of meta- and para-substituted benzylamines by cetyltrimethylammonium permanganate (CTAP) to the corresponding aldimines is first order with respect to both the amine and CTAP. Oxidation of deuteriated benzylamine (PhCD2NH2) exhibited the presence of a substantial kinetic isotope effect (/ = 5.60 at 293 K). This confirmed the cleavage of an -C-H bond in the ratedetermining step. Correlation analyses of the rates of oxidation of 19 monosubstituted benzylamines were performed with various single and multiparametric equations. The rates of the oxidation showed excellent correlations in terms of Yukawa-Tsuno and Brown’s equations. The polar reaction constants are negative. The oxidation exhibited an extensive cross-conjugation, in the transition state, between the electron-donating substituents and the reaction centre. A mechanism involving a hydride-ion transfer from the amine to CTAP in the rate-determining step has been proposed.

  2. The Effects of Solvent and Added Bases on the Protection of Benzylamines with Carbon Dioxide

    Directory of Open Access Journals (Sweden)

    Amy L. Ethier

    2015-06-01

    Full Text Available The introduction and removal of protecting groups is ubiquitous in multi-step synthetic schemes. From a green chemistry standpoint, however, alternative strategies that employ in situ and reversible protection and deprotection sequences would be attractive. The reversible reactions of CO2 with amines could provide a possible vehicle for realizing this strategy. Herein, we present (1 the products of reaction of benzylamines with CO2 in a variety of solvents with and without the presence of basic additives; (2 new adducts associated with CO2 protected benzylamine in acetonitrile containing 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU; and (3 the intermolecular competitive acylation of benzylamine and benzyl alcohol and the intramolecular competitive acylation of (4-aminomethylphenyl methanol with isopropenyl acetate in acetonitrile containing DBU in the absence and presence of CO2.

  3. Electrochemical oxidation of substituted benzylamines in aquo-acetic acid medium: substituent and solvent effects

    Indian Academy of Sciences (India)

    A Thirumoorthi; K P Elango

    2007-07-01

    Electrochemical oxidation of nine para- and meta-substituted benzylamines in varying mole fractions of acetic acid in water has been investigated in the presence of 0.1 M sulphuric acid as supporting electrolyte. The oxidation potentials correlate well with Hammett’s substituent constants affording negative reaction constants. The correlation of potential values with macroscopic solvent parameters is non-linear suggesting that the operation of both specific and non-specific solvent-solvent-solute interaction mechanisms. Multiple correlation analysis of the experimental data with Kamlet-Taft solvatochromic parameters is employed.

  4. Antimycobacterial activity of two natural alkaloids, vasicine acetate and 2-acetyl benzylamine, isolated from Indian shrub Adhatoda vasica Ness. leaves

    Indian Academy of Sciences (India)

    S Ignacimuthu; N Shanmugam

    2010-12-01

    In folk medicine, Adhatoda vasica Ness. (Acanthaceae) is used to treat asthma and cough. The leaves of A.vasica were powdered and extracted with hexane, ethyl acetate and methanol. The hexane extract showed 97% reduction in colony-forming units (CFU) at 100 g/ml. The hexane extract was subjected to column chromatography. Two natural compounds, vasicine acetate and 2-acetyl benzylamine, were isolated from it. They were bioassayed against Mycobacterium tuberculosis. The two compounds showed strong antimycobacterial activity. Vasicine acetate and 2-acetyl benzylamine isolated from hexane extract of A. vasica leaves, significantly inhibited M. tuberculosis and one multi-drug-resistant (MDR) strain and one sensitive strain at 200 and 50 g/ml, respectively. Our study demonstrated that both the compounds, vasicine acetate and 2-acetyl benzylamine, could be evaluated further for developing a drug to control M. tuberculosis.

  5. CuO-Al2O3 catalyzed oxidation of primary benzylamines and secondary dibenzylamines to N-benzylbenzaldimines

    Directory of Open Access Journals (Sweden)

    Jing Hui Zeng

    2013-06-01

    Full Text Available CuO-Al 2O 3 catalyzed one-pot oxidation with O 2 and self-coupling of benzylamines to give N-benzylbenzaldimines was described in good yields. Similarly, secondary dibenzylamines were oxidized to N-benzylbenzaldimines.

  6. Mechanism of Prototropy. III. Kinetics of the Tautomerization of Benzylidene-Benzylamine. comparison of the influence of hydrogen and alkyl groups on the SE2' reaction rate

    International Nuclear Information System (INIS)

    The rate of the proto tropic change of benzylidene-benzylamine has been determined by using azomethine 14C-labelled in the methylenic group and measuring the distribution of activity between benzaldehyde and benzylamine obtained by hydrolysis at different reaction times. this rate has been compared with those of tautomerization of benzylidene-α-alkyl benzylamine and α-alkyl benzylidene-benzyl amines in the same experimental conditions in order to establish ethe influence of alkyl group on this reaction. (Author) 14 refs

  7. Effect of root application of 6-benzylamine purine on auxin transport in Malus domestica

    Energy Technology Data Exchange (ETDEWEB)

    Stutte, G.

    1987-04-01

    The effect of 6-benzylamine purine (BA) on movement of napthalene acetic acid (NAA) applied to the shoot was investigated. Three-month-old York apple seedlings in sand culture were placed under mercury halide lamps (285 ..mu..mol m/sup -2/ s/sup -1/) at 22/sup 0/C for 24 hours; then 13.8, 27.5 or 55 ..mu..Mol of BA was applied as a soil drench. (/sup 14/C)-NAA was injected into the shoot at petiole base of 4th mature leaf. After 24 hours plants were harvested and movement of label acropetally to new shoot growth and basipetally to old shoot growth or roots determined. Seventeen (S.E. 3.3) percent of applied label was recovered away from application site. In controls, 67% of /sup 14/C that moved was recovered from new shoot growth, 9% in roots and 24% in old shoot tissue. The 13.8 ..mu..Mol treatment resulted in 37% of label being recovered in root tissue and 48% in new growth. The 27.5 and 55 ..mu..Mol applications increased the amount recovered in old shoot tissue but did not increase labelling of root tissues.

  8. Correlation of aqueous solubility of salts of benzylamine with experimentally and theoretically derived parameters. A multivariate data analysis approach

    DEFF Research Database (Denmark)

    Parshad, Henrik; Frydenvang, Karla Andrea; Liljefors, Tommy;

    2002-01-01

    Twenty two salts of benzylamine and p-substituted benzoic acids were prepared and characterized. The p-substituent was varied with regard to electronic, hydrophobic, and steric effects as well as hydrogen bonding potential. A multivariate data analysis was used to describe the relationship between...... the aqueous solubility of the salts and experimentally determined physicochemical parameters and theoretically derived molecular descriptors. The model, based on all descriptors, gave R(2)=0.86 and Q(2)=0.72. The most significant descriptors exhibiting VIP (variance of importance) values above 1.0 were...

  9. Oxidative deamination of benzylamine and lysine residue in bovine serum albumin by green tea, black tea, and coffee.

    Science.gov (United States)

    Akagawa, Mitsugu; Shigemitsu, Tomoko; Suyama, Kyozo

    2005-10-01

    Oxidative deamination by various polyphenolic compounds is presumed to be due to the oxidative conversion of polyphenols to the corresponding quinones through autoxidation. Here we examined the oxidative deamination by the polyphenol-rich beverages green tea, black tea, and coffee at a physiological pH and temperature. Green tea, black tea, and coffee extracts oxidatively deaminated benzylamine and the lysine residues of bovine serum albumin to benzaldehyde and alpha-aminoadipic delta-semialdehyde residues, respectively, in sodium phosphate buffer (pH 7.4) at 37 degrees C in both the presence and absence of Cu2+, indicating the occurrence of an amine (lysyl) oxidase-like reaction. We also examined the effects of pH and metal ions on the reaction. The possible biological effects of drinking polyphenol-rich beverages on human are also discussed.

  10. Synthesis and antimicrobial activity of salicylaldehyde-benzylamine Schif base%水杨醛-苄胺席夫碱的合成及其抑菌活性

    Institute of Scientific and Technical Information of China (English)

    杨晓军; 高芬

    2013-01-01

    The synthesis of salicylaldehyde-benzylamine Schif base was introduced. The structure of target molecular was confirmed by element alanysis.IR,1HNMR and MS. The antimicrobial activity indicated that it can effective resistance Pyricularia oryzae.%介绍了水杨醛-苄胺席夫碱的合成,其结构经IR、NMR、MS和元素分析等测试技术进行了确证.用培养皿平板法对标题化合物进行了抗稻瘟病菌试验,结果表明,该化合物对稻瘟病菌具有很好的抗菌活性.

  11. Aqueous solubility study of salts of benzylamine derivatives and p-substituted benzoic acid derivatives using X-ray crystallographic analysis

    DEFF Research Database (Denmark)

    Parshad, Henrik; Frydenvang, Karla Andrea; Liljefors, Tommy;

    2004-01-01

    Twenty two p-substituted benzoic acid derivates were used to prepare salts of N-methylbenzylamine (II) and N,N-dimethylbenzylamine (III), respectively. Only five salts of (II) and two salts of (III) were obtained in a crystalline state. The solubility of these salts was orders of magnitude higher...... than those reported for the corresponding salts of benzylamine (I). Thermal analysis indicated that the increased solubility was caused by reduced crystal lattice energy, which was most likely due to the reduced number of strong hydrogen bonds of the salt of (II) and (III). X-ray crystallographic...... analysis of p-hydroxybenzoic acid salt of (I), (II) and (III) suggested that the reduced number of hydrogen bonds caused the apparent higher solubility. Further analyses of seven salts of (I) were performed. It was not possible to identify any relationship between the number of hydrogen bonds...

  12. Thermodynamics of mixtures containing amines. XIV. C{sub pm}{sup E} of benzylamine with heptane at 293.15 K or with methanol, 1-propanol or 1-pentanol at 293.15–308.15 K

    Energy Technology Data Exchange (ETDEWEB)

    Páramo, Ricardo; Alonso, Víctor; González, Juan Antonio, E-mail: jagl@termo.uva.es; García de la Fuente, Isaías; Casanova, Carlos; Cobos, José Carlos

    2014-06-01

    Graphical abstract: - Highlights: • C{sub pm}{sup E}s are reported for benzylamine + heptane, +methanol, +1-propanol, +1-pentanol systems. • The heptane solution shows a W-shaped C{sub pm}{sup E} concentration dependence. • This reveals the existence of strong non-random effects in that mixture. • Systems with 1-alkanols are characterized by large and positive C{sub pm}{sup E} values. • This remarks that self-association/solvation effects are predominant in such systems. - Abstract: Molar excess heat capacities, C{sub pm}{sup E}, are reported for the benzylamine + heptane mixture at 293.15 K and for methanol, 1-propanol or 1-pentanol + benzylamine systems at 293.15–308.15 K. These values were determined from isobaric molar heat capacities obtained with a Setaram Micro DSC II microcalorimeter using a scanning method. The heptane solution shows a W-shaped C{sub pm}{sup E} concentration dependence, which reveals the existence of strong non-random effects. Systems including 1-alkanols are characterized by large and positive C{sub pm}{sup E} values. This remarks that self-association and/or solvation effects are predominant in such solutions. On the other hand, their C{sub pm}{sup E} curves are skewed towards higher mole fractions of the alcohol, which might be ascribed to the existence of more interactions between unlike molecules in that region.

  13. Synthesis and spectroscopic studies of binuclear metal complexes of a tetradentate N 2O 2 Schiff base ligand derived from 4,6-diacetylresorcinol and benzylamine

    Science.gov (United States)

    Shebl, Magdy

    2008-09-01

    A tetradentate N 2O 2 donor Schiff base ligand, H 2L, was synthesized by the condensation of 4,6-diacetylresorcinol with benzylamine. The structure of the ligand was elucidated by elemental analyses, IR, 1H NMR, electronic and mass spectra. Reaction of the Schiff base ligand with nickel(II), cobalt(II), iron(III), cerium(III), vanadyl(IV) and uranyl(VI) ions in 1:2 molar ratio afforded binuclear metal complexes. Also, reaction of the ligand with several copper(II) salts, including Cl -, NO 3-, AcO -, ClO 4- and SO 42- afforded different metal complexes that reflect the non-coordinating or weakly coordinating power of the ClO 4- anion as compared to the strongly coordinating power of SO 42- and Cl - anions. Characterization and structure elucidation of the prepared complexes were achieved by elemental and thermal analyses, IR, 1H NMR, electronic, mass and ESR spectra as well as magnetic susceptibility measurements. The metal complexes exhibited different geometrical arrangements such as square planar, octahedral, square pyramidal and pentagonal bipyramidal arrangements. The variety in the geometrical arrangements depends on the nature of both the anion and the metal ion.

  14. Synthesis, structure, DNA-binding properties and antioxidant activity of a nickel(II) complex with bis(N-allylbenzimidazol-2-ylmethyl)benzylamine.

    Science.gov (United States)

    Wu, Huilu; Yuan, Jingkun; Bai, Ying; Pan, Guolong; Wang, Hua; Shu, Xingbin

    2012-02-01

    A V-shape ligand bis(N-allylbenzimidazol-2-ylmethyl)benzylamine (babb) and its nickel complex, [Ni(babb)(2)](pic)(2) (pic=picrate), have been synthesized and characterized by physico-chemical and spectroscopic methods. Single-crystal X-ray revealed that the coordination sphere around Ni(II) is distorted octahedral with a N(6) ligand set, in which six nitrogen atoms were afforded by two tridentate ligand babb. The DNA-binding properties of the free ligand babb and Ni(II) complex have been investigated by electronic absorption, fluorescence, and viscosity measurements. The results suggest that babb and Ni(II) complex both bind to DNA via an intercalative binding mode, and the affinity for DNA is more strong in case of Ni(II) complex when compared with babb. The intrinsic binding constants (K(b)) of the Ni(II) complex and ligand with DNA were 3.65×10(4) M(-1) and 2.26×10(3) M(-1), respectively. Additionally, Ni(II) complex also exhibited potential antioxidant properties in vitro studies. PMID:22226085

  15. Validation of two fluoro-analogues of N,N-dimethyl-2-(2'-amino-4'-hydroxymethyl-phenylthio)benzylamine as serotonin transporter imaging agents using microPET

    Energy Technology Data Exchange (ETDEWEB)

    Jarkas, Nachwa; Voll, Ronald J.; Williams, Larry [Department of Radiology, Emory CSI, WWHC, Atlanta, GA 30329 (United States); Goodman, Mark M., E-mail: mgoodma@emory.ed [Department of Radiology, Emory CSI, WWHC, Atlanta, GA 30329 (United States)

    2010-07-15

    Introduction: Carbon-11 (C-11) N,N-dimethyl-2-(2'-amino-4'-hydroxymethyl-phenylthio)benzylamine ([{sup 11}C]HOMADAM) has been reported as highly specific and selective positron emission tomography (PET) radiotracer showing fast kinetics for the human brain serotonin transporter (SERT). In our continued effort to develop appropriate PET SERT radioligand that can be labeled with either C-11 or fluorine-18 (F-18), two new C-11 labeled analogues of HOMADAM, [{sup 11}C]-N,N-dimethyl-2-(2'-amino-5'-fluoro-4'-hydroxymethyl-phenylthio) benzylamine ([{sup 11}C]-(2)) and [{sup 11}C]-N,N-dimethyl-2-(2'-amino-4-fluoro-4'-hydroxymethyl-phenylthio) benzylamine ([{sup 11}C]-(3)) have been synthesized and evaluated along the previously reported [{sup 11}C]-N,N-dimethyl-2-(2'-amino-5-fluoro-4'-hydroxymethyl-phenylthio) benzylamine ([{sup 11}C]-(1)). Methods: The in vitro competitive binding assays were performed in cells transfected with human SERT (hSERT), human dopamine transporter (hDAT), and human norepinephrine transporter (hNET). [{sup 11}C]-(2) and [{sup 11}C]-(3) were prepared by methylation of their monomethylbenzylamine precursors 13 and 22 with cyclotron produced [{sup 11}C]iodomethane ([{sup 11}C]CH{sub 3}I), respectively. Uptake and kinetics of [{sup 11}C]-(2) and [{sup 11}C]-(3) in the brain regions of interest were determined in anesthetized rhesus monkeys using Concorde microPET P4. Results: 2 and 3 displayed moderate and high affinity for the SERT with Kis (SERT) = 5.45 and 1.10 nM (vs [{sup 3}H]citalopram), respectively. After High Performance Liquid Chromatography (HPLC) purification, [{sup 11}C]-(2) and [{sup 11}C]-(3) were obtained in 23 and 9% radiochemical yield (RCY) and log Ps{sub 7.4} of 1.77 and 1.91, respectively. The microPET images of [{sup 11}C]-(2) and [{sup 11}C]-(3) showed clear localization in the monkey brain regions rich in SERT with midbrain to cerebellum ratios of 1.75 and 3.86 at 85 min post

  16. 4-羟基-3-甲氧基苯甲胺盐酸盐的合成研究%Study on the Synthesis of 4-Hydroxy-3-methoxy Benzylamine Hydrochloride

    Institute of Scientific and Technical Information of China (English)

    彭东明; 王福东; 李云耀; 刘艳飞; 李永欣

    2012-01-01

    4-Hydroxy-3-methoxy benzylamine hydrochloride was synthesized from vanillin and hydroxylamine hydrochloride via the processes of oximation, reduction and salification reaction. The affecting factors including the ratio of the raw materials, the reaction time, the reaction temperature and the catalyst were investigated. The product was formed in an overall yield of 89.7%, and the structure was confirmed with elemental analysis, IR and 'H NMR.%以香兰素与盐酸羟胺为原料,经肟化、还原及成盐反应合成4-羟基-3-甲氧基苯甲胺盐酸盐.分别考察反应原料及配比、反应时间、反应温度和催化剂等因素对收率的影响.通过元素分析、IR、1H NMR确证了4-羟基-3-甲氧基苯甲胺盐酸盐结构.该方法总收率达89.7%(以香兰素计),适于实际生产的需要.

  17. Optimization of Cyclic Plasmin Inhibitors: From Benzamidines to Benzylamines.

    Science.gov (United States)

    Hinkes, Stefan; Wuttke, André; Saupe, Sebastian M; Ivanova, Teodora; Wagner, Sebastian; Knörlein, Anna; Heine, Andreas; Klebe, Gerhard; Steinmetzer, Torsten

    2016-07-14

    New macrocyclic plasmin inhibitors based on our previously optimized P2-P3 core segment have been developed. In the first series, the P4 residue was modified, whereas the 4-amidinobenzylamide in P1 position was maintained. The originally used P4 benzylsulfonyl residue could be replaced by various sulfonyl- or urethane-like protecting groups. In the second series, the P1 benzamidine was modified and a strong potency and excellent selectivity was retained by incorporation of p-xylenediamine. Several analogues inhibit plasmin in the subnanomolar range, and their potency against related trypsin-like serine proteases including trypsin itself could be further reduced. Selected derivatives have been tested in a plasma fibrinolysis assay and are more effective than the reference inhibitor aprotinin. The crystal structure of one inhibitor was determined in complex with trypsin. The binding mode reveals a sterical clash of the inhibitor's linker segment with the 99-hairpin loop of trypsin, which is absent in plasmin.

  18. Optimization of Cyclic Plasmin Inhibitors: From Benzamidines to Benzylamines.

    Science.gov (United States)

    Hinkes, Stefan; Wuttke, André; Saupe, Sebastian M; Ivanova, Teodora; Wagner, Sebastian; Knörlein, Anna; Heine, Andreas; Klebe, Gerhard; Steinmetzer, Torsten

    2016-07-14

    New macrocyclic plasmin inhibitors based on our previously optimized P2-P3 core segment have been developed. In the first series, the P4 residue was modified, whereas the 4-amidinobenzylamide in P1 position was maintained. The originally used P4 benzylsulfonyl residue could be replaced by various sulfonyl- or urethane-like protecting groups. In the second series, the P1 benzamidine was modified and a strong potency and excellent selectivity was retained by incorporation of p-xylenediamine. Several analogues inhibit plasmin in the subnanomolar range, and their potency against related trypsin-like serine proteases including trypsin itself could be further reduced. Selected derivatives have been tested in a plasma fibrinolysis assay and are more effective than the reference inhibitor aprotinin. The crystal structure of one inhibitor was determined in complex with trypsin. The binding mode reveals a sterical clash of the inhibitor's linker segment with the 99-hairpin loop of trypsin, which is absent in plasmin. PMID:27280436

  19. Formation of a Ruthenium-Arene Complex, Cyclometallation with a Substituted Benzylamine, and Insertion of an Alkyne

    Science.gov (United States)

    Chetcuti, Michael J.; Ritleng, Vincent

    2007-01-01

    The three step synthesis is presented to allow the functionalization of an aromatic amine by forming new C-C and C-N bonds via an intramolecular C-H activation under mild conditions. The reactions are stoichiometric and allow the students to isolate the different organometallic intermediates.

  20. Mechanism of Prototropy. V. Arrhenius parameters of the tautomerization of Benzylidene Benzylamine and its α-α-alkyl derivatives

    International Nuclear Information System (INIS)

    The reactions were conducted in ethyl alcohol-dioxan, in the presence of EtONa, as catalyst. Rates were followed by a radioactive tracer method when R=H and by spectroscopic method when R= alkyl as described in previous papers. The results suggest that polar effects alone cannot account for the relative Arrhenius parameters obtained. (Author) 3 refs

  1. Investigation of possible methods for removal of nitrogen from coal-derived and coal-related materials. [Melt-treated coal; benzylamine, 1,2,3,4-tetrahydroisoquinoline

    Energy Technology Data Exchange (ETDEWEB)

    Frey, D.D.; Vermeulen, T.

    1980-09-01

    A preliminary study was conducted to determine the feasibility of removing nitrogen from hydrogenated coal products by oxidation. Solvent-refined coal, melt-treated coal, and nitrogen containing model-compounds were used as substrates. In addition, various zinc containing catalytic systems were screened for their hydrogenation and hydrocracking activity towards quinoline. Results indicate that nitrogen can be removed from some of the model-compounds used. Both iron and cobalt salts effectively catalyzed the oxidation reaction. Very little nitrogen could be removed from the compounds that are the most representative of hydrogenated coal. In addition, very little nitrogen was removed from the hydrogenated coals themselves. None of the zinc salts tested in the hydrogenation portion of the study were effective in catalyzing the rate of hydrogenation of quinoline.

  2. PET imaging of the brain serotonin transporters (SERT) with N,N-dimethyl-2-(2-amino-4-[{sup 18}F]fluorophenylthio)benzylamine (4-[{sup 18}F]-ADAM) in humans: a preliminary study

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Wen-Sheng [PET Center, Tri-Service General Hospital, Department of Nuclear Medicine, Neihu, Taipei (China); Changhua Christian Hospital, Department of Nuclear Medicine, Changhua (China); Huang, San-Yuan; Ho, Pei-Shen; Yeh, Chin-Bin [Tri-Service General Hospital, Department of Psychiatry, Taipei (China); Ma, Kuo-Hsing [National Defense Medical Center, Department of Biology and Anatomy, Taipei (China); Huang, Ya-Yao; Shiue, Chyng-Yann [PET Center, Tri-Service General Hospital, Department of Nuclear Medicine, Neihu, Taipei (China); PET Center, National Taiwan University Hospital, Department of Nuclear Medicine, Taipei (China); Liu, Ren-Syuan [Taipei Veterans General Hospital, Department of Nuclear Medicine, Taipei (China); Cheng, Cheng-Yi [PET Center, Tri-Service General Hospital, Department of Nuclear Medicine, Neihu, Taipei (China)

    2013-01-15

    The aim of this study was to assess the feasibility of using 4-[{sup 18}F]-ADAM as a brain SERT imaging agent in humans. Enrolled in the study were 19 healthy Taiwanese subjects (11 men, 8 women; age 33 {+-} 9 years). The PET data were semiquantitatively analyzed and expressed as specific uptake ratios (SUR) and distribution volume ratios (DVR) using the software package PMOD. The SUR and DVR of 4-[{sup 18}F]-ADAM in the raphe nucleus (RN), midbrain (MB), thalamus (TH), striatum (STR) and prefrontal cortex (PFC) were determined using the cerebellum (CB) as the reference region. 4-[{sup 18}F]-ADAM bound to known SERT-rich regions in human brain. The order of the regional brain uptake was MB (RN) > TH > STR > PFC > CB. The DVR (n = 4, t* = 60 min) in the RN, TH, STR and PFC were 3.00 {+-} 0.50, 2.25 {+-} 0.45, 2.05 {+-} 0.31 and 1.40 {+-} 0.13, respectively. The optimal time for imaging brain SERT with 4-[{sup 18}F]-ADAM was 120-140 min after injection. At the optimal imaging time, the SURs (n = 15) in the MB, TH, STR, and PFC were 2.25 {+-} 0.20, 2.28 {+-} 0.20, 2.12 {+-} 0.18 and 1.47 {+-} 0.14, respectively. There were no significant differences in SERT availability between men and women (p < 0.05). The results of this study showed that 4-[{sup 18}F]-ADAM was safe for human studies and its distribution in human brain appeared to correlate well with the known distribution of SERT in the human brain. In addition, it had high specific binding and a reasonable optimal time for imaging brain SERT in humans. Thus, 4-[{sup 18}F]-ADAM may be feasible for assessing the status of brain SERT in humans. (orig.)

  3. Mechanism of Prototropy. V. Arrhenius parameters of the tautomerization of Benzylidene Benzylamine and its {alpha}-{alpha}-alkyl derivatives; Mecanismo de la prototropia V. Parametros de Arrhenius de la toutomerizacion de benciliden-bencilamina y sus {alpha}- y {alpha}-alquilderivados

    Energy Technology Data Exchange (ETDEWEB)

    Perez Ossorio, R.; Gomez Herrera, F.; Utrilla, R. M.; Hidalgo, A.; Gamboa, J. M.

    1961-07-01

    The reactions were conducted in ethyl alcohol-dioxan, in the presence of EtONa, as catalyst. Rates were followed by a radioactive tracer method when R=H and by spectroscopic method when R= alkyl as described in previous papers. The results suggest that polar effects alone cannot account for the relative Arrhenius parameters obtained. (Author) 3 refs.

  4. 6-氟-2-嘧啶氧基-N-取代苯基苄胺类化合物的合成及其除草活性%Synthesis and Herbicidal Activity of 6-Fluoro-2-pyrimindinyloxy-N-substituted Phenyl Benzylamine Derivatives

    Institute of Scientific and Technical Information of China (English)

    龚启孙; 彭伟立; 沈德隆; 陈杰

    2005-01-01

    从起始原料引入氟原子,分别经亚胺化、硼氢化钠还原、嘧啶氧化,及嘧啶氧化、溴化、胺化两条路线合成了28个新型的6-氟-2-嘧啶氧基-N-取代苯基苄胺类化合物;同时测试了该类化合物在温室中对稗草Echinochloa crusgalli等3种禾本科杂草和反枝苋Amaranthus retroflexus等3种阔叶杂草芽前、芽后的抑制率,结果表明,有12种目标化合物在有效剂量75 g/hm2下其抑制率超过80%.

  5. Catalytic transfer hydrogenation of azobenzene by low-valent nickel complexes: a route to 1,2-disubstituted benzimidazoles and 2,4,5-trisubstituted imidazolines.

    Science.gov (United States)

    Zurita, Daniel A; Flores-Alamo, Marcos; García, Juventino J

    2016-06-21

    The one-pot synthesis of 1,2-disubstituted benzimidazoles by the transfer hydrogenation of azobenzene, using benzylamine as a hydrogen donor, sequential rearrangement of hydrazobenzene to semidine and further condensation with N-benzylideneamine is reported, catalyzed by 2 mol% of [Ni(COD)2] : dippe. The N2 substitution on benzimidazole can be controlled by the selection of different azobenzenes and C2 substitution will only depend on the chosen benzylamine. The current methodology avoids the addition of external oxidants, which are needed in the classical benzimidazole synthesis. In addition, the byproduct, N-benzylideneamine, obtained from dehydrogenation of benzylamine produced 2,4,5-trisubstituted imidazolines by cyclization and C-H functionalization, and this route was optimized with the use of 2 mol% of [Ni(COD)2] : 2PPh3. PMID:27254530

  6. Implications of dynamic imine chemistry for the sustainable synthesis of nitrogen heterocycles via transimination followed by intramolecular cyclisation.

    Science.gov (United States)

    Laha, Joydev K; Tummalapalli, K S Satyanarayana; Jethava, Krupal P

    2016-02-28

    An exploration of a tandem approach to the sustainable synthesis of N-heterocycles from readily available N-aryl benzylamines or imines and ortho-substituted anilines is described, which demonstrates, for the first time, an important synthetic application of dynamic imine chemistry. The key features to the successful development of this protocol include the utilisation of N-aryl benzylamines as imine precursors in transimination, the occurrence of transimination in acetonitrile in the absence of any catalysts, an intramolecular nucleophilic addition occurring in the newly formed imine causing irreversible transimination, and the tandem event occurring under green conditions.

  7. Asymmetric Imine Isomerisation in the Enantioselective Synthesis of Chiral Amines from Prochiral Ketones

    NARCIS (Netherlands)

    Willems, Johannes G.H.; Vries, Johannes G. de; Nolte, Roeland J.M.; Zwanenburg, Binne

    1995-01-01

    An asymmetric catalytic synthesis of chiral amines using a chiral base catalysed [1,3]-proton shift reaction of imines is described. The isomerisation reaction of N-benzylimines derived from prochiral ketones (benzylacetone, acetophenone) and p-substituted benzylamines, is catalysed by chiral alcoho

  8. Synthesis of New Racemic α,α-Diaminocarboxylic Ester Derivatives

    Directory of Open Access Journals (Sweden)

    Mabrouk El Houssine

    2010-11-01

    Full Text Available New racemic methyl or ethyl α-aminoglycinate derivatives were synthesized by N-alkylation of amines (aniline, 4-methylaniline, 2-methylaniline, 2,4-dimethoxyaniline, 2-nitroaniline, 4-chloro-2-fluoroaniline, 2-naphthylamine, benzylamine, N,N-dibenzylamine, and cyclohexylamine with methyl or ethyl α-azidoglycinate.

  9. Synthesis of New Racemic α,α-Diaminocarboxylic Ester Derivatives

    OpenAIRE

    Mabrouk El Houssine; Elachqar Abdelrhani; Alami Anouar; El Hallaoui Abdelilah

    2010-01-01

    New racemic methyl or ethyl α-aminoglycinate derivatives were synthesized by N-alkylation of amines (aniline, 4-methylaniline, 2-methylaniline, 2,4-dimethoxyaniline, 2-nitroaniline, 4-chloro-2-fluoroaniline, 2-naphthylamine, benzylamine, N,N-dibenzylamine, and cyclohexylamine) with methyl or ethyl α-azidoglycinate.

  10. The Synthesis of "N"-Benzyl-2-Azanorbornene via Aqueous Hetero Diels-Alder Reaction: An Undergraduate Project in Organic Synthesis and Structural Analysis

    Science.gov (United States)

    Sauvage, Xavier; Delaude, Lionel

    2008-01-01

    The synthesis of "N"-benzyl-2-azanorbornene via aqueous hetero Diels-Alder reaction of cyclopentadiene and benzyliminium chloride formed in situ from benzylamine hydrochloride and formaldehyde is described. Characterization of the product was achieved by IR and NMR spectroscopies. The spectral data acquired are thoroughly discussed. Numerous…

  11. Synthesis of N-protected Galactosamine Building Blocks from D-Tagatose via the Heyns Rearrangement

    DEFF Research Database (Denmark)

    Wrodnigg, Tanja M.; Lundt, Inge; Stütz, Arnold E.

    2006-01-01

    N-Acetyl-D-galactosamine (11), a very important naturally occurring building block of oligosaccharides, is easily accessible via the Heyns rearrangement of D-tagatose (3) with benzylamine. The short and efficient synthesis of various differently N-protected D-galactosamine derivatives is reported....

  12. Adsorption of polar aromatic hydrocarbons on synthetic calcite

    DEFF Research Database (Denmark)

    Madsen, Lene; Grahl-Madsen, Laila; Grøn, Christian;

    1996-01-01

    The wettability of hydrocarbon reservoirs depends on how and to what extent the organic compounds are adsorbed onto the surfaces of calcite, quartz and clay. A model system of synthetic call cite, cyclohexane and the three probe molecules: benzoic acid, benzyl alcohol and benzylamine, have been...

  13. Solid-phase oligosaccharide synthesis with tris(alkoxy)benzyl amine (BAL) safety-catch anchoring

    DEFF Research Database (Denmark)

    Tolborg, Jakob Fjord; Jensen, Knud Jørgen

    2000-01-01

    A tris(alkoxy)benzylamine (BAL) handle strategy was developed for safety-catch anchoring of D-glucosamine derivatives in solid-phase synthesis of oligosaccharides; the linkage between the BAL handle and the amine proved stable to conc. TFA and Lewis acids, but after N-acylation the amide could...

  14. Serological differences between the multiple amine oxidases of yeasts and comparison of the specificities of the purified enzymes from Candida utilis and Pichia pastoris.

    Science.gov (United States)

    Green, J; Haywood, G W; Large, P J

    1983-05-01

    1. Antiserum to purified methylamine oxidase of Candida boidinii formed precipitin lines (with spurs) in double-diffusion tests with crude extracts of methylamine-grown cells of the following yeast species: Candida nagoyaensis, Candida nemodendra, Hansenula minuta, Hansenula polymorpha and Pichia pinus. No cross-reaction was observed with extracts of Candida lipolytica, Candida steatolytica, Candida tropicalis, Candida utilis, Pichia pastoris, Sporobolomyces albo-rubescens, Sporopachydermia cereana or Trigonopsis variabilis. Quantitative enzyme assays enabled the relative titre of antiserum against the various methylamine oxidases to be determined. 2. The amine oxidases from two non-cross-reacting species, C. utilis and P. pastoris, were purified to near homogeneity. 3. The methylamine oxidases, despite their serological non-similarity, showed very similar catalytic properties to methylamine oxidase from C. boidinii. Their heat-stability, pH optima, molecular weights, substrate specificities and sensitivity to inhibitors are reported. 4. The benzylamine oxidases of C. utilis and P. pastoris both oxidized putrescine, and the latter enzyme failed to show any cross-reaction with antibody to C. boidinii methylamine oxidase. Benzylamine oxidase from C. boidinii itself also did not cross-react with antibody to methylamine oxidase. The heat-stability, molecular weights, substrate specificities and sensitivity to inhibitors of the benzylamine/putrescine oxidases are reported. 5. The benzylamine/putrescine oxidase of C. utilis differed only slightly from that of C. boidinii. 6. Benzylamine/putrescine oxidase from P. pastoris differed from the Candida enzymes in heat-stability, subunit molecular weight and substrate specificity. In particular it catalysed the oxidation of the primary amino groups of spermine, spermidine, lysine, ornithine and 1,2-diaminoethane, which are not substrates for either of the Candida benzylamine oxidases that have been purified. 7. Spermine and

  15. Aminoborohydrides. 12. Novel tandem S(N)Ar amination-reduction reactions of 2-halobenzonitriles with lithium N,N-dialkylaminoborohydrides.

    Science.gov (United States)

    Thomas, S; Collins, C J; Cuzens, J R; Spiciarich, D; Goralski, C T; Singaram, B

    2001-03-23

    A novel tandem amination-reduction reaction has been developed in which 2-(N,N-dialkylamino)benzylamines are generated from 2-halobenzonitriles and lithium N,N-dialkylaminoborohydride (LAB) reagents. These reactions are believed to occur through a tandem S(N)Ar amination-reduction mechanism wherein the LAB reagent promotes halide displacement by the N,N-dialkylamino group, and the nitrile is subsequently reduced. This one-pot procedure is complimentary to existing synthetic methods and is an attractive synthetic tool for the nucleophilic aromatic substitution of halobenzenes with less nucleophilic amines. The (N,N-dialkylamino)benzylamine products of this reaction are easily isolated after a simple aqueous workup procedure in very good to excellent yields. PMID:11300892

  16. Organ distribution of biogenic amine derivatives of 103Ru labelled ruthenocenyl - radiopharmaceuticals for adrenal and ovar

    International Nuclear Information System (INIS)

    The organ distribution of 103Ru labelled ruthenocenyl derivatives of tyramine, histamine, benzylamine, phenylethylamine and homoveratrylamine were measured in rats. The derivatives of tyramine, histamine and benzylamine showed a high affinity for the adrenal and ovar. Adrenal/muscle ratios up to 2000/1 were gained but only if the dose was administered i. v. and was below 0,1 μmol/kg. The ruthenocenyl derivatives of tyramine labelled with 103Ru in the ruthenocene moiety or with 14C in the tyramine moiety showed a parallel distribution pattern but completely different from the distribution of 103RuCl3. This indicates that the tyramine derivatives are not destroyed in the body yielding Ru-ions. The advantages of the ruthenocenyl derivatives in comparison with the known amphetamine derivatives labelled with radioactive iodine are discussed. (orig.)

  17. Hydrotropic salt promotes anionic surfactant self-assembly into vesicles and ultralong fibers.

    Science.gov (United States)

    Lin, Yiyang; Qiao, Yan; Cheng, Xinhao; Yan, Yun; Li, Zhibo; Huang, Jianbin

    2012-03-01

    Molecular self-assembly has become a versatile approach to create complex and functional nanoarchitectures. In this work, the self-assembly behavior of an anionic surfactant (sodium dodecylbenzene sulfonate, SDBS) and a hydrotropic salt (benzylamine hydrochloride, BzCl) in aqueous solution is investigated. Benzylamine hydrochloride is found to facilitate close packing of surfactants in the aggregates, inducing the structural transformation from SDBS micelles into unilamellar vesicles, and multilamellar vesicles. The multilamellar vesicles can transform into macroscale fibers, which are long enough to be visualized by the naked eye. Particularly, these fibers are robust enough to be conveniently separated from the surfactant solution. The combined effect of non-covalent interactions (e.g., hydrophobic effect, electrostatic attractions, and π-π interactions) is supposed to be responsible for the robustness of these self-assembled aggregates, in which π-π interactions provide the directional driving force for one-dimensional fiber formation. PMID:22209412

  18. Enhanced reactivities toward amines by introducing an imine arm to the pincer ligand: Direct coupling of two amines to form an imine without oxidant

    KAUST Repository

    He, Lipeng

    2012-07-23

    Dehydrogenative homocoupling of primary alcohols to form esters and coupling of amines to form imines was accomplished using a class of novel pincer ruthenium complexes. The reactivities of the ruthenium pincer complexes for the direct coupling of amines to form imines were enhanced by introducing an imine arm to the pincer ligand. Selective oxidation of benzylamines to imines was achieved using aniline derivatives as the substrate and solvent. © 2012 American Chemical Society.

  19. Syntheses and Crystal Structures of Chiral BINOL Derivatives and Their Applications in Enantioselective Lewis Acid Catalyzed Addition of Diethylzinc to Aldehydes

    Institute of Scientific and Technical Information of China (English)

    LIU Guo-Hua; YU Han; Yang Liang-Zhun; YAO Mei; FANG Hai-Bin; XUE Yun-Ning

    2007-01-01

    Two novel chiral BINOL derivatives with bis(benzylamine) groups at the 3,3' positions have been synthesized through the condensation reaction between 2,2'-bis(methoxy- methyleneoxy)-1,1'-binaphthyl-3,3'-dicarboxylic acid and benzylamine or N-phenyl benzylamine in the presence of triethylamine. Suitable single crystal of (R)-N,N'-dibenzyl-2,2'-dihydroxy-1,1'-binaphthly-3,3'-diformamide (R)-3 for X-ray diffraction was obtained by recrystallization at room temperature from the mixture solvents. Crystallographic data of (R)-3: C40H36N2O6, Mr=640.71, monoclinic, space group P21, a=6.746(3), b=21.883(9), c=11.723(5) (A), β=104.605(7)°, Z=2, V=1674.7(12) (A)3, Dc=1.271 g/cm3, F(000)=676, R=0.0729, Wr=0.1687 and μ(MoKα)=0.086 mm-1. Two chiral BINOL ligands were found to be effective in the enantioselective addition of diethylzinc to aldehydes and much different enantioselectivity was observed both in the presence and absence of Ti(OiPr)4. In the former case, (R)-3 showed moderate enantioselectivity, which was lower than that of (R)-BINOL's; and in the latter case, (R)-4 gave the highest enantioselectivity up to 93.3% ee.*

  20. CHARACTERIZATION OF MOLLUSCICIDAL COMPONENT OF Moringa oleifera LEAF AND Momordica charantia FRUITS AND THEIR MODES OF ACTION IN SNAIL Lymnaea acuminata

    Directory of Open Access Journals (Sweden)

    Aparna Upadhyay

    2013-07-01

    Full Text Available SUMMARY The molluscicidal activity of the leaf powder of Moringa oleifera and lyophilized fruit powder of Momordica charantia against the snail Lymnaea acuminata was time and concentration dependent. M. oleifera leaf powder (96 h LC50: 197.59 ppm was more toxic than M. charantia lyophilized fruit powder (96 h LC50: 318.29 ppm. The ethanolic extracts of M. oleifera leaf powder and Momordica charantia lyophilized fruit powder were more toxic than other organic solvent extracts. The 96 h LC50 of the column purified fraction of M. oleifera leaf powder was 22.52 ppm, while that of M. charantia lyophilized fruit powder was 6.21 ppm. Column, thin layer and high performance liquid chromatography analysis show that the active molluscicidal components in M. oleifera leaf powder and lyophilized fruit of M. charantia are benzylamine (96 h LC50: 2.3 ppm and momordicine (96 h LC50: 1.2 ppm, respectively. Benzylamine and momordicine significantly inhibited, in vivo and in vitro, the acetylcholinesterase (AChE, acid and alkaline phosphatase (ACP/ALP activities in the nervous tissues of L. acuminata. Inhibition of AChE, ACP and ALP activity in the nervous tissues of L. acuminata by benzylamine and momordicine may be responsible for the molluscicidal activity of M. oleifera and M. charantia fruits, respectively.

  1. A straightforward and efficient method for the synthesis of diversely substituted {beta}-aminoketones and {gamma}-aminoalcohols from 3-(N,N-dimethylamino)propiophenones as starting materials

    Energy Technology Data Exchange (ETDEWEB)

    Abonia, Rodrigo; Arteaga, Danny; Castillo, Juan; Insuasty, Braulio; Quiroga, Jairo; Ortiz, Alejandro, E-mail: rodrigo.abonia@correounivalle.edu.co [Universidad del Valle, Cali (Colombia). Department of Chemistry. Research Group of Heterocyclic Compounds

    2013-09-15

    Libraries of novel {beta}-aminoketones and {gamma}-aminoalcohols showing a wide structural diversity were easily obtained from a simple approach, using 3-(N,N-dimethylamino)propiophenone derivatives as key starting material. The procedure involved initially an N-alkylation of secondary benzylamines with propiophenone salts yielding the desired {beta}-aminoketones. Chemical or catalytic reduction of their carbonyl groups provided the final {gamma}-aminoalcohols in good yields. This protocol proved to be convenient as an alternative route for the synthesis of the local anesthetic Falicain Registered-Sign and for the topic antifungal drug Naftifine Registered-Sign . (author)

  2. Conjugated Microporous Poly(Benzochalcogenadiazole)s for Photocatalytic Oxidative Coupling of Amines under Visible Light.

    Science.gov (United States)

    Wang, Zi Jun; Garth, Kim; Ghasimi, Saman; Landfester, Katharina; Zhang, Kai A I

    2015-10-26

    Metal-free visible-light photocatalysts offer a clean, sustainable solution to many pressing environmental issues. Herein, we present a molecular design strategy to fine-tune the valence and conduction band levels of a series of conjugated microporous polymer networks based on poly(benzochalcogenadiazole) for heterogeneous photocatalysis. Enhanced photocatalytic efficiency was observed by altering the chalcogene moieties in the electron-accepting benzochalcogenadiazole unit of the polymer backbone structure. Photooxidative coupling of benzylamines was chosen as a model reaction. This design strategy leading to enhanced efficiency could potentially improve a wide range of photoredox reactions.

  3. Co-polymer Films for Sensors

    Science.gov (United States)

    Ryan, Margaret A. (Inventor); Homer, Margie L. (Inventor); Yen, Shiao-Pin S. (Inventor); Kisor, Adam (Inventor); Jewell, April D. (Inventor); Shevade, Abhijit V. (Inventor); Manatt, Kenneth S. (Inventor); Taylor, Charles (Inventor); Blanco, Mario (Inventor); Goddard, William A. (Inventor)

    2012-01-01

    Embodiments include a sensor comprising a co-polymer, the co-polymer comprising a first monomer and a second monomer. For some embodiments, the first monomer is poly-4-vinyl pyridine, and the second monomer is poly-4-vinyl pyridinium propylamine chloride. For some embodiments, the first monomer is polystyrene and the second monomer is poly-2-vinyl pyridinium propylamine chloride. For some embodiments, the first monomer is poly-4-vinyl pyridine, and the second monomer is poly-4-vinyl pyridinium benzylamine chloride. Other embodiments are described and claimed.

  4. On-line radiochemical assay for monoamine oxidase utilizing high-performance liquid chromatography

    Energy Technology Data Exchange (ETDEWEB)

    Nissinen, E.; Linko-Loeppoenen SMae; Maennistoe P4

    1984-12-01

    A fast and sensitive assay for the determination of monoamine oxidase activity was developed. The method is based on the separation and quantitation of /sup 14/C-labeled assay products by high-performance liquid chromatography, which is interfaced directly into a flow-through radioactivity detector. This allows on-line quantitation of the radioactive compounds with picomole sensitivity. The method makes possible the complete separation and detection of the deaminated products of monoamine oxidase A and B substrates benzylamine and 5-hydroxytryptamine, respectively. This assay has been applied to the measurement of monoamine oxidase A and B activities in rat brain.

  5. Synthesis of naturally occurring iminosugars from D-fructose by the use of a zinc-mediated fragmentation reaction

    DEFF Research Database (Denmark)

    Lauritsen, Anne; Madsen, Robert

    2006-01-01

    A short synthesis of 1,4-dideoxy-1,4-imino-D-arabinitol (DAB) and a formal synthesis of australine are described. In both cases, D-fructose is employed as the starting material and converted into a protected methyl 6-deoxy-6-iodo-furanoside. Zinc-mediated fragmentation produces an unsaturated...... ketone which serves as a key building block for both syntheses. Ozonolysis, reductive amination with benzylamine and deprotection affordfs 1,4-dideoxy-1,4-imino-D-arabinitol in only 7 steps and 11% overall yield from D-fructose. Alternatively, reductive amination with homoallylamine, ring...

  6. Visible Light Induced Selective Photocatalytic Oxidation of Benzyl Amine to N-benzylidene-1-phenylmethanamine by Reduced Graphene Oxide-Titania Nanocomposites.

    Directory of Open Access Journals (Sweden)

    SoumyaGopi

    2015-06-01

    Full Text Available Irradiated semiconductor catalysis in the presence of molecular oxygen can be considered as an innovative and sustainable technique for organic transformations. The present work reports the preparation ofGraphene oxide/TiO2composite by improved Hummer’s method followed by hydrothermal technique. The prepared system was characterized by various physico-chemical techniques such as X-Ray diffraction, IR-Spectroscopy, UV-DRS, XPS, SEM and TEM Analysis.On reaction, benzylamine in CH3CN yieldedN-benzylidene-1- phenylmethanamine as the sole product. The reaction was monitored by GC-MS Analysis.

  7. Synthesis and Characterization of Some New Thermal Stable Polymers - Polymerization of N-[4-N´ -(Benzylamino-carbonyl)phenyl]maleimide

    OpenAIRE

    B. L. Hiran; Jyoti Chadhary; S. N. Paliwal; Suresh Meena; P. R. Chaudhary

    2007-01-01

    This article describes the synthesis and characterization of homopolymer (H-BCPM) of N-[4-N'-(benzylamino-carbonyl) phenyl] maleimide (N-BACPMI) and copolymer (C-BCPM) of N-BACPMI with n-butyl acrylate (BA). The new monomer was synthesized from p-aminobenzoic acid, maleic anhydride and benzylamine. The homopolymerization of N-BACPMI is initiated by free radical using AIBN in THF solvent at 65°C. Radical copolymerization of N-BACPMI with BA, initiated by AIBN, was performed in THF solvent usin...

  8. Imaging the serotonin transporter with positron emission tomography: initial human studies with [11C]DAPP and [11C]DASB

    International Nuclear Information System (INIS)

    Two novel radioligands, N,N-dimethyl-2-(2-amino-4-methoxyphenylthio)benzylamine (DAPP) and N,N-dimethyl-2-(2-amino-4-cyanophenylthio)benzylamine (DASB), were radiolabeled with carbon-11 and evaluated as in vivo probes of the serotonin transporter (SERT) using positron emission tomography (PET). Both compounds are highly selective, with nanomolar affinity for the serotonin transporter and micromolar affinity for the dopamine and norepinephrine transporters. Six volunteers were imaged twice, once with each of the two radioligands. Both ligands displayed very good brain penetration and selective retention in regions rich in serotonin reuptake sites. Both had similar brain uptake and kinetics, but the cyano analogue, [11C]DASB, had a slightly higher brain penetration in all subjects. Plasma analysis revealed that both radiotracers were rapidly metabolized to give mainly hydrophilic species as determined by reverse-phase high-performance liquid chromatography. Inhibition of specific binding to the SERT was demonstrated in three additional subjects imaged with [11C]DASB following an oral dose of the selective serotonin reuptake blocker citalopram. These preliminary studies indicate that both these substituted phenylthiobenzylamines have highly suitable characteristics for probing the serotonin reuptake system with PET in humans. (orig.)

  9. Crystal structure of bis-(benzyl-amine-κN)[5,10,15,20-tetra-kis-(4-chloro-phen-yl)porphyrinato-κ(4) N]iron(II) n-hexane monosolvate.

    Science.gov (United States)

    Dhifaoui, Selma; Harhouri, Wafa; Bujacz, Anna; Nasri, Habib

    2016-01-01

    In the title compound, [Fe(II)(C44H24Cl4N4)(C6H5CH2NH2)2]·C6H14 or [Fe(II)(TPP-Cl)(BzNH2)2]·n-hexane [where TPP-Cl and BzNH2 are 5,10,15,20-tetra-kis-(4-chloro-phen-yl)porphyrinate and benzyl-amine ligands, respectively], the Fe(II) cation lies on an inversion centre and is octa-hedrally coordinated by the four pyrrole N atoms of the porphyrin ligand in the equatorial plane and by two amine N atoms of the benzyl-amine ligand in the axial sites. The crystal structure also contains one inversion-symmetric n-hexane solvent mol-ecule per complex mol-ecule. The average Fe-Npyrrole bond length [1.994 (3) Å] indicates a low-spin complex. The crystal packing is sustained by N-H⋯Cl and C-H⋯Cl hydrogen-bonding inter-actions and by C-H⋯π inter-molecular inter-actions, leading to a three-dimensional network structure. PMID:26870596

  10. Effect of tripeptide-copper complexes on the process of skin wound healing and on cultured fibroblasts.

    Science.gov (United States)

    Buffoni, F; Pino, R; Dal Pozzo, A

    1995-01-01

    The effects of Gly-His-Lys-Cu and of three synthetic analogues (I, II and III) on wound healing of the guinea-pig dorsal skin, as well as on cultured fibroblasts, were examined. Gly-His-Lys-Cu and peptide I-Cu were tested in vivo. Hydroxyproline, proteins, DNA and semicarbazide-sensitive amine oxidase, with a high affinity for benzylamine, were measured, and the histology of the wounds was observed after staining with hematoxylin/eosin. Another set of wounds was treated in parallel with equivalent amounts of copper acetate. Gly-His-Lys-Cu and the analogues caused a decrease of the activity of semicarbazide-sensitive amine oxidase, with a high affinity for benzylamine, 4-8 days after surgery, followed by an increase on day 11 that was higher than in the control group. No significant difference was found between the two peptides. A slower reorganization of the skin and a delayed activation of fibroblasts are the main effects observed with these peptides-Cu complexes. Preliminary studies on cultured fibroblasts were monitored to see whether these peptides had a direct effect on fibroblasts. The products studied at a concentration of 10(-7) M, decreased cell reproduction and increased collagen expression. PMID:8836453

  11. Alkylamino derivatives of 4-aminomethylpyridine as inhibitors of copper-containing amine oxidases.

    Science.gov (United States)

    Bertini, Vincenzo; Buffoni, Franca; Ignesti, Giovanni; Picci, Nevio; Trombino, Sonia; Iemma, Francesca; Alfei, Silvana; Pocci, Marco; Lucchesini, Francesco; De Munno, Angela

    2005-02-10

    The first substratelike, reversible inhibitors of different copper amine oxidases (CAOs) with IC50 (M) as low as 2.0 x 10(-8) corresponding to derivatives of 4-aminomethylpyridine with alkoxy (1a-d), alkylthio (2a,b), and alkylamino (3a-e, 4a-j) groups in the positions 3 and 5 have been prepared and studied. The inhibitors 1a-d are active on benzylamine oxidase and semicarbazide-sensitive amine oxidase and are very selective with respect to diamine oxidase, lysyl oxidase, and monoamine oxidases. The inhibitors 2a,b are selective for benzylamine oxidase whereas 2a is also a new type of good substrate of diamine oxidase. The inhibitors 3a-e and 4a-j are substratelike, reversible, nonselective inhibitors of various CAOs including pea seedling amine oxidase and Hansenula polymorpha amine oxidase, whose enzymatic sites are known from X-ray structure determinations. The inhibitors 3b,c and 4b,c are excellent substratelike tools for studies correlating CAOs that afford crystals suitable for X-ray structure determinations with CAOs from mammals.

  12. Tandem hydrogenation and condensation of fluorinated α,β-unsaturated ketones with primary amines, catalyzed by nickel.

    Science.gov (United States)

    Castellanos-Blanco, Nahury; Flores-Alamo, Marcos; García, Juventino J

    2015-09-21

    A simple homogeneous catalytic system based on nickel phosphine complexes has been developed for the transfer hydrogenation and condensation of α,β-unsaturated ketones to yield saturated ones and saturated imines using primary amines as hydrogen donors. Thus, a wide range of fluorinated 1,5-diaryl-1,4-pentadiene-3-ones were allowed to react with substituted benzylamines in the presence of [(dippe)Ni(μ-H)]2 (dippe = 1,2-bis-(diisopropylphosphino)-ethane) using ethanol as a solvent at 180 °C to give the corresponding saturated carbonyl compounds; here hydrogenation of the C[double bond, length as m-dash]C bond was preferred over the C[double bond, length as m-dash]O bond. Under the same reaction conditions but using an excess of benzylamine, a tandem process is then favoured, starting also with the reduction of the C[double bond, length as m-dash]C bond followed by a nucleophilic addition of the primary amine to yield valuable saturated imines with good to excellent yields (62%-91%). PMID:26250992

  13. Imaging the serotonin transporter with positron emission tomography: initial human studies with [{sup 11}C]DAPP and [{sup 11}C]DASB

    Energy Technology Data Exchange (ETDEWEB)

    Houle, S.; Ginovart, N.; Hussey, D.; Meyer, J.H.; Wilson, A.A. [Vivian Rakoff PET Centre, Centre for Addiction and Mental Health and University of Toronto (Canada)

    2000-11-01

    Two novel radioligands, N,N-dimethyl-2-(2-amino-4-methoxyphenylthio)benzylamine (DAPP) and N,N-dimethyl-2-(2-amino-4-cyanophenylthio)benzylamine (DASB), were radiolabeled with carbon-11 and evaluated as in vivo probes of the serotonin transporter (SERT) using positron emission tomography (PET). Both compounds are highly selective, with nanomolar affinity for the serotonin transporter and micromolar affinity for the dopamine and norepinephrine transporters. Six volunteers were imaged twice, once with each of the two radioligands. Both ligands displayed very good brain penetration and selective retention in regions rich in serotonin reuptake sites. Both had similar brain uptake and kinetics, but the cyano analogue, [{sup 11}C]DASB, had a slightly higher brain penetration in all subjects. Plasma analysis revealed that both radiotracers were rapidly metabolized to give mainly hydrophilic species as determined by reverse-phase high-performance liquid chromatography. Inhibition of specific binding to the SERT was demonstrated in three additional subjects imaged with [{sup 11}C]DASB following an oral dose of the selective serotonin reuptake blocker citalopram. These preliminary studies indicate that both these substituted phenylthiobenzylamines have highly suitable characteristics for probing the serotonin reuptake system with PET in humans. (orig.)

  14. Synthesis and characterization of EADAM: a selective radioligand for mapping the brain serotonin transporters by positron emission tomography

    Energy Technology Data Exchange (ETDEWEB)

    Jarkas, Nachwa [Department of Radiology, Division of Radiological Sciences, Emory University, Atlanta, GA 30322 (United States); McConathy, Jonathan [Department of Radiology, Division of Radiological Sciences, Emory University, Atlanta, GA 30322 (United States); Department of Psychiatry and Behavior Sciences, Emory University, Atlanta, GA 30322 (United States); Votaw, John R. [Department of Radiology, Division of Radiological Sciences, Emory University, Atlanta, GA 30322 (United States); Voll, Ronald J. [Department of Radiology, Division of Radiological Sciences, Emory University, Atlanta, GA 30322 (United States); Malveaux, Eugene [Department of Radiology, Division of Radiological Sciences, Emory University, Atlanta, GA 30322 (United States); Camp, Vernon M. [Department of Radiology, Division of Radiological Sciences, Emory University, Atlanta, GA 30322 (United States); Williams, Larry [Department of Radiology, Division of Radiological Sciences, Emory University, Atlanta, GA 30322 (United States); Goodman, Robin R. [Department of Radiology, Division of Radiological Sciences, Emory University, Atlanta, GA 30322 (United States); Kilts, Clinton D. [Department of Psychiatry and Behavior Sciences, Emory University, Atlanta, GA 30322 (United States); Goodman, Mark M. [Department of Radiology, Division of Radiological Sciences, Emory University, Atlanta, GA 30322 (United States) and Department of Psychiatry and Behavior Sciences, Emory University, Atlanta, GA 30322 (United States)]. E-mail: mgoodma@emory.edu

    2005-01-01

    [{sup 11}C]N,N-Dimethyl-2-(2'-amino-4'-ethylphenylthio)benzylamine ([{sup 11}C]EADAM) was synthesized in the development of a serotonin transporter (SERT) imaging ligand for positron emission tomography (PET). The methods of ligand synthesis, results of in vitro characterization, {sup 11}C labeling and in vivo micro-PET imaging studies of [{sup 11}C]EADAM in cynomolgus monkey brain are described. {sup 11}C was introduced into N,N-dimethyl-2-(2'-amino-4'-ethylphenylthio)benzylamine () by alkylation of N-methyl-2-(2'-amino-4'-ethylphenylthio)benzylamine () in 32% radiochemical yield (end of bombardment [EOB], decay-corrected from [{sup 11}C]methyl iodide). Competition binding assays in cells stably expressing the transfected human dopamine transporter (DAT), SERT and norepinephrine transporter (NET) labeled with [{sup 3}H]WIN 35428 or [{sup 125}I]RTI-55, [{sup 3}H]citalopram and [{sup 3}H]nisoxetine, respectively, indicated the following order of SERT affinity: ADAM>EADAM>>fluvoxamine. The affinity of EADAM for DAT and NET was 500- and >1000-fold lower, respectively, than for SERT. Micro-PET brain imaging studies in a cynomolgus monkey demonstrated high [{sup 11}C]EADAM uptake in the striatum, thalamus and brainstem. [{sup 11}C]EADAM uptake in these brain regions peaked in less than 60 min following administration of [{sup 11}C]EADAM. The tissue-to-cerebellum ratios of the striatum, thalamus and brainstem were 1.67, 1.71 and 1.63, respectively, at 120 min postinjection of [{sup 11}C]EADAM. Analysis of monkey arterial plasma samples using high-pressure liquid chromatography determined there was no detectable formation of lipophilic radiolabeled metabolites capable of entering the brain. In a displacement experiment with citalopram in a cynomolgus monkey, radioactivity in the striatum, thalamus and brainstem was displaced 20-60 min after administration of citalopram. In a blocking experiment with citalopram in a cynomolgus monkey

  15. [Substrate-inhibitory analysis of monoamine oxidase from hepatopancreas of the octopus Bathypolypus arcticus].

    Science.gov (United States)

    Basova, I N; Iagodina, O V

    2012-01-01

    Study of the substrate-inhibitory specificity of mitochondrial monoamine oxidase (MAO) of hepatopancreas of the octopus Bathypolypus arcticus revealed distinctive peculiarities of catalytic properties of this enzyme. The studied enzyme, on one hand, like the classic MAO of homoiothermal animals, is able to deaminate tyramine, serotonin, benzylamine, tryptamine, beta-phenylethylamine, while, on the other hand, deaminates histamine and does not deaminate putrescine--classic substrates of diamine oxidase (DAO). Results of the substrate-inhibitory analysis with use of chlorgiline and deprenyl are indirect proofs of the existence in the octopus hepatopancreas of one molecular MAO form. Semicarbazide and pyronine G turned out to be weak irreversible inhibitors, four derivatives of acridine--irreversible inhibitors of the intermediate effectiveness with respect to the octopus hepatopancreas MAO; specificity of action of inhibitors at deamination of different substrates was equal.

  16. Electronic structure calculations toward new potentially AChE inhibitors

    Science.gov (United States)

    de Paula, A. A. N.; Martins, J. B. L.; Gargano, R.; dos Santos, M. L.; Romeiro, L. A. S.

    2007-10-01

    The main purpose of this study was the use of natural non-isoprenoid phenolic lipid of cashew nut shell liquid from Anacardium occidentale as lead material for generating new potentially candidates of acetylcholinesterase inhibitors. Therefore, we studied the electronic structure of 15 molecules derivatives from the cardanol using the following groups: methyl, acetyl, N, N-dimethylcarbamoyl, N, N-dimethylamine, N, N-diethylamine, piperidine, pyrrolidine, and N-benzylamine. The calculations were performed at RHF level using 6-31G, 6-31G(d), 6-31+G(d) and 6-311G(d,p) basis functions. Among the proposed compounds we found that the structures with substitution by acetyl, N, N-dimethylcarbamoyl, N, N-dimethylamine, and pyrrolidine groups were better correlated to rivastigmine indicating possible activity.

  17. Direct high-performance liquid chromatographic separation of the enantiomers of an aromatic amine and four aminoalcohols using polysaccharide chiral stationary phases and acidic additive.

    Science.gov (United States)

    Caccamese, Salvatore; Bianca, Salvatore; Carter, Guy T

    2007-08-01

    The HPLC enantiomeric separation of N-benzyl-alpha-methyl-benzylamine, phenylalaninol, tryptophanol, 2 (diphenylhydroxymethyl)pyrrolidine, and isoproterenol was accomplished in the normal-phase mode using two polysaccharide-derived chiral stationary phases (CSPs) and various n-hexane/2-propanol mobile phases with acidic (TFA) or basic (DEA) additive. The compounds were separated without any derivatization and separation factor range between 2.09 and 1.09 with resolution factor 3.4 and 0.4, respectively. The best separation of the enantiomers of the amine was achieved on amylose tris (3, 5-dimethylphenylcarbamate) CSP with TFA additive in the mobile phase; in acidic conditions, instead, the best enantioseparation of the aminoalcohols was achieved on cellulose tris (3, 5-dimethylphenilcarbamate). A long equilibration time of the CSP when switching from an undoped mobile phase to a doped one is required to obtain reproducible results. PMID:17568428

  18. Relationship between membrane fluidity and capping of receptors for concanavalin A.

    Science.gov (United States)

    Mak, W W; Wong, J T

    1980-12-01

    The activities of a range of phenylalaninol-related compounds on capping of concanavalin A and induction of rounding of Chinese hamster ovary tsHl cells, as well as on the fluidity of phosphatidylcholine-cholesterol (1:1) liposomes, have been examined. These compounds include phenylalaninol, histidinol, leucinol, benzyl alcohol, benzylamine, 2-phenylethanol, 2-phenylamine, 3-phenyl-1-propanol, 3-phenyl-1-propylamine, and 3-phenylpropionic acid. The results indicate a strong correlation between the capacities of these compounds to enhance fluidity and their capacities to inhibit capping of concanavalin A. The specificity of this correlation is suggested by the finding that both types of capacities are poorly correlated with the capacities of the various compounds to induce cell rounding. PMID:6265046

  19. Synthesis of Some N-Substituted Sulfonamides Derived from Moringine as Lipoxygenase Inhibitors

    Directory of Open Access Journals (Sweden)

    *M. A. Abbasi

    2014-12-01

    Full Text Available Sulfonamides belong to an emerging class having good inhibitory effects. In the present work, a series of N-substituted derivatives of N-benzyl-4-chlorobenzenesulfonamide have been synthesized. The reaction of moringine (benzylamine; 1 with 4-chlorobenzenesulfonyl chloride (2 in aqueous medium yielded the parent molecule, N-benzyl-4-chlorobenzenesulfonamide (3. Alkyl/aralkyl halides, 4a-m, were reacted with 3 in polar aprotic medium to produce N-substituted derivatives, 5a-m. These synthesized products were characterized by 1H-NMR, IR and EI-MS spectra and screened against lipoxygenase (LOX enzyme. These were found to be moderate inhibitors of this enzyme and could find their use as therapeutic agent for various inflammatory ailments.

  20. Meta-iodobenzylguanidine synthesis and labelling with iodine-131

    International Nuclear Information System (INIS)

    Meta-iodo-benzylguanidine (MIBG) synthesis is carried out through m-iodo benzylamine condensation and subsequent formation of the hemisulfate salt. The synthesized product is characterized and identified by IR spectroscopy and m.p. determination. Acute toxicity tests conducted in mice demonstrated that the synthesized product is not toxic. MIBG hemisulfate labelling methods with I-131 is carried out by nucleophilic isotopic exchange; the reaction is catalyzed with cooper sulfate in the presence of ammonium sulfate at temperatures ranging between 140 and 150 oC . Biological distribution tests in wistar rats present an average value of 1,54% of injected dose/organ gram in suprarenal glands. These values show promise for the application of this radiopharmaceutical in radiodiagnosis of suprarenal tumors and procurement of adrenal medulla, myocardium and salivary gland images

  1. Temperament, character and serotonin activity in the human brain

    DEFF Research Database (Denmark)

    Tuominen, L; Salo, J; Hirvonen, J;

    2013-01-01

    The psychobiological model of personality by Cloninger and colleagues originally hypothesized that interindividual variability in the temperament dimension 'harm avoidance' (HA) is explained by differences in the activity of the brain serotonin system. We assessed brain serotonin transporter (5-HTT......-existing Temperament and Character Inventory (TCI) scores. A total of 22 subjects free of psychiatric and somatic disorders were included in the matched high- and low-HA groups. The main outcome measure was regional 5-HTT binding potential (BPND) in high- and low-HA groups estimated with PET and [11C]N,N-dimethyl-2......-(2-amino-4-methylphenylthio)benzylamine ([11C]MADAM). In secondary analyses, 5-HTT BPND was correlated with other TCI dimensions....

  2. Efficacy and safety of butenafine in superficial dermatophytoses (tinea pedis, tinea cruris, tinea corporis).

    Science.gov (United States)

    Saple, D G; Amar, A K; Ravichandran, G; Korde, K M; Desai, A

    2001-05-01

    Superficial dermatophytoses of skin are very common infections seen in clinical practice. Besides topical imidazoles, triazoles and allylamines, topical butenafine (a benzylamine derivative) is a novel agent with broad antifungal activity. One hundred and eleven patients with tinea infections were enrolled in this multicentric, randomised, single-blind non-comparative study, which involved application of butenafine (1%) cream in tinea pedis (4 weeks) and tinea cruris and tinea corporis (2 weeks) cases. The results showed that butenafine causes rapid resolution of signs and symptoms (erythema itching, burning, crusting, scaling, etc), with good patient and physician acceptability of treatment. The broader spectrum fungicidal activity and better drug retention in superficial skin layers may be responsible for this beneficial effect. PMID:11676116

  3. Synthesis of bicyclic alkaloids from the iridoid antirrhinoside

    DEFF Research Database (Denmark)

    Frederiksen, Signe Maria

    The present thesis describes the isolation of the iridoid glucoside antirrhinoside from Antirrhinum majus, and the approaches made towards its transformation into analogues of biologically active compounds, with special interest in syntheses of bicyclic alkaloids.A synthetic piperidine monoterpene...... alkaloid was prepared from antirrhinoside by means of an enzymatic cleavage to afford the aglucone, followed by a double reductive amination with benzylamine hydrochloride and sodium cyanoborohydride. The resulting piperidine was modified by opening of the epoxide on the cyclopropane ring by azide...... strategy was therefore abandoned.A one-pot reaction involving ozonolysis and subsequent reduction of the 5,6-O-isopropylidene-2',3',4',6'-tetra-O-acetyl antirrhinoside yielded a diol, which was considered a potential intermediate in the preparation of enantiopure 3-azabicyclo[3.3.0]octane alkaloids...

  4. σ-Hole bonding in 15N-labeled N-Benzyl- N-(4-iodo-tetrafluorobenzyl)-amine: Synthesis, crystal structure and solid-state structure calculations

    Science.gov (United States)

    Raouafi, Noureddine; Mayer, Peter; Boujlel, Khaled; Schöllhorn, Bernd

    2011-03-01

    Reductive amination of 4-iodo-tetrafluorobenzaldehyde 2 and 15N-enriched benzylamine yielded the title compound 1. Single crystal X-ray diffraction (XRD) revealed that the product crystallizes in the triclinic system of the P-1 space group. The structure is consisting of infinite one-dimensional chair like chains, based on intermolecular N···I halogen bonding. Only intermolecular weak hydrogen bonds N sbnd H···F and C sbnd H···F are observed. Representative XRD data have been compared to the results of theoretical semi-empirical calculations in the solid-state obtained using the PM6 method. Charges of I, N and F atoms are calculated from Natural Bond Orbital (NBO) and Electrostatic Potential Surface maps have been estimated by applying second-order Møller-Plesset (MP2) perturbation theory, and confirmed clearly the assumption of σ-hole bonding formation.

  5. Utilization of Active Ni to Fabricate Pt-Ni Nanoframe/NiAl Layered Double Hydroxide Multifunctional Catalyst through In Situ Precipitation.

    Science.gov (United States)

    Ren, Fumin; Wang, Zheng; Luo, Liangfeng; Lu, Haiyuan; Zhou, Gang; Huang, Weixin; Hong, Xun; Wu, Yuen; Li, Yadong

    2015-09-14

    Integration of different active sites into metallic catalysts, which may impart new properties and functionalities, is desirable yet challenging. Herein, a novel dealloying strategy is demonstrated to decorate nickel-aluminum layered double hydroxide (NiAl-LDH) onto a Pt-Ni alloy surface. The incorporation of chemical etching of Pt-Ni alloy and in situ precipitation of LDH are studied by joint experimental and theoretical efforts. The initial Ni-rich Pt-Ni octahedra transform by interior erosion into Pt3 Ni nanoframes with enlarged surface areas. Furthermore, owing to the basic active sites of the decorated LDH together with the metallic sites of Pt3 Ni, the resulting Pt-Ni nanoframe/NiAl-LDH composites exhibit excellent catalytic activity and selectivity in the dehydrogenation of benzylamine and hydrogenation of furfural. PMID:26241390

  6. Synthesis of phenanthridines via palladium-catalyzed picolinamide-directed sequential C–H functionalization

    Directory of Open Access Journals (Sweden)

    Ryan Pearson

    2013-05-01

    Full Text Available We report a new synthesis of phenanthridines based on palladium-catalyzed picolinamide-directed sequential C–H functionalization reactions starting from readily available benzylamine and aryl iodide precursors. Under the catalysis of Pd(OAc2, the ortho-C–H bond of benzylpicolinamides is first arylated with an aryl iodide. The resulting biaryl compound is then subjected to palladium-catalyzed picolinamide-directed intramolecular dehydrogenative C–H amination with PhI(OAc2 oxidant to form the corresponding cyclized dihydrophenanthridines. The benzylic position of these dihydrophenanthridines could be further oxidized with Cu(OAc2, removing the picolinamide group and providing phenathridine products. The cyclization and oxidation could be carried out in a single step and afford phenathridines in moderate to good yields.

  7. Catalytic Synthesis of Nitriles in Continuous Flow

    DEFF Research Database (Denmark)

    Nordvang, Emily Catherine

    The objective of this thesis is to report the development of a new, alternative process for the flexible production of nitrile compounds in continuous flow. Nitriles are an important class of compounds that find applications as solvents, chemical intermediates and pharmaceutical compounds......, alternative path to acetonitrile from ethanol via the oxidative dehydrogenation of ethylamine. The catalytic activity and product ratios of the batch and continuous flow reactions are compared and the effect of reaction conditions on the reaction is investigated. The effects of ammonia in the reaction...... dehydrogenation of ethylamine and post-reaction purging.Chapter 4 outlines the application of RuO2/Al2O3 catalysts to the oxidative dehydrogenation of benzylamine in air, utilizing a new reaction setup. Again, batch and continuous flow reactions are compared and the effects of reaction conditions, ammonia...

  8. Synthesis of Novel Cellulose Carbamates Possessing Terminal Amino Groups and Their Bioactivity.

    Science.gov (United States)

    Ganske, Kristin; Wiegand, Cornelia; Hipler, Uta-Christina; Heinze, Thomas

    2016-03-01

    Cellulose phenyl carbonates are an excellent platform to synthesize a broad variety of soluble and functional cellulose carbamates. In this study, the synthesis of cellulose carbamates with terminal amino groups, namely ω-aminoethylcellulose- and ω-aminoethyl-p-aminobenzyl-cellulose carbamate, is discussed. The products are well soluble and their structures can be clearly described by NMR spectroscopy. The cellulose carbamates exhibit a bactericide and fungicide activity in vitro. The ω-aminoethylcellulose carbamate possesses a strong activity against Candida albicans and Staphylococcus aureus (IC50 of 0.02 mg mL(-1) and 0.05 mg mL(-1)). The antimicrobial activity and cytotoxicity can be improved by p-amino-benzylamine (ABA) as an additional substituent. The mixed cellulose carbamate exhibits a high biocompatibility (LC50 of 3.18 mg mL(-1)) and forms films on cotton and PES, which exhibit a strong activity against S. aureus and Klebsiella pneumoniae. PMID:26612063

  9. Synthesis of 7-Deoxypancratistatin from Carbohydrates by the Use of Olefin Metathesis

    DEFF Research Database (Denmark)

    Håkansson, Anders Eckart; Palmelund, Anders; Holm, H.;

    2006-01-01

    -deoxy-5-iodo-D-ribofuranoside in the presence of zinc metal. The first strategy involves a total of only 13 steps from D-ribose and piperonal, but suffers from a low yield in the zinc-mediated reaction between ribofuranoside 9, benzylamine, and bromide 7. The second strategy involves a total of 18 steps......The stereocontrolled synthesis of (+)-7-deoxypancratistatin is described. The convergent synthesis has been achieved by two different strategies, both of which commence from a pentose and piperonal. The latter is converted into allylic bromide 7, which is then coupled with a protected methyl 5...... from D-xylose and piperonal. The former is converted into ribofuranoside 28, which is coupled with bromide 7 in the presence of zinc, and this is followed by ring-closing olefin metathesis. Subsequent Overman rearrangement, dihydroxylation, and deprotection then affords the natural product....

  10. Experimental and theoretical approaches to [1,5]-prototropic generation of an azomethine ylide and a 1,3-dipolar cycloaddition for novel spiropyrrolidine oxindoles synthesis

    Science.gov (United States)

    Sarrafi, Yaghoub; Hamzehloueian, Mahshid; Alimohammadi, Kamal; Yeganegi, Saeid

    2012-12-01

    A series of spiropyrrolidine oxindoles was synthesized via a multicomponent 1,3-dipolar cycloaddition reaction of isatin, benzylamine and chalcone derivatives. The regio- and stereochemistry of the products were established by single crystal X-ray structure and spectroscopic techniques. The molecular mechanism of this cycloaddition has been investigated by means of a density functional theory (DFT) method. The energy path in preparing the azomethine ylide via a [1,5]-H shift in an iminium ion was evaluated. The regio- and stereoselectivity were explained on the basis of transition states stabilities, global and local reactivity indices of the reactants. The cycloaddition has been assumed to take place through one-step pathway in which two C-C bonds are formed in a nonsynchronous way.

  11. Multipurpose Nature of Rapid Covalent Functionalization on Carbon Nanotubes.

    Science.gov (United States)

    González-Domínguez, Jose M; Santidrián, Ana; Criado, Alejandro; Hadad, Caroline; Kalbáč, Martin; Da Ros, Tatiana

    2015-12-14

    In the vast field of functionalization routes to carbon nanoforms, the fulfillment of such critical requirements as quick and nonharsh methods, good dispersibility, introduction of reactive groups, short reaction time, and low cost can be quite challenging. Traditional thermally induced diazonium chemistry on single-walled carbon nanotubes (SWCNTs) is revisited by using commercial anilines and providing useful insight into the versatility of this approach. Functionalized SWCNTs with multiple controllable features, such as degree (and ratio) of coverage, orthogonalization, doping, and high water dispersibility, are obtained by introducing benzenesulfonic acid and benzylamine moieties. The scenario opens up an avenue to address relevant applications in which most functionalization methods could not be applied in a straightforward way. PMID:26564100

  12. Preparation of copper sulphide clusters in organic-inorganic composites of Langmuir-Blodgett films of amphiphilic Schiff bases

    Indian Academy of Sciences (India)

    G Hemakanthi; Aruna Dhathathreyan; T Ramasami; D Möbius

    2001-04-01

    Copper sulphide clusters were prepared in Langmuir-Blodgett films of copper complexes of amphiphilic Schiff bases-3,4-dimethoxy-N-benzylidene hexadeylamine (I) and 3,4-dimethoxy-N-benzylidene-4 -(hexadecylamino) benzylamine (II) The clusters obtained were analysed using UV-Vis spectroscopy and optical microscopy. Brewster angle microscopic studies on monolayers of I and II at air/water interface showed formation of needle-like domains which seem to cluster faster in I than in II. Atomic force microscopy (AFM) studies also showed fairly uniform sized clusters in II whereas in the case of I they seem to show varying sizes. From the results it is concluded that -elongation in the polar head groups leads to controlled cluster sizes in compound II as compared to those in compound I.

  13. Cauliflower-like CuI nanostructures: Green synthesis and applications as catalyst and adsorbent

    Energy Technology Data Exchange (ETDEWEB)

    Jiang Yi [College of Chemistry and Environmental Science, Henan Normal University, Xinxiang, Henan 453007 (China); Gao Shuyan, E-mail: shuyangao@htu.cn [College of Chemistry and Environmental Science, Henan Normal University, Xinxiang, Henan 453007 (China); Li Zhengdao; Jia Xiaoxia; Chen Yanli [College of Chemistry and Environmental Science, Henan Normal University, Xinxiang, Henan 453007 (China)

    2011-08-15

    Highlights: > In this study we report a green, environment-friendly, efficient, and direct one-step process for the preparation of CuI cauliflower. > The as-formed CuI cauliflower shows excellent catalytic activity for coupling reaction between benzylamine and iodobenzene. > The cauliflower-like CuI nanostructures have been successfully demonstrated as adsorbent for Cd (II) with high removal capacity. > To the best of our knowledge, it is the first report that nanostructured CuI acts as catalyst for coupling reaction and adsorbent for heavy metal ion. > It is also a good example for the organic combination of green chemistry and functional materials. - Abstract: Cauliflower-like CuI nanostructures is realized by an ampicillin-assisted clean, nontoxic, environmentally friendly synthesis strategy at room temperature. The morphology, composition, and phase structure of as-prepared powders were characterized by field emission scanning electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The results show that ampicillin plays dual roles, reducing and morphology-directing agents, in the formation of the products. A possible growth mechanism of the cauliflower-like CuI nanostructures is tentatively proposed. The preliminary investigations show that the cauliflower-like CuI structure not only exhibits high catalytic activity with respect to coupling reaction between benzylamine and iodobenzene but also possesses high removal capacity for Cd (II), which may be ascribed to the high specific surface area of the special configuration. To the best of our knowledge, it is the first report that cauliflower-like CuI nanoparticles act as catalyst for coupling reaction and adsorbent for heavy metal ion.

  14. Reactions of copper(II)-phenol systems with O2: models for TPQ biosynthesis in copper amine oxidases.

    Science.gov (United States)

    Tabuchi, Kae; Ertem, Mehmed Z; Sugimoto, Hideki; Kunishita, Atsushi; Tano, Tetsuro; Fujieda, Nobutaka; Cramer, Christopher J; Itoh, Shinobu

    2011-03-01

    Copper(II) complexes supported by a series of phenol-containing bis(pyridin-2-ylmethyl)amine N(3) ligands (denoted as L(o)H, L(m)H, and L(p)H) have been synthesized, and their O(2) reactivity has been examined in detail to gain mechanistic insights into the biosynthesis of the TPQ cofactor (2,4,5-trihydroxyphenylalaninequinone, TOPA quinone) in copper-containing amine oxidases. The copper(II) complex of L(o)H (ortho-phenol derivative) involves a direct phenolate to copper(II) coordination and exhibits almost no reactivity toward O(2) at 60 °C in CH(3)OH. On the other hand, the copper(II) complex of L(m)H (meta-phenol derivative), which does not involve direct coordinative interaction between the phenol moiety and the copper(II) ion, reacts with O(2) in the presence of triethylamine as a base to give a methoxy-substituted para-quinone derivative under the same conditions. The product structure has been established by detailed nuclear magnetic resonance (NMR), infrared (IR) spectroscopy, and electrospray ionization-mass spectroscopy (ESI-MS) (including (18)O-labeling experiment) analyses. Density functional theory predicts that the reaction involves (i) intramolecular electron transfer from the deprotonated phenol (phenolate) to copper(II) to generate a copper(I)-phenoxyl radical; (ii) the addition of O(2) to this intermediate, resulting in an end-on copper(II) superoxide; (iii) electrophilic substitution of the phenolic radical to give a copper(II)-alkylperoxo intermediate; (iv) O-O bond cleavage concomitant with a proton migration, giving a para-quinone derivative; and (v) Michael addition of methoxide from copper(II) to the para-quinone ring and subsequent O(2) oxidation. This reaction sequence is similar to that proposed for the biosynthetic pathway leading to the TPQ cofactor in the enzymatic system. The generated para-quinone derivative can act as a turnover catalyst for aerobic oxidation of benzylamine to N-benzylidene benzylamine. Another type of copper

  15. Metal-organic frameworks from chiral square-pyramidal copper(II) complexes: Enantiospecific inclusion and perfectly polar alignment of guest and host molecules

    International Nuclear Information System (INIS)

    The physical properties of [CuL12(H2O)] (1) and [CuL22(H2O)] (2) and preparation and crystal structures of the inclusion compounds 1.(P)-C2H4Br2, 2.(M)-C2H4Br2, 1.CH3CN and 2.CH3CN are described. HL1 and HL2 (H represents the dissociable phenolic proton) are the N,O-donor chiral reduced Schiff bases N-(2-hydroxy-5-nitrobenzyl)-(R)-α-methyl-benzylamine and N-(2-hydroxy-5-nitrobenzyl)-(S)-α-methylbenzylamine, respectively. All the compounds crystallize in the non-centrosymmetric space group C2. In the crystal lattice, the host [CuL n2(H2O)] (1 and 2) molecules connected by O-H...O and C-H...O interactions form perfectly polar two-dimensional networks. In these chiral and polar host frameworks, enantiospecific inclusion with polar ordering of the right-handed (P) and the left-handed (M) gauche form of 1,2-dibromoethane as well as polar alignment of acetonitrile molecules are observed. The host and guest molecules are linked by C-H...O interactions. The O-atoms of the nitro substituent on the ligands of 1 and 2 act as the acceptors in all these intermolecular O-H...O and C-H...O interactions. The structures reported in this work provide rare examples of enantiospecific trapping of the chiral rotamers of 1,2-dibromoethane as well as perfectly polar alignment of both guest and host molecules. - Graphical abstract: The square-pyramidal Cu(II) complexes [CuL n2(H2O)] with the bidentate HL n (HL1=N-(2-hydroxy-5-nitrobenzyl)-(R)-α-methyl-benzylamine and HL2=N-(2-hydroxy-5-nitrobenzyl)-(S)-α-methylbenzylamine) form 1:1 host-guest compounds with Br(CH2)2Br and CH3CN. The X-ray structures of these species reveal the enantiospecific confinement of the chiral rotamers of Br(CH2)2Br and perfectly polar ordering of both host and guest molecules in the crystal lattice. The figure shows the polar alignments of (a) [CuL12(H2O)].(P)-C2H4Br2 and (b) [CuL22(H2O)].CH3CN

  16. Sorption of structurally different ionized pharmaceutical and illicit drugs to a mixed-mode coated microsampler.

    Science.gov (United States)

    Peltenburg, Hester; Timmer, Niels; Bosman, Ingrid J; Hermens, Joop L M; Droge, Steven T J

    2016-05-20

    The mixed-mode (C18/strong cation exchange-SCX) solid-phase microextraction (SPME) fiber has recently been shown to have increased sensitivity for ionic compounds compared to more conventional sampler coatings such as polyacrylate and polydimethylsiloxane (PDMS). However, data for structurally diverse compounds to this (prototype) sampler coating are too limited to define its structural limitations. We determined C18/SCX fiber partitioning coefficients of nineteen cationic structures without hydrogen bonding capacity besides the charged group, stretching over a wide hydrophobicity range (including amphetamine, amitriptyline, promazine, chlorpromazine, triflupromazine, difenzoquat), and eight basic pharmaceutical and illicit drugs (pKa>8.86) with additional hydrogen bonding moieties (MDMA, atenolol, alprenolol, metoprolol, morphine, nicotine, tramadol, verapamil). In addition, sorption data for three neutral benzodiazepines (diazepam, temazepam, and oxazepam) and the anionic NSAID diclofenac were collected to determine the efficiency to sample non-basic drugs. All tested compounds showed nonlinear isotherms above 1mmol/L coating, and linear isotherms below 1mmol/L. The affinity for C18/SCX-SPME for tested organic cations without Hbond capacities increased with longer alkyl chains, ranging from logarithmic fiber-water distribution coefficients (log Dfw) of 1.8 (benzylamine) to 5.8 (triflupromazine). Amines smaller than benzylamine may thus have limited detection levels, while cationic surfactants with alkyl chain lengths >12 carbon atoms may sorb too strong to the C18/SCX sampler which hampers calibration of the fiber-water relationship in the linear range. The log Dfw for these simple cation structures closely correlates with the octanol-water partition coefficient of the neutral form (Kow,N), and decreases with increased branching and presence of multiple aromatic rings. Oxygen moieties in organic cations decreased the affinity for C18/SCX-SPME. Log Dfw values of

  17. Optical storage in azobenzene-containing epoxy polymers processed as Langmuir Blodgett films

    Energy Technology Data Exchange (ETDEWEB)

    Fernández, Raquel; Mondragon, Iñaki [‘Materials - Technologies’ Group, Department of Chemical and Environmental Engineering, Polytechnic School, Universidad País Vasco/Euskal Herriko Unibertsitatea, Pza Europa 1, 20018 Donostia-San Sebastián (Spain); Sanfelice, Rafaela C.; Pavinatto, Felippe J.; Oliveira, Osvaldo N. [Instituto de Física de São Carlos, Universidade de São Paulo, Av. Trabalhador São Carlense, 400, Centro, CEP 13560-970, São Carlos (Brazil); Oyanguren, Patricia [Institute of Materials Science and Technology (INTEMA), University of Mar del Plata and National Research Council (CONICET), J. B. Justo 4302, 7600 Mar del Plata (Argentina); Galante, María J., E-mail: galant@fi.mdp.edu.ar [Institute of Materials Science and Technology (INTEMA), University of Mar del Plata and National Research Council (CONICET), J. B. Justo 4302, 7600 Mar del Plata (Argentina)

    2013-04-01

    In this study, azocopolymers containing different main-chain segments have been synthesized with diglycidyl ether of bisphenol A (DGEBA, DER 332, n = 0.03) and the azochromophore Disperse Orange 3 (DO3) cured with two monoamines, viz. benzylamine (BA) and m-toluidine (MT). The photoinduced birefringence was investigated in films produced with these azopolymers using the spin coating (SC) and Langmuir Blodgett (LB) techniques. In the LB films, birefringence increased with the content of azochromophore and the film thickness, as expected. The nanostructured nature of the LB films led to an enhanced birefringence and faster dynamics in the writing process, compared to the SC films. In summary, the combination of azocopolymers and the LB method may allow materials with tuned properties for various optical applications, including in biological systems were photoisomerization may be used to trigger actions such as drug delivery. Highlights: ► Langmuir Blodgett (LB) films of epoxy-based azopolymers were obtained and analyzed. ► Optical properties of LB and spin coated (SC) films were compared. ► Azo content, structure, laser power and number of layers were main factors studied. ► LB films had larger free volume for the azobenzenes isomerization than SC. ► LB films led to higher birefringence and faster dynamics compared to SC.

  18. Electrochemical impedance study on the corrosion of Al-Pure in hydrochloric acid solution using Schiff bases

    Indian Academy of Sciences (India)

    A S Patel; V A Panchal; N K Shah

    2012-04-01

    The inhibition effect of newly synthesized Schiff bases -benzylidene benzylamine (A) and benzenemethanamine--methyl--(phenylmethylene) (B) on the corrosion behaviour of Al-Pure in 1.0 M HCl was studied using galvanostatic polarization and electrochemical impedance spectroscopy (EIS) and adsorption studies. The effects of inhibitor concentration, temperature and surface coverage are investigated. The effect of inhibitor concentration and other parameters are evaluated for different inhibitor concentrations and the probable mechanism was also proposed. The results show that (A) and (B) possess excellent inhibiting effect for the corrosion of Al-Pure and the inhibitors act as mixed type inhibitors. The inhibitors do not affect the mechanism of the electrode processes and inhibit corrosion by blocking the reaction sites. The high inhibition efficiency of (A) and (B) were due to the adsorption of inhibitor molecules on the metal surface. The decrease of surface area available for electrode reactions to take place is due to the formation of a protective film. Activation energy and free energy of adsorption have been calculated.

  19. Hydrogen peroxide-induced changes in intracellular pH of guard cells precede stomatal closure

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Epidermal bioassay demonstrated that benzylamine,a membrane-permeable weak base,can mimick hydrogen peroxide (H2O2) to induce stomatal closure,and butyric acid,a membrane-permeable weak acid,can partly abolish the H2O2-induced stomatal closure.Confocal pH mapping with the probe 5-(and-6)-carboxy seminaphthorhodafluor-1-acetoxymethylester (SNARF-1-AM) revealed that H2O2 leads to rapid changes in cytoplasmic and vacuolar pH in guard cells of Vicia faba L,i.e.alkalinization of cytoplasmic areas occur red in parallel with a decrease of the vacuolar pH,and that butyric acid pretreatment can abolish alkalinization of cytoplasmic areas and acidification of vacuolar areas of guard cells challenged with H2O2.These results imply that the alkalinization of cytoplasm via efflux of cytosol protons into the vacuole in guard cells challenged with H2O2 is important at an early stage in the signal cascade leading to stomatal closure.

  20. 1,5-二取代六氢三嗪-2-N-硝基亚胺的合成和杀虫活性的测定%Synthesis and Insecticidal Activities of 1,5-Disubstituted-hexahydrotriazine-2-N-nitroimines

    Institute of Scientific and Technical Information of China (English)

    薛思佳; 马旭波; 步洪飞

    2011-01-01

    以S-甲基-N-硝基异硫脲、取代苄胺为原料,依次经过亲核取代反应,Mannich反应合成了12个未见文献报道的1,5-二取代六氢三嗪-2-N-硝基亚胺(2a~21),结构经1H NMR,IR和元素分析确证.初步的杀虫活性测试表明,该类化合物在500mg/L时对稻飞虱具有较好的杀虫活性.%Twelve novel 1,5-disubstituted-hexahydrotriazine-2-N-nitroimines (2a~2l) were synthesized with N-nitro-S-methylisothiourea and substituted benzylamines as raw materials via nucleophilic substitution and Manich reactions in turn.Their structures were elucidated and confirmed by 1H NMR, IR spectra and elemental analysis.The preliminary insecticidal activity tests indicated that all the target compounds have preferable insecticidal activity at the concentration of 500 mg/L.

  1. Biocatalytic Behaviour of Immobilized Rhizopus oryzae Lipase in the 1,3-Selective Ethanolysis of Sunflower Oil to Obtain a Biofuel Similar to Biodiesel

    Directory of Open Access Journals (Sweden)

    Carlos Luna

    2014-08-01

    Full Text Available A new biofuel similar to biodiesel was obtained in the 1,3-selective transesterification reaction of sunflower oil with ethanol using as biocatalyst a Rhizopus oryzae lipase (ROL immobilized on Sepiolite, an inorganic support. The studied lipase was a low cost powdered enzyme preparation, Biolipase-R, from Biocon-Spain, a multipurpose additive used in food industry. In this respect, it is developed a study to optimize the immobilization procedure of these lipases on Sepiolite. Covalent immobilization was achieved by the development of an inorganic-organic hybrid linker formed by a functionalized hydrocarbon chain with a pendant benzaldehyde, bonded to the AlPO4 support surface. Thus, the covalent immobilization of lipases on amorphous AlPO4/sepiolite (20/80 wt % support was evaluated by using two different linkers (p-hydroxybenzaldehyde and benzylamine-terephthalic aldehyde, respectively. Besides, the catalytic behavior of lipases after physical adsorption on the demineralized sepiolite  was also evaluated. Obtained results indicated that covalent immobilization with the p-hydroxybenzaldehyde linker gave the best biocatalytic behavior. Thus, this covalently immobilized lipase showed a remarkable stability as well as an excellent capacity of reutilization (more than five successive reuses without a significant loss of its initial catalytic activity. This could allow a more efficient fabrication of biodiesel minimizing the glycerol waste production.

  2. Benzylammonium Thermometer Ions: Internal Energies of Ions Formed by Low Temperature Plasma and Atmospheric Pressure Chemical Ionization

    Science.gov (United States)

    Stephens, Edward R.; Dumlao, Morphy; Xiao, Dan; Zhang, Daming; Donald, William A.

    2015-12-01

    The extent of internal energy deposition upon ion formation by low temperature plasma and atmospheric pressure chemical ionization was investigated using novel benzylammonium thermometer ions. C-N heterolytic bond dissociation enthalpies of nine 4-substituted benzylammoniums were calculated using CAM-B3LYP/6-311++G(d,p), which was significantly more accurate than B3LYP/6-311++G(d,p), MP2/6-311++G(d,p), and CBS-QB3 for calculating the enthalpies of 20 heterolytic dissociation reactions that were used to benchmark theory. All 4-substituted benzylammonium thermometer ions fragmented by a single pathway with comparable dissociation entropies, except 4-nitrobenzylammonium. Overall, the extent of energy deposition into ions formed by low temperature plasma was significantly lower than those formed by atmospheric pressure chemical ionization under these conditions. Because benzylamines are volatile, this new suite of thermometer ions should be useful for investigating the extent of internal energy deposition during ion formation for a wide range of ionization methods, including plasma, spray and laser desorption-based techniques.

  3. Synthesis of A Series of Substituted 2-Amino-2′-Hydroxy-1,1′-Binaphthyl Compounds Catalyzed by Copper-Amine Complex%铜胺络合物催化合成取代2-氨基-2′-羟基-1,1′-联萘类化合物

    Institute of Scientific and Technical Information of China (English)

    陈之朋; 刘叔文

    2015-01-01

    A serious of substituted NOBIN compounds were synthesized from substituted 2-naphthol and 2-naphthylamine in methanol solvent at room temperature,using the CuCl2 ·2H2 O /benzylamine complex with molar ratio of 1∶4 as a catalyst.The product with mediate yields was purified by precipitation.The chemical structure was characterized using NMR spectroscopy and FAB-MS analysis.%采用 CuCl2·2H2 O 和苄胺(摩尔比为1∶4)的络合物作为氧化偶合试剂,甲醇作溶剂,室温下以取代2-萘酚与2-萘胺为原料进行氧化偶合反应,以中等产率得到一批结构新颖的含取代基的 NOBIN 类似物,目标产物以沉淀析出,反应后处理简单。产物结构经核磁、质谱确证。

  4. Synthesis and in vitro cytotoxicity of novel C-12 substituted-14-deoxy-andrographolide derivatives as potent anti-cancer agents.

    Science.gov (United States)

    Kandanur, Sai Giridhar Sarma; Golakoti, Nageswara Rao; Nanduri, Srinivas

    2015-12-15

    Andrographolide, the major labdane diterpenoid from Andrographis paniculata has been reported to be cytotoxic against various cancer cells in vitro. Our research efforts led to the discovery of novel 12-phenyl thio and 12-aryl amino-14-deoxy-andrographolide derivatives (III q and III r) with potent cytotoxic activity, 12-benzyl amino-14-deoxy-andrographolide analogues showing broad range of cytotoxic activity against most of the cell lines and 12-alkyl amino-14-deoxy-andrographolide derivatives being selective to few cell lines (PC-3 and HOP-92), when the selected analogues were evaluated against 60 human cancer cell line panel at National Cancer Institute (N.C.I.), USA. The SAR (structure activity relationship) studies demonstrated potent activity for the compounds containing the following functionalities at C-12: substituted aryl amino/phenyl thio>benzylamine>alkyl amine. The significant cytotoxic activity observed for compounds III q and III r suggest that these could serve as templates for further optimization. PMID:26561364

  5. Volumetric Behavior of Binary Mixtures of Alkoxyethanols and Some Selected Amines at 298.15 K

    Directory of Open Access Journals (Sweden)

    Ayasen Jermaine Kemeakegha

    2015-01-01

    Full Text Available Densities of binary mixtures of 2-methoxyethanol (2-MeO-EtOH and 2-ethoxyethanol (2-EtO-EtOH with hexylamine (HLA, diethylamine (DEA, triethylamine (TEA, tert-butylamine (TBA, aniline (ANL, and benzylamine (BLA have been determined at varying compositions of the alkoxyalkanols at 298.15 K. The excess molar volumes, VE, of the binary mixtures were calculated from the experimental density data of the mixtures and the component single solvents. The calculated excess molar volumes were fitted into the Redlich-Kister polynomial to obtain the fitting coefficients and standard deviations. The excess molar volumes of the binary mixtures of all the solvent systems investigated were negative over the entire range of the solvents composition. The negative values were attributed to stronger hydrogen bond formations between the unlike molecules of mixtures than those between the like molecules of the pure components. The magnitude of the excess molar volumes of the binary mixtures of 2-methoxyethanol and the aliphatic amines were in the order TBA > TEA > DEA > HEA. For the two aromatic amines, the magnitudes were in the order BLA > ANL. For binary mixtures of the amines and 2-ethoxyethanol, the magnitudes were in the order DEA > TEA > TBA > HEA at compositions where the mole fraction of 2-EtO-EtOH was ≤0.5 and TBA > TEA > DEA > HEA above 0.5 mole fraction of 2-EtO-EtOH.

  6. Lewis basicity, adhesion thermodynamic work and coordinating ability on aminated silicon surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Sánchez, M. Alejandra [Escuela de Química, Universidad de Costa Rica, San José 2060 (Costa Rica); Centro de Energía Química y Electroquímica (CELEQ), Universidad de Costa Rica, San José 2060 (Costa Rica); Paniagua, Sergio A. [School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, GA 30332-0400 (United States); Borge, Ignacio [Escuela de Química, Universidad de Costa Rica, San José 2060 (Costa Rica); Centro de Energía Química y Electroquímica (CELEQ), Universidad de Costa Rica, San José 2060 (Costa Rica); Viales, Christian [Escuela de Química, Universidad de Costa Rica, San José 2060 (Costa Rica); Montero, Mavis L., E-mail: mavis.montero@ucr.ac.cr [Escuela de Química, Universidad de Costa Rica, San José 2060 (Costa Rica); Centro de Energía Química y Electroquímica (CELEQ), Universidad de Costa Rica, San José 2060 (Costa Rica)

    2014-10-30

    Highlights: • Silicon(1 0 0) surfaces with diamines followed by anchoring of copper complexes over the diamine layer, an approach that could be used for advanced functionalization of semiconducting surfaces. • Lewis basicity (using Fowkes–van Oss–Chaudhury–Good surface tension model) and adhesion thermodynamic work (using chemical force microscopy) were determined. • Higher basicity and thermodynamic work correlate with selective copper acetate monolayer grow. The cyclic voltammetry studies confirm the confined copper redox activity. - Abstract: Silicon(1 0 0) surfaces have been modified with three different amines (aniline, benzylamine and dodecylamine) and diamines (4-aminopyridine, 4-aminomethylpyridine, 1,12-dodecyldiamine). The surface energy was measured by contact angle technique. For Si-diamine surfaces, Lewis basicity (using Fowkes–van Oss–Chaudhury–Good surface tension model) and adhesion thermodynamic work (using chemical force microscopy) were determined. We related these data, the amine/diamine nature and their geometry on the surface (via DFT calculations) with the consequent ability to coordinate copper(II) acetate. Finally, copper(II) acetate monolayers behavior was studied by cyclic voltammetry.

  7. Raman and XPS analyses of pristine and annealed N-doped double-walled carbon nanotubes

    CERN Document Server

    Shi, Lei; Domanov, Oleg; Rohringer, Philip; Ayala, Paola; Pichler, Thomas

    2015-01-01

    N-doped single/multi-walled carbon nanotubes (CNTs) were studied for long time from synthesis to properties. However, the stability of N in the CNT lattice still needs further developments. In this work, to obtain more stable N-doped CNTs, concentric double-walled (DW) CNTs with more N were synthesized using benzylamine as C and N source. In order to test the stability of N-doped DWCNTs, high-temperature annealing in vacuum was performed. By XPS and Raman spectroscopic measurements, we found that the N-doped DWCNTs are still stable under 1500 $\\,^{\\circ}\\mathrm{C}$: the graphitic N does not change at all, the molecular N is partly removed, and the pyridinic N ratio greatly increases by more than two times. The reason could be that the N atoms from the surrounded N-contained materials combine into the CNT lattice during the annealing. Compared with the undoped DWCNTs, no Raman frequency shift was observed for the RBM, the G-band, and the G'-band of the N-doped DWCNTs.

  8. Prion-derived copper-binding peptide fragments catalyze the generation of superoxide anion in the presence of aromatic monoamines

    Directory of Open Access Journals (Sweden)

    Tomonori Kawano

    2007-01-01

    Full Text Available Objectives: Studies have proposed two opposing roles for copper-bound forms of prion protein (PrP as an anti-oxidant supporting the neuronal functions and as a pro-oxidant leading to neurodegenerative process involving the generation of reactive oxygen species. The aim of this study is to test the hypothesis in which putative copper-binding peptides derived from PrP function as possible catalysts for monoamine-dependent conversion of hydrogen peroxide to superoxide in vitro. Materials and methods: Four peptides corresponding to the copper (II-binding motifs in PrP were synthesized and used for analysis of peptide-catalyzed generation of superoxide in the presence of Cu (II and other factors naturally present in the neuronal tissues. Results: Among the Cu-binding peptides tested, the amino acid sequence corresponding to the Cu-binding site in the helical region was shown to be the most active for superoxide generation in the presence of Cu(II, hydrogen peroxide and aromatic monoamines, known precursors or intermediates of neurotransmitters. Among monoamines tested, three compounds namely phenylethylamine, tyramine and benzylamine were shown to be good substrates for superoxide-generating reactions by the Cu-bound helical peptide. Conclusions: Possible roles for these reactions in development of prion disease were suggested.

  9. Benzylammonium Thermometer Ions: Internal Energies of Ions Formed by Low Temperature Plasma and Atmospheric Pressure Chemical Ionization.

    Science.gov (United States)

    Stephens, Edward R; Dumlao, Morphy; Xiao, Dan; Zhang, Daming; Donald, William A

    2015-12-01

    The extent of internal energy deposition upon ion formation by low temperature plasma and atmospheric pressure chemical ionization was investigated using novel benzylammonium thermometer ions. C-N heterolytic bond dissociation enthalpies of nine 4-substituted benzylammoniums were calculated using CAM-B3LYP/6-311++G(d,p), which was significantly more accurate than B3LYP/6-311++G(d,p), MP2/6-311++G(d,p), and CBS-QB3 for calculating the enthalpies of 20 heterolytic dissociation reactions that were used to benchmark theory. All 4-substituted benzylammonium thermometer ions fragmented by a single pathway with comparable dissociation entropies, except 4-nitrobenzylammonium. Overall, the extent of energy deposition into ions formed by low temperature plasma was significantly lower than those formed by atmospheric pressure chemical ionization under these conditions. Because benzylamines are volatile, this new suite of thermometer ions should be useful for investigating the extent of internal energy deposition during ion formation for a wide range of ionization methods, including plasma, spray and laser desorption-based techniques. Graphical Abstract ᅟ.

  10. N-(Substituted benzyl)-3,5-bis(benzylidene)-4-piperidones: Synthesis and Preliminary Anti-leukemia Activity (I)%N-(Substituted benzyl)-3,5-bis(benzylidene)-4-piperidones: Synthesis and Preliminary Anti-leukemia Activity (I)

    Institute of Scientific and Technical Information of China (English)

    王静; 孟雯; 倪振杰; 薛思佳

    2011-01-01

    A series of novel N-(substituted benzyl)-3,5-bis(benzylidene)-4-piperidones 5a--50 were synthesized with substituted benzylamines as raw materials via a series of Michael addition, Dieckmann condensation, hydrolysis decarboxylation and aldol condensation. The structures were confirmed by 1↑H NMR, IR, MS techniques and elemental analysis. Assay-based antiproliferative activity study using leukemic cell lines K562 revealed that most of the title compounds have high effectiveness in inhibiting leukemia K562 cells proliferation, among which the compounds 5g (IC50=7.81 μg·mL^-1), 5k (IC50=6.35μg·mL^-1), 51 (IC50=7.20 μg·mL^-1), and 50 (IC50=5.79 μg·mL^-1) have better inhibition activities than standard 5-fluorouracil (IC50=8.56 μg·mL^-1).

  11. C-H Bond Activation of Bisimines by Palladium (Ⅱ) and Platinum (Ⅱ).Synthesis,Characterization of Bis (imino) aryl-palladium (Ⅱ) Pincer Complexes and Their Application in Carbon-Carbon Cross Coupling Reactions%C-H Bond Activation of Bisimines by Palladium (Ⅱ) and Platinum (Ⅱ).Synthesis, Characterization of Bis (imino) aryl-palladium (Ⅱ) Pincer Complexes and Their Application in Carbon-Carbon Cross Coupling Reactions

    Institute of Scientific and Technical Information of China (English)

    CHEN Rong; CHEN Ying; LIU Fang; LI Ping; HU Zhao-xia; WANG Hong-xing

    2013-01-01

    Abstract:The reactions of a variety of 4,6-dimethyl-1,3-bis (imino) benzenes 2a-g derived from 4,6-dimethylisophthalaldehyde and anilines or benzylamine with palladium (Ⅱ) acetate in anhydrous acetic acid under nitrogen were investigated.Experiment results demonstrate that cyclopalladations in such condition are applicable not only to the present system under study but also to the 5-substituted bis(imino)benzenes 6,7.The molecular structure of 3 b was further confirmed by X-Ray single-crystal diffraction.3b Crystallizes in orthorhombic,space groupP2 (1) 2 (1) 2 (1) with a =0.734 53 (8),b =1.683 8 (3),c =1.691 7(2) nm,α =β =γ =90°.Treatment of 2b with K2PtCl4 in anhydrous acetic acid affords the corresponding NCN-platinum pincer.Carbon-carbon cross coupling reactions catalyzed with 3b were investigated.These palladium complexes have been proved to be high effective catalysts for Suzuki coupling reaction.

  12. Diastereotopic analysis of mesoridazine besylate (Serentil).

    Science.gov (United States)

    Morrow, Ryan J; Millership, Jeff S; Collier, Paul S

    2004-10-01

    NMR studies were conducted with the aim of determining the diastereoisomeric ratio of a commercially supplied sample of mesoridazine (MES) and to compare the results with a freshly synthesised sample of MES. The results indicated that the commercially supplied MES consisted almost entirely of one diastereoisomeric pair, which was in agreement with previous findings reported by Eap et al. The synthesised sample of MES was analysed by NMR in two stages: 1) as the initial product isolated as the free base from the direct synthesis, and 2) as the free base isolated from the crystallised besylate salt of the synthetic product. The NMR results show that the initial synthetic product consisted of two equal pairs of diastereoisomers. The diastereoisomeric pairs were further separated by the addition of the chiral shift reagent (R)-(-)-N-(3,5 dinitrobenzoyl)-alpha-benzylamine to reveal equal quantities of all four enantiomers, clearly observed at the methyl sulfoxide proton peak of the NMR scan. The sample obtained from the crystallisation of MES besylate, however, indicated a significant difference, with a diastereoisomeric ratio of 75:25. The results suggest that MES besylate undergoes preferential crystallisation of one pair of diastereoisomers, with the other pair remaining in solution. PMID:15290689

  13. A Peroxidase-linked Spectrophotometric Assay for the Detection of Monoamine Oxidase Inhibitors.

    Science.gov (United States)

    Zhi, Kangkang; Yang, Zhongduo; Sheng, Jie; Shu, Zongmei; Shi, Yin

    2016-01-01

    To develop a new more accurate spectrophotometric method for detecting monoamine oxidase inhibitors from plant extracts, a series of amine substrates were selected and their ability to be oxidized by monoamine oxidase was evaluated by the HPLC method and a new substrate was used to develop a peroxidase-linked spectrophotometric assay. 4-(Trifluoromethyl) benzylamine (11) was proved to be an excellent substrate for peroxidase-linked spectrophotometric assay. Therefore, a new peroxidase-linked spectrophotometric assay was set up. The principle of the method is that the MAO converts 11 into aldehyde, ammonia and hydrogen peroxide. In the presence of peroxidase, the hydrogen peroxide will oxidize 4-aminoantipyrine into oxidised 4-aminoantipyrine which can condense with vanillic acid to give a red quinoneimine dye. The production of the quinoneimine dye was detected at 490 nm by a microplate reader. The ⊿OD value between the blank group and blank negative control group in this new method is twice as much as that in Holt's method, which enables the procedure to be more accurate and avoids the produce of false positive results. The new method will be helpful for researchers to screening monoamine oxidase inhibitors from deep-color plant extracts. PMID:27610153

  14. Metabolism of an alkyl polyamine analog by a polyamine oxidase from the microsporidian Encephalitozoon cuniculi.

    Science.gov (United States)

    Bacchi, Cyrus J; Yarlett, Nigel; Faciane, Evangeline; Bi, Xiangdong; Rattendi, Donna; Weiss, Louis M; Woster, Patrick M

    2009-06-01

    Encephalitozoon cuniculi is a microsporidium responsible for systemic illness in mammals. In the course of developing leads to new therapy for microsporidiosis, we found that a bis(phenylbenzyl)3-7-3 analog of spermine, 1,15-bis{N-[o-(phenyl)benzylamino}-4,12-diazapentadecane (BW-1), was a substrate for an E. cuniculi amine oxidase activity. The primary natural substrate for this oxidase activity was N'-acetylspermine, but BW-1 had activity comparable to that of the substrate. As the sole substrate, BW-1 gave linear reaction rates over 15 min and K(m) of 2 microM. In the presence of N'-acetylspermine, BW-1 acted as a competitive inhibitor of oxidase activity and may be a subversive substrate, resulting in increased peroxide production. By use of (13)C-labeled BW-1 as a substrate and nuclear magnetic resonance analysis, two products were determined to be oxidative metabolites, a hydrated aldehyde or dicarboxylate and 2(phenyl)benzylamine. These products were detected after exposure of (13)C-labeled BW-1 to E. cuniculi preemergent spore preparations and to uninfected host cells. In previous studies, BW-1 was curative in a rodent model of infection with E. cuniculi. The results in this study demonstrate competitive inhibition of oxidase activity by BW-1 and support further studies of this oxidase activity by the parasite and host.

  15. Synthesis, Structure and Solid State Properties of Cyclohexanemethylamine Substituted Phenalenyl Based Molecular Conductor

    Directory of Open Access Journals (Sweden)

    Robert C. Haddon

    2012-05-01

    Full Text Available We report the preparation, crystallization and solid state characterization of a cyclohexanemethylamine substituted spirobiphenalenyl radical; in the solid state the compound is iso-structural with its dehydro-analog (benzylamine-substitued compound, and the molecules packed in a one-dimensional fashion that we refer to as a π-step stack. Neighboring molecules in the stack interact via the overlap of one pair of active (spin bearing carbon atoms per phenalenyl unit. The magnetic susceptibility measurement indicates that in the solid state the radical remains paramagnetic and the fraction of Curie spins is 0.75 per molecule. We use the analytical form of the Bonner-Fisher model for the S = 1/2 antiferromagnetic Heisenberg chain of isotropically interacting spins with intrachain spin coupling constant J = 6.3 cm−1, to fit the experimentally observed paramagnetism [χp (T] in the temperature range 4–330 K. The measured room temperature conductivity (σRT = 2.4 × 10–3 S/cm is comparable with that of the iso-structural benzyl radical, even though the calculated band dispersions are smaller than that of the unsaturated analog.

  16. The unique substrate specificity of human AOC2, a semicarbazide-sensitive amine oxidase.

    Science.gov (United States)

    Kaitaniemi, Sam; Elovaara, Heli; Grön, Kirsi; Kidron, Heidi; Liukkonen, Janne; Salminen, Tiina; Salmi, Marko; Jalkanen, Sirpa; Elima, Kati

    2009-08-01

    Semicarbazide-sensitive amine oxidases (SSAOs) catalyze oxidative deamination of primary amines, but the true physiological function of these enzymes is still poorly understood. Here, we have studied the functional and structural characteristics of a human cell-surface SSAO, AOC2, which is homologous to the better characterized family member, AOC3. The preferred in vitro substrates of AOC2 were found to be 2-phenylethylamine, tryptamine and p-tyramine instead of methylamine and benzylamine, the favored substrates of AOC3. Molecular modeling suggested structural differences between AOC2 and AOC3, which provide AOC2 with the capability to use the larger monoamines as substrates. Even though AOC2 mRNA was expressed in many tissues, the only tissues with detectable AOC2-like enzyme activity were found in the eye. Characterization of AOC2 will help in evaluating the contribution of this enzyme to the pathological processes attributed to the SSAO activity and in designing specific inhibitors for the individual members of the SSAO family. PMID:19588076

  17. Monoamine oxidase B and free radical scavenging activities of natural flavonoids in Melastoma candidum D. Don.

    Science.gov (United States)

    Lee, M H; Lin, R D; Shen, L Y; Yang, L L; Yen, K Y; Hou, W C

    2001-11-01

    Monoamine oxidase type B (MAO-B) activity and free radicals are elevated in certain neurological diseases. Four natural flavonoids, quercitrin, isoquercitrin, rutin, and quercetin, were isolated for the first time from the leaves of Melastoma candidum D. Don. They exhibited an inhibitory effect on MAO-B. These potent flavonoids were purified using bioassay-guided fractionation and were separated by Diaion, Sephadex LH-20, and MCI CHP20P columns. The IC(50) values of the four potent flavonoids, quercitrin, isoquercitrin, rutin, and quercetin on monoamine oxidase were 19.06, 11.64, 3.89, and 10.89 microM and enzyme kinetics analysis revealed apparent inhibition constants (K(i)) of 21.01, 2.72, 1.83, and 7.95 microM, respectively, on the substrate, benzylamine. The four potent compounds also exhibited hydroxyl radical scavenging activity as determined using a spin trapping electron spin resonance method. This suggests that the four flavonoids from M. candidum possess both MAO-B inhibitory and free radical scavenging activities. These important properties may be used for preventing some neurodegenerative diseases in the future. PMID:11714358

  18. Determination of human serum semicarbazide-sensitive amine oxidase activity via flow injection analysis with fluorescence detection after online derivatization of the enzymatically produced benzaldehyde with 1,2-diaminoanthraquinone.

    Science.gov (United States)

    El-Maghrabey, Mahmoud H; Kishikawa, Naoya; Ohyama, Kaname; Imazato, Takahiro; Ueki, Yukitaka; Kuroda, Naotaka

    2015-06-30

    A fast, simple, and sensitive flow injection analysis method was developed for the measurement of semicarbazide-sensitive amine oxidase (SSAO) activity in human serum. Benzaldehyde, generated by the action of SSAO after incubation of serum with benzylamine, was derivatized with a novel aromatic aldehyde-specific reagent (1,2-diaminoanthraquinone) and the fluorescent product was measured by fluorescence detection at excitation and emission wavelengths of 390 and 570nm, respectively. Serum SSAO activity was defined as benzaldehyde (nmol) formed per milliliter serum per hour. The method was linear over SSAO activity of 0.2-150.0nmolmL(-1)h(-1) with a detection limit of 0.06nmolmL(-1)h(-1). The %RSD of intra-day and inter-day precision did not exceed 9.4% and the accuracy ranged from -6.5 to -0.6%. The method was applied for the determination of the serum SSAO activity in healthy controls (C, n=24) and diabetes mellitus patients (DM, n=18). It was demonstrated that the activity (mean±SE) of SSAO in diabetics sera was significantly higher than that in healthy subjects' ones (DM; 73.3±1.8nmolmL(-1)h(-1)vs C; 58.9±2.2nmolmL(-1)h(-1), P<0.01).

  19. Evaluation of brain SERT occupancy by resveratrol against MDMA-induced neurobiological and behavioral changes in rats: A 4-[¹⁸F]-ADAM/small-animal PET study.

    Science.gov (United States)

    Shih, Jui-Hu; Ma, Kuo-Hsing; Chen, Chien-Fu F; Cheng, Cheng-Yi; Pao, Li-Heng; Weng, Shao-Ju; Huang, Yuahn-Sieh; Shiue, Chyng-Yann; Yeh, Ming-Kung; Li, I-Hsun

    2016-01-01

    The misuse of 3,4-methylenedioxymethamphetamine (MDMA) has drawn a growing concern worldwide for its psychophysiological impacts on humans. MDMA abusers are often accompanied by long-term serotonergic neurotoxicity, which is associated with reduced density of cerebral serotonin transporters (SERT) and depressive disorders. Resveratrol (RSV) is a natural polyphenolic phytoalexin that has been known for its antidepressant and neuroprotective effects. However, biological targets of RSV as well as its neuroprotective effects against MDMA remained largely unknown. In this study, we examined binding potency of RSV and MDMA to SERT using small-animal positron emission tomography (PET) with the SERT radioligand, N,N-dimethyl-2-(2-amino-4-[(18)F]fluorophenylthio)benzylamine (4-[(18)F]-ADAM) and investigated the protection of RSV against the acute and long-term adverse effects of MDMA. We found that RSV exhibit binding potentials to SERT in vivo in a dose-dependent manner with variation among brain regions. When the MDMA-treated rats (10mg/kg, s.c.) were co-injected with RSV (20mg/kg, i.p.) twice daily for 4 consecutive days, MDMA-induced acute elevation in plasma corticosterone was significantly reduced. Further, 4-[(18)F]-ADAM PET imaging revealed that RSV protected against the MDMA-induced decrease in SERT availability in the midbrain and the thalamus 2 weeks following the co-treatment. The PET data were comparable to the observation from the forced swim test that RSV sufficiently ameliorated the depressive-like behaviors of the MDMA-treated rats. Together, these findings suggest that RSV is a potential antidepressant and may confer protection against neurobiological and behavioral changes induced by MDMA. PMID:26612383

  20. Characterization of 4-[18F]-ADAM as an imaging agent for SERT in non-human primate brain using PET: a dynamic study

    International Nuclear Information System (INIS)

    Introduction: Serotonin transporter (SERT) has been associated with many psychiatric diseases. This study investigated the biodistribution of a serotonin transporter imaging agent, N,N-dimethyl-2-(2-amino-4-18F-fluorophenylthio)benzylamine (4-[18F]-ADAM), in nonhuman primate brain using positron emission tomography (PET). Methods: Six and four Macaca cyclopis monkeys were used to determine the transit time (i.e., time necessary to reach biodistribution equilibrium) and the reproducibility of 4-[18F]-ADAM biodistribution in the brain, respectively. The sensitivity and specificity of 4-[18F]-ADAM binding to SERT were evaluated in one monkey challenged with different doses of fluoxetine and one monkey treated with 3,4-methylendioxymethamphetamine (MDMA). Dynamic PET imaging was performed for 3 h after 4-[18F]-ADAM intravenous bolus injection. The specific uptake ratios (SURs) in the midbrain (MB), thalamus (TH), striatum (ST) and frontal cortex (FC) were calculated. Results: The distribution of 4-[18F]-ADAM reached equilibrium 120–150 min after injection. The mean SURs were 2.49±0.13 in MB, 1.59±0.17 in TH, 1.35±0.06 in ST and 0.34±0.03 in FC, and the minimum variability was shown 120–150 min after 4-[18F]-ADAM injection. Using SURs and intraclass coefficient of correlation, the test/retest variability was under 8% and above 0.8, respectively, in SERT-rich areas. Challenge with fluoxetin (0.75–2 mg) dose-dependently inhibited the SURs in various brain regions. 4-[18F]-ADAM binding was markedly reduced in the brain of an MDMA-treated monkey compared to that in brains of normal controls. Conclusion: 4-[18F]-ADAM appears to be a highly selective radioligand for imaging SERT in monkey brain.

  1. Analysis of free hydroxytyrosol in human plasma following the administration of olive oil.

    Science.gov (United States)

    Pastor, Antoni; Rodríguez-Morató, Jose; Olesti, Eulàlia; Pujadas, Mitona; Pérez-Mañá, Clara; Khymenets, Olha; Fitó, Montserrat; Covas, María-Isabel; Solá, Rosa; Motilva, María-José; Farré, Magí; de la Torre, Rafael

    2016-03-11

    Hydroxytyrosol (HT) from olive oil, a potent bioactive molecule with health benefits, has a poor bioavailability, its free form (free HT) being undetectable so far. This fact leads to the controversy whether attained HT concentrations after olive oil polyphenol ingestion are too low to explain the observed biological activities. Due to this, an analytical methodology to determine free HT in plasma is crucial for understanding HT biological activity. Plasma HT instability and low concentrations have been major limitations for its quantification in clinical studies. Here, we describe a method to detect and quantify free HT in human plasma by using liquid chromatography coupled to tandem mass spectrometry. The method encompasses different steps of sample preparation including plasma stabilization, protein precipitation, selective derivatization with benzylamine, and purification by solid-phase extraction. A high sensitivity (LOD, 0.3ng/mL), specificity and stability of HT is achieved following these procedures. The method was validated and its applicability was demonstrated by analyzing human plasma samples after olive oil intake. A pharmacokinetic comparison was performed measuring free HT plasma concentrations following the intake of 25mL of ordinary olive oil (nearly undetectable concentrations) versus an extra-virgin olive oil (Cmax=4.40ng/mL). To our knowledge, this is the first time that an analytical procedure for quantifying free HT in plasma after olive oil dietary doses has been reported. The present methodology opens the door to a better understanding of the relationship between HT plasma concentrations and its beneficial health effects.

  2. Volatile Semiochemicals Increase Trap Catch of Green Lacewings (Neuroptera: Chrysopidae) and Flower Flies (Diptera: Syrphidae) in Corn and Soybean Plots

    Science.gov (United States)

    Hesler, Louis S.

    2016-01-01

    This study reports on the attractiveness of volatile chemicals to green lacewings (Neuroptera: Chrysopidae) and flower flies (Diptera: Syrphidae) as measured by catch on yellow sticky traps within corn [Zea mays L. (Cyperales: Poaceae)] and soybean [Glycine max (L.) Merr. (Fabales: Fabaceae)] plots. Green lacewings were attracted to eugenol-baited traps in two tests in soybean plots. Follow-up testing in corn showed that catch of green lacewings was enhanced when traps were baited with eugenol, its structural analog isoeugenol, or 2-phenylethanol; trap catch of green lacewings was greater with these compounds than with structural analog, 4-alllylanisole. In a follow-up test in soybean, more green lacewings were caught on traps baited with isoeugenol than with 4-allylanisole. Catch did not differ among traps baited with eugenol, isoeugenol, or 2-phenylethanol or among those baited with eugenol, 2-phenylethanol, or the ethanol control. In a 6-wk experiment in soybean, green lacewings were attracted to eugenol-baited traps in 5 of 6 wks but to traps baited with structural analog methyl eugenol in only 1 wk. Flower flies were attracted to 2-phenylethanol in initial tests in corn and soybean plots. Subsequent testing in soybeans with 2-phenylethanol and structural analogs confirmed attraction to 2-phenylethanol and also showed attractancy of 2-phenylacetaldehyde but not benzylamine. A 6-wk test in soybean found that flower flies were also attracted to traps baited with either eugenol or methyl eugenol. This is the first report of green lacewing attraction to eugenol and isoeugenol and first report of flower fly attraction to eugenol. Structure-activity relationships among attractants and practical aspects of their use are discussed. PMID:27531905

  3. Syntheses and Antibiotic Evaluation of 2-{[(2R,4R-4-Carboxy-2-hydroxypyrrolidin-1-yl]carbonyl}benzene-1,5-dicarboxylic Acids and 2-Carbamoylbenzene-1,5-dicarboxylic Acid Analogues

    Directory of Open Access Journals (Sweden)

    Abdulrazaq Tukur

    2016-01-01

    Full Text Available Our search for new antibiotics led to the syntheses and biological evaluation of new classes of dicarboxylic acid analogues. The syntheses involve nucleophilic addition of different substituted benzylamine, aniline, alkylamine, and 4-hydroxyl-L-proline with carbamoylbenzoic acid. The results of the antimicrobial activity as indicated by the zone of inhibition (ZOI showed that Z10 is the most active against Pseudomonas aeruginosa (32 mm and least active against Candida stellatoidea (27 mm and Vancomycin Resistant Enterococci (VRE (27 mm, while Z7 shows the least zone of inhibition (22 mm against Methicillin Resistant Staphylococcus aureus (MRSA. The minimum inhibition concentration (MIC determination reveals that Z10 inhibits the growth of tested microbes at a low concentration of 6.25 μg/mL, while Z9 and Z12 inhibits the growth of most microbes at a concentration of 12.5 μg/mL, recording the least MIC. The Minimum Bactericidal/Fungicidal Concentration (MBC/MFC results revealed that Z10 has the highest bactericidal/fungicidal effect on the test microbes, at a concentration of 12.5 μg/mL, with the exception of Candida stellatoidea and Vancomycin Resistant Enterococci (VRE with MBC/MFC of 25 μg/mL. The result of this investigation reveals the potential of the target compounds (Z1–3,5,7–12 in the search for new antimicrobial agents.

  4. The influence of tertiary amine accelerators on the curing behaviors of epoxy/anhydride systems

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Tao; Zhang, Chongfeng; Zhang, Junying, E-mail: zjybuct@gmail.com; Cheng, Jue

    2014-02-10

    Highlights: • The influences of two types of accelerators (BDMA and DMP-30) on curing reaction of DGEBF/MeHHPA systems were studied comparatively. • The activation energy and kinetic parameters of DGEBF/MeHHPA systems with accelerator content of 0.2 phr and 0.5 phr were calculated, respectively. • The dependence of autocatalytic and non-autocatalytic curing reaction on the loading of accelerators was discussed. • The non-catalytic curing reaction dominated absolutely in the curing process of DGEBF/MeHHPA systems when the accelerator contents were 0.2 phr. - Abstract: Accelerators have significant effects on the curing behaviors of epoxy/anhydride (diglycidyl ether of bisphenol-F/methylhexahydrophthalic anhydride, DGEBF/MeHHPA) systems. Non-isothermal DSC was used to investigate the influence of dimethyl benzylamine (BDMA, 0.2 phr/0.5 phr) and Tris-(dimethyl aminomethyl) phenol (DMP-30, 0.2 phr/0.5 phr) on the curing behaviors of DGEBF/MeHHPA systems, respectively. When the amount of accelerators was kept constant, the activation energy calculated by Kissinger method changed slightly in the presence of either BDMA or DMP-30. And, with increasing the accelerator content from 0.2 phr to 0.5 phr, the value of activation energy decreased from 115 kJ/mol to 85 kJ/mol. Furthermore, the calculation results of Málek method identified that all systems in this study fitted Sesták–Berggren (SB) model and the corresponding model parameters, m and n, were obtained. It was found that the contribution of autocatalytic reaction with low accelerator content (0.2 phr) was far less than that with high accelerator content (0.5 phr)

  5. Two-dimensional inorganic–organic hybrid semiconductors composed of double-layered ZnS and monoamines with aromatic and heterocyclic aliphatic rings: Syntheses, structures, and properties

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Sujing; Li, Jing, E-mail: jingli@rutgers.edu

    2015-04-15

    As an addition to the II–VI based inorganic–organic hybrid semiconductor family, five new two-dimensional (2D) double-layered structures have been synthesized employing monoamines with different aromatic or heterocyclic aliphatic rings. Zn{sub 2}S{sub 2}(bza) (1), Zn{sub 2}S{sub 2}(mbza) (2), Zn{sub 2}S{sub 2}(fbza) (3), Zn{sub 2}S{sub 2}(pca) (4), and Zn{sub 2}S{sub 2}(thfa) (5) (bza=benzylamine, mbza=4-methoxybenzylamine, fbza=4-flurobenzylamine, pca=3-picolylamine, and thfa=tetrahydrofurfurylamine) are prepared by solvothermal reactions and characterized by different analytical methods, including powder X-ray diffraction, optical diffuse reflection, thermogravimetric analysis and photoluminescence spectroscopy. The powder X-ray diffraction patterns show that all five compounds adopt 2D double-layered structures. Optical diffuse reflectance spectra of these compounds suggest that they have notably lower band gaps than those of the similar compounds composed of aliphatic alkyl amines. Their photoluminescence properties and thermal stability are also analyzed. - Graphical abstract: Five new members of two-dimensional double-layered 2D-Zn{sub 2}S{sub 2}(L) (L=Ligand) structures employing monoamines with different aromatic or heterocyclic aliphatic rings have been designed, synthesized, and characterized. - Highlights: • A new sub-family of II-VI based hybrid semiconductors are designed, synthesized, and structurally characterized using amines with aromatic or aliphatic cyclic rings. • These compounds have notably lower band gaps than those made of aliphatic alkyl amines, greatly broadening the range of band gaps of this material family. • They emit strongly with systematically tunable emission intensity and energy.

  6. Controlling pyridinic, pyrrolic, graphitic, and molecular nitrogen in multi-wall carbon nanotubes using precursors with different N/C ratios in aerosol assisted chemical vapor deposition.

    Science.gov (United States)

    Bulusheva, L G; Okotrub, A V; Fedoseeva, Yu V; Kurenya, A G; Asanov, I P; Vilkov, O Y; Koós, A A; Grobert, N

    2015-10-01

    Nitrogen-containing multi-wall carbon nanotubes (N-MWCNTs) were synthesized using aerosol assisted chemical vapor deposition (CVD) techniques in conjunction with benzylamine:ferrocene or acetonitrile:ferrocene mixtures. Different amounts of toluene were added to these mixtures in order to change the N/C ratio of the feedstock. X-ray photoelectron and near-edge X-ray absorption fine structure spectroscopy detected pyridinic, pyrrolic, graphitic, and molecular nitrogen forms in the N-MWCNT samples. Analysis of the spectral data indicated that whilst the nature of the nitrogen-containing precursor has little effect on the concentrations of the different forms of nitrogen in N-MWCNTs, the N/C ratio in the feedstock appeared to be the determining factor. When the N/C ratio was lower than ca. 0.01, all four forms existed in equal concentrations, for N/C ratios above 0.01, graphitic and molecular nitrogen were dominant. Furthermore, higher concentrations of pyridinic nitrogen in the outer shells and N2 molecules in the core of the as-produced N-MWCNTs suggest that the precursors were decomposed into individual atoms, which interacted with the catalyst surface to form CN and NH species or in fact diffused through the bulk of the catalyst particles. These findings are important for a better understanding of possible growth mechanisms for heteroatom-containing carbon nanotubes (CNTs) and therefore paving the way for controlling the spatial distribution of foreign elements in the CNTs using CVD processes. PMID:26104737

  7. Enhancing catalytic performance of palladium in gold and palladium alloy nanoparticles for organic synthesis reactions through visible light irradiation at ambient temperatures.

    Science.gov (United States)

    Sarina, Sarina; Zhu, Huaiyong; Jaatinen, Esa; Xiao, Qi; Liu, Hongwei; Jia, Jianfeng; Chen, Chao; Zhao, Jian

    2013-04-17

    The intrinsic catalytic activity of palladium (Pd) is significantly enhanced in gold (Au)-Pd alloy nanoparticles (NPs) under visible light irradiation at ambient temperatures. The alloy NPs strongly absorb light and efficiently enhance the conversion of several reactions, including Suzuki-Miyaura cross coupling, oxidative addition of benzylamine, selective oxidation of aromatic alcohols to corresponding aldehydes and ketones, and phenol oxidation. The Au/Pd molar ratio of the alloy NPs has an important impact on performance of the catalysts since it determines both the electronic heterogeneity and the distribution of Pd sites at the NP surface, with these two factors playing key roles in the catalytic activity. Irradiating with light produces an even more profound enhancement in the catalytic performance of the NPs. For example, the best conversion rate achieved thermally at 30 °C for Suzuki-Miyaura cross coupling was 37% at a Au/Pd ratio of 1:1.86, while under light illumination the yield increased to 96% under the same conditions. The catalytic activity of the alloy NPs depends on the intensity and wavelength of incident light. Light absorption due to the Localized Surface Plasmon Resonance of gold nanocrystals plays an important role in enhancing catalyst performance. We believe that the conduction electrons of the NPs gain the light absorbed energy producing energetic electrons at the surface Pd sites, which enhances the sites' intrinsic catalytic ability. These findings provide useful guidelines for designing efficient catalysts composed of alloys of a plasmonic metal and a catalytically active transition metal for various organic syntheses driven by sunlight. PMID:23566035

  8. Antimicrobial, antioxidant, cytotoxic and molecular docking properties of N-benzyl-2,2,2-trifluoroacetamide

    Science.gov (United States)

    Balachandran, C.; Kumar, P. Saravana; Arun, Y.; Duraipandiyan, V.; Sundaram, R. Lakshmi; Vijayakumar, A.; Balakrishna, K.; Ignacimuthu, S.; Al-Dhabi, N. A.; Perumal, P. T.

    2015-02-01

    N-Benzyl-2,2,2-trifluoroacetamide was obtained by acylation of benzylamine with trifluoroacetic anhydride using Friedel-Crafts acylation method. The synthesised compound was confirmed by spectroscopic and crystallographic techniques. N-Benzyl-2,2,2 -trifluoroacetamide was assessed for its antimicrobial, antioxidant, cytotoxic and molecular docking properties. It showed good antifungal activity against tested fungi and moderate antibacterial activity. The minimum inhibitory concentration values of N-benzyl-2,2,2 -trifluoroacetamide against fungi were 15.62 μg/mL against A. flavus, 31.25 μg/mL against B. Cinerea and 62.5 μg/mL against T. mentagrophytes, Scopulariopsis sp., C. albicans and M. pachydermatis. N-Benzyl-2,2,2-trifluoroacetamide showed 78.97 ± 2.24 of antioxidant activity at 1,000 μg/mL. Cupric ion reducing antioxidant capacity of N-benzyl-2,2,2-trifluoroacetamide was dependent on the concentration. Ferric reducing antioxidant power assay of N-benzyl-2,2,2-trifluoroacetamide showed (1.352 ± 0.04 mM Fe(II)/g) twofold higher value compared to the standard. N-Benzyl-2,2,2-trifluoroacetamide showed 75.3 % cytotoxic activity at the dose of 200 μg/mL with IC50 (54.7 %) value of 100 μg/mL. N-Benzyl-2,2,2-trifluoroacetamide was subjected to molecular docking studies for the inhibition AmpC beta-lactamase, Glucosamine-6-Phosphate Synthase and lanosterol 14 alpha-demethylase (CYP51) enzymes which are targets for antibacterial and antifungal drugs. Docking studies of N-benzyl-2,2,2-trifluoroacetamide showed low docking energy. N-Benzyl-2,2,2-trifluoroacetamide can be evaluated further for drug development.

  9. A comparative randomized open label study to evaluate efficacy, safety and cost effectiveness between topical 2% sertaconazole and topical 1% butenafine in tinea infections of skin

    Directory of Open Access Journals (Sweden)

    Saket J Thaker

    2013-01-01

    Full Text Available Background: Dermatophytoses are the superficial fungal infections of skin, hair, and nail. Butenafine is a benzylamine group of antifungal that inhibits the biosynthesis of ergosterol by blocking squalene epoxidase. Sertaconazole is a newer imidazole antifungal which inhibits the biosynthesis of ergosterol by inhibiting 14-a lanosterol demethylase. The study was done to compare a newer antifungal with a relatively older one. Aim: To compare the efficacy, safety and cost effectiveness of topical 2% sertaconazole cream and 1% butenafine in tinea infections of skin Materials and Methods: Patients were randomly allocated to two treatment groups. They were advised to apply the drug topically twice a day for one month on the lesions. They were followed up at an interval of 10 days. Clinical score and Global Evaluation Response were assessed at baseline and during each follow up. Results: A total 125 patients were recruited, out of them 111 completed the whole study. Median Sign and Symptom Score of tinea on the baseline was 9 [5,9] that was reduced to 0 [0,4] by 2% sertaconazole while it was 9 [6,9] in the butenafine group on the baseline that was reduced to 0 [0,6] at the end of the treatment. 98% and 90% of the patients got complete clearance of the lesions with butenafine and sertaconazole, respectively. Treatment with butenafine was more cost effective as compared to sertaconazole. Conclusion: 1% butenafine is more efficacious, cost effective, and equally safe as compared to 2% sertaconazole in the tinea infections of skin.

  10. High-throughput screening for monoamine oxidase-A and monoamine oxidase-B inhibitors using one-step fluorescence assay

    Institute of Scientific and Technical Information of China (English)

    Hong-mei GUANG; Guan-hua DU

    2006-01-01

    Aim: To develop high-throughput screening (HTS) assays for monoamine oxidase (MAO)-A and MAO-B inhibitors. Methods: A fluorescence probe based method measuring MAO-A and MAO-B activity was established and optimized, with its sensitivity, stability and specificity evaluated. Reaction conditions including enzyme sources, substrate concentrations, incubation volume and reaction time in 384-well format were optimized to achieve sensitive and low consumptive goal. Results: In optimized conditions, dynamic parameters of MAO-A and MAO-B were obtained. The Km value of serotonin to MAO-A was 1.66 μmol/L, while that of benzylamine to MAO-B was 0.80 umol/L. The IC50 value of clorgyline to MAO-A was 2.99 nmol/L, and that of deprenyl to MAO-B was 7.04 nmol/L, matching those obtained from traditional spectrometric assays. Among tested samples, one compound exerted an inhibitory effect on MAO-A activity with IC50 as 0.36 μmol/L, and three compounds had an inhibitory effect on MAO-B activity with IC50 as 0.13,0.19, and 0.13 μmol/L. The Z' factor was 0.71±0.03 and 0.75±0.03 in MAO-A-inhibitor and MAO-B-inhibitor HTS system, respectively. Conclusion: The established assays can be well applied to MAO-A and MAO-B inhibitor screening with high quality, precision and reproducibility.

  11. Purification and characterization of methylamine oxidase induced in Aspergillus niger AKU 3302.

    Science.gov (United States)

    Frébort, I; Matsushita, K; Toyama, H; Lemr, K; Yamada, M; Adachi, O

    1999-01-01

    Crude extract of Aspergillus niger AKU 3302 mycelia incubated with methylamine showed a single amine oxidase activity band in a developed polyacrylamide gel that weakly cross-reacted with the antibody against a copper/topa quinone-containing amine oxidase (AO-II) from the same strain induced by n-butylamine. Since the organism cannot grow on methylamine and the already known quinoprotein amine oxidases of the organism cannot catalyze oxidation of methylamine, the organism was forced to produce another enzyme that could oxidize methylamine when the mycelia were incubated with methylamine. The enzyme was separated and purified from the already known two quinoprotein amine oxidases formed in the same mycelia. The purified enzyme showed a sharp symmetric sedimentation peak in analytical ultracentrifugation showing S20,w0 of 6.5s. The molecular mass of 133 kDa estimated by gel chromatography and 66.6 kDa found by SDS-PAGE confirmed the dimeric structure of the enzyme. The purified enzyme was pink in color with an absorption maximum at 494 nm. The enzyme readily oxidized methylamine, n-hexylamine, and n-butylamine, but not benzylamine, histamine, or tyramine, favorite substrates for the already known two quinoprotein amine oxidases. Inactivation by carbonyl reagents and copper chelators suggested the presence of a copper/topa quinone cofactor. Spectrophotometric titration by p-nitrophenylhydrazine showed one reactive carbonyl group per subunit and redox-cyclic quinone staining confirmed the presence of a quinone cofactor. pH-dependent shift of the absorption spectrum of the enzyme-p-nitrophenylhydrazone (469 nm at neutral to 577 nm at alkaline pH) supported the identity of the cofactor with topaquinone. Nothern blot analysis indicated that the methylamine oxidase encoding gene is largely different from the already known amine oxidase in the organism.

  12. The serotonin transporter in rhesus monkey brain: comparison of DASB and citalopram binding sites

    Energy Technology Data Exchange (ETDEWEB)

    Zeng Zhizhen [Imaging Department, Merck Research Laboratories, West Point, PA 19486 (United States)]. E-mail: zhizhen_zeng@merck.com; Chen, T.-B. [Imaging Department, Merck Research Laboratories, West Point, PA 19486 (United States); Miller, Patricia J. [Imaging Department, Merck Research Laboratories, West Point, PA 19486 (United States); Dean, Dennis [Labeled Compound Synthesis Group, Drug Metabolism, Merck Research Laboratories, Rahway, NJ 07065-0900 (United States); Tang, Y.S. [Labeled Compound Synthesis Group, Drug Metabolism, Merck Research Laboratories, Rahway, NJ 07065-0900 (United States); Sur, Cyrille [Imaging Department, Merck Research Laboratories, West Point, PA 19486 (United States); Williams, David L. [Imaging Department, Merck Research Laboratories, West Point, PA 19486 (United States)

    2006-05-15

    We have characterized the interaction of the serotonin transporter ligand [{sup 3}H]-N,N-dimethyl-2-(2-amino-4-cyanophenylthio)-benzylamine (DASB) with rhesus monkey brain in vitro using tissue homogenate binding and autoradiographic mapping. [{sup 3}H]-DASB, a tritiated version of the widely used [{sup 11}C] positron emission tomography tracer, was found to selectively bind to a single population of sites with high affinity (K {sub d}=0.20{+-}0.04 nM). The serotonin transporter density (B {sub max}) obtained for rhesus frontal cortex was found to be 66{+-}8 fmol/mg protein using [{sup 3}H]-DASB, similar to the B {sub max} value obtained using the reference radioligand [{sup 3}H]-citalopram, a well-characterized and highly selective serotonin reuptake inhibitor (83{+-}22 fmol/mg protein). Specific binding sites of both [{sup 3}H]-DASB and [{sup 3}H]-citalopram were similarly and nonuniformly distributed throughout the rhesus central nervous system, in a pattern consistent with serotonin transporter localization reported for human brain. Regional serotonin transporter densities, estimated from optical densities of the autoradiographic images, were well correlated between the two radioligands. Finally, DASB and fluoxetine showed dose-dependent full inhibition of [{sup 3}H]-citalopram binding in a competition autoradiographic study, with K {sub i} values in close agreement with those obtained from rhesus brain homogenates. This side-by-side comparison of [{sup 3}H]-DASB and [{sup 3}H]-citalopram binding sites in rhesus tissue homogenates and in adjacent rhesus brain slices provides additional support for the use of [{sup 11}C]-DASB to assess the availability and distribution of serotonin transporters in nonhuman primates.

  13. Stability and Reactivity of Cyclometallated Naphthylamine Complexes in Pd-C Bond Insertion Reactions with Coordinated Alkynylphosphanes

    KAUST Repository

    Chen, Shuli

    2013-09-17

    Phenylbis(phenylethynyl)phosphane PhP(C≡CPh)2 coordinates regiospecifically to the α-methyl-chiral ortho-platinated and -palladated naphthylamine units at the positions trans to the nitrogen donors. The P→Pt coordination bond is kinetically inert, whereas the P→Pd bond is labile. Upon heating of these phosphane complexes at 70 °C, one of the C≡C bonds in the coordinated PhP(C≡CPh)2 was activated towards an intermolecular Pd-C bond insertion reaction with an external ortho-palladated naphthylamine ring. No intramolecular insertion reaction occurred. In contrast to its palladium analogue, the ortho-platinated ring is not reactive towards coordinated PhP(C≡CPh)2, although it can promote the Pd-C bond insertion reaction. However, despite the high kinetic stability of the P→Pt coordination, the organoplatinum unit is a noticeably weaker activator than its organopalladium counterpart. The chirality of the reacting ortho-metallated naphthylamine ligand exhibited high stereochemical influence on the formation of the new stereogenic phosphorus center during the course of these C-C bond-formation reactions. The coordination chemistry and the absolute stereochemistry of the dimetallic products were determined by single-crystal X-ray crystallographic analysis. The asymmetric monoinsertion of PhP(C≡CPh)2 coordinated to a cyclometallated N,N-dimethyl naphthyl/benzylamine template into the Pd-C bonds of N,N-dimethylnaphthylamine palladacycles has been demonstrated for the synthesis of a variety of new P-stereogenic homo- or heterodimetallic complexes. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Carrier-Mediated Uptake of 1-(Malonylamino)cyclopropane-1-Carboxylic Acid in Vacuoles Isolated from Catharanthus roseus Cells 1

    Science.gov (United States)

    Bouzayen, Mondher; Latché, Alain; Pech, Jean-Claude; Marigo, Gérard

    1989-01-01

    The uptake of 1-(malonylamino)cyclopropane-1-carboxylic acid (MACC), the conjugated form of the ethylene precursor, into vacuoles isolated from Catharanthus roseus cells has been studied by silicone layer floatation filtering. The transport across the tonoplast of MACC is stimulated fourfold by 5 millimolar MgATP, has a Km of about 2 millimolar, an optimum pH around 7, and an optimum temperature at 30°C. Several effectors known to inhibit ATPase (N,N′-dicyclohexylcarbodiimide) and to collapse the transtonoplastic H+ electrochemical gradient (carbonylcyanide m-chlorophenylhydrazone, gramicidin, and benzylamine) all reduced MACC uptake. Abolishing the membrane potential with SCN− and valinomycin also greatly inhibited MACC transport. Our data demonstrate that MACC accumulates in the vacuole against a concentration gradient by means of a proton motive force generated by a tonoplastic ATPase. The involvement of a protein carrier is suggested by the strong inhibition of uptake by compounds known to block SH—, OH—, and NH2— groups. MACC uptake is antagonized competitively by malonyl-d-tryptophan, indicating that the carrier also accepts malonyl-d-amino acids. Neither the moities of these compounds taken separately [1-aminocyclopropane-1-carboxylic acid, malonate, d-tryptophan or d-phenylalanine] nor malate act as inhibitors of MACC transport. The absence of inhibition of malate uptake by MACC suggests that MACC and malate are taken up by two different carriers. We propose that the carrier identified here plays an important physiological role in withdrawing from the cytosol MACC and malonyl-d-amino acids generated under stress conditions. PMID:16667182

  15. Volatile Semiochemicals Increase Trap Catch of Green Lacewings (Neuroptera: Chrysopidae) and Flower Flies (Diptera: Syrphidae) in Corn and Soybean Plots.

    Science.gov (United States)

    Hesler, Louis S

    2016-01-01

    This study reports on the attractiveness of volatile chemicals to green lacewings (Neuroptera: Chrysopidae) and flower flies (Diptera: Syrphidae) as measured by catch on yellow sticky traps within corn [Zea mays L. (Cyperales: Poaceae)] and soybean [Glycine max (L.) Merr. (Fabales: Fabaceae)] plots. Green lacewings were attracted to eugenol-baited traps in two tests in soybean plots. Follow-up testing in corn showed that catch of green lacewings was enhanced when traps were baited with eugenol, its structural analog isoeugenol, or 2-phenylethanol; trap catch of green lacewings was greater with these compounds than with structural analog, 4-alllylanisole. In a follow-up test in soybean, more green lacewings were caught on traps baited with isoeugenol than with 4-allylanisole. Catch did not differ among traps baited with eugenol, isoeugenol, or 2-phenylethanol or among those baited with eugenol, 2-phenylethanol, or the ethanol control. In a 6-wk experiment in soybean, green lacewings were attracted to eugenol-baited traps in 5 of 6 wks but to traps baited with structural analog methyl eugenol in only 1 wk. Flower flies were attracted to 2-phenylethanol in initial tests in corn and soybean plots. Subsequent testing in soybeans with 2-phenylethanol and structural analogs confirmed attraction to 2-phenylethanol and also showed attractancy of 2-phenylacetaldehyde but not benzylamine. A 6-wk test in soybean found that flower flies were also attracted to traps baited with either eugenol or methyl eugenol. This is the first report of green lacewing attraction to eugenol and isoeugenol and first report of flower fly attraction to eugenol. Structure-activity relationships among attractants and practical aspects of their use are discussed. PMID:27531905

  16. Synthesis and Antimicrobial Activity of 1,2-Benzothiazine Derivatives.

    Science.gov (United States)

    Patel, Chandani; Bassin, Jatinder P; Scott, Mark; Flye, Jenna; Hunter, Ann P; Martin, Lee; Goyal, Madhu

    2016-01-01

    A number of 1,2-benzothiazines have been synthesized in a three-step process. Nine chalcones 1-9 bearing methyl, fluoro, chloro and bromo substituents were chlorosulfonated with chlorosulfonic acid to generate the chalcone sulfonyl chlorides 10-18. These were converted to the dibromo compounds 19-27 through reaction with bromine in glacial acetic acid. Compounds 19-27 were reacted with ammonia, methylamine, ethylamine, aniline and benzylamine to generate a library of 45 1,2-benzothiazines 28-72. Compounds 28-72 were evaluated for their antimicrobial activity using broth microdilution techniques against two Gram-positive bacteria (Bacillus subtilis and Staphylococcus aureus) and two Gram-negative bacteria (Proteus vulgaris and Salmonella typhimurium). The results demonstrated that none of the compounds showed any activity against Gram-negative bacteria P. vulgaris and S. typhimurium; however, compounds 31, 33, 38, 43, 45, 50, 53, 55, 58, 60, 63 and 68 showed activity against Gram-positive bacteria Bacillus subtilis and Staphylococcous aureus. The range of minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC) was 25-600 µg/mL, though some of the MIC and MBC concentrations were high, indicating weak activity. Structure activity relationship studies revealed that the compounds with a hydrogen atom or an ethyl group on the nitrogen of the thiazine ring exerted antibacterial activity against Gram-positive bacteria. The results also showed that the compounds where the benzene ring of the benzoyl moiety contained a methyl group or a chlorine or bromine atom in the para position showed higher antimicrobial activity. Similar influences were identified where either a bromine or chlorine atom was in the meta position. PMID:27376253

  17. Broadband optical absorbance spectroscopy using a whispering gallery mode microsphere resonator

    Science.gov (United States)

    Westcott, Sarah L.; Zhang, Jiangquan; Shelton, Robert K.; Bruce, Nellie M. K.; Gupta, Sachin; Keen, Steven L.; Tillman, Jeremy W.; Wald, Lara B.; Strecker, Brian N.; Rosenberger, A. T.; Davidson, Roy R.; Chen, Wei; Donovan, Kevin G.; Hryniewicz, John V.

    2008-03-01

    We demonstrate the ability to excite and monitor many whispering gallery modes (WGMs) of a microsphere resonator simultaneously in order to make broadband optical absorbance measurements. The 340μm diameter microsphere is placed in a microfluidic channel. A hemispherical prism is used for coupling the WGMs into and out of the microsphere. The flat surface of the prism seals the microfluidic channel. The slight nonsphericity in the microsphere results in coupling to precessed modes whose emission is spatially separated from the reflected excitation light. The evanescent fields of the light trapped in WGMs interact with the surrounding environment. The change in transmission observed in the precessed modes is used to determine the absorbance of the surrounding environment. In contrast to our broadband optical absorbance measurements, previous WGM sensors have used only a single narrow mode to measure properties such as refractive index. With the microfluidic cell, we have measured the absorbance of solutions of dyes (lissamine green B, sunset yellow, orange G, and methylene blue), aromatic molecules (benzylamine and benzoic acid), and biological molecules (tryptophan, phenylalanine, tyrosine, and o-phospho-L-tyrosine) at visible and ultraviolet wavelengths. The microsphere surface was reacted with organosilane molecules to attach octadecyl groups, amino groups, and fluorogroups to the surface. Both electrostatic and hydrophobic interactions were observed between the analytes and the microsphere surface, as indicated by changes in the measured effective pathlength with different organosilanes. For a given analyte and coated microsphere, the pathlength measurement was repeatable within a few percent. Methylene blue dye had a very strong interaction with the surface and pathlengths of several centimeters were measured. Choosing an appropriate surface coating to interact with a specific analyte should result in the highest sensitivity detection.

  18. Air oxygenation chemistry of 4-TBC catalyzed by chloro bridged dinuclear copper(II) complexes of pyrazole based tridentate ligands: synthesis, structure, magnetic and computational studies.

    Science.gov (United States)

    Banerjee, Ishita; Samanta, Pabitra Narayan; Das, Kalyan Kumar; Ababei, Rodica; Kalisz, Marguerite; Girard, Adrien; Mathonière, Corine; Nethaji, M; Clérac, Rodolphe; Ali, Mahammad

    2013-02-01

    Four dinuclear bis(μ-Cl) bridged copper(II) complexes, [Cu(2)(μ-Cl)(2)(L(X))(2)](ClO(4))(2) (L(X) = N,N-bis[(3,5-dimethylpyrazole-1-yl)-methyl]benzylamine with X = H(1), OMe(2), Me(3) and Cl(4)), have been synthesized and characterized by the single crystal X-ray diffraction method. In these complexes, each copper(II) center is penta-coordinated with square-pyramidal geometry. In addition to the tridentate L(X) ligand, a chloride ion occupies the last position of the square plane. This chloride ion is also bonded to the neighboring Cu(II) site in its axial position forming an SP-I dinuclear Cu(II) unit that exhibits small intramolecular ferromagnetic interactions and supported by DFT calculations. The complexes 1-3 exhibit methylmonooxygenase (pMMO) behaviour and oxidise 4-tert-butylcatechol (4-TBCH(2)) with molecular oxygen in MeOH or MeCN to 4-tert-butyl-benzoquinone (4-TBQ), 5-methoxy-4-tert-butyl-benzoquinone (5-MeO-4-TBQ) as the major products along with 6,6'-Bu(t)-biphenyl-3,4,3',4'-tetraol and others as minor products. These are further confirmed by ESI- and FAB-mass analyses. A tentative catalytic cycle has been framed based on the mass spectral analysis of the products and DFT calculations on individual intermediates that are energetically feasible. PMID:23172025

  19. Synthesis and biological evaluation of spirocyclic antagonists of CCR2 (chemokine CC receptor subtype 2).

    Science.gov (United States)

    Strunz, Ann Kathrin; Zweemer, Annelien J M; Weiss, Christina; Schepmann, Dirk; Junker, Anna; Heitman, Laura H; Koch, Michael; Wünsch, Bernhard

    2015-07-15

    Activation of chemokine CC receptors subtype 2 (CCR2) plays an important role in chronic inflammatory processes such as atherosclerosis, multiple sclerosis and rheumatoid arthritis. A diverse set of spirocyclic butanamides 4 (N-benzyl-4-(3,4-dihydrospiro[[2]benzopyran-1,4'-piperidin]-1'-yl)butanamides) was prepared by different combination of spirocyclic piperidines 8 (3,4-dihydrospiro[[2]benzopyran-1,4'-piperidines]) and γ-halobutanamides 11. A key step in the synthesis of spirocyclic piperidines 8 was an Oxa-Pictet-Spengler reaction of β-phenylethanols 5 with piperidone acetal 6. The substituted γ-hydroxybutanamides 11c-e were prepared by hydroxyethylation of methyl acetates 13 with ethylene sulfate giving the γ-lactones 14c and 14e. Aminolysis of the γ-lactones 14c and 14e with benzylamines provided the γ-hydroxybutanamides 15c-e, which were converted into the bromides 11c-e by an Appel reaction using polymer-bound PPh3. In radioligand binding assays the spirocyclic butanamides 4 did not displace the iodinated radioligand (125)I-CCL2 from the human CCR2. However, in the Ca(2+)-flux assay using human CCR2 strong antagonistic activity of butanamides 4 was detected. Analysis of the IC50-values led to clear relationships between the structure and the inhibition of the Ca(2+)-flux. 4g (4-(3,4-dihydrospiro[[2]benzopyran-1,4'-piperidin]-1'-yl)-N-[3,5-bis(trifluoromethylbenzyl)]-2-(4-fluorophenyl)butanamide) and 4o (N-[3,5-bis(trifluoromethyl)benzyl]-2-cyclopropyl-4-(3,4-dihydrospiro[[2]benzopyran-1,4'-piperidin]-1'-yl)butanamide) represent the most potent CCR2 antagonists with IC50-values of 89 and 17nM, respectively. Micromolar activities were found in the β-arrestin recruitment assay with murine CCR2, but the structure-activity-relationships detected in the Ca(2+)-flux assay were confirmed. PMID:25766632

  20. Conformers, infrared spectrum, UV-induced photochemistry, and near-IR-induced generation of two rare conformers of matrix-isolated phenylglycine

    International Nuclear Information System (INIS)

    facile photofragmentation through two photochemical pathways that are favored for different initial conformations of the reactant: (a) decarboxylation, leading to CO2 plus benzylamine (the dominant photofragmentation channel in PG cis-COOH conformers ICa and ICc) and (b) decarbonylation, with generation of CO plus benzonitrile, H2O and H2 (prevalent in the case of the trans-COOH conformer, IITa)

  1. Study on the synthesis of thiirane diacrylate resin%环硫丙烯酸酯树脂的合成反应研究

    Institute of Scientific and Technical Information of China (English)

    李亚锋; 洪旭辉; 程珏

    2011-01-01

    The thiirane diacrylates and thiirane/epoxy diacrylates compound were synthesized from bisphenol A type thiirane resin ES128 and ES128/epoxy resin CYD128 respectively.The product structures were characterized by IR and the reaction mechanism was discussed.The effects of acrylic acid amount,solvent and feeding order on the the synthesis were studied.The results showed that the optimum synthesis conditions were as followed: toluene as solvent,molar ratio of epoxy to acrylic group 1∶ 2,reaction temperature 90 ℃ and reaction time 4.5 h.The process operation was as follewed: joining the acrylic acid,then heating and adding catalyst N,N-dimethyl benzylamine,which could effectively prevent the gel phenomenon.Compared with the epoxy groups,thiirane groups had lower reactivity with acrylic groups.%将双酚A型环硫树脂ES128,ES128/环氧树脂CYD128混合物分别与丙烯酸反应制备了环硫丙烯酸树脂及环硫/环氧丙烯酸酯树脂。以红外光谱表征了产物结构,讨论了反应机理,并对丙烯酸用量,溶剂及加料顺序等对反应的影响进行了研究。结果表明:较佳的合成工艺条件为:甲苯为溶剂,环氧官能团与丙烯酸物质的量比为1∶2,反应温度90℃,反应时间4.5 h。工艺操作为先加入丙烯酸,再升温加入催化剂N,N-二甲基苄胺,可有效防止凝胶现象发生。与环氧官能团相比,环硫官能团与丙烯酸的反应活性较低。

  2. Enzymatic modification of natural and synthetic polymers using lipases and proteases

    Science.gov (United States)

    Chakraborty, Soma

    Enzymatic modification of natural/synthetic polymers [starch nanoparticles, poly (n-alkyl acrylates) and poly(vinyl formamide)] was studied. Enzymes used for catalysis were lipases and proteases. Starch nanoparticles (40nm diameter) were incorporated into AOT-coated reverse micelles. Reactions performed with the acylating agents vinyl stearate, epsilon-caprolactone and maleic anhydride in toluene in presence of Novozyme-435 at 40°C for 36h gave products with degrees of substitution of 0.8, 0.6 and 0.4 respectively. DEPT-135 NMR spectra revealed that the modification occurred regioselectively at the C-6 position of the glucose units. Infrared microspectroscopy showed that the surfactant coated starch nanoparticles diffuse into pores of Novozyme-435 beads, coming in close proximity with CALB to promote modification. The modified products retained nanoscale dimensions. Catalysis of amide bond formation between a low molar mass amine and ester side groups of poly(n-alkyl acrylates)[poly(ethyl acrylate), poly(methyl acrylate) and poly(butyl acrylate)] was also examined. The nucleophiles were mono and diamines. Among the poly(n-alkyl acrylates) and the lipases studied, poly(ethyl acrylate) was the preferred substrate and Novozyme-435 the most active lipase. Poly(ethyl acrylate) in 80% by-volume toluene was reacted with 1 equivalent per repeat unit of hexyl amine at 70°C in presence of Novozyme-435. The product contained 10.6 mol% amide groups. Attempts to increase the amidation beyond 10--11 mol% by increasing the reaction time or use of fresh enzyme were unsuccessful, showing that poly(ethylacrylate-co-10mol%hexylacrylamide) is a poor substrate for further acylation. When chiral amines ([R,S]-alpha-methyl benzylamine, [R,S]-beta-methyl phenyl amine) were used as nucleophiles, Novozyme-435 enantioselectively catalyzed amidation of poly(ethyl acrylate). Poly(vinyl formamide), P(VfAm) by acid or base-catalyzed hydrolysis leads to poly(vinylamine), P(VAm), and

  3. Photo-fragmentation spectroscopy of benzylium and 1-phenylethyl cations

    Energy Technology Data Exchange (ETDEWEB)

    Féraud, Géraldine; Dedonder-Lardeux, Claude; Jouvet, Christophe, E-mail: christophe.jouvet@univ-amu.fr [Physique des Interactions Ioniques et Moleculaires, UMR CNRS 7345, Aix-Marseille Université, Avenue Escadrille Normandie-Niémen, 13397 Marseille Cedex 20 (France); Soorkia, Satchin [Institut des Sciences Moléculaires d’Orsay, CNRS UMR 8214, Université Paris Sud 11, 91405 Orsay Cedex (France)

    2014-01-14

    The electronic spectra of cold benzylium (C{sub 6}H{sub 5}-CH{sub 2}{sup +}) and 1-phenylethyl (C{sub 6}H{sub 5}-CH-CH{sub 3}{sup +}) cations have been recorded via photofragment spectroscopy. Benzylium and 1-phenylethyl cations produced from electrosprayed benzylamine and phenylethylamine solutions, respectively, were stored in a cryogenically cooled quadrupole ion trap and photodissociated by an OPO laser, scanned in parts of the UV and visible regions (600–225 nm). The electronic states and active vibrational modes of the benzylium and 1-phenylethyl cations as well as those of their tropylium or methyl tropylium isomers have been calculated with ab initio methods for comparison with the spectra observed. Sharp vibrational progressions are observed in the visible region while the absorption features are much broader in the UV. The visible spectrum of the benzylium cation is similar to that obtained in an argon tagging experiment [V. Dryza, N. Chalyavi, J. A. Sanelli, and E. J. Bieske, J. Chem. Phys. 137, 204304 (2012)], with an additional splitting assigned to Fermi resonances. The visible spectrum of the 1-phenylethyl cation also shows vibrational progressions. For both cations, the second electronic transition is observed in the UV, around 33 000 cm{sup −1} (4.1 eV) and shows a broadened vibrational progression. In both cases the S{sub 2} optimized geometry is non-planar. The third electronic transition observed around 40 000 cm{sup −1} (5.0 eV) is even broader with no apparent vibrational structures, which is indicative of either a fast non-radiative process or a very large change in geometry between the excited and the ground states. The oscillator strengths calculated for tropylium and methyl tropylium are weak. Therefore, these isomeric structures are most likely not responsible for these absorption features. Finally, the fragmentation pattern changes in the second and third electronic states: C{sub 2}H{sub 2} loss becomes predominant at higher

  4. Synthesis and application of two kinds of polycarboxylate ether superplasticizer%两种醚类聚羧酸减水剂的合成和应用

    Institute of Scientific and Technical Information of China (English)

    马保国; 胡家兵; 谭洪波

    2012-01-01

    Two kinds of polycarboxylate ether superplastieizer(APEG type and TPEG type)with different molecular structures were synthesized respectively under 65℃ and room temperature conditions and characterized by IR. The effects of the type of initiator, reaction temperature on the dispersant's performance of APEC system were investigated. The result showed that when the molar ratio of APEG to MA to SMAS is 1.0:2.40.4, and initiator (benzylamine compound) substitutes initiator (APS), which not only reduced the synthesis temperature but also improved dispersing capability. In addition, by research on compound technology, a series of problems such as high slump-loss owned by APEG type admixture and expensive cost owned by TPEG type admixture have been resolved and the scope of the application of different levels' concrete have also been broadened.%分别在65℃和室温下合成APEG型和TPEG型2种不同分子结构的醚类聚羧酸减水剂.通过红外光谱对其分子结构进行表征,讨论了反应温度、引发剂种类对APEG体系分散性能的影响.结果表明,当n(APEG)∶n (MA)∶n(SMAS)=1.0∶2.4∶0.4,用苄胺复合引发剂(IM)替代常用过硫酸铵(APS)引发剂时,不但能降低合成温度而且提高了减水剂的分散性能.此外,对2种体系减水剂进行复配研究,解决了APEG型减水剂经时损失大和TPEG型价格昂贵等问题,拓宽了2种减水剂在不同等级混凝土中的应用范围.

  5. Drug-likeness approach of 2-aminopyrimidines as histamine H3 receptor ligands.

    Science.gov (United States)

    Sadek, Bassem; Schreeb, Annemarie; Schwed, Johannes Stephan; Weizel, Lilia; Stark, Holger

    2014-01-01

    A small series of compounds containing derivatives of 2,4-diamino- and 2,4,6-triaminopyrimidine (compounds 2-7) was synthesized and tested for binding affinity to human histamine H3 receptors (hH3Rs) stably expressed in HEK-293 cells and human H4Rs (hH4Rs) co-expressed with Gαi2 and Gβ1γ2 subunits in Sf9 cells. Working in part from the lead compound 6-(4-methylpiperazin-1-yl)-N (4)-(3-(piperidin-1-yl)propyl)pyrimidine-2,4-diamine (compound 1) with unsatisfactory affinity and selectivity to hH3Rs, our structure-activity relationship studies revealed that replacement of 4-methylpiperazino by N-benzylamine and substitution of an amine group at the 2-position of the 2-aminopyrimidine core structure with 3-piperidinopropoxyphenyl moiety as an hH3R pharmacophore resulted in N (4)-benzyl-N (2)-(4-(3-(piperidin-1-yl)propoxy)phenyl)pyrimidine-2,4-diamine (compound 5) with high hH3R affinity (k(i) =4.49 ± 1.25 nM) and H3R receptor subtype selectivity of more than 6,500×. Moreover, initial metric analyses were conducted based on their target-oriented drug-likeness for predictively quantifying lipophilicity, ligand efficiency, lipophilicity-dependent ligand efficiency, molecular size-independent efficiency, and topological molecular polar surface. As to the development of potential H3R ligands, results showed that integration of the hH3R pharmacophore in hH4R-affine structural scaffolds resulted in compounds with high hH3R affinity (4.5-650 nM), moderate to low hH4R affinity (4,500-30,000 nM), receptor subtype selectivity (ratio hH4R/hH3R; 8-6,500), and promising calculated drug-likeness properties. PMID:25278747

  6. Drug-likeness approach of 2-aminopyrimidines as histamine H3 receptor ligands

    Directory of Open Access Journals (Sweden)

    Sadek B

    2014-09-01

    Full Text Available Bassem Sadek,1 Annemarie Schreeb,2 Johannes Stephan Schwed,2,3 Lilia Weizel,2 Holger Stark3 1Department of Pharmacology and Therapeutics, College of Medicine and Health Sciences, United Arab Emirates University, Al Ain, United Arab Emirates; 2Biocenter, Institute of Pharmaceutical Chemistry, Johann-Wolfgang Goethe University, Frankfurt, Germany; 3Institute of Pharmaceutical and Medicinal Chemistry, Heinrich Heine University, Duesseldorf, Germany Abstract: A small series of compounds containing derivatives of 2,4-diamino- and 2,4,6-triaminopyrimidine (compounds 2–7 was synthesized and tested for binding affinity to human histamine H3 receptors (hH3Rs stably expressed in HEK-293 cells and human H4Rs (hH4Rs co-expressed with Gαi2 and Gβ1γ2 subunits in Sf9 cells. Working in part from the lead compound 6-(4-methylpiperazin-1-yl-N4-(3-(piperidin-1-ylpropylpyrimidine-2,4-diamine (compound 1 with unsatisfactory affinity and selectivity to hH3Rs, our structure-activity relationship studies revealed that replacement of 4-methylpiperazino by N-benzylamine and substitution of an amine group at the 2-position of the 2-aminopyrimidine core structure with 3-piperidinopropoxyphenyl moiety as an hH3R pharmacophore resulted in N4-benzyl-N2-(4-(3-(piperidin-1-ylpropoxyphenylpyrimidine-2,4-diamine (compound 5 with high hH3R affinity (ki =4.49±1.25 nM and H3R receptor subtype selectivity of more than 6,500×. Moreover, initial metric analyses were conducted based on their target-oriented drug-likeness for predictively quantifying lipophilicity, ligand efficiency, lipophilicity-dependent ligand efficiency, molecular size-independent efficiency, and topological molecular polar surface. As to the development of potential H3R ligands, results showed that integration of the hH3R pharmacophore in hH4R-affine structural scaffolds resulted in compounds with high hH3R affinity (4.5–650 nM, moderate to low hH4R affinity (4,500–30,000 nM, receptor subtype selectivity

  7. Enhanced visible-light photocatalytic activity for selective oxidation of amines into imines over TiO{sub 2}(B)/anatase mixed-phase nanowires

    Energy Technology Data Exchange (ETDEWEB)

    Dai, Jun [Institute of Applied Chemistry, Henan Polytechnic University, Jiaozuo 454003 (China); State Key Laboratory Cultivation Base for Gas Geology and Gas Control, School of Safety Science and Engineering, Henan Polytechnic University, Jiaozuo 454003 (China); Yang, Juan, E-mail: yangjuanhpu@yahoo.com [Institute of Applied Chemistry, Henan Polytechnic University, Jiaozuo 454003 (China); Wang, Xiaohan; Zhang, Lei; Li, Yingjie [Institute of Applied Chemistry, Henan Polytechnic University, Jiaozuo 454003 (China)

    2015-09-15

    Graphical abstract: Visible-light photocatalytic activities for selective oxidation of amines into imines are greatly affected by the crystal structure of TiO{sub 2} catalysts and mixed-phase TiO{sub 2}(B)/anatase possess higher photoactivity because of the moderate adsorption ability and efficient charge separation. - Highlights: • Visible-light photocatalytic oxidation of amines to imines is studied over different TiO{sub 2}. • Photocatalytic activities are greatly affected by the crystal structure of TiO{sub 2} nanowires. • Mixed-phase TiO{sub 2}(B)/anatase exhibits higher catalytic activity than single-phase TiO{sub 2}. • Enhanced activity is ascribed to efficient adsorption ability and interfacial charge separation. • Photoinduced charge transfer mechanism on TiO{sub 2}(B)/anatase catalysts is also proposed. - Abstract: Wirelike catalysts of mixed-phase TiO{sub 2}(B)/anatase TiO{sub 2}, bare anatase TiO{sub 2} and TiO{sub 2}(B) are synthesized via calcining precursor hydrogen titanate obtained from hydrothermal process at different temperatures between 450 and 700 °C. Under visible light irradiation, mixed-phase TiO{sub 2}(B)/anatase TiO{sub 2} catalysts exhibit enhanced photocatalytic activity in comparison with pure TiO{sub 2}(B) and anatase TiO{sub 2} toward selective oxidation of benzylamines into imines and the highest photocatalytic activity is achieved by TW-550 sample consisting of 65% TiO{sub 2}(B) and 35% anatase. The difference in photocatalytic activities of TiO{sub 2} samples can be attributed to the different adsorption abilities resulted from their crystal structures and interfacial charge separation driven by surface-phase junctions between TiO{sub 2}(B) and anatase TiO{sub 2}. Moreover, the photoinduced charge transfer mechanism of surface complex is also proposed over mixed-phase TiO{sub 2}(B)/anatase TiO{sub 2} catalysts. Advantages of this photocatalytic system include efficient utilization of solar light, general suitability to

  8. The prominent role of serotonergic degeneration in apathy, anxiety and depression in de novo Parkinson's disease.

    Science.gov (United States)

    Maillet, Audrey; Krack, Paul; Lhommée, Eugénie; Météreau, Elise; Klinger, Hélène; Favre, Emilie; Le Bars, Didier; Schmitt, Emmanuelle; Bichon, Amélie; Pelissier, Pierre; Fraix, Valérie; Castrioto, Anna; Sgambato-Faure, Véronique; Broussolle, Emmanuel; Tremblay, Léon; Thobois, Stéphane

    2016-09-01

    SEE SCHRAG AND POLITIS DOI101093/AWW190 FOR A SCIENTIFIC COMMENTARY ON THIS ARTICLE: Apathy, which can occur separately or in combination with depression and anxiety, is one of the most frequently encountered neuropsychiatric symptoms in Parkinson's disease. Pathophysiological evidence suggests that parkinsonian apathy is primarily due to a mesolimbic dopaminergic denervation, but the role of the serotonergic alteration has never been examined, despite its well-known involvement in the pathogenesis of depression and anxiety. To fill this gap, we address here the pure model of de novo Parkinson's disease, without the confounding effects of antiparkinsonian treatment. Fifteen apathetic (Lille Apathy Rating Scale scores ≥ -21) and 15 non-apathetic (-36 ≤ Lille Apathy Rating Scale scores ≤ -22) drug-naïve de novo parkinsonian patients were enrolled in the present study and underwent detailed clinical assessment and positron emission tomography imaging, using both dopaminergic [(11)C-N-(3-iodoprop-2E-enyl)-2-beta-carbomethoxy-3-beta-(4-methylphenyl)-nortropane (PE2I)] (n = 29) and serotonergic [(11)C-N,N-dimethyl-2-(-2-amino-4-cyanophenylthio)-benzylamine (DASB)] (n = 27) presynaptic transporter radioligands. Apathetic parkinsonian patients presented higher depression (P = 0.0004) and anxiety (P = 0.004) scores - as assessed using the Beck Depression Inventory and the part B of the State-Trait Anxiety Inventory, respectively - compared to the non-apathetic ones - who were not different from the age-matched healthy subjects (n = 15). Relative to the controls, the non-apathetic parkinsonian patients mainly showed dopaminergic denervation (n = 14) within the right caudate nucleus, bilateral putamen, thalamus and pallidum, while serotonergic innervation (n = 15) was fairly preserved. Apathetic parkinsonian patients exhibited, compared to controls, combined and widespread dopaminergic (n = 15) and serotonergic (n = 12) degeneration within the bilateral caudate nuclei

  9. Reactions of hydridoirida-β-diketones with amines or with 2-aminopyridines: formation of hydridoirida-β-ketoimines, PCN terdentate ligands, and acyl decarbonylation.

    Science.gov (United States)

    Ciganda, Roberto; Garralda, María A; Ibarlucea, Lourdes; Mendicute-Fierro, Claudio; Torralba, M Carmen; Torres, M Rosario

    2012-02-01

    The hydridoirida-β-diketone [IrHCl{(PPh(2)(o-C(6)H(4)CO))(2)H}] (1) reacts with benzylamine (C(6)H(5)CH(2)NH(2)) to give the hydridoirida-β-ketoimine [IrHCl{(PPh(2)(o-C(6)H(4)CO))(PPh(2)(o-C(6)H(4)CNCH(2)C(6)H(5)))H}] (2), stabilized by an intramolecular hydrogen bond. 2 reacts with water to undergo hydrolysis and amine coordination giving hydridodiacylamino [IrH(PPh(2)(o-C(6)H(4)CO))(2)(C(6)H(5)CH(2)NH(2))] (3). Cyclohexylamine or dimethylamine lead to hydridodiacylamino [IrH(PPh(2)(o-C(6)H(4)CO))(2)L] (4-5). In chlorinated solvents hydridodiacylamino complexes undergo exchange of hydride by chloride to afford [IrCl(PPh(2)(o-C(6)H(4)CO))(2)L] (6-9). The reaction of 1 with hydrazine (H(2)NNH(2)) gives hydridoirida-β-ketoimine [IrHCl{(PPh(2)(o-C(6)H(4)CO))(PPh(2)(o-C(6)H(4)CNNH(2)))H}] (10), fluxional in solution with values for ΔH(‡) of 2.5 ± 0.3 kcal mol(-1) and for ΔS(‡) of -32.9 ± 3 eu. A hydrolysis/imination sequence can be responsible for fluxionality. 2-Aminopyridines (RHNC(5)H(3)R'N) react with 1 to afford cis-[IrCl(PPh(2)(o-C(6)H(4)CO))(PPh(2)(o-C(6)H(4)CHNRC(5)H(3)R'N))] (R = R' = H (11), R = CH(3), R' = H (12), R = H, R' = CH(3) (13)) containing new terdentate PCN ligands in a facial disposition and cis phosphorus atoms as kinetic products. The formation of 11-13 requires imination of the hydroxycarbene moiety of 1, coordination of the nitrogen atom of pyridine to iridium, and iridium to carbon hydrogen transfer. In refluxing methanol, complexes 11-13 isomerize to afford the thermodynamic products 14-16 with trans phosphorus atoms. Chloride abstraction from complexes [IrCl(PPh(2)(o-C(6)H(4)CO))(PPh(2)(o-C(6)H(4)CHNRC(5)H(4)N))] (R = H or CH(3)) leads to decarbonylation of the acylphosphine chelating group to afford cationic complexes [Ir(CO)(PPh(2)(o-C(6)H(4)))(PPh(2)(o-C(6)H(4)CHNRC(5)H(4)N))]A, 17 (R = H, A = ClO(4)) and 18 (R = CH(3), A = BF(4)) as a cis/trans = 4:1 mixture of isomers. Single crystal X-ray diffraction analysis was performed

  10. 《化学通报》网络版(Chemistry Online)2001年5月论文摘要

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    catalysts, the concentration of sodium hydroxide, reaction temperature and time are investigated. The optimum conditions of the reaction are presented. [W01045] 乙酰邻苯二甲酰亚氨基半乳糖端基乙酰基脱除的新方法 A Novel Method for Anomeric Deacetylation of β-D-Tetra-O-acetyl-phthalimido-galactopyranose 高拥军 李 庆 蔡孟深 李中军* (北京大学药学院化学生物学系天然药物与仿生药物国家重点实验室 北京 100083)   本文首次使用苄胺作为弱碱选择性脱除四乙酰邻苯二甲酰亚氨基半乳糖的端基乙酰基。本法将1.7∶1.0(摩尔比)的苄胺与1,3,4,6-四-O-乙酰基-2-脱氧-2-邻苯二甲酰亚氨基-β-D-吡喃半乳糖(2)溶于THF中, 室温搅拌24h, 目标产物收率82%。   First use of benzylamine as a mild and efficient reagent for removal of the anomeric acetyl group of 1,3,4,6-tetra-O-acetyl-2-deoxy-2-phthalimido-β-D-galactopyranose(2) is described. Treatment of 2 with an excess of benzylamine in anhydrous THF at room temperature for 24h gave 3,4,6-tetra-O-acetyl-2-deoxy-2-phthalimido-β-D-galactopyranose with the yield of more than 80%.    [W01046] 三链核酸稳定性的阳离子效应研究进展 The Effects of Cations on the Stability of Triple Helix Nucleic Acid 邬瑞光 尉志武* 周 蕊 (清华大学化学系生命有机磷化学教育部重点实验室 北京 100084)   三链DNA的稳定性是其研究领域的热点之一,而阳离子效应又是影响这一稳定性的重要因素。本文总结了近年来这方面工作的实验方法和结论,并讨论了目前还存在的需进一步研究的问题。   The effect of cations on the stability of triple helix DNA is of importance in the understanding of its structure-function relationship. Both experimental methods and latest findings concerning the stability of triple helix DNA are summarized. In the context of discussions of remaining problems, suggestions for