Organic acid doped polyaniline derivatives

Soluble poly (o-toluidine) (POT), poly(o-anisidine) (PAs) and poly (o-chloroaniline) (PCAn) were doped with camphorsulfonic acid (CSA). The conductivity and UV-Vis spectra of the CSA-doped POT, PAs and PCAn were studied. These properties were found to be dependent on the solvent used. The cast films from m-cresol solution exhibit more effective doping and higher conductivity.

SIMULTANEOUS DETERMINATION OF GUANINE, URIC-ACID, HYPOXANTHINE AND XANTHINE IN HUMAN PLASMA BY REVERSED-PHASE HIGH-PERFORMANCE LIQUID-CHROMATOGRAPHY WITH AMPEROMETRIC DETECTION

A reversed-phase high-performance liquid chromatographic method with amperometric detection is described for the separation and quantification of uric acid, guanine, hypoxanthine and xanthine. The isocratic separation of a standard mixture of the compounds was achieved in 5 min on a Spherisorb 5 C-18 reversed-phase column, with a mobile phase of NaH2PO4 (300 mmol dm(-3) pH 3.0)-methanol-acetonitrile-tetrahydrofuran (97.8 + 0.5 + 1.5 + 0.2). Uric acid, guanine, hypoxanthine and xanthine were completely separated, with detection limits in the range 2-20 pmol per injection. The effect of pH and the composition of the mobile phase on the separation are described. The hydrodynamic voltammograms of these compounds were recorded at a glassy carbon electrode. The linear range of the calibration graph for each compound was: uric acid; 1-5000 mu mol dm(-3); guanine, 0.5-2000 mu mol dm(-3); hypoxanthine, 0.1-500 mu mol dm(-3) and xanthine, 0.5-5000 mu mol dm(-3). The within- and between-day precision was good. The uric acid and hypoxanthine content in human plasma was measured using the proposed method. Good recoveries of uric acid (97.9-103%), hypoxanthine (98.0-99.2%), guanine (96.0-98.3%) and xanthine (96.0-102%) were obtained from human plasma. The results of electrochemical detection were in good agreement with those of UV detection.

SOLVENT-EXTRACTION OF SC(III), ZR(IV), TH(IV), FE(III), AND LU(III) WITH THIOSUBSTITUTED ORGANOPHOSPHINIC ACID EXTRACTANTS

The solvent extraction of Sc(III), Zr(IV), Th(IV), Fe(III) and Lu(III) with Cyanex 302 (bis(2,4,4-trimethylpentyl)monothiophosphinic acid) and Cyanex 301 ( bis(2,4,4-trimethylpentyl) dithiophosphinic acid) in n-hexane from acidic aqueous solutions has been investigated systematically. The effect of equilibrium aqueous acidity on the extraction with these reagents was studied. The separation of Th(IV), Fe(III) and Lu(III) from Sc(III), or the separation of other metals from Lu(III) with Cyanex 302, can be achieved by controlling the aqueous acidity. However, Cyanex 301 exhibited a poor selectivity for the above metals, except for Lu(III). The extraction of these metals with Cyanex 272, Cyanex 302 and Cyanex 301 has been compared. The stripping percentages of Sc(III) for Cyanex 302 and Cyanex 301 in a single stage are near 78% and 75% with 3.5 mol/L and 5.8 mol/L sulphuric acid solutions, respectively. The effects of extractant concentration and temperature on the extraction of Sc(III) were investigated. The stoichiometry of the extraction of Sc(III) with Cyanex 302 was determined. The role of different components of Cyanex 302 in the extraction of Sc(III) was discussed.

四-4-(烷氧基-羰基)酞菁铜(Ⅱ)的合成、结构及其成膜性

本文合成了两种新型取代酞菁铜(Ⅱ)配合物:四-4-(戊氧基-羰基)酞菁铜(Ⅱ)(A)和四-4-(癸氧基-羰基)酞菁铜(Ⅱ)(B),并通过元素分析、ESR、~1H-NMR和FT-IR进行了表征.用可见光谱研究了它们在氯仿溶液中的聚集形式;用X-ray粉末衍射方法研究了配合物的固相堆积排列结构.两种配合物的氯仿溶液在亚相(水)上的π-A曲线表明,它们均有明显的“气”“液”“固”变化过程;并能在不同的表面压力区间形成较好的单分子层和多分子层膜.

THE SYNTHESIS AND CRYSTAL-STRUCTURE OF MOLYBDENUM-SILICON BLUE

The single crystal of heteropoly blue, HsSiMo12O40.12H2O, the reduced product of molybdenum-silicon heteropoly acid, was prepared by electrochemical reduction and evaporation in nitrogen atmosphere. The Crystal structure of the product was determined. The heteropoly blue H8SiMo12O40.12H2O, Crystallizes space group P1BAR a = 1.3769 (3) nm, b = 1.4346 (4) nm, c = 1.4134 (4) nm, alpha = 120.47 (2)-degrees, beta = 110.70 (2)-degrees, gamma = 66.11 (2)-degrees, Z = 2, R = 0.0608. The heteropoly blue anion was determined to have Keggin Structure and alpha-isomer and it remained the structure of the unreduced heteropoly acid anion. But the distortion of the structure and the changes of bond length and bond angle take place obviously. The four Mo5+ Positions were determined in the structure.

CRYSTAL-STRUCTURE OF 1, 10-DECANEDIAMMONIUM TETRACHLOROZINCATE

The crystal structure of the title compound has been determined from single crystal X-ray diffraction. The complex crystallizes in the triclinic space group P1 with Z=2. Lattice parameters are: a = 0.7296(1), b = 1.0110(3), c = 1.2814(4) nm; alpha = 90.84(2), beta = 101.17(2), gamma = 92.52(2)-degrees. Intensity data were collected on a Nicolet R3M/E four-circle diffractometer using MoK alpha (lambda = 0.071073 nm) radiation. The structure was solved by Patterson and Fourier techniques and refined by least-squares techniques to R = 0.065. The structure of the complex consists of tetrahedral ZnCl42- anions which form a two-dimensional sheets. Tetrahedral ZnCl42- anions are sandwiched between two hydrocarbon layers which consist of [NH3(CH2)10NH3]2+ cations. Each [NH3(CH2)10NH3]2+ group is in a gauche bond between C atoms near NH3 polar heads.

四氯合锌酸1,10-癸二铵配合物的晶体结构

合成了[NH_3(CH_2)_(10)NH_3]ZnCl_4配合物(简称DDAZn),用X射线衍射法研究了它的晶体结构,晶体属三斜晶系,空间群为P1,晶胞参数为:α=0.7296(1),b=1.0110(3),c=1.2814(4)nm;α=90.84(2),β=101.17(2),γ=92.52(2)°;Z=2.该配合物为层型结构.由单个四面体阴离子ZnCl_4~(2-)构成的阴离子层被夹在烷基铵阳离子层之间,形成“夹心面包”型体系.在层之间的烷基铵链在垂直于层的方向上倾斜排列.

Chemical Constituents of a Marine-Derived Endophytic Fungus Penicillium commune G2M

Cultivation of the endophytic fungus Penicillium commune, which was isolated from the semi-mangrove plant Hibiscus tiliaceus, afforded one new compound 1-O-(2,4-dihydroxy-6-methylbenzoyl)-glycerol (1) along with thirteen known products, including 1-O-acetylglycerol (2), N-acetyltryptophan (3), 3-indolylacetic acid methyl ester (4), 1-(2,4-dihydroxy-3,5-dimethylphenyl)ethanone (5), 2-(2,5-dihydroxyphenyl)acetic acid (6), (4R,5S)-5-hydroxyhexan-4-olide (7), thymidine (8), uracil (9), thymine (10), ergosterol (11), beta-sitosterol (12), beta-daucosterol (13), and ergosta-7,22-dien-3 beta,5 alpha,6 beta-triol (14). The structures of these compounds were established by detailed NMR spectroscopic analysis, as well as by comparison with literature data or with authentic samples.

Natural bromophenols from the marine red alga Polysiphonia urceolata (Rhodomelaceae): Structural elucidation and DPPH radical-scavenging activity

Three new natural occurring bromophenols, 3-(3-bromo-4,5-dihydroxyphenyl)-2-(3,5-dibromo-4-hydroxyphenyl)propionic acid (1), (E)-4-(3-bromo-4,5-dihydroxyphenyl)-but-3-en-2-one (2), and (3,5-dibromo-4-hydroxyphenyl) acetic acid butyl ester (3), together with one known bromophenol, 1,2-bis(3-bromo-4,5-dihydroxyphenyl)ethane (4), were isolated and identified from the marine red alga Polysiphonia urceolata. The structures of these compounds were elucidated by extensive analysis of ID and 2D NMR and IR spectra and MS data. Each of the isolated compounds was evaluated for scavenging alpha,alpha-diphenyl-beta-picrylhydrazyl (DPPH) radical activity and all of them exhibited significant activity with IC50 values ranging from 9.67 to 21.90 mu M, compared to the positive control, a well-known antioxidant butylated hydroxytoluene (BHT), with IC50 83.84 mu M. (C) 2007 Elsevier Ltd. All rights reserved.

皮状丝孢酵母发酵大米草水解液生产微生物油脂

大米草是一种外来引种植物，本来引进的目的是为了保滩护岸、促淤造陆。然而大米草过度繁殖，侵袭海洋沿岸滩涂，所以综合开发大米草有着重要的经济意义和生态意义。本实验研究着力于将大米草水解液通过皮状丝孢酵母发酵而制取生物油脂。并且随着近年来石油价格的攀升和对于汽车尾气对环境造成的日趋严重的污染，生物柴油的开发受到高度重视。微生物油脂则是生物柴油生产的很好的原料，因为它无需占用耕地，而能够把农业加工剩余物或是其它的含纤维素的生物质转化为油脂。 本实验采用产油酵母菌皮状丝孢酵母（Trichosporon cutaneum）直接发酵经过简单脱毒处理的大米草水解液生产微生物油脂。在122℃，固—液比为10%（w/v），分别用1%、2%、4%和6%稀硫酸水解大米草，结果表明在6%的酸浓度下水解40 min后还原糖含量最高，达到22.8 g/L。而同时以1%稀硫酸在140℃下水解大米草，2.8h后，水解液中葡萄糖产量达到最高14.2g/L。确定了摇瓶发酵最适工艺条件：摇床转速200 rpm，接种量10%（v/v），装液量为200 mL (1000-mL三角瓶)。在此基础上，确定了水解液最适浓缩倍数和pH值，水解液浓缩倍数为4.0时产油量高达6.0 g/L，产油率为46.3%。本文为高效利用大米草提供了新的途径。 关键词:皮状丝孢酵母,大米草,水解,发酵,微生物油脂

三种海洋红藻和两株放线菌次级代谢产物研究

海洋是一个巨大的天然产物宝库，约占地球表面积70%的海洋蕴藏着80%的生物资源。由于海洋生态环境的特殊性，导致海洋生物能够产生大量结构独特多变和活性特殊多样的代谢产物。我国海域辽阔，海洋资源丰富，为寻找结构新颖、生理活性独特的先导化合物，加强对海洋资源的开发利用，本论文对中国沿海的三种海洋红藻和两株放线菌次生代谢产物以及生物活性进行研究，为新药研究与开发提供模式结构和药物前体。 对红藻似瘤凹顶藻Laurencia similis乙酸乙酯萃取物进行分离纯化，从中得到单体化合物35个，通过波谱学方法（IR、MS、NMR等）鉴定了他们的结构。分别为：2, 2, 5, 5, 6, 6-sixibromo-3, 3-bi-1H-indole (1)，3,5-dibromo- 1-methyl-indole (2)，3',5',6,6'-tetrabromo-2,4-dimmethyldiphenyl ether (3)，1,2,5- tribromo-3-bromoamino-7-bromomethylnaphthalene (4)，2,5,8-tribromo-3-bromo- amino-7-bromomethylnaphthalene (5)，2,5,6-tribromo-3-bromoamino-7-bromo- methylnaphthalene (6), 2,5,6,5',6'-pentabromo-3,4,3',4'-tetramethoxybenzophenone (7), (4E)-1-bromo-5-[(1'S*,3'R*)-3'-bromo-2',2'-dimethyl-6'-methylenecyclohexyl] -3-methylpent-4-ene-2,3-diol (8)，4-hydroxy-Palisadin C (9)，Isopalisol (10)，Luzonensol (11)，Palisadin B (12)，Aplysistatin (13)，Palisadin A (14)，5-Acetoxypalisadin B (15)，Aristolan-1(10)- en-9-ol (16)，Aristol-8-en-1-one (17)，Aristolan-9-en-1-one (18)，Aristolan-1(10)-en- 9-one (19)，Aristofone (20)，Aristolan-1(10)-8-diene (21)，Aristolan-1,9-diene (22)，10-Hydroxyaristolan-9-one (23)，7,11,15-trimethyl-3-methylene-hexadecan-1,2-diol (24)，3β-Hydroxyergosta- 5,24(28)-dien-7-one (25)，Isofucosterol (26)，β-sitosterol (27)，豆甾-4-烯-3α,6β-二醇 (28)，Cholesta-5-en-3β-ol (29)，Stigmasterol (30)，2,3,5,6-四溴-吲哚 (31)，2,3,6-tribromo-1H-indole (32)，3,5,6-tribromo-1-methylindole (33)，3,5,6-tribromo -1H-indole (34)，2,3,5-tribromo-1-methylindole (35)，其中化合物1-9为新化合物，化合物10-15、20和化合物24-30均为首次从该种海藻中得到。对新化合物1-9进行PTP1B酶抑制剂活性筛选，新化合物1、3、7显示强的PTP1B酶抑制活性。 对红藻齐藤凹顶藻Laurencia saitoi乙酸乙酯萃取物进行分离纯化，从中得到单体化合物11个，通过波谱学方法（IR、MS、NMR等）鉴定了他们的结构，分别为：2-hydroxyl-Luzofuranone (1)，2-hydroxyl-Luzofuranone B (2)，4-hydroxyl-Palisudin C (3)，2-bromo-γ-ionone (4)，Aplysistatin (5)，5-Acetoxypalisadin B (6)，Palisadin B (7)，Palisadin A (8)，Pacifigorgiol (9)，豆甾-4-烯-3α,6β-二醇 (10)，2, 3, 5, 6-四溴-吲哚 (11)，其中化合物1-4为新化合物，所有化合物均为首次从该种海藻中得到。通过MTT法对分离得到的新化合物1-4进行肿瘤细胞毒活性筛选，结果显示4个新化合物对所测肿瘤细胞株均无明显的活性。 对红藻瘤状软骨凹顶藻Chondrophycus papillous乙酸乙酯萃取物进行分离纯化，从中得到单体化合物5个，通过波谱学方法（MS、NMR等）鉴定了他们的结构，分别为邻苯二甲酸二丁酯 (1)，邻苯二甲酸二异辛酯 (2)，胆甾醇 (3)，3,7,11,15-tetramethyl-hexadec-2-en-1-ol (4)，4-羟基苯甲醛 (5)，所有化合物均为首次从该种海藻中得到。 对海洋放线菌M159乙酸乙酯萃取物进行分离纯化，从中得到单体化合物13个，通过波谱学方法（MS、NMR等）鉴定了他们的结构，分别为：5-(4',6'-dihydroxy-6-methyloctyl)furan-2(5H)-one (A)，phenethyl alcohol (1)，4-羟基苯甲醛(2)，anthranilic acid (3)，4-Hydroxy-3-methoxy- phenyl-propionic acid (4)，5-(6,7-dihydroxy-6-methyloctyl)furan-2(5H)-one (5)，p-Hydroxyphenylethyl alcohol (6)，3-Indoleacrylic acid (7)，Indol-3-carboxylic acid (8)，Adenine cordyceposide (9)，腺嘌呤核苷(10)，尿嘧啶核苷(11)，Thymidine (12)，其中化合物A为新化合物。所有化合物均为首次从该株放线菌中得到。 对海洋放线菌L211乙酸乙酯萃取物进行分离纯化，从中得到单体化合物15个，通过波谱学方法（MS、NMR等）鉴定了7个结构，分别为：spatozoate (1)，anthranilic acid (2)，3-Indolylethanol (3)，1-Acetyl-β-carbolin (4)，p-Hydroxyphen- ylethyl alcohol (5)，Indole-3-acetic acid (6)，Indol-3-carboxylic acid (7)，所有化合物均为首次从该株放线菌中得到。

Bromophenols from the red alga Rhodomela confervoides

Six new bromophenols, 3-bromo-4,5-bis(2,3-dibromo-4,5-dihydroxybenzyl)pyrocatechol (1), 2,2',3-tribromo-3',4,4',5-tetrahydroxy-6'-hydroxymethyldiphenylmethane (2), 2,2',3-tribromo-3',4,4',5-tetrahydroxy-6'-ethyloxymethyldiphenylmethane (3),(+/-)-2-methyl-3-(2,3-dibromo-4,5-dihydroxyphenyl)propylaldehyde (4), (+/-)-2-methyl-3-(2,3-dibromo-4,5-dihydroxyphenyl)propylaldehyde dimethyl acetal (5), and 3-bromo-4,5-dihydroxybenzoic acid methyl ester (6), together with eight known bromophenols, 3-bromo-4,5-dihydroxybenzaldehyde (7), 2,3-dibromo-4,5-dihydroxybenzyl alcohol (lanosol, 8), 2,3-dibromo-4,5-dihydroxybenzyl methyl ether (9), 2,3-dibromo-4,5-dihydroxybenzyl ethyl ether (10), 2,3-dibromo-4,5-dihydroxybenzylaldehyde (11), bis(2,3-dibromo-4,5-dihydroxybenzyl) ether (12), 3-bromo-4-(2,3-dibromo-4,5-dihydroxybenzyl)-5-methoxymethylpyrocatechol (13), and 2,2',3,3'-tetrabromo-4,4',5,5'-tetrahydroxydiphenyl methane (14), were isolated from the red alga Rhodomela confervoides. Their structures were elucidated by chemical and spectroscopic methods including IR, HRFABMS, and 1D and 2D NMR techniques.

Adsorption and Corrosion Inhibition Behavior of Mild Steel by One Derivative of Benzoic-Triazole in Acidic Solution

A newly synthesized benzoic-triazole derivative 3,5-dimethylbenzoic acid [1,2,4]triazol-l-ylmethyl ester (DBT) was investigated as a corrosion inhibitor of mild steel in 1 M HCl solution using weight loss measurements, potentiodynamic polarization, SEM, and EIS methods. The results revealed that DBT was an excellent inhibitor, and the inhibition efficiencies obtained from weight loss and electrochemical experiments were in good agreement. Using the potentiodynamic polarization technique, the inhibitor was proved to have a mixed-type character for mild steel by suppressing both anodic and cathodic reactions on the metal surface. The number of water molecules (X) replaced by a molecule of organic adsorbate was determined from the Flory-Huggins, Dhar-Flory-Huggins, and Bockris-Swinkels substitutional adsorption isotherms applied to the data obtained from the gravimetric experiments performed on a mild steel specimen in 1 M HCl solution at 298 K.

Some new triazole derivatives as inhibitors for mild steel corrosion in acidic medium

Two triazole derivatives, 3,4-dichloro-acetophenone-O-1'-(1',3',4'-triazolyl)-methaneoxime (4-DTM) and 2,5-dichloro-acetophenone-O-1'-(1',3',4'-triazolyl)-methaneoxime (5-DTM) were synthesized, and the inhibition effects for mild steel in 1 M HCl solutions were investigated by weight loss measurements, electrochemical tests and scanning electronic microscopy (SEM). The weight loss measurements showed that these compounds have excellent inhibiting effect at a concentration of 1.0 x 10(-3) M. The potentiodynamic polarization experiment revealed that the triazole derivatives are inhibitors of mixed-type and electrochemical impedance spectroscopy (EIS) confirmed that changes in the impedance parameters (R-ct and C-dl) are due to surface adsorption. The inhibition efficiencies obtained from weight loss measurements and electrochemical tests were in good agreement. Adsorption followed the Langmuir isotherm with negative values of the free energy of adsorption Delta G(ads)(o). The thermodynamic parameters of adsorption were determined and are discussed. Results show that both 4-DTM and 5-DTM are good inhibitors for mild steel in acid media.

Chemical Constituents of Nitraira tangutorum Seed from Qaidam Basin

Six compounds were isolated from the 75% ethanol extract of Nitraria tangutorum seed.On the basis of spectroscopic methods including 1H NMR,13C NMR and ESI-MS and comparison with literature,their structures were elucidated as daucosterol(1),4-hydroxypipecolic acid(2),quercetin(3),allantoin(4),1,2,3,4-tetrahydro-1-methyl-β-carboline-3-carboxylic acid(5) and L-tyrosine(6).Compounds 1,2,3,5 and 6 were isolated from Nitraria tangtorum for the first time.