Polyaniline doped with macromolecular acids

Polyaniline was doped with sulfonated PS, PPO and PEEK. The properties of doped polyaniline depended on the processing method and the structure of main chain backbone of the macromolecular acid.

THE CATALYTIC ACTIVITY OF HETEROPOLY ACIDS (SALTS) AND MONO-LACUNARY HETEROPOLY TUNGSTOPHOSPHORIC COMPOUND IN THE OXIDATION OF ALCOHOLS

The catalytic activity of heteropoly compounds in the oxidation of benzyl alcohol and cyclohexa nol under phase transfer conditions has been studied. The catalytic activity of six kinds of heteropoly acids with Keggin structure will drop by the order of GeMo12 (H4GeMo12O40). PW12, PMo12, SiMo12, GeW12 and SiW12. When the three protons of H3PW12O40 Were replaced by Na+ step by step, the catalytic activity will raise gradually with the drop of acidity. The addition of base and trace amount of sulfuric acid to the reaction system resulted in an increase of catalytic activity. It was found that catalytic activity of mono-lacunary heteropoly compounds is higher than that of the primary heteropoly acids (or salts). The catalytic oxidation system of HPA-H2O2-PTC is very active in the oxidation of benzyl alcohol ana cyclohexanol, but it has little activity in the oxidation of inactive compounds such as n(or iso)-proplalcohol. n-butyl alcohol and n-hexanol. Solvent has great effect on reaction, when polar compounds such as water were used as solvent, the catalytic activity is better than that when non-polar compounds were used as solvent.

AMPEROMETRIC DETECTION OF AMINO-ACIDS IN A FLOW-INJECTION SYSTEM WITH A NICKEL(II)-MODIFIED ELECTRODE WITH AN EASTMAN-AQ POLYMER FILM

Amperometic flow measurements were made at +0.55 V (vs. Ag/AgCl) in 0.1 mol l-1 KOH electrolyte with an Ni(II) chemically modified electrode (CME) with an Eastman-AQ polymer film. The use and characteristics of a Ni(II)-containing crystalline and polymer-modified electrode obtained by a double coating step as a detector for amino acids in a flow-injection system using reversed-phase liquid chromatography are described. The detection of these analytes is based on the higher oxidation state of nickel (NiOOH) controlled by the applied potential. The electroanalytical parameters and the detection current for a series of amines and amino acids were investigated. The use of such a CME in the flow-injection technique was found to be suitable in a solution at low pH. The linear range for glycine is 5 X 10(-6)-0.1 mol 1-1 with a detection limit of 1.0 X 10(-6) mol l-1. A 1 X 10(-4) mol 1-1 mixture of serine and tyrosine was also detected after separation on an Nucleosil C18 column.

EASTMAN-AQ/NIII MODIFIED ELECTRODE CHARACTERIZATION AND APPLICATION IN FLOW-INJECTION DETERMINATION OF CARBOHYDRATES AND AMINO-ACIDS

A novel Eastman-AQ/Ni(II) chemically modified electrode (CME) produced by "double coating step" deposition of a poly(ester sulphonic acid) polymer film and Ni2+-containing crystalline species onto glassy carbon instead of a metallic nickel electrode exhibited stable electrocatalytic oxidation of numerous alpha-hydrogen compounds including carbohydrates, amines and amino acids. In cyclic voltammetry, the electrocatalysis appeared with an irreversible anodic wave at +0.55 V (vs. Ag/AgCl). The CME was adapted for constant-potential amperometric detection of these compounds in flow injection analysis. Using the CME, the linear response concentration range was between 1.0 x 10(-5) and 5.0 x 10(-2) mol/l and the detection limit was 5.0 x 10(-6) mol/l for glucose. The stability of the CME was adequate for routine quantitative application.

THE INFLUENCE OF PROTONIC ACIDS ON THE CHEMICAL POLYMERIZATION OF ORTHO-METHYLANILINE

The chemical polymerization of ortho-methylaniline (MAn) is performed in aqueous solution of six protonic acids. The MAn polymerization conversion, and the electrical conductivity and doping level as well as molecular chain structure of the polymers obtained depend not only on the acid concentration but also on their acidity and molecular size.

LIQUID-CHROMATOGRAPHY AMPEROMETRIC DETECTION OF CARBOXYLIC-ACIDS AND PHENOLIC-ACIDS WITH A COPPER-BASED CHEMICALLY-MODIFIED ELECTRODE

A copper-based chemically-modified electrode has been constructed and characterized by various experimental parameters in flow-through amperometric detection of carboxylic acids and phenolic acids. Novel hydrodynamic voltamperograms were first obtained in flow-through amperometric detection with the Cu-based CME and subsequently negative and positive peaks were observed in a single chromatogram. This unique and flexible potential dependence could be of great benefit in chromatographic speciation and quantification. These observations suggest that the detector response was governed by the complexation reaction of copper ions with the solutes.

Positional distribution of fatty acids on the glycerol backbone during the biosynthesis of glycerolipids in Ectocarpus fasciculatus

The biosynthesis of glycolipids in E. fasciculatus was studied by C-14 label and chase. The fatty acids in sulphoquinovosyl diacylglycerol (SQDG) were almost 16-carbon and 18-carbon ones. In addition to the two fatty acids, monogalactosyl diacylglycerol (MGDG) and digalactosyl diacylglycerol (DGDG) contained 8.5 mol% and 31.0 mol% of eicosapentaenoic acid (20 : 5), respectively, and this fatty acid was usually distributed in the sn-1 position of the glycerol backbone. When plants were incubated with [2-C-14] acetate, differences existed in the positional distribution of the labeled fatty acids in sn-1 and sn-2 among the three glycerolipids. In SQDG C-14-labeled fatty acids were distributed uniformly in the sn-1 and sn-2 positions. In DGDG, C-14-labeled fatty acids were mainly distributed in the sn-2 position. In MGDG, the radioactivity of fatty acids in sn-1 position was far greater than that in sn-2 position after a 30 min pulse label, and the difference in radioactivity between the two positions decreased rapidly. The above results indicated that differences in the positional distribution of C-14-labeled fatty acids between sn-1 and sn-2 positions might be related to 20 : 5 and the biosynthesis of DGDG. Our results also suggested that E. fasciculatus had the same DGDG biosynthetic pathway as that in higher plants and galactosyl transferase was selective for MGDC.

Organic geochemical studies of sinking particulate material in China sea area(I) - Organic matter fluxes and distributional features of hydrocarbon compounds and fatty acids

Sinking particulate material collected from Nansha Yongshu reef lagoon and the continental shelf of the East China Sea by sediment traps has been analyzed and studied for the first time using organic geochemical method. The results show that about half of the sinking particulate organic matter in the two study areas are consumed before reaching the depth of 5 m to the sea floor and the degree of this consumption in Yongshu reef lagoon is larger than that in the continental shelf of the East China Sea. The distributions of hydrocarbons and fatty acids indicate that the minor difference of biological sources of sinking particulate organic matter exists between Yongshu reel lagoon and the continental shelf of the East China Sea, but they mainly come from marine plankton. Stronger biological and biochemical transformations of sinking particulate organic matter are also observed and the intensity of this transformation in Yongshu reef lagoon is greater than that in the continental shelf of the East China Sea. It is found that the occurrence of C-25 highly branched isoprenoid (HBI) diene may be related to the composition of diatom species.

Bromophenols coupled with derivatives of amino acids and nucleosides from the red alga Rhodomela confervoides

Three new bromophenols coupled with pyroglutamic acid derivatives and one bromophenol coupled with deoxyguanosine were obtained from the red alga Rhodomela confervoides. By spectroscopic methods including 2D NMR and single-crystal X-ray structure analysis their structures were elucidated as N-(2,3-dibromo-4,5-dihydroxybenzyl)methyl pyroglutamate (1), N-(2,3-dibromo-4,5-dihydroxybenzyl)pyroglutamic acid (2), N-[3-bromo-2-(2,3-dibromo-4,5-dihydroxybenzyl)-4,5-dihydroxybenzyllmethyl pyroglutamate (3), and 2-N-(2,3-dibromo-4,5-dihydroxybenzylamino)deoxyguanosine (4), respectively. Compounds 1-4 were evaluated against several microorganisms and human cancer cell lines, but found inactive. To our knowledge this is the first report of bromophenols coupled with amino acid or nucleoside derivatives through the C-N bond.

Fatty acids of some algae from the Bohai Sea

The fatty acid compositions of 22 species of marine macrophytes, belonging to the Ceramiales, Cryptonemiales, Nemalionales, Laminariales, Chordariales, Scytosiphonales, Desmarestiales, Dictyosiphonales, Fucales, Dictyotales and Ulvales and collected from the Bohai Sea, were determined by capillary gas chromatography. The contents of polyunsaturated fatty acids (FAs) in the Bohai Sea algae, in comparison with the same species from the Yellow Sea were found to be lower. Red algae had relatively high levels of the acids 16:0, 18:1(n-7), 18:1(n-9), 20:5(n-3) and 20:4(n-6), and those examined were rich in C-20 PUFAs, these chiefly being arachidonic and eicosapentaenoic acids. The major FAs encountered in the Phaeophyta were 14:0, 16:0, 18:1(n-9), 18:2(n-6), 18:3(n-3), 18:4(n-3), 20:4(n-6) and 20:5(n-3). C18PUFAs are of greater abundance in the brown algae than in the red algae examined. All three green algae from the Ulvales had similar fatty acid patterns with major components, 16:0, 16:4(n-3), 18:1(n-7), 18:2(n-6), 18:3(n-3), and 18:4(n-3). They contained 16:3(n-3) and more 16:4(n-3), were rich in C18PUFAs, chiefly 18:3(n-3) and 18:4(n-3) and had 18:1(n-7)/18:1 (n-9) ratios higher than 1. (C) 2002 Elsevier Science Ltd. All rights reserved.

LC determination of amino acids in rat plasma with fluorescence detection: Application to exercise physiology

An LC method for the determination of 20 amino acids (AAs), using 1,2-Benzo-3,4-dihydrocarbazole-9-ethyl chloroformate (BCEOC) as fluorescent labeling reagent, has been validated and applied for the analysis of AAs in rat plasma at three different states concerning exercise physiology. Identification of AA derivatives was carried out by LC-MS with electrospray ion (ESI), and the MS-MS cleavage mode of the representative tyrosine (Tyr) derivative was analyzed. Gradient elution on a Hypersil BDS C-18 column gave good separation of the derivatives. Excellent linear responses were observed and good compositional data could be obtained from as little as 50-200 mu L of plasma samples. The contents of 20 AAs in rat plasma of three groups (24 rats, group A: quiet state, group B: at exercising exhaust, group C: 12 h after exercising exhaust) exhibited evident difference corresponding to the physiological states. Facile BCEOC derivatization coupled with LC-FLD-ESI-MS analysis allowed the development of a highly sensitive method for the quantitative analysis of trace level of AAs from plasma or other biochemical samples.

Extraction of Nitraria tangutorum seed oil by supercritical carbon dioxide and determination of free fatty acids by HPLC/APC/IMS with fluorescence detection

The seed oil from Nitraria tangutorum samples was obtained by supercritical carbon dioxide extraction methods. The extraction parameters for this methodology, including pressure, temperature, particle size and extraction time, were optimized. The free fatty acids in the seed oil were separated with a pre-column derivation method and 1,2-benzo-3,4-dihydrocarbazole-9-ethyl-p-toluenesulfonate (BDETS) as a labeling regent, followed by high-performance liquid chromatography (HPLC) with fluorescence detection. The target compounds were identified by mass spectrometry with atmospheric pressure chemical ionization (APCI in positive-ion mode). HPLC analysis shows that the main compositions of the seed oil samples were free fatty acids (FFAs) in high to low concentrations as follows: linoleic acid, oleic acid, hexadecanoic acid and octadecanoic acid. The assay detection limits (at signal-to-noise of 3:1) were 3.378-6.572 nmol/L. Excellent linear responses were observed, with correlation coefficients greater than 0.999. The facile BDETS derivatization coupled with mass spectrometry detection allowed the development of a highly sensitive method for analyzing free fatty acids in seed oil by supercritical CO2 extraction. The established method is highly efficient for seed oil extraction and extremely sensitive for fatty acid profile determination. (C) 2007 Elsevier B.V. All rights reserved.

Determination of free fatty acids in bryophyte plants and soil by HPLC with fluorescence detection and identification by online MS

A method for the determination of long and short chain free fatty acids (FFAs), using 1-[2-(ptoluenesulfonate)-ethyll-2-phenylimidazole-[4,5-f-9,10-phenanthrene (TSPP) as labeling reagent, has been developed. Identification of FFA derivatives was carried out by HPLC-MS with atmospheric pressure chemical ionization (APCI) in positive ion mode. Gradient elution on an Agilent Eclipse XDB-C-8 column gave good separation of the derivatives. Excellent linear responses were observed and good compositional data could be obtained from as little as 200 mg of bryophyte plants and soil samples. Facile TSPP derivatization coupled with HPLC-APCI-MS analysis allowed the development of a highly sensitive method for the quantitative analysis of trace level of FFAs from biological and natural environmental samples.

Determination of free fatty acids in soil and bryophyte plants by precolumn derivatization via HPLC with fluorescence detection and tandem mass spectrometry (HPLC-MS/MS)

A sensitive method for the determination of 30 kinds of free fatty acids (FFAs, C-1-C-30) with 1-[2-(p-toluenesulfonate)-ethyl]-2-phenylimidazole-[4,5-f] 9,10-phenan- threne (TSPP) as labeling reagent and using high performance liquid chromatography with fluorescence detection and identification by online postcolumn mass spectrometry with atmospheric pressure chemical ionization (APCI) source in positive-ion mode (HPLC/MS/APCI) has been developed. TSPP could easily and quickly label FFAs in the presence of K2CO3 catalyst at 90 degrees C for 30 min in N,N-dimethylformamide (DMF) solvent, and maximal labeling yields close to 100% were observed with a 5-fold excess of molar reagent. Derivatives were stable enough to be efficiently analyzed by high performance liquid chromatography. TSPP was introduced into fatty acid molecules and effectively augmented MS ionization of fatty acid derivatives and led to regular MS and MS/MS information. The collision induced cleavage of protonated molecular ions formed specific fragment ions at m/z [MH](+)(molecular ion), m/z [M'+CH2CH2](+)(M' was molecular mass of the corresponding FFA) and m/z 295.0 (the, mass of protonated molecular core structure of TSPP). Fatty acid derivatives were separated on a reversed-phase Eclipse XDB-C-8 column (4.6 x 150 mm, 5 mu m, Agilent) with a good baseline resolution in combination with a gradient elution. Linear ranges of 30 FFAs are 2.441 x 10(-3) to 20 mu mol/L, detection limits are 3.24 similar to 36.97 fmol (injection volume 10 mu L, at a signal-to-noise ratio of 3, S/N 3:1). The mean interday precision ranged from 93.4 to 106.2% with the largest mean coefficients of variation (R.S.D.) < 7,5%. The mean intraday precision for all standards was < 6.4% of the expected concentration. Excellent linear responses were observed with correlation coefficients of > 0.9991. Good compositional data could be obtained from the analysis of extracted fatty acids from as little as 200 mg of bryophyte plant samples.Therefore, the facile TSPP derivatization coupled with HPLC/MS/APCI analysis allowed the development of a highly sensitive method for the quantitation of trace levels of short and long chain fatty acids from biological and natural environmental samples.

Determination of long-chain fatty acids in bryophyte plants extracts by HPLC with fluorescence detection and identification with MS

A sensitive method for the determination of long-chain fatty acids (LCFAs) (>C20) using 1-[2-(p-toluenesulfonate)-ethyl]-2-phenylimidazole-[4.5-f]-9,10-phenanthrene (TSPP) as tagging reagent with fluorescence detection and identification with post-column APCI/MS has been developed. The LCFAs in bryophyte plant samples were obtained based on distillation extraction with 1: 1 (v/v) chloroform/methanol as extracting solvent. TSPP could easily and quickly label LCFAs at 90 degrees C in the presence of K2CO3 catalyst in DMF. Eleven free LCFAs from the extracts of bryophyte plants were sensitively determined. Maximal labeling yields close to 100% were observed with a five-fold excess of molar reagent. Separation of the derivatized fatty acids exhibited a good baseline resolution in combination with a gradient elution on a reversed-phase Eclipse XDB-C-8 column. Calculated detection limits from 1.0 pmol injection, at a signal-to-noise ratio of 3, were 26.19-76.67 fmol. Excellent linear responses were observed with coefficients of >0.9996. Good compositional data were obtained from the analysis of the extracted LCFAs containing as little as 0.2 g of bryophyte plant samples. Therefore, the facile TSPP derivatization coupled with HPLC/APCI/MS analysis allowed the development of a highly sensitive method for the quantitation of trace levels of LCFAs from biological and natural environmental samples. (c) 2006 Elsevier B.V. All rights reserved.