Synthesis and properties of thermoplastic propyl-etherified amylose

Amylose was etherified with 1-bromopropane in DMSO. The degree of substitution (DS) was varied by altering the feed ratio of 1-bromopropane. The structures of the products were characterized by IR and 1H-NMR spectroscopy. When the molar feed ratio of 1-bromopropane to hydroxyl groups of amylose was beyond 7.5, the hydroxyl groups were completely substituted with propyl ether groups. The etherified amylose with DS 1.9 showed a glass transition temperature (T_g), and that with DS 2.3 or 3.0 showed both T_g and melting temperature (T_m) (DS 3.0 means complete substitution). The etherification imparted melt processability and solubility in nonpolar organic solvent to amylose.     

二茂铁化学修饰电极测定丙二醛的研究

报道了在玻碳电极上共价键合二茂铁的新型化学修饰电极。研究了该电极对丙二醛的电催化作用。以微分脉冲伏安法测定丙二醛，方法具有较好的灵敏度和选择性。丙二醛的峰电流与其浓度在２０×１０－６～２０×１０－３ｍｏｌ／Ｌ呈良好的线性关系。     

Bioactive steroidal glycosides from the marine sponge Erylus lendenfeldi

Bioassay-guided fractionation of the methanol extract of Erylus lendenfeldi using engineered strains of budding yeast (Saccharomyces cerevisiae) has resulted in the isolation of the known compound eryloside A (1) and two new compounds, erylosides K (2) and L (3). The structures were established based mainly on 1D and 2D NMR data. The absolute stereochemistry of eryloside A, which had never been fully characterized, was determined using the modified Mosher's method. The absolute stereochemistry of eryloside K was determined by comparison with tetrahydroeryloside A. Compounds 1-3 exhibited selective cytotoxicity against a yeast strain (Δrad50) deficient in double strand break (DSB) repair.     

NMR study of some diastereomeric nucleoside-3′-thiophosphate derivatives in solution

The conformational properties of diastereomeric P-modified nucleotides are reported as reflected by different NMR parameters. Some conformational trends can be rationalized by consideration of the ³J(C4,P) and ³J(C2,P) coupling values of the isomers and the nature of the substituent on the phosphorus. Configurational assessment of the phosphorus is inferred from NOE experiments. The effects of temperature, solvent and size of substituents are presented.     

Electrocatalytic Reduction of H2O2 and Oxygen on the Surface of Thionin Incorporated onto MWCNTs Modified Glassy Carbon Electrode: Application to Glucose Detection

A new H₂O₂ enzymeless sensor has been fabricated by incorporation of thionin onto multiwall carbon nanotubes (MWCNTs) modified glassy carbon electrode. First 50 μL of acetone solution containing dispersed MWCNTs was pipetted onto the surface of GC electrode, then, after solvent evaporations, the MWCNTs modified GC electrode was immersed into an aqueous solution of thionin (electroless deposition) for a short period of time <5–50 s. The adsorbed thin film of thionin was found to facilitate the reduction of hydrogen peroxide in the absence of peroxidase enzyme. Also the modified electrode shows excellent catalytic activity for oxygen reduction at reduced overpotential. The rotating modified electrode shows excellent analytical performance for amperometric determination of hydrogen peroxide, at reduced overpotentials. Typical calibration at ?0.3 V vs. reference electrode, Ag/AgCl/3 M KCl, shows a detection limit of 0.38 μM, a sensitivity of 11.5 nA/μM and a liner range from 20 μM to 3.0 mM of hydrogen peroxide. The glucose biosensor was fabricated by covering a thin film of sol–gel composite containing glucose oxides on the surface of thionin/MWCNTs modified GC electrode. The biosensor can be used successfully for selective detection of glucose based on the decreasing of cathodic peak current of oxygen. The detection limit, sensitivity and liner calibration rang were 1 μM, 18.3 μA/mM and 10 μM–6.0 mM, respectively. In addition biosensor can reach 90% of steady currents in about 3.0 s and interference effect of the electroactive existing species (ascorbic acid–uric acid and acetaminophen) is eliminated. The usefulness of biosensor for direct glucose quantification in human blood serum matrix is also discussed. This sensor can be used as an amperometric detector for monitoring oxidase based biosensors.     

Capillary gas chromatographic separation of C10–C12 secondary phenylalkanes on modified cyclodextrin stationary phases

The separation of isomers and enantiomers of branched C₁₀-C₁₂ phenylalkanes by gas chromatography on fused silica capillary columns coated with some modified β- and γ-cyclodextrins was studied. It was shown that the separation of positional isomers of C₁₀-C₁₂ phynylalkanes on modified cyclodextrin capillary columns is not better than that on a column coated with modified polyethylene glycol. Differences were found in the enantioselectivity of modified β- and γ-cyclodextrins for the separation of C₁₀-C₁₂ secondary phenylalkane enantiomers. While alkylderivatives of β-CDs resolve enantiomers of 3-phenylalkanes, alkyl derivatives of γ-CD resolve enantiomers of 2-phenylalkanes. Since shape selectivity factors of modified cyclodextrins have indicated no inclusion of the considered solutes in cyclodextrin cavities, enantioselective interactions most probably occur on the outer sphere of cyclodextrins.     

PREPARATION OF PERFLUOROOCTANOYL-MODIFIED POLY(VINYL-ALCOHOL)S AND THEIR ADSORPTION AT AN AIR-WATER INTERFACE

Perfluorooctanoyl modified poly(vinyl alcohol)s (FPVA) were prepared by means of substituting a small amountof hydroxyl groups on the backbone of poly(vinyl alcohol), for which the initial degree of polymerization is equal to 1750.The substitution extent, defined by the number of substituting units in a chain, for the four FPVA samples was in the range of0.5-5 perfluorooctanoyl groups per chain. The FPVA samples with the highest substitution extent still had good solubility inwater. It was shown by experimental measurement at 30.0±0.1℃ that the surface tension of the aqueous solution of thehighest substituted FPVA decreased to 16.6 mN/In at a higher concentration, e.g about 0.1 g/mL. Obviously,macromolecules of FPVA exhibit a very strong tendency to adsorb at the air-water interface, because the hydrophobicperfluorooctanoyl groups in FPVA have a very high surface activity as they are in small molecular fluorinated surfactants.The chain conformation of such a model polymer adsorbed on the air-water interface was also discussed.     

Removal of Mn(II) and Cd(II) from wastewaters by natural and modified clays

The adsorption capacities of commercial and Brazilian natural clays were evaluated to test their applications in wastewater control. We investigated the process of sorption of manganese(II) and cadmium(II) present in synthetic aqueous effluents, by calculating the adsorption isotherms at 298 K using batch experiments. The influence of temperature and pH on the adsorption process was also studied. Adsorption of metals was best described by a Langmuir isotherm, with values of Q ₀ parameter, which is related to the sorption capacity, corresponding to 6.3 mg g^{− 1} for K-10/Cd(II), 4.8 mg g^{− 1} for K-10/Mn(II), 11.2 mg g^{− 1} for NT-25/Cd(II) and 6.0 mg g^{− 1} for NT-25/Mn(II). We observed two distinct adsorption mechanisms that may influence adsorption. At the first 5 min of interaction, a cation exchange mechanism that takes place at exchange sites located on (001) basal planes is predominant. This process is inhibited by low pH values. After this first and fast step, a second sorption mechanism can be related to formation of inner-sphere surface complexes, which is formed at edges of the clay. The rate constants and the initial sorption rates correlate positively with temperature in all studied systems, denoting the predominance of a physisorption process. The addition of complexing agents that are incorporated within the K10 structure, enhance metal uptake by the adsorbent. The results have shown that both Cd(II) and Mn(II) were totally retained from a 50 mg L^{− 1} solution when K10 grafted with ammonium pyrrolidinedithiocarbamate (APDC) was used as adsorbent.     

Improved Flexural Strength of N-Vinyl-Pyrrolidone Modified Acrylic Acid Copolymers for Glass-Ionomers

Abstract

The flexural strengths of N-vinylpyrrolidone modified glass-ionomer cements were investigated. The optimal molar ratio of the monomers in copolymers, composed of the three components acrylic acid, itaconic acid and N-vinylpyrrolidone, was determined using a SAS statistical program. The copolymers were prepared using a free-radical polymerization process. The viscosities of aqueous solutions of these polymers were determined. Cements were formed by the reaction of these solutions with glass particles. Flexural strength (FS) was used as the basic screening property to find the optimum molar ratio. Statistical models were applied to predict the optimum molar ratios. All strength values were recorded on the specimens conditioned in distilled water at 37°C for 7 days. The optimal molar ratio for these copolymers was 7:1:3 for poly(acrylic acid-co-itaconic acid-co-N-vinylpyrrolidone), based on flexural strength and viscosity. The effect of molecular weight (MW) on FS was also evaluated. Copolymer with a MW of 10, 800 (M_n) showed 85% higher FS than the Ketac-Molar (KM) system, along with a reasonable working viscosity.