Covalent immobilization of glucose oxidase onto new modified acrylonitrile copolymer/silica gel hybrid supports

New polymer/silica gel hybrid supports were prepared by coating high surface area of silica gel with modified acrylonitrile copolymer. The concentrations of the modifying agent (NaOH) and the modified polymer were varied. GOD was covalently immobilized on these hybrid supports and the relative activity and the amount of bound protein were determined. The highest relative activity and sufficient amount of bound protein of the immobilized GOD were achieved in 10% NaOH and 2% solution of modified acrylonitrile copolymer. The influence of glutaraldehyde concentration and the storage time on enzyme efficiency were examined. Glutaraldehyde concentration of 0.5% is optimal for the immobilized GOD. It was shown that the covalently bound enzyme (using 0.5% glutaraldehyde) had higher relative activity than the activity of the adsorbed enzyme. Covalently immobilized GOD with 0.5% glutaraldehyde was more stable for four months in comparison with the one immobilized on pure silica gel, hybrid support with 10% glutaraldehyde and the free enzyme. The effect of the pore size on the enzyme efficiency was studied on four types of silica gel with different pore size. Silica with large pores (CPC-Silica carrier, 375 A) presented higher relative activity than those with smaller pore size (Silica gel with 4, 40 and 100 A). The amount of bound protein was also reduced with decreasing the pore size. The effect of particle size was studied and it was found out that the smaller the particle size was, the greater the activity and the amount of immobilized enzyme were. The obtained results proved that these new polymer/silica gel hybrid supports were suitable for GOD immobilization.     

Barrier property of clay/Acrylonitrile‐butadiene copolymer nanocomposite

The resistance to air permeation was investigated for ­an intercalated clay/acrylonitrile‐butadiene copolymer ­nanocomposite. The nanocomposite is prepared by melt mixing the organo‐treated montmorillonite into a rubber matrix, together with peroxide curative, and crosslinked by conventional compression molding for typical rubbers. In the case of intercalated nanocomposite, the air permeability decreases considerably with increasing clay content, and the decreasing trend agrees reasonably with the Neilson's tortuous model. No considerable improvement is found when the pure montmorillonite is added. Copyright © 2002 John Wiley & Sons, Ltd.     

Syntheses Based on Natural α-Amino Acids. Cyanoethylation of 3-Substituted 5-Methyl-2-thiohydantoins

Starting from α-alanine, the C- and S-cyanoethyl derivatives of 5-methyl-3-phenyl(allyl)-2-thiohydantoins have been synthesized. It was shown that the products of hydrolysis of C-cyanoethyl derivatives, 5-methyl-3-phenyl(allyl)-(β-carboxyethyl)-2-thiohydantoins, are formed in addition. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1657–1661, November, 2005.     

相转移催化合成β-酞酰亚胺基丙腈

用固-液相转移催化法，以酞酰亚胺和丙烯腈为原料，无水K2CO3为催化剂，经Michael反应合成了β-酞酰亚胺基丙腈，并研究了不同条件下的反应结果。实验表明，利用Michael反应在温和条件下可获得较高产率的产物，克服了以往用季铵碱作催化剂或用DMF作溶剂的缺点。     

Modification on liquid retention property of cassava starch by radiation grafting with acrylonitrile. I. Effect of γ-irradiation on grafting parameters

Radiation modification on liquid retention properties of native cassava starch, gelatinized at 85°C, by graft copolymerization with acrylonitrile was carried out by mutual irradiation to gamma-rays. A thin aluminum foil was used to cover the inner wall of the reaction vessel, so that the homopolymer concentration was reduced to be less than 1.0% with a distilled water retention value of 665 g/g of the dry weight of the saponified grafted product. Confirmation of graft copolymerization and saponification reactions was made by the infrared spectrophotometric technique. The combined effect of radiation parameters in terms of an irradiation time and a dose rate to the total dose on the extent of the grafting reaction expressed in terms of grafting parameters which directly influenced liquid retention values was evaluated in conjunction with statistical analysis.     

Preparation and performance analysis of PE-supported P(AN-co-MMA) gel polymer electrolyte for lithium ion battery application

Copolymer, poly(acrylonitrile-co-methyl methacrylate) (P(AN-co-MMA)), was synthesized by solution polymerization with different mole ratios of monomers, acrylonitrile (AN) and methyl methacrylate (MMA). Polyethylene (PE) supported copolymer and gel polymer electrolyte (GPE) were prepared with this copolymer and their performances were characterized with FTIR, TGA, SEM, and electrochemical methods. It is found that the GPE using the PE-supported copolymer with AN to MMA = 4:1 (mole) exhibits an ionic conductivity of 2.06 × 10⁻³ S cm⁻¹ at room temperature. The copolymer is stable up to 270 °C. The PE-supported copolymer shows a cross-linked porous structure and has 150 wt% of electrolyte uptake. The GPE is compatible with anode and cathode of lithium ion battery at high voltage and its electrochemical window is 5.5 V (vs. Li/Li⁺). With the application of the PE-supported GPE in lithium ion battery, the battery shows its good rate and initial discharge capacity and cyclic stability.     

2-甲基-2-丁烯二酸单甲酯的合成及其与丙烯腈二元共聚的 表观竞聚率的测定

以柠糠酸酐为原料, 合成了一种可以与丙烯腈(AN, acrylonitrile)共聚的新单体: 2-甲基-2-丁烯二酸单甲酯(MBAME). 以偶氮二异丁腈(AIBN, 2,2’-azobis isobutyronitrile)为引发剂, 70 ℃下引发MBAME与AN在N,N-二甲基甲酰胺(DMF, N,N-dimethylformamide)中进行无规共聚, 通过Fineman-Ross法测定了两者在DMF溶液聚合体系的表观竞聚率, γ1(AN)＝7.985, γ2(MBAME)＝0.599, 有助于优化聚丙烯腈基碳纤维用树脂的生产工艺.     

Preparation of antimicrobial sutures by preirradiation grafting onto polypropylene monofilament

Antimicrobial sutures were prepared by the radiation grafting of acrylonitrile monomer onto polypropylene (PP) monofilament. The grafted sutures were subsequently hydrolyzed to transform nitrile groups into carboxylic groups for the immobilization of antimicrobial drug, tetracycline hydrochloride (TC). The modified sutures show continuous release of drug for a period of 4–5 days. The antimicrobial activity of the sutures was determined against both Gram positive and Gram negative bacteria by the zone of inhibition technique. Zone of inhibition was observed around the drug‐containing sutures in the plate inoculated with Escherichia coli (E. coli), Klebsiella pneumonea (K. pneumonea), and Staphylococcus aureus (S. aureus). The results of infection studies in albino rats against S. aureus showed no infection even after fourth postoperative day of surgery. This is because of the release of the TC drug at the site of injury, which inhibits the bacterial growth. Copyright © 2008 John Wiley & Sons, Ltd.     

Synergistic effect of polyfunctional silane coupling agent and styrene acrylonitrile copolymer on the water‐resistant and mechanical performances of glass fiber–reinforced polyamide 6

Adverse effects of a high‐water absorption rate on properties of a glass fiber–reinforced polyamide 6 (GF‐PA6) composite significantly reduce performance and limit application in humid environments. In this paper, a polyfunctional silane (PFS) coupling agent with amino (–NH₂) and imino (–NH) groups and styrene acrylonitrile copolymer (SAN) were added to a composite, GF‐PA6, to prepare GF‐PA6/SAN/PFS composites via melt blending in a twin‐screw extruder. The effects of SAN and PFS content on the static and dynamic mechanical properties of the composites before and after water absorption were investigated in detail. The microstructure of the fracture surface was analyzed by a scanning electron microscope (SEM). The results show that the addition of SAN and PFS could effectively inhibit water absorption of the GF‐PA6 composites. The alkoxyl groups on PFS reacted chemically with the nitrile groups of SAN, which enriched SAN on the interface between the fiber and matrix during the extrusion and mixing process to improve the effect of water prevention. Therefore, the mechanical properties of the wet state were notably improved while preventing water from permeating the interface by only the addition of a small amount of SAN and PFS. Dynamic mechanical analysis (DMA) results showed that the addition of PFS improved the compatibility of PA6 with SAN and enhanced the interface adhesion between fiber and PA6. In terms of test result of the comprehensive performance, 10 phr SAN with 0.6 phr PFS was the best dosage.     

Thermal Decomposition Kinetics and Mechanism of Low-temperature Hydrogenated Acrylonitrile Butadiene Rubber Composites with Sodium Methacrylate

Thermal decomposition processes and mechanism of low-temperature grade hydrogenated acrylonitrile butadiene rubber(LTG-HNBR) composites with sodium methacrylate(NaMAA) were investigated by thermogravimetric analysis(TGA) and Fourier transform infrared spectroscopy(FTIR) coupling technology in this article. The results of TGA demonstrate that the addition of NaMAA can enhance the thermal decomposition temperature of the rubber. Moreover, it was found that the composites spent more activation energies to decompose than pure rubber by the calculations of multiply heating rate method. Time-resolved FTIR spectra show that NaMAA affects the initial decomposition of the composites. But in the following process, the composites maintained a similar behavior to the matrix. During the decomposition, PNaMAA nanostructures, in-situ generated by NaMAA, helped reduce the diffusion speed of decomposition products and thus improved the thermal stability of the composites. We believe that these findings can provide some guides to direct the applications of LTG-HNBR composites with unsaturated metal methacrylates.