Synthesis of boronate-containing copolymers of N,N-dimethylacrylamide, their interaction with poly(vinyl alcohol) and rheological behaviour of the gels

Cross-linking of polyvinylalcohol (PVA) by boronate-containing copolymer of N,N-dimethylacrylamide (DMAA, 1) was studied and compared to cross-linking of PVA by borate buffers in weakly alkaline solutions. The copolymer of M_w=19,000 g mol⁻¹ containing 9 mol% N-acryloyl-m-aminophenylboronic acid (NAAPBA, 2) was prepared by free radical polymerization of the monomers, exhibiting copolymerization constants r₁=0.84 and r₂=2.2. Due to multipoint interaction of the copolymer with PVA via monodiols, the intermolecular cross-linking required for seven-fold and 10-fold lower boron concentrations as compared to borate buffers of pH 8.6 and 7.5, respectively. In rheological measurements, PVA-copolymer gels exhibited storage moduli (G′_max) comparable to those of PVA-borate gels prepared at 7.5-fold higher boron concentration and the same pH 8.6, what testified to the similar concentration of cross-links in the gels. Therefore, DMAA-NAAPBA copolymer is a more effective cross-linker of PVA than borate. The PVA-copolymer gel exhibited much higher relaxation time (97 s) compared to PVA-borate gels (≤20 s) indicating a longer lifetime of junction zones. The ‘shape stability’ of the gel is suggested to originate in the structure of junctions, containing several boronate-diol complexes, between the macromolecules of PVA and the copolymer.     

Sorption/diffusion of aqueous mixtures of 1,4‐dioxane/tetrahydrofuran through blend membranes of poly(vinyl alcohol) and sodium alginate: Their compatibility and pervaporation separation studies

Blend membranes of poly(vinyl alcohol) (PVA) and sodium alginate (NaAlg) were prepared by solution casting and crosslinked with glutaraldehyde (GA). Polymer blend compatibility was studied in water by measuring solution viscosity at 30°C. From the viscosity data, interaction parameters were determined to find the blend compatibility. Thickness of the membranes ranged between 35 and 40 μm. Circular disc‐shaped samples were cut from the thin membranes to perform gravimetric sorption experiments in water + 1,4‐dioxane and water + tetrahydrofuran mixtures at 30°C. Diffusion coefficients were calculated using Fick's equation. Concentration profiles of liquids were computed by solving Fick's equation under suitable boundary conditions. Diffusion coefficients show a dependence on the composition of the blends as well as composition of binary mixtures. A correlation was attempted between concentration profiles and diffusion coefficients of the transporting liquids. Degree of swelling and sorption coefficients were calculated from the gravimetric sorption data. Sorption kinetics was studied using an empirical equation to understand the nature of sorption–diffusion anomalies. Membrane selectivity for water + 1,4‐dioxane and water + tetrahydrofuran mixtures were calculated from the pervaporation experiments. A correlation between sorption and membrane selectivity was attempted. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 178–188, 2005     

Protein engineering of alcohol dehydrogenases; effects of amino acid changes at positions 93 and 48 of yeast ADH1

By protein engineering we have investigated changes to two aminoacid residues (Trp93 and Ser48) in the substrate pocket of yeastalcohol dehydrogenase 1. Upon changing Thr48 to serine we producedan enzyme which has markedly greater activity towards aliphaticalcohols with chain length up to 8, together with a generalincrease in catalytic activity (V/K). Changes at position 93were less pronounced, with the Phe enzyme being more activethan the parent towards the range of alcohols but with the alanineenzyme showing very little difference from the wild-type. Enzymeswith the double changes at 48 and 93 showed increased activitytowards alcohols with 3–8 carbons but the increases werenot additive over the single changes. The enzymes with changesat the two positions would metabolize both stereoisomers of2-octanol whereas the parent ADH would attack only one of them.None of the engineered enzymes would attack cyclohexanol oraromatic alcohols. The results are in general agreement withthe prediction that reducing the size of amino acids in thesubstrate pocket would enhance the ability to oxidize alcoholslarger than ethanol.     

Blend membranes of chitosan and poly(vinyl alcohol) in pervaporation dehydration of isopropanol and tetrahydrofuran

Blend membranes of a natural polymer, chitosan, with a synthetic polymer, poly(vinyl alcohol) (PVA), were prepared by solution casting and crosslinked with a urea formaldehyde/sulfuric acid (UFS) mixture. Chitosan was used as the base component in the blend system, whereas PVA concentration was varied from 20 to 60 wt %. Blend compatibility was studied by differential scanning calorimetry, and Fourier transform infrared spectroscopy was used to study membrane crosslinking. Membranes were tested for pervaporation dehydration of isopropanol and tetrahydrofuran (THF) at 30°C in close proximity to their azeotropic compositions. Membrane performance was assessed by calculating flux and selectivity. Swelling experiments performed in water + organic mixtures at 30°C were used to explain the pervaporation results. The blend membrane containing 20 wt % PVA when tested for 5 and 10 wt % water–containing THF and isopropanol feeds exhibited selectivity of 4203 and 17,991, respectively. Flux increased with increasing concentration of water in the feed. Selectivity was highest for the 20 wt % PVA‐containing blend membrane. The results of this study are unique in the sense that the crosslinking agent used—the UFS mixture—was novel. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1918–1926, 2007     

脂肪醇生物活性和理化性质的QSAR/QSPR研究

为了研究脂肪醇结构-性质(活性)的定量关系,用相对键长取代拓扑距离,结合距离矩阵,提出了距离调和拓扑指数Te,Te和醇的许多理化性质和生物活性具有良好的相关性.用Te及δ(醇中和羟基相连的碳原子的支化度)与脂肪醇的溶解度、辛醇/水分配系数、急性生物毒性、蒸发热、摩尔磁化率关联,复相关系数分别为0.9955,0.9951,0.9941,0.9964,0.9968,优于文献.同时与脂肪醇的气相色谱保留指数也相关得很好,相关系数为0.9956.结果表明,Te指数可用于醇多种理化性质和生物活性的预测.     

爪形大分子CBC—NO的合成、表征及降滤性能研究

以1,3-丁二醇、柠檬酸为原料、甲苯为溶剂,在120℃油浴中反应,合成了柠檬酸-1,3-丁二醇-柠檬酸（CBC）爪状物小分子;然后,以甲基苯磺酸为催化剂,使CBC依次与环烷酸、十八醇分别在140℃和180℃油浴下接枝,合成了新型的爪形大分子柠檬酸-1,3-丁二醇-柠檬酸-环烷酸-十八醇（CBC—NO）。采用^1H—NMR及IR对合成的两种化合物进行了结构表征。结果表明,合成的CBC和CBC—NO与所设计的分子结构相吻合。用元素分析确定了CBC的化学组成为C16H22O14。合成的CBC—NO溶于有机溶剂,不溶于水。将CBC—NO按600μg／g的加剂量添加到不同的轻柴油中,柴油的冷滤点最大可降低8℃。     

纸质基材抗菌包装及性能研究

以纳米银为抗菌剂、聚乙烯醇为黏结剂处理普通成纸,制备了包装用抗菌纸。采用抑菌圈法评价了该抗菌纸对大肠杆菌的抑制效果,研究了聚乙烯醇和纳米银的含量对抗菌纸抗菌性能、抗张强度和伸长率的影响。结果表明:抗菌纸的抗张强度及伸长率均能满足包装需求,且具有良好的抗菌性能,其抗菌效果随纳米银和聚乙烯醇含量的增加而增强。     

五倍子醇提物的抗氧化活性

从还原力、清除DPPH自由基、清除超氧阴离子、清除羟自由基和抗脂质过氧化作用等方面研究了五倍子乙醇提取物的抗氧化活性,并同Vc或VE进行比较.实验结果表明,五倍子提取物对以上测定方法均表现出明显的抗氧化活性,其抗氧化活性均随其浓度的增加而增强.五倍子提取物和Vc(或VE)在同等浓度下,五倍子提取物的还原力和清除超氧阴离...     

透性化酒精酵母细胞产海藻糖发酵培养基的优化

为提高酒精酵母细胞发酵液中海藻糖的含量,在制备出透性化酒精酵母细胞的基础上,用单因素实验和响应面分析法,优化了酒精酵母的发酵培养基,确定了最适培养基组成.实验结果表明,酵母膏、蔗糖及氯化钠的添加量对海藻糖积累影响显著,影响程度依次为:酵母膏＞蔗糖＞氯化钠.优化后的培养基组成为:酵母膏14.7 g/L,蔗糖32.5 g/...     

Methods of Modifying the Brittle Behavior of Cementitious Composites

We put forward effective methods of increasing the tensile strain of cementitious composites with 2% PVA fiber and high fly ash content. The test results show that curing condition has a significantly effect on the tensile performance. It is approved that the specimens incorporated appropriate volume fraction rubber powder and lightweight aggregate greatly increase the tensile strain of composites at medium-term age, but indefinitely at long-term age. To a certain extent, EVA can limitedly enhance the tensi...