脂肪醇聚氧乙烯醚的厌氧与好氧生物降解性

以脂肪醇聚氧乙烯醚(AEO)为目标污染物，在等同条件下做厌氧消化污泥和好氧活性污泥对其生物降解性能的对比实验，得出了同一系列AEO分子中聚氧乙烯基与整个分子的降解难易程度的关系。表明：①污泥会对AEO分子产生吸附一脱附作用而出现假降解率，克服假降解率的干扰是准确测定AEO生物降解性的关键因素；②厌氧和好氧条件下，AEO均可降解，但厌氧降解要稍优于好氧降解；③AEO中聚氧乙烯基的单元数(n)是影响其生物降解的重要因素，相同碳链的直链烷基，生物降解率随n的增加而明显降低。     

Study of the amination of fatty alcohols catalyzed by Cu−Ni catalysts

Amination of fatty alcohols by hydrogenation and dehydrogenation catalysis is one of the main commercial processes for the production of dimethylalkylamines. The key factor in this process is the preparation of catalysts with high selectivity. A study of amination catalyzed by Cu−Ni catalysts supported on CaCO₃ is reported in this paper. Selectivity of the catalysts was adjustable by varying the ratio of Cu to Ni or by adding a third element (Zn or Mg). The promotion of catalyst selectivity was mainly attributable to the effect of the components on the reducibility of Ni²⁺ in the catalysts. Lower reducibility of Ni²⁻ led to higher catalyst selectivity.     

PVA基活性碳纤维的研制

探索了由民用大丝束聚乙烯醇纤维(PVAF)试制活性碳纤维(ACF)的可能性,以开辟新的原料路线,降低产品成本。PVAF首先用脱水剂处理,脱水剂浓度为10%(质量),然后在200—300℃进行热处理,处理后的纤维再经预氧化和碳化活化转化为ACF,ACF的收率为37.7%,比表面积为1050m~2/g。此外,还探索了用O_3处理PVAF。用差热、热失重和红外等手段对产物进行了表征,推论了相应的反应机理。结果表明:经适当处理的PVAF可制得具有较好吸附性能的ACF。     

Bubble temperature data for phenol-alcohol systems: Phenol-I-Amyl alcohol and phenol-n-Amyl alcohol systems

In order to supplement the literature data on VLE, isobaric bubble temperature data were collected for the binary systems phenol-i-amyl alcohol and phenol-n-amyl alcohol over the entire composition range by indirect method using a standard Swietoslawski type ebulliometer. The measurements were made at three sub-atmospheric pressures. The experimental t-x data were correlated with both equation of state method and gamma-phi methods. In the former approach, the Soave equation of state is used, whereas in the latter case Wilson, NRTL and UNIQUAC equations are used.     

Properties of cuticular oxidases used for sex pheromone biosynthesis byHeliothis zea

Biosynthesis of the aldehydic sex pheromone components released by females ofHeliothis zea was found to be catalyzed by primary alcohol oxidases residing in the cuticle that covers the glands. Activity, as indicated by conversion of primary alcohol to aldehyde, was as high in cell-free cuticle as it was in intact pheromone glands. Studies indicated that some activity was associated with the surface of the epicuticle and could be removed, into buffer, by sonication. However, the majority of activity lies within the inner epicuticle and exo- and endocuticular layers. The oxidase was not functional in pharate pupae that did not have mature adult cuticle but became functional just prior to adult emergence. The enzyme in individual glands was saturated at alcohol concentrations above 100 n. moles. Nonionic detergents did not affect the activity of the oxidase in the cuticle but treatment with either 7 M urea or 1% SDS resulted in total loss of activity. Studies on the effect of pH indicated an optimum at 6.4; however, activity was high throughout the range of 5–9. The oxidase was functional in both dichloromethane and hexane, suggesting that this enzyme system may have applications for organic synthesis of aldehydes.     

乳液聚合中单体醋酸乙烯酯与保护胶体聚乙烯醇的接枝反应研究

研究了以聚乙烯醇为保护胶体的醋酸乙烯乳液聚合中,聚乙烯醇与单体的接枝反应。探讨了引发剂用量、聚合反应温度、保护胶体聚合度等因素对接枝反应的影响。     

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.     

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.     

Research on the friction and wear mechanism of Poly(vinyl alcohol)/hydroxylapatite composite hydrogel

Poly(vinyl alcohol)/Hydroxylapatite (PVA/HA) composite hydrogel was prepared with poly(vinyl alcohol) and hydroxylapatite as raw materials, using the method of repeated freezing and thawing. The morphologies of PVA/HA composite hydrogel were observed by means of high-accuracy 3D profiler and scanning electron microscope (SEM). The compressive elastic modulus and the stress relaxation characteristics of PVA/HA composite hydrogel were measured using the flat-head cylinder indenter. The friction and wear tests between PVA/HA composite hydrogel and bovine knee articular cartilage were performed on the micro-tribometer. The worn morphologies of PVA/HA composite hydrogel were observed with environmental scanning electron microscope (ESEM). The results showed that PVA/HA composite hydrogel has the cross-link network microstructure which is similar to that of the natural bovine knee articular cartilages. With the increase of freezing-thawing cycles and the HA content, the degree of cross-link and the crystallization of PVA/HA composite hydrogel both increase, the elastic modulus increases evidently, the rate of stress relaxation is improved and the value of balance stress decreases. The friction coefficient decreases with the increase of the freezing-thawing cycles and the HA content. The more the freezing-thawing cycles are, the earlier the friction coefficient reaches the stable balance value. The friction deformation depth between PVA/HA composite hydrogel and bovine knee articular cartilage is inversely proportional to freezing-thawing cycles and the HA content. The main wear mechanisms of PVA/HA composite hydrogel are plastic flowing and adhesive flaking. The wear severity degree decreases with the increase of freezing-thawing cycles and the HA content. Supported by Key Program of the National Natural Science Foundation of China (Grant No. 50535050), Program for New Century Excellent Talents in University (Grant No. NCET-06-0479) and Natural Science Foundation of Jiangsu Province (Grant No. BK2005403)     

国内外聚乙烯醇工业的进展及市场展望

简述了国内外聚乙烯醇工业情况，介绍了聚乙烯醇及其衍生物的应用领域，展望了聚乙烯醇的发展形势和市场状况。