丁腈胶乳的加氢反应

采用水合肼/过氧化氢氧化还原体系，以硼酸为催化剂，在常压下进行丁腈胶乳的氢化反应，研究了过氧化氢加入方式，硼酸和水合肼用量，反应温度及反应时间对丁腈胶乳加氢度的影响。结果表明，过氧化氢连续滴加再附加室温条件，氢化反应效果最好。当硼酸用量为2.64mmol，水合肼用量为95.2mmol，过氧化氮用量为79.3mmol。在60℃，6h下，丁腈胶乳的加氢度可达到90%以上。     

有效增强重组腈代谢酶系表达活性的策略

讨论并提出了有效增强重组腈代谢酶系表达活性的多种策略。根据所选用的载体和宿主的不同表达特性,同时克隆目的基因上、下游的正向调控序列可直接增强酶表达水平;强化翻译后的修饰,可有效提高活性;除了常用的大肠杆菌克隆表达体系外,开发新型宿主-载体系统可为重组酶的活性表达提供新的途径;随着生物信息学技术的迅速发展,利用已知三维结构的蛋白对目标酶进行突变位点设计及结构与功能预测,将有望加快腈代谢酶系的定点突变研究进程。     

Studies on epoxidized rubber seed oil as plasticizer for acrylonitrile butadiene rubber

The application of rubber seed oil (RSO) and epoxidized RSO (ERSO) as a plasticizer in acrylonitrile butadiene rubber (NBR) was studied using RSO and ERSO with different levels of epoxidation. The results indicated that ERSO could be used as a less leachable and low volatility plasticizer for NBR. The use of ERSO in NBR gave better abrasion resistance whereas the tensile strength and tear strength were comparable to those vulcanizates that contained dioctyl phthalate as a plasticizer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 668–673, 2003     

ATBN/MP复合增容NBR/PP热塑性硫化胶

研究了端氨基液体丁腈橡胶(ATBN)和马来酸酐接枝聚丙烯(MP)对NBR／PP共混体系的增容效果。采用TEM,SEM,DSC分析了NBR／PP共混体系的相态结构及其PP的结晶行为。结果表明,ATBN／MP是NBR／PP共混体系较理想的增容剂,当ATBN用量为5份,MP为10份时,增容效果最佳;增容剂存在一个临界胶束浓度(CMC),当增容剂浓度大于CMC时,增客剂的增容作用变差。增容良好的NBR／PP共混体系经过动态硫化后,可制备相态结构精细、性能优异的NBR／PP热塑性硫化胶;界面结合加强后,其流动性能略有下降。     

Nocardia sp.腈水合酶的纯化过程研究

对Nocardiasp.高活力腈水合酶进行了纯化研究。在细胞破碎中,超声时间对腈水合酶比酶活存在一个最优值,超声时间为20.00min时得到的比酶活最高。在离子交换层析过程中,采用DEAE-Sepharose作为层析介质,分别对平衡缓冲液pH、离子强度和线性梯度洗脱体积进行了优化。结果表明,采用pH7.20、50mmolL-1的Na2HPO4-NaH2PO4溶液作为平衡缓冲液,0.00~1.00molL-1的NaCl线性梯度洗脱,洗脱体积为20~25倍柱体积,此条件下腈水合酶的纯化倍数和酶活收率较佳。以Phenyl-SepharoseFF为层析介质研究了疏水层析精制腈水合酶的工艺过程,采用两步层析优化方法纯化出的Nocardiasp.腈水合酶比酶活达到2648.0U穖g-1,酶活收率为40.84%,用SDS-PAGE检测其纯度为99.00%以上。Nocardiasp.腈水合酶的两个亚基分子量分别为22.90kDa和27.38kDa。     

Novel method for preparation of carboxylated nitrile rubber–natural rubber blends using bis(diisopropyl)thiophosphoryl polysulfides

Bis(diisopropyl)thiophosphoryl trisulfide (DIPTRI) and bis(diisopropyl)thiophosphoryl tetrasulfide (DIPTET) are successfully used as a novel coupling agent and accelerator, respectively, to covulcanize an elastomer blend comprising polar carboxylated nitrile rubber (XNBR) and nonpolar natural rubber (NR). These compounds are capable of forming a chemical link between these dissimilar rubbers to produce a technologically compatible blend as judged by a swelling experiment. The blend vulcanizates thus produced exhibit enhanced physical properties that can further be improved by adopting the two‐stage vulcanization technique and also by judicious selection of the NR:XNBR ratio. The blend morphology assessed by scanning electron microcroscopy micrographs accounts for significant improvement in the physical properties of the blend vulcanizates, particularly in two‐stage vulcanization. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1725–1736, 2001     

Active Site Mapping of Human Cathepsin F with Dipeptide Nitrile Inhibitors

Cleavage of the invariant chain is the key event in the trafficking pathway of major histocompatibility complex class II. Cathepsin S is the major processing enzyme of the invariant chain, but cathepsin F acts in macrophages as its functional synergist which is as potent as cathepsin S in invariant chain cleavage. Dedicated low‐molecular‐weight inhibitors for cathepsin F have not yet been developed. An active site mapping with 52 dipeptide nitriles, reacting as covalent–reversible inhibitors, was performed to draw structure–activity relationships for the non‐primed binding region of human cathepsin F. In a stepwise process, new compounds with optimized fragment combinations were designed and synthesized. These dipeptide nitriles were evaluated on human cysteine cathepsins F, B, L, K and S. Compounds 10 (N‐(4‐phenylbenzoyl)‐leucylglycine nitrile) and 12 (N‐(4‐phenylbenzoyl)leucylmethionine nitrile) were found to be potent inhibitors of human cathepsin F, with K_i values <10 nM . With all dipeptide nitriles from our study, a 3D activity landscape was generated to visualize structure–activity relationships for this series of cathepsin F inhibitors.     

丁腈橡胶的烯烃复分解及其产物的非均相加氢

采用烯烃复分解方式制备低相对分子质量的丁腈橡胶并对其进行非均相加氢,考察了烯烃复分解催化剂加入量、反应温度及反应时间对丁腈橡胶相对分子质量及其分布的影响。结果表明,在10 m L三氯甲烷中溶解1 g丁腈橡胶、催化剂用量0.001 g、反应温度30℃及反应时间3 h的条件下,所制备丁腈橡胶的数均分子量为(1.5~5.5)×104,重均分子量为(3.0~12.0)×104。采用非均相催化剂对低相对分子质量丁腈橡胶进行加氢的氢化度可达99%以上。     

丙烯酸酯橡胶与丁腈橡胶并用研究

对丙烯酸酯橡胶（ACM）与丁腈橡胶（NBR）并用胶的物理机构性能及耐热耐油性能进行了测试考察。实验结果表明,m(ACM):m(NBR)≥70:30的并用胶,综合性能比丁腈橡胶及丙烯酸酯橡胶好、成本低,可代替丙烯酸酯橡胶用作耐热耐油密封件胶料。     

HDPE／NBR共混物流变性能研究

通过熔融共混法制备了HDPE／NBR共混物,用毛细管流变仪研究了其流变特性,此共混物属于假塑性流体,表观粘度随剪切速率和温度的升高而降低,随NBR和增容剂含量的降低而降低。