面包酵母催化不对称还原芳香酮的研究

以苯乙酮(ACP)为模型底物研究了水相体系中面包酵母的不对称还原催化特性,考察了多个因素对产率及ee值的影响,确定了最佳反应条件。考察了面包酵母细胞对苯丙酮,4-氯苯乙酮,4-羟基苯乙酮,4-硝基苯乙酮等不对称还原催化效果。结果表明:产物的立体选择性受到羰基相连基团的体积和苯环上连接基团电子效应的共同作用。基团的体积差异越大,产物的立体选择性越高;苯环上吸电子基团提高产物的立体选择性,供电子基团降低产物的立体选择性。产率只同羰基相连基团体积大小有关,体积增大使反应产率降低。     

水-有机溶剂两相体系中面包酵母不对称还原苯乙酮合成手性苯乙醇的研究

以面包酵母细胞不对称还原苯乙酮合成S-α-苯乙醇为模型反应,研究了水-有机溶剂两相体系促进面包酵母细胞催化芳香酮的不对称还原情况.首先研究了适合于活性细胞催化的两相溶剂体系,实验表明合适的有机溶剂为logp3的溶剂,这与有机相中的酶催化对溶剂的要求相一致.在所选用的溶剂中,正辛烷获得的效果最好.在此基础上进一步考察了两相之间的比率、辅助溶剂、底物浓度以及水相体系的pH等对反应的影响.实验表明两相之间的比率和辅助溶剂对反应有显著的影响,合理改变这些因素可以改善底物在两相之间的分配进而促进反应的进行.反应对底物浓度的敏感性较单相水相体系反应要小得多,而pH对反应的影响与水相中反应相同.在有机溶剂与水相体积比为1:4、添加1%乙醇以及底物浓度为30 mmol·L-1时,产物得率可达到45%左右,这较在水相中反应有显著的提高.     

手性磺酰胺醇催化苯乙酮的不对称还原反应

由天然氨基酸合成了6个手性磺酰胺醇,并对其在NaBH4/BF3.Et2O还原苯乙酮中的不对称催化性能进行了研究。这些磺酰胺醇催化苯乙酮的还原反应获得了很高的化学产率和较低的对映体过量。     

表面活性剂对面包酵母细胞催化2-辛酮不对称还原反应的影响

实验研究了表面活性剂(SDS,CTAB,Emulsifier OP-6)对面包酵母细胞催化2-辛酮不对称还原反应的影响.结果表明,当底物浓度为10mmol/L时,在不含表面活性剂的体系中,副反应和逆反应使反应96h后的得率和产物(S)-2-辛醇对映体过量率(Enantiomeric Excess,e.e.)仅为77.4%和78.8%.一定浓度的表面活性剂可提高正反应速率、降低逆反应和副反应速率,在含0.4mmol/L Emulsifier OP-6或0.04mmol/L CTAB的体系中反应96h,得率分别达到88.4%和91.1%,产物e.e.值为97.0%和94.5%.反应得率和产物e.e.值提高与表面活性剂对细胞生长、细胞膜透性的改变有关.EmulsifierOP-6的作用效果优于其他2种表面活性剂.     

面包酵母生物催化不对称不对称合成丹参素冰片酯

针对已有报道的丹参素冰片酯合成工艺中成本高、实验条件相对苛刻、原料利用率低等缺陷和不足,以3,4-二羟基苯甲醛为起始原料,利用文献方法,在合成β-(3,4-二羟基苯基)丙酮酸冰片酯的基础上,利用活性酵母细胞代谢过程中产生的辅酶,生物催化不对称合成了丹参素冰片酯。系统考察了葡萄糖的加入量、反应时间、pH及β-环糊精加入量等因素对面包酵母生物催化合成不对称丹参素冰片酯的影响,实验结果表明：在底物β-(3,4-二羟基苯基)丙酮酸冰片酯加入量为为0.5g时,其最佳反应条件为葡萄糖30g、β-环糊精1.5g、pH为7、反应时间24h,最佳实验条件下ee值高达84.9%,产物主要为S构型的丹参素冰片酯。该工艺反应条件温和、成本较低,是一条极具价值的丹参素冰片酯生产工艺。     

左旋多巴醇在不对称还原中的应用研究

在NaBH4/Cd2+、NaBH4/Co2+、NaB4/Ce3+、NaBH4/Ni3+还原体系中,采用加入手性源左旋多巴醇和不加入左旋多巴醇两种方法,分别对苯乙酮进行不对称还原,结果表明,加入手性源左旋多巴醇后,反应速度快,产率高.同时在这4种还原体系中NaBH4/Ce3+的催化效果最好.     

面包酵母在手性化合物不对称合成中的类型

药物分子的立体化学决定其生物活性，手性已成为药物研究的一个关键因素。利用微生物或酶催化的方法进行手性化合物的不对称合成已经成为一个极具吸引力的方向。综述了近年来利用面包酵母催化不对称合成手性化合物的研究进展，着重讨论了利用面包酵母可进行的多种手性试剂的催化合成的反应类型。     

苯乙酮不对称加氢催化剂的研究

制备了钯-壳聚糖催化剂并用于苯乙酮的氢转移不对称催化加氢反应.考察了催化剂制备过程中所采用的溶剂、N/P物质的量比等对苯乙酮的不对称催化加氢反应性能的影响.以无水乙醇为溶剂,制备的n(N)n(Pd)=1的钯-壳聚糖催化剂上,苯乙酮不对称加氢反应的转化率为48.1%,苯乙醇的对映体过量值为100%.     

影响面包酵母催化还原羰基的因素探究

利用活性微生物细胞催化还原羰基是不对称合成手性醇的重要方法。微生物催化羰基还原反应的效率和立体化学选择性要受多种因素的影响,这些因素包括有机溶剂种类、水分含量、微生物形式、底物结构和辅酶再生等。     

活性干酵母与湿酵母催化不对称还原合成(R)-2-羟基-4-苯基丁酸乙酯的对比研究

研究有机溶剂中面包酵母催化2-氧代-4-苯基丁酸乙酯(OPBE)不对称还原合成标题化合物((R)-HPBE),分别考察用干酵母和湿酵母作催化、底物浓度、反应体系和湿酵母保存时间等凶素对OPBE转化率(X<,OPBE>)、HPBE产率(Y<,HPBE>)及(R)-HPBE的光学纯度(e.e.%)的影响.实验结果表明,湿酵母的立体选择性好于干酵母,但转化率和产率很低;乙醚为湿酵母催化较为适宜的介质.另外,湿酵母培养好后应立即反应.     

烯丙基化合物对面包酵母立体选择性的影响机理

添加烯丙基化合物可以控制酵母催化不对称还原反应的立体选择性,以4-氯-3-羰基丁酸乙酯(COBE)为模型底物,用丙烯酰胺和烯丙基醇对酵母进行预处理,产物(S)-4-氯-3-羟基丁酸乙酯(S-CHBE)的对映体过量值(e.e.)可以增加至94%;而用烯丙基溴预处理,则可以得到R型产物. 通过DNS法和API ZYM试验条证明烯丙基类化合物对细胞及胞内酶系存在毒害作用,且作用大小取决于烯丙基所带基团. 预处理后的酵母细胞经PBS缓冲液多次洗涤后,其活性可以逐渐得到恢复. 随着底物浓度的增加,经烯丙基醇预处理的酵母细胞,其S型产物的e.e.值维持在90%左右,而经烯丙基溴处理后,反应得到的R型产物的e.e.值则从90%下降到45%左右. 说明烯丙基类化合物竞争性地吸附于酶的活性区域,且其所带基团决定了被吸附酶的类型. 以抑制剂类似物处理酵母细胞,其反应结果说明酵母体内催化不对称还原反应的两类酶存在着空间位阻效应.     

离子液体中酵母细胞催化的不对称还原反应

以咪唑类离子液体/水两相为反应体系,考察了咪唑类离子液体的不同咪唑环取代烷基链、离子液体与水相的体积比、反应温度、摇床转速和水相pH对酵母Candida Pseudotropicalis催化还原2'-氯-苯乙酮制备S-2'-氯-苯乙醇反应的影响。结果表明,随着离子液体咪唑环上取代烷基的增大,S-2'-氯-苯乙醇的收率呈下降趋势。以1-己基-3-甲基咪唑六氟磷酸盐/水两相为反应体系,在2'-氯-苯乙酮初始浓度为3 g/L,辅助底物葡萄糖浓度为50 g/L的条件下,较合适的反应条件为离子液体与水的体积比1:50,水相pH值6.8,反应温度30℃,摇床转速200 r/min,反应24 h,产物S-2'-氯-苯乙醇产率可达85.9%,ee值大于99.9%。酵母细胞催化剂的重复使用实验表明,随着使用次数增加,离子液体/水两相体系中酵母细胞的催化作用明显下降。     

面包酵母研究进展

面包酵母是面包生产过程中最重要的微生物,在面包生产中起着关键作用。面包酵母菌种改良的研究主要集中在耐高糖的机制、麦芽糖的利用、低温适应性、蜜二糖的利用和乳糖的利用等方面。商品面包酵母生产的主要原料是甜菜糖蜜或甘蔗糖蜜,其发酵过程要求用补料的方法添加培养基,并要求适当的通风。     

Asymmetric Reduction of 3,5-Bistrifluoromethyl Acetophenone with NADH Regeneration by Immobilized Cells of Saccharomyces rhodotorula in Aqueous-Organic Solvent Biphasic System

Asymmetric reduction of 3,5-bistrifluoromethyl acetophenone to produce(S)-3,5-bistrifluoromethylphenyl ethanol was successfully carried out with sodium alginate immobilized Saccharomyces rhodotorula cells in an aqueous-organic solvent biphasic system.The possible influential factors were examined thoroughly according to their effects on conversion rate and e.e of the product.Organic solvents were rated by their biocompatibility and conversion potential.The immobilized cells [125 mg/mL in 20 mmol/L Tris-HCl ...     

Baker's Yeast Behavior during Vacuum Agitated Contact Drying

Drying is considered as an intensive operation that consumes large quantities of energy. Usually, baker's yeast is obtained using freeze drying or fluidized‐bed drying, both of which are considered as expensive technologies. So, exploring other techniques such as contact drying could limit this disadvantage. In addition, no work dealing with contact drying of baker's yeast has been accomplished yet. Therefore, here, the behavior of baker's yeast during vacuum agitated contact drying is presented. The results show that the drying process can be divided into three phases: the pasty phase, the lumpy phase, and the granular phase. The influence of the drying parameters, such as the temperature, the impeller velocity, and the initial mass, was also studied. It was found that the wall temperature and the impeller velocity have a positive effect on the drying kinetics, as their increase allows a reduction in the drying time. Nevertheless, an increase in the pressure level or the initial mass of the product caused the drying time to increase.     

离子液体在苯乙酮不对称加氢反应中的应用

过渡金属配合物催化的潜手性酮不对称加氢反应是制备手性仲醇的一个有效方法,在医药、精细化工及先进材料等领域具有非常重要的应用。采用离子液体-有机溶剂双液相体系,以手性二胺及非手性单膦配体修饰的Ru配合物为催化剂,催化潜手性酮的不对称加氢反应。考察了反应温度、氢气压力、溶剂和离子液体用量等因素对反应结果的影响,同时也考察了催化剂在反应体系中的流失情况。结果表明离子液体可以有效地负载手性催化剂,催化剂在反应过程中的流失量很低,可以实现简单的萃取分离     

Filtration Behavior of Baker's Yeast Suspensions at Very High Concentrations

Abstract

Pritchard et al. observed the phenomenon that the flux began to rise when the baker's yeast suspension was concentrated to a very high concentration in a thin-channel membrane module under laminar conditions. A further investigation of this interesting finding through both filtration experiments and rheological measurements has been conducted using baker's yeast suspensions. The separate filtrations of the suspensions and their supernatants suggest that for baker's yeast suspensions at very high concentrations there might be no cake layer. On the basis of the above results, an alternative to the normal membrane concentration process is put forward. Using this novel approach, particularly in its batch mode, a low-concentration feed can be directly transferred into a high-concentration product at a much higher flux.     

酵母细胞催化(S)-6-氯-5-羟基-3-羰基己酸叔丁酯的不对称还原

通过实验筛选出了对(S)-6-氯-5-羟基-3-羰基己酸叔丁酯具有较强还原能力的菌株。利用热预处理的方法提高了反应的立体选择性,并以稳定期的菌株为催化剂,考察菌龄、底物的加入量、菌体浓度、转化时间、转化温度和pH值对该反应的影响,得到较佳的反应条件是30℃,pH值6.0,底物浓度1 g/L,湿菌体浓度100 g/L,转化48 h。在此条件下进行反应,产物的收率和d.e.值可分别达到68.3%和95.1%。     

Numerical Modeling of Differential Kinetics in the Asymmetric Hydrogenation of Acetophenone by Noyori's Catalyst

A combination of numerical integration of the rate equations and experimental measurement of the time‐dependence of rates rather than concentrations is described for the analysis of the catalytic cycle by which Noyori's catalyst, trans‐RuCl₂[(S)‐binap][(S,S)‐dpen], hydrogenates acetophenone. The method is simpler in practice than usual kinetic methods and yields furthermore rate constants for activation, dihydrogen cleavage, and hydride transfer to substrate under realistic catalytic conditions. The specific results for the asymmetric hydrogenation of acetophenone show that the turnover‐limiting step changes from dihydrogen cleavage to hydride transfer if the H₂ pressure is increased, but also during the course of the reaction when the hydrogenation is performed under typical conditions.     

Asymmetric Ketone Reduction by Imine Reductases

The rapidly growing area of asymmetric imine reduction by imine reductases (IREDs) has provided alternative routes to chiral amines. Here we report the expansion of the reaction scope of IREDs by showing the stereoselective reduction of 2,2,2‐trifluoroacetophenone. Assisted by an in silico analysis of energy barriers, we evaluated asymmetric hydrogenations of carbonyls and imines while considering the influence of substrate reactivity on the chemoselectivity of this novel class of reductases. We report the asymmetric reduction of C=N as well as C=O bonds catalysed by members of the IRED enzyme family.