100g/L噁草酸乳油高效液相色谱分析方法研究

采用高效液相色谱法,以正己烷+异丙醇为流动相,用CHIRALPAK–IC手性色谱柱和二极管阵列检测器,在230 nm波长下对100 g/L草酸乳油进行定量分析。结果表明,草酸的线性相关系数为0.9999,标准偏差为0.60,变异系数为0.59%,平均回收率为99.94%。     

Asymmetric Autocatalysis Triggered by Chiral Crystals Formed from Achiral Compounds and Chiral Isotopomers

Asymmetric autocatalysis with amplification of enantiomeric excess is found in the enantioselective addition of diisopropylzinc to pyrimidine-5-carbaldehyde using pyrimidyl alkanol as an asymmetric autocatalyst. Asymmetric autocatalysis has been employed as a method for clarifying the origin of homochirality. Circularly polarized light, inorganic chiral crystals and statistical fluctuation of enantiomeric imbalance act as chiral initiators in asymmetric autocatalysis to afford highly enantioenriched products. We have investigated asymmetric autocatalysis using chiral crystals formed from achiral and racemic compounds as an origin of chirality. Absolute control of the crystal chirality of cytosine was achieved by the removal of crystal water. Enantioselective carbon-carbon bond formation at the enantiotopic crystal face of aldehydes was established using diisopropylzinc vapor. In addition, asymmetric autocatalysis triggered by chiral compounds arising from H, C and O isotope substitution has been achieved.     

手性金属磷酸盐催化2-萘酚与亚胺不对称反应

以2,6-二异丙基-4-金刚烷基苯取代的BINOL骨架磷酸镁盐作为催化剂,催化2-萘酚与N-(叔丁氧羰基)-苯甲醛亚胺(Ⅲa)的不对称反应。在常温、反应时间15h,甲苯作溶剂,催化剂用量5%(以底物的物质的量为基准,下同)的条件下,反应生成的叔丁基(2-羟基萘-1-基)(苯基)氨基甲酸甲酯(Ⅳa)达到97%的产率和90%的对映选择性。用NMR和HPLC对产物进行了表征。对反应条件进行了优化,确定了催化剂、反应时间、溶剂、反应温度等关键参数。该催化方法能使用少量的催化剂进行高效催化,且反应条件温和、经济高效、绿色环保。     

Immobilization of lipase onto metal–organic frameworks for enantioselective hydrolysis and transesterification

Enzyme immobilization enhances the catalytic activity and stability of the enzyme, and also improves reusability. Metal–organic frameworks (MOFs), which possess diversified structures and porosity, have been used as excellent carriers for enzyme immobilization. Pseudomonas fluorescens lipase (PFL) has been successfully immobilized onto MOFs by covalent cross-linking to obtain a series of immobilized lipase (PFL@MOFs). PFL@MOFs are used for catalytic enantioselective hydrolysis of 2-(4-hydroxyphenyl) propionic acid ethyl ester enantiomers (2-HPPAEE) in aqueous medium and transesterification of 4-methoxymandelic acid enantiomers (4-MMA) in organic medium. The experimental results indicated that PFL@Uio-66(Zr) exhibits excellent enzymatic catalysis performances and high enantioselectives. In addition, to improve catalytic activity and reusability, PFL is modified by the polyethylene glycol (PEG) to prepare PEG-modified lipase (PFL-PEG), then PFL-PEG is immobilized onto Uio-66(Zr) to prepare PFL-PEG@Uio-66(Zr), demonstrating better reusability and catalytic activity compared with PFL@Uio-66(Zr).     

手性伯胺催化剂催化Michael加成反应的研究进展

在许多不对称有机反应中,手性伯胺催化剂已被证实是一种高效的催化剂,被广泛应用于各种Michael加成反应中。Michel加成是有机合成中构建碳一碳键的重要反应之一,本文综述了近年来手性伯胺催化剂在Michael加成反应中的研究新进展。     

Heterologous Expression and Partial Characterization of a Putative Opine Dehydrogenase from a Metagenomic Sequence of Desulfohalobium retbaense

The aim of this research was to prove the function of the putative opine dehydrogenase from Desulfohalobium retbaense and to characterize the enzyme in terms of functional and kinetic parameters. A putative opine dehydrogenase was identified from a metagenomic library by a sequence-based technique search of the metagenomic library, and afterward was successfully heterologously produced in Escherichia coli. In order to examine its potential for applications in the synthesis of secondary amines, first the substrate specificity of the enzyme towards different amino donors and amino acceptors was determined. The highest affinity was observed towards small amino acids, preferentially L-alanine, and when it comes to α-keto acids, pyruvate proved to be a preferential amino acceptor. The highest activity was observed at pH 6.5 in the absence of salts. The enzyme showed remarkable stability in a wide range of experimental conditions, such as broad pH stability (from 6.0–11.0 after 30 min incubation in buffers at a certain pH), stability in the presence of NaCl up to 3.0 M for 24 h, it retained 80 % of the initial activity after 1 h incubation at 45 °C, and 65 % of the initial activity after 24 h incubation in 30 % dimethyl sulfoxide.     

DuPHOS在不对称催化氢化中的研究进展

介绍了一种新颖的具有C2对称性的手性双磷杂环戊烷配体DuPHOS，此配体在烯酰胺类、2－烷基琥珀酸类、α－羟基醌类、开链烯醇酯类、酮类等众多类型底物的不对称催化氢化反应中显示出了极高的对映体选择性，本文对此配体的最新研究进展进行了综述。     

脱氢枞胺键合交联聚苯乙烯树脂的制法和应用

分3个步骤制备脱氢枞胺键合交联聚苯乙烯树脂：醚化反应，双键环氧化和脱氢枞胺与环氧基开环反应。为了提高树脂中功能基的转化率，针对每一步合成做了正交实验，得出了最佳工艺条件。采用红外光谱对每一步合成产物进行结构表征。并用脱氢枞胺键合交联聚苯乙烯树脂进行对映体分离的初步应用。     

L-脯氨酸键合手性配体交换色谱固定相的制备及手性拆分

合成了L－脯氨酸键合手性配体交换固定相，用元素分析和红外光谱对固定相进行了表征。该固定相在反相条件下对DL－氨基酸对映异构体有良好的拆分能力。