碳糖苷合成的新进展

本文介绍了近几年来有关碳糖苷合成的最新进展, 包括亲电取代、亲核糖取代、过渡金属催化、异头碳自由基反应、重排和环加成反应以及糖环形成反应等。     

Enantioseparation of Amino Acid Derivatives with a Cellulose-Based Chiral Stationary Phase

Five structurally related amino acid derivatives were enantioseparated by HPLC with a commercially available chiral stationary phase, Chiralcel OD-H. The chromatographic experiments were performed in the normal phase mode. n-Hexane/polar alcohol was used as mobile phase. Excellent baseline enantioseparations could be obtained for all these solutes. The effects of the concentration of polar alcohol and the column temperature on the retentions and enantioseparations were studied in detail. From the van't Hoff plots the corresponding apparent thermodynamic parameters were derived. Mechanism aspects of chiral recognition were discussed based on the relationship between the thermodynamic parameters and the structures of the solutes. It was found that the substituent of the phenyl group on the residual group of the amino acid derivatives was close relevant to thermodynamic origin of enantioseparation. Much better enthalpy–entropy compensation effect was obtained by plotting the differential, rather than the original, thermodynamic parameters.     

聚醚桥连二异羟肟酸单核和双核过渡金属配合物催化PNPP水解

Two polyether bridged dihydroxamic acids and their mono-and binuclear manganese(Ⅱ), zinc(Ⅱ) complexes have been synthesized and employed as models to mimic hydrolase in catalytic hydrolysis of p-nitrophenyl picolinate (PNPP). The reaction kinetics and the mechanism of hydrolysis of PNPP have been investigated. The kinetic mathematical model for PNPP cleaved by the complexes has been proposed. The effects of the different central metal ion, mono-and binuclear metal, the pseudo-macrocyclic polyether constructed by polyethoxy group of the complexes, and reactive temperature on the rate for catalytic hydrolysis of PNPP have been examined. The results showed that the transition metal dthydroxamates exhibited high catalytic activity to the hydrolysis of PNPP, the catalytic activity of binuclear complexes was higher than that of mononuclear ones, and the pseudo-macrocyclic polyether might synergetically activate H20 coordinated to metal ion with central metal ion together and promote the catalytic hydrolysis of PNPP.     

Enantioseparation of amino acid derivatives on an immobilized network polymer derived from L-tartaric acid

Seven structurally related amino acid derivatives were successfully enantioseparated by HPLC with a commercially available column containing a chiral immobilized network polymer derived from L-tartaric acid. The experiments were carried out under normal-phase conditions. All the solutes could be baseline separated using n-hexane/2-propanol (95/5) as eluent at a flow rate of 1 ml/min at 25 degrees C, with reasonable retention time (<12 min). The effects of the polar alcohol modifier (type and content) in the mobile phase and the column temperature on the enantioseparation were studied. Apparent thermodynamic parameters were also calculated from the plots of ln alpha or ln k' versus 1/T. Some mechanistic aspects of chiral recognition were discussed with respect to the structures of the solutes. It was found that the enantioseparations are all enthalpy driven, and the N-acyl groups of the solutes have significant influence on the chiral recognition.     

Two new C18-norditerpenoid alkaloids from Aconitum delavayi

Further phytochemical investigation of the unique C18-norditerpenoid alkaloids from the roots of Aconitum delavayi Franch ledto the isolation of two new norditerpenoid alkaloids,delavaconitine F 1 and delavaconitine G 2.Their structures were determinedfrom spectroscopic evidence.     

A Clean Synthesis of 1,4‐Diarylquinoline Derivatives Catalyzed by TEBAC in Aqueous Media

A series of 1,4‐diarylquinoline derivatives were synthesized by the reaction of arylmethylidenemalononitriles or 2‐cyano‐3‐aryl‐1‐acrylate and 3‐arylamino‐5,5‐dimethylcyclohex‐2‐enone in aqueous media at 100 °C catalyzed by TEBAC. Meanwhile, the water medium was chosen as green solvent.     

毛细管电泳-单链构象多态性分析检测K-ras基因突变

K ras癌基因的点突变在结直肠癌的发生起重要作用。以异丙醇为聚合反应链转移剂,水相法合成 特性粘度为0.70×10-3m3/kg,分子量为6.5×104的低粘度短链线性聚丙烯酰胺。以6%线性聚丙烯酰胺为 筛分介质,分离温度27℃,分离电压9kV为电泳条件,建立了检测K ras基因突变的毛细管电泳 单链构象多 态性方法。利用该方法检测36例结直肠癌患者肿瘤组织,发现12例K ras基因突变。结果表明:该方法具有 快速、高灵敏的优点,为大规模进行结直肠肿瘤的早期诊断提供了可靠方法。     

用胆甾型苯并—15—冠—5气相色谱固定相分离乳酸和乳酸乙酯光学异构体

胆甾型苯并－１５－冠－５（简称ＣＨ－Ｂ－１５－Ｃ－５）在不同温度范围内的相态不同，在同一温 度范围内因处理方式不同而物性亦相去甚远，用其作成的ＧＣ固定相兼具气固色谱（ＧＳＣ）、 普通气液色谱（ＧＬＣ）和冠醚液晶气液色谱（ＣＬ－ＧＬＣ）多种功能。用该固定相在不同条件下对 乳酸和乳酸乙酯光学异构体混合物的分高效果进行了比较研究，并探讨了手性拆分机理。     

SET8 suppression mediates high glucose-induced vascular endothelial inflammation via the upregulation of PTEN

Hyperglycemia-mediated endothelial inflammation participates in the pathogenesis of cardiovascular complications in subjects with diabetes. Previous studies reported that phosphatase and tensin homolog deleted on chromosome ten (PTEN) and SET8 participate in high glucose-mediated endothelial inflammation. In this study, we hypothesize that SET8 regulates PTEN expression, thus contributing to high glucose-mediated vascular endothelial inflammation. Our data indicated that plasma soluble intercellular adhesion molecule-1 (sICAM-1) and endothelial selectin (e-selectin) were increased in patients with diabetes and diabetic rats. PTEN expression was augmented in the peripheral blood mononuclear cells of patients with diabetes and in the aortic tissues of diabetic rats. Our in vitro study indicated that high glucose increased monocyte/endothelial adhesion, endothelial adhesion molecule expression and p65 phosphorylation in human umbilical vein endothelial cells (HUVECs). Moreover, high glucose led to endothelial inflammation via upregulation of PTEN. Furthermore, high glucose inhibited SET8 expression and histone H4 lysine 20 methylation (H4K20me1), a downstream target of SET8. SET8 overexpression reversed the effects of high-glucose treatment. shSET8-mediated endothelial inflammation was counteracted by siPTEN. Furthermore, SET8 was found to interact with FOXO1. siFOXO1 attenuated high glucose-mediated endothelial inflammation. FOXO1 overexpression-mediated endothelial inflammation was counteracted by siPTEN. H4K20me1 and FOXO1 were enriched in the PTEN promoter region. shSET8 increased PTEN promoter activity and augmented the positive effect of FOXO1 overexpression on PTEN promoter activity. Our in vivo study indicated that SET8 was downregulated and FOXO1 was upregulated in the peripheral blood mononuclear cells of patients with diabetes and the aortic tissues of diabetic rats. In conclusion, SET8 interacted with FOXO1 to modulate PTEN expression in vascular endothelial cells, thus contributing to hyperglycemia-mediated endothelial inflammation.Subject terms: Diabetes complications, Vascular diseases     

Theoretical Studies on the Abstraction Reaction of Atomic O（^3p） with Si2H6

The hydrogen abstraction reaction of O(^3P) with Si2H6 has been studied theoretially. Two transition states of ^3A″ and ^3A′ symmetries have been located for this abstraction reaction. Geometries have been optimized at the UMP2 leve with 6-311G (d) basis set. G3MP2 has been used for the final single-point energy calculation. The rate constants have been calculated over a wide temperature range of 200-3000K using canonical variational transition-state sheory (CVT) with small curvature tunneling effect(SCT). The calculated CVT/SCT rate constants match well with the experimental value.