Biological fingerprinting analysis of the interactome of a kinase inhibitor in human plasma by a chemiproteomic approach

In this study, a gel free chemiproteomic method based on chromatography was developed and applied for the biological fingerprinting analysis of complex biological system. p-Aminobenzamidine (ABA), an inhibitor of trypsin-like serine proteases, was immobilized for characterizing their interacting proteins in human plasma. By the proteomic analysis method, 214 proteins were identified with obvious affinity to the immobilized ABA. By searching the sequences of above proteins with consensus patterns of the two active sites, seven proteins belong to trypsin-like serine protease group were found. Based on the Gene Ontology annotation, the identified trypsin-like serine proteases have the function of catalytic activity and calcium ion binding, and are mainly involved in the biological process of blood coagulation. Eight more other proteins related to calcium ion binding and blood coagulation were found. Nearly all of these proteins cannot be identified by directly analyzing the plasma sample demonstrating the chemiproteomics a useful approach to characterize interacting proteins in the low abundance range.     

Monolithic silica columns with mixed mode of hydrophilic interaction and weak anion-exchange stationary phase for pressurized capillary electrochromatography

A silica-based monolithic column as polar stationary phase is proposed for pressurized CEC (pCEC). The monolithic silica matrix from a sol-gel process was chemically modified by 3-aminopropyltrimethoxysilane to produce a column for hydrophilic interaction applications. The amino groups on the surface of the polar stationary phase generated anodic EOF under acidic conditions and served at the same time as a weak anion-exchanger. The anion solutes such as nucleotides were separated by the mixed mode mechanism, which comprised hydrophilic interaction, weak anion-exchange, and electrophoresis. The influences of buffer concentration and organic modifier content on the separation of nucleotides by pCEC have been investigated. In addition, the monolithic silica columns were also able to separate various polar compounds such as phenols, nucleic acid bases, and nucleosides in the hydrophilic interaction CEC mode.     

功能化离子液体[bmim]OTs催化乙酰化反应

以离子液体1-丁基-3-甲基咪唑四氟硼酸盐([bmim]BF4)为溶剂,对甲基苯磺酸根(OTs-)为阴离子的功能化离子液体[bmim]OTs为催化剂进行苯甲醇的乙酰化反应.结果表明,该体系循环使用10次后仍能保持良好的催化活性和稳定性,并对各种(伯、仲、叔)醇类、酚类和胺类化合物的乙酰化反应表现出良好的普适性.核磁共振波谱(13C NMR)分析结果表明,具有亲核性的[bmim]OTs和酰化试剂乙酸酐(Ac2O)形成的活性中间体AcOTs,是催化反应的活性物种.     

Preparative isolation and purification of three rotenoids and one isoflavone from the seeds of Millettia pachycarpa Benth by high-speed counter-current chromatography

Both analytical and preparative high-speed counter-current chromatography (HSCCC) were used to isolate and separate chemical bioactive constituents from the seeds of Millettia pachycarpa Benth, a famous traditional Chinese medicine. Three rotenoids and one isoflavone were successfully purified for the first time by HSCCC with a two-phase solvent system composed of n-hexane-ethyl acetate-methanol-water (HEMWat) (1:0.8:1:0.6, v/v/v/v). The separation parameters were first performed on the analytical HSCCC and optimized conditions were then scaled up to preparative HSCCC. The separation produced 160.2 mg tephrosin, 14.6 mg 4',5'-dimethoxy-6,6-dimethylpyranoisoflavone, 109.4 mg deguelin, 6.7 mg 6a,12a-dehydrodeguelin with respective purities of 95, 93, 95, 95%, in one single run from 400 mg crude extract of the seeds of M. pachycarpa Benth. The purity of the isolated compounds was analyzed by high-performance liquid chromatography (HPLC) and their structures were identified by electrospray ionization mass spectrometry (ESI-MS); (1)H nuclear magnetic resonance ((1)H NMR) and (13)C nuclear magnetic resonance ((13)C NMR) analysis. This paper is an excellent example of the role that CCC is playing in isolating active compounds for pre-clinical trials of new chemical entities, even when scaling up between centrifuges from different manufacturers.     

渗透汽化芳烃/烷烃分离膜材料

芳烃/烷烃混合物的分离在石油化工及环保领域都具有重大意义.与传统的萃取精馏等技术相比,渗透汽化膜技术以其清洁、节能和高效的优点,应用于芳烃/烷烃混合物的分离并受到重视.本文综述了渗透汽化芳烃/烷烃分离膜的研究进展,概述了渗透汽化技术的基本原理和应用,重点介绍了用于渗透汽化芳烃/烷烃分离的聚酰亚胺、聚氨酯等高分子膜材料的结构特点和分离性能.总结了膜材料的接枝、共聚和共混,添加传质促进剂的改性方法.分析了渗透汽化芳烃,烷烃分离膜材料的研究思路,在此基础上对渗透汽化芳烃/烷烃分离膜材料的研究方向和发展前景进行了展望.     

Catalytic selective oxidation or oxidative functionalization of methane and ethane to organic oxygenates

Selective oxidation or oxidative functionalization of methane and ethane by both homogeneous and heterogeneous catalysis is presented concerning: (1) selective oxidation of methane and ethane to organic oxygenates by hydrogen peroxide in a water medium in the presence of homogeneous osmium catalysts, (2) selective oxidation of methane to formaldehyde over highly dispersed iron and copper heterogeneous catalysts, (3) selective oxidation of ethane to acetaldehyde and formaldehyde over supported molybdenum cat...     

以Au(PPh3)(NO3)为前体制备的Au/13X结构及其CO催化氧化性能

分别以金的有机配合物Au(PPh₃)(NO₃)和无机化合物HAuCl₄为前驱体, 采用常规浸渍法分别制备了Au/13X-Org和Au/13X-Ino, 并以后者作为对照. 采用N₂-吸附/脱附、SEM-EDS、XRD和XPS等技术对所制样品的织构、晶体结构和价态进行了表征, 并研究了所制样品对CO的催化氧化性能. N₂-吸附/脱附、SEM-EDS和XRD结果表明, 对于Au/13X-Org样品, Au 较均匀地分布在13X载体上, 而Au/13X-Ino样品, Au 聚集地分布在13X载体上. 通过XRD和SEM测定表明Au/13X-Ino上金粒子(平均粒径≈26.6 nm)明显大于Au/13X-Org上金粒子(平均粒径＜5 nm). CO催化氧化结果表明, Au/13X-Org催化性能明显优于Au/13X-Ino, Au/13X-Org在低温25 ℃时CO转化30%, 150 ℃完全转化; 而Au/13X-Ino在低温无活性, CO完全转化温度高于400 ℃. 对于这种“惰性”13X载体负载Au活性的差别可能归因于金粒子的大小和前驱体中有无氯物种两方面的原因. XPS结果表明, 在Au/13X-Org和Au/13X-Ino催化剂上催化氧化的活性中心为金属态Au⁰.     

水滑石负载钯催化剂上的醇无氧脱氢反应

 研究了多种载体负载 Pd 催化剂上苯甲醇无氧脱氢反应. 结果发现, 以兼具较强酸性和碱性的水滑石 (HT) 为载体时, Pd 催化剂具有优异的苯甲醇转化活性和苯甲醛选择性, 当 Pd 含量为 0.32%~0.55% 时催化性能最佳. Pd/HT 催化剂可重复使用, 且对于含推电子取代基的芳香醇、2-噻吩甲醇、α,β-不饱和醇与环状脂肪醇等的直接脱氢反应均具有较好催化性能. HT 表面的 Pd(II) 物种反应后转变为平均粒径为 2.0~2.5 nm 的 Pd 纳米粒子或纳米簇. 具有较高分散度的 Pd(II) 物种易转变为较小的 Pd 纳米粒子, 从而具有较佳的催化性能. 本文推测, 催化剂表面的碱性位可促进苯甲醇 O–H 键的活化, 形成 Pd-苯甲氧基中间体, 该中间体进一步脱氢生成苯甲醛和 Pd-H 物种; 而催化剂表面的质子酸位可与 Pd-H 作用, 促进 H2 的脱除.     

同位素内标超高效液相色谱-串联质谱法检测大鼠血清中丙烯酰胺和环氧丙酰胺

建立了检测大鼠血清中丙烯酰胺和环氧丙酰胺的超高效液相色谱-串联质谱法(UPLC-MS/MS).血清样品中加入乙腈沉淀蛋白质,超高速离心取上清液,离心浓缩后,采用ACQUITY UPLC T3 C18色谱柱(50 mm×2.1 mm, 1.7 μm),以0.1%甲酸溶液和甲醇为流动相进行梯度洗脱,经UPLC分离,电喷雾离子化四级杆串联质谱以正离子多反应监测方式(MRM)检测,用同位素内标法定量.丙烯酰胺和环氧丙酰胺在0.5～20.0 mg/L浓度范围内线性良好,相关系数r均大于0.999;检出限均为0.1 mg/L;在3个浓度水平(2.0, 8.0, 和15.0 mg/L)进行添加实验,样品的加标回收率分别为98.0%～108.3%和99.6%～106.7%;日内精密度(RSD)为0.54%～5.8%和1.1%～5.8%;每个样品测试时间仅为6 min.本方法测定大鼠血清中的丙烯酰胺和环氧丙酰胺操作简单快速, 重现性好, 灵敏度高.     

脂质组成对硫辛酸脂质纳米粒的制备及其稳定性的影响

采用高压均质法制备硫辛酸(ALA)脂质纳米粒(ALA-NLC),确定了负载ALA的最佳体系。通过高效液相色谱、动态光散射、流变等测试研究了脂质成分、含量对ALA负载、ALA-NLC稳定性和分散液流变性质的影响,并用原子力显微镜观察了ALA-NLC的形貌。结果表明,脂质/ALA质量比在4.5∶1～6∶1之间,得到的脂质纳米粒分散均匀,颗粒规则;脂质中液态油脂的增加有利于保持ALA-NLC的粒径,储存稳定性和分散液的低粘度,并得到两个有望用于食品工业的ALA-NLC配方。