Preparation and optical properties of worm-like gold nanorods

A type of worm-like nanorods was successfully synthesized through conventional gold nanorods reacting with Na2S2O3 or Na2S. The generated worm-like gold nanorods comprise shrunk nanorod cores and enwrapped shells. Therefore, a gold-gold sulfide core-shell structure is formed in the process, distinguishing from their original counterparts. The formation of the gold chalcogenide layers was confirmed by transmission electron microscopy and X-ray photoelectron spectroscopy. Experimental results showed that the thickness of the gold chalcogenide layers is controllable. Since the increase of shell thickness and decrease of gold nanorod core take place simultaneously, it allows one to tune the plasmon resonance of nanorods. Proper adjustment of reaction time, temperature, additives and other experimental conditions will produce worm-like gold nanorods demonstrating desired longitudinal plasmon wavelength (LPW) with narrow size distributions, only limited by properties of starting original gold nanorods. The approach presented herein is capable of selectively changing LPW of the gold nanorods. Additionally, the formed worm-like nanorods possess higher sensitive property in localized surface plasmon resonance than the original nanorods. Their special properties were characterized by spectroscopic methods such as Vis-NIR, fluorescence and resonance light scattering. These features imply that the gold nanorods have potential applications in biomolecular recognition study and biosensor fabrications.     

Two-dimensional supercritical fluid chromatography/mass spectrometry for the enantiomeric analysis and purification of pharmaceutical samples

A new analytical two-dimensional supercritical fluid chromatography/mass spectrometry system (2D SFC/SFC/MS) has been designed and implemented to enhance the efficiency and quality of analytical support in drug discovery. The system consists of a Berger analytical SFC pump and a modifier pump, a Waters ZQ 2000 mass spectrometer, a set of switching valves, and a custom software program. The system integrates achiral and chiral separations into a single run to perform enantiomeric analysis and separation of a racemic compound from a complex mixture without prior clean up. The achiral chromatography in the first dimension separates the racemate from all other impurities, such as un-reacted starting materials and by-products. Mass-triggered fractionation is used to selectively fractionate the targeted racemic compound based on its molecular weight. The purified racemate from the achiral chromatography in the first dimension is then transferred to the chiral column in the second dimension to conduct the enantiomeric separation and analysis. A control software program, we coined SFC2D, was developed and integrated with MassLynx to retrieve acquisition status, current sample information, and real time mass spectrometric data as they are acquired. The SFC2D program also monitors the target ion signal to carry out mass-triggered fractionation by switching the valve to fractionate the desired peak. The 2D SFC/SFC/MS system uses one CO(2) pump and one modifier pump for both first and second dimension chromatographic separations using either gradient or isocratic elution. Similarly, a preparative 2D SFC/SFC/MS system has been constructed by modifying an existing Waters preparative LC/MS system. All components except the back pressure regulator are from the original LC/MS system. Applications of the 2D SFC/SFC/MS methods to the separation and the analysis of racemic pharmaceutical samples in complex mixtures demonstrated that an achiral separation (in first dimension) and a chiral separation (in second dimension) can be successfully combined into a single, streamlined process both in analytical and preparative scale.     

Species-specific and inhibitor-dependent conformations of LpxC: implications for antibiotic design

LpxC is an essential enzyme in the lipid A biosynthetic pathway in gram-negative bacteria. Several promising antimicrobial lead compounds targeting LpxC have been reported, though they typically display a large variation in potency against different gram-negative pathogens. We report that inhibitors with a diacetylene scaffold effectively overcome the resistance caused by sequence variation in the LpxC substrate-binding passage. Compound binding is captured in complex with representative LpxC orthologs, and structural analysis reveals large conformational differences that mostly reflect inherent molecular features of distinct LpxC orthologs, whereas ligand-induced structural adaptations occur at a smaller scale. These observations highlight the need for a molecular understanding of inherent structural features and conformational plasticity of LpxC enzymes for optimizing LpxC inhibitors as broad-spectrum antibiotics against gram-negative infections.     

Fe3O4 nanoparticle-supported copper(I) pybox catalyst: magnetically recoverable catalyst for enantioselective direct-addition of terminal alkynes to imines

An Fe(3)O(4) nanoparticle-supported copper(I) pybox catalyst, which exhibits excellent reactivity and yields products with good enantioselectivity, was developed. As a proof of concept, six optically active propargyl amines were obtained in excellent yields. The catalyst can be magnetically removed and recycled easily six times without a decrease in activity or enantioselectivity.     

Preparation and gas chromatographic characterization of dibenzyl crown ether stationary phases

Summary Two crown ethers, di(tert-butylbenzo)-propyl-15-crown-5 polysiloxane (PSO-DTB-15C5) and dibenzo-propyl-15-crown-5 polysiloxane (PSO-DB-15C5) have been synthesized and coated onto fused-silica capillary columns. The chromatographic characteristics, including column efficiency, polarity, phase transition temperature, operating temperature range and selectivity, were studied.Excellent selectivity was obtained for the separation of polar position isomers, especially phenol and dinitrotoluene isomers. The separation mechanism is discussed.     

乙酰水扬酸在CTAB胶束溶液中的水解反应

乙酰水扬酸(阿斯匹林)具有较高的药用价值,对它的性质有较多的研究,如在水中的稳定性和水解等。乙酰水扬酸有一个脂键和一个羰基。脂键易水解,水解后药用价值虽未降低,但有很大的副作用,因而研究抑制乙酰水扬酸水解是很有意义的。本文用RD—Ⅲ型热导式自动量热计研究了在十六烷基三甲基溴化胺(CTAB)胶束溶液中乙酰水扬酸的水解反应热动力学。     

人γ晶体蛋白的一级结构测定 1.γ晶体蛋白的分离提纯及其顺序测定方法(GC/MS法)的研究

成功地从人眼晶体中分离出单纯组分的γ晶体蛋白,对γ晶体蛋白的纯度、相对分子质量、氨基酸组成、N末端氨基酸组成等进行了测定,利用酸水解法和酶解法对γ晶体蛋白进行了水解和酶解条件的摸索、找出了使γ晶体蛋白断裂成适合于GC/MS联用仪进行结构测定的肽段的裂解条件。对进行氨基酸顺序测定的GC/MS法化学衍生化条件作了一系列的摸索,找出了化学衍生化的合适条件。对衍生化过程中的一些影响因素也进行了探讨。     

新型含金属元素二胺的合成与表征

本文分别用液相法和固相法合成了一系列含不同金属元素的二胺,并通过红外光谱,~1HNMR、~(13)CNMR,紫外光谱,电化学分析及元素分析对其进行表征,还通过DSC和TG对其热性能进行了研究,结果发现这些二胺具有良好的耐热性,是合成一些耐热高聚物的优良原料.     

常见饮料中痕量铝的分光光度法研究

新试剂5-溴水杨基荧光酮可在pH5.5～6.8的六次甲基四胺缓冲溶液中,与铝,溴化十六烷基吡啶形成稳定的红色三元配合物。最大吸收波长约为568nm,摩尔吸光系数高达1.7×10~5L mol~(-1)·cm~1,常见金属离子很少干扰。据此,建立了测定微量铝的方法。其线性范围为0～6μg/25ml回收率在96％～103％之间。本文测定了常见饮茶,饮料及饮水中的微量铝。     

流动注射在线柱预富集-电感耦合等离子体原子发射光谱测定痕量金属元素

本文报道了流动注射在线柱预富集ICP光谱测定痕量金属的方法,以meso-四(4-磺基苯)卟啉为柱前衍生试剂,硅胶作固定相和盐酸作洗脱液,对痕量金属离子Cu、Mn、Ni、Fe、Pb、Cd进行在线预富集检测。在给定实验条件下,方法的富集倍数为9.3～11.3,检出限和测定的相对标准偏差(n=6)分别在0.32～26.8ng/ml和1.3％～3.0％范围内。方法用于小牛肝和西红柿叶样品分析,结果与参考值吻合。