A method for the analysis of low-mass molecules by MALDI-TOF mass spectrometry

We report a novel method termed matrix suppressed laser desorption/ionization to improve the analysis of low-mass molecules by MALDI-TOF mass spectrometry. In this method, the surfactant of cetrimonium bromide (CTAB) is added to the conventional matrix of alpha-cyano-4-hydroxycinnamic acid solution to prepare the MALDI samples. During the MALDI process, the presence of CTAB could substantially or even completely suppress the matrix-related ion background. As a result, very clean mass spectra can be routinely obtained in the low-mass range. In addition, the presence of CTAB can significantly improve the mass resolution of low-mass molecules. It is seen that high-quality spectra were routinely obtained at a matrix/CTAB ratio of 1000:1. This method has been successfully used to analyze a variety of low-mass molecules.

A New Method for Analysis of Disulfide-Containing Proteins by Matrix-Assisted Laser Desorption Ionization (MALDI) Mass Spectrometry

A simple and high-throughput method for the identification of disulfide-containing peptides utilizing peptide-matrix adducts is described. Some commonly used matrices in MALDI mass spectrometry were found to specifically react with sulfhydryl groups within peptide, thus allowing the observation of the peptide-matrix adduct ion [M + n + n' matrix + H](+) or [M + n + n' matrix + Na](+) (n = the number of cysteine residues, n' = 1, 2, ..., n) in MALDI mass spectra after chemical reduction of disulfide-linked peptides. Among several matrices tested, alpha-cyano-4-hydroxycinnamic acid (CHCA, molecular mass 189 Da) and alpha-cyano-3-hydroxycinnamic acid (3-HCCA) were found to be more effective for MALDI analysis of disulfide-containing peptides/proteins. Two reduced cysteines involved in a disulfide bridge resulted in a mass shift of 189 Da per cysteine, so the number of disulfide bonds could then be determined, while for the other matrices (sinapinic acid, ferulic acid, and caffeic acid), a similar addition reaction could not occur unless the reaction was carried out under alkaline conditions. The underlying mechanism of the reaction of the matrix addition at sulfhydryl groups is proposed, and several factors that might affect the formation of the peptide-matrix adducts were investigated.

基质辅助激光解吸电离飞行时间质谱表征细胞色素C

A matrix-assisted laser desorption ionization time-of-flight mass spectrometry(MALDI-TOF—MS) technique was used for analysis of moleculear weight of cytochrome C.The effects of three kinds of matrix,such as 2,5-dihydroxybenzoic acid(DHB),a-cyano-4-hydroxycinnamic acid(a-CHC) and sinapinic acid(SA),were used to compared and a suitable a-CHC was found.Experimental data showed that this method was properable to analysis of the congeneric biochemical samples.

Using oxidized carbon nanotubes as matrix for analysis of small molecules by MALDI-TOF MS

Oxidized carbon nanotubes are tested as a matrix for analysis of small molecules by matrix assisted laser desorption/ionization time of flight mass spectrometry (MALDI-TOF-MS). Compared with nonoxidized carbon nanotubes, oxidized carbon nanotubes facilitate sample preparation because of their higher solubility in water. The matrix layer of oxidized carbon nanotubes is much more homogeneous and compact than that of nonoxidized carbon nanotubes. The efficiency of desorption/ionization for analytes and the reproducibility of peak intensities within and between sample spots are greatly enhanced on the surface of oxidized carbon nanotubes. The advantage of the oxidized carbon nanotubes in comparison with alpha-cyano-4-hydroxycinnamic acid (CCA) and carbon nanotubes is demonstrated by MALDI-TOF-MS analysis of an amino acid mixture. The matrix is successfully used for analysis of synthetic hydroxypropyl P-cyclodextrin, suggesting a great potential for monitoring reactions and for product quality control. Reliable quantitative analysis of jatrorrhizine and palmatine with a wide linear range (1-100 ng/mL) and good reproducibility of relative peak areas (RSD less than 10 %) is achieved using this matrix. Concentrations of jatrorrhizine (8.65 mg/mL) and palmatine (10.4 mg/mL) in an extract of Coptis chinensis Franch are determined simultaneously using the matrix and a standard addition method. (c) 2005 American Society for Mass Spectrometry.

Rapid molecular weight determination of recombinant hirudin by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

The molecular weight of recombinant hirudin ( rHV-2) was determined rapidly by matrix-assisted laser desorption/ionization time of fight mass spectrometry (MALDI-TOF-MS). The effects of the three types of matrixes were compared and discussed, alpha-cynao-4-hydroxycinnamic acid was proved to be the best matrix. It showed that MALDI-TOF-MS was superior to the traditional method of molecular weight determination of the biological macromolecules. The mass spectrum data proved that the primary structure of rHV-2 was correct and there was no amino acid deletion, mutation and modification in its expression, refolding and purification.

Photoluminescence enhancement of porous silicon by organic cyano compounds

A pronounced photoluminescence enhancement on chemically oxidized porous silicon was induced by a series of organic cyano compounds including 1,2-dicyanoethylene (CE), 1,3-dicyanobenzene (1,3-CB), 1,4-dicyanobenzene (1,4-CB), 1-cyanonaphthalene (1-CN), and 9-cyanoanthracene (9-CA). Photoluminescence enhancement effects were reversible for all compounds studies in this work. A dependence of photoluminescence enhancement on the steric effect and the electronic characteristics of these compounds and the structure of the porous silicon substrates were analyzed in terms of the photoluminescence enhancing factors. Surface chemical composition examined by Fourier transform infrared (FTIR) spectra demonstrated that the surface Si-H bonds were not changed and no new luminescent compounds were formed on porous silicon surface during adsorption of cyano compounds. A mechanism based on induced surface states acting as radiative recombination centers by cyano compounds adsorption was suggested.

Liquid crystal properties of a mesogenic polyacetylene, poly(11-[(4 '-heptoxy-4-biphenylyl)carbonyloxy]-1-undecyne)

The liquid crystalline properties of a mesogenic poly(1-alkyne) and the corresponding monomer were studied using transmission electron microscopy, X-ray diffraction, polarizing optical microscopy and differential scanning calorimetry. The monomer exhibits a monotropic smectic A phase and a metastable crystalline phase. The rigid polymer backbones do not prevent the mesogenic moieties from packing into smectic A and B phases in the temperature ranges 127.6 - 74.1degreesC and 74.1degreesC - room temperature, respectively, on cooling from the isotropic melt.

渤海4号钻井船的疲劳损伤计算与分析

文章对渤海４号钻井船在我国渤中、辽东湾、东海和南海４大海域作业的疲劳损伤进行了详细的计算和分析，讨论了平台薄弱部位桩靴加强程度对平台疲劳损伤大小的影响及海流对平台损伤的作用。最后对渤海４号进行了充分的技术经济评价，为今后平台的合理使用、经济使用、安全作业提出了重要的建议。

涠11-4平台结构动态响应监测结果分析(涠11-4平台原位监测研究之二)

本文总结了针对涠１１－４平台一年多时间的应变和加速度监测数据的处理分析工作，详细介绍了所用的数据处理方法，给出了应变数据的统计结果及长期分布规律。通过对应变和加速度信号进行频谱分析，揭示了平台在多种环境条件下的振动特性。

涠11-4平台综合强度监测技术及实施运行系统(涠11-4平台结构原位监测研究之一)

本文介绍了一种固定式导管架平台综合强度监测系统，它用于对涠１１－４平台关键部位的应力、加速度及与结构响应相关的环境参数进行长期监测。讨论的重点内容是结构响应的测量方案、设备及实施方法，并对运行结果作了说明

以1-苯基-3-甲基-4-苯甲酰基代吡唑酮[5]萃取稀土和钍铀钛锆及其在分析化学中的某些应用

本文研究了以PMBP-苯萃取稀土和钍、铀、钛、锆的萃取行为。测定了La、Ce、Pr、Nd、Sm、Gd、Dy、Yb、Y、U(Ⅵ)、Ti、Th和Zr的pH_(1/2)值,计算了它们的萃取平衡常数。并介绍了近十年来作者将此萃取剂应用于铀、钍、稀土、鋰、钢铁合金及岩石中痕量稀土、钍和钙的分离和测定方面的工作。实践证明,PMOP合成简便、价格低廉、萃取能力较强,是比TTA更为优越的萃取剂。

KD-4型可动凝胶调驱体系研究与应用

针对中高温油藏调驱中使用的含醇类酚醛树脂类交联剂在现场应用中存在结块、醇的挥发性等问题，开展了可动凝胶合成技术、配方组成、成胶时间、热稳定性考察等试验研究，形成了以全水溶、高羟甲基化的预聚树脂交联剂为主体的KD-4型调驱体系配方。对KD-4型调驱体系成胶时间、热稳定性等进行了室内实验，并开展了前置段塞物模试验和可动性物模试验研究。依据试验结果，将总体段塞设计为“前置段塞＋主段塞＋保护段塞＋驱油段塞（视井况而定）”，成胶黏度由低到高。自2006年7月以来，该技术进行了6口井的现场应用，井组有效率100％，截至2007年10月底，按驻点法统计，累计阶段增产原油16158．7t，目前继续有效，措施效果显著，说明调驱性能稳定，方案设计科学.

PZT-4紧凑拉伸试样的断裂分析

基于线性压电材料的复势理论,通过解析分析,导出了一种分析有限压电板裂纹问题的解析数值方法.首先,计算了含中心裂纹有限板的断裂参数,与Woo和Wang的解析数值法(Int J Fract,1993,62:203～218)相比较,表明该方法具有很高的精度和很好的计算效率.随后,采用该方法和有限元法计算了PZT-4紧凑拉伸试样在绝缘裂纹面边界条件下断裂时的断裂参数,发现各断裂参数的临界值分散性很大,不能作为压电材料的单参数断裂准则.进而,针对试样真实的裂隙形状,采用有限元法计算了裂隙尖端的应力、电位移场,比较了裂隙内介质的介电性能对裂隙尖端场的影响,计算了带微裂纹的真实裂隙模型的断裂参数并进行了理论分析.

“神舟4号”飞船搭载微重力流体物理实验获得圆满成功

由中国科学院力学研究所胡文瑞院士和解京昌研究员领导的研究小组承担的“微重力液滴热毛细迁移实验”项目，利用自行研制的“通用流体实验装置”，于2002年12月30日搭载“神舟4号”飞船，圆满完成了各项预定空间实验任务。对飞船下传数据和图像的初步分析表明，实验装置全部工作正常，实验获得了圆满成功，可望得到有价值的学术成果，并在相关理论研究中取得突破。此次空间实验的成功，显示了科学家和工程师的完美结合，标志着力学所在“两弹一箭”后重返空间技术领域，再铸辉煌！