TIME-DEPENDENT DENSITY FUNCTIONAL STUDY OF MULTIELECTRON TRANSFER IN Cq+-Na-4 COLLISIONS

The process of multielectron transfer from a Na-4 cluster induced by highly charged C6+, C4+, C2+ and C+ ions is studied using the method of time-dependent density functional theory within the local density approximation combined with the use of pseudopotential. The evolution of dipole moment changes and emitted electrons in Na-4 isobtained and the time-dependent probabilities with various charges are deduced. It is shown that the Na-4 cluster is strongly ionized by C6+ and that the number of emitted electrons per atom of Na-4 is larger than that of Na-2 under the same condition. One can find that the detailed information of the emitted electrons from Na-4 is different from the same from Na-2, which is possibly related to the difference in structure between the two clusters.

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.

三聚氰胺的基质辅助激光解吸/电离飞行时间质谱研究

Oxidized carbon nanotubes are tested as the matrix for analysis of the melamine by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS). Traditional MALDI matrix are not suit for analysis of the low molecular compounds due to the interference associated to the matrix clusters. Oxidized carbon nanotubes can transfer energy to the analyte under the laser irradiation, which makes analyte well ionized or desorbed. Moreover, the interference of the intrinsic matrix ions can be eliminated. Melamine as the a toxic additive which had been added in the milk powder, then it is necessary to establish a new method for detection of the melamine rapid and sensitive.

金属离子与钙调蛋白相互作用的基质辅助激光解析电离飞行时间质谱研究

Calmodulin is a ubiquitous calcium-binding protein in eukaryote cells and engages in various important biological pathways. In the present study, binding interactions between several metal ions and calmodulin were nvestigated by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS).The results revealed that the specific binding of metal ions with the protein could be detected using MALDI-TOF MS.

含二硫键多肽的基质辅助激光解析电离飞行时间质谱研究

The determination of disulfide bonds becomes an important aspect of obtaining a comprehensive understanding of the chemical structure of a protein. Numerous experimental methods have been developed for the determination of disulfide bonds in proteins. Modern mass spectrometry has developed as an important tool for the analysis of disulfide bond patterns due to its advantages of being simple, rapid and sensitive. The dissociations of the disulfide bonds were detected during the matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) analysis. These fragment ions were attributed to prompt fragmentation or “in-source decay” rather than “post-source decay”. For the double disulfide bonds, ions of plus sulfur and minus sulfur atoms corresponding to cleavages at different sites within the carbon-sulfur-sulfur-carbon disulfide bonds were also observed.

Characterization of linear epitope of the beta(2)-microglobulin via combination of MALDI-TOF-MS with immunoaffinity

Matrix-assisted laser desorption ionization time-of-flight mass spectrometry(MALDI-TOF-MS), in combination with immunoaffinity provided a powerful tool for determining epitope (antigenic determinant) in protein. The linear epitope of the beta(2)-microglobulin was characterized in the paper. The method as follows: at first beta(2)-microglobulin was digested by a proteolytic enzyme to produce an appropriate set of peptide fragments, then peptide fragments containing the linear epitope were selected and separated from the pool of peptide fragments by immunoprecipitation with the monoclonal antibody. The agarose beads were collected carefully after the reaction. Unbound peptides would be washed away, while the peptides containing the epitope would remain bound to the immobilized antibody after. the beads were washed several times with appropriate buffer. At last the masses of the bound peptides were identified directly by MALDI-TOF MS. Using Endoproteinase Glu-C Endoproteinase Lys-C and Trypsin in the experiment, the linear epitope of beta(2)-microglobulin was located within peptide fragment 59-69, that is, DWSFYLLYYTE.

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.

马鹿茸多肽的提取分离及基质辅助激光解吸飞行时间质谱分析

In this paper,active components of velvet antler polypeptide were extracted and separated.The molecular weight and purity of velvet antler polypeptide were determined by MALDI-TOFMS.The different influence factors such as matrix,sample concentration and laser energy were studied.This method is convenient and suitable for the identification of congener biochemical samples.

Synthesis and properties of novel polyimides derived from 2,2 ',3,3 '-benzophenonetetracarboxylic dianhydride

A new synthetic route to 2,2',3,3'-BTDA (where BTDA is benzophenonetetracarboxylic dianhydride), an isomer of 2,3',3',4'-BTDA and 3,3',4,4'-BTDA, is described. Single-crystal X-ray diffraction analysis of 2,2',3,3'-BTDA has shown that this dianhydride has a bent and noncoplanar structure. The polymerizations of 2,2',3,3'-BTDA with 4,4'-oxydianiline (ODA) and 4,4'-bis(4-aminophenoxy)benzene (TPEQ) have been investigated with a conventional two-step process. A trend of cyclic oligomers forming in the reaction of 2,2',3,3'-BTDA and ODA has been found and characterized with IR, NMR, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry, and elemental analyses. Films based on 2,2',3,3'-BTDA/TPEQ can only be obtained from corresponding polyimide (PI) solutions prepared by chemical imidization because those from their polyamic acids by thermal imidization are brittle. PIS from 2,2',3,3'-BTDA have lower inherent viscosities and worse thermal and mechanical properties than the corresponding 2,3',3',4'-BTDA- and 3,3',4,4'-BTDA-based PIs. PIs from 2,2',3,3'-BTDA and 2,3',3',4'-BTDA are amorphous, whereas those from 3,3',4,4'-BTDA have some crystallinity, according to wide-angle X-ray diffraction.

Synthesis, characterization and ring-opening polymerization of cyclic (arylene phosphonate) oligomers

A series of cyclic (arylene phosphonate) oligomers were prepared by reaction of phenylphosphonic dichloride (PPD) with various bisphenols under pseudo-high dilution conditions via interfacial polycondensation. The yield of cyclic (arylene phosphonate) oligomers is over 85% by using hexadecyltrimethylammonium bromide as phase transfer catalyst (PTC) at 0 degreesC. The structures of the cyclic oligomers were confirmed by a combination of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) and IR analysis. These cyclic oligomers undergo facile ring-opening polymerization in the melt by using potassium 4,4'-biphenoxide as the initiator to give linear polyphosphonate. Free-radical ring-opening polymerization of cyclic(arylene phosphonate) oligomers containing sulfur linkages was also performed in the melt using 2,2'-dithiobis(benzothiazole) (DTB) as the initiator at 270degreesC and the resulting polymer had a M-w of 8 x 10(3) with a molecular weight distribution of 4. Ring-opening copolymerization of these cyclic oligomers with cyclic carbonate oligomers was also achieved. The average molecular weight of the resulting copolymer is higher than the corresponding, homopolymer and the thermal stability of the copolymer is better than the corresponding homopolymer.

Dibenzyl trithiocarbonate mediated reversible addition-fragmentation chain transfer polymerization of acrylonitrile

Reversible addition-fragmentation chain transfer polymerization has been successfully applied to polymerize acrylonitrile with dibenzyl trithiocarbonate as the chain-transfer agent. The key to success is ascribed to the improvement of the interchange frequency between dormant and active species through the reduction of the activation energy for the fragmentation of the intermediate. The influence of several experimental parameters, such as the molar ratio of the chain-transfer agent to the initiator [azobis(isobutyronitrile)], the molar ratio of the monomer to the chain-transfer agent, and the monomer concentration, on the polymerization kinetics and the molecular weight as well as the polydispersity has been investigated in detail. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and H-1 NMR analyses have confirmed the chain-end functionality of the resultant polymer.

Polyimides from isomeric oxydiphthalic anhydrides

2,2',3,3'-Oxydiphthalic dianhydride (2,2',3,3'-ODPA) and 2,3,3',4'-ODPA were synthesized from 3-chlorophthalic anhydride with 2,3-xylenol and 3,4-xylenol, respectively. Their structures were determined via single-crystal X-ray diffraction. A series of polyimides derived from isomeric ODPAs with several diamines were prepared in dimethylacetamide (DMAc) with the conventional two-step method. Matrix-assisted laser desorption/ionization time-of-flight spectra showed that the polymerization of 2,2',3,3'-ODPA with 4,4'-oxydianiline (ODA) has a greater trend to form cyclic oligomers than that of 2,3,3',4'-ODPA. Both 2,2',3,3'-ODPA and 2,3,3',4'-ODPA based polyimides have good solubility in polar aprotic solvents such as DMAc, dimethylformamide, and N-methylpyrrolidone. The 5% weight-loss temperatures of all polyimides were obtained near 500 degreesC in air. Their glass-transition temperatures measured by dynamic mechanical thermal analysis or differential scanning calorimetry decreased according to the order of polyimides on the basis of 2,2',3,3'-ODPA, 2,3,3',4'-ODPA, and 3,3',4,4'-ODPA. The wide-angle X-ray diffraction of all polyimide films from isomeric ODPAs and ODA showed some certain extent of crystallization after stretching. Rheological properties revealed that polyimide (2,3,3',4'-ODPA/ODA) has a comparatively lower melt viscosity than its isomers, which indicated its better melt processability.

High-sensitivity molecular mass determination of lysozyme prior to MALDI-MS

Sodium dodecyl sulfate(SDS) is a powerful solubilizing detergent which is often used during the separation of highly complex protein mixtures by one- or two-dimensional (2D) gel electrophoresis. Matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) is a widely used technique for mass spectrometric analysis of some protein molecules compared to other techniques. But the presence of SDS or some salts usually leads to signal deterioration when using MALDI-MS. A method for using nitrocellulose membrane as the solid-phase carrier combined with n-octyl-beta-D-glucopyranoside in the matrix highly enhances the sensitivity of the molecular mass determination of lysozyme. This technique has the advantage that the signal-to-noise of the molecular weight profile is improved compared with the mass spectrum and the profile is relatively easy to interpret.

Acid effects on protein molecular weight determination

The acid effects of some proteins on measuring their molecular weights were studied using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry ( MALDI-TOF-MS) and electrospray ionization mass spectrometry (ESI-MS). It was found that the signal intensity was enhanced through adjusting the acid concentration in some protein samples. In this paper, both MALDI-MS and ESI-MS was applied to examine the molecular weights of several standard proteins. And the proper acid concentration was detected in these spectra. In the meanwhile, it demonstrates that some associations of proteins in solution can be preserved into the gas phase and observed by the "soft ionization" mass spectrometry.

Use of nitrocellulose films for affinity-directed mass spectrometry for the analysis of antibody/antigen interactions

Combination of affinity extraction procedures with mass spectrometric analyses is termed affinity-directed mass spectrometry, a technique that has gained broad interest in immunology and is extended here with several improvements from methods used in previous studies. A monoclonal antibody was immobilized on a nitrocellulose (NC) membrane, allowing the corresponding antigen to be selectively captured from a complex solution for analysis by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS). This method was also used to rapidly determine the approximate binding region responsible for the antibody/antigen interaction. The tryptic fragments of antigen protein in buffer were applied to the antibody immobilized on NC film and allowed to interact. The NC film was then washed to remove salts and other unbound components, and subjected to analysis by MALDI-TOFMS. Using interferon-alpha (2a) and anti-interferon-alpha (2a) monoclonal antibody IgG as a model system, we successfully extracted the antigen protein and determined the approximate binding region for the antigen/antibody interaction (i.e., the tryptic fragment responsible). Copyright (C) 2001 John Wiley & Sons, Ltd.