GAS PHASE CHEMISTRY OF IONS PRODUCED BY ELECTROSPRAY

电喷雾产生的离子的气相化学

• 批准号: 2415264
• 负责人: CAROLYN J CASSADY
• 金额: $ 7.49万
• 依托单位: MIAMI UNIVERSITY OXFORD
• 依托单位国家: 美国
• 财政年份: 1995
• 资助国家: 美国
• 起止时间: 1995-05-01 至 1998-11-30
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/2415264
• 关键词: albumins; carbonate dehydratase; chemical kinetics; chemical structure; chemistry; cytochrome c; electrospray ionization mass spectrometry; fast atom bombardment mass spectrometry; fibrinopeptide; gas; gastrins; insulin; ion cyclotron resonance spectrometry; ions; lysozyme; neuropeptides; protein tyrosine kinase; somatostatin; thermodynamics; ubiquitin

The gas-phase chemistry of multiply charged protein ions generated by electrospray ionization mass spectrometry will be investigated. Ion/molecule reactions ad dissociation techniques will be used to obtain structural information on high mass biological ions. Fundamental kinetic, thermodynamic, and mechanistic aspects of these processes will also be considered. The development of Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR or FTMS) as a tool for studies of ions generated by electrospray is an additional goal of this research. Reactivity studies will center on proton transfer and hydrogen/deuterium exchange. The effect of the gas-phase basicity of the neutral reaction partner on product formation and kinetics will be investigated. Proton transfer reactions will also include anionic partners. The impact of a protein's structure on its reactivity will be explored by varying the molecular weight of the protein, the number of protons in the ion, the basicities of the amino acid residues present, the sequence of residues, and the conformation of the ions. Multiply protonated protein ions will be subjected to low-energy collision-induced dissociation (CID) experiments. These studies will provide knowledge of the effects of protein structure on dissociation patterns. A goal is to determine which charge states, or combinations of charge states, provide the most informative fragmentation. A wide range of charge states will be investigated. Proton transfer reactions will be used to lower the degree of protonation for some proteins. Where possible, comparisons will be made between the CID pathways of multiply charged ions and those of singly charged ions produced by fast atom bombardment (FAB). The effect of experimental parameters on the spectra will be considered, with single and multiple collision conditions and sustained off-resonance irradiation being explored. Studies of both native and denaturized proteins will be performed to establish the influence of conformational features on the CID spectra. In addition, electron-induced dissociation (EID) will be evaluated as an alternative to CID for obtaining structural information on multiply charged protein ions.

多电荷蛋白质离子的气相化学 将对电喷雾电离质谱仪进行研究。 将使用离子/分子反应和解离技术来获得 高质量生物离子的结构信息。基本原理 这些过程的动力学、热力学和机械学方面将 也要考虑。傅里叶变换离子回旋加速器的发展 共振质谱(FT-ICR或FTMS)作为研究的工具 电喷雾产生的离子是这项研究的另一个目标。 反应性研究将集中在质子转移和氢/氚上。 交换。中性反应的气相碱性对反应的影响 将对产品形成和动力学方面的合作伙伴进行调查。质子 转移反应还将包括阴离子伙伴。A的影响 蛋白质的结构对其反应性的影响将通过改变 蛋白质的相对分子质量，离子中的质子数， 存在的氨基酸残基的碱性，残基的序列， 以及离子的构象。 多个质子化的蛋白质离子将受到低能量的影响 碰撞诱导解离(CID)实验。这些研究将 提供蛋白质结构对解离的影响的知识 模式。目标是确定哪些电荷状态或组合 在电荷态中，提供了信息最丰富的碎片。宽阔的 我们将研究电荷状态的范围。质子转移反应 将被用来降低某些蛋白质的质子化程度。哪里 可能的情况下，将对乘法的CID途径进行比较 带电离子和快原子产生的单电荷离子 轰炸(FAB)。实验参数对光谱的影响 将被考虑，具有单一和多个碰撞条件 持续的非共振辐射正在探索中。对两者的研究 将进行天然和变性蛋白质的检测，以确定 构象特征对CID谱的影响。此外, 电子诱导解离(EID)将作为一种替代方案进行评估 TO CID用于获取多电荷蛋白质的结构信息 离子。