Studies on Molecular Weight Estimation System of Organic Compounds by High Level Utilization of Ion/Molecule Reactions

为了扩大化学电离（CI）中分子量估计的适用范围，研究了反应物离子体系中容易产生加合离子的碰撞活化解离（CAD）方法。在反应离子体系中，甲烷/盐酸胺混合物可同时生成NH_4^+和Cl^-，因此可以生成（M+NH_4）^+和（M+Cl）^-，用于许多化合物，如蔗糖和醇。在甲烷/水混合试剂气体中，H_3O^+作为反应物离子生成，对于一些通常没有加合离子的化合物，如烷烃，可以生成（M+H_3O）^+。在利用CAD估计分子质量的研究中，首先研究了CAD产生的几种加合离子的子离子谱。由此证明了（M+R）^+ -> R^+ + M {(M+R)^+：加合离子，R^+：反应物离子，M：分子}和（M+R）^+ -> MH^+ + (R- h)与分子量的估计是相关的，（M+R）^+的鉴定等于分子量的测定。在第一种方法中，首先通过母离子扫描模式提取出与已知反应物离子R^+对应的母离子，并通过确认离子的子离子光谱中有对应的MH^+和R^+峰来鉴定（M+R）^+。在第二种方法中，首先以同样的方法提取候选加合离子对应的母离子，通过在中性损失谱中观察到相应分子的中性种消除来鉴定（M+R）^+。用这些方法测定了新合成的有机样品中主要成分的分子量。这些方法也适用于

Reactant ion system tend to generate adduct ion and molecular weight estimation method utilizing collisionally activated dissociation (CAD) of adduct ion have been investigated for the purpose of extension of applicationable range of molecular weight estimation in chemical ionization (CI). In case of reactant ion system, NH_4^+ and Cl^- were formed simultaneously using methane/amine hydrochloride mixture, consequently it was possible to produce (M+NH_4)^+ and (M+Cl)^- for many compounds such as succharides and alcohols. In case of methane/water mixture reagent gas, H_3O^+ was formed as reactant ion and it was possible to generate (M+H_3O)^+ for some compounds such as alkanes which usually hadn't adduct ions. In the study of molecular weight estimation utilizing CAD, firstly daughter ion spectra of several kinds ofadduct ions resulting from CAD were investigated. Consequently, it was proved that (M+R)^+ -> R^+ + M {(M+R)^+ : adduct ion, R^+ : reactant ion, M : molecule } and (M+R)^+ -> MH^+ + (R-H) were correlated with the molecular weight estimation and identification of (M+R)^+ was equal to determination ofmolecular weight. In first method, parent ions corresponded to adduct ion candidates produce known reactant ion R^+ were extracted by parent ion scan mode at first, and identification of (M+R)^+ was carried out by confirmation of daughter ion spectra of the ions had peaks corresponding MH^+ and R^+. In second method, firstly parent ions corresponded to adduct ion candidates were extracted in the same way, and identification of (M+R)^+ was achieved by the fact that elimination of neutral species corresponding molecule was observed in neutral loss spectrum. Molecular weight of main constituent of organic sample which was newly synthesized was determined by these methods. These methods were also applicationable to