Schramm Haley M, Tamadate Tomoya, Hogan Christopher J, Clowers Brian H
Department of Chemistry, Washington State University, Pullman, WA 99163, USA.
Department of Mechanical Engineering, University of Minnesota, Minneapolis, MN 55455, USA.
Phys Chem Chem Phys. 2023 Feb 8;25(6):4959-4968. doi: 10.1039/d2cp04388b.
The rates and mechanisms of chemical reactions that occur at a phase boundary often differ considerably from chemical behavior in bulk solution, but remain difficult to quantify. Ion-neutral interactions are one such class of chemical reactions whose behavior during the nascent stages of solvation differs from bulk solution while occupying critical roles in aerosol formation, atmospheric chemistry, and gas-phase ion separations. Through a gas-phase ion separation technique utilizing a counter-current flow of deuterated vapor, we quantify the degree of hydrogen-deuterium exchange (HDX) and ion-neutral clustering on a series of model chemical systems ( amino acids). By simultaneously quantifying the degree of vapor association and HDX, the effects of cluster formation on reaction kinetics are realized. These results imply that cluster formation cannot be ignored when modeling complex nucleation processes and biopolymer structural dynamics.
发生在相界面处的化学反应速率和机制通常与本体溶液中的化学行为有很大差异，但仍难以量化。离子 - 中性相互作用就是这类化学反应之一，其在溶剂化初始阶段的行为与本体溶液不同，同时在气溶胶形成、大气化学和气相离子分离中起着关键作用。通过利用氘化蒸汽的逆流的气相离子分离技术，我们量化了一系列模型化学体系（氨基酸）上的氢 - 氘交换（HDX）程度和离子 - 中性簇集情况。通过同时量化蒸汽缔合程度和HDX，实现了簇形成对反应动力学的影响。这些结果表明，在对复杂的成核过程和生物聚合物结构动力学进行建模时，簇形成不能被忽略。
