Development of a Time Correlation Spectroscopy for Liquid Phase Reactions using a Liquid Micro Jet in Combination with a Synchrotron Radiation

本研究的目的是开发一种新的光谱学，为辐射损伤的产生和恢复提供一个新的方面，这已经通过弥合首席研究员和主要合作研究者在气相原子和分子光谱学以及湿系统中辐射与生物分子相互作用方面的不同背景而进行了尝试。我们打算用真空液体微射流结合单色同步辐射激发的化学分析电子能谱来观察生物功能分子的结构和能量状态，这些结构和能量状态是由它们周围的水化网络决定的。这有助于通过分析发射光电子的动能，选择性地观察分子的初始（完整的）结构和相对于原子元素的能量，特定原子的键合位置，以及与它们的水合作用。这种电子的抛射是初级辐射相互作用部位经历弛豫直至最终固定损伤的标志。在形成固定损伤的过程中，在特定的时间域中出现的中间物质是用质谱法和光谱学来确定的。因此，在本工作中，我们开发了一种产生液体微射流的技术，用于在高真空条件下保持和稳定液体样品的光电子能谱。这是通过改进微射流源和真空系统来实现的。我们还开发了反射式高分辨率飞行时间质谱仪和可见光到紫外范围的光学检测系统，用于光电子能量分析的时间相关光谱。同时，对光电子能谱系统进行了改进，以实现高精度测量。

The objective of the present research has been the development of a new spectroscopy for a new aspect of production and restoration of radiation damage, which has been attempted by bridging the different background of the head investigator and the main collaborating investigator in atomic and molecular spectroscopy in gas phase and the radiation interaction with bio-molecules in wet systems, respectively. We have intended the observation of the structures and the energy states of bio-functional molecules, which are determined by the hydration network surrounding them in water solution, by means of a liquid micro jet in vacuum in combination with an electron spectroscopy for chemical analysis employing a monochromatic synchrotron radiation excitation. This has been expected to facilitate the selective observation of initial (intact) structures and energies of the molecules with respect to the atomic elements, bonding site of particular atoms, and hydration with them by analyzing the kinetic energies of ejected photoelectrons. Ejection of such electrons is the signature of the site of the primary radiation interaction undergoing to relaxation to the final fixed damage. The intermediate species emerging specifically in particular time domains on the way to fixed damage are specified by the use of a mass spectrometry and an optical spectroscopy.1. Thus, in the present work, we have developed the technique of generating a liquid micro jet to retain and stabilize liquid samples for a photoelectron spectroscopy in high vacuum. This has been achieved by improving the micro jet source and vacuum system.2. We have also achieved development of both a reflectron type high-resolution time-of-flight mass spectrometer and an optical detection system in the visible to ultraviolet range for a time correlation spectroscopy with the photoelectron energy analysis. Improvement of the system of photoelectron spectroscopy for high precision measurement is also made in advance.