氣膠（aerosol）是氣體中懸浮微粒的泛稱。這些懸浮微粒可以極細微之固態顆粒或是液滴形式存在。它們的尺寸範圍通常介於數個奈米乃至微米量級。由於氣膠本身的化學組成、外在形狀甚至是內部結構都對其物理、化學及光學性質有絕對的影響力，故其在環境化學、大氣化學以及星際化學等領域都扮演重要的角色。不同成分、大小之氣膠其價電子能級結構直接影響到它們與其他物質發生化學作用時的化學活性，因此，對於氣膠價殼層電子結構及尺寸效應之探討顯得格外重要。為了能夠從原子及分子層級了解氣膠奈米粒子的化學性質與結構特性，我們利用新建置的氣膠真空紫外光光電子光譜儀(VUV Aerosol Photoelectron Spectroscopy)，並以同步輻射產生之真空紫外光 (Vacuum Ultraviolet Radiation, VUV)作為游離光源，來探測氣膠粒子之價殼層電子能階結構。氣膠粒子是經由霧化器(Atomizer)產生，並藉由可調式氣動聚焦系統(Adjustable aerodynamic lens, AADL) 引入紫外光光電子光譜儀內進行紫外光光電子光譜之偵測。氣膠粒子的尺寸分布情形及粒子密度則藉由可動性掃描粒徑分析儀(Scanning Mobility Particle Sizer, SMPS)來得知。藉由氣膠真空紫外光光電子光譜儀，我們首先測得純水氣膠液滴的光電子光譜，並得到了較過去相關文獻中解析度更好的凝態水之光電子光譜圖。有鑒於目前吾人對於胺基酸在不同酸鹼環境下的電子結構的了解尚不清楚，我們透過形成氣膠的方式，深入探討了胺基酸中結構最簡單的甘胺酸(Glycine)與含有硫醇基(-SH)的半胱胺酸(Cysteine)在不同的酸鹼值的水溶液環境中，由於質子化與去質子化(protonated/deprotonated)所形成的陰離子(anion)、陽離子(cation)及兩性離子(zwitterion)的光電子光譜。本工作除了測量了於不同酸鹼性水溶液環境下物質之價殼層電子結構產生的變化以及游離能的改變外，也從微觀的角度來探討一般對親核性(nucleophilicity)概念的認知以及其對於生物體系中的電荷轉移反應可能造成的影響。

“Aerosols” are broadly referred to ultrafine particulate matters suspended in a gas. These ultrafine suspensions may exist in the form of solid paprticles or liquid droplets with the size ranging from sub-nm up to a few microns. Since aerosols have a great variety in size, shape, composition and architecture, their fundamental physical, chemical and optical properties often deviate considerably from their gaseous and bulk counterparts. To fully understand the underlying origins responsible for their importance in environmental sciences, atmospheric chemistry and planetary sciences, it is crucial to understand the fundamental structural properties of aerosols from the atomic and molecular level. Of particular significance is the valence electronic energetic structure of aerosols, as this property directly governs the chemical activities of aerosols when they undergo chemical reactions with other substances. To address this issue, we have newly constructed an Aerosol VUV Photoelectron Spectroscopy apparatus to probe the valence electron energy structure of aerosols. Aerosols of interest are generated by an atomizer and introduced into the aerosol VUV photoelectron spectroscopy chamber via a set of adjustable aerodynamics lens from which aerosols form a highly collimated aerosol beam. The size distribution and number density of aerosols are pre-characterized by the Scanning Mobility Particle Sizer (SMPS).

In this thesis, we first investigated the VUV photoelectron spectra of pure water aerosols utilizing this new VUV aerosol photoelectron spectroscopy. With the superior spectral resolution of the newly constructed aerosol apparatus, the vibrationally resolved fine structure of condensed water is resolved for the first time. Considering that the valence electronic structures of amino acid molecules under the aqueous environments of varying pH values are largely unknown, we interrogated the VUV photoelectron spectra of glycine aqueous aerosols and the thiol (-SH)-containing cysteine aqueous aerosols of varying pH conditions. Under various pH conditions, the solvated amino acid molecules undergo protonation/ deprotonation processes and the amino acid molecule dominate in different form of anion, cation and zwitterion. By probing the evolution of the valence electronic structure of aqueous amino acid aerosols as a function of pH value, this work provides the microscopic insight to illustrate the conventionally macroscopic concept of nucleophilicity and its potential impact in the charge transfer process of many important biological reactions.

謝誌 ii
摘要 iii
Abstract v
Table of contents vii
List of Figures x
List of Tables xvi
Chapter 1 Introduction 1
1.1. Introduction of aerosols 1
1.1.1. Aerosols in atmospheric chemistry 2
1.1.2. Aerosols in environment sciences 4
1.1.3. Aerosols in biomedical chemistry 6
1.2. Conventional techniques for aerosol measurements 8
1.2.1. Aerosol mass spectrometry (AMS) 8
1.2.2. Optical measurement techniques 9
1.3. Novel multi-functional aerosol instrument 11
1.4. Motivation and scope of this thesis 12
Chapter 2. Experiments 14
2.1. Introduction 14
2.1.1. Principle of photoelectron spectroscopy (UPS) 14
2.2. Overview of the newly built aerosol VUV photoelectron spectroscopy 21
2.4. Aerosol pre-characterization 26
2.5. Aerosol beam formation via aerodynamic focusing 31
2.5.1. The components of AADL system 33
2.5.2. Functions of AADL system 34
2.5.3. Simulation of AADL for optimal aerodynamic focusing 34
2.5.4. Final design of the AADL system 36
2.6. Ionization light sources 40
2.6.1. He(I) discharge lamp 40
2.6.2. VUV synchrotron radiation 41
2.7. Hemispherical electron energy analyzer 44
Chapter 3. Preliminary test on the aerosol VUV photoelectron spectroscopy instrument 47
3.1. Comparisons of photoelectron spectra of effusive Ar gas obtained from different ionization sources 48
3.1.1. Photoelectron spectrum of effusive Ar gas obtained from He(I) discharge lamp 48
3.1.2. Photoelectron spectrum of effusive At gas obtained from synchrotron based VUV radiation (Bending and Undulator, hν = 21.2 eV) 50
3.2. Photoelectron spectrum of pure water aerosols at 25 eV 54
Chapter 4. VUV photoelectron spectroscopy of glycine aqueous aerosols 59
4.1. Introduction 59
4.2. VUV photoelectron spectra of glycine aqueous aerosols at varying pH conditions 61
4.3. Summary 71
5.1.1. The biological significance of cysteine 72
5.1.2. Microscopic properties of cysteine from previous experimental/calculated studies 74
5.2. VUV photoelectron spectra of cysteine aqueous aerosols at varying pH conditions 78
5.2.1. pH dependence of the binding energy of Cys nS. 88
5.2.2. pH dependence of the binding energy of Cys nO and Cys nN. 90
5.2.3. The new feature of 6.97 eV, Cys nS’ 92
5.3. DFT Simulation of various possible forms of cysteine in the solution 93
5.4. Summary 101
Chapter 6. Conclusions 102
Reference： 105

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