臺灣博碩士論文加值系統

no abstract in chinese

In this study, protoporphyrin zinc IX (ZnPP) is spun onto cleaned glass substrate. The changes of their UV-Visible spectra are investigated upon exposure to amine vapors. ZnPP as sensing materials shows good sensitivity, fast response and reproducible towards amine vapors sensing. In the presence of amine vapor, Soret band wavelength spectrum response of ZnPP will be red shifted. This red-shift phenomenon in the wavelength spectrum cause by changes in electronic structure of ZnPP. The experimental results are verified by TDDFT Calculation by Gaussian 03.
Gaussian 03 is performed to simulate gas adsorption process and the accompanying changes in the electronic spectra. The adsorption process is carried on the central ring position and the peripheral of porphyrin ring. Based on adsorption energies calculated, the peripheral of porphyrin interaction shows a significant value which is important to note that the central ring position is not the only position which attack by analyte species could occur. TDDFT calculated shift in wavelength spectrum of the central ring adsorption site and substituent ring adsorption site respectively are 12.3 nm and 3.38 nm. Because of the experimental result shows significant red shift in the Soret Band after amine adsorption, therefore the central ring position is chosen as adsorption sites.
Upon exposure to various kinds of primary amines, the ZnPP responses show enhancement of absorbance increases with the alkyl chain length. This can be due to amine basicity. Increasing alkyl chain length will increase amine basicity. The electron-rich alkyl group donates electron density to the N atom and enhances interaction between amine and ZnPP.
In order to quantify concentration dependence of the ZnPP response towards amines, a number of isothermal models can be applied. A plot of c/∆A versus c is linear, therefore ZnPP response is following Langmuir adsorption model.
The sensing properties of porphyrin mixed with polymer and porphyrin mixed with calixarene is also studied. The responses show ∆A porphyrin mixed tbu-Calix[8]arene > ∆A porphyrin > ∆A porphyrin mixed PEG. These results can be explained by the difference surface character for each material.

Abstract 4
Acknowledgments 6
Contents 7
List of Tables 11
List of Figures 13
Chapter 1 Introduction
1.1 Reason of Study 24
1.2 Objectives 27

Chapter 2 Literature Review
2.1 Introduction to Porphyrin 28
2.2 Porphyrin Deposition Technique 30
2.2.1 Spin Coating Method 31
2.2.2 Langmuir-Blodgett Technique 34
2.2.3 Self Assembled Monolayer Method 36
2.2.4 Electropolymerization Technique 37
2.2.5 Vacuum Deposition Technique 38
2.3 Transducer for Metalloporphyrin 40
2.3.1 Mass Transduction 40
2.3.2 Optical Absorbance Transduction 45
2.4 The Electronic Structure of Porphyrin 49
2.4.1 The Spectra of Porphyrin 49
2.4.2 Gouterman Four Orbital Model 50
2.5 UV-Visible Absorption Spectroscopy Theoretical Principles 53
2.5.1 The Beer-Lambert Law 53
2.5.2 Electronic Transition 54

Chapter 3 Experimental Section
3.1 Chemical Material 58
3.1.1 Volatile Organic Compounds (VOCs) 58
3.1.2 Solvents 58
3.1.3 Porphyrins 58
3.2 Experimental Equipments 59
3.3 Instrumental Analysis 59
3.4 Experimental Methods 60
3.4.1 The Substrates Cleaning Procedures 60
3.4.2 The Thin Film Preparation 60
3.4.3 UV-Visible Spectroscopy Procedures 61
3.4.4 VOC Concentration Calculation 63
3.4.5 Absorbance Measurement 63
3.5 Experimental Setup 64
3.6 Computational Chemistry Method 65
3.6.1 Introduction of Computational Chemistry 66
3.6.2 Density Functional Theory 67

Chapter 4 Results and Discussions
4.1 Surface Morphology from Atomic Force Microscopy (AFM) 70
4.2 Thickness Profile from Stylus Profilometry 72
4.3 The UV-Visible Spectra of ZnPP in Solution and in Spin-coated
Film 74
4.4 Interaction between ZnPP Film and Amine Vapors 76
4.4 The Red-Shifted Phenomena in ZnPP-Amine Adsorption Wavelength
Spectrum and its explanation 83
4.4.1 Time Dependent Density Functional Theory (TD-DFT) 83
4.4.2 Natural Bond Orbital Analysis (NBO Analysis) 86
4.4.3 Molecular Orbital of ZnPP and its Interaction with Amine88
4.5 The Effect of Alkyl Chain Length in ZnPP Absorbance Responses 91
4.6 The Amine-ZnPP Adsorption by Gaussian 03 102
4.7 The Effect of Amine Structure in ZnPP Absorbance Responses 107
4.8 Kinetics of Amine Exposure in ZnPP Film 112
4.8.1 The Langmuir Model for ZnPP-Amine Adsorption 112
4.8.2 The Elovich Kinetics of Amine Exposure in ZnPP Film 117
4.9 Optical Sensing of Porphyrin mixed tbu-Calix[8]arene towards
Amines 118
4.1 Kinetics of Amine Exposure in ZnPP tbu-Calix[8]arene Film 131
4.10.1 The Langmuir Adsorption of Porphyrin/tbu-Calix[8]arene 131
4.10.1 The Elovich Kinetics of Porphyrin/tbu-Calix[8]arene 133
4.11 Film Surface Characterization 134
4.12 Sensing Response Reproducibility 138

Chapter 5 Conclusions and Suggestions
5.1 Conclusions 140
5.2 Suggestions 141

References 142

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