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研究生： 李翎潔
Lee, Ling-Chieh
論文名稱： 利用基質輔助雷射脫附/游離裝置瞭解雙醣分裂片段與功能性碳質材料的關聯
Understanding the Correlation between the Functional Carbonaceous Materials and Disaccharides Fragmentation by Using Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry
指導教授： 鍾博文
Chung, Po-Wen
學位類別： 碩士
Master
系所名稱： 化學系
Department of Chemistry
論文出版年： 2017
畢業學年度： 105
語文別： 英文
論文頁數： 79
中文關鍵詞： 中孔碳材 、吸附 、水解 、雙醣 、分裂片段 、基質輔助雷射脫附/游離裝置
英文關鍵詞： Mesoporous carbon material, Adsorption, Hydrolysis, Disaccharide, Fragment, MALDI
DOI URL： https://doi.org/10.6345/NTNU202202820
論文種類： 學術論文
相關次數： 點閱：124  下載：0 
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    • 醣類除了是身體主要的能量來源之外，在生物運行上也扮演很重要的腳色。例如醣蛋白是由蛋白質連接醣類而成，廣泛存在於細胞膜表面，目前研究認為在細胞膜上的醣蛋白有傳遞細胞間訊息的功能，也可以阻擋病毒、細菌入侵人體健康的細胞。然而到現在為止，還沒有一個系統化的方法鑑定醣類的結構和組成。為了解決醣類結構鑑定的問題，我們利用基質輔助雷射脫附/游離(MALDI)當游離源和修飾不同酸根的中孔洞碳材(MCN)當基質，試著去分析具有最簡單鍵結結構的雙醣。MALDI有高靈敏度，分析時間短，操作簡單等優點，且不需要在分析前先進行衍生化，是常見分析糖類的離子化方法。由於MALDI是一種軟離子化技術，只能得到完整分子的質譜信息，一般會使用二次質譜的方式得到離子片段，但MCN強大的光學吸收能力及能量傳遞能力可以使分析物得到足夠能量且產生離子碎片，改善傳統使用二次質譜得到離子片段的方法。
    我們已經證明利用MCN和具有酸性功能表面的MCN作為基質相較於傳統的有機基質2,5-二羥基苯甲酸（DHB）更適合研究雙醣的分裂片段，實驗結果顯示雙醣的分裂碎片也許會因為（1）MCN的酸性表面官能基催化水解醣類和（2）雙醣在碳質表面上的吸附能量會藉由CH-π相互作用而受到影響。我們希望透過以上兩種因素，分辨具有同分子量而有不同鍵結結構的雙醣。

    Not only does saccharide be the energy source, but also can it play an important role in the human body. For example, glycoprotein which composed of protein linked to saccharides is widely present on the surface of the cell membrane. It has been well studied and suggested that glycoprotein might have governed the function of intercellular information transferring, viruses blocking, and bacteria invading in human cells. However, there was not such a universal method to identify the structural and compositional of saccharides. Herein, to solve aforementioned problem, matrix-assisted laser desorption/ionization was as ion source and acid modified mesoporous carbon nanoparticles (MCN) were employed as matrice to analyze the disaccharide which consist of different orientation and structure. There are many well known advantages for MALDI, such as high sensitivity, short analysis time, simple operation and no derivatization prior to analysis, which lead to be a common method for the characterization of saccharide structure. The secondary mass spectrometry is mainly employed for understanding the fragmentation of the full saccharide molecular in MALDI owing to its limit of soft ionization. Nevertheless, MCN might have advantages of strong optical absorption and high energy transfer capability, which can assist to produce fragmentation of the saccharide simultaneously.
    Herein, we have demonstrated using functional MCN as matrice to investigate the characteristic fragments of disaccharides, in comparison with the conventional organic matrix of 2,5-dihydroxybenzoic acid (DHB). Experimental results suggest that the fragmentation might be influenced by (1)the hydrolysis of disaccharides from acidic functional surface of MCN and (2)the adsorption energetic of disaccharides on carbonaceous surface through CH-π interaction. Above all, we have discovered that disaccharides of the same molecular weight with different linkages can be possibly identified through different adsorption and hydrolysis phenomena.

    Content Chapter1 Introduction 1 1.1 Introduction of saccharide 1 1.1.1 The importance of saccharide 1 1.1.2 Composition of saccharide 3 1.1.3 Common saccharides analysis methods and dilemmas 5 1.2 Matrix-Assisted Laser Desorption/Ionization 6 1.2.1 Introduction of MALDI 6 1.2.2 Development and history of MALDI 6 1.2.3 The characteristics of the matrix 7 1.2.4 The mechanism of MALDI 9 1.2.5 MALDI improvements in low molecular weight 10 1.2.6 Identification of carbohydrate structure in MALDI 12 1.3 Mesoporous material 13 1.3.1 The advantages of mesoporous carbon materials in identifying carbohydrate structure 13 1.3.2 Introduction of mesoporous silica materials 14 1.3.3 Classified of surfactants for mesoporous silica materials 15 1.3.4 Synthetic mechanism of mesoporous materials 17 1.3.5 Introduction porous carbon material 18 1.4 Purpose of the study 20 Chapter2 Experimental 21 2.1 Chemical samples and reagents 21 Barium chloride 22 2.2 Sample preparation and treatment 23 2.2.1 Synthesis of Mesoporous Carbon Nanoparticles (MCN) 23 2.2.2 Modified functional group on Mesoporous Carbon Nanoparticles 25 2.2.3 Acid−base back-titration for functional MCNs48 26 2.2.4 Adsorption of disaccharide on mesoporos carbon material 27 2.2.5 Hydrolysis of disaccharide 27 2.2.6 Prepare the sample for MALDI-TOF MS 29 Chapter3 Results and discussion 30 3.1 Characterization of mesoporous carbon material 30 3.1.1 X-ray Diffraction (XRD) 30 3.1.2 Thermogravimetric analysis (TGA) 34 3.1.3 Nitrogen adsorption-desorption isotherm (BET) 35 3.1.4 Scanning Electron Microscope (SEM) 39 3.1.5 Fourier Transform Infrared (FTIR) 40 3.1.6 Ultraviolet–visible spectroscopy (UV-VIS) 42 3.2 MCN as matrix in MALDI-TOF MS 43 3.2.1 Compare traditional matrix with MCN in MALDI 43 3.2.2 MCN dispersion ability 45 3.2.3 Comparison of different concentrations of MCN matrix 47 3.2.4 Comparison of different functional group of the matrix 48 3.2.5 Produce fragment when using carbon material be matrix 54 3.2.6 Fragment of different linkage of disaccharide 55 3.3 The possibility of hydrolysis to produce fragment in MALDI 57 3.3.1 Hydrolysis of disaccharide 58 3.3.2 Catalytic hydrolysis of disaccharide 62 3.3.3 Different acidic matrix effect in MALDI 66 3.4 Adsorption ability 67 3.4.1 Adsorption capacity of different linkage disaccharide 67 3.4.2 Discussion on the adsorption capacity of energy transfer in MALDI 72 Chapter 4 Conclusion 73 Chapter 5 References 75

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