開發預測雙子型界面活性劑之自組裝結構的方法

以作者查詢圖書館館藏

、以作者查詢臺灣博碩士

、以作者查詢全國書目

、勘誤回報

、線上人數：28

、訪客IP：3.142.212.225

姓名

余佳穎(Chia-Ying Yu) 查詢紙本館藏

畢業系所

化學工程與材料工程學系

論文名稱

開發預測雙子型界面活性劑之自組裝結構的方法
(DEVELOPING THE METHOD OF PREDICTING THE SELF-ASSEMBLES STRUCTURE OF GEMINI SURFACTANTS)

相關論文

★ 雙連續相中孔二氧化鈦光催化以及電子結構之實驗與模擬研究	★ 聚合物-奈米粒子複合材料在玻璃轉移溫度下的結構與動力學相關性之實驗與模擬研究
★ 新興糖基雙子型界面活性劑之結構以及其對基因轉染效率之影響	★ 自發曲率、金屬離子吸附以及微脂體膜融合效率三者間之相關性探討
★ 脂質組成成分對細胞膜物理性質與生物功能的影響	★ 添加具有抗菌潛力的胜肽對磷脂質自組裝結構與彈性性質的影響
★ 分子構型與表面電荷密度對雙子型陰陽離子界面活性劑系統之相行為影響	★ 探討具有不同間隔長度的陰、陽離子雙子型界面活性劑對於DNA壓實與解壓實之影響
★ 具抗菌潛力之胜肽如何影響脂質膜的彈性性質與結構完整性	★ CoCrFeMnNi 高熵合金形變行為之探討
★ 透過改變磷脂質排列密度減少Amyloid β與膜之間交互作用	★ 對生物膜具活性的胜肽誘導相分離脂質膜產生結構上擾動
★ 人類脂肪幹細胞於生醫材料塗佈細胞外間質之純化及分化	★ 發展量測雙層脂質膜的排列密度之實驗技術
★ 利用酸鹼度敏感型雙子型界面活性劑製作之基因載體對核內體脂質膜結構之影響	★ 抗肌萎縮蛋白的膜結合錨如何影響其與脂質膜的相互作用

檔案

[Endnote RIS 格式]

[Bibtex 格式]

[相關文章]

[文章引用]

[完整記錄]

[館藏目錄]

[檢視]

[下載]

本電子論文使用權限為同意立即開放。
已達開放權限電子全文僅授權使用者為學術研究之目的，進行個人非營利性質之檢索、閱讀、列印。
請遵守中華民國著作權法之相關規定，切勿任意重製、散佈、改作、轉貼、播送，以免觸法。

摘要(中)

以往人們都是以得到的物質之性質來選擇適合它的用途，然而我們都知道世界上所有物質都是以分子或是原子組裝而成；所以理論上，我們可以調整自組裝結構來設計出我們想要的物理性質的物質，也就是說，以往是使用由上而下的方式，而此篇研究想以由下而上的方式來設計我們想要的物質。
為了要用由下而上的方式設計材料，我們必須先找到自組裝行為如何受到物質本身的化學結構、外在環境因素及外力影響，並且了解結構與物理性質間的關聯性。
堆疊參數是描述分子結構與自組裝結構的關係，我們能從分子結構計算出某環境下的堆疊參數，且推測自組裝結構，但堆疊參數有些缺點。所以我們利用連續體力學的描述，由自由能的角度解釋自組裝行為。
透過此研究，我們得知能從自發曲率及彎曲模數觀察自組裝行為，所以只要知道其參數便能設計我們想要的物質。

摘要(英)

Materials are assembled molecule by molecule, theoretically, as long as understanding of their structures, assembly properties of individual molecular, this is likely to use ‘bottom-up’ approach to design the materials which we want by changing their structures.
In order to design materials, finding out how self-assembly behavior is affected by the chemical structure of the substance, external environmental factors and external forces, and coming to understand the relationship between them.
The relation between molecular structure and self-assembly properties can describe by packing parameter, but it exists some disadvantage, on the contrary, at continuum mechanics, the monolayer formed self-assembly behavior is considered a continuous flexible solid thin film, and it can describe by the elastic energy density.
Through our experiment (SAXS and SANS), We think that we could use the spontaneous curvature and bending modulus to check the self-assembly structure, so when we know these parameters, we could develop the structure we wanted.

關鍵字(中)

★ 自組裝結構
★ 雙子型界面活性劑
★ 由下而上
★ 堆疊參數
★ 自由能

關鍵字(英)

★ self-assembly structure
★ gemini surfactant
★ bottom-up
★ packing parameter
★ free energy

論文目次

摘要 ............................................................................................................................................ I
ABSTRACTS ............................................................................................................................ II
致謝 ......................................................................................................................................... III
TABLE OF CONTENTS ........................................................................................................ IV
LIST OF FIGURE .................................................................................................................. VII
LIST OF TABLE ..................................................................................................................... IX
LIST OF EQUATION ............................................................................................................... X
LIST OF ABBREVIATION.................................................................................................... XI
CHAPTER 1 INTROUDCTION ........................................................................................... 1
1-1. Designer’s materials ................................................................................................. 1
1-2. Surfactants ................................................................................................................ 2
1-2-1. Self-assembly behavior of surfactant .............................................................. 5
1-2-2. Gemini surfactant ............................................................................................ 7
1-3. Packing parameter .................................................................................................... 9
1-4. Elastic properties .................................................................................................... 12
1-4-1. Spontaneous curvature (C0) ........................................................................... 14
1-4-2. Bending modulus ........................................................................................... 15
1-5. Motivation .............................................................................................................. 16
CHAPTER 2 MATERIALS AND EXPERIMENTAL METHOD ..................................... 18
2-1. Materials ................................................................................................................ 18
2-1-1. Lipid .............................................................................................................. 18
2-1-2. General chemicals ......................................................................................... 19
2-2. Sample Preparation ................................................................................................ 21

2-2-1. Gemini surfactant synthesis ........................................................................... 21
2-2-2. Lipid dispersion preparation .......................................................................... 30
2-2-3. Neutron sample preparation .......................................................................... 38
2-3. Experimental Method ............................................................................................. 43
2-3-1. Small angle X-ray scattering (SAXS) ........................................................... 43
2-3-2. Small angle neutron scattering (SANS) ........................................................ 46
2-3-3. Langmuir trough ............................................................................................ 49
2-4. Analytical instruments and data processing ........................................................... 51
2-4-1. Nuclear magnetic resonance spectroscopy (NMR) ....................................... 51
2-4-2. Mass spectrometry ......................................................................................... 52
2-4-3. Reconstruction electron density .................................................................... 53
2-4-4. Quantify spontaneous curvature .................................................................... 57
2-4-5. Quantify bending modulus ............................................................................ 58
CHAPTER 3 RESULT ........................................................................................................ 60
3-1. 1H NMR spectrum and 13C NMR spectrum ........................................................... 61
3-1-1. C12412 .......................................................................................................... 62
3-1-2. C12612 .......................................................................................................... 63
3-1-3. C16416 .......................................................................................................... 65
3-1-4. C16616 .......................................................................................................... 66
3-2. Mass spectrum ....................................................................................................... 68
3-2-1. C12412 .......................................................................................................... 68
3-2-2. C12612 .......................................................................................................... 69
3-2-3. C16416 .......................................................................................................... 69
3-2-4. C16616 .......................................................................................................... 70
3-3. Spontaneous curvature of gemini surfactant .......................................................... 71
3-4. Bending modulus of gemini surfactant .................................................................. 76
3-5. The surface per molecule from Langmuir trough .................................................. 82
3-6. The properties of micelle structure from SANS .................................................... 83

3-6-1. C12412 .......................................................................................................... 88
3-6-2. C12612 .......................................................................................................... 94
3-6-3. C16416 .......................................................................................................... 99
3-6-4. C16616 ........................................................................................................ 106
3-7. The elastic energy per unit area (gE) for C16416 ................................................. 111
3-7-1. The Cylinder Model .................................................................................... 113
3-7-2. The Ellipsoid Model .................................................................................... 115
CHAPTER 4 DISCUSSION ............................................................................................. 118
4-1. Spontaneous curvature and bending modulus ...................................................... 118
4-2. The relationship between packing parameter and spontaneous curvature ........... 120
CHAPTER 5 CONCULSION ........................................................................................... 122
REFERENCE ........................................................................................................................ 123

參考文獻

Alami, E., Beinert, G., Marie, P., and Zana, R. Alkanediyl-. alpha.,. omega.-bis (dimethylalkylammonium bromide) surfactants. 3. Behavior at the air-water interface. Langmuir 1993, 9(6), 1465-1467.
Als-Nielsen, J., and McMorrow, D. Elements of modern X ray physics, Wiley: West Sussex, U.K., 2001.
Aswal, V. K., De, S., Goyal, P. S., Bhattacharya, S., and Heenan, R. K. Small-angle neutron scattering study of micellar structures of dimeric surfactants. Physical Review E 1998, 57(1), 776-783.
Bagha, A. R. T., Bahrami, H., Movassagh, B., Arami, M., and Menger, F. M. Interactions of gemini cationic surfactants with anionic azo dyes and their inhibited effects on dyeability of cotton fabric. Dyes and Pigments 2007, 72(3), 331-338.
Chen, Q., Zhang, D., Li, R., Liu, H., and Hu, Y. Effect of the spacer group on the behavior of the cationic gemini surfactant monolayer at the air/water interface. Thin Solid Films 2008, 516(23), 8782-8787.
Chen, Y. F., Tsang, K. Y., Chang, W. F., and Fan, Z. A. Differential dependencies on [Ca2+] and temperature of the monolayer spontaneous curvatures of DOPE, DOPA and cardiolipin: effects of modulating the strength of the inter-headgroup repulsion. Soft Matter 2015, 11(20), 4041-4053.
Chen, Z., and Rand, R. P. The influence of cholesterol on phospholipid membrane curvature and bending elasticity. Biophysical journal 1997, 73(1), 267-276.
Dave, N., and Joshi, T. A Concise Review on Surfactants and Its Significance. International Journal of Applied Chemistry 2017, 13(3), 663-672.
De Jeu, W. H. Basic X-ray scattering for soft matter. Oxford University Press, 2016, 87.
De, S., Aswal, V. K., Goyal, P. S., and Bhattacharya, S. Role of spacer chain length in dimeric micellar organization. Small angle neutron scattering and fluorescence studies. The Journal of Physical Chemistry 1996, 100(28), 11664-11671.
Dennison, S. R., Harris, F., & Phoenix, D. A. Langmuir–Blodgett approach to investigate antimicrobial peptide–membrane interactions. In Advances in Planar Lipid Bilayers and Liposomes 2014, 20, 83-110.
Dutt, S., Siril, P. F., and Remita, S. Swollen liquid crystals (SLCs): a versatile template for the synthesis of nano structured materials. RSC Advances 2017, 7(10), 5733-5750.
Fan, Z. A., Tsang, K. Y., Chen, S. H., and Chen, Y. F. Revisit the Correlation between the Elastic Mechanics and Fusion of Lipid Membranes. Scientific reports 2016, 6, 31470.
Fuller, N., Benatti, C. R., and Rand, R. P. Curvature and bending constants for phosphatidylserine-containing membranes. Biophysical Journal 2003, 85(3), 1667-1674.
Goyal, P. S., and Aswal, V. K. Combined SANS and SAXS in studies of nanoparticles with core-shell structure. Indian Journal of Pure & Applied Physics 2006, 44, 724-728.
Guest, P. C. The Importance of Biomarkers: The Required Tools of the Trade. In Biomarkers and Mental Illness.Copernicus, Cham 2017, 31-41.
Guinier, A., Fournet, G., and Yudowitch, K. L. Small-angle scattering of X-rays, New York: John Wiley and Sons incorporated 1955.
Harper, P. E., Mannock, D. A., Lewis, R. N., McElhaney, R. N., and Gruner, S. M. X-Ray Diffraction Structures of Some Phosphatidylethanolamine Lamellar and Inverted Hexagonal Phases. Biophysical Journal 2001, 81(5), 2693-2706.
Hu, M., Briguglio, J. J., and Deserno, M. Determining the Gaussian curvature modulus of lipid membranes in simulations. Biophysical journal 2012, 102(6), 1403-1410.
Jacrot, B. The study of biological structures by neutron scattering from solution. Reports on progress in physics 1976, 39(10), 911-953.
Kabir-ud-Din, Fatma, W., Khan, Z. A., and Dar, A. A. 1H NMR and viscometric studies on cationic gemini surfactants in presence of aromatic acids and salts. The Journal of Physical Chemistry B 2007, 111(30), 8860-8867.
Kell, G. S. Precise representation of volume properties of water at one atmosphere. Journal of Chemical and Engineering data 1967, 12(1), 66-69.
Kollmitzer, B., Heftberger, P., Rappolt, M., and Pabst, G. Monolayer spontaneous curvature of raft-forming membrane lipids. Soft Matter 2013, 9(45), 10877-10884.
Kumar, A., Banjare, M. K., Sinha, S., Yadav, T., Sahu, R., Satnami, M. L., and Ghosh, K. K. Imidazolium‐Based Ionic Liquid as Modulator of Physicochemical Properties of Cationic, Anionic, Nonionic, and Gemini Surfactants. Journal of Surfactants and Detergents 2018, 21(3), 355-366.
Leikin, S., Kozlov, M. M., Fuller, N. L., and Rand, R. P. Measured effects of diacylglycerol on structural and elastic properties of phospholipid membranes. Biophysical journal 1996, 71(5), 2623-2632.
Marsh, D. Pivotal surfaces in inverse hexagonal and cubic phases of phospholipids and glycolipids. Chemistry and Physics of Lipids 2011, 164, 177-183.
Menger, F. M., and Littau, C. A. Gemini-surfactants: synthesis and properties. Journal of the American Chemical Society 1991, 113(4), 1451-1452.
Mir, M. A., Khan, J. M., Khan, R. H., Rather, G. M., and Dar, A. A. Effect of spacer length of alkanediyl-α,ω-bis(dimethylcetylammonium bromide) gemini homologues on the interfacial and physicochemical properties of BSA. Colloids and Surfaces B: Biointerfaces 2010, 77(1), 54–59.
Rangel-Yagui, C. O., Pessoa-Jr, A., and Blankschtein, D. Two-phase aqueous micellar systems: an alternative method for protein purification. Brazilian Journal of Chemical Engineering 2004, 21(4), 531-544.
Rosen, M. J., and Tracy, D. J. Gemini surfactants. Journal of Surfactants and Detergents 1998, 1(4), 547–554.
Sears, V. F. Neutron scattering lengths and cross sections. Neutron news 1992, 3(3), 26-37.
Seddon, J. M. Structure of the inverted hexagonal (HII) phase, and non-lamellar phase transitions of lipids. Biochimica et Biophysica Acta 1990, 1031(1), 1-69.
Shearman, G. C., Ces, O., Templer, R. H., and Seddon, J. M. Inverse lyotropic phases of lipids and membrane curvature. Journal of Physics: Condensed Matter 2006, 18(28), S1105-S1124.
Shinoda, K., Yamaguchi, T., and Hori, R. The surface tension and the critical micelle concentration in aqueous solution of β-D-alkyl glucosides and their mixtures. Bulletin of the Chemical Society of Japan 1961, 34(2), 237-241.
Siegel, D. P., and Kozlov, M. M. The Gaussian curvature elastic modulus of N-monomethylated dioleoylphosphatidylethanolamine: relevance to membrane fusion and lipid phase behavior. Biophysical journal 2004, 87(1), 366-374.
Sinha, S., Tikariha, D., Lakra, J., Tiwari, A. K., Saha, S. K., and Ghosh, K. K. Effect of Polar Organic Solvents on Self-Aggregation of Some Cationic Monomeric and Dimeric Surfactants. Journal of Surfactants and Detergents 2015, 18(4), 629-640.
Sorenson, G. P., Coppage, K. L., and Mahanthappa, M. K. Unusually stable aqueous lyotropic gyroid phases from gemini dicarboxylate surfactants. Journal of the American Chemical Society 2011, 133(38), 14928-14931.
Stanley, C. B., and Strey, H. H. Measuring osmotic pressure of poly (ethylene glycol) solutions by sedimentation equilibrium ultracentrifugation. Macromolecules 2003, 36(18), 6888-6893.
Wettig, S. D., and Verrall, R. E. Thermodynamic Studies of Aqueous m–s–m Gemini Surfactant Systems. Journal of Colloid and Interface Science 2001, 235(2), 310-316.
Whitten, A. E., Cai, S., and Trewhella, J. MULCh: modules for the analysis of small-angle neutron contrast variation data from biomolecular assemblies. Journal of Applied Crystallography 2008 41(1), 222-226.
Zana, R., Benrraou, M., and Rueff, R. Alkanediyl-α, ω-bis (dimethylalkylammonium bromide) surfactants. 1. Effect of the spacer chain length on the critical micelle concentration and micelle ionization degree. Langmuir 1991, 7(6), 1072-1075.
Zhang, S. Fabrication of novel biomaterials through molecular self-assembly. Nature biotechnology 2003, 21(10), 1171-1178.
Zhang, S., Marini, D. M., Hwang, W., and Santoso, S. Design of nanostructured biological materials through self-assembly of peptides and proteins. Current opinion in chemical biology 2002, 6(6), 865-871.
Zhao, J., Christian, S. D., and Fung, B. M. Mixtures of monomeric and dimeric cationic surfactants. The Journal of Physical Chemistry B 1998, 102(39), 7613-7618.

指導教授

陳儀帆(Yi-Fan Chen)

審核日期

2019-8-22

推文