本研究利用反射吸收式紅外光譜法（infrared reflection-absorption spectroscopy, IRRAS），探討在添加不同莫耳分率之雙碳氫鏈二甲基溴化銨(dialkyldimethylammonium bromide, DXDAB)的情況下，氣／液界面上具不同碳氫鏈之離子對雙親分子（ion pair amphiphile, IPA）單分子層的穩定性及分子排列特性。本研究所使用的IPA是由十六烷基三甲基溴化銨(hexadecyltrimethylammonium bromide, HTMAB, CH3(CH2)15N(CH3)3Br)和十六烷基硫酸鈉(sodium hexadecylsulfate, SHS, CH3(CH2)15SO4Na )製備而成的HTMA-HS。結果並和HTMA-DS／DXDAB混合系統的結果比較。
實驗結果顯示，純HTMA-HS單分子層的穩定性比HTMA-DS單分子層佳，這可能是由於HTMA-HS分子的碳氫鏈較長也較對稱，使得分子與分子間的作用較強，分子自由度較小，因此可以規則排列並穩定存在於氣／液界面上。
添加DXDAB於HTMA-HS單分子層中，會使得HTMA-HS的HTMA+被DXDA+置換而形成新的IPA分子。而當DXDAB的比率上升會接近完全取代，取代後所形成的三碳鏈IPA分子結構較穩定，分子碳氫鏈的不匹配度也下降，降低了分子的自由度，因此在固定單分子層佔據面積的鬆弛過程中，添加DXDAB可提升IPA單分子層的穩定性。
將鬆弛結果與同系統之陰陽離子液胞粒徑的穩定性比較，發現當DXDAB的添加量上升時，液胞的粒徑穩定性也隨之提升，推測添加DXDAB分子除了使液胞表面帶電，降低彼此間碰撞頻率外，還能改善液胞雙層膜結構的穩定性。

In this study, infrared reflection-absorption spectroscopy technique is applied to obtain information on the molecular packing properties of mixed IPA/DXDAB monolayers at the air/water interface. The results show that, the HTMA-HS monolayer is stable at the air/water interface while the HTMA-DS monolayer is not. The reason is that the structure of HTMA-DS molecule is asymmetry, and thus the degree of freedom of the carbon tails will be high. For three kinds of DXDAB, the results show that the DODAB monolayer can be stable at the air/water interface and the others can not. It is because DODAB has the longest carbon tails, leading to the strongest molecule interaction. The results of monolayer relaxation experiments show that HTMA-HS and DODAB monolayers can be stable at the air/water interface, while HTMA-DS, DTDAB, and DHDAB monolayers can not. Compared these results with size stability of the vesicles, one can find that vesicles formed of HTMA-HS or DODAB have higher size stability. This suggests that the physical stability of vesicles is controlled by the symmetry structure and number of carbon chains. For the two-component systems, the results show that HTMA+ of IPA will be replaced by DXDA+.This phenomenon will reduce the degree of freedom of the carbon tails, and the mixed IPA/DXDAB monolayers are then stable at the air/water interface. Therefore, adding DXDAB will not only reduce the collision frequency of the vesicles, but also increase the bilayer stability of the vesicles.

Aroti, A., Leontidis, E., Maltseva, E., and Brezesinski, G., “Effects of Hofmeister anions on DPPC Langmuir monolayers at the air-water interface”, Journal of Chemical Physics B, 108, 15238-15245, 2004.
Buontempo, J.T., and Rice, S.A.,“Infrared external reflection spectroscopic studies of phase transitions in Langmuir monolayers of heneicosanol”, Journal of Chemical Physics 99, 5835, 1993a.
Buontempo, J.T., and Rice, S.A.,“Infrared external reflection spectroscopic studies of phase transitions in Langmuir monolayers of stearyl alcohol”, Journal of Chemical Physics 99, 7030, 1993b.
Chen, X., Huang, Z., Hua, W., Castada, H., and Allen, H.C., “Reorganization and caging of DPPC, DPPE, DPPG, and DPPS monolayers caused by dimethylsulfoxide observed using Brewster angle microscopy”, Langmuir, 26, 18902-18908, 2010.
Chou, T.H., and Chang, C.H., “Thermodynamic characteristics of mixed DPPC/DHDP monolayers on water and phosphate buffer subphases”, Langmuir, 16, 3385-3390, 2000.
Claesson, P., Carmona-Ribeiro, A.M., and Kurihara, K., “Dlhexadecyl phosphate monolayers: intralayer and interlayer interactions”, Journal of Chemical Physics, 93, 917-922, 1989.
Dluhy, R.A., “Infrared spectroscopy of biophysical monomolecular films at interfaces: theory and applications”, Appl. Spectrosc. Rev., 35, 315-351, 2000.
Dluhy, R.A., “Quantitative external reflection infrared spectroscopic analysis of insoluble monolayers spread at the air-water interface”, Journal of Chemical Physics, 90, 1373-1379, 1986.
Dluhy, R.A., and Cornell, D.G., “In situ measurement of the infrared spectra of insoluble monolayers at the air-water interface”, Journal of Chemical Physics, 89, 3195-3197, 1985.
Dluhy, R.A., Wright, N.A., and Griffith, P.R., “In situ measurement of the FT-IR spectra of phospholipids monolayers at the air/water interface”, Appl. Spectrosc., 42, 138-141, 1988.
Du, X., Miao, W., and Liang, Y., “IRRAS studies on chain orientation in the monolayers of amino acid amphiphiles at the air-water interface depending on metal complex and hydrogen bond formation with the headgroups”, Journal of Chemical Physics B, 109, 7428-7434, 2005.
Dynarowicz-Łątka, P., Dhanabalan, A., and Oliverira, O. N. Jr., “Modern physicochemical research on Langmuir monolayers”, Advances in Colloid and Interface Science, 91, 221-293, 2001.
Feng , S.S., “Interpretation of mechanochemical properties of lipid bilayer vesicles from the equation of state or pressure-area measurement of the monolayer at the air-water or oil-water interface”, Langmuir, 15, 998-1010, 1999.
Feng , S.S., and MacDonald, R.C., “Effects of chain unsaturation on the equation of state for lipid monolayers at the air-water interface”, Biophysical Journal, 69, 460-469, 1995.
Filhoa, J.M.N., Melob, C.P., Santos-Magalhães, N.S., Rosilio, V., Maciel, M.A.M., and Andrade, C.A.S., “Thermodynamic investigation of mixed monolayers of trans-dehydrocrotonin and phospholipids”, Colloids and Surfaces A: Physicochem. Eng. Aspects, 358, 42-49, 2010.
Flach, C.R., Gericke, A., and Mendelsohn, R., “Quantitative determination of molecular chain tilt angles in monolayer films at the air/water interface: infrared reflection/absorption spectroscopy of behenic acid methyl ester”, Journal of Chemical Physics B, 101, 58-65, 1997.
Gericke, A., and Huhnerfuss, H., “In situ investigation of saturated long-chain fatty acids at the air/water interface by external infrared reflection-adsorption spectrometry”, Journal of Chemical Physics, 97, 12899-12908, 1993.
Gromelski, S., and Brezesinski, G., “DNA condensation and intercation with zwitterionic phospholipids mediated by divalent cations”, Langmuir, 22, 6293-6301, 2006.
Kaler, E.W., Murthy, A.K., Rodriguez, B.E., and Zasadzinski, J.A., “Spontaneous vesicle formation in aqueous mixtures of single-tailed surfactants”, Science, 245, 1371-1374, 1989.
Karewicza, A., Bielskaa, D., Gzyl-Malchera, B., Kepczynskia, M., Lach, R., and Nowakowska, M., “Interaction of curcumin with lipid monolayers and liposomal bilayers”, Colloids and Surfaces B: Biointerfaces, 88, 231- 239, 2011.
Kim, Y.H., Tero, R.,Takizawa, M., and Urisu, T., “Characterization of dipalmitoylphosphatidylcholine / cholesterol Langmuir-Blodgett monolayers investigated by atomic force microscopy and Fourier transform infrared spectroscopy”, Japanese Journal of Applied Physics, 43, No. 6B, 3860–3864, 2004.
Kong, X., and Du, X., “In situ IRRAS studies of molecular recognition of barbituric acid lipids to melamine at the air-water interface”, Journal of Chemical Physics B, 115, 13191-13198, 2011.
Lasic, D.D., Liposomes in gene delivery, CRC Press, New York, 1997.
Lasic, D.D., and Papahadjopoulos, D., “Liposomes and biopolymers in drug and gene delivery”, Solid State and Materials Science, 1, 392-400, 1996.
Liu, H., Zeng, H., Miao, W., and Du, X., “In situ studies of metal coordinations and molecular orientations in monolayers of amino-acid-derives Schiff bases at the air-water interface”, Langmuir, 25, 2941-2948, 2009.
MacDonald, R.C., in: M. Rosoff, ed., Vesicles, Marcel Dekker, New York, 1996, Chapter 1.
Marques, E.F., Regev, O., Khan, A., and Lindman, B., “Self-organization of double-chained and pseudodouble-chained surfactants: counterion and geometry effects”, Advances in Colloid and Interface Science, 100, 83-104, 2003.
Mendelsohn, R., Brauner, J.W., and Gericke, A., “External infrared reflection absorption spectrometry of monolayer films at the air-water interface”, Annu. Rev. Phys. Chem., 46, 305-334, 1995.
Mendelsohn, R., and Flach, C.R., Infrared reflection-absorption spectroscopy of lipids, peptides, and proteins in aqueous monolayers, In Peptide-Lipid Interactions; Simon, S.A., and Mclntosh, T.J., Eds., Academic Press, Inc., California, 2002, Chapter 3.
Mendelsohn, R., Mao, G., and Flach, C.R.,“Infrared reflection–absorption spectroscopy: Principles and applications tolipid–protein interaction in Langmuir films”, Biochimica et Biophysica Acta, 1798, 788–800, 2010.
Mitchell, M.L., and Dluhy, R.A., “In situ FT-IR investigation of phospholipid monolayer phase transitions at the air-water interface”, J. Am. Chem. Soc., 110, 712-718, 1988.
Myers, D., Surfaces, interfaces, and colloids: principles and applications, VCH, 1999, Chapter 8.
New, R. R. C., “Liposomes: a practical approach,” Oxford University Press, New York, 1-32, 1990.
Smaby, J.M., Momsen, M., Kulkarni, V.S., and Brown, R.E., “Cholesterol-induced interfacial area condensations of galactosylceramides and sphingomyelins with identical acyl chains”, Biochemistry, 35, 5696-5704, 1996.
Tondre, C., and Caillet, C., “Properties of the amphiphilic films in mixed cationic/anionic vesicles: a comprehensive view from a literature analysis”, Advances in Colloid and Interface Science, 93, 115-134, 2001.
Viseu, M.I., Silva, A.M.G., and Costa, S.M.B., “Reorganization and desorption of catanionic monolayers. Kinetics of -t and A-t relaxation”, Langmuir, 17, 1529-1537, 2001.
Wang, Y., Pereira, C.M., Marques, E.F., Brito, R.O., Ferreira, E.S., and Silva, F., “Catanionic surfactant films at the air-water interface”, Thin Solid Films, 515, 2031-2037, 2006.
Wen, X., Lauterbach, J., and Franses, E., “Surface densities of adsorbed layers of aqueous sodium myristate inferred from surface tension and infrared reflection absorption spectroscopy”, Langmuir, 16, 6987-6994, 2000.
Wydro, P., Knapczyk, S., and Łapczyńska, M., “Variations in the condensing effect of cholesterol on saturated versus unsaturated phosphatidylcholines at low and high sterol concentration”, Langmuir, 27, 5433-5444, 2011.
杜承霖,“白蛋白對含雙鏈陽離子型界面活性劑之陰陽離子液胞物化特性的影響,”國立成功大學化學工程學系碩士論文,2012。
李威達, “陰陽離子型液胞組成材料之混合單分子層中分子作用的探討”, 國立成功大學化學工程學系博士論文, 2008.
吳靜昀, “雙十六碳鏈離子對雙親分子/添加劑形成之液胞及Langmuir
單分子層的特性分析”, 國立成功大學化學工程學系碩士論文, 2013.
林冠豪, “帶電的陰陽離子液胞之製備及物理穩定性研究”, 國立成功大學化學工程學系碩士論文, 2004.
陸雯馨, “以紅外光譜法探討離子對雙親分子/雙十八碳鏈陽離子型界面活性劑/膽固醇之混合Langmuir單分子層的分子排列特性”, 國立成功大學化學工程學系碩士論文, 2010.
張宇能, “反射－吸收式紅外光譜技術”, 化工, 43, 53, 1996.
張曉明,“離子對雙親分子/雙十六碳鏈陰離子型界面活性劑/膽固醇之混合Langmuir單分子層行為的反射吸收式紅外光譜分析”, 國立成功大學化學工程學系碩士論文, 2012.
嚴慧婷, “膽固醇的添加對於離子對雙親分子/雙十六碳鏈陰離子型脂質混合Langmuir單分子層行為的影響”, 國立成功大學化學工程學系碩士論文, 2011.