单分子膜成膜性能及循环曲线研究
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摘要
在新材料的研究中，要求材料本身具有多重功能外，还要将材料组装成特殊的结构，如单层或多层薄膜、纳米结构、超分子体系等，以充分发挥材料的功能。利用LB技术可以在分子水平上对材料进行控制性组装，所制得的LB膜具有超薄有序而厚度可控的特点，非常有利于它在半导体技术、非线性光学材料、仿生材料等高技术领域的应用。
目前LB膜还没有得到大规模的工业应用，最主要的原因就是其机械力学强度和稳定性还不够高。这涉及到多方面的问题，如膜的凝聚态结构、成膜分子间的相互作用力、膜的表面粘弹性和松弛特性、膜在二维状态下的反应性、分子层与基片间的附着力等等。单分子膜的表面力学性质及稳定性对LB膜的沉积过程也有直接的影响。
从力学性质着手，我们讨论了成膜条件对相态结构(分子排列)、分子间作用力、稳定性等物理化学性质的影响；在此基础上，利用现有的理论模型讨论小分子化合物(二十二酸)及其磷脂分子压缩、扩张过程分子聚集、扩散机理及其热力学问题。
研究内容如下：
(1)二十二酸、DPPC单分子膜成膜性能研究
主要研究典型的小分子成膜化合物(二十二酸)在纯水和金属离子Cd~(2+)两种亚相下分子聚集过程，详细讨论了膜的形成和相变过程，分析了纯水和金属离子Cd~(2+)两种亚相情况对各状态下膜的静态弹性的影响；同时考查DPPC单分子膜相变过程，同时研究了在不同压力处、不同压膜速度条件下对分子膜稳定性的影响。
(2)纯水亚相上二十二酸、DPPC循环曲线研究
河南大学凝聚态物理专业2001级硕士学位论文
摘要
二十二酸、DPPC单分子膜循环曲线进行了实验研究，对二十二酸、DPPC在
不同压力处单分子膜循环曲线进行系统研究，并在现有一些理论模型基础上对其
成膜过程分子聚集状态和热力学特征进行了理论探讨。
To prepare advanced materials with multifunction, it is necessary to endure the materials with special structural architecture, such as monolayer, multilayer, nano-structure, supramolecular assembly and so on. LB teschnique is a proper method to fabricate multilayer in a molecular scale and with controllable. LB film has ultrathin thickness and ordered molecular packing, which is very favorable to its application in high-technological fields, such as semiconductor nonlinearopticsN bionics and so on.
LB films have not gained mass industrial production at present due to the poor mechanical properties and stability. This is related to many basic problems, such as the condensed structure, intermolecular interaction, relaxation, etc. The mechanical properties and stability of Langmuir films have strong and direct effect on the deposition process of LB films.
The effects of the monolayer-formation conditions on the monolayer behavior, including the phase structure (molecular packing), intermolecular interactions, stability, and so on, were discussed. Based on the theory model we study low molecule weight surfactant (behenic acid ) and phospholipid monolayer and the cyclic isotherms of their mono layers; Including the standard thermodynamic characteristics and aggregation of the cyclic isotherms.
The main works are shown as the below: (1). Langmuir monolayer of behenic acid and DPPC surfactants
Behenic acid is a classical amphiphile, it has been applied to prepare functional LB
films and quantum semiconducting particle films. Therefore, it is of essential
importance to study behenic acid monolayer at the air /aqueous interface; At additional,
in the different subphase(H2O CdCl2) conditions behaviors of behenic acid
monolayers have been studied; Moreover, we study DPPC monolayer at the aqueous subphase, stability of DPPC at the different surface pressures and speed rates.
(2). The cyclic isotherms study of behenic acid and DPPC surfactants
We investigate the cyclic isotherms of behenic acid and DPPC monolayer at different surface pressures, based on the existing theory, we discuss the standard free energy of the system on aggregation of the cyclic isotherms.
目前LB膜还没有得到大规模的工业应用，最主要的原因就是其机械力学强度和稳定性还不够高。这涉及到多方面的问题，如膜的凝聚态结构、成膜分子间的相互作用力、膜的表面粘弹性和松弛特性、膜在二维状态下的反应性、分子层与基片间的附着力等等。单分子膜的表面力学性质及稳定性对LB膜的沉积过程也有直接的影响。
从力学性质着手，我们讨论了成膜条件对相态结构(分子排列)、分子间作用力、稳定性等物理化学性质的影响；在此基础上，利用现有的理论模型讨论小分子化合物(二十二酸)及其磷脂分子压缩、扩张过程分子聚集、扩散机理及其热力学问题。
研究内容如下：
(1)二十二酸、DPPC单分子膜成膜性能研究
主要研究典型的小分子成膜化合物(二十二酸)在纯水和金属离子Cd~(2+)两种亚相下分子聚集过程，详细讨论了膜的形成和相变过程，分析了纯水和金属离子Cd~(2+)两种亚相情况对各状态下膜的静态弹性的影响；同时考查DPPC单分子膜相变过程，同时研究了在不同压力处、不同压膜速度条件下对分子膜稳定性的影响。
(2)纯水亚相上二十二酸、DPPC循环曲线研究
河南大学凝聚态物理专业2001级硕士学位论文
摘要
二十二酸、DPPC单分子膜循环曲线进行了实验研究，对二十二酸、DPPC在
不同压力处单分子膜循环曲线进行系统研究，并在现有一些理论模型基础上对其
成膜过程分子聚集状态和热力学特征进行了理论探讨。
To prepare advanced materials with multifunction, it is necessary to endure the materials with special structural architecture, such as monolayer, multilayer, nano-structure, supramolecular assembly and so on. LB teschnique is a proper method to fabricate multilayer in a molecular scale and with controllable. LB film has ultrathin thickness and ordered molecular packing, which is very favorable to its application in high-technological fields, such as semiconductor nonlinearopticsN bionics and so on.
LB films have not gained mass industrial production at present due to the poor mechanical properties and stability. This is related to many basic problems, such as the condensed structure, intermolecular interaction, relaxation, etc. The mechanical properties and stability of Langmuir films have strong and direct effect on the deposition process of LB films.
The effects of the monolayer-formation conditions on the monolayer behavior, including the phase structure (molecular packing), intermolecular interactions, stability, and so on, were discussed. Based on the theory model we study low molecule weight surfactant (behenic acid ) and phospholipid monolayer and the cyclic isotherms of their mono layers; Including the standard thermodynamic characteristics and aggregation of the cyclic isotherms.
The main works are shown as the below: (1). Langmuir monolayer of behenic acid and DPPC surfactants
Behenic acid is a classical amphiphile, it has been applied to prepare functional LB
films and quantum semiconducting particle films. Therefore, it is of essential
importance to study behenic acid monolayer at the air /aqueous interface; At additional,
in the different subphase(H2O CdCl2) conditions behaviors of behenic acid
monolayers have been studied; Moreover, we study DPPC monolayer at the aqueous subphase, stability of DPPC at the different surface pressures and speed rates.
(2). The cyclic isotherms study of behenic acid and DPPC surfactants
We investigate the cyclic isotherms of behenic acid and DPPC monolayer at different surface pressures, based on the existing theory, we discuss the standard free energy of the system on aggregation of the cyclic isotherms.
引文
1. C.L.Bevins, M.Zasloff, Annu. Rev.Biochem., 1990, 59, 395.
2. C.E.Dempsey, Biochim. Biophys.Acta., 1990, 1041,141.
3. A.Argolias, J. Biol. Chem., 1985, 260,1437.
4. M.Zasloff, B.Martin, Ch.Hetru, J.A.Hoffmann, M.Patak, F.Vovelle,Structure, 1995, 3, 435.
5. B.Frankin, Phil.Trans.R.Soc., 1974, 64, 445.
6．欧阳键明，LB膜原理与应用，广州暨南大学出版社，1999．
7. D.Tabor, J.Colloid Interface Sci., 1980, 75,240.
8. I.Langmuir, J. Am. Chem. Soc., 1917, 39, 1848.
9. J.Engelking, M.Wittemann, M.Rehahn, Langrnuir, 2000, 16, 3407.
10. J.W.McBain, R.C.Bacon, H.D.Bruce, J. Chem. Phys., 1939, 7,818.
11. A.F.Ward, L.Tordai, J. Chem. Phys., 1993, 76, 159.
12. P.Suttiprasit, V.Krisdhasima, J.McGuire, J. Colloid Interface Sci., 1992, 154, 316.
13. G.Schwarz, S.Taylor, Langmuir, 1995, 11, 4341.
14. G.Signor, S.Mammi, E.Peggion, H.Ringsdorf, A.Wzagenknecht, Biochemistry, 1994, 33, 6659.
15．林童，贺庆国，白凤莲，高分子通报，2000，9，61．
16. G.Sessa, J.H.Freer, G.Colacicco, G.Weissmann, J. Biol. Chem., 1969, 244, 3575.
17. H.Brockman, Curr. Opin.. Struct. Biol., 1999, 9, 438.
18. Swalen, J.D., Allara, D.L., Andrade,J.D., Chandross E.A.,Garoff, S.,Israchvili. J., McCarthy, T.J.,Murray, R.,Pease,R.F.,Wynne, K.J., Yu.H. Langmuir,1987, 3,932.
19. Laughlin, R.G. The Aqueous Phase Behaviour of Surfactants, Academic press Inc.,San Diego 1994.
20. Lee EM, Thomas RK, Penfold J, Ward RC, J. Phys. Chem. 1989, 93,381.
21. I.K.Ledenv, M.C.Petty, Langmuir, 1994, 10, 4190.
22．朱步瑶，赵振国，界面化学基础，化学工业出版社，北京，1999．
23. Fainerman VB, Vollhardt D J. Phys. Chem. 1999, 103,243.
24. M.B.Temsamani, M.Maeck, I.E.Hassani, et al. J. Phys. Chem. B., 1998, 102, 3335.
25. L.Valkova, N. Borovkov, M. Pisani, E Rustichelli, Langmuir, 2001, 17, 3639.
26. Frank Armand, et al. Langmuir, 2001, 17, 3431.
27. R.Maget-Dana, M. Ptak, Biophys. J., 1997, 73, 2527.
28. S.Castano, B.Desbat, M.Laguerre, J.Dufourq, Biophys., 1997, 72, 2783.
29. N.Van Mau, V.Vie, L.Chaloin, E.Lesniewska, F.Heitz, C.Le Grimellec, J. Membr. Biol., 1999, 167, 241.
30. Van Oss NM, Daane GJ J Colloid Interface Sci. 1987,115, 402.
31. Janczuk B, Bruque JM, GonzalezMartin ML Langmuir, 1995, 11, 4515.
32. Rosen MJ, Aranson S Colloids Surf 1981, 3, 201.
33. Taneva. S. G., Keough, K.M.W.biochim. Biophys.Acta 1995,1236,185.
34. Koppenol, S.T.Sao, F.H.C. Yu. H, Zografi, G. Biochim. Biophys.Acta 1998,1369,221.
35. Mulder, W.H.J.Phys.Chem.B. 1997,101,7744.
36. Overbeek, J. Th. G.,Verhoeckx, G.. J., de Bruyn, EL., Leker, H. N.W.J.Colloid. Surf.A 1995,97,83.
37. McConnel, H.M., De Koker, R.E. Langmuir, 1996, 12, 4897.
38. Vysotsky, YU. B.; Bryantsev, V.S., Fainerman, V.B Vollhardt, D. Miller, R., J. Phys.Chem. B. 2002, 106, 121.
39. Krasteva, D., Fainerman,V.B., Brezesinski, G., Mohwald. H.Langmuir,2001,17,1209.
40. Weijiang He, Chaoyang Jiang, Longgen Zhu, J.Colloid Interface Sci., 2002, 246, 335.
41. Sishen Feng, Guanhua zhu, Meiyin Low, Langmuir, 2000, 16,7401.
42. J.D.Wringt, Progress in Surface Science, 1989, 31, 1.
43. 1801 M. Schurr, J. Hassmann, R. Kugler, Ch. Tomaschko, H. Voit, Thin Solid Films, 1997, 307, 260.
44. D.T. Amm, D. J. Johnson, N. Matsuura, Laursen, G Palmer, Thin Solid Films, 1994, 241, 74.
45. D. M. Taylor, J. N. Lambi, Thin Solid Films, 1994, 243,384
46. D. V. Paranjape, M. Sastry, P. Ganguly, Appl. Phys. Lett., 1993, 63, 18.
47. Lu, K. Fang, H. B. Wang,WH. Gun, P. S. He, M. R. Ji, Thin Solid Films, 2002, 418, 175.
48. W. X. Lu, H. B. Wang,WH. Gun, P. S. He, J Mater. Sci. Lett., 2001, 20, 423.
49. Z. F. Liu, K. Hashimoto, A. Fujishima, Nature, 1990, 347, 658.
50. E. Ando, 1. Miyazaki, K. Morimoto, H. Nakahara, K. Fukuda, Thin Solid Films
1985, 21, 21.
51. K. T61 lner, R. Popovitz-Biro, M. Lahav, D. Milstein, Science, 1977, 278, 2100.
52. S. T. Koweil, R. Selfridge, C. Eldering, N. Matloff, P. Stroeve, B. G Higgins, M. P. Srinivasan, L. B. Coleman, Thin Solid Films, 1987, 152, 377.
53. F. Monmy, F. Ortega, R.GRubio, J Phys. Chem. B., 1999, 103, 2061.
54. A. R. Esker, L. -H. Zhang, B. B. Sauer, W. Lee, H. Yu, Colloids. Surf. A., 2000, 171,131.
55. 1. M. Rodriguez Patina, C. Carrera, M. R. Rodriguez Nine, M. C. Femirndez Langmuir, 2001, 17, 4003.
56. 1. M. Rodriguez Patino, C. Carrera, M. R. Rodriguez Nine, M. C. Fem'andez, J. Colloid Interface Sci., 2001, 242, 141.
57. M. R. Rodriguez Nino, P. J. Wilde, D. C. Clark, J. M. Rodriguez Patino, Ind. Eng. Chem. Res., 1996, 35, 4449.
58. M. R. Rodriguez Nino, P. J. Wilde, D. C. Clark, J. M. Rodriguez Patina, Langmuir, 1998, 14, 2160.
59. M. Rodriguez Patino, M. R. Rodriguez Nino, C. Carrera, Ind. Eng. Chem. Res., 2002, 41, 2652.
60. J. M. Rodriguez Patina, M. R. Rodriguez Nino, C. Can'era, J Agric. Food Chem., 1999, 47, 40.
2. C.E.Dempsey, Biochim. Biophys.Acta., 1990, 1041,141.
3. A.Argolias, J. Biol. Chem., 1985, 260,1437.
4. M.Zasloff, B.Martin, Ch.Hetru, J.A.Hoffmann, M.Patak, F.Vovelle,Structure, 1995, 3, 435.
5. B.Frankin, Phil.Trans.R.Soc., 1974, 64, 445.
6．欧阳键明，LB膜原理与应用，广州暨南大学出版社，1999．
7. D.Tabor, J.Colloid Interface Sci., 1980, 75,240.
8. I.Langmuir, J. Am. Chem. Soc., 1917, 39, 1848.
9. J.Engelking, M.Wittemann, M.Rehahn, Langrnuir, 2000, 16, 3407.
10. J.W.McBain, R.C.Bacon, H.D.Bruce, J. Chem. Phys., 1939, 7,818.
11. A.F.Ward, L.Tordai, J. Chem. Phys., 1993, 76, 159.
12. P.Suttiprasit, V.Krisdhasima, J.McGuire, J. Colloid Interface Sci., 1992, 154, 316.
13. G.Schwarz, S.Taylor, Langmuir, 1995, 11, 4341.
14. G.Signor, S.Mammi, E.Peggion, H.Ringsdorf, A.Wzagenknecht, Biochemistry, 1994, 33, 6659.
15．林童，贺庆国，白凤莲，高分子通报，2000，9，61．
16. G.Sessa, J.H.Freer, G.Colacicco, G.Weissmann, J. Biol. Chem., 1969, 244, 3575.
17. H.Brockman, Curr. Opin.. Struct. Biol., 1999, 9, 438.
18. Swalen, J.D., Allara, D.L., Andrade,J.D., Chandross E.A.,Garoff, S.,Israchvili. J., McCarthy, T.J.,Murray, R.,Pease,R.F.,Wynne, K.J., Yu.H. Langmuir,1987, 3,932.
19. Laughlin, R.G. The Aqueous Phase Behaviour of Surfactants, Academic press Inc.,San Diego 1994.
20. Lee EM, Thomas RK, Penfold J, Ward RC, J. Phys. Chem. 1989, 93,381.
21. I.K.Ledenv, M.C.Petty, Langmuir, 1994, 10, 4190.
22．朱步瑶，赵振国，界面化学基础，化学工业出版社，北京，1999．
23. Fainerman VB, Vollhardt D J. Phys. Chem. 1999, 103,243.
24. M.B.Temsamani, M.Maeck, I.E.Hassani, et al. J. Phys. Chem. B., 1998, 102, 3335.
25. L.Valkova, N. Borovkov, M. Pisani, E Rustichelli, Langmuir, 2001, 17, 3639.
26. Frank Armand, et al. Langmuir, 2001, 17, 3431.
27. R.Maget-Dana, M. Ptak, Biophys. J., 1997, 73, 2527.
28. S.Castano, B.Desbat, M.Laguerre, J.Dufourq, Biophys., 1997, 72, 2783.
29. N.Van Mau, V.Vie, L.Chaloin, E.Lesniewska, F.Heitz, C.Le Grimellec, J. Membr. Biol., 1999, 167, 241.
30. Van Oss NM, Daane GJ J Colloid Interface Sci. 1987,115, 402.
31. Janczuk B, Bruque JM, GonzalezMartin ML Langmuir, 1995, 11, 4515.
32. Rosen MJ, Aranson S Colloids Surf 1981, 3, 201.
33. Taneva. S. G., Keough, K.M.W.biochim. Biophys.Acta 1995,1236,185.
34. Koppenol, S.T.Sao, F.H.C. Yu. H, Zografi, G. Biochim. Biophys.Acta 1998,1369,221.
35. Mulder, W.H.J.Phys.Chem.B. 1997,101,7744.
36. Overbeek, J. Th. G.,Verhoeckx, G.. J., de Bruyn, EL., Leker, H. N.W.J.Colloid. Surf.A 1995,97,83.
37. McConnel, H.M., De Koker, R.E. Langmuir, 1996, 12, 4897.
38. Vysotsky, YU. B.; Bryantsev, V.S., Fainerman, V.B Vollhardt, D. Miller, R., J. Phys.Chem. B. 2002, 106, 121.
39. Krasteva, D., Fainerman,V.B., Brezesinski, G., Mohwald. H.Langmuir,2001,17,1209.
40. Weijiang He, Chaoyang Jiang, Longgen Zhu, J.Colloid Interface Sci., 2002, 246, 335.
41. Sishen Feng, Guanhua zhu, Meiyin Low, Langmuir, 2000, 16,7401.
42. J.D.Wringt, Progress in Surface Science, 1989, 31, 1.
43. 1801 M. Schurr, J. Hassmann, R. Kugler, Ch. Tomaschko, H. Voit, Thin Solid Films, 1997, 307, 260.
44. D.T. Amm, D. J. Johnson, N. Matsuura, Laursen, G Palmer, Thin Solid Films, 1994, 241, 74.
45. D. M. Taylor, J. N. Lambi, Thin Solid Films, 1994, 243,384
46. D. V. Paranjape, M. Sastry, P. Ganguly, Appl. Phys. Lett., 1993, 63, 18.
47. Lu, K. Fang, H. B. Wang,WH. Gun, P. S. He, M. R. Ji, Thin Solid Films, 2002, 418, 175.
48. W. X. Lu, H. B. Wang,WH. Gun, P. S. He, J Mater. Sci. Lett., 2001, 20, 423.
49. Z. F. Liu, K. Hashimoto, A. Fujishima, Nature, 1990, 347, 658.
50. E. Ando, 1. Miyazaki, K. Morimoto, H. Nakahara, K. Fukuda, Thin Solid Films
1985, 21, 21.
51. K. T61 lner, R. Popovitz-Biro, M. Lahav, D. Milstein, Science, 1977, 278, 2100.
52. S. T. Koweil, R. Selfridge, C. Eldering, N. Matloff, P. Stroeve, B. G Higgins, M. P. Srinivasan, L. B. Coleman, Thin Solid Films, 1987, 152, 377.
53. F. Monmy, F. Ortega, R.GRubio, J Phys. Chem. B., 1999, 103, 2061.
54. A. R. Esker, L. -H. Zhang, B. B. Sauer, W. Lee, H. Yu, Colloids. Surf. A., 2000, 171,131.
55. 1. M. Rodriguez Patina, C. Carrera, M. R. Rodriguez Nine, M. C. Femirndez Langmuir, 2001, 17, 4003.
56. 1. M. Rodriguez Patino, C. Carrera, M. R. Rodriguez Nine, M. C. Fem'andez, J. Colloid Interface Sci., 2001, 242, 141.
57. M. R. Rodriguez Nino, P. J. Wilde, D. C. Clark, J. M. Rodriguez Patino, Ind. Eng. Chem. Res., 1996, 35, 4449.
58. M. R. Rodriguez Nino, P. J. Wilde, D. C. Clark, J. M. Rodriguez Patina, Langmuir, 1998, 14, 2160.
59. M. Rodriguez Patino, M. R. Rodriguez Nino, C. Carrera, Ind. Eng. Chem. Res., 2002, 41, 2652.
60. J. M. Rodriguez Patina, M. R. Rodriguez Nino, C. Can'era, J Agric. Food Chem., 1999, 47, 40.
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