此研究自組裝的特性，利用帶正電荷的離子型團聯式共聚物PS-b-P4VP(CH3I)及P4VP(CH3I)與生物分子DNA上的磷酸根負電荷，藉由物質間靜電吸引力形成錯合物，控制在高鹽類濃度的製備條件，稀釋所得到的產物可以達到系統的穩定平衡態，討論在過量水下的型態變化。主要針對block copolymer與DNA等電荷劑量形成中性錯合物作討論。除此外，並控制不同條件下，改變不同陽離子類型，離子強度，溫度變化，藉由POM，SAXS，TEM等實驗研究，觀察錯合物型態。POM的介相結果得到P4VP(CH3I)/DNA系統具有方向的規則，但對PS-b-P4VP(CH3I)/DNA而言，PS的存在導致介相的消失。靜電作用力致使的錯合物，P4VP(CH3I)/DNA的相轉變為鹽類濃度的函數，為一可逆過程，升溫可提高錯合物中的DNA規則結構程度，但為一不可逆反應。SAXS圖譜中PS-b-P4VP(CH3I)之親水、疏水鏈段與不相容的特性，在水中形成微胞型態，對應的PS-b-P4VP(CH3I)/DNA錯合物中，存在著由PS sphere與P4VP(CH3I)/DNA連續相的階級性結構，升溫可同時誘導PS sphere形成BCC規則排列與DNA以六角圓柱堆積的規則結構。分別針對兩個系統提出錯合物結構模型來幫助瞭解。

The interaction of polycation-DNA can form complexes with DNA resulting in the coil–globule conformational transition in the DNA molecules and DNA condensation. It was proposed that polycation-DNA complex formation is entropy driven and electrostatic force due to the ion pairs formed between positively charged groups of polycation molecule and the phosphate groups of DNA. In our studies, we try to use cationic diblock copolymer and homopolymer as polycations, and complex with DNA to investigate the actual internal structure. This is more one parameter in cationic diblock copolymer than homo-polycation to control the structure of complexes. The level of aggregation is related to the properties of the components as well as to the medium and external conditions of the polyplexes formation, so that we carried out studies that effect of ionic strength, temperature on polyplexes. The internal structure of DNA polyplexes formed with P4VP(CH3I) and PS-P4VP(CH3I) are investigated by POM, SAXS and TEM. The results were hexagonal packing of DNA in both complexes in aqueous solution. This salt-induced phase behavior was found for P4VP(CH3I)/DNA. The surprising studies are temperature-induced ordering packing for DNA and PS sphere in the complexes and the processes were irreversible. According to our results, we proposed simple models for both complexes to reveal the structures.

[1] Olli Ikkala, Gerrit ten Brinke, Science, 2002, 295, 2407
[2] George M. W., Bartosz G., Science, 2002, 295, 2418
[3] Stupp S. I., LeBonheur V.,Walker K., Li L. S., Huggins K. E., Keser M., Amstutz A., Science, 1997, 276, 384
[4] R. A. L. Jones, Soft Condensed Matter, Oxford, New York, 2002
[5] Hamley I. W., Angew. Chem. Int. Ed., 2003, 42, 1692
[6] Hamley I. W., Nanotechnology, 2003, 14, 39
[7] Robert L., Nicholas A. P., AICHE Journal., 2003, 49, 2990
[8] Ramaswamy N., Wei L., Jayant K., and Sukant K. T., Macromolecules, 2001, 34, 3921
[9] Jeffrey L. C., Shelli R. B., Xin L., Appl. Phys. Lett., 1996, 69, 3851
[10] Torimoto T., Yamashita M., Kuwabata S., Sakata T., Mori H., Yoneyama H., Phys. Chem., 1999,103,8799
[11] Richter J., Mertig M. Pompe W., Appl. Phys. Lett., 2001, 78, 536
[12] Mertig M., Ciacchi L. C., Seidel R., Pompe W., NANO LETTERS, 2002, 2, 841
[13] Hongjun L., Thomas E. A., James H., Paul V. B.,Gerard C. L. W. J. Amer. Chem. Soc. ,2003, Communications
[14] Warner M. G., Hutchison J. E., Nature, 2003, Articles
[15] I. W. Hamley, The Physics of Block Copolymer, Oxford, New York, 1998
[16] Meier, D. J., J. Polym. Sci., part C 1969, 26, 81.
[17] Helfand E., Macromolecules 1975, 8, 552
[18] Helfand E.; Wasserman Z. R., Macromolecules 1976, 9, 879
[19] Helfand E.; Wasserman Z. R., Macromolecules 1980, 13, 994
[20] Helfand E.; Wasserman Z. R., Macromolecules 1978, 11, 960
[21] Leibler L., Macromolecules 1980, 13, 1602
[22] Vavasour J. D.; Whitemore M. D., Macromolecules 1992, 25, 5477
[23] M. W. Matsen; M. Schick, Physical Review Letters, 1994, 72, 2660
[24] M. W. Matsen; F. S. Bates, Macromolecules 1996, 29, 1091
[25] M. W. Matsen; F. S. Bates, Macromolecules 1996, 29, 7641
[26] Ashish K. Khandpur; Stephan Farster; Frank S. Bates, Macromolecules 1995, 28, 8796
[27] Zhisheng G., Eisenberg A., Macromolecules 1993, 26, 7353
[28] Alexandris P, Langmuir 1996, 12, 2690
[29] Gerard R., Prog. Polym. Sci. 2003, 28, 1107
[30] de Gennes, P.-G. In Solid State Physics; Leibert, L., Ed.; Academic Press:
New York, 1978; Supplement 4.
[31] Noolandi, J.; Hong, K. M. Macromolecules, 1982, 15, 482
[32] Noolandi, J.; Hong, K. M. Macromolecules, 1983, 16, 1443
[33] Whitmore, M. D.; Noolandi, J. Macromolecules, 1986, 18, 657
[34] Leibler, L.; Orland, H.; Wheeler, J. C. J. Chem. Phys. 1983, 79, 3550
[35] Halperin, A. Macromolecules, 1987, 20, 2943
[36] Halperin, A. Macromolecules, 1989, 22, 3806
[37] Halperin, A.; Alexander, S. Macromolecules, 1989, 22, 2403
[38] Yuan, X, F.; Masters, A. J.; Price, C. Macromolecules, 1992, 25, 6876
[39] Bue.A. L. R.: Gates. M. E.: Safran. S. A,: Witten. T. A. J. Chem. Phys. 1987, 87, 1824
[40] Maraues. C.: Joannv. J. F.: Leibler. L. Macromolecules, 1988, 21, 1051
[41] Fredrickson, G. H.; Helfand, E. J. Chem. Phys. 1987, 87, 697
[42] Nagarajan, R.; Ganesh, K. J. Phys. Chem. 1989, 90, 5843
[43] Marko, J. F.; Rabin, Y. Macromolecules, 1992, 25, 1503
[44] Lindman, B.; Wennerstrom, H. Top. Curr. Chem., 1980, 87, 1
[45] Rosen, M. J. Surfactants and Interfacial Phenomena, 2nd ed.; John Wiley & Sons: New York, 1989.
[46] Fendler, J. H. Membrane Mimetic Chemistry; John Wiley & Sons: New York, 1982
[47] Mayers, D. Surfactant Science and Technology; VCH Publishers, Inc.: New York, 1988
[48] Tanford, C. The Hydrophobic Effect: Formation of Micelles and Biological Membranes; John Wiley & Sons: New York, 1980
[49] Price, C.; Chan, E. K. M.; Stubbersfield, R. B. Eur. Polym. J, 1987, 23, 649
[50] Price, C.; Stubbersfield, R. B.; El-Kafrawy, S.; Kendall, K. D. Br. Polym. J. 1989, 21, 391
[51] Zhao, C. L.; Winnik, M. A.;Riess, G.; Croucher,M. D. Langmuir,1990, 6, 514.
[52] Wilhelm, M.; Zhao, C. L.; Wang, Y.; Xu, R.; Winnik, M. A. Macromolecules, 1991, 24, 1033
[53] AuMieva, I.; Zhong, X. F.; Eisenberg, A. Macromolecules, preceding paper in this issue
[54] Gonzalez-Mozuelos, Olvera da la Cruz, J. Chem. Phys., 1994, 100, 507
[54]Shusharina N. P., Nyrkova I. A., Khokhlov A. R., Macromolecules, 1996, 29, 3167
[55]Otsuka H, Kataoka K, Nagasaki Y, Curr Opin Colloid Interf Sci, 2001, 6, 3
[56] Kiserow D.; Prochazka K.; Ramireddy C.; Tuzar, Z.; Munk P.; Webber S. E., Macromolecules 1992, 25, 461
[57] Khougaz K.; Astafieva I.; Eisenberg A. Macromolecules 1995, 28, 7135
[58] Amiel C.; Sikka M.; Schneider J. W.; Tsao Y. H.; Tirrell M.; Mays J. W. Macromolecules 1995, 28, 3125
[59] (a) Guenoun P.; Delsanti M.; Gaseau D.; Auvray L.; Cook D. C.; Mays J. W.; Tirrell M Eur. Phys. J. B 1998, 1, 77 (b)Guenoun P.; Davis H. T.; Tirrell M.; Mays J. W. Macromolecules 1996, 29, 3965 (c) Guenoun P.; Muller F.;Delsanti, M.; Auvray, L.; Chen, Y. J. Mays, J. W.; Tirrell, M. Phys. Rev. Lett. 1998, 81, 3872. (d) Muller, F.; Delsanti, M.; Auvray, L.; Yang, J.; Chen, Y. J.; Mays, J. W.; Deme´, B.; Tirrell, M.; Guenoun, P. Eur. Phys. J. E 2000, 3, 45.
[60] Fo¨rster, S.; Hemsdorf, N.; Leube, W.; Schnablegger, H.;Regenbrecht, M.; Akari, S.; Lindner, P.; Bo¨ttcher, C. J. Phys. Chem. 1999, 103, 6657.
[61] (a) Groenewegen, W.; Egelhaalf, S. U.; Lapp, A.; van der Maarel, J. R. C. Macromolecules 2000, 33, 3283. (b) Groenewegen, W.; Lapp, A.; Egelhaalf, S. U.; van der Maarel, J. R. C. Macromolecules 2000, 33, 4080.
[62] Schuch, H.; Klingler, J.; Rossmanith, P.; Frechen, T.; Gerst, M.; Feldthusen, J.; Mu¨ ller, A. H. E. Macromolecules 2000, 33, 3687.
[63] Fo¨rster, S.; Hermsdorf, N.; Bo¨ttcher, C.; Lindner, P. Macromolecules 2002, 35, 4096.
[64] Napper, D. H. Polymeric Stabilization of Colloidal Dispersions; Academic Press: London, 1985.
[65] Stealth Liposomes; Lasic, D., Martin, F., Eds.; CRC Press: Boca Raton, FL, 1995. [66] Allen, C.; Maysinger, D.; Eisenberg, A. Colloids Surf. B 1999, 16, 3.
[67] Cammas-Marion, S.; Okano, T.; Kataoka, K. Colloids Surf. B 1999, 16, 207.
[68] Boyce R., Life Itself, Garland, 1998
[69] MOLLER J. J., J. Appl. Cryst. 1983, 16, 74
[70] Livolant F. et al., Prog. Polym. Sci., 1996, 21, 1115
[71] Durand D,. Doucet J., Livolant F., J. Phys. II France, 1992, 2, 1769-1783
[72] Arscott P. G., An-Zhi L., Bloomfield V. A., Biopolymers, 1990, 30, 619
[73] Plum G. E., Arscott P. G., An-Zhi L., Bloomfield V. A., Biopolymers, 1990, 30, 631
[74] Bloomfield V. A., Biopolymers, 1991, 31, 1471
[75] Arscott P. G., Chenglie M., Wenner J. R., Bloomfield V. A., Biopolymers, 1995, 36, 344
[76] Pelta J., Durand D., Doucet J., Livolant F., Biophysical J. 1996, 71, 48
[77] Golan R., Pietrasanta L. I., Heish W., Hansma H. G., Biochemistry, 1999, 38, 14069
[78] Wilson R.W., Bloomfield V. A., Biochemistry, 1979, 18, 2192
[79] Manning G. S., Rev. Biophys. 1978, 11, 179
[80] Nguyen T. T., Grosberg A. Yu., Shklovskii B. I., J. Chem. Phys.,2000, 113, 1110
[81]. Kunze K.-K., Europhys. Lett., 2002, 58, 299
[82] Koltover I.,. Salditt T, Radler J.O., Safinya C.R., Science, 1998, 281, 78
[83] DeRoucheya J., Netz R.R., and. Radler J.O., Eur. Phys. J. E, 2005,16, 17
[84] Harada A, Kataoka K. J Controlled Release, 2001, 72, 85
[85] Harada A, Kataoka K. Science, 1999, 283, 65
[86] Kabanov AV, Alakhov VY. Amsterdam: Elsevier, 2000 , p.347
[87] De Smedt SC, Demeester J, Hennink WE., Pharm Res, 2000, 17, 113
[88] Wolfert MA, Schacht EH, Toncheva V, Ulbrich K, Nazarova O, Seymour LW. , Hum Gene Ther, 1996, 7, 2123
[89] Katayose S, Kataoka K. Bioconjug Chem., 1997, 8, 702
[90] Harada A, Kataoka K., Macromolecules, 1995, 28 ,5294
[91] Kataoka K, Harada A, Wakebayashi D, Nagasaki Y., Macromolecules, 1999, 32, 6892
[92] Nagasaki Y, Wakebayashi D, Akiyama Y, Harada A, Kataoka K., ACS Polym Prepr (Div Polym Chem), 2000, 41, 1649
[93] Oupicky D ., Journal of Controlled Release, 2000, 65, 149
[94] Kabanov A. V., Bioconjugafe Chem., 1995, 6, 7
[95] Oosawa F., Polyelectrolytes, Marcel Dekker, Inc., New York, 1971
[96] Wagner K., Harries D., May S., Kahl V., Radler J.O., Ben-Shaul A., Langmuir , 2000, 16, 303
[97] Mita K., Zama M., Ichimura S., Biopolymers, 1977, 16, 1993
[98] Selb J., Gallot Y. In Polymeric Amines and Ammonium Salts; Goethals, E. J., Ed.; Pergamon Press: New York, 1980; p 205.
[99] Selb J.; Gallot Y. In Development in Block Copolymers; Goodman,I., Ed.; Elsevier Applied Science: London, U.K., 1985, 2, 27
[100] Roe, R. J., Method of X-ray and Neutron Scattering in Polymer Science；Oxford University Press：New York 2000
[101] Hashimoto, T.; Fujimura, M.; Kawai, H., Macromolecules 1980, 13, 1660
[102] Manning G. S., J. Phys. Chem. B, 2003, 107, 11485
[103] Zhang X., Tasaka S., Inagaki N., Journal of Polymer Science: Part B: Polymer Physics, 2000, 38, 654