Hierarchical amplification of macromolecular helicity in a lyotropic liquid crystalline charged poly(phenylacetylene) by nonracemic dopants in waterrand its helical structure

Macromolecules

Volumn 39, Issue 16, 2006, Pages 5371-5380

  Nagai, Kanji ^a   Sakajiri, Koichi ^b,d   Maeda, Katsuhiro ^a   Okoshi, Kento ^b   Sato, Takahiro ^c   Yashima, Eiji ^a,b  

^a NAGOYA UNIVERSITY   (Japan)

^b JAPAN SCIENCE AND TECHNOLOGY AGENCY   (Japan)

^c OSAKA UNIVERSITY   (Japan)

^d GIFU UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ELECTROSTATICS; NEMATIC LIQUID CRYSTALS; SOLUTIONS; SUPRAMOLECULAR CHEMISTRY; X RAY ANALYSIS;

CHIRALITY TRANSFER; ELECTROSTATIC INTERACTIONS; MACROMOLECULAR HELICITY;

ORGANIC POLYMERS;

EID: 33748309472     PISSN: 00249297     EISSN: None     Source Type: Journal    
DOI: 10.1021/ma0606760     Document Type: Article

References (181)

1. (a) Robinson, C.; Ward, J. C. Nature 1957, 180, 1183-1184.
2. (b) Tsujita, Y.; Yamanaka, I.; Takizawa, A. Polymer J. 1979, 11, 749-754.
3. (c) Livolant, F.; Bouligand, Y. J. Phys. 1986, 47, 1813-1827.
4. (d) Strzelecka, T. E.; Davidson, M. W.; Rill, R. L. Nature 1988, 331, 457-460.
5. (e) Livolant, F.; Levelut, A. M.; Doucet, J.; Benoit, J. P. Nature 1989, 339, 724-726.
6. (f) Fortin, S.; Charlet, G. Macromolecules 1989, 22, 2286-2292.
7. (g) Wen, X.; Meyer, R. B.; Casper, D. L. D. Phys. Rev. Lett. 1989, 63, 2760-2763.
8. (h) Inatomi, S.; Jinbo, Y.; Sato, T.; Teramoto, A. Macromolecules 1992, 25, 5013-5019.
9. (i) Yu, S. M.; Conticello, V. P.; Zhang, G.; Kayser, C.; Fournier, M. J. ; Mason, T. L.; Tirrel, D. A. Nature 1997, 359, 167-170.
10. (j) Dogic, Z.; Fraden. S. Phys. Rev. Lett. 1997, 78, 2417-2420.
11. Reviews: (a) Green, M. M.; Peterson, N. C.; Sato, T.; Teramoto, A.; Cook, R.; Lifson, S. Science 1995, 268, 1860-1866.
12. (b) Green, M. M.; Park, J.-W.; Sato, T.; Teramoto, A.; Lifson, S.; Selinger, R. L. B.; Selinger, J. V. Angew. Chem., Int. Ed. 1999, 38, 3138-3154.
13. (c) Nielsen, P. E. Acc. Chem. Res. 1999, 32, 624-630.
14. (d) Nakano, T.; Okamoto, Y. Chem. Rev. 2001, 101, 4013-4038.
15. (e) Cornelissen, J. J. L. M.; Rowan, A. E.; Nolte, R. J. M.; Sommerdijk, N. A. J. M. Chem. Rev. 2001, 101, 4039-4070.
16. (f) Fujiki, M. Macromol. Rapid Commun. 2001, 22, 539-563.
17. (g) Nomura, R.; Nakako, H.; Masuda, T. J. Mol. Catal. A: Chem. 2002, 190, 197-205.
18. (h) Fujiki, M.; Koe, J. R.; Terao, K.; Sato, T.; Teramoto, A.; Watanabe, J. Polym. J. 2003, 35, 297-344.
19. (i) Elemans, J. A. A. W.; Rowan, A. E.; Nolte, R. J. M. J. Mater. Chem. 2003, 13, 2661-2670.
20. (j) Yashima, E.; Maeda, K.; Nishimura, T. Chem.-Eur. J. 2004, 10, 42-51.
21. For reviews of helical oligomers (foldamers) and helical assemblies, see: (k) Lehn, J. M. Supramolecular Chemistry, VCH: Weinheim, Germany, 1995.
22. (1) Gellman, S. H. Acc. Chem. Res. 1998, 31, 173-180.
23. (m) Srinivasarao, M. Curr. Opin. Colloid Interface Sci. 1999, 4, 370-376.
24. (n) Hill, D. J.; Mio, M. J.; Prince, R. B.; Hughes, T. S.; Moore, J. S. Chem. Rev. 2001, 101, 3893-4011.
25. (o) Brunsveld, L.; Folmer, B. J. B.; Meijer, E. W.; Sijbesma, R. P. Chem. Rev. 2001, 101, 4071-4097.
26. (p) Hue, I. Eur. J. Org. Chem. 2004, 17-29.
27. (q) Seebach, D.; Beck, A. K.; Bierbaum, D. J. Chem. Biodiversity 2004, 1, 1111-1239.
28. (r) Hoeben, F. J. M.; Jonkheijm, P.; Meijer, E. W.; Schenning, A. P. H. J. Chem. Rev. 2005, 105, 1491-1546.
29. (s) Tanatani, A.; Yokoyama, A.; Azumaya, L; Takakura, Y.; Mitsui, C.; Shiro, M.; Uchiyama, M.; Muranaka, A.; Kobayashi, N.; Yokozawa, T. J. Am. Chem. Soc. 2005, 127, 8553-8561.
30. (a) Chandrasekaran, S. Liquid Crystals, 2nd ed.; Cambridge University Press: Cambridge, 1992; Chapter 4.
31. (b) Okamoto, Y.; Yashima, E. Angew. Chem., Int. Ed. 1998, 37, 1021-1043.
32. (c) Amabilino, D. B.; Pérez-García, L. Chem. Soc. Rev. 2002, 31, 342-356.
33. (d) Kato, T. Science 2002, 295, 2414-2418.
34. (e) Yamamoto, C.; Okamoto, Y. Bull. Chem. Soc. Jpn. 2004, 77, 227-257.
35. (f) Reggelin, M.; Doerr, S.; Klussmann, M.; Schultz, M.; Holbach, M. Proc. Natl. Acad. Sci. U.S.A. 2004, 101, 5461-5466.
36. For leading references for liquid crystalline polyisocyanates: (a) Aharoni, S. M. Macromolecules 1979, 12, 94-103.
37. (b) Itou, T.; Teramoto, A. Macromolecules 1988, 21, 2225-2230.
38. (c) Green, M. M.; Weng, D.; Shang, W.; Labes, M. M. Angew. Chem., Int. Ed. Engl. 1992, 31, 88-90.
39. (d) Sato, T.; Sato, Y.; Umemura, Y.; Teramoto, A.; Nagamura, Y.; Wagner, J.; Weng, D.; Okamoto, Y.; Hatada, K.; Green, M. M. Macromolecules 1993, 26, 4551-4559.
40. (e) Green, M. M.; Zanella, S.; Gu, H.; Sato, T.; Gottarelli, G.; Jha, S. K.; Spada, G. P.; Schoevaars, A. M.; Feringa, B.; Teramoto, A. J. Am. Chem. Soc. 1998, 120, 9810-9817.
41. (f) Tang, K.; Green, M. M.; Cheon, K. S.; Selinger, J. V.; Garetz, B. A. J. Am. Chem. Soc. 2003, 125, 7313-7323.
42. Liquid crystalline polysilanes: (g) Watanabe, J.; Kamee, H.; Fujiki, M. Polym. J. 2001, 33, 495-497.
43. (h) Okoshi, K.; Kamee, H.; Suzaki, G.; Fujiki, M.; Watanabe, J. Macromolecules 2002, 35, 4556-4559.
44. (i) Okoshi, K.; Saxena, A.; Naito, M.; Suzaki, G.; Tokita, M.; Watanabe, J.; Fujiki, M. Liq. Cryst. 2004, 31, 279-283.
45. Liquid crystalline polyisocyanides: (j) Cornelissen, J. J. L. M.; Donners, J. J. M.; de Gelder, R.; Graswinckel, W. S.; Metselaar, G. A.; Rowan, A. E.; Sommerdijk, N. A. J. M.; Nolte, R. J. M. Science 2001, 293, 676-680.
46. (k) Samorí, P.; Ecker, C.; Gösell, I.; de Witte, P. A. J.; Cornelissen, J. J. L. M.; Metselaar, G. A.; Otten, M. B. J.; Rowan, A. E.; Nolte, R. J. M.; Rabe, J. P. Macromolecules 2002, 35, 5290-5294.
47. (1) Cornelissen, J. J. L. M.; Graswinckel, W. S.; Rowan, A. E.; Sommerdijk, N. A. J. M.; Nolte, R. J. M. J. Polym. Sci., Part A: Polym. Chem. 2003, 41, 1725-1736.
48. Liquid crystalline polyguanidines: (m) Kim, J.; Novak, B. M.; Waddon, A. J. Macromolecules 2004, 37, 1660-1662.
49. (n) Kim, J.; Novak, B. M.; Waddon, A. J. Macromolecules 2004, 37, 8286-8292.
50. Bellomo, E. G.; Davidson, P.; Impéror-Clerc, M.; Deming, T. J. J. Am. Chem. Soc. 2004, 126, 9101-9105.
51. (a) Yashima, E.; Matsushima, T.; Okamoto, Y. J. Am. Chem. Soc. 1995, 117, 11596-11597.
52. (b) Yashima, E.; Nimura, T.; Matsushima, T.; Okamoto, Y. J. Am. Chem. Soc. 1996, 118, 9800-9801.
53. (c) Yashima, E.; Maeda, Y.; Okamoto, Y. Chem. Lett. 1996, 955-956.
54. (d) Yashima, E.; Maeda, Y.; Matsushima, T.; Okamoto, Y. Chirality 1997, 9, 593-600.
55. (e) Yashima, E.; Matsushima, T.; Okamoto, Y. J. Am. Chem. Soc. 1997, 119, 6345-6359.
56. (f) Yashima, E.; Maeda, K.; Okamoto, Y. Nature 1999, 399, 449-451.
57. (g) Nonokawa, R.; Yashima, E. J. Am. Chem. Soc. 2003, 125, 1278-1283.
58. (h) Maeda, K.; Morino, K.; Okamoto, Y.; Sato, T.; Yashima, E. J. Am. Chem. Soc. 2004, 126, 4329-4342.
59. (i) Kamikawa, Y.; Kato, T.; Onouchi, H.; Kashiwagi, D.; Maeda, K.; Yashima, E. J. Polym. Sci., Part A: Polym. Chem. 2004, 42, 4580-4586.
60. (j) Morino, K.; Watase, N.; Maeda, K.; Yashima, E. Chem.-Eur. J. 2004, 10, 4703-4707.
61. (k) Onouchi, H.; Kashiwagi, D.; Hayashi, K.; Maeda, K.; Yashima, E. Macromolecules 2004, 37, 5495-5503.
62. (l) Nishimura, T.; Tsuchiya, K.; Ohsawa, S.; Maeda, K.; Yashima, E.; Nakamura, Y.; Nishimura, J. J. Am. Chem. Soc. 2004, 126, 11711-11717.
63. (m) Miyagawa, T.; Furuko, A.; Maeda, K.; Katagiri, H.; Furusho, Y.; Yashima, E. J. Am. Chem. Soc. 2005, 127, 5018-5019.
64. (n) Onouchi, H.; Hasegawa, T.; Kashiwagi, D.; Ishiguro, H.; Maeda, K.; Yashima, E. Macromolecules 2005, 38, 8625-8633.
65. Ashida, Y.; Sato, T.; Morino, K.; Maeda, K.; Okamoto, Y.; Yashima, E. Macromolecules 2003, 36, 3345-3350.
66. For helicity induction through noncovalent chiral interactions in related aliphatic polyacetylenes and other polymers bearing functional groups as the pendants, see: (a) Schlitzer, D. S.; Novak, B. M. J. Am. Chem. Soc. 1998, 120, 2196-2197.
67. (b) Morris, I. D.; Kane-Maguire, L. A. P.; Wallace, G. G. Macromolecules 1998, 31, 6529-6533.
68. (c) Maeda, K.; Yamamoto, N.; Okamoto, Y. Macromolecules 1998, 31, 5924-5926.
69. (d) Yashima, E.; Maeda, K.; Yamanaka, T. J. Am. Chem. Soc. 2000, 122, 7813-7814.
70. (e) Inai, Y.; Ishida, Y.; Tagawa, K.; Takasu, A.; Hirabayashi, T. J. Am. Chem. Soc. 2002, 124, 2466-2473.
71. (f) Ishikawa, M.; Maeda, K.; Yashima, E. J. Am. Chem. Soc. 2002, 124, 7448-7458.
72. (g) Sakai, R.; Satoh, T.; Kakuchi, R.; Kaga, H.; Kakuchi, T. Macromolecules 2003, 36, 3709-3713.
73. (h) Tabei, J.; Nomura, R.; Sanda, F.; Masuda, T. Macromolecules 2003, 36, 8603-8608.
74. (i) Guo, Y.-M.; Oike, H.; Aida, T. J. Am. Chem. Soc. 2004, 126, 716-717.
75. (j) Ishikawa, M.; Maeda, K.; Mitsutsuji, Y.; Yashima, E. J. Am. Chem. Soc. 2004, 126, 732-733.
76. (k) Arnt, L.; Tew, G. N. Macromolecules 2004, 37, 1283-1288.
77. (l) Sakai, R.; Satoh, T.; Kakuchi, R.; Kaga, H.; Kakuchi, T. Macromolecules 2004, 37, 3996-4003.
78. (m) Nilsson, K. P. R.; Rydberg, J.; Baltzer, L.; Inganäs, O. Proc. Natl. Acad. Sci., U.S.A. 2004, 107, 11197-11202.
79. (n) Kakuchi, R.; Sakai, R.; Otsuka, I.; Satoh, T.; Kaga, H.; Kakuchi, T. Macromolecules 2005, 38, 9441-9447.
80. (a) Maeda, K.; Takeyama, Y.; Sakajiri, K.; Yashima, E. J. Am. Chem. Soc. 2004, 126, 16284-16285.
81. (b) Nagai, K.; Maeda, K.; Takeyama, Y.; Sakajiri, K.; Yashima, E. Macromolecules 2005, 38, 5444-5451.
82. For reviews of liquid crystalline polyacetylenes with mesogenic pendants, see: (a) Akagi, K.; Shirakawa, H. In Electrical and Optical Polymer Systems; Donald, L. W., Eds.; Marcel Dekker: New York, 1998; Chapter 28.
83. (b) Lam, J. W. Y.; Tang, B. Z. J. Polym. Sci., Part A: Polym. Chem. 2003, 41, 2607-2629.
84. (c) Lam, J. W. Y.; Tang, B. Z. Acc. Chem. Res. 2005, 38, 745-754.
85. For thermotropic liquid crystalline polyacetylenes, see: (d) Schenning, A. P. H. J.; Fransen, M.; Meijer, E. W. Macromol. Rapid Commun. 2002, 23, 265-270.
86. (e) Percec, V.; Obata, M.; Rudick, J. G.; De, B. B.; Glodde, M.; Bera, T. K.; Magonov, S. N.; Balagurusamy, V. S. K.; Heiney, P. A. J. Polym. Sci., Part A: Polym. Chem. 2002, 40, 3509-3533.
87. (f) Lam, J. W. Y.; Dong, Y.; Law, C. C. W.; Dong, Y.; Cheuk, K. K. L.; Lai, L. M.; Li, Z.; Sun, J.; Chen, H.; Zheng, Q.; Kwok, H. S.; Wang, M.; Feng, X.; Shen, J.; Tang, B. Z. Macromolecules 2005, 38, 3290-3300.
88. 9a
89. Cholesteric induction by doping nematic LCs with nonracemic chiral compounds is a typical and versatile example of chiral amplification on a macroscopic level and allows the detection of even trace amounts of chiral dopants, (a) Penot, J. P.; Billard, J. J. et J. Tetrahedron Lett. 1968, 4013-4016.
90. (b) Bertocchi, G.; Gottarelli, G.; Prati, R. Talanta 1984, 31, 138-140.
91. (c) Huck, N. P. M.; Jager, W. F.; Lange, B.; Feringa, B. L. Science 1996, 273, 1686-1688.
92. (d) Gottarelli, G.; Samori, B.; Fuganti, C.; Grasselli, P. J. Am. Chem. Soc. 1997, 119, 471-472.
93. (e) Proni, G.; Spada, G. Enantiomer 2001, 6, 171-179.
94. (f) Delden, R. A.; Feringa, B. L. Angew. Chem., Int. Ed. 2001, 40, 3198-3200.
95. For reviews of chirality sensing by CD, see: ref 2j and (g) Ogoshi, H.; Mizutani, T. Acc. Chem. Res. 1998, 31, 81-89.
96. (h) Nakanishi, K.; Berova, N. In Circular Dichroism: Principles and Applications, 2nd ed.; Nakanishi, K., Berova, N., Woody, R. W., Eds.; VCH: New York, 2000; Chapter 12.
97. (i) Canary, J. W.; Holmes, A. E.; Liu, J. Enantiomer 2001, 6, 181-188.
98. (j) Shinkai, S.; Ikeda, M.; Sugasaki, A.; Takeuchi, M. Acc. Chem. Res. 2001, 34, 494-503.
99. (k) Tsukube, H.; Shinoda, S. Chem. Rev. 2002, 102, 2389-2403.
100. (l) Allenmark, S. Chirallty 2003, 15, 409-422.
101. (m) Borovkov, V. V.; Hembury, G. A.; Inoue, Y. Acc. Chem. Res. 2004, 37, 449-459.
102. Recently, a similar hierarchical amplification of chirality in LC media has been reported for small molecular systems. Eelkema, R.; Feringa, B. L. J. Am. Chem. Soc. 2005, 127, 13480-13481.
103. For reviews: (a) Simionescu, C. I.; Percec, V. Prog. Polym. Sci. 1982, 8, 133-214.
104. (b) Masuda, T.; Higashimura, T. Adv. Polym. Sci. 1987, 81, 121-165.
105. (c) Shirakawa, H.; Masuda, T.; Takeda, K. In The Chemistry of Triple-Bond Functional Groups; Patai, S., Ed.; John Wiley & Sons: New York, 1994; Chapter 17.
106. (d) Mayershofer, M. G.; Nuyken, O. J. Polym. Sci., Part A: Polym. Chem. 2005, 43, 5723-5747.
107. (e) Aoki, T.; Kaneko, T. Polym. J. 2005, 37, 717-735.
108. For recent examples of helical polyacetylenes with optically active substituents, see refs 10c-e, g, and: (f) Nomura, R.; Fukushima, Y.; Nakako, H. ; Masuda, T. J. Am. Chem. Soc. 2000, 122, 8830-8836.
109. (g) Li, B. S.; Cheuk, K. K. L.; Salhi, F.; Lam, J. W. Y.; Cha, J. A. K.; Xiao. X.; Bai, C.; Tang, B. Z. Nano Lett. 2001, 7, 323-328.
110. (h) Yashima, E.; Maeda, K.; Sato, O. J. Am. Chem. Soc. 2001, 123, 8159-8160.
111. (i) Morino, K.; Maeda, K.; Okamoto, Y.; Yashima, E.; Sato, T. Chem-Eur. J. 2002, 8, 5112-5120.
112. (j) Li, B. S.; Cheuk, K. K. L.; Ling, L.; Chen, J.; Xiao, X.; Bai, C.; Tang, B. Z. Macromolecules 2003, 36, 77-85.
113. (k) Aoki, T.; Fukuda, T.; Shinohara, K.; Kaneko, T.; Teraguchi, M.; Yagi, M. J. Polym. Sci., Part A: Polym. Chem. 2004,42, 4502-4517.
114. (l) Lam, J. W. Y.; Dong, Y.; Cheuk, K. K. L.; Law, C. C. W.; Lai, L. M.; Tang, B. Z. Macromolecules 2004, 37, 6695-6704.
115. (m) Tabei, J.; Shiotsuki, M.; Sanda, F.; Masuda, T. Macromolecules 2005, 38, 5860-5867.
116. (n) Percec, V.; Rudick, J. G.; Aqad, E. Macromolecules 2005, 38, 7205-7206.
117. (o) Kaneko, T.; Umeda, Y.; Yamamoto, T.; Teraguchi, M.; Aoki, T. Macromolecules 2005,38,9420-9426.
118. (p) Tabei, J.; Shiotsuki, M.; Sanda, F.; Masuda, T. Macromolecules 2005, 38, 9448-9454.
119. (a) Simionescu, C. I.; Percec, V.; Dumitrescu, S. J. Polym. Sci., Polym. Chem. Ed. 1977, 15, 2497-2509.
120. (b) Lee, D.-H.; Lee, D.-H.; Soga, K. Makromol. Chem., Rapid Commun. 1990, 11, 559-563.
121. (c) Tabata, M.; Sadahiro, Y.; Nozaki, Y.; Inaba, Y.; Yokota, K. Macromolecules 1996, 29, 6673-6675.
122. (d) Lam, J. W. Y.; Kong, X.; Dong, Y.; Cheuk, K. K. L.; Xu, K.; Tang, B. Z. Macromolecules 2000, 33, 5027-5040.
123. (e) Kozuka, M.; Sone, T.; Sadahiro, Y.; Tabata, M.; Endo, T. Macromol. Chem. Phys. 2002, 203, 66-70.
124. (f) Ye, C.; Xu, G.; Yu, Z.-Q.; Lam, J. W. Y.; Jang, J. H.; Peng, H.-L.; Tu, Y.-F.; Liu, Z.-F.; Jeong, K.-U.; Cheng, S. Z. D.; Chen, E.-Q.; Tang, B. Z. J. Am. Chem. Soc. 2005, 127, 7668-7669.
125. (a) Yashima, E.; Huang, S.; Matsushima, T.; Okamoto, Y. Macro molecules 1995, 28, 4184-4193.
126. (b) Nakako, H.; Nomura, R.; Masuda, T. Macromolecules 2001, 34, 1496-1502.
127. (a) Murakami, H.; Norisuye, T.; Fujita, H. Macromolecules 1980, 13, 345-352.
128. (b) Itou, S.; Chikiri, H.; Teramoto, A.; Aharoni, S. M. Polym. J. 1988, 20, 143-151.
129. (c) Takada, S.; Itou, T.; Chikiri, H. Einaga, Y.; Teramoto, A. Macromolecules 1989, 22, 973-979.
130. (d) Sato, T.; Teramoto, A. Adv. Polym. Sci. 1996, 126, 85-161.
131. Natsume, T.; Wu, L.; Sato, T.; Terao, K.; Teramoto, A.; Fujiki, M. Macromolecules 2001, 34, 7899-7904.
132. 7 and a polypropargylamide, respectively. For the q value of a polypropargylamide, see: Nomura, R.; Tabei, J.; Nishiura, S.; Masuda, T. Macromolecules 2003, 36, 561-564.
133. 5 and 1.43, respectively, as estimated by atomic force microscopy (AFM) (Figure S5 in the Supporting Information). For the molecular weight determination by AFM, see: (a) Prokhorova, S. A.; Sheiko, S. S.; Möller, M.; Ahn, C.-H.; Percec, V. Macromol. Rapid Commun. 1998, 19, 359-366.
134. (b) Thomas, B. N.; Corcoran, R. C.; Cotant, C. L.; Lindemann, C. M.; Kirsch, J. E.; Persichini. P. J. J. Am. Chem. Soc. 1998, 120, 12178-12186.
135. (c) Börner, H. G.; Beers, K.; Matyjaszewski, K.; Sheiko, S. S.; Möller, M. Macromolecules 2001, 34, 4375-4383.
136. (d) Cornellissen, J. J. L. M.; Graswinckel, W. S.; Adams, P. J. H. M.; Nachtegaal, G. H.; Kentgens, A. P. M.; Sommerdijk, N. A. J. M.; Nolle, R. J. M. J. Polym. Sci., Part A: Polym. Chem. 2001, 39, 4255-4264.
137. n). Moreover, the CD intensity did not change after leaving the sample for 15 days at room temperature. These results suggest that the polymer is quite stable in water. For the thermal stability of poly-(phenylacetylene) derivatives, see: refs 13a, n, and 14a
138. and (f) Morino, K.; Asari, T.; Maeda, K.; Yashima, E. J. Polym. Sci., Part A: Polym. Chem. 2004, 42, 4711-4722.
139. (g) Percec, V.; Rudick, J. G. Macromolecules 2005, 38, 7241-7250.
140. (a) Sato, T.; Nakamura, J.; Teramoto, A.; Green, M. M. Macromolecules, 1998, 31, 1398-1405.
141. (b) Gu, H. Doctoral Thesis, Osaka University, 1997.
142. ∈2nd values were estimated from their intercepts (see Figures S3 and S4 in the Supporting Information).
143. 4e
144. 24 because the amino group of poly-1-HCl must take one of the two following forms: the complex form with 2 (20% ee) and the free ammonium ion in an aqueous solution. The determined /c value thus obtained for the solutions with the polymer concentrations ranging from 0.1 to 1.0 wt % in the presence of 0.1 equiv 2 (20% ee) was almost 0.1 irrespective of the polymer concentration. This indicates that all the 2 (20% ee) in the polymer solution is complexed with the amino groups of the polymer. Because we can expect that the degree of complexation maintains this value with the further increasing polymer concentration under the condition of [2 (20% ee)]/[poly-l-HC1] = 0.1, we concluded that the content of the complexed monomer units in the poly-1-HCl does not depend on the polymer concentration. This is consistent with the polymer concentration independence of the lCD intensity, and furthermore, verifies that the chiral amplification in the LC phase takes place at the constant content of the complexed monomer units in the poly-1-HCl.
145. Kimura, Y.; Sato, T. Polym. J. 2006, 38, 190-196.
146. (a) Khokhlov, A. R.; Semenov, A. N. Physica A 1981, 108, 546-556.
147. (b) Khokhlov, A. R.; Semenov, A. N. Physica A 1982, 112, 605-614.
148. (c) Stroobants, A.; Lekkerkerker, H. N. W.; Odijk, Th. Macromolecules 1986, 19, 2232-2238.
149. (d) Itou, T.; Teramoto, A. Macromolecules 1988, 21, 2225-2230.
150. Onsager, L. Ann. N.Y. Acad. Sci. 1949, 51, 627-659.
151. Recently, we found that helical poly(phenylacetylene)s bearing L- or D- and DL-alanine residues with a long alkyl chain as the pendants form lyotropic cholesteric and nematic LC phases, respectively, in organic solvents due to a rigid-rod helical conformation, and their q values were determined to be ca. 40 and 16 nm, respectively. Okoshi, K.; Sakajiri, K.; Kumaki, J.; Yashima, E. Macromolecules 2005, 38, 4061-4064.
152. Shmueli, U.: Traub, W.; Rosenheck, K. J. Polym. Sci., Part A-2 1969, 7, 515-524.
153. Klemann, B.; West, R.; Koutsky, J. A. Macromolecules 1993, 26, 1042-1046.
154. Very recently, we have proposed a helical structure of poly-(phenylacetylene)s bearing L- or D-alanine residues with a long alkyl chain as the pendants by AFM observations together with their X-ray structural analyses. Sakurai, S.; Okoshi, K.; Kumaki, J.; Yashima, E. Angew. Chem., Int. Ed. 2006, 45, 1245-1248.
155. Any heat treatment of the samples was not performed because the poly-1-HCl is thermally unstable and cis-to-trans isomerization took place at high temperature (> 100 °C), although the poly-1-HCl is quite stable in solution and in the solid state at ambient temperature (2025 °C) for a long time and the diffraction patterns did not change after ca. one month at ambient temperature (20-25 °C).
156. In Figure 3A and B, the WAXD intensities were not perfectly symmetrical and the meridian directions in both the WAXD patterns are not perfectly vertical-aligned. Because the samples were made by piling up several uniaxially oriented, thin, and rectangle-shaped films of ca. 10 mm length, 1.5 mm width, and 0.02 mm thickness (Supporting Information), it was difficult to align perfectly the samples with the orientation axes in each film. In addition, the samples were so soft and flexible and had a slightly arclike shape, which made it difficult to set the oriented samples perfectly normal to the beam, that is, the helical axes of the films were not perfectly parallel to the meridian direction, which may also cause the different pass lengths in the top and bottom half, resulting in slightly dissymmetrical WAXD intensities. Similar dissymmetrical WAXD patterns were reported. For example, see: Miller, R. D.; Farmer, B. L.; Fleming, W.; Sooriya-kumaran, R.; Rabolt, J. J. Am. Chem. Soc. 1987, 109, 2509-2510.
157. As for other helical polymers reported so far, helical chains are often packed with a hexagonal symmetry, but orthorhombic unit cells with hexagonal symmetry like poly-1-HCl have been reported for some helical polymers: for examples, see: (a) Sasaki, S.; Yasumoto, Y.; Uematsu, I. Macromolecules 1981, 14, 1797-1801.
158. (b) Kusanagi, H.; Chatani, Y.; Tadokoro, H. Polymer 1994, 35, 2028-2039.
159. (c) Chatani, Y.; Kobatake, T.; Tadokoro, H.; Tanaka, R. Macromolecules 1982, 15, 170-176.
160. (d) Sasaki, S.; Asakura, T. Macromolecules 2003, 36, 8385-8390.
161. (e) Klemann, B.; West, R.; Koutsky, J. A. Macromolecules 1993, 26, 1042-1046.
162. 3) for this unit cell containing four helices of the poly-1-HCl chain complexed with 0.1 equiv (S)-2. The reason is not clear at the present, but highly disordered location of the 0.1 equiv (S)-2 molecules in the film and NaCl precipitation during the sample preparation, resulting in the formation of defects and giving rise to voids between polymer films and NaCl particles, respectively, should be taken into consideration for the lower observed density of the poly-1-HCl-(S)-2 film.
163. The densities of the poly-1-HCl and poly-1-HCl-(S)-2 ([(S)-2]/[poly1-HCl] = 0.1) films were measured by the standard flotation method in a carbon tetrachloride/n-heptane mixture at ambient temperature (20-25 °C).
164. 37 the rather strong reflection observed in the 8th layer line reflection is not clearly understood.
165. Cochran, W.; Crick, F. H. C.; Vand, V. Acta Crystallogr. 1956, 5, 581-586.
166. 33a-e In this packing mode, the hexagonal symmetry is also maintained. In addition, the systematic absence of the reflections (h + k) odd for hk0, may be reasonable. Such single- and double-helix packing structures must influence the observed X-ray intensities. Further three-dimensional structural refinements including a double helix are in progress.
167. (a) Crick, F. H. C. Acta Crystallogr. 1953, 6, 689-697.
168. (b) Cho, K. C.; Nemethy, G.; Sheraga, H. A. J. Phys. Chem. 1983, 87, 2869-2881.
169. (c) Chothia, C.; Levitt, M.; Richardson, D. Proc. Natl. Acad. Sci. U.S.A. 1977, 74, 4130-4134.
170. (d) Parsons, D. F.; Martius, U. J. Mol. Biol. 1964, 10, 530.
171. (e) Sasaki, S. Polymer 1986, 27, 849-855.
172. (f) Watanabe, J.; Ono, H. Macromolecules 1986, 19, 1079-1083.
173. 41 before and after the preferred-sense helicity induction in a dilute water solution.
174. (a) Lifson, S.; Andreola, C.; Peterson, N.; Green, M. M. J. Am. Chem. Soc. 1989, 111, 8850-8858.
175. (b) Gu, H.; Sato, T.; Teramoto, A.; Varichon, L.; Green, M. M. Polym. J. 1997, 29, 77-84.
176. (c) Selinger, J. V.; Selinger, R. L. B. Phys. Rev. E 1997, 55, 1728-1731.
177. (d) Gu, H.; Sato, T.; Teramoto, A.; Green, M. M.; Jha, S. K.; Andreola, C.; Reidy, M. P. Macromolecules 1998, 31, 6362-6368.
178. (e) Teramoto, A. Prog. Polym. Sci. 2001, 26, 667-720.
179. (f) Morino, K.; Maeda, K.; Okamoto, Y.; Yashima, E.; Sato, T. Chem.-Eur. J. 2002, 8, 5112-5120.
180. Green, M. M.; Reidy, M. P.; Johnson, R. J.; Darling, G.; O'Leary, D. J.; Willson, G. J. Am. Chem. Soc. 1989, 111, 6452-6454.
181. Green, M. M.; Garetz, B. A.; Muñoz, B.; Chang, H.; Hoke, S.; Cooks, R. G. J. Am. Chem. Soc. 1995, 117, 4181-4182.