Study of Charge-Conjugated Self-Assembly Behavior of Amphiphilic Block Copolypeptides/Helicene

doi:10.6023/cjoc201904038

Chinese Journal of Organic Chemistry ›› 2019, Vol. 39 ›› Issue (10): 2973-2979.DOI: 10.6023/cjoc201904038 Previous Articles Next Articles

Special Issue: 有机超分子化学合辑

NOTES

两亲聚肽/螺烯的电荷复合自组装行为研究

王婧琳^a, 沈程硕^b, 唐颂超^a^*(), 姚远^a^*()

a 华东理工大学材料科学与工程学院高分子材料与工程教研室上海 200237
b 上海交通大学化学化工学院上海 200240

收稿日期:2019-04-15 修回日期:2019-05-07 发布日期:2019-05-21
通讯作者: 唐颂超,姚远 E-mail:schtang@ecust.edu.cn;yaoyuan@ecust.edu.cn
基金资助:
国家自然科学基金(No. 51573088)

Study of Charge-Conjugated Self-Assembly Behavior of Amphiphilic Block Copolypeptides/Helicene

Wang, Jinglin^a, Shen, Chengshuo^b, Tang, Songchao^a^*(), Yao, Yuan^a^*()

a Teaching and Research Department of Polymer Materials and Engineering, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237
b School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240

Received:2019-04-15 Revised:2019-05-07 Published:2019-05-21
Contact: Tang, Songchao,Yao, Yuan E-mail:schtang@ecust.edu.cn;yaoyuan@ecust.edu.cn
Supported by:
Project supported by the National Natural Science Foundation of China(No. 51573088)

Amphiphilic block copolypeptides of polyethylene glycol-b-poly(L-glutamic acid) (PEG-b-PGlu) were synthesized to self-assemble with 4-methyl-4-aza[4]helicene onium ion (Me[4]H) in water through charge-conjugation. The morphology of the assemblies was studied by varying PGlu block length, the molar ratio of Glu unit/Me[4]H and pH value. It was found that when rigid-flexible block copolymers were assembled together with small molecules which had rigid, large size and inductive effect, they would follow a completely different law from the charge-conjugated assembly of flexible macromolecules. The self-assemblies were controlled by the π-π stacking of helicene, together with the volume fraction of the hydrophobic parts and the rigidity of PGlu segments. These effects restricted each other in the assembly process. When π-π stacking was dominant, assembly morphologies with pointer-like and strip-like planar structures were obtained.

Key words: charge-conjugated self-assembly, amphiphilic block copolymer, helicene

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Wang, Jinglin, Shen, Chengshuo, Tang, Songchao, Yao, Yuan. Study of Charge-Conjugated Self-Assembly Behavior of Amphiphilic Block Copolypeptides/Helicene[J]. Chinese Journal of Organic Chemistry, 2019, 39(10): 2973-2979.

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Fig. & Tab. 13

Scheme 1. Synthetic route of PEG-b-Pglu

Copolymer	M_n_(exp)^a (×10⁴)	M_n_(obt)^b (×10⁴)	DP_exp,PBLG^c	DP_obt,PBLG^d	PDI
PEG₄₅-b-PBLG₁₀	0.38	0.40	10	10	1.13
PEG₄₅-b-PBLG₂₄	0.58	0.66	20	24	1.18
PEG₄₅-b-PBLG₃₆	0.83	0.89	30	36	1.19
PEG₄₅-b-PBLG₅₀	1.10	1.17	50	50	1.06
PEG₄₅-b-PBLG₇₁	1.44	1.57	70	71	1.08

Table 1. Parameters of PEG45-b-PBLGn

Figure 1. TEM images of the self-assembly of PEG-b-PGlu with various hydrophobic block lengths charge-conjugated Me[4]H in water (pH=6.0, carboxyl group and onium ion ratio is 1∶0.5) (A) PEG45-b-PGlu10; (B) PEG45-b-PGlu24; (C) PEG45-b-PGlu36; (D) PEG45-b-PGlu50; (E) PEG45-b-PGlu71; (F) Me[4]H as a comparison

n^a	ζ-Potential/mV
10	–5.74
24	–7.19
36	–2.45
50	–1.56
71	–1.03

Table 2. ζ-Potential values of self-assembly of PEG-b-PGlu with various hydrophobic block lengths charge-conjugated Me[4]H in water (pH=6.0, carboxyl group and onium ion ratio is 1∶0.5)

Figure 2. Charge-conjugated self-assembly of PEG-b-PGlu and Me[4]H into long pointer-like morphology

Figure 3. TEM images of the self-assembly of PEG45-b-PGlu10 charge-conjugated Me[4]H with different molar ratios in water (pH=6.0) (A) 1∶0.1; (B) 1∶0.2; (C) 1∶0.5; (D) 1∶0.7; (E) 1∶1.0

Figure 4. CD spectra of self-assembly of PEG45-b-PGlu10 charge-conjugated Me[4]H with different molar ratios in water (pH=6.0)

Glu∶Me[4]H	ζ-Potential/mV
1∶0.1	–12.31
1∶0.2	–9.85
1∶0.5	–5.74
1∶0.7	–4.94
1∶1.0	–.72

Table 3. ζ-Potential values of self-assembly of PEG45-b-PGlu10 charge-conjugated Me[4]H with different molar ratios in water (pH=6.0)

Figure 5. TEM images of the self-assembly of PEG45-b-PGlu24 charge-conjugated Me[4]H with different molar ratios in water (pH=6.0) (A) 1∶0.1; (B) 1∶0.2; (C) 1∶0.5; (D) 1∶0.7; (E) 1∶1.0

Figure 6. CD spectra of self-assembly of PEG45-b-PGlu24 charge-conjugated Me[4]H with different molar ratios in water (pH=6.0)

Glu∶Me[4]H	ζ-Potential/mV
1∶0.1	–19.10
1∶0.2	–15.13
1∶0.5	–7.19
1∶0.7	–6.83
1∶1.0	–4.42

Table 4. ζ-Potential values of self-assembly of PEG45-b-PGlu24 charge-conjugated Me[4]H with different molar ratios in water (pH=6.0)

Figure 7. TEM images of the self-assembly of PEG45-b-PGlu24 charge-conjugated Me[4]H in water of different pH values (carboxyl group and onium ion ratio is 1∶0.5) (A) pH=3.0; (B) pH=4.0; (C) pH=5.0; (D) pH=6.0; (E) pH=7.5; (F) pH=8.5

pH	ζ-Potential/mV
3.0	–1.46
4.0	–4.34
5.0	–6.48
6.0	–7.19
7.5	–10.03
8.5	–15.93

Table 5. ζ-Potential values of self-assembly of PEG45-b-PGlu24 charge-conjugated Me[4]H in water of different pH values (carboxyl group and onium ion ratio is 1∶0.5)

References 39

[1]	Gröhn, F. Soft Matter 2010, 6, 4296. doi: 10.1039/c0sm00411a
[2]	Rybtchinski, B. ACS Nano 2011, 5, 6791. doi: 10.1021/nn2025397
[3]	Faul, C. F. Acc. Chem. Res. 2014, 47, 3428. doi: 10.1021/ar500162a
[4]	Kim, B. G.; Kim, M. S.; Kim, J . ACS Nano 2010, 4, 2160. doi: 10.1021/nn901568w
[5]	Malinsky, J. E.; Jabbour, G. E.; Shaheen, S. E.; Anderson, J. D.; Richter, A. G.; Marks, T. J.; Armstrong, N. R.; Kippelen, B.; Dutta, P.; Peyghambarian, N . Adv. Mater. 1999, 11, 227. doi: 10.1002/(ISSN)1521-4095
[6]	Palma, A.; Satta, M. J. Chem. Theory Comput. 2016, 12, 4042. doi: 10.1021/acs.jctc.6b00430
[7]	Li, Y.; Zhang, X.; Cao, D. J. Phys. Chem. B 2013, 117, 6733. doi: 10.1021/jp312124x
[8]	Zhao, Y.; Mei, L.; Lu, Q . Langmuir 2008, 24, 3937. doi: 10.1021/la703673s
[9]	Wicklein, A.; Ghosh, S.; Sommer, M.; Würthner, F.; Thelakkat, M . ACS Nano 2009, 3, 1107. doi: 10.1021/nn9001165
[10]	Wang, C.; Guo, Y.; Wang, Z.; Zhang, X . Langmuir 2010, 26, 14509. doi: 10.1021/la102586b
[11]	Yao, Y.; Zhang, L.; Leydecker, T.; Samorì, P. J. Am. Chem. Soc. 2018, 140, 6984. doi: 10.1021/jacs.8b03526
[12]	Liu, W.; Liu, J.; Liu, W.; Li, T. J. Agric. Food Chem. 2013, 61, 4133. doi: 10.1021/jf305329n
[13]	Omura, Y.; Kyung, K. H.; Shiratori, S.; Kim, S. H. Ind. Eng. Chem. Res. 2014, 53, 11727. doi: 10.1021/ie403736r
[14]	Fang, R.; Zhang, H.; Yang, L.; Wang, H.; Tian, Y.; Zhang, X.; Jiang, L. J. Am. Chem. Soc. 2016, 138, 16372. doi: 10.1021/jacs.6b09601
[15]	Pappa, A. M.; Inal, S.; Roy, K.; Zhang, Y. ACS Appl. Mater. Inter. 2017, 9, 10427. doi: 10.1021/acsami.6b15522
[16]	Dochter, A.; Garnier, T.; Pardieu, E.; Chau, N. T. T.; Maerten, C.; Senger, B.; Schaaf, P.; Jierry, L.; Boulmedais, F . Langmuir 2015, 31, 10208. doi: 10.1021/acs.langmuir.5b02749
[17]	Bianchi, R. C.; Silva, E. R. D.; Antonia, L. H. D.; Ferreira, F. F.; Alves, A. W . Langmuir 2014, 30, 11464. doi: 10.1021/la502315m
[18]	Deng, T.; Wang, J.; Li, Y. Y.; Han, Z. H.; Peng, Y. N.; Zhang, J.; Gao, Z.; Gu, Y. Q.; Deng, D. W. ACS Appl. Mater. Interfaces 2018, 10, 27657. doi: 10.1021/acsami.8b08512
[19]	Huang, X. H.; Jeong, Y. I.; Moon, B. K.; Zhang, L. D.; Kang, D. H.; Kim, I . Langmuir 2013, 29, 3223. doi: 10.1021/la305069e
[20]	Bui, L.; Abbou, S.; Ibarboure, E.; Guidolin, N.; Staedel, C.; Toulme, J. J.; Schatz, C. J. Am. Chem. Soc. 2012, 134, 20189. doi: 10.1021/ja310397j
[21]	Kumar, R. J.; Macdonald, J. M.; Singh, T. B.; Waddington, L. J.; Holmes, A. B. J. Am. Chem. Soc. 2011, 133, 8564. doi: 10.1021/ja110858k
[22]	Zhang, Y.; Yin, Q.; Lu, H.; Xia, H.; Lin, Y.; Cheng, J. ACS Macro Lett. 2013, 2, 809. doi: 10.1021/mz4003672
[23]	Shaikh, A. Y.; Das, S.; Pati, D.; Dhaware, V.; Sen, G. S.; Hotha, S . Biomacromolecules 2014, 15, 3679. doi: 10.1021/bm5009537
[24]	Ramasamy, T.; Choi, J. Y.; Cho, H. J.; Umadevi, S. K.; Shin, B. S.; Choi, H. G.; Yong, C. S.; Kin, J. O . Pharm. Res. 2015, 32, 1947. doi: 10.1007/s11095-014-1588-8
[25]	He, W.; Yan, J.; Jiang, W.; Li, S.; Qu, Y.; Niu, F.; Yan, Y.; Sui, F.; Wang, S.; Zhou, Y.; Jin, L.; Li, Y.; Ji, M.; Ma, P. X.; Liu, W.; Hou, P . Chem. Mater. 2018, 30, 7034. doi: 10.1021/acs.chemmater.8b02572
[26]	Yan, J.; Korolev, N.; Eom, K. D.; Tam, J. P.; Nordenskiöld, L . Biomacromolecules 2012, 13, 124. doi: 10.1021/bm201359r
[27]	Nishimura, T.; Yamada, A.; Umezaki, K.; Sawada, S. I.; Mukai, S. A.; Sasaki, Y.; Akiyoshi, K . Biomacromolecules 2017, 18, 3913. doi: 10.1021/acs.biomac.7b00937
[28]	Ryu, K.; Lee, M.; Park, J.; Kim, T. ACS Appl. Bio. Mater. 2018, 1, 1496. doi: 10.1021/acsabm.8b00428
[29]	Zhang, S.; Cai, C.-H.; Huang, Q.-J.; Lin, J.-P.; Xu, Z.-W . Acta Polym. Sin. 2018,109(in Chinese).
	( 张朔, 蔡春华, 黄琦婧, 林嘉平, 徐占文 , 高分子学报, 2018,109.)
[30]	Hu, Y.; Lin, R.; Zhang, P.; Fern, J.; Cheetham, A. G.; Patel, K.; Schulman, R.; Kan, C.; Cui, H . ACS Nano 2015, 10, 880. doi: 10.1021/acsnano.5b06011
[31]	Schuster, N. J.; Hernández, S. R.; Bukharina, D.; Kotov, N. A.; Berova, N.; Nq, F.; Steiqerwald, M. L.; Nuckolls, C. J. Am. Chem. Soc. 2018, 140, 6235. doi: 10.1021/jacs.8b03535
[32]	Nishiyma, N.; Okazaki, S.; Cabral, H.; Miyamto, M.; Kato, Y.; Suqiyama, Y.; Nishio, K.; Matsumura, Y.; Kataoka, K . Cancer Res. 2003, 63, 8977.
[33]	Lv, S.; Li, M.; Tang, Z.; Song, W.; Sun, H.; Liu, H.; Chen, X . Acta Biomater. 2013, 9, 9330. doi: 10.1016/j.actbio.2013.08.015
[34]	Song, W.; Tang, Z.; Li, M.; Lv, M.; Sun, H.; Deng, M.; Liu, H.; Chen, X . Acta Biomater. 2014, 10, 1392. doi: 10.1016/j.actbio.2013.11.026
[35]	Verbiest, T.; Elshocht, S. V.; Kauranen, M.; Hellemans, L.; Snauwaert, J.; Nuckolls, C.; Katz, T. J.; Persoons, A . Science 1999, 561, 913.
[36]	Fang, L.; Lin, W.-B.; Shen, Y.; Chen, C.-F. Chin. J. Org. Chem. 2018, 38, 541 (in Chinese). doi: 10.6023/cjoc201710028
	( 房蕾, 林伟彬, 沈赟, 陈传峰, 有机化学, 2018, 38, 541.) doi: 10.6023/cjoc201710028
[37]	Kaseyama, T.; Furumi, S.; Zhang, X.; Takeuchi, M. Angew. Chem., Int. Ed. 2011, 123, 3768. doi: 10.1002/ange.201007849
[38]	Hewlins, M, J, E.; Salter, R . Synthesis 2007,2164.
[39]	Yao, Y.; Li, W. W.; Wang, S. B.; Yan, D. Y.; Chen, X. S . Macromol. Rapid Commun. 2006, 27, 2019. doi: 10.1002/(ISSN)1521-3927

两亲聚肽/螺烯的电荷复合自组装行为研究

Study of Charge-Conjugated Self-Assembly Behavior of Amphiphilic Block Copolypeptides/Helicene

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Fig. & Tab. 13

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