两亲聚肽/螺烯的电荷复合自组装行为研究

doi:10.6023/cjoc201904038

摘要/Abstract

研究了包含聚肽嵌段的两亲共聚物聚乙二醇-b-聚(L-谷氨酸)(PEG-b-PGlu)与4-甲基-4-氮杂[4]螺烯鎓离子(Me[4]H)的电荷复合自组装行为, 讨论了聚肽链段长度、谷氨酸单元与螺烯物质的量比、pH值等因素对组装体形貌的影响. 研究发现, 当刚-柔型嵌段聚合物与刚性、大尺寸并具有诱导作用的小分子共同组装时, 遵循与柔性大分子电荷复合组装完全不同的规律. PEG-b-PGlu/Me[4]H的电荷复合组装体形貌由π-π堆叠作用、两亲嵌段聚肽的亲疏水比、PGlu链段的刚硬程度共同决定, 这些作用在组装过程中相互制约, 当π-π堆叠作用占主导地位时, 得到以指针状和条带状等平面结构为主的组装形貌.

关键词: 电荷复合自组装, 两亲嵌段共聚物, 螺烯

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

引用此文

王婧琳, 沈程硕, 唐颂超, 姚远. 两亲聚肽/螺烯的电荷复合自组装行为研究[J]. 有机化学, 2019, 39(10): 2973-2979.

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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图/表 13

图式1. PEG-b-PGlu的合成路线

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

表1. PEG45-b-PBLGn的参数

Table 1. Parameters of PEG45-b-PBLGn

图1. 不同疏水嵌段长度的PEG-b-PGlu与Me[4]H在水中电荷复合自组装的TEM照片(pH=6.0, 羧基与鎓离子之比为1∶0.5)

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

表2. 不同疏水嵌段长度的PEG-b-PGlu与Me[4]H在水中电荷复合自组装的ζ-电位值(pH=6.0, 羧基与鎓离子之比为1∶0.5)

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)

图2. PEG-b-PGlu与Me[4]H电荷复合自组装为长指针状的组装体示意图

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

图3. PEG45-b-PGlu10与Me[4]H的不同物质的量比下在水中电荷复合自组装的TEM照片(pH=6.0)

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

图4. PEG45-b-PGlu10与Me[4]H的不同物质的量比下在水中电荷复合自组装的圆二色谱图(pH=6.0)

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

表3. PEG45-b-PGlu10与Me[4]H的不同物质的量比下在水中电荷复合自组装的ζ-电位值(pH=6.0)

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)

图5. PEG45-b-PGlu24与Me[4]H的不同物质的量比下在水中电荷复合自组装的TEM照片(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

图6. PEG45-b-PGlu24与Me[4]H的不同物质的量比下在水中电荷复合自组装的圆二色谱图(pH=6.0)

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

表4. PEG45-b-PGlu24与Me[4]H的不同物质的量比下在水中电荷复合自组装的ζ-电位值(pH=6.0)

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)

图7. PEG45-b-PGlu24与Me[4]H在pH值不同的水中电荷复合自组装的TEM照片(羧基与鎓离子之比为1∶0.5)

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

表5. PEG45-b-PGlu24与Me[4]H在不同pH值的水中电荷复合自组装的ζ-电位值(羧基与鎓离子之比为1∶0.5)

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)

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