Effect of Phosphotungstic Acid on Self-seeding of Oligo(p-phenylenevinylene)-b-poly(2-vinylpyridine)※

doi:10.6023/A21120557

Abstract

Self-seeding route of living crystallization-driven self-assembly with merits of easily-handling and excellent compatibility with various block copolymers (BCPs) has been considered as one of the most important strategies to generate uniform nanofibers of controlled length and composition. Polyoxometalates with unique structure and shape are usually endowed with attractive electric/magnetic/optical properties. Herein, the influence of phosphotungstic acid (H₃O₄₀PW₁₂) on the self-seeding of oligo(p-phenylenevinylene)-b-poly(2-vinylpyridine) (OPV₅-b-P2VP₄₂, the subscripts represent the number of repeat unit of each block) was systematically examined aiming to get more insight on the effect of polyoxometalates on living crystallization-driven self-assembly. Uniform fiber-like micelles of OPV₅-b-P2VP₄₂ are formed with addition of different molar ratios of phosphotungstic acid to pyridyls of P2VP, α_acid/v, from 0 to 0.20. The percentage of surviving seed micelles decreased exponentially with increasing annealing temperature regardless of α_acid/v from 0 to 0.10, demonstrating the typical characteristics of self-seeding behaviors. The most striking finding of this work is that the resistance of seed micelles toward the dissolution upon annealing is enhanced significantly with the increasing of α_acid/v, leading to the formation of shorter fiber-like micelles with a higher α_acid/v. For example, fiber-like micelles with average length of 1325, 232, 137 and 73 nm were formed with α_acid/v of 0, 0.01, 0.05 and 0.10, respectively, upon the heating of seed micelles of OPV₅-b-P2VP₄₂ with average length of 22 nm at 60 ℃ for 45 min, followed by cooling/aging at 30 ℃ for 24 h. It is likely that the coordination, instead of hydrogen bonding interaction, between phosphotungstic acid and pyridyls, contributes to the enhancement of resistance of seed micelles toward the dissolution. The tight and multi-dentate coordination between phosphotungstic acid and pyridyls of P2VP chains would make the P2VP chain crosslink. The crosslinking would weaken the repulsion within P2VP chains and increase the energy for the dissolution of micelles. This work not only provides more information to deepen our understanding on the influence of nature of corona chains on living crystallization-driven self-assembly (CDSA), especially self-seeding process, but also presents a new platform to generate uniform hybrid polyoxometalate/polymer nanofibers of controlled length.

Key words: living crystallization-driven self-assembly, self-seeding, nanofiber, polyoxometalate, π-conjugated polymer

Cite this article

Zhiqin Wang, Bo Xiang, Xiaoyu Huang, Guolin Lu. Effect of Phosphotungstic Acid on Self-seeding of Oligo(p-phenylenevinylene)-b-poly(2-vinylpyridine)^※[J]. Acta Chimica Sinica, 2022, 80(3): 297-302.

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Fig. & Tab. 5

Figure 1. Schematic illustration of structures of OPV5-b-P2VP42 and phosphotungstic acid

Figure 2. TEM images of (A) seed micelles of OPV5-b-P2VP42 (0.05 mg/mL in ethanol) and obtained fiber-like micelles by self-seeding with annealing temperature of 50 ℃ and αacid/v of (B) 0, (C) 0.03 and (D) 0.15, (E) dependence of Ln of obtained fiber-like micelles and (F) corresponding Ps on αacid/v in self-seeding of OPV5-b-P2VP42 with annealing temperature of 50 ℃

Figure 3. TEM images of fiber-like micelles of OPV5-b-P2VP42 obtained by self-seeding with annealing temperature of 60 ℃ and αacid/v of (A) 0, (B) 0.01, (C) 0.05 and (D) 0.10, (E) dependence of Ln of obtained fiber-like micelles and (F) corresponding Ps on annealing temperature in self-seeding with different αacid/v of 0, 0.01, 0.05 and 0.10

Figure 4. TEM images of the micelles formed by annealing the OPV5-b-P2VP42 seed solution (0.05 mg/mL in ethanol) at 55 ℃, followed by aging at 30 ℃ for 24 h with addition of citric acid with αacid/v of (A) 0, (B) 0.01, (C) 0.05, (D) 0.10, (E) 0.15 and (F) 0.20, (G) dependence of Ln of obtained fiber-like micelles and corresponding Ps on αacid/v of citric acid for self-seeding of OPV5-b-P2VP42 (0.05 mg/mL in ethanol) with annealing temperature of 55 ℃ and (H) photograph of ethanol solution of P2VP (0.05 mg/mL) with addition of different amount of phosphotungstic acid

Scheme 1. Schematic illustration of self-seeding of OPV5-b-P2VP42 in the presence of phosphotungstic acid

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