Hydrogen‐Bond‐Regulated Distinct Functional‐Group Display at the Inner and Outer Wall of Vesicles

Abstract

A unique supramolecular strategy enables the unidirectional assembly of two bola-shaped unsymmetric pamphiphiles, NDI-1 and NDI-2, which feature a naphthalenediimide chromophore connected to nonionic and anionic head groups on opposite arms. The amphiphiles differ only in the location of a hydrazide group, which is placed either on the nonionic or on the anionic arm of NDI-1 and NDI-2, respectively. The formation of hydrogen bonds between the hydrazides, which compensates for electrostatic and steric factors, promotes unidirectional alignment and the formation of monolayer vesicles. The zeta potentials and cation-assisted quantitative precipitation reveal negatively charged and nonionic outer surfaces for NDI-1 and NDI-2, respectively, indicating that hydrogen bonding also dictates the directionality of the monolayer curvature, ensuring that in both cases, the hydrazides remain at the inner wall to benefit from stronger hydrogen bonding where they are in closer proximity. This is reflected in their different abilities to inhibit a-chymotrypsin, which possesses a positively charged surface: NDI-1 induced an inhibition of 80 % whereas hardly any inhibition was observed with NDI-2.

Self-assembly of supra-amphiphiles building block fabricated by β-cyclodextrin and adamantane-based ionic liquid

“…Thus, the zeta potential (z) measurement may be useful to make a thorough inquiry about how the AD-C 11 im@1b-CD molecules arrayed in the vesicle wall. 34,35 Due to AD-C 11 im containing an imidazole group with positive charge, the zeta potential value of micelles formed by AD-C 11 im only was +32.3 mV in aqueous solution when the concentration was 10 mM. However, the z value of vesicles formed by AD-C 11 im@1b-CD at 10 mM was just +10.4 mV, which was much smaller than that of AD-C 11 im.…”

Photochemical Phase Transition Behavior of Supramolecular Polymer with a Triazine Core

“…최근 고분자 및 유기 소재에 관한 연구는 단위 분자 수준 에 직접 기능성을 도입하여 소재가 갖는 기능성을 증가시키 는 방향으로 진행되고 있다. [1][2][3] 특히 그 중에서도 다양한 작용 기가 도입된 초분자 구조체의 물리, 화학적 거동에 관한 연 구는 많은 연구자들의 과제가 되고 있다. 초분자는 단량체의 유기 합성을 통해 기능성 작용기의 도입이 쉽고, 추가적으로 고분자화 과정을 거치지 않아도 되기 때문에 다른 소재에 비 해서 접근성이 상대적으로 높다는 장점이 있다.…”

Precise control over supramolecular nanostructuresviamanipulation of H-bonding in π-amphiphiles

“…In a different design, Ghosh and co-workers demonstrated the effect of the presence/absence and nature of the H-bonding group as well as the precise position of the H-bonding unit on the morphology and functional group display in bola-amphiphilic systems. [42][43][44] Our group has reported a H-bonding-driven co-assembly in adenine and thymine appended amphiphilic block-copolymers and highlighted the effect of complementary multiple H-bonding in controlling the nanostructure morphology and surface chemistry. [45][46][47] Based on these works, we aimed to further explore the effect of multiple H-bonding units on the self-assembly of π-amphiphiles.…”