Understanding the Impact of Polymer Architecture and Solvophobic Sequences on the Self assembly Behaviour in Solution and at Liquid Crystal water Interfaces

Abstract

Nature exemplifies the extraordinary phenomenon of self-assembly, encompassing the intricate newlinefolding of proteins and the assembly of cells into complex structures. Over the years, extensive newlineresearch has focused on the self-assembly of synthetic and macromolecular systems driven by newlinevarious noncovalent interactions. Among these, self-assembly of amphiphilic copolymers newlinestands out as a versatile platform for engineering nanomaterials with diverse structures and newlinefunctionalities. Amphiphilic molecules, featuring both hydrophilic and lipophilic segments, newlinecan form a variety of 3D morphologies mainly driven by hydrophobic effects. Copolymers of newlinesolvophobic monomers are commonly used for designing amphiphilic polymers (Block, newlinerandom etc.). Block copolymers are extensively studied for their well-defined structure and newlineefficient self-assembly, but their sequential monomer addition is impractical for large-scale newlineapplications. The self-assembly of random copolymers offers a unique opportunity for creating newlinetunable and dynamically responsive structures. Although they require substantial chain newlinereconfiguration, these amphiphiles are cost-effective and easily scalable. Their less ordered newlineprimary structure enables dynamic morphological transitions and responsiveness to external newlinestimuli. The intricate interplay of factors such as HLB, polymerization degree, pendant length, newlineand solvent properties influences the morphology of the self-assembled structures. Recent newlineinnovative designs such as grafted copolymers, amphiphiles with alternating sequences, and newlinedouble-brush copolymers have further expanded the possibilities in this field. Furthermore, the newlineimpact of amphiphile topology on self-assembly has garnered considerable interest, making newlinethis area of research increasingly compelling. This work aims to examine how the polymer newlinearchitecture (linear/branched) affects the reorganization of randomly grafted amphiphilic newlinecopolymers into nanoaggregates and their photo-responsive behaviour. An Azo-chromophore newlinewas integrated into the hydrophobic segm