Self-Assembly of Bispentadecylphenol Substituted Perylenediimide with PS-b-P4VP for Structure–Property Insight into the Core of Core–Shell Micelles

Abstract

We report the use of a ditopic molecular probe bispentadecylphenol substituted perylenediimide (PBI–PDP) to examine the molecular level self-assembly of polystyrene-b-poly­(4-vinylpyridine) (PS-b-P4VP) in tetrahydrofuran (THF). A series of complexes were prepared between PS-b-P4VP copolymers with varying lengths of the 4-vinylpyridine chain and PBI–PDP. Light scattering and NMR spectroscopic studies reveal that the self-assembled structures of the solid complexes are not fully disrupted when the complexes are dissolved in THF. NMR experimental parameters measured for the small probe molecule provide detailed insights into the structure of the assemblies in solution as well as the interaction between the small molecule and the block copolymer. Such insights can have important implications in manipulating the nanostructure of block copolymer micelles to suit various application requirements. The dynamics and distribution of the PBI–PDP molecules within the assemblies in solution show a dependence on the length of the P4VP block. Transmission electron microscopy was employed to study the evolution of morphologies in films prepared from the self-assembled structures in THF solutions.

Enantioselective Separation of Amino Acids Using Chiral Polystyrene Microspheres Synthesized by a Post-Polymer Modification Approach

“…The biochemistry-grade amino acids such as d / l -leucine and d / l -alanine were purchased from Spectrochem Pvt., Ltd., India. The RAFT agent was previously synthesized in the laboratory and was used directly without further purification . Phthalic anhydride and hydrazine hydrate were purchased from Sigma-Aldrich.…”

Computational and experimental studies on the micellar morphology and emission mechanisms of AIE and H-bonding fluorescent composites

“…16,17 In addition to external factors (temperature and pH), the nature of the self-assembly behaviors depends primarily on the Flory-Huggins parameter (c) of each block with the solvent, and block length, volume fraction, the dispersity index (DI) of polymer, as well as selective solvent [18][19][20] and hydrogen bonds. 21,22 Poly(styrene-block-4-vinylpyridine) (PSb-P4VP) is among the most studied block copolymers due to the versatility of the P4VP block, 23 especially, the P4VP block can act as a hydrogen (H)-bond proton acceptor so that PS-b-P4VP becomes an popular amphiphilic block copolymer in solution state self-assembly. Extensive work has been done on the selfassembly of PS-b-P4VP with small molecule through Hbonding, ionic interaction, and halogen bonding to form functional materials that have a morphological change with the volume fraction of P4VP block as well as owing to solvent vapor annealing.…”

“…Extensive work has been done on the selfassembly of PS-b-P4VP with small molecule through Hbonding, ionic interaction, and halogen bonding to form functional materials that have a morphological change with the volume fraction of P4VP block as well as owing to solvent vapor annealing. 23 Some researchers have reported the aggregation behavior of P4VP block with other molecules via hydrogen bonding with the pyridine nitrogen of 4VP. 3,23 Kuo and coworkers investigated diblock copolymer/homopolymer blends of poly(methyl methacrylate-b-4-vinylpyridine)/poly vinylphenol (PMMA-b-P4VP/PVPh), where PVPh acted as H-bond donor and PMMA and P4VP as H-bond acceptors.…”

“…23 Some researchers have reported the aggregation behavior of P4VP block with other molecules via hydrogen bonding with the pyridine nitrogen of 4VP. 3,23 Kuo and coworkers investigated diblock copolymer/homopolymer blends of poly(methyl methacrylate-b-4-vinylpyridine)/poly vinylphenol (PMMA-b-P4VP/PVPh), where PVPh acted as H-bond donor and PMMA and P4VP as H-bond acceptors. Based on the different Hbonding strength between the binary pairs of PVPh/P4VP and PVPh/PMMA, short range ordered self-assembled structures were formed for pure PMMA-b-P4VP copolymer and for its blends with PVPh at lower concentrations, whereas miscible disordered structures were found at higher PVPh concentrations because the OH units of PVPh could both interact with P4VP and PMMA segments.…”

“…And the insights could have important implications in tuning the block copolymer micellar structures to suit various application requirements. 23 Although many experimental studies have been done, 24,25 the difficulties in characterization limited the ne understanding of the structure-property control of the self-assembled uorescent composites (SAFCs). Yet, thoroughly understanding the underlying factors that determines the self-assembled structures is essential to help design new materials and nano-devices.…”