Supramolecular assembly of helical homopolymers to form stable chiral entities in water is highly valuable for creating chiral nanostructures and fabricating chiral biomaterials. Here we report on thermally induced supramolecular assembly of helical dendronized poly(phenylacetylene)s (PPAs) in aqueous solutions, and their in-situ photo-crosslinking at elevated temperatures to afford crosslinked nano-assemblies with hierarchical structures and stabilized helicities. These helical dendronized homopolymers carry cinnamate-cored dendritic oligoethylene glycol (OEG) pendants, which exhibit characteristic thermoresponsive behavior. Their thermal aggregation confers hexagonal packing of the polymer chains, and simultaneously resulting in enhancement of their chiralities. Assisted by radial amphiphilicity and worm-like molecular geometry, these dendronized PPAs form supramolecular twisted fibers, spheroid particles or toroids via thermal aggregation. Through UV photoirradiation above their cloud points (Ts), cycloaddition of cinnamate moieties from the dendritic pendants promotes intermolecular crosslinking of dendronized PPA chains within the thermal aggregates, and simultaneously, the dynamic morphologies and supramolecular chirality from the dendronized PPAs through thermally induced aggregation can be fixed. In addition, photo-crosslinking can be occurred solely within individual aggregates due to the protection of densely packed dendritic OEGs. Therefore, various crosslinked assemblies from the dendronized homopolymers with tailorable morphologies and stabilized chirality are fabricated by tuning their thermally induced dynamic aggregations followed by in-situ photo-crosslinking. We believe that this work paves a convenient route to fabricate chiral assemblies with stabilized morphologies and fixed chiralities from dynamic helical homopolymers through intermolecular crosslinking, which can be promising for various chiral applications.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1016/j.jcis.2024.08.001 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Smart β-cyclodextrin-dominated helical supramolecular dendritic assemblies improve the foliar affinity and biofilm disruption for treating alarming bacterial diseases.
Carbohydr Polym
January 2025
State Key Laboratory of Green Pesticide, Key Laboratory of Green Pesticide and Agricultural Bioengineering, Ministry of Education, Center for Research and Development of Fine Chemicals of Guizhou University, Guiyang 550025, China. Electronic address:
Recent outbreaks of alarming bacterial diseases have significantly impacted global agricultural productivity. Conventional bactericides exhibit certain limitations in efficiently impeding biofilm formation and annihilating biofilm-dispersed pathogens, and often expose to high off-target movement during foliar spraying. Here, we produce an innovative helical dendrimer-like supramolecular material (PhA28@β-CD) assembled by a bioactive small-molecule 2-chlorophenylisopropanolamine (PhA28) and β-cyclodextrin (β-CD) through host-guest recognition principle.
View Article and Find Full Text PDFUnwinding Spherical Helices Increases Entropy and Stability of Frank-Kasper and Body-Centered-Cubic Periodic Arrays To Facilitate Discrimination between Self-Organization Mechanisms.
J Am Chem Soc
November 2024
Roy & Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6323, United States.
Spherical supramolecular dendrimers including helical, self-organize soft Frank-Kasper, other cubic such as body-centered cubic, and quasicrystal periodic and quasiperiodic arrays. When any of these periodic or quasiperiodic arrays forms immediately above a columnar phase, a supramolecular orientational memory effect was found to discriminate between mechanisms of self-organization of supramolecular spheres and generate unprecedented periodic arrays of helical columns which cannot be constructed by any other methodology. Here, we demonstrate that unwinding spherical helices, via their precursor nonhelical columns, increases the entropy and stability of their periodic and quasiperiodic spherical arrays and places the Frank-Kasper and other cubic phases immediately above the columnar phase.
View Article and Find Full Text PDFPorous helical supramolecular columns self-organized the fluorophobic effect of a semifluorinated tapered dendron.
J Mater Chem B
December 2024
Roy & Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6323, USA.
The self-organizable dendron (4-3,4-3,5)12G2X with X = -CO2CH3 and -CH2OH, an already classic dendron, facilitating the formation of a large diversity of columnar hexagonal phases including crystalline, with intracolumnar order, and liquid crystalline, and providing access for the first time to mimics of the transmembrane protein water channel Aquaporin was semifluorinated at eight of the sp hybridized carbons of its alkyl groups to provide (4-3,4-3,5)4F8G2X. The self-organization of (4-3,4-3,5)4F8G2X was analyzed by a combination of oriented fiber intermediate angle X-ray scattering, wide angle X-ray scattering, electron density maps, and reconstructed X-ray diffractograms by emplying molecular models. These experiments demonstrated that fluorophobic effect of (4-3,4-3,5)4F8G2X mediated mostly the helical confiormation of the fluorinated fragments sharper miocrosegregation of the fluorinated fragments in the most ordered states of the resulting 12 helical porous columns.
View Article and Find Full Text PDFHierarchical Self-Organization and Disorganization of Helical Supramolecular Columns Mediated by H-Bonding and Shape Complementarity.
J Am Chem Soc
October 2024
Roy & Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6323, United States.
H-bonding, shape complementarity, and quasi-equivalence are widely accepted as some of the most influential molecular recognition events mediating biological and synthetic self-organizations. H-bonds are weaker than ionic but stronger than van der Waals forces. However, the directionality of H-bonds makes them the most powerful among all nonbonding interactions.
View Article and Find Full Text PDFHierarchical assembly of thermoresponsive helical dendronized poly(phenylacetylene)s through photo-crosslinking of the thermal aggregates.
J Colloid Interface Sci
January 2025
International Joint Laboratory of Biomimetic and Smart Polymers, School of Materials Science and Engineering, Shanghai University, Mailbox 152, 99 Shangda Road, Shanghai 200444, China.
Supramolecular assembly of helical homopolymers to form stable chiral entities in water is highly valuable for creating chiral nanostructures and fabricating chiral biomaterials. Here we report on thermally induced supramolecular assembly of helical dendronized poly(phenylacetylene)s (PPAs) in aqueous solutions, and their in-situ photo-crosslinking at elevated temperatures to afford crosslinked nano-assemblies with hierarchical structures and stabilized helicities. These helical dendronized homopolymers carry cinnamate-cored dendritic oligoethylene glycol (OEG) pendants, which exhibit characteristic thermoresponsive behavior.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!