Dynamic Implications of Noncovalent Interactions in Amphiphilic Single-Chain Polymer Nanoparticles DOI

Peter A. Dykeman-Bermingham,

Laura R. Stingaciu, Changwoo Do

et al.

ACS Macro Letters, Journal Year: 2024, Volume and Issue: 13(7), P. 889 - 895

Published: July 3, 2024

Single-chain polymer nanoparticles (SCNPs) combine the chemical diversity of synthetic polymers with intricate structure biopolymers, generating versatile biomimetic materials. The mobility chain segments at length scales similar to secondary structural elements in proteins is critical SCNP and thus function. However, influence noncovalent interactions used form SCNPs (e.g., hydrogen-bonding secondary-like structure) on these conformational dynamics challenging quantitatively assess. To isolate effects dynamics, we synthesized a series amphiphilic copolymers containing dimethylacrylamide monomers capable forming different interactions: (1) di(phenylalanine) acrylamide that forms intramolecular β-sheet-like cross-links, (2) phenylalanine hydrogen-bonds but lacks defined local structure, (3) benzyl has lowest propensity for hydrogen-bonding. Each formed folded structures comparable those intrinsically disordered proteins, as observed by size exclusion chromatography small angle neutron scattering. polymers, characterized combination dynamic light scattering spin echo spectroscopy, was well described using Zimm internal friction (ZIF) model, highlighting role each interaction additively restrict relaxations SCNPs. These results demonstrate utility scale control guiding design functional materials refined binding sites tunable kinetics.

Language: Английский

Artificial Photosynthases: Single-Chain Nanoparticles with Manifold Visible-Light Photocatalytic Activity for Challenging “in Water” Organic Reactions DOI Creative Commons

Davide Arena,

Ester Verde‐Sesto, Iván Rivilla

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(21), P. 14397 - 14403

Published: April 19, 2024

Photocatalyzed reactions of organic substances in aqueous media are challenging transformations, often because scarce solubility substrates and catalyst deactivation. Herein, we report single-chain nanoparticles, SCNPs, capable efficiently catalyzing four different "in water" by employing visible light as the only external energy source. Specifically, decorated a high-molecular-weight copolymer, poly(OEGMA300-r-AEMA), with iridium(III) cyclometalated complex pendants at varying content amounts. The isolated functionalized copolymers demonstrated self-assembly into noncovalent, amphiphilic SCNPs water, which enabled efficient visible-light photocatalysis two unprecedentedly reported namely, [2 + 2] photocycloaddition vinyl arenes α-arylation N-arylamines. Additionally, aerobic oxidation 9-substituted anthracenes β-sulfonylation α-methylstyrene were successfully carried out media. Hence, merging metal-mediated for fabrication artificial photoenzyme-like nano-objects─i.e., photosynthases (APS)─our work broadens possibilities performing transformations via photocatalysis.

Language: Английский

Citations

11
Triarylmethyl Cations as Photocatalysts for Radical-Mediated Cycloaddition Reactions DOI

Tomoya Hisada,

Kazuyuki Maeda, Yasuhiro Yamashita

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: April 14, 2025

We have developed a novel photocatalytic system using readily available triarylmethyl cations for radical-mediated (4 + 2) and (2 cycloaddition reactions. A variety of substituted were investigated, the optimal catalyst exhibited high efficiency broad substrate scope, affording desired cycloadducts in good to excellent yields with regio- diastereoselectivities. Furthermore, could be immobilized on polymer support reused multiple times without significant loss activity.

Language: Английский

Citations

0
Visible light photoflow synthesis of a Cu(ii) single-chain polymer nanoparticle catalyst DOI Creative Commons
Sebastian Gillhuber, Joshua O. Holloway, Kai Mundsinger

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(37), P. 15280 - 15290

Published: Jan. 1, 2024

Single-chain nanoparticles (SCNPs) are folded linear polymer chains inspired by the active state of natural enzymes. The current study addresses synthetic scalability issue SCNP via photoflow synthesis catalytically SCNPs.

Language: Английский

Citations

1
Integration of N-Aryl Phenoxazine Photosensitizers and Nickel Catalysts in Polymer Supports Enhances Photocatalytic Organic Transformations DOI
Chen Zhu, Yan‐Xiang Li, Chun‐Hua Liu

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: unknown, P. 17609 - 17621

Published: Nov. 14, 2024

Enhancing the catalytic activity of photosensitizers is critical for photocatalysis, especially in dual systems. We present integration N-aryl phenoxazine and nickel-bipyridine catalysts into linear cross-linked polyacrylate matrices, creating robust polymer-supported photocatalysts. The flexible polymer confers good solubility organic solvents to ensure efficient interactions between sites substrates. proximity units nickel complexes copolymer P1-Ni boosts electron, energy, radical transfers, significantly enhancing photosensitizers. exhibits high catalyzing visible-light-driven sulfonylation, esterification, etherification reactions across a broad substrate scope at extraordinarily low catalyst loadings (0.1 0.2 mol %) with exceptionally turnover numbers approaching 1000. outperforms its homogeneous control by 27- 38-fold. Additionally, an insoluble (P2-Ni) was synthesized incorporating divinyl cross-linking agent. P2-Ni swells solvents, displays comparable that P1-Ni, readily recovered via centrifugal separation used six cycles minimal loss activity. This work demonstrates ability supports enhance activities photocatalytic transformations facilitating and/or transfers.

Language: Английский

Citations

1
Dynamic Implications of Noncovalent Interactions in Amphiphilic Single-Chain Polymer Nanoparticles DOI

Peter A. Dykeman-Bermingham,

Laura R. Stingaciu, Changwoo Do

et al.

ACS Macro Letters, Journal Year: 2024, Volume and Issue: 13(7), P. 889 - 895

Published: July 3, 2024

Single-chain polymer nanoparticles (SCNPs) combine the chemical diversity of synthetic polymers with intricate structure biopolymers, generating versatile biomimetic materials. The mobility chain segments at length scales similar to secondary structural elements in proteins is critical SCNP and thus function. However, influence noncovalent interactions used form SCNPs (e.g., hydrogen-bonding secondary-like structure) on these conformational dynamics challenging quantitatively assess. To isolate effects dynamics, we synthesized a series amphiphilic copolymers containing dimethylacrylamide monomers capable forming different interactions: (1) di(phenylalanine) acrylamide that forms intramolecular β-sheet-like cross-links, (2) phenylalanine hydrogen-bonds but lacks defined local structure, (3) benzyl has lowest propensity for hydrogen-bonding. Each formed folded structures comparable those intrinsically disordered proteins, as observed by size exclusion chromatography small angle neutron scattering. polymers, characterized combination dynamic light scattering spin echo spectroscopy, was well described using Zimm internal friction (ZIF) model, highlighting role each interaction additively restrict relaxations SCNPs. These results demonstrate utility scale control guiding design functional materials refined binding sites tunable kinetics.

Language: Английский

Citations

0