2,2′‐Tethered Binaphthyl‐Embedded One‐Handed Helical Ladder Polymers: Impact of the Tether Length on Helical Geometry and Chiroptical Property DOI Creative Commons
Tomoyuki Ikai,

N. Mishima,

Takehiro Matsumoto

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(10)

Published: Jan. 23, 2024

Synthetic breakthroughs diversify the molecules and polymers available to chemists. We now report first successful synthesis of a series optically-pure 2,2'-tethered binaphthyl-embedded helical ladder based on quantitative chemoselective ladderization by modified alkyne benzannulations using 4-alkoxy-2,6-dimethylphenylethynyl group as source, inaccessible conventional approach lacking 2,6-dimethyl substituents. Due defect-free helix formation, circular dichroism signal increased more than 6 times previously reported value. The resulting secondary structure can be fine-tuned controlling binaphthyl dihedral angle in repeating unit with variations 2,2'-alkylenedioxy tethering groups one carbon atom at time. optimization structures led strong circularly polarized luminescence high fluorescence quantum yield (28 %) dissymmetry factor (2.6×10

Language: Английский

Asymmetric Living Supramolecular Polymerization: Precise Fabrication of One‐Handed Helical Supramolecular Polymers DOI
Chao Wang, Lei Xu, Li Zhou

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(33)

Published: June 23, 2022

Programming the organization of semiconducting polymers to form well-defined nanoarchitectures is desirable for fabricating functional materials. In this work, copolymers, poly(cholesterol allene)-b-poly(3-hexylthiophene) (PCA-b-P3HT) containing helical PCA and poly(alkoxy (PAA-b-P3HT) achiral PAA segments, were prepared. Crystallization P3HT helicity drove PCA-b-P3HT self-assemble into spherical nanoparticles that gradually transformed one-handed nanofibers. The chirality was transferred supramolecular architectures, induced high optical activity in P3HT. Interestingly, chiral seed micelles asymmetric copolymerization PAA-b-P3HT, which led block copolymers with defined controlled length. Remarkably, showed white-light emission circularly polarized luminescence.

Language: Английский

Citations

49
Self‐Assembly of Helical Nanofibrous Chiral Covalent Organic Frameworks DOI Creative Commons

Xihao Tang,

Xiang‐Ji Liao,

Xinting Cai

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(4)

Published: Nov. 29, 2022

Despite significant progress on the design and synthesis of covalent organic frameworks (COFs), precise control over microstructures such materials remains challenging. Herein, two chiral COFs with well-defined one-handed double-helical nanofibrous morphologies were constructed via an unprecedented template-free method, capitalizing diastereoselective formation aminal linkages. Detailed time-dependent experiments reveal spontaneous transformation initial rod-like aggregates into microstructures. We have further demonstrated that helical chirality circular dichroism signal can be facilely inversed by simply adjusting amount acetic acid during synthesis. Moreover, transferring to achiral fluorescent molecular adsorbents, COF nanostructures effectively induce circularly polarized luminescence highest luminescent asymmetric factor (glum ) up ≈0.01.

Language: Английский

Citations

42
Enhanced Bacterial‐Infected Wound Healing by Nitric Oxide‐Releasing Topological Supramolecular Nanocarriers with Self‐Optimized Cooperative Multi‐Point Anchoring DOI Creative Commons
Guowei Li, Kai Lv,

Qikun Cheng

et al.

Advanced Science, Journal Year: 2023, Volume and Issue: 10(11)

Published: Feb. 15, 2023

Polymeric systems that provide cationic charges or biocide-release therapeutics are used to treat the bacteria-infected wound. However, most antibacterial polymers based on topologies with restricted molecular dynamics still do not satisfy clinical requirements due their limited efficacy at safe concentrations in vivo. Here a NO-releasing topological supramolecular nanocarrier rotatable and slidable entities is reported conformational freedom promote interactions between carrier pathogenic microbes, hence greatly improving performance. With improved contacting-killing efficient delivery of NO biocide from molecularly dynamic ligand design, NO-loaded achieves excellent anti-biofilm effects via destroying bacterial membrane DNA. MRSA-infected rat model also brought out demonstrate its wound-healing effect neglectable toxicity Introducing flexible motions into therapeutic polymeric general design enhance healing range diseases.

Language: Английский

Citations

29
Precise Synthesis of Optically Active and Thermo‐degradable Poly(trifluoromethyl methylene) with Circularly Polarized Luminescence DOI
Xunhui Xu, Shu‐Ming Kang,

Run‐Tan Gao

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(20)

Published: March 14, 2023

Developing high performance and environment-friendly fluoropolymers is greatly desired. In this work, we found that 2-diazo-1,1,1-trifluoroethane can be polymerized by air-stable alkyne-palladium(II) catalysts following a living polymerization mechanism, affording fluoropolymer, poly(trifluoromethyl methylene) in yield with controlled molar mass low dispersity. This polymer bears trifluoromethyl on every main chain atom thus has good resistance to chemical corrosion, hydrophobicity, excellent dielectric constant loss. Due the steric hindrance between pendants, synthetic twist into stable helix. The one-handed preferred helices synthesized using chiral PdII -catalysts exhibit optical activity circularly polarized luminescence. Remarkably, such completely degraded (E)-1,1,1,4,4,4-hexafluorobut-2-ene at temperatures (>280 °C). Additionally, taking advantage of end, further modified.

Language: Английский

Citations

28
Rational Construction of Protein-Mimetic Nano-Switch Systems Based on Secondary Structure Transitions of Synthetic Polypeptides DOI
Chenglong Ge, Junliang Zhu, Huan Ye

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(20), P. 11206 - 11214

Published: May 11, 2023

The manipulation of the flexibility/rigidity polymeric chains to control their function is commonly observed in natural macromolecules but largely unexplored synthetic systems. Herein, we construct a series protein-mimetic nano-switches consisting gold nanoparticle (GNP) core, polypeptide linker, and an optically functional molecule (OFM), whose biological can be dynamically regulated by flexibility linker. At dormant state, adopts flexible, random-coiled conformation, bringing GNP OFM close proximity that leads "turn-off" OFM. Once treated with alkaline phosphatase (ALP), are activated due increased separation distance between driven coil-to-helix flexible-to-rigid transition therefore enable selective fluorescence imaging or photodynamic therapy response ALP overproduced tumor cells. over polymer represents effective strategy manipulate optical activity nano-switches, which mimics delicate structure-property relationship proteins.

Language: Английский

Citations

27
Chiral macromolecules and supramolecular assemblies: Synthesis, properties and applications DOI
Mingyue Zhang, Minju Kim, Woosung Choi

et al.

Progress in Polymer Science, Journal Year: 2024, Volume and Issue: 151, P. 101800 - 101800

Published: Feb. 8, 2024

Language: Английский

Citations

16
Nanoparticles destabilizing the cell membranes triggered by NIR light for cancer imaging and photo-immunotherapy DOI Creative Commons
Dongsheng Tang,

Minhui Cui,

Bin Wang

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: July 17, 2024

Abstract Cationic polymers have great potential for cancer therapy due to their unique interactions with cells. However, clinical application remains limited by high toxicity. Here we show a cell membrane-targeting cationic polymer antineoplastic activity (P mt ) and second near-infrared (NIR-II) fluorescent biodegradable photosensitizer Bodipy units reactive oxygen species (ROS) responsive thioketal bonds ). Subsequently, these two can self-assemble into nanoparticles (denoted mt-NP which could further accumulate at the tumor destroy membranes through electrostatic interactions, resulting in membrane destabilization. Meanwhile, produces ROS induce damage membranes, proteins, DNAs kill cells concertedly, finally lysis death. This work highlights use of light spatially temporarily control photodynamic therapy, photo-immunotherapy, NIR-II fluorescence bio-imaging.

Language: Английский

Citations

16
Helical peptide structure improves conductivity and stability of solid electrolytes DOI

Yingying Chen,

Tianrui Xue, Chen Chen

et al.

Nature Materials, Journal Year: 2024, Volume and Issue: 23(11), P. 1539 - 1546

Published: Aug. 6, 2024

Language: Английский

Citations

11
Incorporation of hydrogen‐bonding units into polymeric semiconductors toward boosting charge mobility, intrinsic stretchability, and self‐healing ability DOI Creative Commons
Xiaobo Yu, Cheng Li,

Chenying Gao

et al.

SmartMat, Journal Year: 2021, Volume and Issue: 2(3), P. 347 - 366

Published: Sept. 1, 2021

Abstract The soft nature has endowed conjugated polymers with promising applications in a wide range of field‐effect transistor (FET) based flexible electronics. With unremitting efforts on revealing the molecular structure–property relationships, numerous novel high mobility and excellent mechanical property have been developed past decades. Incorporating hydrogen‐bonding (H‐bonding) units into semiconducting is one most successful strategies for designing high‐performance materials. In this review, we aim to highlight roles H‐bonding performances polymeric FETs from three aspects. These include (i) charge enhancement after incorporation side chains, (ii) effects stretchability polymers, (iii) improvement self‐healing properties containing dynamic hydrogen bonds due chains or backbones.

Language: Английский

Citations

51
Biodegradable Hydrophobic Injectable Polymers for Drug Delivery and Regenerative Medicine DOI
Yuvaraj Arun, Radhakanta Ghosh, Abraham J. Domb

et al.

Advanced Functional Materials, Journal Year: 2021, Volume and Issue: 31(44)

Published: Feb. 19, 2021

Abstract Biodegradable, hydrophobic, and injectable liquid polymers are capable of achieving the minimally invasive, sustained, local release drugs. These hydrophobic also have potential in area regenerative medicine where biomaterial should be stable for a certain period then degrade to allow growth cells/tissues. This review presents exclusive coverage biocompatible pasty or that can injected without use any solvent drug delivery, tissue augmentation, application. The synthesis methodologies several major types used biomedical fields their properties with foremost criteria serve as localized delivery is described. biodegradable discussed aliphatic polyesters, polycarbonates polyanhydrides, prepared from: lactic acid, glycolic caprolactone, diols diacids, hydroxy fatty acids, triglycerides such castor oil.

Language: Английский

Citations

47