MOLECULES
·
2024
·Vol. 29
·期 10
·2377
·
IF 4.2
Zhilei Wang,Zipeng Zhang,Chenyu Wu,Zikuan Wang,Wenjian Liu
The photocatalyst (PC) zinc tetraphenylporphyrin (ZnTPP) is highly efficient for photoinduced electron/energy transfer reversible addition-fragmentation chain transfer (PET-RAFT) polymerization. However, ZnTPP suffers from poor absorbance of orange light by the so-called Q-band of the absorption spectrum (maximum absorption wavelengthλmax= 600 nm, at which molar extinction coefficientεmax=1.0×104L/(mol·cm)), hindering photo-curing applications that entail long light penetration paths. Over the past decade, there has not been any competing candidate in terms of efficiency, despite a myriad of efforts in PC design. By theoretical evaluation, here we rationally introduce a peripheral benzo moiety on each of the pyrrole rings of ZnTPP, giving zinc tetraphenyl tetrabenzoporphyrin (ZnTPTBP). This modification not only enlarges the conjugation length of the system, but also alters thea1uoccupiedπmolecular orbital energy level and breaks the accidental degeneracy between thea1uanda2uorbitals, which is responsible for the low absorption intensity of the Q-band. As a consequence, not only is there a pronounced hyperchromic and bathochromic effect (λmax= 655 nm andεmax=5.2×104L/(mol·cm)) of the Q-band, but the hyperchromic effect is achieved without increasing the intensity of the less useful, low wavelength absorption peaks of the PC. Remarkably, this strong 655 nm absorption takes advantage of deep-red (650–700 nm) light, a major component of solar light exhibiting good atmosphere penetration, exploited by the natural PC chlorophyll a as well. Compared with ZnTPP, ZnTPTBP displayed a 49% increase in PET-RAFT polymerization rate with good control, marking a significant leap in the area of photo-controlled polymerization.
研究领域:
材料科学
·
化学
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产品关联
DOI
PubMed
高影响因子
RSC Advances
·
2020
·Vol. 10
·期 12
·6850-6857
·
IF 3.119
Lingjuan Hu,Qi Wang,Xiaomeng Zhang,Haitao Zhao,Zhe Cui,Peng Fu,Minying Liu,Nan Liu,Shengbao He,Xinchang Pang,Xiaoguang Qiao
A novel raspberry-like γ-Fe2O3@carbon dot (CD) nanocatalyst was prepared and applied for photoinduced electron transfer-reversible addition–fragmentation chain transfer (PET-RAFT) polymerization. The nanocatalyst was found to be an efficient photocatalyst in visible light-regulated PET-RAFT polymerization owing to the oxidative quenching mechanism between the photoexcited γ-Fe2O3@CDs and the RAFT agent in the PET process. Notably, polymerization can be reversibly ceased in the absence of light or under an external magnetic field. The superparamagnetic nature and high saturation magnetization value (∼30.4 emu g−1) of the nanocatalyst contribute to convenient recycling of the nanocatalyst after polymerization. The PET-RAFT polymerization with the nanocatalyst before and after recycling was investigated, which displayed all the characteristics of controlled/living polymerization systems.
研究领域:
材料化学
·
高分子科学
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产品关联
DOI
PubMed
高影响因子
Gels
·
2025
·Vol. 11
·期 9
·734
·
IF 5.3
Lihan Rong,Jiajiang Xie,Shigao Zhou,Tianqi Guan,Xinyi Fan,Wenjie Zhi,Rui Zhou,Feng Li,Yuyan Liu,Tingting Tang,Xiang Chen,Liyuan Zhang
The scalable fabrication of hydrogels with high toughness and low hysteresis is critically hindered by oxygen inhibition, which typically produces brittle, highly crosslinked (HC) networks. This study presents an oxygen-tolerant photoinduced electron transfer–reversible addition–fragmentation chain transfer (PET-RAFT) strategy for synthesizing highly entangled (HE) polyacrylamide hydrogels under open-vessel conditions. By optimizing the water-to-monomer ratio (W = 3.9) and introducing lithium chloride (LiCl) for spatial confinement, we achieved a fundamental shift in mechanical performance. The optimized HE hydrogel exhibited a fracture energy of 1.39 MJ/m3and a fracture strain of ~900%, starkly contrasting the brittle failure of the HC control (W = 20, C = 10−2) at ~50% strain. This represents an order-of-magnitude improvement in deformability. Furthermore, the incorporation of 15 wt% LiCl amplified the HE hydrogel’s fracture energy to 2.17 MJ/m3while maintaining its low hysteresis. This method enables the rapid, scalable production of robust, transparent thin films that exhibit dual passive cooling via radiative emission (>89% emissivity) and evaporation, rapid self-healing, and reliable strain sensing at temperatures as low as −20 °C. The synergy of entanglement design and confinement engineering establishes a versatile platform for manufacturing multifunctional hydrogels that vastly outperform their crosslink-dominated predecessors.
研究领域:
高分子科学
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材料科学
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生物医学工程
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软物质物理
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功能材料
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环境能源材料
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DOI
PubMed
高影响因子
Gels
·
2025
·Vol. 11
·期 8
·586
·
IF 5.3
Lihan Rong,Tianqi Guan,Xinyi Fan,Wenjie Zhi,Rui Zhou,Feng Li,Yuyan Liu
Fe3+-incorporated hydrogels are particularly valuable for wearable devices due to their tunable mechanical properties and ionic conductivity. However, conventional immersion-based fabrication fundamentally limits hydrogel performance because of heterogeneous ion distribution, ionic leaching, and scalability limitations. To overcome these challenges, we report a novel one-pot strategy where controlled amounts of Fe3+are directly added to polyacrylamide-sodium acrylate (PAM-SA) precursor solutions, ensuring homogeneous ion distribution. Combining this with Photoinduced Electron/Energy Transfer Reversible Addition–Fragmentation Chain Transfer (PET-RAFT) polymerization enables efficient hydrogel fabrication under open-vessel conditions, improving its scalability. Fe3+concentration achieves unprecedented modulation of mechanical properties: Young’s modulus (10 to 150 kPa), toughness (0.26 to 2.3 MJ/m3), and strain at break (800% to 2500%). The hydrogels also exhibit excellent compressibility (90% strain recovery), energy dissipation (>90% dissipation efficiency at optimal Fe3+levels), and universal adhesion to diverse surfaces (plastic, metal, PTFE, and cardboard). Finally, these Fe3+-incorporated hydrogels demonstrated high effectiveness as strain sensors for monitoring finger/elbow movements, with gauge factors dependent on composition. This work provides a scalable, oxygen-tolerant route to tunable hydrogels for advanced wearable devices.
研究领域:
材料科学
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高分子化学
·
可穿戴电子器件
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柔性机器人
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传感器
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产品关联
DOI
PubMed
高影响因子
COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS
·
2021
·
IF 4.539
Jinsheng Zhou,Yanming Lin,Ling Wang,Li Zhou,Bin Yu,Xianghui Zou,Zhongkuan Luo,Huiyuan Hu
A novel near-infrared (NIR) light induced photoinduced electron transfer-reversible addition - fragmentation chain-transfer (PET-RAFT) polymerization was developed and carboxybetaine methacrylate (CBMA) polymer brush was constructed on the PVA hydrogel via this one-spot method to enhance the antifouling properties. PVA-g-pCBMA hydrogel displayed higher hydrophilicity , while the thermal properties decreased due to the lower decomposition properties of pCBMA and the partly destruction of crystal structure inside the PVA hydrogel. The antifouling properties of PVA-g-pCBMA hydrogel was improved significantly because the surface hydration and steric repulsion effect of pCBMA polymer brush. Importantly, PVA-g-pCBMA hydrogel PVA-g-pCBMA hydrogel could be considered as no cytotoxic effect or reduction of proliferation to primary human eyelid fibroblast cells following the guidelines stated by ISO 10993-5:2009 (direct contact test). Considering the excellent penetration ability of NIR, AlPc catalyzed PET-RAFT polymerization provided a new modification approach for various biological or medical materials on industrial scale.
研究领域:
材料科学
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高分子化学
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生物医学工程
·
表面科学
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DOI
高影响因子
危险品化学品经营许可证（带存储）