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Rapid and high-resolution 3D printing via photoacid generator induced cationic RAFT polymerization

Science China Chemistry 2025年第05期68卷 2010-2016页

作者： Bowen Zhao Jiajia Li Chongyang Yang Xiangqiang Pan Zhengbiao Zhang Jian Zhu State Local Joint Engineering Laboratory for Novel Functional Polymeric Materials Jiangsu Key Laboratory of Advanced Functional Polymer Design and ApplicationSuzhou Key Laboratory of Macromolecular Design and Precision SynthesisDepartment of Polymer Science and EngineeringCollege of ChemistryChemical Engineering and Materials ScienceSoochow University

Vinyl ethers, while being typical monomers for living cationic polymerization, have limited commercial use due to the poor mechanical properties of their polymers at room temperature. We explored the use of photoacid generators to induce cationic reversible addition-fragmentation chain transfer（RAFT） polymerization for the rapid high-resolution three-dimensional（3D） printing of various vinyl ethers. The process demonstrated controlled molecular weights and narrow molecular weight distributions（MWD）, with monomer conversions exceeding 90% in minutes. Incorporating a crosslinker enabled 3D printing at speeds up to 8.46 cm h-1with layer thicknesses as thin as 50 μm. The mechanical properties of the printed objects were tunable by adjusting resin components, allowing for a range of material characteristics from brittle to elastomeric（tensile strength ranging from 13.9 to 31.7 MPa, Young's modulus ranging from 185.6 to 992.7 MPa and elongation at break ranging from 2.8%to 68.3%）. Moreover, polymer welding facilitated the creation of gradient materials, showcasing the potential for engineered applications of poly（vinyl ethers）(PVEs).

关键词： 3D printing cationic RAFT polymerization vat photopolymerization vinyl ether

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“Sergeants-and-soldiers” effect and modified Ising model in chiral polymer materials

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Science China Chemistry 2025年

作者： Liyuan Shi Fu Tian Sheng Wang Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application College of Chemistry Chemical Engineering and Materials Science Soochow University

The “sergeants-and-soldiers” effect is a significant feature of helical copolymers, where a small fraction of chiral components can endow the copolymers with an intense optical activity close to that of chiral homopolymer. With the development of helical polymers, some abnormal examples have also been discovered, in which the twisting sense of main chain can be inversed with the increment of chiral unit content, termed as abnormal “sergeants-and-soldiers” effect. In this review, we detailedly summarize the development of “sergeants-and-soldiers” effect and its theoretical model in chiral polymer systems, including normal and abnormal “sergeants-and-soldiers” effects, modification of Ising model, dynamic transformation of the above two chiral amplification effects, as well as their applications in chiral separation, asymmetric catalysis, and circularly polarized ***, the remaining challenges are discussed to provide an outlook on the future directions.

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埋底界面增韧助力实现机械稳定和高效的宽带隙柔性钙钛矿太阳能电池（英文）

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Science China Materials 2025年第5期68卷 1415-1423页

作者：曹建磊陈炜杰赵晨荔徐佳诚郑佳磊亢帅青朱娟章建东李耀文 Laboratory of Advanced Optoelectronic Materials Suzhou Key Laboratory of Novel Semiconductor-optoelectronics Materials and DevicesCollege of ChemistryChemical Engineering and Materials ScienceSoochow University State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials Jiangsu Key Laboratory of Advanced Functional Polymer Design and ApplicationCollege of ChemistryChemical Engineering and Materials ScienceSoochow University Jiangsu Key Laboratory of Advanced Negative Carbon Technologies Soochow University

柔性宽带隙钙钛矿太阳能电池具有构筑高效叠层太阳能电池的独特优势.具有低温加工和优异稳定性的氧化镍是制备柔性宽带隙钙钛矿太阳能电池的理想空穴传输层.然而,钙钛矿埋底界面存在大量缺陷以及氧化镍和钙钛矿界面结合力较弱,严重影响... 详细信息

柔性宽带隙钙钛矿太阳能电池具有构筑高效叠层太阳能电池的独特优势.具有低温加工和优异稳定性的氧化镍是制备柔性宽带隙钙钛矿太阳能电池的理想空穴传输层.然而,钙钛矿埋底界面存在大量缺陷以及氧化镍和钙钛矿界面结合力较弱,严重影响了柔性器件的效率和机械稳定性.我们通过引入多功能分子N-乙酰-L-谷氨酸(NALG)开发了一种埋底界面修饰策略来解决上述问题.理论计算和实验结果表明NALG分子的羧基和酰胺可以分别与氧化镍和钙钛矿结合,能够钝化界面缺陷以及增强钙钛矿的结晶.更重要的是, NALG作为桥连分子大幅增强氧化镍和钙钛矿的界面韧性.最终,柔性宽带隙钙钛矿太阳能电池实现了16.28%的能量转化效率.同时,柔性器件表现出优异的机械稳定性,循环弯曲10000次仍能保持初始效率的83%(弯曲半径为5 mm).器件也具有优越的长期运行稳定性和湿热稳定性.

关键词： wide-bandgap perovskite flexible perovskite solar cells buried interface defect passivation mechanical stability

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High Antibacterial Activity and Selectivity of Cationic Disubstituted Polypeptoids with Stable Helices and Enzymatic Resistance

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ACS Applied Materials and Interfaces 2025年第19期17卷 27950-27963页

作者： Ma, Anyao Deng, Xuehua Wei, Luxin Dong, Yutong Zhang, Peizhuo Xuan, Sunting Zhang, Zhengbiao State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis College of Chemistry Chemical Engineering and Materials Science Soochow University Suzhou215123 China State Key Laboratory of Radiation Medicine and Protection Soochow University Suzhou215123 China The Fourth Affiliated Hospital of Soochow University Suzhou215124 China Suzhou GenePharma Co. Ltd. Suzhou215123 China

High antibacterial activity, low mammalian cell toxicity, and serum stability are crucial parameters for designing efficient antibacterial materials under physiological conditions. This relies on a deep understanding of the structure-property relationship of antibacterial materials. In this study, a series of cationic amphiphilic disubstituted polypeptoids were synthesized by using ring-opening polymerization (ROP) followed by thiol-ene click reactions. This new class of peptidomimetic materials, with chiral centers at backbones and ammonium alkyl N-substituents, exhibited remarkably stable helical structures independent of pH, temperature, salt, and denaturing agents. The helical analogs were found to show higher antibacterial activity against both Gram-negative and Gram-positive strains than the racemic, nonhelical counterparts. The helical structure and the balance of cationic charges and hydrophobicity were key parameters to achieve high selectivity for bacteria over mammalian cells. Moreover, unlike poly(l-lysine), the disubstituted polypeptoids, with stable helices and enzymatic resistance, retained high antibacterial activity even in the presence of salts, human serum albumin (HSA), and protease trypsin at physiological concentrations. This study deepens our understanding of how structural elements correlate with antibacterial activity and selectivity. In addition, the helical and enzymatically stable disubstituted polypeptoids have shown promise as an attractive platform for the design of new antibacterial materials with high efficiency and low toxicity. © 2025 American Chemical Society.

关键词： Ring opening polymerization

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Enhancing performance of fullerene-based organic electrochemical transistors via side-chain engineering

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Nano Research 2025年第2期18卷 905-912页

作者： Wenxin Fang Zijie Li Chengdong Wang Xiaowei Zhao Junyu Li Gang Ye Fengwei Huo Li Qiu Yanxi Zhang Wei Huang Institute of Flexible Electronics(IFE Future Technologies)Xiamen UniversityXiamen 361005China Yunnan Key Laboratory of Electromagnetic Materials and Devices National Center for International Research on Photoelectric and Energy MaterialsSchool of Materials and EnergyYunnan UniversityKunming 650091China Sinopec Shanghai Research Institute of Petrochemical Technology Shanghai 201028China Key Laboratory for the Green Preparation and Application of Functional Materials Hubei Key Laboratory of Polymer MaterialsSchool of Materials Science and EngineeringHubei UniversityWuhan 430062China Key Laboratory of Flexible Electronics(KLOFE)&Institute of Advanced Materials(IAM) Jiangsu National Synergetic Innovation Center for Advanced Materials(SICAM)Nanjing Tech University(NanjingTech)Nanjing 211800China Frontiers Science Center for Flexible Electronics MIIT Key Laboratory of Flexible Electronics(KLoFE)Northwestern Polytechnical UniversityXi'an 710072China

The performance of organic electrochemical transistors(OECTs)relies on the interaction between organic semiconductors and ***,hydrophilic ethylene glycol(EG)side chains are incorporated into organic semiconductors to improve the channel’s capacity to absorb ***,the EG substituted organic semiconductors tend to swell when immersed in aqueous electrolytes and exhibit microstructural changes induced by dopant *** our research,we introduce an alkyl spacer to create distance between the fullerene and EG *** approach is designed to reduce the negative effects of swelling and balance the ion and electron *** conducted an analysis of OECTs using four fullerene derivatives:no alkyl spacer,butyl,hexyl,and octyl *** OECTs based on fullerene derivatives with butyl and hexyl spacers exhibit enhanced transconductance(g_(m)=11.8 and 19.4 mS)compared to the ones without alkyl *** has also been observed that the butyl and hexyl spacers lead to a more than tenfold increase in volumetric *** increasing the alkyl spacer(octyl group)leads to no transistor *** study uncovers the relationship between alkyl spacers and the performance of OECTs based on fullerene *** will serve as a guideline for designing n-type small molecules for ***,we showcased the potential of utilizing OECTs based on these fullerene derivatives in cation sensing,which is promising for developing sweat sensors.

关键词： organic electrochemical transistors fullerene derivatives ethylene glycol side chains ion and electron conduction

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Transparent and Extremely Stretchable Piezoelectric Device for Sensors and Energy Harvesters

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ACS Applied Materials and Interfaces 2025年第21期17卷 31499-31510页

作者： He, Jian Qian, Zihao Hu, Zhijun Guo, Mingyu State-Local Joint Engineering Laboratory for Novel Functional Polymer Materials Jiangsu Key Laboratory of Advanced Functional Polymer Materials Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis College of Chemistry Chemical Engineering and Materials Science Soochow University Suzhou 215123 China Key Laboratory of Advanced Optical Manufacturing Technologies of Jiangsu Province Key Laboratory of Modern Optical Technologies of Education Ministry of China School of Optoelectronic Science and Engineering Collaborative Innovation Center of Suzhou Nano Science and Technology Soochow University Suzhou 215123 China

Piezoelectric devices have garnered significant interests due to their dual functionality as both sensors and energy harvesters, as well as the rapid development in Internet of Things (IoT) and artificial intelligence (AI). However, the fabrication of stretchable and transparent piezoelectric devices remains a great challenge, largely due to the inherent crystalline nature of piezoelectric materials and electrodes. In this work, for the first time, we report the fabrication of a highly transparent and stretchable piezoelectric device based entirely on polyurethane-urea (PUU) elastomers/composites. Specifically, nano ZnO hybrid hydrophobic PUU serves as the elastic inner piezoelectric layer;conductive ionic liquid composite hydrophilic PUU forms the middle electrode layer;and hydrophobic PUU elastomer acts as the outer encapsulation layer. The obtained device exhibits exceptional stretchability (elongation at break >1000%) and excellent optical transparency (∼86%). It can generate distinct, stable, and reliable output signals for monitoring both small- and large-scale mechanical motions along with a mechanical energy output of 48 μW m^-2 at a pressure of 38.2 kPa, highlighting its outstanding sensing and energy harvesting capabilities. This work presents valuable new insights into the design and development of novel, reliable, transparent, and stretchable piezoelectric devices, paving the way for the new generation of flexible electronics. © 2025 American Chemical Society.

关键词： energy harvester nano ZnO piezoelectric device polyurethane urea transparent and stretchable sensor

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Synthesis of bio-based polyethylene-like materials via ring-opening polymerization of ethylene brassylate in the presence of reduced graphene oxide

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European polymer Journal 2025年 233卷

作者： Lu, Rongyu You, Meng Ma, Jianxiang Zhang, Xinghua Tu, Yingfeng Yang, Xiaoming State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis Jiangsu Key Laboratory of Advanced Functional Polymer Materials Jiangsu Engineering Laboratory of Novel Functional Polymeric Materials Department of Polymer Science and Engineering College of Chemistry Chemical Engineering and Materials Science Soochow University Suzhou215123 China

Polyethylene (PE) is widely investigated and used due to its excellent mechanical properties, chemical stability, and cost-effectiveness. However, its reliance on fossil resources poses environmental concerns. This study explores the ring-opening polymerization (ROP) of ethylene brassylate (EB), a 17-membered macrocyclic dilactone derived from castor oil, as a route to polyethylene-like materials. However, the low ring strain of EB typically limits the molecular weight of poly(ethylene brassylate) (PEBs), affecting its mechanical performance. To address this, we developed a Ti(n-C4H9O)4/reduced graphene oxide (rGO) catalytic system, enabling the synthesis of high-molecular-weight PEBs (Mn = 78.0 kg/mol). The resulting PEB-rGO composites exhibit outstanding mechanical properties, with an elongation at break exceeding 1157 ± 23 %, a modulus above 503 ± 18 MPa, and an ultimate tensile strength over 46.2 ± 1.7 MPa-surpassing commercial High-density PE and previously reported PEB-based materials. Additionally, rGO incorporation enhances photothermal properties, enabling laser-assisted self-healing. This study provides an efficient approach to producing high-performance polyethylene-like materials with advanced functionalities. © 2025

关键词： Ring opening polymerization

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Thermodynamics of Aromatic Cyclic Ester polymerization in Bulk

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Chinese Journal of polymer Science 2019年第1期37卷 89-93页

作者： Chong He Xiang Zhu Xiao-Hong Li Xiao-Ming Yang Ying-Feng Tu Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application College of Chemistry Chemical Engineering and Materials ScienceSoochow University

We present here the thermodynamic investigation of in situ cascade polycondensation-coupling ring-opening polymerization(PROP)for three cyclic aromatic ester monomers,i.e.,cyclic oligo(2-methyl-1,3-propylene terephthalate)s(COMPTs),cyclic oligo(neopentylene terephthalate)s(CONTs)and cyclic oligo(2-methyl-2-propyl-1,3-propylene terephthalate)s(COMPPTs).The equibrium monomer to polymer weight ratio in bulk at different polymerization temperatures for each monomer was estimated by the size exclusion chromatography(SEC),and the thermodynamic parameters were estimated by Dainton *** different from the thermodynamics of aliphatic lactones polymerization,which is an exothermic process with entropy reduction,our results showed the polymerization thermodynamics for three cyclic aromatic ester monomers was a weak exothermic process with slight entropy increment,i.e.,a both enthalpy and entropy driving *** them,CONTs showed the largest value of enthalpy change,due to its symmetric dimethyl substitution onβ-position of propandiol segments.

关键词： Lactone Polyester Polycondensation-coupling ring-opening polymerization Thermodynamic parameters

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Iron-mediated AGET ATRP of Styrene and Methyl Methacrylate Using Ascorbic Acid Sodium Salt as Reducing Agent

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Chinese Journal of polymer Science 2014年第8期32卷 1010-1018页

作者： Jin-long Pan Zhen Li Li-fen Zhang 程振平朱秀林 Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application Department of Polymer Science and Engineering College of Chemistry Chemical Engineering and Materials Science Soochow University

Atom transfer radical polymerization of styrene （St） and methyl methacrylate （MMA） in bulk and in different solvents using activators generated by electron transfer （AGET ATRP） were investigated in the presence of a limited amount of air using FeC13-6H2O as the catalyst, ascorbic acid sodium salt （AsAc-Na） as the reducing agent, and a cheap and commercially available tetrabutylammonium bromide （TBABr） as the ligand. It was found that polymerization in THF resulted in shorter induction period than that in bulk and in toluene for AGET ATRP of St, while referring to AGET ATRP of MMA, polymerization in THF showed three advantages compared with that in bulk and toluene：1） shortening the induction period, 2） enhancing the polymerization rate and 3） having better controllability. The living features of the obtained polymers were verified by chain end analysis and chain-extension experiments.

关键词： Atom transfer radical polymerization （ATRP） AGET ATRP Iron catalyst Kinetics （polym.）.

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ALTERED ENZYMATIC ACTIVITY OF LYSOZYMES BOUND TO VARIOUSLY SULFATED CHITOSANS

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Chinese Journal of polymer Science 2012年第6期30卷 893-899页

作者：袁琳陈红 Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application Department of Polymer Science and EngineeringCollege of ChemistryChemical Engineering and Materials ScienceSoochow University

The purpose of this research is to investigate the effects of the variously sulfated chitosans on lysozyme activity and structure. It was shown that the specific enzymatic activity of lysozyme remained almost similar to the native protein after being bound to 6-O-sulfated chitosan （6S-chitosan） and 3,6-O-sulfated chitosan （3,6S-chitosan）, but decreased greatly after being bound to 2-N-6-O-sulfated chitosan （2,6S-chitosan）. Meanwhile, among these sulfated chitosans, 2,6S-chitosan induced the greatest conformational change in lysozyme as indicated by the fluorescence spectra. These findings demonstrated that when sulfated chitosans of different structures bind to lysozyme, lysozyme undergoes conformational change of different magnitudes, which results in corresponding levels of lysozyme activity. Further study on the interaction of sulfated chitosans with lysozyme by surface plasmon resonance （SPR） suggested that their affinities might be determined by their molecular structures.

关键词： Lysozyme Sulfated chitosan Activity Structure Regioselective modification.

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