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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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Polyethyleneimine modified Au core Rh shell nanodendrites for light-promoted nitrite reduction reaction at low concentration

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Journal of Energy chemistry 2025年第4期103卷 400-407页

作者： Zhe Wang Xiaohui Wang Mengzhu Yun Xinyao Shi Xue Xiao Yan Liu Fan Yang Yucheng Jiang Yu Chen Key Laboratory of Macromolecular Science of Shaanxi Province School of Chemistry and Chemical EngineeringShaanxi Normal UniversityXi’an 710062ShaanxiChina School of Materials Science and Engineering Shaanxi Normal UniversityXi’an 710062ShaanxiChina Department of Public Security Northwest University of Political Science and LawXi’an 710122ShaanxiChina College of Chemistry and Materials Science Weinan Normal UniversityWeinan 714099ShaanxiChina

Ammonia(NH_(3))is a fundamental chemical in agriculture and an ideal hydrogen ***,NH_(3)synthesis strategies with high efficiency,energy conservation,environmental friendliness,and sustainability are desired *** nitrite(NO_(2)~-)reduction reaction(NO_(2-)RR)to NH_(3)offers a feasibly low-energy consumption and continuable approach to replace industrial NH_(3)***,polyethyleneimine(PEI)modified Au core Rh shell nanodendrites(Au@Rh-NDs)nanohybrid(Au@Rh-NDs/PEI)with branched structure is synthesized,which achieves the high NH_(3)yield(1.68 mg h^(-1)mg_(cat)^(-1))and Faradaic efficiency(FE)of 95.86%for NO_(2)~--RR at-0.39 V potential in neutral ***,the introduction of PEI significantly enhances the electroactivity of Au@Rh-NDs at low concentration of 1 mM NaNO_(2),which originates from the enrichment function of PEI for NO_(2)~-*** addition,the Au basement permits the sustainable solar power to expedite the NO_(2)~--RR at Au@Rh-NDs/PEI owing to the localized surface plasmon resonance(LSPR)of the Au core *** work may provide an admissible tactic to build excellent catalysts on account of organic molecule-mediated interfacial engineering in a variety of fields of catalysis and electrocatalysis.

关键词： Ammonia Shell-core structure Interfacial engineering Nitrite reduction reaction Photothermal and photoelectric effect

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Light-driven Self-sustained Rolling of Cylinder Hydrogels with Fast and Anisotropic Responses

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Chinese Journal of Polymer science 2025年第4期43卷 548-555页

作者： Qing-Li Zhu Han-Lei Cheng Wei-Xuan Liu Yin-Bin Xiao Xin-Lei Wu Josef Breu Wei Hong Zhi-Jian Wang Qiang Zheng Zi-Liang Wu Ministry of Education Key Laboratory of Macromolecular Synthesis and Functionalization Department of Polymer Science and EngineeringZhejiang UniversityHangzhou310058China Department of Mechanics and Aerospace Engineering Southern University of Science and TechnologyShenzhen518055China Bavarian Polymer Institute and Department of Chemistry University of BayreuthUniversitätsstrasse 3095440BayreuthGermany Institute for Chemical Reaction Design and Discovery Hokkaido UniversitySapporo001-0021Japan

Achieving continuous motions typically requires dynamic external stimuli for cyclic deformation,or crafted geometries with intricate modules to form a self-regulated feedback loop upon static *** is still a grand challenge to realize self-sustained motion in soft robots subject to unchanging environment,without complex geometry or a control *** this work,we report soft robots based on an anisotropic cylindrical hydrogel showing self-regulated,continuous rolling motions under constant light *** robots are animated by mirror-symmetry-breaking induced by photothermal strain *** self-sustained motion is attributed to the fast and reversible deformation of the gel and the autonomous refresh of the irradiated region during the rolling *** hydrogel robots can reach a rolling speed of 1.27 mm·s^(-1)on a horizonal surface and even climb a ramp of 18°at a speed of 0.57 mm·s^(-1)in an aqueous ***,the hydrogel robots can overcome an obstacle,with rolling direction controllable through irradiation angle of the light and local irradiation on selective *** work suggests a facile strategy to develop hydrogel robots and may provide unforeseen inspirations for the design of self-regulated soft robots by using other intelligent materials.

关键词： Self-sustained motions Light-driven Rolling Anisotropic hydrogels Soft robots

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Reduced erosion and its erosion reducing mechanism of gun propellants by octaphenylsilsesquioxane

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材料科学技术（英文版） 2025年第4期207卷 86-94页

作者： Taixin Liang Jiaxin Lu Fei Xiao Hua Guo Chunzhi Li Mukun He Baosheng Liu Zeinhom M.El-Bahy Nawaa Ali H.Alshammari Xin Liao Salah M.El-Bahy Zhongliang Xiao Zhanhu Guo School of Environment and Safety Engineering North University of ChinaTaiyuan 030051China School of Chemistry and Chemical Engineering Nanjing University of Science and TechnologyNanjing 210094China Luzhou North Chemical Industries Co. LTDLuzhou 646000China School of Environment and Safety Engineering North University of ChinaTaiyuan 030051China Shaanxi Key Laboratory of Macromolecular Science and Technology School of Chemistry and Chemical EngineeringNorthwestern Polytechnical UniversityXi'an 710072China Luzhou North Chemical Industries Co. LTDLuzhou 646000China College of Materials Science and Engineering Taiyuan University of Science and TechnologyTaiyuan 030024China Department of Chemistry Faculty of ScienceAl-Azhar UniversityNasr City 11884CairoEgypt Department of Chemistry Faculty of ScienceNorthern Border UniversityArar 73222Saudi Arabia School of Chemistry and Chemical Engineering Nanjing University of Science and TechnologyNanjing 210094China Department of Chemistry Turabah University CollegeTaif UniversityP.O.Box 11099Taif21944Saudi Arabia Department of Mechanical and Civil Engineering Faculty of Engineering and EnvironmentNorthumbria UniversityNewcastle Upon TyneNE1 8STUK

Low erosion high-energy propellant is one of the research directions to extend the weapon's life and improve the weapon's *** this study,energetic propellants containing different corrosion in-hibitors were designed and *** bomb tests and semi-confined bomb experiments were used to investigate the burning and erosion properties of the *** mechanism of erosion-reducing of titanium dioxide(titania,TiO2),talc,and octaphenylsilsesquioxane(OPS)on the propellant was com-paratively *** results show that OPS has the lowest burning rate and the longest burning time,and a minimized loss of fire force,with the best effect of explosion heat *** erosion reduction efficiency of OPS is twice that of TiO2 and *** mechanism analysis shows that the decomposition and heat absorption of OPS can effectively reduce the thermal erosion effect and carbon erosion,and the gas produced can reduce the loss of chamber pressure and form a uniformly distributed nano-SiO2 protective *** solid-state high-efficiency organosilicon erosion inhibitor is an important guide for designing high-energy low-erosion gun propellants.

关键词： Octaphenylsilsesquioxane Propellant Erosion inhibitors High efficiency

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Dense carbon nanofiber self-supporting electrode fabricated by orientation/compaction strategy for high volumetric lithium storage capacity

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Progress in Natural science:Materials International 2025年第1期35卷 229-237页

作者： Haihui Liu Chaoqun Chen Qiang Xu Yan Song Xiangwu Zhang Chang Ma Tianjin Municipal Key Lab of Advanced Fiber and Energy Storage Technology Tiangong University CAS Key Laboratory of Carbon Materials Institute of Coal Chemistry Chinese Academy of Sciences Fiber and Polymer Science Program Department of Textile Engineering Chemistry and Science Wilson College of Textiles North Carolina State University

Low bulk density greatly restricts the large-scale application of electrospun carbon-based fiber membrane as electrode in energy storage devices. To solve the above challenges, herein an orientation-compaction densification strategy is proposed to enhance the bulk density and volumetric capacity of PAN-based carbon nanofiber membranes as self-supporting electrode used in lithium-ion batteries（LIBs）. Specifically, highly-oriented fibers are achieved by high-speed roller collecting during electrospinning, and compaction densification is conducted by hot-pressing treatment. The effects of collecting speed and hot-pressing pressure on the morphology, conductivity,bulk density, tensile strength, and flexibility of the obtained carbon nanofiber membrane are *** to conventional fiber membranes, of which fibers are disorderly stacked, the oriented fiber membrane is much easier to achieve dense stacking by compaction. The obtained dense carbon nanofiber membrane demonstrates a bulk density of 0.566 g cm-3, and shows a significantly-enhanced volumetric capacity(318.3 mA h cm-3), high-rate performance(86.6 mA h cm-3at 5 A g-1), and satisfactory cycling stability when used as selfsupporting electrode of LIBs.

关键词： Bulk density Densification Electrospinning Orientation-compaction Volumetric capacity

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Halogen-Free Epoxy with Enhanced Corrosion Resistance for Microelectronics Packaging via γ SN2 Nucleophilic Substitution

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chemistry of Materials 2025年第9期37卷 3311-3318页

作者： Qian, Zizhao Zhu, Xiao-Feng Chen, Zhiyu Li, Bo Yang, Guan-Wen Wu, Guang-Peng MOE Key Laboratory of Macromolecular Synthesis and Functionalization Key Laboratory of Adsorption and Separation Materials & Technologies of Zhejiang Province Department of Polymer Science and Engineering Zhejiang University Hangzhou310058 China College of Material Chemistry and Chemical Engineering Key Laboratory of Organosilicon Chemistry and Material Technology Ministry of Education Hangzhou Normal University Zhejiang Hangzhou311121 China

Bisphenol A diglycidyl ether (DGEBA) is an essential epoxy resin in the microelectronics industry. However, circuit corrosion caused by hydrolyzable chlorine─a persistent issue associated with DGEBA─poses significant challenges in this field. In this study, we present a novel strategy for producing halogen-free DGEBA with high purity (up to 99%) and isolated yield (up to 94%) by utilizing glycidyl sulfonates as the starting material. A distinctive γ SN2 nucleophilic substitution pathway between glycidyl sulfonates and phenolic compounds effectively suppresses the formation of ring-opening byproducts and oligomers, as demonstrated through model reactions and kinetic studies. The scalability and versatility of our method are validated by its straightforward synthesis process and expanded substrate scope. Finally, the halogen-free DGEBA exhibits noncorrosive properties when employed as a matrix resin for prepreg and underfill applications. Our research underscores the potential of glycidyl sulfonate as a viable alternative to epichlorohydrin in large-scale epoxy production for electronics. © 2025 American Chemical Society.

关键词： Corrosion resistance

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Smartly tuning supramolecular chirality in polymer gels via photoexcitation-induced cooperative self-assembly

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science China chemistry 2025年第3期68卷 1126-1135页

作者： Bingbing Yue Yulong Shi Fan Yang Danfeng Ye Jian Jin Pilan Zhang Shen Song Yifei Xu Hui Lin Shihui Zhu Liangliang Zhu School of Materials and Chemistry University of Shanghai for Science and TechnologyShanghai 200093China State Key Laboratory of Molecular Engineering of Polymers Department of Macromolecular ScienceFudan UniversityShanghai 200438China College of Material Science and Chemical Engineering Ningbo University of TechnologyNingbo 315211China Shanghai Depeac Biotechnology Co. Ltd.Shanghai 201900China Burn and Plastic Surgery Department Children’s Medical Center Affiliated to Shanghai Jiao Tong University School of MedicineShanghai 200120China

Although supramolecular chirality tuning is prosperous in systems with small molecular building blocks,these systems lack structural strength and have limited practical ***,polymer systems do not exhibit these drawbacks but suffer from topological chain entanglement,which often leads to large dynamic obstacles and therefore limits the tunability of supramolecular ***,we report that by manipulating stoichiometry and employing light to alter the H-bond crosslinking between a photoexcitation-induced aggregatable molecule and high molecular weight poly(L-lactic acids),supramolecular chirality tuning of the polymer gel systems can be achieved in different ways through a cooperative ***,the Cotton effects of the examined systems can be negatively tuned by varying their stoichiometry,while positive tuning can be realized by *** deexcitation,negative Cotton effect tuning occurs again spontaneously in some *** supramolecular chirality tuning is accompanied by rheological property tuning,demonstrating that our strategy can overcome polymer chain entanglement *** proposed strategy inspires further works on the precise control of polymer chirality and,hence,development of asymmetric materials with changeable optical activity and modulus.

关键词： supramolecular chirality polymer gels phototuning self-assembly rheological property

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A review on reactive oxygen species-induced mechanism pathways of pharmaceutical waste degradation:Acetaminophen as a drug waste model

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Journal of Environmental sciences 2025年第1期147卷 688-713页

作者： Saba Humayun Maan Hayyan Yatimah Alias Department of Chemistry Faculty of ScienceUniversity of MalayaKuala Lumpur 50603Malaysia University of Malaya Centre for Ionic Liquids University of MalayaKuala Lumpur 50603Malaysia Chemical Engineering Program Faculty of Engineering and TechnologyMuscat UniversityMuscat P.C.130Oman

Innately designed to induce physiological changes,pharmaceuticals are foreknowingly hazardous to the *** oxidation processes(AOPs)are recognized as a set of contemporary and highly efficient methods being used as a contrivance for the removal of pharmaceutical *** reactive oxygen species(ROS)are formed in these processes to interact and contribute directly toward the oxidation of target contaminant(s),a profound insight regarding the mechanisms of ROS leading to the degradation of pharmaceuticals is fundamentally *** conceptualization of some specific reaction mechanisms allows the design of an effective and safe degradation process that can empirically reduce the environmental impact of *** review mainly deliberates themechanistic reaction pathways for ROS-mediated degradation of pharmaceuticals often leading to complete mineralization,with a focus on acetaminophen as a drug waste model.

关键词： Wastewater treatment Ionic liquid Hydroxyl radical Superoxide Pharmaceutical contaminant Advanced oxidation process Deep eutectic solvent Hydrogen peroxide

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Time-resolved fluorescence measurements of dissolved organic matter (DOM) as a function of environmental parameters in estuarine waters

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Environmental science and Pollution Research 2025年第4期32卷 1952-1970页

作者： de Bruyn, Warren J. Manickam, Dhivya Harrison, Aaron W. Clark, Catherine D. Chemistry and Biochemistry Program Schmid College of Science Chapman University One University Drive OrangeCA92866 United States Department of Chemistry Austin College 900 N. Grand Ave. ShermanTX75090 United States Department of Chemistry College of Science and Engineering Western Washington University 516 High Street BellinghamWA98229 United States

Fluorescent lifetimes of dissolved organic matter (DOM) and associated physicochemical parameters were measured over 14 months in an estuary in Southern California, USA. Measurements were made on 77 samples from sites near the inlet, mid-estuary, and outlet to maximize the range of physicochemical variables. Time-resolved fluorescence data were well fit to a triexponential model with an intermediate lifetime component (τ1: 1 to 5 ns), a long lifetime component (τ2: 2 to 15 ns), and a short lifetime component (τ3: © The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature 2025.

关键词： Fluorescence quenching

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Advances in vat photopolymerization: early-career researchers shine light on a path forward

RSC Applied Polymers

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RSC Applied Polymers 2025年第3期3卷 574-591页

作者： Dhand, Abhishek P. Bean, Ren H. Chiaradia, Viviane Commisso, Alex J. Dranseike, Dalia Fowler, Hayden E. Fraser, Julia M. Howard, Holden Kaneko, Takashi Kim, Ji-Won Kronenfeld, Jason M. Mason, Keldy S. Pashley-Johnson, Fred Porcincula, Dominique H. Segal, Maddison I. Yu, Siwei Saccone, Max A. Department of Bioengineering University of Pennsylvania Philadelphia PA United States Sandia National Laboratories Albuquerque NM United States Department of Chemistry RCSI University of Medicine and Health Sciences Dublin Ireland Macromolecular Engineering Laboratory Department of Mechanical and Process Engineering ETH Zurich Zurich Switzerland Department of Chemistry University of Wisconsin-Madison Madison WI United States Materials Engineering Division Lawrence Livermore National Laboratory United States Department of Chemistry and Biochemistry University of California Santa Barbara CA United States Department of Chemical Engineering Kyungpook National University Daegu South Korea Department of Chemistry Stanford University Stanford CA United States Department of Chemistry The University of Texas at Austin Austin TX United States School of Chemistry and Physics Centre for Materials Science Queensland University of Technology (QUT) Brisbane QLD Australia Centre of Macromolecular Chemistry (CMaC) Department of Organic and Macromolecular Chemistry Faculty of Sciences Ghent University Ghent Belgium Thomas Lord Department of Mechanical Engineering & Material Science Duke University Durham NC United States Department of Chemistry University of Washington Seattle WA United States Department of Chemical Engineering Stanford University Stanford CA United States Paul M. Rady Department of Mechanical Engineering University of Colorado Boulder Boulder CO United States

Vat photopolymerization (VP) has emerged as a promising additive manufacturing technique to allow rapid light-based fabrication of 3D objects from a liquid resin. Research in the field of vat photopolymerization spans across multiple disciplines from engineering and materials science to applied chemistry and physics. This perspective brings together early-career researchers from various disciplines in academia and national laboratories around the world to summarize the most recent advancements with special emphasis on the research highlighted as part of the Gordon Research Conference (GRC) 2024 meeting on Additive Manufacturing of Soft Materials. We provide an outlook on next-generation polymer processing methods from synthesis of novel materials to multimodality manufacturing and performance engineering. Further, this article combines the ideas of many of these junior researchers to present a vision for the future of the field by highlighting the challenges and opportunities that lie ahead. © 2025 RSC.

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