A multifunctional polymeric nanofilm of triazinedithiolsilane monosodium salt, which can resist corrosion and activatecopper surface concurrently, was prepared by galvanostatic technique and the following hydrolysis-c...A multifunctional polymeric nanofilm of triazinedithiolsilane monosodium salt, which can resist corrosion and activatecopper surface concurrently, was prepared by galvanostatic technique and the following hydrolysis-condensation approach.Electrochemical tests were carried out to evaluate the resistant ability of nanofilm. The changes of functional groups atop thenanofilms were monitored with Fourier transform infrared spectroscopy （FT-IR） and contact angles （CA） simultaneously. Thechemical composition and the morphology of the polymeric nanofilm were investigated by X-ray photoelectron spectroscopy （XPS）and scanning electron microscope （SEM）, respectively. The results reveal that the preferentially developed disulfide units protect thecopper during the whole preparation process, and the subsequently hydrolyzed nanofilms without/with heating shape into newinterface phases bearing the multifunctionality. This multifunctional interface （the polymeric nanofilm on copper surface） opens upthe possibilities for other OH-containing reagents to be anchored onto copper surface in demanding researches or industrialapplications.展开更多
Polymeric materials have a broad range of mechanical and physical properties.They have been widely used in material science,biomedical engineering,chemical engineering,and mechanical engineering.The introduction of ac...Polymeric materials have a broad range of mechanical and physical properties.They have been widely used in material science,biomedical engineering,chemical engineering,and mechanical engineering.The introduction of active elements into the soft matrix of polymers has enabled much more diversified functionalities of polymeric materials,such as self-healing,electroactive,magnetosensitive,pH-responsive,and many others.To further enable applications of these multifunctional polymers,a mechanistic modeling method is required and of great significance,as it can provide links between materials’micro/nano-structures and their macroscopic mechanical behaviors.Towards this goal,molecular simulation plays an important role in understanding the deformation and evolution of polymer networks under external loads and stimuli.These molecular insights provide physical guidance in the formulation of mechanistic-based continuum models for multifunctional polymers.In this perspective,we present a molecular simulation-guided and physics-informed modeling framework for polymeric materials.Firstly,the physical theory for polymer chains and their networks is briefly introduced.It serves as the foundation for mechanistic-models of polymers,linking their chemistry,physics,and mechanics together.Secondly,the deformation of the polymer network is used to derive the strain energy density functions.Thus,the corresponding continuum models can capture the intrinsic deformation mechanisms of polymer networks.We then highlight several representative examples across multiphysics coupling problems to describe in detail for this proposed framework.Last but not least,we discuss potential challenges and opportunities in the modeling of multifunctional polymers for future research directions.展开更多
A new multifunctional mPEG-b-PAA-grafted chitosan copolymer possessing amino and carboxyl groups,mPEG-b-PAA-g-CHI(compound 6) ,was designed for a potential application in gene/drug delivery and synthesized by the meth...A new multifunctional mPEG-b-PAA-grafted chitosan copolymer possessing amino and carboxyl groups,mPEG-b-PAA-g-CHI(compound 6) ,was designed for a potential application in gene/drug delivery and synthesized by the methods of reversible addition-fragmentation chain transfer(RAFT) polymerization of acrylic acid(AA) and grafting reaction of a biodegradable chitosan(CHI) derivative.Completion of the reactions and characterization of the resulting compounds were demonstrated by 1 H NMR,FTIR and gel permeation chtomatography(GPC) studies.The results show that the molar ratio of amino groups to carboxyl groups in the copolymer(compound 6) is 0.41-0.59.展开更多
Most of the conventional chemotherapeutic agents used for cancer chemotherapy suffer from multidrug resistance of tumor cells and poor antitumor efficacy.Based on physiological differences between the normal tissue an...Most of the conventional chemotherapeutic agents used for cancer chemotherapy suffer from multidrug resistance of tumor cells and poor antitumor efficacy.Based on physiological differences between the normal tissue and the tumor tissue,one effective approach to improve the efficacy of cancer chemotherapy is to develop pH-sensitive polymeric micellar delivery systems.The copolymers with reversible protonationedeprotonation core units or acid-liable bonds between the therapeutic agents and the micelle-forming copolymers can be used to form pH-sensitive polymeric micelles for extracellular and intracellular drug smart release.These systems can be triggered to release drug in response to the slightly acidic extracellular fluids of tumor tissue after accumulation in tumor tissues via the enhanced permeability and retention effect,or they can be triggered to release drug in endosomes or lysosomes by pH-controlled micelle hydrolysis or dissociation after uptake by cells via the endocytic pathway.The pH-sensitive micelles have been proved the specific tumor cell targeting,enhanced cellular internalization,rapid drug release,and multidrug resistance reversal.The multifunctional polymeric micelles combining extracellular pH-sensitivity with receptor-mediated active targeting strategies are of great interest for enhanced tumor targeting.The micelles with receptor-mediated and intracellular pH targeting functions are internalized via receptor-mediated endocytosis followed by endosomal-pH triggered drug release inside the cells,which reverses multidrug resistance.The pH sensitivity strategy of the polymeric micelles facilitates the specific drug delivery with reduced systemic side effects and improved chemotherapeutical efficacy,and is a novel promising platform for tumor-targeting drug delivery.展开更多
A novel kind of multifunctional polysiloxane containing charge-transporting agent and as electro-optical chromophore has been prepared for photorefractive application. The structural characterization of this kind of p...A novel kind of multifunctional polysiloxane containing charge-transporting agent and as electro-optical chromophore has been prepared for photorefractive application. The structural characterization of this kind of polymer is presented by IR spectra and elemental analysis.展开更多
CONSPECTUS:Polyoxadiazole(POD),a rigid-chain conductive polymer featuring alternating aromatic and electron-deficient oxadiazole rings,has emerged as a versatile platform for advanced energy technologies.Due to its in...CONSPECTUS:Polyoxadiazole(POD),a rigid-chain conductive polymer featuring alternating aromatic and electron-deficient oxadiazole rings,has emerged as a versatile platform for advanced energy technologies.Due to its intrinsic n-type conductivity,exceptional thermal stability(>440℃),and dual ion-electron transport capabilities,it overcomes critical limitations in lithium-ion batteries(LIBs),lithium metal anodes(LMAs),pseudocapacitors,and fuel cells.While conventional conductive polymers prioritize flexibility,POD excels in harsh electrochemical environments.One-step acid-mediated polymerization using oleum enables near-quantitative cyclization(DC≈100%)and in situ sulfonation,bypassing structural defects of traditional two-step methods.Nevertheless,the reliance on corrosive solvents presents scalability challenges,driving innovations in molecular engineering.In this Account,we detail molecular design strategies that address performance trade-offs across energy storage systems through tailored POD-based materials.(1)LIB electrodes:Sulfonated POD binders enable stable dual conduction in Si anodes,with recent advances showing that optimized binder networks facilitate efficient energy dissipation and maintain structural integrity over extended cycling.For graphite anodes,π−πinteractions enhance electron transfer and rate capability,retaining significant capacity at high C-rates.(2)Lithium metal systems:Gel polymer electrolytes with high Li^(+)transference numbers and robust artificial SEI layers effectively suppress dendrite growth,enabling stable long-term cycling under high current densities.(3)Pseudocapacitors:Conjugationengineered POD anodes achieve high specific capacitance with exceptional cycling stability and Coulombic efficiency,benefiting from molecular optimization and electrolyte engineering.(4)Fuel cells:Sulfonated POD derivatives leverage oxadiazole N-sites for efficient proton transport,demonstrating performance competitive with that of commercial benchmarks.We further examine how(i)backbone functionalization tunes electronic structure for specific redox activity;(ii)cross-linking architectures balance mechanical resilience with ionic conduction;and(iii)controlled carbonization creates doped conductive networks for binder-free electrodes.These strategic approaches highlight the versatility of POD in bridging molecular design with macroscopic performance in advanced energy technologies.Finally,we outline key challenges and future priorities:replacing corrosive solvents with sustainable synthesis,decoding interfacial degradation via machine learning,and expanding into solid-state photovoltaics/bioelectronics.Integration with 2D materials(MXenes and COFs)represents a promising frontier for next-generation hybrid devices.展开更多
基金Project(2013DFR40700)supported by International S&T Cooperation Program of ChinaProjects(21174034,51003019,51302280)supported by the National Natural Science Foundation of China
文摘A multifunctional polymeric nanofilm of triazinedithiolsilane monosodium salt, which can resist corrosion and activatecopper surface concurrently, was prepared by galvanostatic technique and the following hydrolysis-condensation approach.Electrochemical tests were carried out to evaluate the resistant ability of nanofilm. The changes of functional groups atop thenanofilms were monitored with Fourier transform infrared spectroscopy （FT-IR） and contact angles （CA） simultaneously. Thechemical composition and the morphology of the polymeric nanofilm were investigated by X-ray photoelectron spectroscopy （XPS）and scanning electron microscope （SEM）, respectively. The results reveal that the preferentially developed disulfide units protect thecopper during the whole preparation process, and the subsequently hydrolyzed nanofilms without/with heating shape into newinterface phases bearing the multifunctionality. This multifunctional interface （the polymeric nanofilm on copper surface） opens upthe possibilities for other OH-containing reagents to be anchored onto copper surface in demanding researches or industrialapplications.
基金the support from the Interdisciplinary Multi-Investigator Materials Proposals(IMMP)program of the Institute of Materials Science at the University of Connecticutfunding support from the National Science Foundation(CMMI-1762661 and CMMI-1934829)the funding support from the National Science Foundation(CMMI-1762567 and CMMI-1943598).
文摘Polymeric materials have a broad range of mechanical and physical properties.They have been widely used in material science,biomedical engineering,chemical engineering,and mechanical engineering.The introduction of active elements into the soft matrix of polymers has enabled much more diversified functionalities of polymeric materials,such as self-healing,electroactive,magnetosensitive,pH-responsive,and many others.To further enable applications of these multifunctional polymers,a mechanistic modeling method is required and of great significance,as it can provide links between materials’micro/nano-structures and their macroscopic mechanical behaviors.Towards this goal,molecular simulation plays an important role in understanding the deformation and evolution of polymer networks under external loads and stimuli.These molecular insights provide physical guidance in the formulation of mechanistic-based continuum models for multifunctional polymers.In this perspective,we present a molecular simulation-guided and physics-informed modeling framework for polymeric materials.Firstly,the physical theory for polymer chains and their networks is briefly introduced.It serves as the foundation for mechanistic-models of polymers,linking their chemistry,physics,and mechanics together.Secondly,the deformation of the polymer network is used to derive the strain energy density functions.Thus,the corresponding continuum models can capture the intrinsic deformation mechanisms of polymer networks.We then highlight several representative examples across multiphysics coupling problems to describe in detail for this proposed framework.Last but not least,we discuss potential challenges and opportunities in the modeling of multifunctional polymers for future research directions.
基金Project(20704011) supported by the National Natural Science Foundation of ChinaProject(09JJ3027) supported by the Natural Science Foundation of Hunan Province,ChinaProject(50725825) supported by the National Science Foundation for Distinguished Young Scholars
文摘A new multifunctional mPEG-b-PAA-grafted chitosan copolymer possessing amino and carboxyl groups,mPEG-b-PAA-g-CHI(compound 6) ,was designed for a potential application in gene/drug delivery and synthesized by the methods of reversible addition-fragmentation chain transfer(RAFT) polymerization of acrylic acid(AA) and grafting reaction of a biodegradable chitosan(CHI) derivative.Completion of the reactions and characterization of the resulting compounds were demonstrated by 1 H NMR,FTIR and gel permeation chtomatography(GPC) studies.The results show that the molar ratio of amino groups to carboxyl groups in the copolymer(compound 6) is 0.41-0.59.
基金This work was financially supported from the National Nature Science Foundation of China(NO.81360483)from the Nature Science Foundation of Ningxia(No.NZ12193).
文摘Most of the conventional chemotherapeutic agents used for cancer chemotherapy suffer from multidrug resistance of tumor cells and poor antitumor efficacy.Based on physiological differences between the normal tissue and the tumor tissue,one effective approach to improve the efficacy of cancer chemotherapy is to develop pH-sensitive polymeric micellar delivery systems.The copolymers with reversible protonationedeprotonation core units or acid-liable bonds between the therapeutic agents and the micelle-forming copolymers can be used to form pH-sensitive polymeric micelles for extracellular and intracellular drug smart release.These systems can be triggered to release drug in response to the slightly acidic extracellular fluids of tumor tissue after accumulation in tumor tissues via the enhanced permeability and retention effect,or they can be triggered to release drug in endosomes or lysosomes by pH-controlled micelle hydrolysis or dissociation after uptake by cells via the endocytic pathway.The pH-sensitive micelles have been proved the specific tumor cell targeting,enhanced cellular internalization,rapid drug release,and multidrug resistance reversal.The multifunctional polymeric micelles combining extracellular pH-sensitivity with receptor-mediated active targeting strategies are of great interest for enhanced tumor targeting.The micelles with receptor-mediated and intracellular pH targeting functions are internalized via receptor-mediated endocytosis followed by endosomal-pH triggered drug release inside the cells,which reverses multidrug resistance.The pH sensitivity strategy of the polymeric micelles facilitates the specific drug delivery with reduced systemic side effects and improved chemotherapeutical efficacy,and is a novel promising platform for tumor-targeting drug delivery.
文摘A novel kind of multifunctional polysiloxane containing charge-transporting agent and as electro-optical chromophore has been prepared for photorefractive application. The structural characterization of this kind of polymer is presented by IR spectra and elemental analysis.
基金supported by the State Key Laboratory of Polymer Materials Engineering(Grant No.:sklpme2022-2-04).
文摘CONSPECTUS:Polyoxadiazole(POD),a rigid-chain conductive polymer featuring alternating aromatic and electron-deficient oxadiazole rings,has emerged as a versatile platform for advanced energy technologies.Due to its intrinsic n-type conductivity,exceptional thermal stability(>440℃),and dual ion-electron transport capabilities,it overcomes critical limitations in lithium-ion batteries(LIBs),lithium metal anodes(LMAs),pseudocapacitors,and fuel cells.While conventional conductive polymers prioritize flexibility,POD excels in harsh electrochemical environments.One-step acid-mediated polymerization using oleum enables near-quantitative cyclization(DC≈100%)and in situ sulfonation,bypassing structural defects of traditional two-step methods.Nevertheless,the reliance on corrosive solvents presents scalability challenges,driving innovations in molecular engineering.In this Account,we detail molecular design strategies that address performance trade-offs across energy storage systems through tailored POD-based materials.(1)LIB electrodes:Sulfonated POD binders enable stable dual conduction in Si anodes,with recent advances showing that optimized binder networks facilitate efficient energy dissipation and maintain structural integrity over extended cycling.For graphite anodes,π−πinteractions enhance electron transfer and rate capability,retaining significant capacity at high C-rates.(2)Lithium metal systems:Gel polymer electrolytes with high Li^(+)transference numbers and robust artificial SEI layers effectively suppress dendrite growth,enabling stable long-term cycling under high current densities.(3)Pseudocapacitors:Conjugationengineered POD anodes achieve high specific capacitance with exceptional cycling stability and Coulombic efficiency,benefiting from molecular optimization and electrolyte engineering.(4)Fuel cells:Sulfonated POD derivatives leverage oxadiazole N-sites for efficient proton transport,demonstrating performance competitive with that of commercial benchmarks.We further examine how(i)backbone functionalization tunes electronic structure for specific redox activity;(ii)cross-linking architectures balance mechanical resilience with ionic conduction;and(iii)controlled carbonization creates doped conductive networks for binder-free electrodes.These strategic approaches highlight the versatility of POD in bridging molecular design with macroscopic performance in advanced energy technologies.Finally,we outline key challenges and future priorities:replacing corrosive solvents with sustainable synthesis,decoding interfacial degradation via machine learning,and expanding into solid-state photovoltaics/bioelectronics.Integration with 2D materials(MXenes and COFs)represents a promising frontier for next-generation hybrid devices.
