The four-decade quest for synthesizing ambient-stable polymeric nitrogen,a promising high-energy-density material,remains an unsolved challenge in materials science.We develop a multi-stage computational strategy empl...The four-decade quest for synthesizing ambient-stable polymeric nitrogen,a promising high-energy-density material,remains an unsolved challenge in materials science.We develop a multi-stage computational strategy employing density functional tight-binding-based rapid screening combined with density functional theory refinement and global structure searching,effectively bridging computational efficiency with quantum accuracy.This integrated approach identifies four novel polymeric nitrogen phases(Fddd,P3221,I4m2,and𝑃P6522)that are thermodynamically stable at ambient pressure.Remarkably,the helical𝑃6522 configuration demonstrates exceptional thermal resilience up to 1500 K,representing a predicted polymeric nitrogen structure that maintains stability under both atmospheric pressure and high-temperature extremes.Our methodology establishes a paradigm-shifting framework for the accelerated discovery of metastable energetic materials,resolving critical bottlenecks in theoretical predictions while providing experimentally actionable targets for polymeric nitrogen synthesis.展开更多
Photocatalytic conversion of CO_(2) is pivotal for mitigating the global greenhouse effect and fostering sustainable energy development.Nowadays,polymeric carbon nitride(PCN)has gained widespread application in CO_(2)...Photocatalytic conversion of CO_(2) is pivotal for mitigating the global greenhouse effect and fostering sustainable energy development.Nowadays,polymeric carbon nitride(PCN)has gained widespread application in CO_(2) solar reduction due to its excellent visible light response,suitable conduction band position,and good cost-effectiveness.However,the amorphous nature and low conductivity of PCN limit its photocatalytic efficiency by leading to low carrier concentrations and facile electron–hole recombination during photocatalysis.Addressing this bottleneck,in this study,potassium-doped PCN(KPCN)/copper(Ⅱ)-complexed bipyridine hydroxyquinoline carboxylic acid(Cu(Ⅱ)(bpy)(H_(2)hqc))composite catalysts were synthesized through a multistep microwave heating process.In the composite,the formation of an S-scheme junction facilitates the enrichment of more negative electrons on the conduction band of KPCN via intermolecular electron–hole recombination between Cu(Ⅱ)(bpy)(H_(2)hqc)(CuPyQc)and KPCN,thereby promoting efficient photoreduction of CO_(2) to CO.Microwave heating enhances the amidation reaction between these two components,achieving the immobilization of homogeneous molecular catalysts and forming amidation chemical bonds that serve as key channels for the S-scheme charge transfer.This work not only presents a new PCN-based catalytic system for CO_(2) reduction applications,but also offers a novel microwave-practical approach for immobilizing homogeneous catalysts.展开更多
Arsenic(As)pollution seriously threatens human and ecological health.Microalgal cell wall and extracellular polymeric substances(EPS)are known to interactwith As,but their roles in the As resistance,accumulation and s...Arsenic(As)pollution seriously threatens human and ecological health.Microalgal cell wall and extracellular polymeric substances(EPS)are known to interactwith As,but their roles in the As resistance,accumulation and speciation inmicroalgae remain unclear.Here,we used two strains of Chlamydomonas reinhardtii,namely CC-125(wild type)and CC-503(cell walldeficientmutant),to examine the algal growth,EPS synthesis,As adsorption,absorption and transformation under 10–1000μg/L As(III)and As(V)treatments for 96 h.In both strains,the As absorption increased after the EPS removal,but the growth,As adsorption,and transformation of C.reinhardtii declined.The CC-125 strain was more tolerant to As stress and more efficient in EPS production,As accumulation,and redox transformation than CC-503,irrespective of EPS presence or absence.Three-dimension excitation-emission matrix(3DEEM)and attenuated total reflectance infrared spectroscopy(ATR-IR)analyses showed that As was bound with functional groups in the EPS and cell wall,such as-COOH,NH and-OH in proteins,polysaccharides and amino acids.Together,this study demonstrated that EPS and cell wall acted as barriers to lower the As uptake by C.reinhardtii.However,the cell wall mutant strain wasmore susceptible to As toxicity due to lower EPS induction and higher As absorption.展开更多
The recent commercialization of gene products has sparked significant interest in gene therapy,necessitating efficient and precise gene delivery via various vectors.Currently,viral vectors and lipid-based nanocarriers...The recent commercialization of gene products has sparked significant interest in gene therapy,necessitating efficient and precise gene delivery via various vectors.Currently,viral vectors and lipid-based nanocarriers are the predominant choices and have been extensively investigated and reviewed.Beyond these vectors,polymeric nanocarriers also hold the promise in therapeutic gene delivery owing to their versatile functionalities,such as improving the stability,cellar uptake and endosomal escape of nucleic acid drugs,along with precise delivery to targeted tissues.This review presents a brief overview of the status quo of the emerging polymeric nanocarriers for therapeutic gene delivery,focusing on key cationic polymers,nanocarrier types,and preparation methods.It also highlights targeted diseases,strategies to improve delivery efficiency,and potential future directions in this research area.The review is hoped to inspire the development,optimization,and clinical translation of highly efficient polymeric nanocarriers for therapeutic gene delivery.展开更多
Molecular-level interactions between polymeric inhibitors and wax crystals are essential for mitigating wax deposition in crude oils,a major operational and environmental challenge.This study investigates the mechanis...Molecular-level interactions between polymeric inhibitors and wax crystals are essential for mitigating wax deposition in crude oils,a major operational and environmental challenge.This study investigates the mechanisms by which specific inhibitors target wax crystals to prevent aggregation.Extracted wax and inhibitor were characterized using gas chromatography,X-ray diffraction,and spectroscopy to determine the molecular structures.The wax primarily comprised of straight-chain nC28 alkanes,while the inhibitor was an ethylene/vinyl acetate copolymer.Rheological tests demonstrated a reduced gelation point upon inhibitor addition.Molecular dynamics(MD)simulations,performed using the COMPASS II force field,revealed interactions at the molecular level.Structural validation of molecules was done through comparative analysis of the experimental infrared and simulated vibrational analysis spectra whereas that of the rhombohedral wax crystal was achieved using the Pawley method,yielding a Profile R-factor of 9.26%.Morphological studies revealed five symmetrically unique facets,with the(110)plane being the fastestgrowing due to its inter-planar distance and attachment energy(-157.25 kcal/mol).Adsorption energy calculations(-180 kcal/mol)confirmed that the inhibitor effectively disrupted crystal growth on the surface by adsorbing its polar section onto the wax surface while repelling the non-polar groups,thereby reducing waxaggregation.展开更多
Developing efficient,non-toxic,and low-cost emitters is a key issue in promoting the applications of electrochemiluminescence(ECL).Among varied ECL emitters,polymeric emitters are attracting dramatically increasing in...Developing efficient,non-toxic,and low-cost emitters is a key issue in promoting the applications of electrochemiluminescence(ECL).Among varied ECL emitters,polymeric emitters are attracting dramatically increasing interest due to tunable structure,large surface area,brilliant transfer capability,and sustainable raw materials.In this review,we present a general overview of recent advances in developing polymeric luminophores,including their structural and synthetic methodologies.Methods rooted in straightforward unique structural modulation have been comprehensively summarized,aiming at enhancing the efficiency of ECL along with the underlying kinetic mechanisms.Moreover,as several conjugated polymers were just discovered in recent years,promising prospects and perspectives have also been deliberated.The insight of this review may provide a new avenue for helping develop advanced conjugated polymer ECL emitters and decode ECL applications.展开更多
Photoswitchable fluorescent polymeric nanoparticles were widely concerned because of their excellent features including the flexible design,easy preparation and functionalization,and thus exhibited great application p...Photoswitchable fluorescent polymeric nanoparticles were widely concerned because of their excellent features including the flexible design,easy preparation and functionalization,and thus exhibited great application potential in information encryption,anti-counterfeiting,but remained challenging in improving the security.Herein,we described a self-erased time-resolved information encryption via using photoswitchable dual-color fluorescent polymeric nanoparticles(PDFPNs)containing two fluorescence dyes(blue and red)and photochromic spiroxazine derivatives.In view of the different thermo-induced isomerization rates of photochromic spiroxazine derivatives in different flexible substrates,the decoloration rate of PDFPNs can be programmatically tuned by regulating ratio between rigid polymer and flexible polymer.Therefore,after ultraviolet light(UV)irradiation,correct information could only be recognized in preestablished time during the self-erased process.Our results indicated that PDFPNs exhibited fast photo-responsibility(2 min),high fluorescence contrast,well-pleasing photo-reversibility(>20 times),and programmable thermo-responsiveness(24 s-6 h).We thus demonstrated their application in the selferased time-resolved information encryption and anti-counterfeiting with high security.展开更多
Designing advanced hydrogels with controlled mechanical properties,drug delivery manner and multifunctional properties will be beneficial for biomedical applications.However,the further development of hydrogel is limi...Designing advanced hydrogels with controlled mechanical properties,drug delivery manner and multifunctional properties will be beneficial for biomedical applications.However,the further development of hydrogel is limited due to its poor mechanical property and structural diversity.Hydrogels combined with polymeric micelles to obtain micelle-hydrogel composites have been designed for synergistic enhancement of each original properties.Incorporation polymeric micelles into hydrogel networks can not only enhance the mechanical property of hydrogel,but also expand the functionality of hydrogel.Recent advances in polymeric micelle-hydrogel composites are herein reviewed with a focus on three typical micelle incorporation methods.In this review,we will also highlight some emerging biomedical applications in developing micelle-hydrogel composite with multiple functionalities.In addition,further development and application prospects of the micelle-hydrogels composites have also been addressed.展开更多
Owing to their excellent biocompatibility and potential for durability enhancement,polymeric heart valves(PHVs)are emerging as a promising alternative to traditional prostheses.Unlike conventional materials,PHVs can b...Owing to their excellent biocompatibility and potential for durability enhancement,polymeric heart valves(PHVs)are emerging as a promising alternative to traditional prostheses.Unlike conventional materials,PHVs can be manufactured under precise design criteria,enabling targeted performance improvements.This study introduces a geometric optimization strategy for enhancing the durability of PHVs.The finite element method(FEM)is combined with a dip-molding technique to develop a novel polymeric aortic valve with improved mechanical properties.The tri-leaflet geometry is parameterized using B-spline curves,and the maximum stress in the valve is reduced from 2.4802 to 1.7773 MPa using a multiobjective optimization algorithm NSGA-II(non-dominated sorting genetic algorithm II).Pre-optimized and optimized valve prototypes were fabricated via dip-molding and evaluated during pulsatile-flow tests and accelerated wear tests.The optimized design meets the ISO 5840 standards,with an effective orifice area of 2.019 cm^(2),a regurgitant fraction of 5.693%,and a transvalvular pressure gradient of 7.576 mmHg.Moreover,the optimized valve maintained its structural integrity and functionality over 14 million cycles of the accelerated wear test,whereas the unoptimized valve failed after two million cycles.These findings confirm that the FEM-based geometric optimization method enhances both the mechanical performance and durability of PHVs.展开更多
Solar-driven photocatalytic overall water splitting(POWS)has emerged as a sustainable pathway for hydrogen production,yet faces intrinsic challenges in developing robust catalysts that balance efficiency,stability,and...Solar-driven photocatalytic overall water splitting(POWS)has emerged as a sustainable pathway for hydrogen production,yet faces intrinsic challenges in developing robust catalysts that balance efficiency,stability,and cost-effectiveness.Polymeric carbon nitride(PCN)represents as a promising metal-free photocatalyst for hydrogen production due to the merits of unique electronic structure and exceptional thermal stability.Nevertheless,limited by rapid charge recombination and insufficient oxidative capability,little success has been achieved on pristine PCN photocatalyst in POWS.In this context,recent advances have demonstrated multi-dimensional modification strategies for improving POWS performance.Based on the fundamental principles of photocatalysis,this review discusses the advantages and challenges of PCN-based photocatalysts in POWS systems.With critical evaluation on one-step excitation systems and Z-scheme two-step excitation systems,modification strategies including crystallinity engineering,supramolecular precursor design,cocatalyst modulation,and construction of PCN-based heterojunctions and homojunctions were highlighted by introducing representative advances in POWS application over the past five years.Future perspectives for PCN-based photocatalysts are proposed,aiming to provide new insights for the design of advanced photocatalytic system for efficient POWS.展开更多
Nanocarriers are an efficient drug delivery tool used for cancer treatment.Among various nanocarriers,polymeric micelles(PMs)have garnered attention in recent years due to their excellent properties,including improved...Nanocarriers are an efficient drug delivery tool used for cancer treatment.Among various nanocarriers,polymeric micelles(PMs)have garnered attention in recent years due to their excellent properties,including improved solubility of insoluble drugs,enhanced targeting and accumulation of drugs at the cancer site,increased sensitivity of cancer cells to chemotherapeutic drugs,and prolonged circulation time.This review summarizes the preparation methods,characterization,advantages,and classification of PMs as drug delivery systems for oncology therapeutics.In particular,the self-assembly mechanisms of active ingredients into PMs,the anticancer activities of PMs associated with various cell death pathways,and the research cases of PMs as drug delivery vehicles in cancer therapy are described.Finally,this review summarizes the status of the clinical trials and real-world applications of PMs and briefly analyzes the reasons for the unsatisfactory commercialized states.This review supports further research on the role of PMs as nanocarriers in cancer therapy and adds insights for the successful clinical translation of PM-based products.展开更多
Polymeric nitrogen is a potential high-energy-density material with the advantages of high energy density, easy availability of raw materials, and non-pollution. The design and synthesis of polymeric nitrogen are impo...Polymeric nitrogen is a potential high-energy-density material with the advantages of high energy density, easy availability of raw materials, and non-pollution. The design and synthesis of polymeric nitrogen are important in the research field of energetic materials. The cubic gauche nitrogen was successfully synthesized at high pressure in the diamond anvil cell, which stimulated the theoretical and experimental investigations. To date, several hundred kinds of polymeric nitrogen have been reported. This review introduces the progressive development of polymeric nitrogen with high energy density, the challenges faced by the synthesized polymeric nitrogen under high-pressure,and the importance to improve the stability of polymeric nitrogen at ambient pressure. Furthermore, alternative methods for synthesizing polymeric nitrogen under moderate conditions are also presented. In this field, more efforts are needed to develop strategies for stabilizing more polymeric nitrogen to ambient conditions, especially the stability of free surfaces.展开更多
In the context of global COVID-19 epidemic preparedness,the extensive use of disposable surgical masks(DSM)may lead to its emergence as a main new source of microplastics in the environment.Nowadays,DSMs have become a...In the context of global COVID-19 epidemic preparedness,the extensive use of disposable surgical masks(DSM)may lead to its emergence as a main new source of microplastics in the environment.Nowadays,DSMs have become a non-negligible source of plastic waste in aquatic environment,however,less research has been done on DSM after biofilm colonization in freshwater environment.The study investigated the microbial community of DSM-associated biofilms by 16S rRNA gene sequencing.Analysis of the microbial community in the middle and inner/outer layers of the DSM showed that the middle layer was different from the remaining two layers and that potential pathogens were enriched only in the middle layer of the DSM.Herein,we focused on the middle layer and explored the characterization properties and extracellular polymeric substances(EPS)components changes during biofilm formation.The results showed that the EPS components varied with the biofilm incubation time.As the formation of biofilm,the protein(PN)and polysaccharide(PS)in EPS showed an overall increasing trend,and the growth of PS was well synchronized with PN.Three fluorescent components of EPS were determined by the three-dimensional excitation emission matrix(3D-EEM),including humic acid-like,fulvic acid-like,and aromatic protein-like components.The percentage of fluorescent components varied with increasing biofilm development time and then stabilized.Fourier transform infrared spectroscopy(FTIR)characterization results elucidated the emergence of oxygen-containing functional groups during biofilm formation.Moreover,the hydrophilicity increased with biofilm development.In conclusion,the environmental behavior and ecological risks of DSM in aquatic environment deserve urgent attention in future studies.展开更多
Organic solvent nanofiltration(OSN) is an efficient,low-energy and environmentally friendly phase-free separation process.Obviously,the core of OSN lies in the fabrication of solvent-resistant nanofiltration membranes...Organic solvent nanofiltration(OSN) is an efficient,low-energy and environmentally friendly phase-free separation process.Obviously,the core of OSN lies in the fabrication of solvent-resistant nanofiltration membranes.Although membrane materials reported in the literature such as 2D membranes,porous organic cages,etc.have the potential for ultra-high performance,polymeric membranes provide key advantages in mass production and processability.Therefore,this review focuses on polymeric materials for OSN.This review summarizes the recent progress of polymeric materials,including emerging and traditional polymeric membranes.Then,a summary of recent progress about strategies developed for perm-selective nanofilms are presented,followed by a brief overview of commercial membrane technology for OSN.Finally,major challenges of OSN and future research directions are presented.Close interaction between the academic research and practical application would help improve greener and more sustainable manufacturing processes.展开更多
The changes of pH,redox potential,concentrations of soluble iron ions and Cu^2＋ with the time of bioleaching chalcopyrite concentrates by acidithiobacillus ferrooxidans were investigated under the different condition...The changes of pH,redox potential,concentrations of soluble iron ions and Cu^2＋ with the time of bioleaching chalcopyrite concentrates by acidithiobacillus ferrooxidans were investigated under the different conditions of initial total-iron amount as well as mole ratio of Fe（III） to Fe（II） in the solutions containing synthetic extracellular polymeric substances （EPS）.When the solution potential is lower than 650 mV （vs SHE）,the inhibition of jarosites to bioleaching chalcopyrite is not vital as EPS produced by bacteria can retard the contamination through flocculating jarosites even if concentration of Fe（III） ions is up to 20 g/L but increases with increasing the concentration of Fe（III） ions;jarosites formed by bio-oxidized Fe3＋ ions are more easy to adhere to outside surface of EPS space on chalcopyrite;the EPS layer with jarosites acts as a weak diffusion barrier to further rapidly create a high redox potential of more than 650 mV by bio-oxidizing Fe^2＋ ions inside and outside EPS space into Fe^3＋ ions,resulting in a rapid deterioration of ion diffusion performance of the EPS layer to inhibit bioleaching chalcopyrite severely and irreversibly.展开更多
The extracellular polymeric substances（EPS） of Acidithiobacillus ferrooxidans ATCC 23270,and iron and copper enclosed in EPS were extracted by ultrasonication and centrifugation methods to determine the interaction ...The extracellular polymeric substances（EPS） of Acidithiobacillus ferrooxidans ATCC 23270,and iron and copper enclosed in EPS were extracted by ultrasonication and centrifugation methods to determine the interaction mechanism of Cu2＋,Fe3＋ and EPS during bioleaching chalcopyrite.Generally,Cu2＋ ions can stimulate bacteria to produce more EPS than Fe3＋ ions.The mass ratio of Fe3＋/Cu2＋ enclosed in EPS decreased gradually from about 4：1 to about 2：1 when the concentration of Cu2＋ ions increased from 0.01 to 0.04 mol/L.The amount of iron and copper bound together by EPS in ferrous-free 9K medium containing 1% chalcopyrite was about 2 times of that in 9K medium containing 0.04 mol/L Cu2＋ ions.It was inferred that the EPS with jarosites on the surface of chalcopyrite gradually acted as a weak diffusion barrier for Cu2＋,Fe3＋ ions transference during bioleaching chalcopyrite.展开更多
The surface and interfacial properties of polymeric bonding agents and nitramine crystal fillers were studied. The surface free energy and adhesion work of polymeric bonding agents and nitramine fillers were calculate...The surface and interfacial properties of polymeric bonding agents and nitramine crystal fillers were studied. The surface free energy and adhesion work of polymeric bonding agents and nitramine fillers were calculated by using Kaeble′s equations. It was observed that the hydroxyl values of neutral polymeric bonding agents (NPBA) correlate well with the polar components of surface free energies. On the basis of the measurements of swelling ratio and initial modulus, the interfacial bonding through highly crosslinked polymeric shell formation around the nitramine particles and generating interfacial reinforcement were rationalized. The application of Tapping Mode AFM (atomic force micro scope) to observing the surface morphology of NPBA reveals that methyl acrylate monomer appears to play a role for aiding the formation of network like structure when nanometer scale images of NPBA are created.展开更多
The interfacial adhesive properties ofpolypropylene/stainless steel were studied by the blister test. The polypropylene film with a squared free-standing window was pressured by oil from one side of film. The correspo...The interfacial adhesive properties ofpolypropylene/stainless steel were studied by the blister test. The polypropylene film with a squared free-standing window was pressured by oil from one side of film. The corresponding deformation field was observed by a digital speckle correlation method. The experimental results show that the squared film deforms and debonds from stainless steel with the increase of pressure. The debonding of the squared film in initiates from the center of edge and extends to the comer, and then the deformation of film evolves from square to circle shape. The interfacial adhesive energy of polypropylene/stainless steel is （22.60±1.55） J/m2, which is in agreement with that measured by film with a circular window.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
[Objective] To explore the optimal extraction conditions of extracellular polymeric substances （EPS） from activated sludge. [Method] The efficiency of five methods （H2SO4, formaldehyde-NaOH, mixing, heating and NaO...[Objective] To explore the optimal extraction conditions of extracellular polymeric substances （EPS） from activated sludge. [Method] The efficiency of five methods （H2SO4, formaldehyde-NaOH, mixing, heating and NaOH） on the extraction of EPS was investigated comparatively. The optimal extraction conditions of the most suitable method were determined. [Result] NaOH method is most effective in extracting EPS with less DNA contamination and shortened extraction period. The optimal extraction condition was pH of 11, extraction time of 10 min and agitation speed of 80-120 r/min. [Conclusion] The determined optimal extraction condition provided theoretical basis for EPS study.展开更多
基金supported by the National Natural Science Foundation of China(Grant Nos.11974154,and 12304278)the Taishan Scholars Special Funding for Construction Projects(Grant No.tstp20230622)+1 种基金the Natural Science Foundation of Shandong Province(Grant Nos.ZR2022MA004,ZR2023QA127,and ZR2024QA121)the Special Foundation of Yantai for Leading Talents above Provincial Level。
文摘The four-decade quest for synthesizing ambient-stable polymeric nitrogen,a promising high-energy-density material,remains an unsolved challenge in materials science.We develop a multi-stage computational strategy employing density functional tight-binding-based rapid screening combined with density functional theory refinement and global structure searching,effectively bridging computational efficiency with quantum accuracy.This integrated approach identifies four novel polymeric nitrogen phases(Fddd,P3221,I4m2,and𝑃P6522)that are thermodynamically stable at ambient pressure.Remarkably,the helical𝑃6522 configuration demonstrates exceptional thermal resilience up to 1500 K,representing a predicted polymeric nitrogen structure that maintains stability under both atmospheric pressure and high-temperature extremes.Our methodology establishes a paradigm-shifting framework for the accelerated discovery of metastable energetic materials,resolving critical bottlenecks in theoretical predictions while providing experimentally actionable targets for polymeric nitrogen synthesis.
基金supported by the National Natural Science Foundation of China(Nos.22106105 and 22201180)the Innovation Program of Shanghai Municipal Education Commission(No.2019-01-07-00-E00015)+2 种基金Shanghai Science and Technology Innovation Program(No.21DZ1206300)the Central Local Science and Technology Development Guidance Fund(No.YDZX20213100003002)Shanghai Science and Technology Commission Program(No.20060502200).
文摘Photocatalytic conversion of CO_(2) is pivotal for mitigating the global greenhouse effect and fostering sustainable energy development.Nowadays,polymeric carbon nitride(PCN)has gained widespread application in CO_(2) solar reduction due to its excellent visible light response,suitable conduction band position,and good cost-effectiveness.However,the amorphous nature and low conductivity of PCN limit its photocatalytic efficiency by leading to low carrier concentrations and facile electron–hole recombination during photocatalysis.Addressing this bottleneck,in this study,potassium-doped PCN(KPCN)/copper(Ⅱ)-complexed bipyridine hydroxyquinoline carboxylic acid(Cu(Ⅱ)(bpy)(H_(2)hqc))composite catalysts were synthesized through a multistep microwave heating process.In the composite,the formation of an S-scheme junction facilitates the enrichment of more negative electrons on the conduction band of KPCN via intermolecular electron–hole recombination between Cu(Ⅱ)(bpy)(H_(2)hqc)(CuPyQc)and KPCN,thereby promoting efficient photoreduction of CO_(2) to CO.Microwave heating enhances the amidation reaction between these two components,achieving the immobilization of homogeneous molecular catalysts and forming amidation chemical bonds that serve as key channels for the S-scheme charge transfer.This work not only presents a new PCN-based catalytic system for CO_(2) reduction applications,but also offers a novel microwave-practical approach for immobilizing homogeneous catalysts.
基金supported by the National Natural Science Foundation of China(Nos.32171623 and 31770548)the National Key Research and Development Program of China(Nos.2016YFD0800306 and 2017YFD0800305).
文摘Arsenic(As)pollution seriously threatens human and ecological health.Microalgal cell wall and extracellular polymeric substances(EPS)are known to interactwith As,but their roles in the As resistance,accumulation and speciation inmicroalgae remain unclear.Here,we used two strains of Chlamydomonas reinhardtii,namely CC-125(wild type)and CC-503(cell walldeficientmutant),to examine the algal growth,EPS synthesis,As adsorption,absorption and transformation under 10–1000μg/L As(III)and As(V)treatments for 96 h.In both strains,the As absorption increased after the EPS removal,but the growth,As adsorption,and transformation of C.reinhardtii declined.The CC-125 strain was more tolerant to As stress and more efficient in EPS production,As accumulation,and redox transformation than CC-503,irrespective of EPS presence or absence.Three-dimension excitation-emission matrix(3DEEM)and attenuated total reflectance infrared spectroscopy(ATR-IR)analyses showed that As was bound with functional groups in the EPS and cell wall,such as-COOH,NH and-OH in proteins,polysaccharides and amino acids.Together,this study demonstrated that EPS and cell wall acted as barriers to lower the As uptake by C.reinhardtii.However,the cell wall mutant strain wasmore susceptible to As toxicity due to lower EPS induction and higher As absorption.
基金supported by National Natural Science Foundation of China(82104082)Natural Science Foundation of Qinghai Province(2024-ZJ-911).
文摘The recent commercialization of gene products has sparked significant interest in gene therapy,necessitating efficient and precise gene delivery via various vectors.Currently,viral vectors and lipid-based nanocarriers are the predominant choices and have been extensively investigated and reviewed.Beyond these vectors,polymeric nanocarriers also hold the promise in therapeutic gene delivery owing to their versatile functionalities,such as improving the stability,cellar uptake and endosomal escape of nucleic acid drugs,along with precise delivery to targeted tissues.This review presents a brief overview of the status quo of the emerging polymeric nanocarriers for therapeutic gene delivery,focusing on key cationic polymers,nanocarrier types,and preparation methods.It also highlights targeted diseases,strategies to improve delivery efficiency,and potential future directions in this research area.The review is hoped to inspire the development,optimization,and clinical translation of highly efficient polymeric nanocarriers for therapeutic gene delivery.
基金the China Sponsorship Council for the scholarship funding(2022GXZ006306)The authors would like to acknowledge contributions from colleagues and support from the Sinopec Company project(No.P23138)the National Natural Science Foundation of China(No.52174047).We also appreciate the editors and the anonymous reviewers for reviewing the manuscript.
文摘Molecular-level interactions between polymeric inhibitors and wax crystals are essential for mitigating wax deposition in crude oils,a major operational and environmental challenge.This study investigates the mechanisms by which specific inhibitors target wax crystals to prevent aggregation.Extracted wax and inhibitor were characterized using gas chromatography,X-ray diffraction,and spectroscopy to determine the molecular structures.The wax primarily comprised of straight-chain nC28 alkanes,while the inhibitor was an ethylene/vinyl acetate copolymer.Rheological tests demonstrated a reduced gelation point upon inhibitor addition.Molecular dynamics(MD)simulations,performed using the COMPASS II force field,revealed interactions at the molecular level.Structural validation of molecules was done through comparative analysis of the experimental infrared and simulated vibrational analysis spectra whereas that of the rhombohedral wax crystal was achieved using the Pawley method,yielding a Profile R-factor of 9.26%.Morphological studies revealed five symmetrically unique facets,with the(110)plane being the fastestgrowing due to its inter-planar distance and attachment energy(-157.25 kcal/mol).Adsorption energy calculations(-180 kcal/mol)confirmed that the inhibitor effectively disrupted crystal growth on the surface by adsorbing its polar section onto the wax surface while repelling the non-polar groups,thereby reducing waxaggregation.
基金supported by the National Natural Science Foundation of China(Nos.22174014 and 22074015)China Postdoctoral Science Foundation(No.2023M740595)+1 种基金Postdoctoral Fellowship Program of CPSF(No.GZC20230427)Jiangsu Funding Program for Excellent Postdoctoral Talent(No.2023ZB353).
文摘Developing efficient,non-toxic,and low-cost emitters is a key issue in promoting the applications of electrochemiluminescence(ECL).Among varied ECL emitters,polymeric emitters are attracting dramatically increasing interest due to tunable structure,large surface area,brilliant transfer capability,and sustainable raw materials.In this review,we present a general overview of recent advances in developing polymeric luminophores,including their structural and synthetic methodologies.Methods rooted in straightforward unique structural modulation have been comprehensively summarized,aiming at enhancing the efficiency of ECL along with the underlying kinetic mechanisms.Moreover,as several conjugated polymers were just discovered in recent years,promising prospects and perspectives have also been deliberated.The insight of this review may provide a new avenue for helping develop advanced conjugated polymer ECL emitters and decode ECL applications.
基金financially supported by the National Key R&D Program of China(Nos.2023YFB3812400,2023YFB3812403)National Natural Foundation of China(Nos.52273206,52350233)+1 种基金Hunan Provincial Natural Science Foundation(No.2021JJ10029)Huxiang High-level Talent Gathering Project(No.2022RC4039).
文摘Photoswitchable fluorescent polymeric nanoparticles were widely concerned because of their excellent features including the flexible design,easy preparation and functionalization,and thus exhibited great application potential in information encryption,anti-counterfeiting,but remained challenging in improving the security.Herein,we described a self-erased time-resolved information encryption via using photoswitchable dual-color fluorescent polymeric nanoparticles(PDFPNs)containing two fluorescence dyes(blue and red)and photochromic spiroxazine derivatives.In view of the different thermo-induced isomerization rates of photochromic spiroxazine derivatives in different flexible substrates,the decoloration rate of PDFPNs can be programmatically tuned by regulating ratio between rigid polymer and flexible polymer.Therefore,after ultraviolet light(UV)irradiation,correct information could only be recognized in preestablished time during the self-erased process.Our results indicated that PDFPNs exhibited fast photo-responsibility(2 min),high fluorescence contrast,well-pleasing photo-reversibility(>20 times),and programmable thermo-responsiveness(24 s-6 h).We thus demonstrated their application in the selferased time-resolved information encryption and anti-counterfeiting with high security.
基金the Natural Science Basic Research Program of Shaanxi Province(No.2023-JC-YB-101)the Basic Science Research Program of Shaanxi Basic Sciences Institute(Chemistry,Biology)(No.22JHQ079)National Natural Science Foundation of China(No.82272150).
文摘Designing advanced hydrogels with controlled mechanical properties,drug delivery manner and multifunctional properties will be beneficial for biomedical applications.However,the further development of hydrogel is limited due to its poor mechanical property and structural diversity.Hydrogels combined with polymeric micelles to obtain micelle-hydrogel composites have been designed for synergistic enhancement of each original properties.Incorporation polymeric micelles into hydrogel networks can not only enhance the mechanical property of hydrogel,but also expand the functionality of hydrogel.Recent advances in polymeric micelle-hydrogel composites are herein reviewed with a focus on three typical micelle incorporation methods.In this review,we will also highlight some emerging biomedical applications in developing micelle-hydrogel composite with multiple functionalities.In addition,further development and application prospects of the micelle-hydrogels composites have also been addressed.
基金funded by the National Natural Science Foundation of China(No.82400370)the Interdisciplinary Innovation Team Incubation Project of Children’s Hospital of Fudan University(No.EKYX202416).
文摘Owing to their excellent biocompatibility and potential for durability enhancement,polymeric heart valves(PHVs)are emerging as a promising alternative to traditional prostheses.Unlike conventional materials,PHVs can be manufactured under precise design criteria,enabling targeted performance improvements.This study introduces a geometric optimization strategy for enhancing the durability of PHVs.The finite element method(FEM)is combined with a dip-molding technique to develop a novel polymeric aortic valve with improved mechanical properties.The tri-leaflet geometry is parameterized using B-spline curves,and the maximum stress in the valve is reduced from 2.4802 to 1.7773 MPa using a multiobjective optimization algorithm NSGA-II(non-dominated sorting genetic algorithm II).Pre-optimized and optimized valve prototypes were fabricated via dip-molding and evaluated during pulsatile-flow tests and accelerated wear tests.The optimized design meets the ISO 5840 standards,with an effective orifice area of 2.019 cm^(2),a regurgitant fraction of 5.693%,and a transvalvular pressure gradient of 7.576 mmHg.Moreover,the optimized valve maintained its structural integrity and functionality over 14 million cycles of the accelerated wear test,whereas the unoptimized valve failed after two million cycles.These findings confirm that the FEM-based geometric optimization method enhances both the mechanical performance and durability of PHVs.
基金the National Natural Science Foundation of China(Nos.52488201,52376209)the Fundamental Research Funds for the Central Universities.Zhenxiong Huang thanks the Key Project of Jiangxi Academy of Science(No.2022YYB05)the Science and Technology Innovation Project for Carbon Peak and Neutrality of Jiangxi Carbon Neutralization Research Center(2022JXST02).
文摘Solar-driven photocatalytic overall water splitting(POWS)has emerged as a sustainable pathway for hydrogen production,yet faces intrinsic challenges in developing robust catalysts that balance efficiency,stability,and cost-effectiveness.Polymeric carbon nitride(PCN)represents as a promising metal-free photocatalyst for hydrogen production due to the merits of unique electronic structure and exceptional thermal stability.Nevertheless,limited by rapid charge recombination and insufficient oxidative capability,little success has been achieved on pristine PCN photocatalyst in POWS.In this context,recent advances have demonstrated multi-dimensional modification strategies for improving POWS performance.Based on the fundamental principles of photocatalysis,this review discusses the advantages and challenges of PCN-based photocatalysts in POWS systems.With critical evaluation on one-step excitation systems and Z-scheme two-step excitation systems,modification strategies including crystallinity engineering,supramolecular precursor design,cocatalyst modulation,and construction of PCN-based heterojunctions and homojunctions were highlighted by introducing representative advances in POWS application over the past five years.Future perspectives for PCN-based photocatalysts are proposed,aiming to provide new insights for the design of advanced photocatalytic system for efficient POWS.
基金supported by the National Natural Science Foundation of China (Nos. 82373800 and 82104070)the General Program of Administration of Traditional Chinese Medicine of Guangdong Province (No. 20241071)+1 种基金the Science and Technology Innovation Project of Drug Administration of Guangdong Province (No. 2023YDZ06)the Hainan Provincial Natural Science Foundation of China (No. 823MS032)
文摘Nanocarriers are an efficient drug delivery tool used for cancer treatment.Among various nanocarriers,polymeric micelles(PMs)have garnered attention in recent years due to their excellent properties,including improved solubility of insoluble drugs,enhanced targeting and accumulation of drugs at the cancer site,increased sensitivity of cancer cells to chemotherapeutic drugs,and prolonged circulation time.This review summarizes the preparation methods,characterization,advantages,and classification of PMs as drug delivery systems for oncology therapeutics.In particular,the self-assembly mechanisms of active ingredients into PMs,the anticancer activities of PMs associated with various cell death pathways,and the research cases of PMs as drug delivery vehicles in cancer therapy are described.Finally,this review summarizes the status of the clinical trials and real-world applications of PMs and briefly analyzes the reasons for the unsatisfactory commercialized states.This review supports further research on the role of PMs as nanocarriers in cancer therapy and adds insights for the successful clinical translation of PM-based products.
基金supported by the CASHIPS Director’s Fund (Grant No. YZJJ202207-CX)。
文摘Polymeric nitrogen is a potential high-energy-density material with the advantages of high energy density, easy availability of raw materials, and non-pollution. The design and synthesis of polymeric nitrogen are important in the research field of energetic materials. The cubic gauche nitrogen was successfully synthesized at high pressure in the diamond anvil cell, which stimulated the theoretical and experimental investigations. To date, several hundred kinds of polymeric nitrogen have been reported. This review introduces the progressive development of polymeric nitrogen with high energy density, the challenges faced by the synthesized polymeric nitrogen under high-pressure,and the importance to improve the stability of polymeric nitrogen at ambient pressure. Furthermore, alternative methods for synthesizing polymeric nitrogen under moderate conditions are also presented. In this field, more efforts are needed to develop strategies for stabilizing more polymeric nitrogen to ambient conditions, especially the stability of free surfaces.
基金Supported by the Natural Science Foundation of Shandong Province(Nos.ZR2022MD115,ZR202111160067)。
文摘In the context of global COVID-19 epidemic preparedness,the extensive use of disposable surgical masks(DSM)may lead to its emergence as a main new source of microplastics in the environment.Nowadays,DSMs have become a non-negligible source of plastic waste in aquatic environment,however,less research has been done on DSM after biofilm colonization in freshwater environment.The study investigated the microbial community of DSM-associated biofilms by 16S rRNA gene sequencing.Analysis of the microbial community in the middle and inner/outer layers of the DSM showed that the middle layer was different from the remaining two layers and that potential pathogens were enriched only in the middle layer of the DSM.Herein,we focused on the middle layer and explored the characterization properties and extracellular polymeric substances(EPS)components changes during biofilm formation.The results showed that the EPS components varied with the biofilm incubation time.As the formation of biofilm,the protein(PN)and polysaccharide(PS)in EPS showed an overall increasing trend,and the growth of PS was well synchronized with PN.Three fluorescent components of EPS were determined by the three-dimensional excitation emission matrix(3D-EEM),including humic acid-like,fulvic acid-like,and aromatic protein-like components.The percentage of fluorescent components varied with increasing biofilm development time and then stabilized.Fourier transform infrared spectroscopy(FTIR)characterization results elucidated the emergence of oxygen-containing functional groups during biofilm formation.Moreover,the hydrophilicity increased with biofilm development.In conclusion,the environmental behavior and ecological risks of DSM in aquatic environment deserve urgent attention in future studies.
基金Knowledge Innovation Program of Wuhan-Basic Research(2022010801010321)Wuhan Limo Technology Limited Company(2022420111000256)。
文摘Organic solvent nanofiltration(OSN) is an efficient,low-energy and environmentally friendly phase-free separation process.Obviously,the core of OSN lies in the fabrication of solvent-resistant nanofiltration membranes.Although membrane materials reported in the literature such as 2D membranes,porous organic cages,etc.have the potential for ultra-high performance,polymeric membranes provide key advantages in mass production and processability.Therefore,this review focuses on polymeric materials for OSN.This review summarizes the recent progress of polymeric materials,including emerging and traditional polymeric membranes.Then,a summary of recent progress about strategies developed for perm-selective nanofilms are presented,followed by a brief overview of commercial membrane technology for OSN.Finally,major challenges of OSN and future research directions are presented.Close interaction between the academic research and practical application would help improve greener and more sustainable manufacturing processes.
基金Project(2010CB630904) supported by the National Basic Research Program of ChinaProject(50621063) supported by the Chinese Science Foundation for Distinguished Group
文摘The changes of pH,redox potential,concentrations of soluble iron ions and Cu^2＋ with the time of bioleaching chalcopyrite concentrates by acidithiobacillus ferrooxidans were investigated under the different conditions of initial total-iron amount as well as mole ratio of Fe（III） to Fe（II） in the solutions containing synthetic extracellular polymeric substances （EPS）.When the solution potential is lower than 650 mV （vs SHE）,the inhibition of jarosites to bioleaching chalcopyrite is not vital as EPS produced by bacteria can retard the contamination through flocculating jarosites even if concentration of Fe（III） ions is up to 20 g/L but increases with increasing the concentration of Fe（III） ions;jarosites formed by bio-oxidized Fe3＋ ions are more easy to adhere to outside surface of EPS space on chalcopyrite;the EPS layer with jarosites acts as a weak diffusion barrier to further rapidly create a high redox potential of more than 650 mV by bio-oxidizing Fe^2＋ ions inside and outside EPS space into Fe^3＋ ions,resulting in a rapid deterioration of ion diffusion performance of the EPS layer to inhibit bioleaching chalcopyrite severely and irreversibly.
基金Project(50621063) supported by the National Natural Science Foundation of ChinaProject(2010CB630903) supported by the National Basic Research Program of China
文摘The extracellular polymeric substances（EPS） of Acidithiobacillus ferrooxidans ATCC 23270,and iron and copper enclosed in EPS were extracted by ultrasonication and centrifugation methods to determine the interaction mechanism of Cu2＋,Fe3＋ and EPS during bioleaching chalcopyrite.Generally,Cu2＋ ions can stimulate bacteria to produce more EPS than Fe3＋ ions.The mass ratio of Fe3＋/Cu2＋ enclosed in EPS decreased gradually from about 4：1 to about 2：1 when the concentration of Cu2＋ ions increased from 0.01 to 0.04 mol/L.The amount of iron and copper bound together by EPS in ferrous-free 9K medium containing 1% chalcopyrite was about 2 times of that in 9K medium containing 0.04 mol/L Cu2＋ ions.It was inferred that the EPS with jarosites on the surface of chalcopyrite gradually acted as a weak diffusion barrier for Cu2＋,Fe3＋ ions transference during bioleaching chalcopyrite.
文摘The surface and interfacial properties of polymeric bonding agents and nitramine crystal fillers were studied. The surface free energy and adhesion work of polymeric bonding agents and nitramine fillers were calculated by using Kaeble′s equations. It was observed that the hydroxyl values of neutral polymeric bonding agents (NPBA) correlate well with the polar components of surface free energies. On the basis of the measurements of swelling ratio and initial modulus, the interfacial bonding through highly crosslinked polymeric shell formation around the nitramine particles and generating interfacial reinforcement were rationalized. The application of Tapping Mode AFM (atomic force micro scope) to observing the surface morphology of NPBA reveals that methyl acrylate monomer appears to play a role for aiding the formation of network like structure when nanometer scale images of NPBA are created.
基金Projects(11102176,11172258,10828205)supported by the National Natural Science Foundation of China
文摘The interfacial adhesive properties ofpolypropylene/stainless steel were studied by the blister test. The polypropylene film with a squared free-standing window was pressured by oil from one side of film. The corresponding deformation field was observed by a digital speckle correlation method. The experimental results show that the squared film deforms and debonds from stainless steel with the increase of pressure. The debonding of the squared film in initiates from the center of edge and extends to the comer, and then the deformation of film evolves from square to circle shape. The interfacial adhesive energy of polypropylene/stainless steel is （22.60±1.55） J/m2, which is in agreement with that measured by film with a circular window.
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.
基金Supported by the National High-tech Research and Develop Program of China("863"Program)(2009AA064704)the National Natural Science Foundation of China(51038003)the Program for New Century Excellent Talents in University by the State Education Ministry(NCET-08-161)~~
文摘[Objective] To explore the optimal extraction conditions of extracellular polymeric substances （EPS） from activated sludge. [Method] The efficiency of five methods （H2SO4, formaldehyde-NaOH, mixing, heating and NaOH） on the extraction of EPS was investigated comparatively. The optimal extraction conditions of the most suitable method were determined. [Result] NaOH method is most effective in extracting EPS with less DNA contamination and shortened extraction period. The optimal extraction condition was pH of 11, extraction time of 10 min and agitation speed of 80-120 r/min. [Conclusion] The determined optimal extraction condition provided theoretical basis for EPS study.
