Liver is a vital organ in the human body and plays a central role in the metabolism and detoxification of endotoxins and exotoxins.Bilirubin is an endotoxin derived from hemoglobin(Hb).Removing excess bilirubin in the...Liver is a vital organ in the human body and plays a central role in the metabolism and detoxification of endotoxins and exotoxins.Bilirubin is an endotoxin derived from hemoglobin(Hb).Removing excess bilirubin in the blood is crucial for the treatment of liver diseases.Hemoperfusion,which relies on adsorbents to efficiently adsorb toxins,is a widely applied procedure for the removal of blood toxins.To broaden and improve the range and performance of hemoperfusion adsorbents,we synthesized cationic hyper crosslinked polymers(HCPs)with strong affinity for bilirubin.This material exhibited outstanding adsorption performance,with a maximum adsorption capacity of 934 mg/g and a removal efficiency of 96%.Further investigation confirmed their excellent selectivity,reusability,and biocompatibility.These findings expand the potential applications of HCPs and provide insight into strategies for constructing promising hemoperfusion adsorbent materials.展开更多
Under solvothermal conditions,1,4‑naphthalenedicarboxylic acid(H_(2)ndc)and 9,9′‑dihexyl‑2,7‑di(pyridin‑4‑yl)fluorene(hfdp)reacted with Co^(2+)ions and Cd^(2+)ions to form two coordination polymers,[Co(hfdp)(ndc)(H2O...Under solvothermal conditions,1,4‑naphthalenedicarboxylic acid(H_(2)ndc)and 9,9′‑dihexyl‑2,7‑di(pyridin‑4‑yl)fluorene(hfdp)reacted with Co^(2+)ions and Cd^(2+)ions to form two coordination polymers,[Co(hfdp)(ndc)(H2O)]·DMA}n(1)and{[Cd(hfdp)(ndc)(H_(2)O)]·DMA}_(n)(2),respectively(DMA=N,N‑dimethylacetamide).Single‑crystal X‑ray diffraction analyses showed that both complexes 1 and 2 contain similar structures.Topological analysis indicates that complexes 1 and 2 have a{44·62}planar structure.In addition,both complexes reveal good thermal stability and fluorescence sensing performance.They exhibited good sensitivity and selectivity towards 2,4,6‑trinitrophenol(TNP)by fluorescent quenching.The limits of detection of 1 and 2 for TNP were 0.107 and 0.327μmol·L^(-1),respectively.CCDC:2475515,1;2475516,2.展开更多
Antibiotics,as an emerging pollutant due to their extensive use and difficulty in biodegradation,can cause harm to health through bioaccumulation.To address this,various photocatalysts have been developed for rapid an...Antibiotics,as an emerging pollutant due to their extensive use and difficulty in biodegradation,can cause harm to health through bioaccumulation.To address this,various photocatalysts have been developed for rapid antibiotic removal.However,their low concentrations limit mass transfer efficiency,resulting in suboptimal performance.Adsorption is crucial for enhancing photocatalytic efficiency.In this study,a series of binary heterojunction catalysts(x%BWO@STHP)were synthesized,consisting of Bi_(2)WO_(6)(BWO)grafted with sulfonated triptycene-based hypercrosslinked polymer(STHP).The high specific surface area of STHP,combined withπ-πconjugation and ionic interactions with antibiotics,significantly enhances adsorption capacity.This facilitates effective contact between low-concentration pollutants in aqueous solutions and the active sites of the catalyst.The formation of a Z-scheme heterojunction between BWO and STHP facilitates photogenerated charge separation,and further significantly improves photocatalytic degradation performance.Specifically,the 20%BWO@STHP catalyst achieved rapid adsorption equilibrium for oxytetracycline(OTC),doxycycline(DOX),and tetracycline(TC)within 2 min and completely degraded them after 15 min of irradiation.Compared to pristine BWO,the photocatalytic reaction rate constants are significantly increased,being 9.69 times higher for OTC and 13.45 times higher for DOX.The catalyst exhibits excellent reusability and holds promising potential for practical applications.展开更多
Star-shaped six-arm polymers with hexaaza[2_(6)]orthoparacyclophane core and arms of block copolymers of poly-2-ethyl-5,6-dihydrooxazine with poly-2-isopropyl-5,6-dihydrooxazine were synthesized successfully using cat...Star-shaped six-arm polymers with hexaaza[2_(6)]orthoparacyclophane core and arms of block copolymers of poly-2-ethyl-5,6-dihydrooxazine with poly-2-isopropyl-5,6-dihydrooxazine were synthesized successfully using cationic ring-opening polymerization.The ratio of blocks,the order of their attachment to the core,and arm length were varied.Conformation of synthesized stars was determined by methods of molecular hydrodynamics and optics.It has been shown that star-shaped molecules were characterized by high intramolecular density,and the arm folding increased with their lengthening.The influence of the structure of block copolymers and their molar mass on the critical micelle concentration has been established.Complexes of synthesized star-shaped block copolymers with curcumin were obtained and the efficient binding of curcumin to polymer molecules was demonstrated.The behavior of the aqueous solutions of the prepared polymer stars and their complexes with curcumin was investigated by light scattering and turbidimetry methods.The influence of the structure and molar mass of star polymers on their thermoresponsiveness and the phase separation temperatures in aqueous solutions was analyzed.A slight increase in the phase separation temperature was found on passage from polymer solutions to solutions of polymer complexes with hydrophobic curcumin.展开更多
Acceptorless dehydrogenative coupling of pyridinemethanol with ketones is one of the most reliable methodologies to access functionalized 1,8-naphthyridine derivatives.However,it is challenging to develop environmenta...Acceptorless dehydrogenative coupling of pyridinemethanol with ketones is one of the most reliable methodologies to access functionalized 1,8-naphthyridine derivatives.However,it is challenging to develop environmentally friendly catalytic systems,especially in constructing efficient and recyclable catalysts under water or solvent-free conditions.Here,we designed two novel coordination polymers Cd-CPs and Fe-CPs to investigate their catalytic performance in water.Gratifyingly,it was observed that Cd-CPs as a multifunctional catalyst was successfully applied to establish a universal pathway for direct fabrication of 1,8-naphthyridine derivatives under water conditions,while it was effective for the synthesis of1,3,5-triazines through acceptorless dehydrogenative coupling strategies.The features of broad substrate,high atom efficiency,and good catalyst reusability highlight the feasibility of this transformation.In additional,we demonstrated the spindle-like structures Fe-P,derived from the Fe-CPs via phosphorylation,which can be used as an efficient electrocatalyst for oxygen evolution reaction with good stability.This work provides two highly efficient non-noble metal catalysts for functionalized 1,8-naphthyridine derivatives production and oxygen evolution reaction,and opens a new avenue to further fabricate diverse metal catalysts with high catalytic performance in water.展开更多
Among various architectures of polymers,end-group-free rings have attracted growing interests due to their distinct physicochemical performances over the linear counterparts which are exemplified by reduced hydrodynam...Among various architectures of polymers,end-group-free rings have attracted growing interests due to their distinct physicochemical performances over the linear counterparts which are exemplified by reduced hydrodynamic size and slower degradation.It is key to develop facile methods to large-scale synthesis of polymer rings with tunable compositions and microstructures.Recent progresses in large-scale synthesis of polymer rings against single-chain dynamic nanoparticles,and the example applications in synchronous enhancing toughness and strength of polymer nanocomposites are summarized.Once there is the breakthrough in rational design and effective large-scale synthesis of polymer rings and their functional derivatives,a family of cyclic functional hybrids would be available,thus providing a new paradigm in developing polymer science and engineering.展开更多
Four distinct coordination polymers(CPs)were successfully synthesized by altering solvent types and adjusting ligand concentrations,and their crystal structures were investigated.[Co(L)(FDCA)(H_(2)O)_(2)]·0.5H_(2...Four distinct coordination polymers(CPs)were successfully synthesized by altering solvent types and adjusting ligand concentrations,and their crystal structures were investigated.[Co(L)(FDCA)(H_(2)O)_(2)]·0.5H_(2)O(1)was synthesized as a 2D structure using Coas the metal source,methanol‑water(4∶6,V/V)as the solvent,and specific concentrations of 2,5‑furandicarboxylic acid(H_(2)FDCA)and 1,3,5‑triimidazole benzene(L).Adjusting to pure water and lowering the concentration of L yielded the 1D chain structure of[Co(HL)2(H_(2)O)_(2)](FDCA)_(2)·6H_(2)O(2).Using Cu(Ⅱ)as the metal source,methanol/water(9∶1,V/V)as the solvent,and specific concentrations of L and H2FDCA,the 1D chain structure of[Cu(L)(FDCA)(H_(2)O)]·2H_(2)O(3)was synthesized.Upon increasing the concentrations of L and H2FDCA,and switching the solvent to pure water,the 1D chain structure of[Cu(HL)_(2)(H_(2)O)_(2)](FDCA)_(2)·6H_(2)O(4)was obtained.This shows that changing the solvent and ligand concentrations can affect the structural changes of CPs.In addition,the solid‑state photoluminescence of CPs 1‑4 at room temperature was studied,and their morphological changes were observed via scanning electron microscopy.Density functional theory calculations revealed that the negative charge concentrates on the O and N atoms of the ligand,facilitating ligand‑metal ion coordination.CCDC:2403934,1;2403935,2;2403936,3;2403938,4.展开更多
Organic pollutants,a pivotal factor in water pollution,have persistently menaced the aquatic ecosystem,as well as the sustainable development of human health,economy,and society.Consequently,there is an urgent need fo...Organic pollutants,a pivotal factor in water pollution,have persistently menaced the aquatic ecosystem,as well as the sustainable development of human health,economy,and society.Consequently,there is an urgent need for advanced techniques to efficiently eliminate organic micropollutants from water.Here,we present the synthesis of three nonporous cavitand-crosslinked polymers capable of adsorbing diverse organic pollutants from aqueous solutions.These polymeric adsorbents exhibit outstanding adsorptive performance towards the tested micropollutants,characterized by high apparent adsorption rate constants(kobs)and maximum adsorption capacities(qmax,e).Notably,Compound NCCP-1 demonstrated a remarkable qmax,e of 459 mg/g for bisphenol A(BPA),ranking among the highest values reported for organic polymer adsorbents.In-depth investigation of the adsorption mechanism of the nonporous polymer revealed that it involves the recognition of pollutants by the deep cavities of the cavitand moieties and the interstitial spaces between them,primarily mediated by the hydrophobic effect.Furthermore,NCCP-1 was applied in situ water purification simulations and was proven to maintain its removal efficiency over more than four cycles,highlighting its potential for practical applications in water treatment.展开更多
To precisely control intrachain π-electron delocalization and interchain interaction simultaneously is the prerequisite to obtain stable and efficient deep-blue light-emitting p-n polymer semiconductors for the polym...To precisely control intrachain π-electron delocalization and interchain interaction simultaneously is the prerequisite to obtain stable and efficient deep-blue light-emitting p-n polymer semiconductors for the polymer light-emitting diodes(PLEDs).Herein,we introduced the steric carbazole-fluorene nanogrid into light-emitting diphenyl sulfone-based p-n polymer semiconductors(PG and PDG) via metal-free C-N coupling polymerization for the fabrication of deep-blue PLEDs.The steric,rigid and twisted configuration between nanogrid and diphenyl sulfone in PG and PDG present the unique characteristic of large steric hindrance interaction to suppress interchain aggregation in solid state.Due to the different length of electron-deficient diphenyl sulfone monomers,PG showed a deep-blue emission with a maximum peak at 428 nm but red-shifted to 480 nm for the PDG films.Interestingly,similar deep-blue emission behavior of PG in diluted non-polar solution and films suggested the extremely weak interchain aggregation.Finally,PLEDs based on PG are fabricated with a stable deep-blue emission of CIE(0.15,0.10),and corresponding EL spectral profile is also completely identical to PL ones of diluted solution,revealed the intrachain emission without obvious interchain excited state,confirmed effectiveness of the steric hindrance functionalization of nanogrid in p-n polymer semiconductor for deep-blue light-emitting organic optoelectronics.展开更多
Glassy polymers are widely used in biomedical applications in a solvent environment,yet their long-term performance is governed by the competing effects of physical aging and solvent-induced plasticization.Here,we dev...Glassy polymers are widely used in biomedical applications in a solvent environment,yet their long-term performance is governed by the competing effects of physical aging and solvent-induced plasticization.Here,we develop a constitutive model that explicitly couples the solvent concentration,structural relaxation,and mechanical response.This framework is built on a multiplicative decomposition of deformation and an Eyring-type flow rule,with structural evolution described by an effective temperature.A generalized shift factor is introduced to quantify how the solvent concentration and effective temperature jointly affect the relaxation time,thereby integrating physical aging and plasticization.The model is subsequently applied to methacrylate(MA)-based copolymer networks immersed in phosphate-buffered saline for up to nine months.Simulations accurately capture key experimental features,including the strong softening of highly swellable networks,the partial recovery due to aging,and the mitigating role of hydrophobic crosslinking in reducing solvent uptake.While the current single-mode description cannot reproduce the full relaxation spectrum,it establishes an efficient framework for predicting the long-term mechanical performance under coupled environmental and mechanical loading.This study provides a constitutive description of solvent-swollen glassy polymers,offering mechanistic insight into the interplay between plasticization and aging.Beyond biomedical MA networks,this framework establishes a foundation for predicting the long-term performance of polymer glasses under coupled aqueous environmental and mechanical loading.展开更多
Three-dimensional(3 D)printing has revolutionized the design and production of customized scaffolds,but the minimally invasive implantation of 3 D-printed structures into the human body remains challenging.This has pr...Three-dimensional(3 D)printing has revolutionized the design and production of customized scaffolds,but the minimally invasive implantation of 3 D-printed structures into the human body remains challenging.This has prompted the exploration of innovative materials and technical solutions.Shape-memory polymers,as advanced intelligent materials,exhibit considerable potential in minimally invasive surgical applications.Herein,we developed a novel thermosetting shape-memory polymer,poly(L-lactic acid)-trimethylene carbonate-glycolic acid(PLLA-TMC-GA),for the fabrication of bioengineered scaffolds with body temperature-activated shape-memory functionality.We comprehensively evaluated the mechanical properties,thermal stability,shape-memory capabilities,biocompatibility,biodegradability,and 3 D printing performance of PLLA-TMC-GA terpolymers with various compositions.The results indicate that PLLA-TMC-GA exhibits exceptional shape-memory performance,adjustable material properties,favorable biocompatibility,and the potential for controlled biodegradation and reabsorption.The use of PLLA-TMC-GA as a biodegradable shape-memory polymer allows the reduction of implant volume,simplifies implantation,and enables on-demand activation at body temperature.These characteristics present new opportunities for the advancement of minimally invasive surgical techniques.展开更多
Development of polymers with underwater self-healing and antifouling properties is crucial,particularly in harsh marine environments.In this study,polydimethylsiloxane(PDMS)-based antifouling polymers with tunable sel...Development of polymers with underwater self-healing and antifouling properties is crucial,particularly in harsh marine environments.In this study,polydimethylsiloxane(PDMS)-based antifouling polymers with tunable self-healing capabilities in aqueous conditions were fabricated by incorporating amphiphilic segments and Fe^(3+)-catechol dynamic coordination crosslinking.The microphase formed within the PDMS matrix imparted static antifouling properties to the coatings.The mechanical properties of the damaged sample were restored at room temperature in an aqueous environment for 24 h,achieving a self-healing efficiency of almost 100%.The synthesized material exploited the dynamic coordination between Fe^(3+) and catechol to facilitate underwater self-healing.No bacterial adhesion was observed at the scratch site after the coating was repaired.This material enables the long-term antifouling and autonomous repair of marine vessels and sensors,thereby reducing maintenance costs.展开更多
In recent years,smart materials have emerged as a groundbreaking innovation in the field of water filtration,offering sustainable,efficient,and environmentally friendly solutions to address the growing global water cr...In recent years,smart materials have emerged as a groundbreaking innovation in the field of water filtration,offering sustainable,efficient,and environmentally friendly solutions to address the growing global water crisis.This review explores the latest advancements in the application of smart materials—including biomaterials,nanocomposites,and stimuli-responsive polymers—specifically for water treatment.It examines their effectiveness in detecting and removing various types of pollutants,including organic contaminants,heavy metals,and microbial infections,while adapting to dynamic environmental conditions such as fluctuations in temperature,pH,and pressure.The review highlights the remarkable versatility of these materials,emphasizing their multifunctionality,which allows them to address a wide range of water quality issues with high efficiency and low environmental impact.Moreover,it explores the potential of smart materials to overcome significant challenges in water purification,such as the need for real-time pollutant detection and targeted removal processes.The research also discusses the scalability and future development of these materials,considering their cost-effectiveness and potential for large-scale application.By aligning with the principles of sustainable development,smart materials represent a promising direction for ensuring global water security,offering both innovative solutions for current water pollution issues and long-term benefits for the environment and public health.展开更多
Herein,an external crosslinker facilitated the hypercrosslinking of ferrocene and a nitrogen heterocyclic compound(either melamine or imidazole)through a direct Friedel-Crafts reaction,which led to the formation of ni...Herein,an external crosslinker facilitated the hypercrosslinking of ferrocene and a nitrogen heterocyclic compound(either melamine or imidazole)through a direct Friedel-Crafts reaction,which led to the formation of nitrogen-containing hypercrosslinked fer-rocene polymer precursors(HCP-FCs).Subsequent carbonization of these precursors results in the production of iron-nitrogen-doped por-ous carbon absorbers(Fe-NPCs).The Fe-NPCs demonstrate a porous structure comprising aggregated nanotubes and nanospheres.The porosity of this structure can be modulated by adjusting the iron and nitrogen contents to optimize impedance matching.The uniform dis-tribution of Fe-N_(x)C,N dipoles,andα-Fe within the carbon matrix can be ensured by using hypercrosslinked ferrocenes in constructing porous carbon,providing the absorber with numerous polarization sites and a conductive network.The electromagnetic wave absorption performance of the specially designed Fe-NPC-M_(2)absorbers is satisfactory,revealing a minimum reflection loss of-55.3 dB at 2.5 mm and an effective absorption bandwidth of 6.00 GHz at 2.0 mm.By utilizing hypercrosslinked polymers(HCPs)as precursors,a novel method for developing highly efficient carbon-based absorbing agents is introduced in this research.展开更多
Tactile perception plays a vital role for the human body and is also highly desired for smart prosthesis and advanced robots.Compared to active sensing devices,passive piezoelectric and triboelectric tactile sensors c...Tactile perception plays a vital role for the human body and is also highly desired for smart prosthesis and advanced robots.Compared to active sensing devices,passive piezoelectric and triboelectric tactile sensors consume less power,but lack the capability to resolve static stimuli.Here,we address this issue by utilizing the unique polarization chemistry of conjugated polymers for the first time and propose a new type of bioinspired,passive,and bio-friendly tactile sensors for resolving both static and dynamic stimuli.Specifically,to emulate the polarization process of natural sensory cells,conjugated polymers(including poly(3,4-ethylenedioxythiophen e):poly(styrenesulfonate),polyaniline,or polypyrrole)are controllably polarized into two opposite states to create artificial potential differences.The controllable and reversible polarization process of the conjugated polymers is fully in situ characterized.Then,a micro-structured ionic electrolyte is employed to imitate the natural ion channels and to encode external touch stimulations into the variation in potential difference outputs.Compared with the currently existing tactile sensing devices,the developed tactile sensors feature distinct characteristics including fully organic composition,high sensitivity(up to 773 mV N^(−1)),ultralow power consumption(nW),as well as superior bio-friendliness.As demonstrations,both single point tactile perception(surface texture perception and material property perception)and two-dimensional tactile recognitions(shape or profile perception)with high accuracy are successfully realized using self-defined machine learning algorithms.This tactile sensing concept innovation based on the polarization chemistry of conjugated polymers opens up a new path to create robotic tactile sensors and prosthetic electronic skins.展开更多
Mixed matrix membranes(MMMs)have demonstrated significant promise in energy-intensive gas separations by amalgamating the unique properties of fillers with the facile processability of polymers.However,achieving a sim...Mixed matrix membranes(MMMs)have demonstrated significant promise in energy-intensive gas separations by amalgamating the unique properties of fillers with the facile processability of polymers.However,achieving a simultaneous enhancement of permeability and selectivity remains a formidable challenge,due to the difficulty of achieving an optimal match between polymers and fillers.In this study,we incorporate a porous carbon-based zinc oxide composite(C@ZnO)into high-permeability polymers of intrinsic microporosity(PIMs)to fabricate MMMs.The dipole–dipole interaction between C@ZnO and PIMs ensures their exceptional compatibility,mitigating the formation of non-selective voids in the resulting MMMs.Concurrently,C@ZnO with abundant interconnected pores can provide additional low-resistance pathways for gas transport in MMMs.As a result,the CO_(2) permeability of the optimized C@ZnO/PIM-1 MMMs is elevated to 13,215 barrer,while the CO_(2)/N_(2) and CO_(2)/CH_(4) selectivity reached 21.5 and 14.4,respectively,substantially surpassing the 2008 Robeson upper bound.Additionally,molecular simulation results further corroborate that the augmented membrane gas selectivity is attributed to the superior CO_(2) affinity of C@ZnO.In summary,we believe that this work not only expands the application of MMMs for gas separation but also heralds a paradigm shift in the application of porous carbon materials.展开更多
Two new Mn(Ⅱ)coordination polymers,namely{[Mn_(2)(HL)(phen)_(3)(H_(2)O)_(2)]·7.5H_(2)O}_n(1)and[Mn_(4)(HL)_(2)(1,4-bib)_(3)(H_(2)O)_(2)]_n(2),were synthesized under hydrothermal conditions by using Mn(Ⅱ)ions an...Two new Mn(Ⅱ)coordination polymers,namely{[Mn_(2)(HL)(phen)_(3)(H_(2)O)_(2)]·7.5H_(2)O}_n(1)and[Mn_(4)(HL)_(2)(1,4-bib)_(3)(H_(2)O)_(2)]_n(2),were synthesized under hydrothermal conditions by using Mn(Ⅱ)ions and 6-(3',4'-dicarboxylphenoxy)-1,2,4-benzenetricarboxylic acid(H_(5)L)in the presence of N-auxiliary ligands 1,10-phenanthroline(phen)and1,4-bis(1H-imidazol-1-yl)benzene(1,4-bib).The structures of coordination polymers 1 and 2 were characterized by infrared spectroscopy,single-crystal X-ray diffraction,thermogravimetric analysis,and powder X-ray diffraction.Single-crystal X-ray diffraction reveals that 1 has a 1D chain structure based on binuclear Mn(Ⅱ)units,while 2 features a(3,8)-connected 3D network structure based on tetranuclear Mn(Ⅱ)units.Magnetic studies show that 1 and 2exhibit antiferromagnetic interactions between manganese ions.2 shows stronger antiferromagnetic interactions due to the shorter Mn…Mn distances within the tetranuclear manganese units.CCDC:2357601,1;2357602,2.展开更多
Light transmission spectra of THF solutions of poly (C-60-co-methyl methacrylate)s and poly(C-60-co-styrene)s continuously red-shift with increasing concentration. Formation of fullerene nanoclusters may be responsibl...Light transmission spectra of THF solutions of poly (C-60-co-methyl methacrylate)s and poly(C-60-co-styrene)s continuously red-shift with increasing concentration. Formation of fullerene nanoclusters may be responsible for the unusual spectral shift, with concentration. It has long been scientists' dream to ''tune'' material's properties by simple means, and the C-60-containing polymers represent such a group of novel materials whose optical properties are predictably and reversibly tunable by a simple change in concentration.展开更多
Multiphase copolymers of styrene (S) and ethylene oxide (EO) are amphiphilic, because of the hydrophobic and amorphous polystyrene (PS) segments and the hydrophilic and crystalline polyoxyethylene (PEO). They have man...Multiphase copolymers of styrene (S) and ethylene oxide (EO) are amphiphilic, because of the hydrophobic and amorphous polystyrene (PS) segments and the hydrophilic and crystalline polyoxyethylene (PEO). They have many uses including polymeric surfactants, electrostatic charge reducers, compatibilizer in polymer展开更多
Driven by the dual imperatives of global plastic pollution control and carbon neutrality,research on depolymerizable polymers has become a cutting-edge focus in polymer science.With the continuous emergence of innovat...Driven by the dual imperatives of global plastic pollution control and carbon neutrality,research on depolymerizable polymers has become a cutting-edge focus in polymer science.With the continuous emergence of innovative materials,strengthened policy support,and maturing industrial chains,these polymers are demonstrating transformative potential in critical sectors,such as environmental protection,healthcare,and industrial manufacturing,promising for reshaping the future landscape of the plastics industry.展开更多
基金financially supported by the International Cooperation Program of the Ministry of Science and Technology of Hubei Province(No.2023EHA069)Shenzhen Science and Technology Program(No.JCYJ20230807143702005)the National Foreign Experts Program(No.G2022027015L)。
文摘Liver is a vital organ in the human body and plays a central role in the metabolism and detoxification of endotoxins and exotoxins.Bilirubin is an endotoxin derived from hemoglobin(Hb).Removing excess bilirubin in the blood is crucial for the treatment of liver diseases.Hemoperfusion,which relies on adsorbents to efficiently adsorb toxins,is a widely applied procedure for the removal of blood toxins.To broaden and improve the range and performance of hemoperfusion adsorbents,we synthesized cationic hyper crosslinked polymers(HCPs)with strong affinity for bilirubin.This material exhibited outstanding adsorption performance,with a maximum adsorption capacity of 934 mg/g and a removal efficiency of 96%.Further investigation confirmed their excellent selectivity,reusability,and biocompatibility.These findings expand the potential applications of HCPs and provide insight into strategies for constructing promising hemoperfusion adsorbent materials.
文摘Under solvothermal conditions,1,4‑naphthalenedicarboxylic acid(H_(2)ndc)and 9,9′‑dihexyl‑2,7‑di(pyridin‑4‑yl)fluorene(hfdp)reacted with Co^(2+)ions and Cd^(2+)ions to form two coordination polymers,[Co(hfdp)(ndc)(H2O)]·DMA}n(1)and{[Cd(hfdp)(ndc)(H_(2)O)]·DMA}_(n)(2),respectively(DMA=N,N‑dimethylacetamide).Single‑crystal X‑ray diffraction analyses showed that both complexes 1 and 2 contain similar structures.Topological analysis indicates that complexes 1 and 2 have a{44·62}planar structure.In addition,both complexes reveal good thermal stability and fluorescence sensing performance.They exhibited good sensitivity and selectivity towards 2,4,6‑trinitrophenol(TNP)by fluorescent quenching.The limits of detection of 1 and 2 for TNP were 0.107 and 0.327μmol·L^(-1),respectively.CCDC:2475515,1;2475516,2.
基金the financial support provided by the National Natural Science Foundation of China(22478267,22438009,U24A20535)Basic Research Program of Jiangsu province(BK20243002)+1 种基金Prospective Application Research Project of Suzhou(SYC2022042)the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD).
文摘Antibiotics,as an emerging pollutant due to their extensive use and difficulty in biodegradation,can cause harm to health through bioaccumulation.To address this,various photocatalysts have been developed for rapid antibiotic removal.However,their low concentrations limit mass transfer efficiency,resulting in suboptimal performance.Adsorption is crucial for enhancing photocatalytic efficiency.In this study,a series of binary heterojunction catalysts(x%BWO@STHP)were synthesized,consisting of Bi_(2)WO_(6)(BWO)grafted with sulfonated triptycene-based hypercrosslinked polymer(STHP).The high specific surface area of STHP,combined withπ-πconjugation and ionic interactions with antibiotics,significantly enhances adsorption capacity.This facilitates effective contact between low-concentration pollutants in aqueous solutions and the active sites of the catalyst.The formation of a Z-scheme heterojunction between BWO and STHP facilitates photogenerated charge separation,and further significantly improves photocatalytic degradation performance.Specifically,the 20%BWO@STHP catalyst achieved rapid adsorption equilibrium for oxytetracycline(OTC),doxycycline(DOX),and tetracycline(TC)within 2 min and completely degraded them after 15 min of irradiation.Compared to pristine BWO,the photocatalytic reaction rate constants are significantly increased,being 9.69 times higher for OTC and 13.45 times higher for DOX.The catalyst exhibits excellent reusability and holds promising potential for practical applications.
基金financially supported by the Russian Science Foundation(No.23-13-00205)。
文摘Star-shaped six-arm polymers with hexaaza[2_(6)]orthoparacyclophane core and arms of block copolymers of poly-2-ethyl-5,6-dihydrooxazine with poly-2-isopropyl-5,6-dihydrooxazine were synthesized successfully using cationic ring-opening polymerization.The ratio of blocks,the order of their attachment to the core,and arm length were varied.Conformation of synthesized stars was determined by methods of molecular hydrodynamics and optics.It has been shown that star-shaped molecules were characterized by high intramolecular density,and the arm folding increased with their lengthening.The influence of the structure of block copolymers and their molar mass on the critical micelle concentration has been established.Complexes of synthesized star-shaped block copolymers with curcumin were obtained and the efficient binding of curcumin to polymer molecules was demonstrated.The behavior of the aqueous solutions of the prepared polymer stars and their complexes with curcumin was investigated by light scattering and turbidimetry methods.The influence of the structure and molar mass of star polymers on their thermoresponsiveness and the phase separation temperatures in aqueous solutions was analyzed.A slight increase in the phase separation temperature was found on passage from polymer solutions to solutions of polymer complexes with hydrophobic curcumin.
基金financial support of this work by the National Natural Science Foundation of China(No.21861039)Postgraduate Research&Practice Innovation Program of Jiangsu Province(No.KYCX24_2530)the Fundamental Research Funds for the Central Universities。
文摘Acceptorless dehydrogenative coupling of pyridinemethanol with ketones is one of the most reliable methodologies to access functionalized 1,8-naphthyridine derivatives.However,it is challenging to develop environmentally friendly catalytic systems,especially in constructing efficient and recyclable catalysts under water or solvent-free conditions.Here,we designed two novel coordination polymers Cd-CPs and Fe-CPs to investigate their catalytic performance in water.Gratifyingly,it was observed that Cd-CPs as a multifunctional catalyst was successfully applied to establish a universal pathway for direct fabrication of 1,8-naphthyridine derivatives under water conditions,while it was effective for the synthesis of1,3,5-triazines through acceptorless dehydrogenative coupling strategies.The features of broad substrate,high atom efficiency,and good catalyst reusability highlight the feasibility of this transformation.In additional,we demonstrated the spindle-like structures Fe-P,derived from the Fe-CPs via phosphorylation,which can be used as an efficient electrocatalyst for oxygen evolution reaction with good stability.This work provides two highly efficient non-noble metal catalysts for functionalized 1,8-naphthyridine derivatives production and oxygen evolution reaction,and opens a new avenue to further fabricate diverse metal catalysts with high catalytic performance in water.
基金Supported by the National Natural Science Foundation of China(Nos.52293472,22473096 and 22471164)。
文摘Among various architectures of polymers,end-group-free rings have attracted growing interests due to their distinct physicochemical performances over the linear counterparts which are exemplified by reduced hydrodynamic size and slower degradation.It is key to develop facile methods to large-scale synthesis of polymer rings with tunable compositions and microstructures.Recent progresses in large-scale synthesis of polymer rings against single-chain dynamic nanoparticles,and the example applications in synchronous enhancing toughness and strength of polymer nanocomposites are summarized.Once there is the breakthrough in rational design and effective large-scale synthesis of polymer rings and their functional derivatives,a family of cyclic functional hybrids would be available,thus providing a new paradigm in developing polymer science and engineering.
文摘Four distinct coordination polymers(CPs)were successfully synthesized by altering solvent types and adjusting ligand concentrations,and their crystal structures were investigated.[Co(L)(FDCA)(H_(2)O)_(2)]·0.5H_(2)O(1)was synthesized as a 2D structure using Coas the metal source,methanol‑water(4∶6,V/V)as the solvent,and specific concentrations of 2,5‑furandicarboxylic acid(H_(2)FDCA)and 1,3,5‑triimidazole benzene(L).Adjusting to pure water and lowering the concentration of L yielded the 1D chain structure of[Co(HL)2(H_(2)O)_(2)](FDCA)_(2)·6H_(2)O(2).Using Cu(Ⅱ)as the metal source,methanol/water(9∶1,V/V)as the solvent,and specific concentrations of L and H2FDCA,the 1D chain structure of[Cu(L)(FDCA)(H_(2)O)]·2H_(2)O(3)was synthesized.Upon increasing the concentrations of L and H2FDCA,and switching the solvent to pure water,the 1D chain structure of[Cu(HL)_(2)(H_(2)O)_(2)](FDCA)_(2)·6H_(2)O(4)was obtained.This shows that changing the solvent and ligand concentrations can affect the structural changes of CPs.In addition,the solid‑state photoluminescence of CPs 1‑4 at room temperature was studied,and their morphological changes were observed via scanning electron microscopy.Density functional theory calculations revealed that the negative charge concentrates on the O and N atoms of the ligand,facilitating ligand‑metal ion coordination.CCDC:2403934,1;2403935,2;2403936,3;2403938,4.
基金supported by the National Natural Science Foundation of China(Nos.22322107,22101169 and 22071144)by Shanghai Scientific and Technological Committee(No.22010500300).
文摘Organic pollutants,a pivotal factor in water pollution,have persistently menaced the aquatic ecosystem,as well as the sustainable development of human health,economy,and society.Consequently,there is an urgent need for advanced techniques to efficiently eliminate organic micropollutants from water.Here,we present the synthesis of three nonporous cavitand-crosslinked polymers capable of adsorbing diverse organic pollutants from aqueous solutions.These polymeric adsorbents exhibit outstanding adsorptive performance towards the tested micropollutants,characterized by high apparent adsorption rate constants(kobs)and maximum adsorption capacities(qmax,e).Notably,Compound NCCP-1 demonstrated a remarkable qmax,e of 459 mg/g for bisphenol A(BPA),ranking among the highest values reported for organic polymer adsorbents.In-depth investigation of the adsorption mechanism of the nonporous polymer revealed that it involves the recognition of pollutants by the deep cavities of the cavitand moieties and the interstitial spaces between them,primarily mediated by the hydrophobic effect.Furthermore,NCCP-1 was applied in situ water purification simulations and was proven to maintain its removal efficiency over more than four cycles,highlighting its potential for practical applications in water treatment.
基金the support from the Jiangsu Provincial Senior Talent Program (Dengfeng,Jiangsu University)the support from the National Key R&D Program of China (No.2024YFB3612600)+3 种基金the National Natural Science Foundation of China (Nos.22275098,62288102)Basic Research Program of Jiangsu (No.BK20243057)the Natural Science Research Start-up Foundation of Recruiting Talents of Nanjing University of Posts and Telecommunications (No.NY222097)the National Natural Science Foundation of China (No.62205035)。
文摘To precisely control intrachain π-electron delocalization and interchain interaction simultaneously is the prerequisite to obtain stable and efficient deep-blue light-emitting p-n polymer semiconductors for the polymer light-emitting diodes(PLEDs).Herein,we introduced the steric carbazole-fluorene nanogrid into light-emitting diphenyl sulfone-based p-n polymer semiconductors(PG and PDG) via metal-free C-N coupling polymerization for the fabrication of deep-blue PLEDs.The steric,rigid and twisted configuration between nanogrid and diphenyl sulfone in PG and PDG present the unique characteristic of large steric hindrance interaction to suppress interchain aggregation in solid state.Due to the different length of electron-deficient diphenyl sulfone monomers,PG showed a deep-blue emission with a maximum peak at 428 nm but red-shifted to 480 nm for the PDG films.Interestingly,similar deep-blue emission behavior of PG in diluted non-polar solution and films suggested the extremely weak interchain aggregation.Finally,PLEDs based on PG are fabricated with a stable deep-blue emission of CIE(0.15,0.10),and corresponding EL spectral profile is also completely identical to PL ones of diluted solution,revealed the intrachain emission without obvious interchain excited state,confirmed effectiveness of the steric hindrance functionalization of nanogrid in p-n polymer semiconductor for deep-blue light-emitting organic optoelectronics.
基金the funding support from the Smart Medicine and Engineering Interdisciplinary Innovation Project of Ningbo University(No.ZHYG003)。
文摘Glassy polymers are widely used in biomedical applications in a solvent environment,yet their long-term performance is governed by the competing effects of physical aging and solvent-induced plasticization.Here,we develop a constitutive model that explicitly couples the solvent concentration,structural relaxation,and mechanical response.This framework is built on a multiplicative decomposition of deformation and an Eyring-type flow rule,with structural evolution described by an effective temperature.A generalized shift factor is introduced to quantify how the solvent concentration and effective temperature jointly affect the relaxation time,thereby integrating physical aging and plasticization.The model is subsequently applied to methacrylate(MA)-based copolymer networks immersed in phosphate-buffered saline for up to nine months.Simulations accurately capture key experimental features,including the strong softening of highly swellable networks,the partial recovery due to aging,and the mitigating role of hydrophobic crosslinking in reducing solvent uptake.While the current single-mode description cannot reproduce the full relaxation spectrum,it establishes an efficient framework for predicting the long-term mechanical performance under coupled environmental and mechanical loading.This study provides a constitutive description of solvent-swollen glassy polymers,offering mechanistic insight into the interplay between plasticization and aging.Beyond biomedical MA networks,this framework establishes a foundation for predicting the long-term performance of polymer glasses under coupled aqueous environmental and mechanical loading.
基金supported by the National Natural Science Foundation of China(Nos.82402822,82360427,82372425,82072443,and 32200559)the Priority Union Foundation of Yunnan Provincial Science and Technology Department and Kunming Medical University(No.202301AY070001-164)+1 种基金the Natural Science Foundation of Sichuan Province(No.23NSFSC5880)the Central Government of Sichuan Province Guiding the Special Project of Local Science and Technology Development(No.2024ZYD0155).
文摘Three-dimensional(3 D)printing has revolutionized the design and production of customized scaffolds,but the minimally invasive implantation of 3 D-printed structures into the human body remains challenging.This has prompted the exploration of innovative materials and technical solutions.Shape-memory polymers,as advanced intelligent materials,exhibit considerable potential in minimally invasive surgical applications.Herein,we developed a novel thermosetting shape-memory polymer,poly(L-lactic acid)-trimethylene carbonate-glycolic acid(PLLA-TMC-GA),for the fabrication of bioengineered scaffolds with body temperature-activated shape-memory functionality.We comprehensively evaluated the mechanical properties,thermal stability,shape-memory capabilities,biocompatibility,biodegradability,and 3 D printing performance of PLLA-TMC-GA terpolymers with various compositions.The results indicate that PLLA-TMC-GA exhibits exceptional shape-memory performance,adjustable material properties,favorable biocompatibility,and the potential for controlled biodegradation and reabsorption.The use of PLLA-TMC-GA as a biodegradable shape-memory polymer allows the reduction of implant volume,simplifies implantation,and enables on-demand activation at body temperature.These characteristics present new opportunities for the advancement of minimally invasive surgical techniques.
基金supported by Beijing Municipal Natural Science Foundation(No.2242053)National Natural Science Foundation of China(No.22275012).
文摘Development of polymers with underwater self-healing and antifouling properties is crucial,particularly in harsh marine environments.In this study,polydimethylsiloxane(PDMS)-based antifouling polymers with tunable self-healing capabilities in aqueous conditions were fabricated by incorporating amphiphilic segments and Fe^(3+)-catechol dynamic coordination crosslinking.The microphase formed within the PDMS matrix imparted static antifouling properties to the coatings.The mechanical properties of the damaged sample were restored at room temperature in an aqueous environment for 24 h,achieving a self-healing efficiency of almost 100%.The synthesized material exploited the dynamic coordination between Fe^(3+) and catechol to facilitate underwater self-healing.No bacterial adhesion was observed at the scratch site after the coating was repaired.This material enables the long-term antifouling and autonomous repair of marine vessels and sensors,thereby reducing maintenance costs.
文摘In recent years,smart materials have emerged as a groundbreaking innovation in the field of water filtration,offering sustainable,efficient,and environmentally friendly solutions to address the growing global water crisis.This review explores the latest advancements in the application of smart materials—including biomaterials,nanocomposites,and stimuli-responsive polymers—specifically for water treatment.It examines their effectiveness in detecting and removing various types of pollutants,including organic contaminants,heavy metals,and microbial infections,while adapting to dynamic environmental conditions such as fluctuations in temperature,pH,and pressure.The review highlights the remarkable versatility of these materials,emphasizing their multifunctionality,which allows them to address a wide range of water quality issues with high efficiency and low environmental impact.Moreover,it explores the potential of smart materials to overcome significant challenges in water purification,such as the need for real-time pollutant detection and targeted removal processes.The research also discusses the scalability and future development of these materials,considering their cost-effectiveness and potential for large-scale application.By aligning with the principles of sustainable development,smart materials represent a promising direction for ensuring global water security,offering both innovative solutions for current water pollution issues and long-term benefits for the environment and public health.
基金supported by the National Natural Science Foundation of China(No.51803041)the University and Local Integration Development Project of Yantai,China(No.2022 XDRHXMXK08).
文摘Herein,an external crosslinker facilitated the hypercrosslinking of ferrocene and a nitrogen heterocyclic compound(either melamine or imidazole)through a direct Friedel-Crafts reaction,which led to the formation of nitrogen-containing hypercrosslinked fer-rocene polymer precursors(HCP-FCs).Subsequent carbonization of these precursors results in the production of iron-nitrogen-doped por-ous carbon absorbers(Fe-NPCs).The Fe-NPCs demonstrate a porous structure comprising aggregated nanotubes and nanospheres.The porosity of this structure can be modulated by adjusting the iron and nitrogen contents to optimize impedance matching.The uniform dis-tribution of Fe-N_(x)C,N dipoles,andα-Fe within the carbon matrix can be ensured by using hypercrosslinked ferrocenes in constructing porous carbon,providing the absorber with numerous polarization sites and a conductive network.The electromagnetic wave absorption performance of the specially designed Fe-NPC-M_(2)absorbers is satisfactory,revealing a minimum reflection loss of-55.3 dB at 2.5 mm and an effective absorption bandwidth of 6.00 GHz at 2.0 mm.By utilizing hypercrosslinked polymers(HCPs)as precursors,a novel method for developing highly efficient carbon-based absorbing agents is introduced in this research.
基金financially supported by the Sichuan Science and Technology Program(2022YFS0025 and 2024YFFK0133)supported by the“Fundamental Research Funds for the Central Universities of China.”。
文摘Tactile perception plays a vital role for the human body and is also highly desired for smart prosthesis and advanced robots.Compared to active sensing devices,passive piezoelectric and triboelectric tactile sensors consume less power,but lack the capability to resolve static stimuli.Here,we address this issue by utilizing the unique polarization chemistry of conjugated polymers for the first time and propose a new type of bioinspired,passive,and bio-friendly tactile sensors for resolving both static and dynamic stimuli.Specifically,to emulate the polarization process of natural sensory cells,conjugated polymers(including poly(3,4-ethylenedioxythiophen e):poly(styrenesulfonate),polyaniline,or polypyrrole)are controllably polarized into two opposite states to create artificial potential differences.The controllable and reversible polarization process of the conjugated polymers is fully in situ characterized.Then,a micro-structured ionic electrolyte is employed to imitate the natural ion channels and to encode external touch stimulations into the variation in potential difference outputs.Compared with the currently existing tactile sensing devices,the developed tactile sensors feature distinct characteristics including fully organic composition,high sensitivity(up to 773 mV N^(−1)),ultralow power consumption(nW),as well as superior bio-friendliness.As demonstrations,both single point tactile perception(surface texture perception and material property perception)and two-dimensional tactile recognitions(shape or profile perception)with high accuracy are successfully realized using self-defined machine learning algorithms.This tactile sensing concept innovation based on the polarization chemistry of conjugated polymers opens up a new path to create robotic tactile sensors and prosthetic electronic skins.
基金financial support from the National Natural Science Foundation of China(Nos.22108258 and 52003251)Program for Science&Technology Innovation Talents in Universities of Henan Province(24HASTIT004)+1 种基金Outstanding Youth Fund of Henan Scientific Committee(222300420085)Science and Technology Joint Project of Henan Province(222301420041)。
文摘Mixed matrix membranes(MMMs)have demonstrated significant promise in energy-intensive gas separations by amalgamating the unique properties of fillers with the facile processability of polymers.However,achieving a simultaneous enhancement of permeability and selectivity remains a formidable challenge,due to the difficulty of achieving an optimal match between polymers and fillers.In this study,we incorporate a porous carbon-based zinc oxide composite(C@ZnO)into high-permeability polymers of intrinsic microporosity(PIMs)to fabricate MMMs.The dipole–dipole interaction between C@ZnO and PIMs ensures their exceptional compatibility,mitigating the formation of non-selective voids in the resulting MMMs.Concurrently,C@ZnO with abundant interconnected pores can provide additional low-resistance pathways for gas transport in MMMs.As a result,the CO_(2) permeability of the optimized C@ZnO/PIM-1 MMMs is elevated to 13,215 barrer,while the CO_(2)/N_(2) and CO_(2)/CH_(4) selectivity reached 21.5 and 14.4,respectively,substantially surpassing the 2008 Robeson upper bound.Additionally,molecular simulation results further corroborate that the augmented membrane gas selectivity is attributed to the superior CO_(2) affinity of C@ZnO.In summary,we believe that this work not only expands the application of MMMs for gas separation but also heralds a paradigm shift in the application of porous carbon materials.
文摘Two new Mn(Ⅱ)coordination polymers,namely{[Mn_(2)(HL)(phen)_(3)(H_(2)O)_(2)]·7.5H_(2)O}_n(1)and[Mn_(4)(HL)_(2)(1,4-bib)_(3)(H_(2)O)_(2)]_n(2),were synthesized under hydrothermal conditions by using Mn(Ⅱ)ions and 6-(3',4'-dicarboxylphenoxy)-1,2,4-benzenetricarboxylic acid(H_(5)L)in the presence of N-auxiliary ligands 1,10-phenanthroline(phen)and1,4-bis(1H-imidazol-1-yl)benzene(1,4-bib).The structures of coordination polymers 1 and 2 were characterized by infrared spectroscopy,single-crystal X-ray diffraction,thermogravimetric analysis,and powder X-ray diffraction.Single-crystal X-ray diffraction reveals that 1 has a 1D chain structure based on binuclear Mn(Ⅱ)units,while 2 features a(3,8)-connected 3D network structure based on tetranuclear Mn(Ⅱ)units.Magnetic studies show that 1 and 2exhibit antiferromagnetic interactions between manganese ions.2 shows stronger antiferromagnetic interactions due to the shorter Mn…Mn distances within the tetranuclear manganese units.CCDC:2357601,1;2357602,2.
基金This work was in part supported by a grant from the Hong Kong Government Research Grants Council(DAG96/97.SC11)
文摘Light transmission spectra of THF solutions of poly (C-60-co-methyl methacrylate)s and poly(C-60-co-styrene)s continuously red-shift with increasing concentration. Formation of fullerene nanoclusters may be responsible for the unusual spectral shift, with concentration. It has long been scientists' dream to ''tune'' material's properties by simple means, and the C-60-containing polymers represent such a group of novel materials whose optical properties are predictably and reversibly tunable by a simple change in concentration.
文摘Multiphase copolymers of styrene (S) and ethylene oxide (EO) are amphiphilic, because of the hydrophobic and amorphous polystyrene (PS) segments and the hydrophilic and crystalline polyoxyethylene (PEO). They have many uses including polymeric surfactants, electrostatic charge reducers, compatibilizer in polymer
文摘Driven by the dual imperatives of global plastic pollution control and carbon neutrality,research on depolymerizable polymers has become a cutting-edge focus in polymer science.With the continuous emergence of innovative materials,strengthened policy support,and maturing industrial chains,these polymers are demonstrating transformative potential in critical sectors,such as environmental protection,healthcare,and industrial manufacturing,promising for reshaping the future landscape of the plastics industry.
