Hollow noble microspheres have garnered considerable interest owing to their potential applications in fields such as catalysis,electronics,and chemical detection.However,their inherent brittleness remains a critical ...Hollow noble microspheres have garnered considerable interest owing to their potential applications in fields such as catalysis,electronics,and chemical detection.However,their inherent brittleness remains a critical limitation,significantly restricting their practical use in broader applications.In this work,we report a scalable methodology for the fabrication of vesicle-like polymer-silver composite microspheres with excellent toughness.The process begins with dispersion polymerization to produce uniform polystyrene(PS)microspheres,which are subsequently sulfonated to facilitate the electrostatic adsorption of Sn^(2+)ions.This is followed by the chemical reduction of[Ag(NH_(3))_(2)]^(+),enabling the formation of well-defined core-shell SPS/Ag composite microspheres with tunable shell thickness through multiple reduction steps.Finally,the core template is removed using DMF solvent,resulting in vesicle-like SPS@Ag composite microspheres.Such hollow microspheres exhibit excellent toughness due to the presence of SPS within the silver membrane.Moreover,the surface-enhanced Raman scattering(SERS)performance of these microspheres is influenced by the thickness of the silver membrane.The findings of this study demonstrate their potential for the development of highly efficient SERS substrates,with broad application in analytical chemistry,sensing technologies,and catalytic processes.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
Polymer-modified bentonite(PMB)is much more effective at containing chemically aggressive liquids than conventional bentonite.The PMB manufacturing process typically utilizes natural,high-quality sodium bentonite(NaB)...Polymer-modified bentonite(PMB)is much more effective at containing chemically aggressive liquids than conventional bentonite.The PMB manufacturing process typically utilizes natural,high-quality sodium bentonite(NaB)owing to its excellent hydrophilicity and swelling capacity.However,calcium bentonite(CaB),which is much more abundant worldwide,is rarely used for containment applications owing to its poor hydrophilicity.This study proposed a polymerization method that transforms sodium-activated calcium bentonite(NCB)into PMB to achieve low hydraulic conductivity(k)to aggressive liquids.The mechanism for its low k was revealed through characterization techniques and analyses(e.g.X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FTIR),scanning electron microscopy(SEM),and Brunauer-Emmett-Teller(BET)).The results showed that the PMB had a small amount of polymer elution(indicating better interface stability)and thus exhibited excellent barrier properties under chemically aggressive conditions,with the k of<10^(-11) m/s for 0.6 mol/L NaCl solution,which is four orders of magnitude lower than that of the NCB(k=3×10^(-7) m/s).Various microscopic analyses indicated that the selected monomers were successfully polymerized,and intercalated into and grafted onto the montmorillonite layers of bentonite.The formed polymer network increased the swelling capability of PMB granules,decreased the pore size,and created narrow and tortuous flow pathways leading to a very low k to aggressive liquids.展开更多
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
With the global push for energy conservation and the rapid development of low-power,flexible and wearable optical displays,the demand for electrochromic technology has surged.Gel polymer electrolytes(GPEs),a crucial c...With the global push for energy conservation and the rapid development of low-power,flexible and wearable optical displays,the demand for electrochromic technology has surged.Gel polymer electrolytes(GPEs),a crucial component of electrochromic devices(ECDs),show great promise in applications.This is attributed to their efficient ion-transport capabilities,excellent mechanical properties and strong adhesion.All of these characteristics are conducive to enhancing the safety of the devices,streamlining the packaging process,significantly improving the electrochromic performance of ECDs and boosting their commercial application potential.This review provides a comprehensive overview of GPEs for ECDs,focusing on their basic designs,functional modifications and practical applications.Firstly,this review outlines the fundamental design of GPEs for ECDs,encompassing key performance index,classification,gelation mechanism and preparation methods.Building on this foundation,it provides an in-depth discussion of functionalized GPEs developed to enhance device performance or expand functionality,including electrochromic,temperature-responsive,photo-responsive and stretchable self-healing GPE.Furthermore,the integration of GPEs into various ECD applications,including smart windows,displays,energy storage devices and wearable electronic,are summarized to highlight the advantages that the design of GPEs brings to the practical application of ECDs.Finally,based on the summary of GPEs employed for ECDs,the challenges and development expectations in this direction were indicated.展开更多
Succinonitrile(SN)-based polymer plastic crystal electrolytes(PPCEs)are regarded as promising candidates for lithium metal batteries but suffer from serious side reactions with Li metal.Herein,we propose a multi-dimen...Succinonitrile(SN)-based polymer plastic crystal electrolytes(PPCEs)are regarded as promising candidates for lithium metal batteries but suffer from serious side reactions with Li metal.Herein,we propose a multi-dimensional optimization strategy to alleviate the side reactions between SN and Li metal,and develop a highly stable poly-vinylethylene carbonate-based PPCE(PPCE-VEC).Moreover,we identify the intrinsic factors of multi-dimensional polymer structures on the electrolyte stability by three typical classes of polyesters.The PPCE-VEC constructed by in situ polymerization exhibits much better stability than poly-vinylene carbonate-based PPCE(PPCE-VCA)and poly-trifluoroethyl acrylate-based PPCE(PPCE-TFA),which is verified by its fewer SN-decomposition species in X-ray photoelectron spectroscopy(XPS)and outstanding full cell performance.The PPCE-VEC-enabled LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)full cell achieve 73.7%capacity retention after 1400 cycles,which outperforms PPCE-VCA-and PPCE-TFA-enabled full cells(61.9%and 46.9%).Spectral analysis and theoretical calculation reveal that the high solvation ability of the carbonyl site,flexible polymer chain,and homogeneous electrolyte phase of PPCE-VEC are favorable to maximizing competition coordination with Li^(+)to weaken the Li^(+)–SN binding and shape an anion-rich solvation structure.This optimized polymer-involved Li^(+)solvation enhances SN stability and facilitates the formation of B/F enriched solid-electrolyte interphase(SEI),thus significantly improving PPCE stability.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
In this review,the synthesis,functions,and applications of the polymers containing germanium and tin,which are heavy group 14 elements,in their polymer frameworks are summarized.Germanium and tin can form similar skel...In this review,the synthesis,functions,and applications of the polymers containing germanium and tin,which are heavy group 14 elements,in their polymer frameworks are summarized.Germanium and tin can form similar skeletal structures with their homologues carbon and silicon,whereas the polymers containing germanium and tin show unique properties derived from their large atomic radii and weak binding energies.For example,polygermane and polystannane exhibited light absorption in the UV–visible region and conductivity because of theσ-conjugation through the polymer main-chain constructed byσ-bonds between heavy elements.Theσ-conjugation was affected by the conformational change of the polymer main-chain,and thermochromic properties can be induced.Furthermore,the weak bonds were able to be cleaved homolytically upon photoirradiation,and radicals were subsequently generated.By incorporating hypervalent heavy elements into theπ-conjugated system,it was possible to modulate the electronic structures of theπ-conjugated system throughσ*–π*conjugation with highly coordinated elements.Finally,applications for organic solar cells,organic lightemitting materials,and chemical sensors have been achieved.Herein,representative synthetic methods and unique properties for creating smart materials with germanium and tin will be explained.展开更多
Thermoelectric(TE)materials,being capable of converting waste heat into electricity,are pivotal for sustainable energy solutions.Among emerging TE materials,organic TE materials,particularly conjugated polymers,are ga...Thermoelectric(TE)materials,being capable of converting waste heat into electricity,are pivotal for sustainable energy solutions.Among emerging TE materials,organic TE materials,particularly conjugated polymers,are gaining prominence due to their unique combination of mechanical flexibility,environmental compatibility,and solution-processable fabrication.A notable candidate in this field is poly(2,5-bis(3-alkylthiophen-2-yl)thieno[3,2-b]thiophene)(PBTTT),a liquid-crystalline conjugated polymer,with high charge carrier mobility and adaptability to melt-processing techniques.Recent advancements have propelled PBTTT’s figure of merit from below 0.1 to a remarkable 1.28 at 368 K,showcasing its potential for practical applications.This review systematically examines strategies to enhance PBTTT’s TE performance through doping(solution,vapor,and anion exchange doping),composite engineering,and aggregation state controlling.Recent key breakthroughs include ion exchange doping for stable charge modulation,multi-heterojunction architectures reducing thermal conductivity,and proton-coupled electron transfer doping for precise Fermi-level tuning.Despite great progress,challenges still persist in enhancing TE conversion efficiency,balancing or decoupling electrical conductivity,Seebeck coefficient and thermal conductivity,and leveraging melt-processing scalability of PBTTT.By bridging fundamental insights with applied research,this work provides a roadmap for advancing PBTTT-based TE materials toward efficient energy harvesting and wearable electronics.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
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
Shear stress overshoot in entangled polymer rheology is a hallmark of transient dynamics,but its microscopic origin remains under debate.Using molecular dynamics simulations,we investigate a two-step shear protocol co...Shear stress overshoot in entangled polymer rheology is a hallmark of transient dynamics,but its microscopic origin remains under debate.Using molecular dynamics simulations,we investigate a two-step shear protocol consisting of successive startup shears separated by a waiting period,with the first shear interrupted before the overshoot.In the homogeneous flow,the GLaMM theory captures the stress response during the first shear,but fails to reproduce the nonmonotonic dependence of the second stress overshoot(σ_(2max))on the waiting time.Contrary to the prediction of a nonmonotonic normal stress component σ_(yy)during the waiting period,our simulations show that σ_(yy),like the tube segment orientation(S_(xy)),the contour length of the primitive chain(L),and the entanglement number per chain(Z),relaxes monotonically toward equilibrium.At the strain corresponding to σ_(2max),both the tube segment orientation and the entanglement number per chain exhibit a nonmonotonic dependence on the waiting time that closely mirrors the behavior of σ_(2max),indicating that both factors play significant roles in governing(σ_(2max).Our findings are consistent with the interpretation of lanniruberto and Ma rrucci[ACS Macro.Lett.2014,3,552]for orientation effects and with the viewpoint of Wang et al.[Macromolecules 2013,46,3147]for entanglement effects,although the two explanations are rooted in distinct physical pictu res.These results provide new insights into the stress responses of entanglement polymer fluids and underscore the need for a more unified theoretical framework.展开更多
To investigate the pore structure of graphene oxide modified polymer cement mortar(GOPM)under salt-freeze-thaw(SFT)coupling effects and its impact on deterioration,this study modifies polymer cement mortar(EMCM)with g...To investigate the pore structure of graphene oxide modified polymer cement mortar(GOPM)under salt-freeze-thaw(SFT)coupling effects and its impact on deterioration,this study modifies polymer cement mortar(EMCM)with graphene oxide(GO).The micro-pore structure of GOPM is characterized using LF-NMR and SEM.Fractal theory is applied to calculate the fractal dimension of pore volume,and the deterioration patterns are analyzed based on the evolution characteristics of capillary pores.The experimental results indicate that,after 25 salt-freeze-thaw cycles(SFTc),SO2-4 ions penetrate the matrix,generating corrosion products that fill existing pores and enhance the compactness of the specimen.As the number of cycles increases,the ongoing formation and expansion of corrosion products within the matrix,combined with persistent freezing forces,and result in the degradation of the pore structure.Therefore,the mass loss rate(MLR)of the specimens shows a trend of first decreasing and then increasing,while the relative dynamic elastic modulus(RDEM)initially increases and then decreases.Compared to the PC group specimens,the G3PM group specimens show a 28.71% reduction in MLR and a 31.42% increase in RDEM after 150 SFTc.The fractal dimensions of the transition pores,capillary pores,and macropores in the G3PM specimens first increase and then decrease as the number of SFTc increases.Among them,the capillary pores show the highest correlation with MLR and RDEM,with correlation coefficients of 0.97438 and 0.98555,respectively.展开更多
When a ceramic ionic-crystal nanocluster is group-substituted with polymer chain segments to form an ionomeric aggregate,is the ordered structure maintained within the sterically hindered nanocluster?We observed,for N...When a ceramic ionic-crystal nanocluster is group-substituted with polymer chain segments to form an ionomeric aggregate,is the ordered structure maintained within the sterically hindered nanocluster?We observed,for Na-salt sulfonated polystyrene ionomer,the electron-diffraction lattice fringes of the nanoclusters,which proved their internal crystalline ordering driven by electrostatic attractions overcoming steric hindrance.Kinetically,the nanoclusters'enhanced melting endotherm upon aging indicate their quasi-,slow-ordering character.Extended tight binding molecular dynamics simulations provide an insight into the mechanism underlying the ionic-group aggregation during nanoclustering.We hence proposed an uncommon state of order,polymer-bound ceramic quasicrystal,supplementary to the order phenomena in crystalline ceramics.展开更多
Magnetic resonance imaging(MRI)is one of the most widely used diagnostic techniques.Iron oxide nanoparticles,as a promising kind of contrast agents,have attracted intense research interest due to their low toxicity an...Magnetic resonance imaging(MRI)is one of the most widely used diagnostic techniques.Iron oxide nanoparticles,as a promising kind of contrast agents,have attracted intense research interest due to their low toxicity and superparamagnetism.However,it is still a great challenge to prepare ideal iron oxide based contrast agents with high uniformity,excellent water solubility and biocompatibility.In this paper,a novel water-soluble polymer ligand pentaerythritol tetrakis 3-mercaptopropionate-poly(N-vinyl-2-pyrrolidone)(PTMP-PVP)was used as a capping reagent to prepare iron oxide nanoparticles MIONs@PTMP-PVP through one-step co-precipitation of iron precursors in aqueous solution at 100℃.The obtained nanoparticles MIONs@PTMP-PVP had a small size and narrow size distribution,and they were found to be biocompatible as determined through CCK-8 assay and histology analysis.In vivo MRI study demonstrated that the obtained MIONs@PTMP-PVP can be potentially used as an effective T_(2)-weighted MRI contrast agent.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
Carbon-fiber-reinforced plastics(CFRP)with improved mechanical properties based on modified epoxy binders were investigated in this study.By adding 15 parts by weight(p.b.w.)of copolymer of polysulfone with cardo phth...Carbon-fiber-reinforced plastics(CFRP)with improved mechanical properties based on modified epoxy binders were investigated in this study.By adding 15 parts by weight(p.b.w.)of copolymer of polysulfone with cardo phthalide group(PSFP-70C)to the epoxyanhydride binder,the flexural strength of the epoxy polymer was increased by 60%,the CFRP based on it by 57%,the flexural modulus of the epoxy polymer was increased by 83%,and the composite by 96%.The adhesion strength of the binder to carbon fiber reached a high level at 10 p.b.w.of thermoplastic modifier and increased by 65%compared to the unmodified binder.Scanning electron microscopy(SEM)was used to determine that in epoxyanhydride systems with a polysulfone content of 5–15 p.b.w.,the structure belongs to the"matrix dispersion"type and with a content of 20 p.b.w.to the"interpenetrating phase"type.A heterogeneous structure was also observed using dynamic mechanical analysis.展开更多
Polymer matrix composites with high dielectric constants and low dielectric losses are in high demand for flexible electronics.However,simultaneously satisfying these requirements poses a significant scientific challe...Polymer matrix composites with high dielectric constants and low dielectric losses are in high demand for flexible electronics.However,simultaneously satisfying these requirements poses a significant scientific challenge owing to the intrinsic trade-off relationship.Herein,we utilized the in situ controllable reduction of graphene oxide(GO)within a poly(vinylidene fluoride-trifluoroethylene-chlorofluoroethylene)(P(VDF-Tr FE-CFE))matrix to regulate the dielectric properties.The as-obtained composite exhibited a high relative dielectric constant of 1415coupled with a low loss tangent of 0.380 at 100 Hz.Experimental and theoretical studies indicate that the increased degree of electron conjugation and conductivity of the reduced GO(RGO)are responsible for the high-k.The constrained reduction degree of GO,combined with its homogeneous dispersion in the polymer matrix,effectively suppresses long-range charge carrier migration,thereby minimizing dielectric loss.This novel strategy could be successfully applied to both organic and aqueous systems.Furthermore,a high-performance flexible capacitive proximity sensor was exemplified by the optimization of both the dielectric layer and electrode pattern,exhibiting excellent sensitivity and stability.The fundamental mechanisms elucidated in this study provide crucial design principles for developing dielectric PMCs with tailored properties,thereby opening new avenues for advanced flexible electronic applications.展开更多
Bone regeneration for non-load-bearing defects remains a significant clinical challenge requiring advanced biomaterials and cellular strategies.Adiposederived mesenchymal stem cells(AD-MSCs)have garnered significant i...Bone regeneration for non-load-bearing defects remains a significant clinical challenge requiring advanced biomaterials and cellular strategies.Adiposederived mesenchymal stem cells(AD-MSCs)have garnered significant interest in bone tissue engineering(BTE)because of their abundant availability,minimally invasive harvesting procedures,and robust differentiation potential into osteogenic lineages.Unlike bone marrow-derived mesenchymal stem cells,AD-MSCs can be easily obtained in large quantities,making them appealing alternatives for therapeutic applications.This review explores hydrogels containing polymers,such as chitosan,collagen,gelatin,and hyaluronic acid,and their composites,tailored for BTE,and emphasizes the importance of these hydrogels as scaffolds for the delivery of AD-MSCs.Various hydrogel fabrication techniques and biocompatibility assessments are discussed,along with innovative modifications to enhance osteogenesis.This review also briefly outlines AD-MSC isolation methods and advanced embedding techniques for precise cell placement,such as direct encapsulation and three-dimensional bioprinting.We discuss the mechanisms of bone regeneration in the AD-MSC-laden hydrogels,including osteoinduction,vascularization,and extracellular matrix remodeling.We also review the preclinical and clinical applications of AD-MSC-hydrogel systems,emphasizing their success and limitations.In this review,we provide a comprehensive overview of AD-MSC-based hydrogel systems to guide the development of effective therapies for bone regeneration.展开更多
The equilibrium dynamics and nonlinear rheology of unentangled polymer blends remain inadequately understood,especially regarding the influence of short-chain matrix length N_(S) on the structure and rheological behav...The equilibrium dynamics and nonlinear rheology of unentangled polymer blends remain inadequately understood,especially regarding the influence of short-chain matrix length N_(S) on the structure and rheological behavior of dispersed long chains.Using molecular dynamics simulations based on the Kremer-Grest model,we systematically explore the N_(S)-dependence of static conformations,equilibrium dynamics,and nonlinear shear responses in unentangled long-chain/short-chain polymer blends.Our results demonstrate a decoupling between the static and dynamic sensitivity to N_(S):while the static chain size,R_g,follows Flory theory with slight swelling at small N_(S) due to incomplete excluded volume screening,the diffusion coefficient,D,and the relaxation time,τ_(0),exhibit a strong,non-monotonic N_(S)-dependence,transitioning from monomeric friction dominance at small N_(S) to collective segmental rearrangement at large N_(S).Additionally,we observe partial decoupling between the viscous and normal stress responses:while the zero-shear viscosity,η,is strongly N_(S)-dependent,the first and second normal stress coefficients,Ψ_(1) and Ψ_(2),collapse onto universal curves when scaled by the dimensionless shear rate,γτ_(0),suggesting a common mechanism of orientation and stretching.Under shear,long chains compress in the vorticity direction λ_(z)~Wi^(-0.2),which reduces collision frequency and contributes to shear thinning,while the scaling of weaker orientation resistance m_(G)~Wi^(0.35)reflects hydrodynamic screening by the short-chain matrix.These findings highlight the limitations of single-chain models and emphasize the necessity of considering N_(S)-dependent matrix dynamics and flow-induced structural changes in understanding the rheology of unentangled polymer blends.展开更多
基金supported by the National Natural Science Foundation of China(22475084,22431006,92461309)the Guangdong Basic and Applied Basic Research Foundation(2024A1515012114 and 2025A1515012931)the College Students’Innovation and Entrepreneurship Training Program.
文摘Hollow noble microspheres have garnered considerable interest owing to their potential applications in fields such as catalysis,electronics,and chemical detection.However,their inherent brittleness remains a critical limitation,significantly restricting their practical use in broader applications.In this work,we report a scalable methodology for the fabrication of vesicle-like polymer-silver composite microspheres with excellent toughness.The process begins with dispersion polymerization to produce uniform polystyrene(PS)microspheres,which are subsequently sulfonated to facilitate the electrostatic adsorption of Sn^(2+)ions.This is followed by the chemical reduction of[Ag(NH_(3))_(2)]^(+),enabling the formation of well-defined core-shell SPS/Ag composite microspheres with tunable shell thickness through multiple reduction steps.Finally,the core template is removed using DMF solvent,resulting in vesicle-like SPS@Ag composite microspheres.Such hollow microspheres exhibit excellent toughness due to the presence of SPS within the silver membrane.Moreover,the surface-enhanced Raman scattering(SERS)performance of these microspheres is influenced by the thickness of the silver membrane.The findings of this study demonstrate their potential for the development of highly efficient SERS substrates,with broad application in analytical chemistry,sensing technologies,and catalytic processes.
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.
基金supported by the National Natural Science Foundation of China(Grant Nos.52478351,52208329)the Shenzhen Science and Technology Innovation Commission(Grant No.JCYJ20240813143306009)support is gratefully acknowledged.
文摘Polymer-modified bentonite(PMB)is much more effective at containing chemically aggressive liquids than conventional bentonite.The PMB manufacturing process typically utilizes natural,high-quality sodium bentonite(NaB)owing to its excellent hydrophilicity and swelling capacity.However,calcium bentonite(CaB),which is much more abundant worldwide,is rarely used for containment applications owing to its poor hydrophilicity.This study proposed a polymerization method that transforms sodium-activated calcium bentonite(NCB)into PMB to achieve low hydraulic conductivity(k)to aggressive liquids.The mechanism for its low k was revealed through characterization techniques and analyses(e.g.X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FTIR),scanning electron microscopy(SEM),and Brunauer-Emmett-Teller(BET)).The results showed that the PMB had a small amount of polymer elution(indicating better interface stability)and thus exhibited excellent barrier properties under chemically aggressive conditions,with the k of<10^(-11) m/s for 0.6 mol/L NaCl solution,which is four orders of magnitude lower than that of the NCB(k=3×10^(-7) m/s).Various microscopic analyses indicated that the selected monomers were successfully polymerized,and intercalated into and grafted onto the montmorillonite layers of bentonite.The formed polymer network increased the swelling capability of PMB granules,decreased the pore size,and created narrow and tortuous flow pathways leading to a very low k to aggressive liquids.
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.
基金supported by the National Natural Science Foundation of China(52103299)。
文摘With the global push for energy conservation and the rapid development of low-power,flexible and wearable optical displays,the demand for electrochromic technology has surged.Gel polymer electrolytes(GPEs),a crucial component of electrochromic devices(ECDs),show great promise in applications.This is attributed to their efficient ion-transport capabilities,excellent mechanical properties and strong adhesion.All of these characteristics are conducive to enhancing the safety of the devices,streamlining the packaging process,significantly improving the electrochromic performance of ECDs and boosting their commercial application potential.This review provides a comprehensive overview of GPEs for ECDs,focusing on their basic designs,functional modifications and practical applications.Firstly,this review outlines the fundamental design of GPEs for ECDs,encompassing key performance index,classification,gelation mechanism and preparation methods.Building on this foundation,it provides an in-depth discussion of functionalized GPEs developed to enhance device performance or expand functionality,including electrochromic,temperature-responsive,photo-responsive and stretchable self-healing GPE.Furthermore,the integration of GPEs into various ECD applications,including smart windows,displays,energy storage devices and wearable electronic,are summarized to highlight the advantages that the design of GPEs brings to the practical application of ECDs.Finally,based on the summary of GPEs employed for ECDs,the challenges and development expectations in this direction were indicated.
基金supported by the National Natural Science Foundation of China(22072048)the Guangdong Provincial Department of Science and Technology(2021A1515010128 and 2022A0505050013).
文摘Succinonitrile(SN)-based polymer plastic crystal electrolytes(PPCEs)are regarded as promising candidates for lithium metal batteries but suffer from serious side reactions with Li metal.Herein,we propose a multi-dimensional optimization strategy to alleviate the side reactions between SN and Li metal,and develop a highly stable poly-vinylethylene carbonate-based PPCE(PPCE-VEC).Moreover,we identify the intrinsic factors of multi-dimensional polymer structures on the electrolyte stability by three typical classes of polyesters.The PPCE-VEC constructed by in situ polymerization exhibits much better stability than poly-vinylene carbonate-based PPCE(PPCE-VCA)and poly-trifluoroethyl acrylate-based PPCE(PPCE-TFA),which is verified by its fewer SN-decomposition species in X-ray photoelectron spectroscopy(XPS)and outstanding full cell performance.The PPCE-VEC-enabled LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)full cell achieve 73.7%capacity retention after 1400 cycles,which outperforms PPCE-VCA-and PPCE-TFA-enabled full cells(61.9%and 46.9%).Spectral analysis and theoretical calculation reveal that the high solvation ability of the carbonyl site,flexible polymer chain,and homogeneous electrolyte phase of PPCE-VEC are favorable to maximizing competition coordination with Li^(+)to weaken the Li^(+)–SN binding and shape an anion-rich solvation structure.This optimized polymer-involved Li^(+)solvation enhances SN stability and facilitates the formation of B/F enriched solid-electrolyte interphase(SEI),thus significantly improving PPCE stability.
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supported by Japan Society for the Promotion of Science(JSPS),a Grant-in-Aid for Scientific Research(B)(JP23K23398)(for M.G.)and(JP24K01570)(for K.T.).
文摘In this review,the synthesis,functions,and applications of the polymers containing germanium and tin,which are heavy group 14 elements,in their polymer frameworks are summarized.Germanium and tin can form similar skeletal structures with their homologues carbon and silicon,whereas the polymers containing germanium and tin show unique properties derived from their large atomic radii and weak binding energies.For example,polygermane and polystannane exhibited light absorption in the UV–visible region and conductivity because of theσ-conjugation through the polymer main-chain constructed byσ-bonds between heavy elements.Theσ-conjugation was affected by the conformational change of the polymer main-chain,and thermochromic properties can be induced.Furthermore,the weak bonds were able to be cleaved homolytically upon photoirradiation,and radicals were subsequently generated.By incorporating hypervalent heavy elements into theπ-conjugated system,it was possible to modulate the electronic structures of theπ-conjugated system throughσ*–π*conjugation with highly coordinated elements.Finally,applications for organic solar cells,organic lightemitting materials,and chemical sensors have been achieved.Herein,representative synthetic methods and unique properties for creating smart materials with germanium and tin will be explained.
基金financial support by Guangdong Basic and Applied Basic Research Foundation(2025A1515012415)National Natural Science Foundation of China(52242305)the Stable Support Project of Shenzhen(Project No.20231122125728001).
文摘Thermoelectric(TE)materials,being capable of converting waste heat into electricity,are pivotal for sustainable energy solutions.Among emerging TE materials,organic TE materials,particularly conjugated polymers,are gaining prominence due to their unique combination of mechanical flexibility,environmental compatibility,and solution-processable fabrication.A notable candidate in this field is poly(2,5-bis(3-alkylthiophen-2-yl)thieno[3,2-b]thiophene)(PBTTT),a liquid-crystalline conjugated polymer,with high charge carrier mobility and adaptability to melt-processing techniques.Recent advancements have propelled PBTTT’s figure of merit from below 0.1 to a remarkable 1.28 at 368 K,showcasing its potential for practical applications.This review systematically examines strategies to enhance PBTTT’s TE performance through doping(solution,vapor,and anion exchange doping),composite engineering,and aggregation state controlling.Recent key breakthroughs include ion exchange doping for stable charge modulation,multi-heterojunction architectures reducing thermal conductivity,and proton-coupled electron transfer doping for precise Fermi-level tuning.Despite great progress,challenges still persist in enhancing TE conversion efficiency,balancing or decoupling electrical conductivity,Seebeck coefficient and thermal conductivity,and leveraging melt-processing scalability of PBTTT.By bridging fundamental insights with applied research,this work provides a roadmap for advancing PBTTT-based TE materials toward efficient energy harvesting and wearable electronics.
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financially supported by the National Natural Science Foundation of China(Nos.22341303,22103079,and 22503003)the Shandong Provincial Natural Science Foundation(No.ZR2023QB232)the Beijing Institute of Technology Research Fund Program for Young Scholars(No.RCPT-6120250009)。
文摘Shear stress overshoot in entangled polymer rheology is a hallmark of transient dynamics,but its microscopic origin remains under debate.Using molecular dynamics simulations,we investigate a two-step shear protocol consisting of successive startup shears separated by a waiting period,with the first shear interrupted before the overshoot.In the homogeneous flow,the GLaMM theory captures the stress response during the first shear,but fails to reproduce the nonmonotonic dependence of the second stress overshoot(σ_(2max))on the waiting time.Contrary to the prediction of a nonmonotonic normal stress component σ_(yy)during the waiting period,our simulations show that σ_(yy),like the tube segment orientation(S_(xy)),the contour length of the primitive chain(L),and the entanglement number per chain(Z),relaxes monotonically toward equilibrium.At the strain corresponding to σ_(2max),both the tube segment orientation and the entanglement number per chain exhibit a nonmonotonic dependence on the waiting time that closely mirrors the behavior of σ_(2max),indicating that both factors play significant roles in governing(σ_(2max).Our findings are consistent with the interpretation of lanniruberto and Ma rrucci[ACS Macro.Lett.2014,3,552]for orientation effects and with the viewpoint of Wang et al.[Macromolecules 2013,46,3147]for entanglement effects,although the two explanations are rooted in distinct physical pictu res.These results provide new insights into the stress responses of entanglement polymer fluids and underscore the need for a more unified theoretical framework.
基金Funded by the National Natural Science Foundation of China(Nos.5226804252468035)。
文摘To investigate the pore structure of graphene oxide modified polymer cement mortar(GOPM)under salt-freeze-thaw(SFT)coupling effects and its impact on deterioration,this study modifies polymer cement mortar(EMCM)with graphene oxide(GO).The micro-pore structure of GOPM is characterized using LF-NMR and SEM.Fractal theory is applied to calculate the fractal dimension of pore volume,and the deterioration patterns are analyzed based on the evolution characteristics of capillary pores.The experimental results indicate that,after 25 salt-freeze-thaw cycles(SFTc),SO2-4 ions penetrate the matrix,generating corrosion products that fill existing pores and enhance the compactness of the specimen.As the number of cycles increases,the ongoing formation and expansion of corrosion products within the matrix,combined with persistent freezing forces,and result in the degradation of the pore structure.Therefore,the mass loss rate(MLR)of the specimens shows a trend of first decreasing and then increasing,while the relative dynamic elastic modulus(RDEM)initially increases and then decreases.Compared to the PC group specimens,the G3PM group specimens show a 28.71% reduction in MLR and a 31.42% increase in RDEM after 150 SFTc.The fractal dimensions of the transition pores,capillary pores,and macropores in the G3PM specimens first increase and then decrease as the number of SFTc increases.Among them,the capillary pores show the highest correlation with MLR and RDEM,with correlation coefficients of 0.97438 and 0.98555,respectively.
基金Funded by the Hubei Province Key Research Foundation for Water Resources,China(No.HBSLKY2023035)as well as by the Technology Foundation for Selected Overseas Scholars,Ministry of Human Resources and Social Security,China(No.[2013]277)+2 种基金the Natural Science Foundation of the Hubei Province of China(No.2014CFA094)the Overseas High-level Talents Scientific-research Starting Fund of Hubei University of Technology,China(HBUTscience-[2005]2)the National Natural Science Foundation of China(No.51703053)。
文摘When a ceramic ionic-crystal nanocluster is group-substituted with polymer chain segments to form an ionomeric aggregate,is the ordered structure maintained within the sterically hindered nanocluster?We observed,for Na-salt sulfonated polystyrene ionomer,the electron-diffraction lattice fringes of the nanoclusters,which proved their internal crystalline ordering driven by electrostatic attractions overcoming steric hindrance.Kinetically,the nanoclusters'enhanced melting endotherm upon aging indicate their quasi-,slow-ordering character.Extended tight binding molecular dynamics simulations provide an insight into the mechanism underlying the ionic-group aggregation during nanoclustering.We hence proposed an uncommon state of order,polymer-bound ceramic quasicrystal,supplementary to the order phenomena in crystalline ceramics.
基金financially supported by the International Cooperation Program from the Ministry of Science and Technology of Hubei Province(No.2023EHA069)Shenzhen Science and Technology Program(No.JCYJ20230807143702005)National Foreign Experts Program(No.G2022027015L)。
文摘Magnetic resonance imaging(MRI)is one of the most widely used diagnostic techniques.Iron oxide nanoparticles,as a promising kind of contrast agents,have attracted intense research interest due to their low toxicity and superparamagnetism.However,it is still a great challenge to prepare ideal iron oxide based contrast agents with high uniformity,excellent water solubility and biocompatibility.In this paper,a novel water-soluble polymer ligand pentaerythritol tetrakis 3-mercaptopropionate-poly(N-vinyl-2-pyrrolidone)(PTMP-PVP)was used as a capping reagent to prepare iron oxide nanoparticles MIONs@PTMP-PVP through one-step co-precipitation of iron precursors in aqueous solution at 100℃.The obtained nanoparticles MIONs@PTMP-PVP had a small size and narrow size distribution,and they were found to be biocompatible as determined through CCK-8 assay and histology analysis.In vivo MRI study demonstrated that the obtained MIONs@PTMP-PVP can be potentially used as an effective T_(2)-weighted MRI contrast agent.
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financially supported by the Ministry of Science and Higher Education of the Russian Federation。
文摘Carbon-fiber-reinforced plastics(CFRP)with improved mechanical properties based on modified epoxy binders were investigated in this study.By adding 15 parts by weight(p.b.w.)of copolymer of polysulfone with cardo phthalide group(PSFP-70C)to the epoxyanhydride binder,the flexural strength of the epoxy polymer was increased by 60%,the CFRP based on it by 57%,the flexural modulus of the epoxy polymer was increased by 83%,and the composite by 96%.The adhesion strength of the binder to carbon fiber reached a high level at 10 p.b.w.of thermoplastic modifier and increased by 65%compared to the unmodified binder.Scanning electron microscopy(SEM)was used to determine that in epoxyanhydride systems with a polysulfone content of 5–15 p.b.w.,the structure belongs to the"matrix dispersion"type and with a content of 20 p.b.w.to the"interpenetrating phase"type.A heterogeneous structure was also observed using dynamic mechanical analysis.
基金financially supported by the Innovation and Technology Commission of the Hong Kong SAR Government(No.MRP/020/21)Hong Kong Polytechnic University(No.847A)+1 种基金RI-Wear Seed Fund of Poly U(1-CD8J)Start-up Fund of Poly U(1-BD49)。
文摘Polymer matrix composites with high dielectric constants and low dielectric losses are in high demand for flexible electronics.However,simultaneously satisfying these requirements poses a significant scientific challenge owing to the intrinsic trade-off relationship.Herein,we utilized the in situ controllable reduction of graphene oxide(GO)within a poly(vinylidene fluoride-trifluoroethylene-chlorofluoroethylene)(P(VDF-Tr FE-CFE))matrix to regulate the dielectric properties.The as-obtained composite exhibited a high relative dielectric constant of 1415coupled with a low loss tangent of 0.380 at 100 Hz.Experimental and theoretical studies indicate that the increased degree of electron conjugation and conductivity of the reduced GO(RGO)are responsible for the high-k.The constrained reduction degree of GO,combined with its homogeneous dispersion in the polymer matrix,effectively suppresses long-range charge carrier migration,thereby minimizing dielectric loss.This novel strategy could be successfully applied to both organic and aqueous systems.Furthermore,a high-performance flexible capacitive proximity sensor was exemplified by the optimization of both the dielectric layer and electrode pattern,exhibiting excellent sensitivity and stability.The fundamental mechanisms elucidated in this study provide crucial design principles for developing dielectric PMCs with tailored properties,thereby opening new avenues for advanced flexible electronic applications.
文摘Bone regeneration for non-load-bearing defects remains a significant clinical challenge requiring advanced biomaterials and cellular strategies.Adiposederived mesenchymal stem cells(AD-MSCs)have garnered significant interest in bone tissue engineering(BTE)because of their abundant availability,minimally invasive harvesting procedures,and robust differentiation potential into osteogenic lineages.Unlike bone marrow-derived mesenchymal stem cells,AD-MSCs can be easily obtained in large quantities,making them appealing alternatives for therapeutic applications.This review explores hydrogels containing polymers,such as chitosan,collagen,gelatin,and hyaluronic acid,and their composites,tailored for BTE,and emphasizes the importance of these hydrogels as scaffolds for the delivery of AD-MSCs.Various hydrogel fabrication techniques and biocompatibility assessments are discussed,along with innovative modifications to enhance osteogenesis.This review also briefly outlines AD-MSC isolation methods and advanced embedding techniques for precise cell placement,such as direct encapsulation and three-dimensional bioprinting.We discuss the mechanisms of bone regeneration in the AD-MSC-laden hydrogels,including osteoinduction,vascularization,and extracellular matrix remodeling.We also review the preclinical and clinical applications of AD-MSC-hydrogel systems,emphasizing their success and limitations.In this review,we provide a comprehensive overview of AD-MSC-based hydrogel systems to guide the development of effective therapies for bone regeneration.
基金financially supported by the National Natural Science Foundation of China(Nos.22341304,22303100 and 12205270)the National Key R&D Program of China(Nos.2023YFA1008800 and 2020YFA0713601)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDC0180303)。
文摘The equilibrium dynamics and nonlinear rheology of unentangled polymer blends remain inadequately understood,especially regarding the influence of short-chain matrix length N_(S) on the structure and rheological behavior of dispersed long chains.Using molecular dynamics simulations based on the Kremer-Grest model,we systematically explore the N_(S)-dependence of static conformations,equilibrium dynamics,and nonlinear shear responses in unentangled long-chain/short-chain polymer blends.Our results demonstrate a decoupling between the static and dynamic sensitivity to N_(S):while the static chain size,R_g,follows Flory theory with slight swelling at small N_(S) due to incomplete excluded volume screening,the diffusion coefficient,D,and the relaxation time,τ_(0),exhibit a strong,non-monotonic N_(S)-dependence,transitioning from monomeric friction dominance at small N_(S) to collective segmental rearrangement at large N_(S).Additionally,we observe partial decoupling between the viscous and normal stress responses:while the zero-shear viscosity,η,is strongly N_(S)-dependent,the first and second normal stress coefficients,Ψ_(1) and Ψ_(2),collapse onto universal curves when scaled by the dimensionless shear rate,γτ_(0),suggesting a common mechanism of orientation and stretching.Under shear,long chains compress in the vorticity direction λ_(z)~Wi^(-0.2),which reduces collision frequency and contributes to shear thinning,while the scaling of weaker orientation resistance m_(G)~Wi^(0.35)reflects hydrodynamic screening by the short-chain matrix.These findings highlight the limitations of single-chain models and emphasize the necessity of considering N_(S)-dependent matrix dynamics and flow-induced structural changes in understanding the rheology of unentangled polymer blends.
