Poly(butylene adipate-terephthalate)(PBAT),as one of the most common and promising biodegradable plastics,has been widely used in agriculture,packaging,and other industries due to its strong biodegradability propertie...Poly(butylene adipate-terephthalate)(PBAT),as one of the most common and promising biodegradable plastics,has been widely used in agriculture,packaging,and other industries due to its strong biodegradability properties.It is well known that PBAT suffers a series of natural weathering,mechanical wear,hydrolysis,photochemical transformation,and other abiotic degradation processes before being biodegraded.Therefore,it is particularly important to understand the role of abiotic degradation in the life cycle of PBAT.Since the abiotic degradation of PBAT has not been systematically summarized,this review aims to summarize the mechanisms and main factors of the three major abiotic degradation pathways(hydrolysis,photochemical transformation,and thermochemical degradation)of PBAT.It was found that all of them preferentially destroy the chemical bonds with higher energy(especially C-O and C=O)of PBAT,which eventually leads to the shortening of the polymer chain and then leads to reduction in molecular weight.The main factors affecting these abiotic degradations are closely related to the energy or PBAT structure.These findings provide important theoretical and practical guidance for identifying effective methods for PBAT waste management and proposing advanced schemes to regulate the degradation rate of PBAT.展开更多
Polymeric materials which can undergo controlled degradation and recycling are of great significance for a sustainable society.Although tremendous progress has been made in the degradation and recycling of both thermo...Polymeric materials which can undergo controlled degradation and recycling are of great significance for a sustainable society.Although tremendous progress has been made in the degradation and recycling of both thermoplastic and thermoset plastics,the development of high-performance degradable polymer adhesives is rare.Here,we have prepared high-performance nucleobase-containing thioctic acid-based supramolecular polymer adhesives through free radical polymerization.The specific hydrogen-bonding interactions between complementary nucleobases greatly improve the weak cohesion of the thioctic acid-based polymers and enhance the environmental stability of the thioctic acidbased polymers simultaneously.Degradation of the nucleobase-containing thioctic acid-based supramolecular polymers is achieved by the reduction of the disulfide backbone,and the cycle of degradation and repolymerization is further achieved via oxidative polymerization.The adhesion strength of the nucleobase-containing thioctic acid-based supramolecular polymers after two cycles of degradation and repolymerization still reaches as high as 4.7±0.3 MPa.This work provides an approach for the development of environmentally stable and high-performance degradable thioctic acid-based adhesives.展开更多
Chain-growth radical polymerization of vinyl monomers is essential for producing a wide range of materials with properties tailored to specific applications.However,the inherent resistance of the polymer's C―C ba...Chain-growth radical polymerization of vinyl monomers is essential for producing a wide range of materials with properties tailored to specific applications.However,the inherent resistance of the polymer's C―C backbone to degradation raises significant concerns regarding long-term environmental persistence,which also limits their potential in biomedical applications.To address these challenges,researchers have developed strategies to either degrade preexisting vinyl polymers or incorporate cleavable units into the backbone to modify them with enhanced degradability.This review explores the various approaches aimed at achieving backbone degradability in chain-growth radical polymerization of vinyl monomers,while also highlighting future research directions for the development of application-driven degradable vinyl polymers.展开更多
Incorporation of acetal groups in the backbone is a potent strategy to create polymers that are cleavable or degradable under acidic conditions.We report here an in-depth study on the ring-closing-opening copolymeriza...Incorporation of acetal groups in the backbone is a potent strategy to create polymers that are cleavable or degradable under acidic conditions.We report here an in-depth study on the ring-closing-opening copolymerization of o-phthalaldehyde(OPA)and epoxide using Lewis pair type two-component organocatalysts for producing acetal-functionalized polyether and polyurethane.Notably,triethylborane as the Lewis acid,in comparison with tri(n-butyl)borane,more effectively enhances the polymerization activity by mitigating borane-induced reduction of the aldehyde group into extra initiating(borinic ester)species.Density functional theory(DFT)calculations present comparable energy barriers of OPA-epoxide cross-propagation and epoxide self-propagation,which is consistent with the experimental finding that an alternating-rich copolymer comprising mostly OPA-epoxide units but also epoxide-epoxide linkages is produced.In particular,when epoxide is added in a large excess,the product becomes a polyether containing acetal functionalities in the central part of the backbone and thus being convertible into polyurethane with refined acid degradability.展开更多
The development of degradable and chemically recyclable polymers is a promising strategy to address pressing environmental and resource-related challenges.Despite significant progress,there is a need for continuous de...The development of degradable and chemically recyclable polymers is a promising strategy to address pressing environmental and resource-related challenges.Despite significant progress,there is a need for continuous development of such recyclable polymers.Herein,PPDOPLLA-PU copolymers were synthesized from poly(p-dioxanone)-diol(PPDO-diol)and poly(L-lactide)-diol(PLLA-diol)by chain extension reaction.The chemical structures and microphase structures of PPDO-PLLA-PU were characterized,and their crystalline properties,mechanical properties,and degradation behaviors were further investigated.Significantly,the distribution of PLLA phase in the copolymer matrix showed a rod-like microstructure with a slight orientation,despite the thermodynamic incompatibility of PPDO and PLLA segments.Moreover,on the basis of this microphase separation,PPDO spherulites can crystallize using the interface of the two phases as nucleation sites.Accordingly,the combined effect of above two contributes to the enhanced mechanical properties.In addition,PPDO-PLLA-PU copolymers have good processability and recyclability,making them valuable for a wide range of applications.展开更多
As a powerful synthetic tool,ruthenium-catalyzed ring-opening metathesis polymerization(ROMP)has been widely utilized to prepare diverse heteroatom-containing polymers.In this contribution,we report the synthesis of t...As a powerful synthetic tool,ruthenium-catalyzed ring-opening metathesis polymerization(ROMP)has been widely utilized to prepare diverse heteroatom-containing polymers.In this contribution,we report the synthesis of the novel imine-based polymer through the copolymerization of cyclooctene with cyclic imine comonomer via ROMP.Because of the efficient hydrolysis reactions of the imine group,the generated copolymer can be easily degraded under mild condition.Moreover,the generated degradable product was the telechelic polymer bearing amine group,which was highly challenged for its direct synthesis.And this telechelic polymer could also be used for the further synthesis of new polymer through post-transformation.The introduction of imine unit in this work provides a new example of the degradable polymer synthesis.展开更多
Traditional packaging plastics derived from fossil fuels for perishable foods have caused severe environmental pollution and resource depletion.To promote sustainable development and reduce wastage of perishable produ...Traditional packaging plastics derived from fossil fuels for perishable foods have caused severe environmental pollution and resource depletion.To promote sustainable development and reduce wastage of perishable products,there is a significant challenge in developing biobased packaging plastics that offer excellent preservation,satisfactory mechanical performance,and inherent degradability.In this study,poly(urethane-urea)(PUU)plastics are fabricated using a one-pot polyaddition reaction involving castor oil(CO),tannic acid(TA),lysine-derived ethyl 2,6-diisocyanatohexanoate(LDI),and H2O.The resulting PUU plastics demonstrate a high breaking strength of about 32.7 MPa and a strain at break of ca.102%.Due to the reversibility of hydrogen bonds,PUU plastics can be easily shaped into various forms.They are non-cytotoxic and suitable for food packaging.With a high TA content of ca.38.2 wt%,PUU plastics exhibit excellent antioxidant capacity.Consequently,PUU plastics show outstanding freshness preservation performance,extending the shelf life of cherry tomatoes and winter jujubes for at least 8 days at room temperature.Importantly,PUU plastics can autonomously degrade into non-toxic substances within ca.298 days when buried in soil.展开更多
In practical engineering construction,multi-layered barriers containing geomembranes are extensively applied to retard the migration of pollutants.However,the associated analytical theory on pollutants diffusion still...In practical engineering construction,multi-layered barriers containing geomembranes are extensively applied to retard the migration of pollutants.However,the associated analytical theory on pollutants diffusion still needs to be further improved.In this work,general analytical solutions are derived for one-dimensional diffusion of degradable organic contaminant(DOC)in the multi-layered media containing geomembranes under a time-varying concentration boundary condition,where the variable substitution and separated variable approaches are employed.These analytical solutions with clear expressions can be used not only to study the diffusion behaviors of DOC in bottom and vertical composite barrier systems,but also to verify other complex numerical models.The proposed general analytical solutions are then fully validated via three comparative analyses,including comparisons with the experimental measurements,an existing analytical solution,and a finite-difference solution.Ultimately,the influences of different factors on the composite cutoff wall’s(CCW,which consists of two soil-bentonite layers and a geomembrane)service performance are investigated through a composite vertical barrier system as the application example.The findings obtained from this investigation can provide scientific guidance for the barrier performance evaluation and the engineering design of CCWs.This application example also exhibits the necessity and effectiveness of the developed analytical solutions.展开更多
In recent years,the biodegradable plastics has extensively used in industry,agriculture,and daily life.Herein,the effects of two biodegradable microplastics(BMPs),poly(butyleneadipate-co-terephthalate)(PBAT)and polyhy...In recent years,the biodegradable plastics has extensively used in industry,agriculture,and daily life.Herein,the effects of two biodegradable microplastics(BMPs),poly(butyleneadipate-co-terephthalate)(PBAT)and polyhydroxyalkanoate(PHA),on soil sulfamethoxazole(SMX)degradation and sul genes development were comparatively studied based on the type,dosage,and state.The addition of virgin BMPs significantly increased soil DOC following a sequential order PBAT>PHA and high dose>low dose.Meanwhile virgin PBAT significantly reduced soil pH.In general,the addition of BMPs not only promoted soil SMX degradation but also increased the abundance of sul genes,with an exception that pH reduction in virgin PBAT inhibited the proliferation of sul genes.The driving effects of BMPs on soil microbial diversity following the same order as that on DOC.Specific bacteria stimulated by BMPs,such as Arthrobacter and two genera affiliated with phylum TM7,accounted for the accelerated degradation of SMX.Intriguingly,UV-aging hindered the release of DOC from BMPs and the reduction in pH,mitigated the stimulation of microbial communities,and ultimately reduced the promotion effect of BMPs on SMX degradation and sul genes proliferation.Our results suggest that more attention should be paid to the proliferation risk of ARGs in the environment affected by BMPs and UV-aging can be employed sometimes to reduce this risk.展开更多
Zinc(Zn)and its alloys are considered promising biodegradable metallic materials for biomedical implants.However,the correlation between the dynamic degradation evolution of Zn and its biocompatibility remains unclear...Zinc(Zn)and its alloys are considered promising biodegradable metallic materials for biomedical implants.However,the correlation between the dynamic degradation evolution of Zn and its biocompatibility remains unclear.This study evaluates the long-term degradation/corrosion behavior of pure Zn under dynamic immersion in Hank’s solution containing bovine serum albumin(BSA),and investigates the impact of its dynamic degradation evolution on cytocompatibilities of the representative human umbilical vein endothelial cells(HUVECs)and bone marrow mesenchymal stem cells(BMSCs).Degradation behavior results demonstrate that the dynamic fluidic medium led to speeding-up of the corrosion rate of Zn and exacerbation of the localized corrosion,with this phenomenon being more pronounced under influence of BSA.Correspondingly,the cells’viability increased with prolonged immersion time under both static and dynamic conditions,alleviating a certain level of cytotoxicity initiated at an earlier stage.Nonetheless,as compared to the static cases the dynamic fluidic environments induced a poorer cell viability,although the BSA helped to offset this impact.Our findings provide not only new insights into better-understanding Zn-based biodegradable metals but also clarify the critical concern in their clinical translations,offering therefore important guidance for development of new biodegradable metallic medical implants.展开更多
Biliary system,which is responsible for transporting bile from the liver into the intestine,is commonly damaged by inflammation or tumors eventually causing liver failure or death.The implantation of biliary stents ca...Biliary system,which is responsible for transporting bile from the liver into the intestine,is commonly damaged by inflammation or tumors eventually causing liver failure or death.The implantation of biliary stents can effectively alleviate both benign and malignant biliary strictures,but the plastic and metal stents that are currently used cannot degrade and nearly has no beneficial biological effects,therefore their long-term service can result into inflammation,the formation of sludges and re-obstruction of bile duct.In recent years,magnesium(Mg)metal has been received increasing attention in the field of biomedical application due to its excellent biocompatibility,adequate mechanical properties,biodegradability and other advantages,such as anti-inflammatory and anti-tumor properties.The research on biliary stents made of magnesium metals(BSMM)has also made significant progress and a series of experiments in vitro and vivo has proved their possibility.However,there are still some problems holding back BSMM’s clinical use,including rapid corrosion rate and potential harmful reaction.In this review,we would summarize the current research of BSMM,evaluate their clinical benefits,find the choke points,and discuss the solving method.展开更多
Mg and its alloys show high potential to be applied as implant materials due to their superior properties like biodegradability,bioactivity,biocompatibility,and suitable mechanical behaviors.Nevertheless,the fast and ...Mg and its alloys show high potential to be applied as implant materials due to their superior properties like biodegradability,bioactivity,biocompatibility,and suitable mechanical behaviors.Nevertheless,the fast and uncontrolled degradation of Mg alloys in biological environment severely restricts their wide applications as biomedical materials.In comparison with alloying,surface coatings can not only improve corrosion resistance but also impart other bio-functional properties to achieve diverse clinical requirements.This review analyzes and summarizes the most recent developments in popular coating technologies,including micro-arc oxidation,electrophoretic deposition,chemical conversion,anodic oxidation,layered double hydroxide,and sol-gel coatings.Considering inevitable damages under complex service conditions,smart self-healing coatings are also introduced in each coating technology.The existing issues and future perspectives are finally discussed to facilitate applications of Mg alloys as biomedical materials in the medical industry.展开更多
The introduction of dynamic covalent bonds into the structure of epoxy resins can improve the degradation performance of the materials.But to a certain extent,it will affect the insulating properties of the resin,and ...The introduction of dynamic covalent bonds into the structure of epoxy resins can improve the degradation performance of the materials.But to a certain extent,it will affect the insulating properties of the resin,and how to balance the insulating properties and degradation performance has become an urgent problem.In this paper,the effects of different catalysts on the thermal-force-electrical properties of sorbitolbased resins were systematically investigated based on the dynamic ester bonding to construct the resin crosslinking network,and the biobased sorbitol glycidyl ether was used as the resin matrix.The experiments show that the resin system catalyzed by triethanolamine(TEOA)exhibits excellent comprehensive performance,which combines good thermal stability and mechanical properties with excellent electrical properties(breakdown field strength of 44.21 k V/mm and dielectric loss factor of 0.29%).In addition,chemical degradation tests were conducted on the resin systems with different catalysts,and the experiments showed that the produced resins could be degraded in benzyl alcohol and exhibited good degradation performance.This study provides a theoretical basis and technical path for the development of new bio-based electrical insulating materials with both high insulation and degradation properties,which is conducive to the popularization and application of bio-based resins in the field of electrical equipment.展开更多
Incorporating a low density of ester units into the backbone of polyethylene materials enhances their sustainability and recyclability while maintaining the main material properties of polyethylenes.Here we report a n...Incorporating a low density of ester units into the backbone of polyethylene materials enhances their sustainability and recyclability while maintaining the main material properties of polyethylenes.Here we report a new way to access degradable polyethylene materials with a low content of in-chain ester units via mechanochemical backbone editing.Initially,ester groups are incorporated as side groups through catalytic copolymerization of ethylene with a cyclobutene-fused lactone monomer(CBL),yielding polyethylene materials with high molecular weights and adjustable thermomechanical properties.Subsequent solid-state ball-milling treatment selectively introduces side-chain ester groups into the main chain of the polyethylene materials via force-induced cycloreversion of the cyclobutane units.Under acidic conditions,hydrolysis of the resultant polyethylene materials with in-chain ester units facilitates further degradation into oligomers.展开更多
The increasing interest in Mg-Zn binary alloys as temporary implant materials is attributed to their outstanding biocompatibility,biodegradability,and favourable mechanical properties.However,their application is cons...The increasing interest in Mg-Zn binary alloys as temporary implant materials is attributed to their outstanding biocompatibility,biodegradability,and favourable mechanical properties.However,their application is constrained by high degradation rates in the physiological environment,resulting in the release of hydrogen gas and a rapid decline in mechanical properties.Additionally,the material's biocompatibility is contingent upon its degradability.Researchers have demonstrated that addressing these issues is possible through strategies such as controlling Zn content,employing thermo-mechanical processing to achieve suitable microstructures,and applying surface coatings.This manuscript provides a comprehensive review of published literature on Mg-Zn alloys,exploring the challenges and outlining future research directions in this field.展开更多
The poor degradability and limited recyclability of epoxy resins are key challenges hindering the efficient recycling of ex-service wind turbine blades(EWTBs).Herein,we proposed a selective degradation strategy for di...The poor degradability and limited recyclability of epoxy resins are key challenges hindering the efficient recycling of ex-service wind turbine blades(EWTBs).Herein,we proposed a selective degradation strategy for direct recycling and high-value recovery of epoxy resins by introducing degradable Schiff base groups into the molecular structure and utilizing the resulting oligomers as curing agents.To realize this strategy,a series of Schiff base compounds were synthesized using bio-based vanillin and diamines and subsequently functionalized with epichlorohydrin to yield bio-based epoxy resins.The cured epoxy resins demonstrated remarkable improvements in the mechanical properties of diglycidyl ether of bisphenol-A(DGEBA),with an increases of 44.49%in the tensile strength of 38.55%,bending strength,and impact strength of 71.20%.The introduction of dynamic Schiff base bonds enabled the selective degradation of the vanillin-2,2-bis[4-(4-aminophenoxy)phenyl]propane-based epoxy resin(VBEP)/DGEBA copolymer,producing 84.20% oligomers that can be directly recycled and reused.Replacing 30 wt% of the curing agent with the oligomer increased the tensile strength of the cured sample to 75.40 MPa,surpassing that of the cured DGEBA.Under simulated acid rain and seawater exposure,the copolymer exhibited a service life of 27 years at 40℃,significantly exceeding the currently reported service life of 20 years.This study presents a sustainable strategy for the direct recycling and high-value reuse of epoxy resin,offering a promising solution for EWTBs.展开更多
Poly(lactic acid)(PLA)is a biodegradable and eco-friendly polymer that is increasingly being incorporated into various applications in contemporary society.However,the limited stability of PLA-based products remains a...Poly(lactic acid)(PLA)is a biodegradable and eco-friendly polymer that is increasingly being incorporated into various applications in contemporary society.However,the limited stability of PLA-based products remains a significant challenge for their broader use in various applications.In this study,poly(L-lactic acid)(PLLA)/poly(D-lactic acid)(PDLA)melt-blown nonwovens were prepared by melt spinning.The structure,thermal properties,thermal stability,biodegradability and crystalline morphology of the melt-blown nonwovens were investigated.DSC and WAXD confirmed the formation of stereocomplex(SC)crystallites in the PLLA matrix.The storage modulus(G′),loss modulus(G″),and complex viscosity(∣η^(*)∣)of the PLLA/PDLA blend increased with an increase in SC crystallite content.The thermal degradation temperatures of PLLA/PDLA melt-blown nonwovens increased with the incorporation of SC crystallites,and the maximum rate of decomposition increased to 385.5℃,thus enhancing the thermal stability.Compared with neat PLLA melt-blown nonwovens,the hydrophobicity of PLLA/PDLA melt-blown nonwovens was improved,and WCA increased to 139.7°.The SC crystallites were more resistant to degradation by proteinase K compared to neat PLLA.However,the degradation rate of PLLA/PDLA melt-blown nonwovens remained at a high level.This work provides an effective strategy to obtain high-performance PLLA melt-blown nonwovens.展开更多
A study of the effect of rotary swaging(RS)at 350℃ on mechanical properties,corrosion resistance and biocompatibility in vitro and in vivo of biodegradable Mg-1%Zn-0.6%Ca alloy was conducted.It is shown that the form...A study of the effect of rotary swaging(RS)at 350℃ on mechanical properties,corrosion resistance and biocompatibility in vitro and in vivo of biodegradable Mg-1%Zn-0.6%Ca alloy was conducted.It is shown that the formation of a recrystallized microstructure after RS with a grain size of 3.2±0.2μm leads to an increase in the strength of the alloy without reduction of level of ductility and corrosion resistance.At the same time,aging of the quenched alloy at 100℃ for 8 h leads to a slight increase in strength,but significantly reduces its ductility and corrosion resistance.The study of the degradation process of the alloy in the quenched state and after RS,both under in vitro and in vivo conditions,did not reveal a significant difference between these two microstructural states.However,an increase in the duration of incubation of the alloy in a complete growth medium from 4 h to 24 days leads to a decrease in the degradation rate(DR)by 4times(from~2 to~0.5 mm/year)due to the formation of a dense layer of degradation products.The study of biocompatibility in vitro did not reveal a significant effect of RS on the hemolytic and cytotoxic activity of the alloy.No signs of systemic toxicity were observed after subcutaneous implantation of alloy samples into mice before and after RS.However,it was found that RS promotes uniform degradation of the alloy over the entire contact surface.In summary,RS at 350℃ allows to increase the strength of Mg-1%Zn-0.6%Ca alloy up to348±5 MPa at a ductility level of 17.3±2.8%and a DRin vivoequal to 0.56±0.12 mm/year without impairing its biocompatibility in vitro and in vivo.展开更多
Most commercial plastics cannot easily degrade,which raises a number of sustainability issues.To address the current problem of plastic pollution,the research and development of easily degradable and recyclable polyme...Most commercial plastics cannot easily degrade,which raises a number of sustainability issues.To address the current problem of plastic pollution,the research and development of easily degradable and recyclable polymers has become an attractive subject.Herein,a new monomer of thiosalicylic methyl glycolide(TSMG)was synthesized using one-pot method and high molecular weight poly(thiosalicylic methyl glycolide)(PTSMG,M_(n) up to 300 kDa)can be obtained via the ring-opening polymerization(ROP)of TSMG.PTSMG exhibits good closed-loop recyclability and hydrolytic degradability,where PTSMG can generate pristine monomers through sublimation thermal depolymerization conditions due to the presence of thiophenol ester bond in the polymer chains,and can be degraded rapidly in aqueous solution,which provides a potential solution to the current plastic pollution problem.展开更多
The most widely used bisphenol A-type epoxy resin(DGEBA)in electrical engineering demonstrates excellent mechanical and electrical properties.However,the insoluble and infusible characteristics of cured DGEBA make it ...The most widely used bisphenol A-type epoxy resin(DGEBA)in electrical engineering demonstrates excellent mechanical and electrical properties.However,the insoluble and infusible characteristics of cured DGEBA make it difficult to efficiently degrade and recycle decommissioned electrical equipment.In this study,a degradable itaconic acid-based epoxy resin incorporating dynamic covalent bonds was prepared through the integration of ester bonds and disulfide bonds,with itaconic acid as the precursor.The covalent bonding effects on the mechanical,thermal,electrical,and degradation characteristics were systematically evaluated.The experimental results revealed that the introduction of dynamic ester bonds enhanced the mechanical properties and thermal stability of the resin system,achieving a flexural strength of 141.57 MPa and an initial decomposition temperature T_(5%)of up to 344.9℃.The resin system containing dynamic disulfide bonds exhibited a dielectric breakdown strength of 41.11 k V/mm.Simultaneously,the incorporation of disulfide bonds endowed the epoxy resin with remarkable degradability,enabling complete dissolution within 1.5 h at 90℃ in a mixed solution of dithiothreitol(DTT)and N-methylpyrrolidone(NMP).This research provides a valuable reference for the application of itaconic acid-based vitrimer with dynamic covalent bonds in electrical materials,contributing to the development and utilization of environmentally friendly electrical equipment.展开更多
基金supported by the National Key R&D Program of China(No.2022YFC3901800)the National Natural Science Foundation of China(No.22176041)Guangzhou Science and Technology Planning Project(No.2023A04J0918)。
文摘Poly(butylene adipate-terephthalate)(PBAT),as one of the most common and promising biodegradable plastics,has been widely used in agriculture,packaging,and other industries due to its strong biodegradability properties.It is well known that PBAT suffers a series of natural weathering,mechanical wear,hydrolysis,photochemical transformation,and other abiotic degradation processes before being biodegraded.Therefore,it is particularly important to understand the role of abiotic degradation in the life cycle of PBAT.Since the abiotic degradation of PBAT has not been systematically summarized,this review aims to summarize the mechanisms and main factors of the three major abiotic degradation pathways(hydrolysis,photochemical transformation,and thermochemical degradation)of PBAT.It was found that all of them preferentially destroy the chemical bonds with higher energy(especially C-O and C=O)of PBAT,which eventually leads to the shortening of the polymer chain and then leads to reduction in molecular weight.The main factors affecting these abiotic degradations are closely related to the energy or PBAT structure.These findings provide important theoretical and practical guidance for identifying effective methods for PBAT waste management and proposing advanced schemes to regulate the degradation rate of PBAT.
基金supported by the National Natural Science Foundation of China(Nos.22273098,22373003,22103002 and 52033001)the Key Project of Anhui Province Science and Technology Innovation Platform(No.202305a12020030)the financial support from the Anhui Provincial Natural Science Foundation(No.2408085Y004)。
文摘Polymeric materials which can undergo controlled degradation and recycling are of great significance for a sustainable society.Although tremendous progress has been made in the degradation and recycling of both thermoplastic and thermoset plastics,the development of high-performance degradable polymer adhesives is rare.Here,we have prepared high-performance nucleobase-containing thioctic acid-based supramolecular polymer adhesives through free radical polymerization.The specific hydrogen-bonding interactions between complementary nucleobases greatly improve the weak cohesion of the thioctic acid-based polymers and enhance the environmental stability of the thioctic acidbased polymers simultaneously.Degradation of the nucleobase-containing thioctic acid-based supramolecular polymers is achieved by the reduction of the disulfide backbone,and the cycle of degradation and repolymerization is further achieved via oxidative polymerization.The adhesion strength of the nucleobase-containing thioctic acid-based supramolecular polymers after two cycles of degradation and repolymerization still reaches as high as 4.7±0.3 MPa.This work provides an approach for the development of environmentally stable and high-performance degradable thioctic acid-based adhesives.
基金funding from the National Natural Science Foundation of China(No.22401037)funding from JST CREST(No.JPMJCR23L1)。
文摘Chain-growth radical polymerization of vinyl monomers is essential for producing a wide range of materials with properties tailored to specific applications.However,the inherent resistance of the polymer's C―C backbone to degradation raises significant concerns regarding long-term environmental persistence,which also limits their potential in biomedical applications.To address these challenges,researchers have developed strategies to either degrade preexisting vinyl polymers or incorporate cleavable units into the backbone to modify them with enhanced degradability.This review explores the various approaches aimed at achieving backbone degradability in chain-growth radical polymerization of vinyl monomers,while also highlighting future research directions for the development of application-driven degradable vinyl polymers.
基金financially supported by the National Key R&D Program of China(No.2022YFC2805103)the National Natural Science Foundation of China(Nos.52022031 and 52263001)the Foundation from Qinghai Science and Technology Department(No.2022-ZJ-944Q)。
文摘Incorporation of acetal groups in the backbone is a potent strategy to create polymers that are cleavable or degradable under acidic conditions.We report here an in-depth study on the ring-closing-opening copolymerization of o-phthalaldehyde(OPA)and epoxide using Lewis pair type two-component organocatalysts for producing acetal-functionalized polyether and polyurethane.Notably,triethylborane as the Lewis acid,in comparison with tri(n-butyl)borane,more effectively enhances the polymerization activity by mitigating borane-induced reduction of the aldehyde group into extra initiating(borinic ester)species.Density functional theory(DFT)calculations present comparable energy barriers of OPA-epoxide cross-propagation and epoxide self-propagation,which is consistent with the experimental finding that an alternating-rich copolymer comprising mostly OPA-epoxide units but also epoxide-epoxide linkages is produced.In particular,when epoxide is added in a large excess,the product becomes a polyether containing acetal functionalities in the central part of the backbone and thus being convertible into polyurethane with refined acid degradability.
基金financially supported by the National Key R&D Program of China(No.2021YFB3801901)the National Natural Science Foundation of China(Nos.52403138 and U19A2095)+1 种基金Institutional Research Fund from Sichuan University(No.2020SCUNL205)Fundamental Research Funds for the Central Universities,and 111 Project(No.B20001)。
文摘The development of degradable and chemically recyclable polymers is a promising strategy to address pressing environmental and resource-related challenges.Despite significant progress,there is a need for continuous development of such recyclable polymers.Herein,PPDOPLLA-PU copolymers were synthesized from poly(p-dioxanone)-diol(PPDO-diol)and poly(L-lactide)-diol(PLLA-diol)by chain extension reaction.The chemical structures and microphase structures of PPDO-PLLA-PU were characterized,and their crystalline properties,mechanical properties,and degradation behaviors were further investigated.Significantly,the distribution of PLLA phase in the copolymer matrix showed a rod-like microstructure with a slight orientation,despite the thermodynamic incompatibility of PPDO and PLLA segments.Moreover,on the basis of this microphase separation,PPDO spherulites can crystallize using the interface of the two phases as nucleation sites.Accordingly,the combined effect of above two contributes to the enhanced mechanical properties.In addition,PPDO-PLLA-PU copolymers have good processability and recyclability,making them valuable for a wide range of applications.
基金financially supported by National Key R&D Program of China(No.2021YFA1501700)CAS Project for Young Scientists in Basic Research(No.YSBR-094)+1 种基金Natural Science Foundation of Anhui Province(Nos.2308085Y35 and 2023AH030002)Hefei Natural Science Foundation(No.202304)。
文摘As a powerful synthetic tool,ruthenium-catalyzed ring-opening metathesis polymerization(ROMP)has been widely utilized to prepare diverse heteroatom-containing polymers.In this contribution,we report the synthesis of the novel imine-based polymer through the copolymerization of cyclooctene with cyclic imine comonomer via ROMP.Because of the efficient hydrolysis reactions of the imine group,the generated copolymer can be easily degraded under mild condition.Moreover,the generated degradable product was the telechelic polymer bearing amine group,which was highly challenged for its direct synthesis.And this telechelic polymer could also be used for the further synthesis of new polymer through post-transformation.The introduction of imine unit in this work provides a new example of the degradable polymer synthesis.
基金supported by the National Natural Science Foundation of China(Nos.21935004 and 22350011)。
文摘Traditional packaging plastics derived from fossil fuels for perishable foods have caused severe environmental pollution and resource depletion.To promote sustainable development and reduce wastage of perishable products,there is a significant challenge in developing biobased packaging plastics that offer excellent preservation,satisfactory mechanical performance,and inherent degradability.In this study,poly(urethane-urea)(PUU)plastics are fabricated using a one-pot polyaddition reaction involving castor oil(CO),tannic acid(TA),lysine-derived ethyl 2,6-diisocyanatohexanoate(LDI),and H2O.The resulting PUU plastics demonstrate a high breaking strength of about 32.7 MPa and a strain at break of ca.102%.Due to the reversibility of hydrogen bonds,PUU plastics can be easily shaped into various forms.They are non-cytotoxic and suitable for food packaging.With a high TA content of ca.38.2 wt%,PUU plastics exhibit excellent antioxidant capacity.Consequently,PUU plastics show outstanding freshness preservation performance,extending the shelf life of cherry tomatoes and winter jujubes for at least 8 days at room temperature.Importantly,PUU plastics can autonomously degrade into non-toxic substances within ca.298 days when buried in soil.
基金Project(2023YFC3707800)supported by the National Key Research and Development Program of China。
文摘In practical engineering construction,multi-layered barriers containing geomembranes are extensively applied to retard the migration of pollutants.However,the associated analytical theory on pollutants diffusion still needs to be further improved.In this work,general analytical solutions are derived for one-dimensional diffusion of degradable organic contaminant(DOC)in the multi-layered media containing geomembranes under a time-varying concentration boundary condition,where the variable substitution and separated variable approaches are employed.These analytical solutions with clear expressions can be used not only to study the diffusion behaviors of DOC in bottom and vertical composite barrier systems,but also to verify other complex numerical models.The proposed general analytical solutions are then fully validated via three comparative analyses,including comparisons with the experimental measurements,an existing analytical solution,and a finite-difference solution.Ultimately,the influences of different factors on the composite cutoff wall’s(CCW,which consists of two soil-bentonite layers and a geomembrane)service performance are investigated through a composite vertical barrier system as the application example.The findings obtained from this investigation can provide scientific guidance for the barrier performance evaluation and the engineering design of CCWs.This application example also exhibits the necessity and effectiveness of the developed analytical solutions.
基金supported by the National Key Plan for Research and Development of China(Nos.2022YFE0120300 and 2020YFC1806902)the National Natural Science Foundation of China(Nos.42161134002,81991535,and 41877058)the Natural Science Foundation of Fujian Province,China(No.2022J01509).
文摘In recent years,the biodegradable plastics has extensively used in industry,agriculture,and daily life.Herein,the effects of two biodegradable microplastics(BMPs),poly(butyleneadipate-co-terephthalate)(PBAT)and polyhydroxyalkanoate(PHA),on soil sulfamethoxazole(SMX)degradation and sul genes development were comparatively studied based on the type,dosage,and state.The addition of virgin BMPs significantly increased soil DOC following a sequential order PBAT>PHA and high dose>low dose.Meanwhile virgin PBAT significantly reduced soil pH.In general,the addition of BMPs not only promoted soil SMX degradation but also increased the abundance of sul genes,with an exception that pH reduction in virgin PBAT inhibited the proliferation of sul genes.The driving effects of BMPs on soil microbial diversity following the same order as that on DOC.Specific bacteria stimulated by BMPs,such as Arthrobacter and two genera affiliated with phylum TM7,accounted for the accelerated degradation of SMX.Intriguingly,UV-aging hindered the release of DOC from BMPs and the reduction in pH,mitigated the stimulation of microbial communities,and ultimately reduced the promotion effect of BMPs on SMX degradation and sul genes proliferation.Our results suggest that more attention should be paid to the proliferation risk of ARGs in the environment affected by BMPs and UV-aging can be employed sometimes to reduce this risk.
基金financially supported by the Sichuan Science and Technology Program(No.2024YFHZ0310)the China Postdoctoral Science Foundation(No.2024M752092)+1 种基金the Shenzhen Medical Research Fund(No.A2402040)the Shenzhen Science and Technology Program(No.JCYJ20240813180905008).
文摘Zinc(Zn)and its alloys are considered promising biodegradable metallic materials for biomedical implants.However,the correlation between the dynamic degradation evolution of Zn and its biocompatibility remains unclear.This study evaluates the long-term degradation/corrosion behavior of pure Zn under dynamic immersion in Hank’s solution containing bovine serum albumin(BSA),and investigates the impact of its dynamic degradation evolution on cytocompatibilities of the representative human umbilical vein endothelial cells(HUVECs)and bone marrow mesenchymal stem cells(BMSCs).Degradation behavior results demonstrate that the dynamic fluidic medium led to speeding-up of the corrosion rate of Zn and exacerbation of the localized corrosion,with this phenomenon being more pronounced under influence of BSA.Correspondingly,the cells’viability increased with prolonged immersion time under both static and dynamic conditions,alleviating a certain level of cytotoxicity initiated at an earlier stage.Nonetheless,as compared to the static cases the dynamic fluidic environments induced a poorer cell viability,although the BSA helped to offset this impact.Our findings provide not only new insights into better-understanding Zn-based biodegradable metals but also clarify the critical concern in their clinical translations,offering therefore important guidance for development of new biodegradable metallic medical implants.
基金supported by Natural Science Foundation of Hunan Province(2021JJ31081,2024JJ5619)the Science Fund of State Key Laboratory of Advanced Design and Manufacturing Technology for Vehicle(No 32215004).
文摘Biliary system,which is responsible for transporting bile from the liver into the intestine,is commonly damaged by inflammation or tumors eventually causing liver failure or death.The implantation of biliary stents can effectively alleviate both benign and malignant biliary strictures,but the plastic and metal stents that are currently used cannot degrade and nearly has no beneficial biological effects,therefore their long-term service can result into inflammation,the formation of sludges and re-obstruction of bile duct.In recent years,magnesium(Mg)metal has been received increasing attention in the field of biomedical application due to its excellent biocompatibility,adequate mechanical properties,biodegradability and other advantages,such as anti-inflammatory and anti-tumor properties.The research on biliary stents made of magnesium metals(BSMM)has also made significant progress and a series of experiments in vitro and vivo has proved their possibility.However,there are still some problems holding back BSMM’s clinical use,including rapid corrosion rate and potential harmful reaction.In this review,we would summarize the current research of BSMM,evaluate their clinical benefits,find the choke points,and discuss the solving method.
基金supported by the Chongqing Natural Science Foundation(No.CSTB2023NSCQ-MSX0512)Municipal Human Resources and Social Security Bureau(No.cx2022098)China Postdoctoral Science Foundation(Nos.2022T150767 and 2021M693708).
文摘Mg and its alloys show high potential to be applied as implant materials due to their superior properties like biodegradability,bioactivity,biocompatibility,and suitable mechanical behaviors.Nevertheless,the fast and uncontrolled degradation of Mg alloys in biological environment severely restricts their wide applications as biomedical materials.In comparison with alloying,surface coatings can not only improve corrosion resistance but also impart other bio-functional properties to achieve diverse clinical requirements.This review analyzes and summarizes the most recent developments in popular coating technologies,including micro-arc oxidation,electrophoretic deposition,chemical conversion,anodic oxidation,layered double hydroxide,and sol-gel coatings.Considering inevitable damages under complex service conditions,smart self-healing coatings are also introduced in each coating technology.The existing issues and future perspectives are finally discussed to facilitate applications of Mg alloys as biomedical materials in the medical industry.
基金financially supported by the National Natural Science Foundation of China(No.52377025)。
文摘The introduction of dynamic covalent bonds into the structure of epoxy resins can improve the degradation performance of the materials.But to a certain extent,it will affect the insulating properties of the resin,and how to balance the insulating properties and degradation performance has become an urgent problem.In this paper,the effects of different catalysts on the thermal-force-electrical properties of sorbitolbased resins were systematically investigated based on the dynamic ester bonding to construct the resin crosslinking network,and the biobased sorbitol glycidyl ether was used as the resin matrix.The experiments show that the resin system catalyzed by triethanolamine(TEOA)exhibits excellent comprehensive performance,which combines good thermal stability and mechanical properties with excellent electrical properties(breakdown field strength of 44.21 k V/mm and dielectric loss factor of 0.29%).In addition,chemical degradation tests were conducted on the resin systems with different catalysts,and the experiments showed that the produced resins could be degraded in benzyl alcohol and exhibited good degradation performance.This study provides a theoretical basis and technical path for the development of new bio-based electrical insulating materials with both high insulation and degradation properties,which is conducive to the popularization and application of bio-based resins in the field of electrical equipment.
基金financially supported by the National Natural Science Foundation of China(No.52473097)the Fundamental Research Funds for the Central Universities(No.24X010301678)Shanghai Jiao Tong University 2030 Initiative(No.WH510363002/002)。
文摘Incorporating a low density of ester units into the backbone of polyethylene materials enhances their sustainability and recyclability while maintaining the main material properties of polyethylenes.Here we report a new way to access degradable polyethylene materials with a low content of in-chain ester units via mechanochemical backbone editing.Initially,ester groups are incorporated as side groups through catalytic copolymerization of ethylene with a cyclobutene-fused lactone monomer(CBL),yielding polyethylene materials with high molecular weights and adjustable thermomechanical properties.Subsequent solid-state ball-milling treatment selectively introduces side-chain ester groups into the main chain of the polyethylene materials via force-induced cycloreversion of the cyclobutane units.Under acidic conditions,hydrolysis of the resultant polyethylene materials with in-chain ester units facilitates further degradation into oligomers.
文摘The increasing interest in Mg-Zn binary alloys as temporary implant materials is attributed to their outstanding biocompatibility,biodegradability,and favourable mechanical properties.However,their application is constrained by high degradation rates in the physiological environment,resulting in the release of hydrogen gas and a rapid decline in mechanical properties.Additionally,the material's biocompatibility is contingent upon its degradability.Researchers have demonstrated that addressing these issues is possible through strategies such as controlling Zn content,employing thermo-mechanical processing to achieve suitable microstructures,and applying surface coatings.This manuscript provides a comprehensive review of published literature on Mg-Zn alloys,exploring the challenges and outlining future research directions in this field.
基金financially supported by the National Natural Science Foundation of China(No.U23A20691)Innovation Group of National Ethnic Affairs Commission of China(No.MZR20006)+2 种基金Fund for Academic Innovation Teams of SouthCentral Minzu University(No.XTZ24012)Fundamental Research Fund for the Central Universities of South-Central Minzu University(Nos.CZD24001 and CZQ25012)Scientific Research Fund of South-Central Minzu University(No.YZY25007)。
文摘The poor degradability and limited recyclability of epoxy resins are key challenges hindering the efficient recycling of ex-service wind turbine blades(EWTBs).Herein,we proposed a selective degradation strategy for direct recycling and high-value recovery of epoxy resins by introducing degradable Schiff base groups into the molecular structure and utilizing the resulting oligomers as curing agents.To realize this strategy,a series of Schiff base compounds were synthesized using bio-based vanillin and diamines and subsequently functionalized with epichlorohydrin to yield bio-based epoxy resins.The cured epoxy resins demonstrated remarkable improvements in the mechanical properties of diglycidyl ether of bisphenol-A(DGEBA),with an increases of 44.49%in the tensile strength of 38.55%,bending strength,and impact strength of 71.20%.The introduction of dynamic Schiff base bonds enabled the selective degradation of the vanillin-2,2-bis[4-(4-aminophenoxy)phenyl]propane-based epoxy resin(VBEP)/DGEBA copolymer,producing 84.20% oligomers that can be directly recycled and reused.Replacing 30 wt% of the curing agent with the oligomer increased the tensile strength of the cured sample to 75.40 MPa,surpassing that of the cured DGEBA.Under simulated acid rain and seawater exposure,the copolymer exhibited a service life of 27 years at 40℃,significantly exceeding the currently reported service life of 20 years.This study presents a sustainable strategy for the direct recycling and high-value reuse of epoxy resin,offering a promising solution for EWTBs.
基金financially supported by the fund of the Science and Technology Development Plan Project of Jilin Province of China(No.20240304161SF)the Science and Technology Development Plan Project of Jilin Province of China(No.20220203019SF)+1 种基金the Science and Technology Bureau of Changchun City of China(Nos.23SH11,23SH08)the Chinese Science Academy(Changchun Branch)(No.2024SYHZ0038).
文摘Poly(lactic acid)(PLA)is a biodegradable and eco-friendly polymer that is increasingly being incorporated into various applications in contemporary society.However,the limited stability of PLA-based products remains a significant challenge for their broader use in various applications.In this study,poly(L-lactic acid)(PLLA)/poly(D-lactic acid)(PDLA)melt-blown nonwovens were prepared by melt spinning.The structure,thermal properties,thermal stability,biodegradability and crystalline morphology of the melt-blown nonwovens were investigated.DSC and WAXD confirmed the formation of stereocomplex(SC)crystallites in the PLLA matrix.The storage modulus(G′),loss modulus(G″),and complex viscosity(∣η^(*)∣)of the PLLA/PDLA blend increased with an increase in SC crystallite content.The thermal degradation temperatures of PLLA/PDLA melt-blown nonwovens increased with the incorporation of SC crystallites,and the maximum rate of decomposition increased to 385.5℃,thus enhancing the thermal stability.Compared with neat PLLA melt-blown nonwovens,the hydrophobicity of PLLA/PDLA melt-blown nonwovens was improved,and WCA increased to 139.7°.The SC crystallites were more resistant to degradation by proteinase K compared to neat PLLA.However,the degradation rate of PLLA/PDLA melt-blown nonwovens remained at a high level.This work provides an effective strategy to obtain high-performance PLLA melt-blown nonwovens.
基金Funding support of this work was carried out within the governmental task#075-00319-25-00.
文摘A study of the effect of rotary swaging(RS)at 350℃ on mechanical properties,corrosion resistance and biocompatibility in vitro and in vivo of biodegradable Mg-1%Zn-0.6%Ca alloy was conducted.It is shown that the formation of a recrystallized microstructure after RS with a grain size of 3.2±0.2μm leads to an increase in the strength of the alloy without reduction of level of ductility and corrosion resistance.At the same time,aging of the quenched alloy at 100℃ for 8 h leads to a slight increase in strength,but significantly reduces its ductility and corrosion resistance.The study of the degradation process of the alloy in the quenched state and after RS,both under in vitro and in vivo conditions,did not reveal a significant difference between these two microstructural states.However,an increase in the duration of incubation of the alloy in a complete growth medium from 4 h to 24 days leads to a decrease in the degradation rate(DR)by 4times(from~2 to~0.5 mm/year)due to the formation of a dense layer of degradation products.The study of biocompatibility in vitro did not reveal a significant effect of RS on the hemolytic and cytotoxic activity of the alloy.No signs of systemic toxicity were observed after subcutaneous implantation of alloy samples into mice before and after RS.However,it was found that RS promotes uniform degradation of the alloy over the entire contact surface.In summary,RS at 350℃ allows to increase the strength of Mg-1%Zn-0.6%Ca alloy up to348±5 MPa at a ductility level of 17.3±2.8%and a DRin vivoequal to 0.56±0.12 mm/year without impairing its biocompatibility in vitro and in vivo.
基金supported by the National Key R&D Program of China(No.2023YFA1506804)the National Natural Science Foundation of China(Nos.22471110,22171111,22131007 and 22071093)+1 种基金the Science Foundation of Gansu Province of China(No.22JR5RA406)the Fundamental Research Funds for the Central Universities(No.lzujbky-2023-15)。
文摘Most commercial plastics cannot easily degrade,which raises a number of sustainability issues.To address the current problem of plastic pollution,the research and development of easily degradable and recyclable polymers has become an attractive subject.Herein,a new monomer of thiosalicylic methyl glycolide(TSMG)was synthesized using one-pot method and high molecular weight poly(thiosalicylic methyl glycolide)(PTSMG,M_(n) up to 300 kDa)can be obtained via the ring-opening polymerization(ROP)of TSMG.PTSMG exhibits good closed-loop recyclability and hydrolytic degradability,where PTSMG can generate pristine monomers through sublimation thermal depolymerization conditions due to the presence of thiophenol ester bond in the polymer chains,and can be degraded rapidly in aqueous solution,which provides a potential solution to the current plastic pollution problem.
基金financially supported by the National Natural Science Foundation of China(No.52377025)。
文摘The most widely used bisphenol A-type epoxy resin(DGEBA)in electrical engineering demonstrates excellent mechanical and electrical properties.However,the insoluble and infusible characteristics of cured DGEBA make it difficult to efficiently degrade and recycle decommissioned electrical equipment.In this study,a degradable itaconic acid-based epoxy resin incorporating dynamic covalent bonds was prepared through the integration of ester bonds and disulfide bonds,with itaconic acid as the precursor.The covalent bonding effects on the mechanical,thermal,electrical,and degradation characteristics were systematically evaluated.The experimental results revealed that the introduction of dynamic ester bonds enhanced the mechanical properties and thermal stability of the resin system,achieving a flexural strength of 141.57 MPa and an initial decomposition temperature T_(5%)of up to 344.9℃.The resin system containing dynamic disulfide bonds exhibited a dielectric breakdown strength of 41.11 k V/mm.Simultaneously,the incorporation of disulfide bonds endowed the epoxy resin with remarkable degradability,enabling complete dissolution within 1.5 h at 90℃ in a mixed solution of dithiothreitol(DTT)and N-methylpyrrolidone(NMP).This research provides a valuable reference for the application of itaconic acid-based vitrimer with dynamic covalent bonds in electrical materials,contributing to the development and utilization of environmentally friendly electrical equipment.
