We developed a fluorescent double network hydrogel with ionic responsiveness and high mechanical properties for visual detection.The nanocomposite hydrogel of laponite and polyacrylamide serves as the first network,wh...We developed a fluorescent double network hydrogel with ionic responsiveness and high mechanical properties for visual detection.The nanocomposite hydrogel of laponite and polyacrylamide serves as the first network,while the ionic cross-linked hydrogel of terbium ions and sodium alginate serves as the second network.The double-network structure,the introduction of nanoparticles and the reversible ionic crosslinked interactions confer high mechanical properties to the hydrogel.Terbium ions are not only used as the ionic cross-linked points,but also used as green emitters to endow hydrogels with fluorescent properties.On the basis of the “antenna effect” of terbium ions and the ion exchange interaction,the fluorescence of the hydrogels can make selective responses to various ions(such as organic acid radical ions,transition metal ions) in aqueous solutions,which enables a convenient strategy for visual detection toward ions.Consequently,the fluorescent double network hydrogel fabricated in this study is promising for use in the field of visual sensor detection.展开更多
Bio-based phenol-formaldehyde polymer (BioNovolac) was developed by reacting molar excess of bio-oil/phenolwith formaldehyde in acidic medium. Glycidyl 3,5-diglycidoxybenzoate (GDGB), was prepared by directglycidylati...Bio-based phenol-formaldehyde polymer (BioNovolac) was developed by reacting molar excess of bio-oil/phenolwith formaldehyde in acidic medium. Glycidyl 3,5-diglycidoxybenzoate (GDGB), was prepared by directglycidylation of α-resorcylic acid (RA), a naturally occurring phenolic monomer. GDGB was crosslinked in thepresence of BioNovolac by anionic polymerization. Fourier transform infrared spectroscopy (FTIR) confirmedthe formation of semi-interpenetrating polymer networks. The glass transition temperature and moduli of biobasedcrosslinked systems were observed to increase with increasing GDGB content. Active chain density andmass retention measured by dynamic mechanical analysis (DMA) and Soxhlet extraction, respectively, indicated ahigh crosslink density of the cured networks. Scanning electron microscopy (SEM) images depicted thehomogeneity of the bulk phase. The preparation of bio-based epoxy-novolac thermoset network resulted inreduced consumption of petroleum-based chemicals.展开更多
The semi-interpenetrating network anion exchange membranes(AEMs)based on quaternized polyvinyl alcohol(QPVA)and poly(-diallyldimethylammonium chloride)(PDDA)are synthesized.The chemical cross-linking structure is form...The semi-interpenetrating network anion exchange membranes(AEMs)based on quaternized polyvinyl alcohol(QPVA)and poly(-diallyldimethylammonium chloride)(PDDA)are synthesized.The chemical cross-linking structure is formed between hydroxyl groups of QPVA and aldehyde groups of glutaraldehyde(GA),which makes PDDA more stable embed in the QPVA matrix and also improves the mechanical properties and dimensional stability of AEMs.Due to the phase separation phenomenon of AEMs swelling in water,a microporous structure may be formed in the membrane,which reduces the transmission resistance of hydroxide ions and provides a larger space for the transfer of hydroxide ions,thus improving the conductivity.The ring structure of PDDA is introduced as a cationic group to transfer hydroxide ions,and shields the nucleophilic attack of the hydroxide ions through the steric hindrance effect,which improves alkaline stability.The hydroxide conductivity of semi-interpenetrating network membrane(QPVA/PDDA0.5-GA)is 36.5 mS cm^(-1) at 60℃.And the membrane of QPVA/PDDA0.5-GA exhibits excellent mechanical property with maximum tensile strength of 19.6 MPa.After immersing into hot 3 mol L^(-1) NaOH solutions at 60℃ for 300 h,the OHconductivity remains 78%of its initial value.The semi-interpenetrating network AEMs with microporous structure exhibit good ionic conductivity,mechanical strength and alkaline durability.展开更多
Semi-interpenetrating(semi-IPN)hydrogels formed by the continuous interpenetration of cross-linked polymer network and linear non-crosslinked polymer with multifunctionality are widely used in biomedical and other fie...Semi-interpenetrating(semi-IPN)hydrogels formed by the continuous interpenetration of cross-linked polymer network and linear non-crosslinked polymer with multifunctionality are widely used in biomedical and other fields.However,the negative impact of linear polymer on the homogeneity of the cross-linked network often leads to a decrease in the mechanical properties of semi-IPN hydrogels and severely limits their applications.Herein,a bioinspired hydrogen-bonding induced phase separation strategy is presented to construct the tough semi-IPN polyvinylpyrrolidone/polyacrylamide hydrogels(named PVP/PAM hydrogels),including the linear polymer polyvinylpyrrolidone(PVP)and cross-linked polyacrylamide(PAM)network.The resultant PVPx/PAM hydrogels exhibit unique phase separation induced by the hydrogen bonding between PVP and PAM and affected by the amount of substance of PVP.Meanwhile,the phase separation of PVPx/PAM hydrogels results in excellent mechanical properties with a strain of 2590%,tensile strength of 0.28 MPa and toughness of 2.17 MJ/m^(3).More importantly,the hydrogen bonding between PVP and PAM firstly disrupts to dissipate energy under external forces,so the PVPx/PAM hydrogels exhibit good self-recovery properties and outperform chemically cross-linked PAM hydrogels in impact resistance and damping applications.It is believed that the PVPx/PAM hydrogels with hydrogen-bonding induced phase separation possess more potential application prospects.展开更多
Double network(DN)hydrogels as one kind of tough gels have attracted extensive at-tention for their potential applications in biomedical and load-bearing fields.Herein,we import more functions like shape memory into t...Double network(DN)hydrogels as one kind of tough gels have attracted extensive at-tention for their potential applications in biomedical and load-bearing fields.Herein,we import more functions like shape memory into the conventional tough DN hydro-gel system.We synthesize the PEG-PDAC/P(AAm-co-AAc)DN hydrogels,of which the first network is a well-defined PEG(polyethylene glycol)network loaded with PDAC(poly(acryloyloxyethyltrimethyl ammonium chloride))strands,while the second network is formed by copolymerizing AAm(acrylamide)with AAc(acrylic acid)and cross-linker MBAA(N;N′-methylenebisacrylamide).The PEG-PDAC/P(AAm-co-AAc)DN gels exhibits high mechanical strength.The fracture stress and toughness of the DN gels reach up to 0.9 MPa and 3.8 MJ/m^3,respectively.Compared with the conventional double network hydrogels with neutral polymers as the soft and ductile second network,the PEG-PDAC/P(AAm-co-AAc)DN hydrogels use P(AAm-co-AAc),a weak polyelectrolyte,as the second network.The AAc units serve as the coordination points with Fe^3+ions and physically crosslink the second network,which realizes the shape memory property activated by the reducing ability of ascorbic acid.Our results indicate that the high mechanical strength and shape memory properties,probably the two most important characters related to the potential application of the hydrogels,can be introduced simultaneously into the DN hydrogels if the functional monomer has been integrated into the network of DN hydrogels smartly.展开更多
Current animal models of nerve root compression due to lumbar disc herniation only assess the mechanical compression of nerve roots and the inflammatory response. Moreover, the pressure applied in these models is stat...Current animal models of nerve root compression due to lumbar disc herniation only assess the mechanical compression of nerve roots and the inflammatory response. Moreover, the pressure applied in these models is static, meaning that the nerve root cannot be dynamically compressed. This is very different from the pathogenesis of lumbar disc herniation. In this study, a chitosan/polyacrylamide double-network hydrogel was prepared by a simple two-step method. The swelling ratio of the double-network hydrogel increased with prolonged time, reaching 140. The compressive strength and compressive modulus of the hydrogel reached 53.6 and 0.34 MPa, respectively. Scanning electron microscopy revealed the hydrogel's crosslinked structure with many interconnecting pores. An MTT assay demonstrated that the number of viable cells in contact with the hydrogel extracts did not significantly change relative to the control surface. Thus, the hydrogel had good biocompatibility. Finally, the double-network hydrogel was used to compress the L4 nerve root of male sand rats to simulate lumbar disc herniation nerve root compression. The hydrogel remained in its original position after compression, and swelled with increasing time. Edema appeared around the nerve root and disappeared 3 weeks after operation. This chitosan/polyacrylamide double-network hydrogel has potential as a new implant material for animal models of lumbar nerve root compression. All animal experiments were approved by the Animal Ethics Committee of Neurosurgical Institute of Beijing, Capital Medical University, China(approval No. 201601006) on July 29, 2016.展开更多
Hydrogel is a kind of three-dimensional crosslinked polymer material with high moisture content.However,due to the network defects of polymer gels,traditional hydrogels are usually brittle and fragile,which limits the...Hydrogel is a kind of three-dimensional crosslinked polymer material with high moisture content.However,due to the network defects of polymer gels,traditional hydrogels are usually brittle and fragile,which limits their practical applications.Herein,we present a Hofmeister effect-aided facile strategy to prepare high-performance poly(vinyl alcohol)/montmorillonite nanocomposite hydrogels.Layered montmorillonite nanosheets can not only serve as crosslinking agents to enhance the mechanical properties of the hydrogel but also promote the ion conduction.More importantly,based on the Hofmeister effect,the presence of(NH_(4))_(2)SO_(4)can endow nanocomposite hydrogels with excellent mechanical properties by affecting PVA chains'aggregation state and crystallinity.As a result,the as-prepared nanocomposite hydrogels possess unique physical properties,including robust mechanical and electrical properties.The as-prepared hydrogels can be further assembled into a high-performance flexible sensor,which can sensitively detect large-scale and small-scale human activities.The simple design concept of this work is believed to provide a new prospect for developing robust nanocomposite hydrogels and flexible devices in the future.展开更多
The design principles and preparation methods of the double-network hydrogels are reviewed. In addition,the application of the double-network hydrogels in different fields is also introduced.
Herein, the effect of fluoropolymer binders on the properties of polymer-bonded explosives(PBXs) was comprehensively investigated. To this end, fluorinated semi-interpenetrating polymer networks(semiIPNs) were prepare...Herein, the effect of fluoropolymer binders on the properties of polymer-bonded explosives(PBXs) was comprehensively investigated. To this end, fluorinated semi-interpenetrating polymer networks(semiIPNs) were prepared using different catalyst amounts(denoted as F23-CLF-30-D). The involved curing and phase separation processes were monitored using Fourier-transform infrared spectroscopy, differential scanning calorimetry, a haze meter and a rheometer. Curing rate constant and activation energy were calculated using a theoretical model and numerical method, respectively. Results revealed that owing to its co-continuous micro-phase separation structure, the F23-CLF-30-D3 semi-IPN exhibited considerably higher tensile strength and elongation at break than pure fluororubber F2314 and the F23-CLF-30-D0 semi-IPN because the phase separation and curing rates matched in the initial stage of curing.An arc Brazilian test revealed that F23-CLF-30-D-based composites used as mock materials for PBXs exhibited excellent mechanical performance and storage stability. Thus, the matched curing and phase separation rates play a crucial role during the fabrication of high-performance semi-IPNs;these factors can be feasibly controlled using an appropriate catalyst amount.展开更多
Zn metal anode suffers from dendrite issues and passive byproducts,which severely plagues the practical application of aqueous Zn metal batteries.Herein,a polyzwitterionic cross-linked double network hydrogel electrol...Zn metal anode suffers from dendrite issues and passive byproducts,which severely plagues the practical application of aqueous Zn metal batteries.Herein,a polyzwitterionic cross-linked double network hydrogel electrolyte composed of physical crosslinking(hyaluronic acid)and chemical crosslinking(synthetic zwitterionic monomer copolymerized with acrylamide)is introduced to overcome these obstacles.On the one hand,highly hydrophilic physical network provides an energy dissipation channel to buffer stress and builds a H_(2)O-poor interface to avoid side reactions.On the other hand,the charged groups(sulfonic and imidazolyl)in chemical crosslinking structure build anion/cation transport channels to boost ions’kinetics migration and regulate the typical solvent structure[Zn(H_(2)O)_(6)]^(2+)to R-SO_(3)^(−)[Zn(H_(2)O)_(4)]^(2+),with uniform electric field distribution and significant resistance to dendrites and parasitic reactions.Based on the above functions,the symmetric zinc cell exhibits superior cycle stability for more than 420 h at a high current density of 5 mA·cm^(−2),and Zn||MnO_(2)full cell has a reversible specific capacity of 150 mAh·g^(−1)after 1000 cycles at 2 C with this hydrogel electrolyte.Furthermore,the pouch cell delivers impressive flexibility and cyclability for energy-storage applications.展开更多
基金Funded by the National Natural Science Foundation of China(No.51873167)the National Innovation and Entrepreneurship Training Program for College Students(No.226801001)。
文摘We developed a fluorescent double network hydrogel with ionic responsiveness and high mechanical properties for visual detection.The nanocomposite hydrogel of laponite and polyacrylamide serves as the first network,while the ionic cross-linked hydrogel of terbium ions and sodium alginate serves as the second network.The double-network structure,the introduction of nanoparticles and the reversible ionic crosslinked interactions confer high mechanical properties to the hydrogel.Terbium ions are not only used as the ionic cross-linked points,but also used as green emitters to endow hydrogels with fluorescent properties.On the basis of the “antenna effect” of terbium ions and the ion exchange interaction,the fluorescence of the hydrogels can make selective responses to various ions(such as organic acid radical ions,transition metal ions) in aqueous solutions,which enables a convenient strategy for visual detection toward ions.Consequently,the fluorescent double network hydrogel fabricated in this study is promising for use in the field of visual sensor detection.
文摘Bio-based phenol-formaldehyde polymer (BioNovolac) was developed by reacting molar excess of bio-oil/phenolwith formaldehyde in acidic medium. Glycidyl 3,5-diglycidoxybenzoate (GDGB), was prepared by directglycidylation of α-resorcylic acid (RA), a naturally occurring phenolic monomer. GDGB was crosslinked in thepresence of BioNovolac by anionic polymerization. Fourier transform infrared spectroscopy (FTIR) confirmedthe formation of semi-interpenetrating polymer networks. The glass transition temperature and moduli of biobasedcrosslinked systems were observed to increase with increasing GDGB content. Active chain density andmass retention measured by dynamic mechanical analysis (DMA) and Soxhlet extraction, respectively, indicated ahigh crosslink density of the cured networks. Scanning electron microscopy (SEM) images depicted thehomogeneity of the bulk phase. The preparation of bio-based epoxy-novolac thermoset network resulted inreduced consumption of petroleum-based chemicals.
基金The authors gratefully acknowledge the financial support of this work by Natural Science Foundation of China(grant no.s 51673030,51603017 and 51803011)Jilin Provincial Science&Technology Department(grant no.s 20200801011GH,20180101209JC,20160520138JH,20160519020JH)+1 种基金Jilin Province Development and Reform Commission(Grant nos:2019C042-5)ChangBai Mountain Scholars Program of Jilin Province.
文摘The semi-interpenetrating network anion exchange membranes(AEMs)based on quaternized polyvinyl alcohol(QPVA)and poly(-diallyldimethylammonium chloride)(PDDA)are synthesized.The chemical cross-linking structure is formed between hydroxyl groups of QPVA and aldehyde groups of glutaraldehyde(GA),which makes PDDA more stable embed in the QPVA matrix and also improves the mechanical properties and dimensional stability of AEMs.Due to the phase separation phenomenon of AEMs swelling in water,a microporous structure may be formed in the membrane,which reduces the transmission resistance of hydroxide ions and provides a larger space for the transfer of hydroxide ions,thus improving the conductivity.The ring structure of PDDA is introduced as a cationic group to transfer hydroxide ions,and shields the nucleophilic attack of the hydroxide ions through the steric hindrance effect,which improves alkaline stability.The hydroxide conductivity of semi-interpenetrating network membrane(QPVA/PDDA0.5-GA)is 36.5 mS cm^(-1) at 60℃.And the membrane of QPVA/PDDA0.5-GA exhibits excellent mechanical property with maximum tensile strength of 19.6 MPa.After immersing into hot 3 mol L^(-1) NaOH solutions at 60℃ for 300 h,the OHconductivity remains 78%of its initial value.The semi-interpenetrating network AEMs with microporous structure exhibit good ionic conductivity,mechanical strength and alkaline durability.
基金This work was financially supported by the National Natural Science Foundation of China(No.52273210).
文摘Semi-interpenetrating(semi-IPN)hydrogels formed by the continuous interpenetration of cross-linked polymer network and linear non-crosslinked polymer with multifunctionality are widely used in biomedical and other fields.However,the negative impact of linear polymer on the homogeneity of the cross-linked network often leads to a decrease in the mechanical properties of semi-IPN hydrogels and severely limits their applications.Herein,a bioinspired hydrogen-bonding induced phase separation strategy is presented to construct the tough semi-IPN polyvinylpyrrolidone/polyacrylamide hydrogels(named PVP/PAM hydrogels),including the linear polymer polyvinylpyrrolidone(PVP)and cross-linked polyacrylamide(PAM)network.The resultant PVPx/PAM hydrogels exhibit unique phase separation induced by the hydrogen bonding between PVP and PAM and affected by the amount of substance of PVP.Meanwhile,the phase separation of PVPx/PAM hydrogels results in excellent mechanical properties with a strain of 2590%,tensile strength of 0.28 MPa and toughness of 2.17 MJ/m^(3).More importantly,the hydrogen bonding between PVP and PAM firstly disrupts to dissipate energy under external forces,so the PVPx/PAM hydrogels exhibit good self-recovery properties and outperform chemically cross-linked PAM hydrogels in impact resistance and damping applications.It is believed that the PVPx/PAM hydrogels with hydrogen-bonding induced phase separation possess more potential application prospects.
基金supported by the National Natural Science Foundation of China (No.51273189)the National Science and Technology Major Project of the Ministry of Science and Technology of China (No.2016ZX05016),the National Science and Technology Major Project of the Ministry of Science and Technology of China (No.2016ZX05046)
文摘Double network(DN)hydrogels as one kind of tough gels have attracted extensive at-tention for their potential applications in biomedical and load-bearing fields.Herein,we import more functions like shape memory into the conventional tough DN hydro-gel system.We synthesize the PEG-PDAC/P(AAm-co-AAc)DN hydrogels,of which the first network is a well-defined PEG(polyethylene glycol)network loaded with PDAC(poly(acryloyloxyethyltrimethyl ammonium chloride))strands,while the second network is formed by copolymerizing AAm(acrylamide)with AAc(acrylic acid)and cross-linker MBAA(N;N′-methylenebisacrylamide).The PEG-PDAC/P(AAm-co-AAc)DN gels exhibits high mechanical strength.The fracture stress and toughness of the DN gels reach up to 0.9 MPa and 3.8 MJ/m^3,respectively.Compared with the conventional double network hydrogels with neutral polymers as the soft and ductile second network,the PEG-PDAC/P(AAm-co-AAc)DN hydrogels use P(AAm-co-AAc),a weak polyelectrolyte,as the second network.The AAc units serve as the coordination points with Fe^3+ions and physically crosslink the second network,which realizes the shape memory property activated by the reducing ability of ascorbic acid.Our results indicate that the high mechanical strength and shape memory properties,probably the two most important characters related to the potential application of the hydrogels,can be introduced simultaneously into the DN hydrogels if the functional monomer has been integrated into the network of DN hydrogels smartly.
基金supported by the High Levels of Health Technical Personnel in Beijing Health System of China,No.2013-3-050(to JZY)
文摘Current animal models of nerve root compression due to lumbar disc herniation only assess the mechanical compression of nerve roots and the inflammatory response. Moreover, the pressure applied in these models is static, meaning that the nerve root cannot be dynamically compressed. This is very different from the pathogenesis of lumbar disc herniation. In this study, a chitosan/polyacrylamide double-network hydrogel was prepared by a simple two-step method. The swelling ratio of the double-network hydrogel increased with prolonged time, reaching 140. The compressive strength and compressive modulus of the hydrogel reached 53.6 and 0.34 MPa, respectively. Scanning electron microscopy revealed the hydrogel's crosslinked structure with many interconnecting pores. An MTT assay demonstrated that the number of viable cells in contact with the hydrogel extracts did not significantly change relative to the control surface. Thus, the hydrogel had good biocompatibility. Finally, the double-network hydrogel was used to compress the L4 nerve root of male sand rats to simulate lumbar disc herniation nerve root compression. The hydrogel remained in its original position after compression, and swelled with increasing time. Edema appeared around the nerve root and disappeared 3 weeks after operation. This chitosan/polyacrylamide double-network hydrogel has potential as a new implant material for animal models of lumbar nerve root compression. All animal experiments were approved by the Animal Ethics Committee of Neurosurgical Institute of Beijing, Capital Medical University, China(approval No. 201601006) on July 29, 2016.
基金Project supported by the National Natural Science Foundation of China(Grant No.12274356)the Fundamental Research Funds for the Central Universities(Grant No.20720220022)the 111 Project(Grant No.B16029)。
文摘Hydrogel is a kind of three-dimensional crosslinked polymer material with high moisture content.However,due to the network defects of polymer gels,traditional hydrogels are usually brittle and fragile,which limits their practical applications.Herein,we present a Hofmeister effect-aided facile strategy to prepare high-performance poly(vinyl alcohol)/montmorillonite nanocomposite hydrogels.Layered montmorillonite nanosheets can not only serve as crosslinking agents to enhance the mechanical properties of the hydrogel but also promote the ion conduction.More importantly,based on the Hofmeister effect,the presence of(NH_(4))_(2)SO_(4)can endow nanocomposite hydrogels with excellent mechanical properties by affecting PVA chains'aggregation state and crystallinity.As a result,the as-prepared nanocomposite hydrogels possess unique physical properties,including robust mechanical and electrical properties.The as-prepared hydrogels can be further assembled into a high-performance flexible sensor,which can sensitively detect large-scale and small-scale human activities.The simple design concept of this work is believed to provide a new prospect for developing robust nanocomposite hydrogels and flexible devices in the future.
文摘The design principles and preparation methods of the double-network hydrogels are reviewed. In addition,the application of the double-network hydrogels in different fields is also introduced.
基金supported by Wuxi HIT New Material Research Institute and China Academy of Engineering Physics。
文摘Herein, the effect of fluoropolymer binders on the properties of polymer-bonded explosives(PBXs) was comprehensively investigated. To this end, fluorinated semi-interpenetrating polymer networks(semiIPNs) were prepared using different catalyst amounts(denoted as F23-CLF-30-D). The involved curing and phase separation processes were monitored using Fourier-transform infrared spectroscopy, differential scanning calorimetry, a haze meter and a rheometer. Curing rate constant and activation energy were calculated using a theoretical model and numerical method, respectively. Results revealed that owing to its co-continuous micro-phase separation structure, the F23-CLF-30-D3 semi-IPN exhibited considerably higher tensile strength and elongation at break than pure fluororubber F2314 and the F23-CLF-30-D0 semi-IPN because the phase separation and curing rates matched in the initial stage of curing.An arc Brazilian test revealed that F23-CLF-30-D-based composites used as mock materials for PBXs exhibited excellent mechanical performance and storage stability. Thus, the matched curing and phase separation rates play a crucial role during the fabrication of high-performance semi-IPNs;these factors can be feasibly controlled using an appropriate catalyst amount.
基金the Science Technology and Innovation Team in University of Henan Province(No.24IRTSTHN002)the National Natural Science Foundation of China(No.22279121)China Postdoctoral Science Foundation(No.2022M712863),and DFT calculations were supported by the National Supercomputing Centre in Zhengzhou and the funding of Zhengzhou University.
文摘Zn metal anode suffers from dendrite issues and passive byproducts,which severely plagues the practical application of aqueous Zn metal batteries.Herein,a polyzwitterionic cross-linked double network hydrogel electrolyte composed of physical crosslinking(hyaluronic acid)and chemical crosslinking(synthetic zwitterionic monomer copolymerized with acrylamide)is introduced to overcome these obstacles.On the one hand,highly hydrophilic physical network provides an energy dissipation channel to buffer stress and builds a H_(2)O-poor interface to avoid side reactions.On the other hand,the charged groups(sulfonic and imidazolyl)in chemical crosslinking structure build anion/cation transport channels to boost ions’kinetics migration and regulate the typical solvent structure[Zn(H_(2)O)_(6)]^(2+)to R-SO_(3)^(−)[Zn(H_(2)O)_(4)]^(2+),with uniform electric field distribution and significant resistance to dendrites and parasitic reactions.Based on the above functions,the symmetric zinc cell exhibits superior cycle stability for more than 420 h at a high current density of 5 mA·cm^(−2),and Zn||MnO_(2)full cell has a reversible specific capacity of 150 mAh·g^(−1)after 1000 cycles at 2 C with this hydrogel electrolyte.Furthermore,the pouch cell delivers impressive flexibility and cyclability for energy-storage applications.