A betaine-type styrene monomer with the quaternary ammonium-borate anion inner-salt pair was synthesized through the quatemization reaction and polymerized to afford the target polybetaine of poly（4-vinylbenzyl methy...A betaine-type styrene monomer with the quaternary ammonium-borate anion inner-salt pair was synthesized through the quatemization reaction and polymerized to afford the target polybetaine of poly（4-vinylbenzyl methyl-diethanol ammonium borate） （PVMAB）. The chemical structures of the monomer and polymer were well demonstrated with 1H-NMR and llB-NMR spectra analysis. The thermal-sensitive experiment showed that PVMAB in water afforded gradually well- defined sigmoidal transmittance-temperature （T-t） curves along with the increasing polymer concentration. However, the phase transition temperatures at the bottom of the S-shaped curves were always below l0 ~C due to the very weak zwitterionic association of the ammonium-borate inner-salt pairs. The UCST phase transition could also be tuned by changing the ethanol content in the ethanol/water mixture. And the cytotoxicity experiment demonstrated the good biomimetic property of PVMAB. This study enriches the toolbox of polybetaines by introducing the quaternary ammonium- borate anion zwitterionic pair in the repeat units, therefore broadens the scope of synthetic polybetaines.展开更多
Water-soluble thermoresponsive polymers present either upper critical solution temperature(UCST) or lower critical solution tempe rature(LCST) depending on the location of their miscibility range with water at high te...Water-soluble thermoresponsive polymers present either upper critical solution temperature(UCST) or lower critical solution tempe rature(LCST) depending on the location of their miscibility range with water at high temperatures or at low temperatures.Compared with LCST polymers,the water-soluble UCST polymers are still less explored until now.In this work three copolymers of P(AAm-co-GAA) were synthesized by copolymerizing two acrylamide monomers,acrylamide(AAm) and acrylamide functionalized with natural glycyrrhetinic acid(GAA),using reversible addition-fragmentation chain transfer(RAFT) polymerization.These copolymers exhibited the typical UCST thermoresponsive behavior,and their phase transition temperatures could be easily tuned to around 37℃ for potential biological applications.Moreover,the UCST of P(AAm-co-GAA) can be adjusted not only by the content of glycyrrhetinic acid(GA) and polymer concentrations,but also by the host-vip interactions between GA and cyclodextrins(β-and γ-CD).The suitable value of UCST and the biocompatible nature of GA and CDs may endow these copolymers with practical applications in biomedical chemistry.展开更多
Human life is not determined by mechanical fatalism or a single material factor;instead,based on the dualistic ontology and active force mechanism in the Unified Complex Systems Theory(UCST),it can be actively designe...Human life is not determined by mechanical fatalism or a single material factor;instead,based on the dualistic ontology and active force mechanism in the Unified Complex Systems Theory(UCST),it can be actively designed under the guidance of mind,in accordance with causal laws,and through systematic interactions.This study integrates the dualistic ontology of UCST,as well as the cooperative mechanism of active force(Fa)and passive force(Fp).Furthermore,by incorporating Master Jiqun’s philosophy of“life design”and the practical principle of“destiny establishment and transformation”from The Four Lessons of Liaofan Yuan,it constructs a three-dimensional framework for life design encompassing the dimensions of science,philosophy,and practice.The significance of this research lies in breaking through the predicament of materialism in the AI(artificial intelligence)era,explaining the autonomy and initiative of life,providing feasible pathways for life design,and ultimately achieving the in-depth integration of scientific rationality and the wisdom of traditional Eastern culture.展开更多
The development of hydrogels capable of emitting multicolor fluorescence presents a promising avenue for addressing concerns related to information leakage and distortion of sensitive data.The integration of multifact...The development of hydrogels capable of emitting multicolor fluorescence presents a promising avenue for addressing concerns related to information leakage and distortion of sensitive data.The integration of multifactorinduced tunable fluorescence with a unique upper critical solution temperature(UCST)behavior in hydrogels significantly contributes to the development of multi-dimensional and multi-level information storage materials that can dynamically display information as well as offer a high level of security and protection for information.However,the fusion of these advantageous properties into hydrogels intended for information storage and display remains a considerable challenge.In this context,we introduce a novel three-dimensional(3D)fluorescent code-producing hydrogel array fabricated via vat photopolymerization(VP)3D printing,a technique offers a sustainable and efficient approach.This array unites the desired properties,capable of sequentially revealing concealed information through two distinct steps:(i)a heat-induced phase transition,and(ii)multicolor fluorescence triggered by ultraviolet(UV)/temperature exposure under specific conditions(i.e.,certain UV irradiation duration,heating time,and wavelength).The reversible transparency and reprogrammable fluorescence emission properties of these hydrogels are expected to significantly enhance the processes of information encryption and anti-counterfeiting.This advancement could potentially revolutionize the field of information security.展开更多
The present calculations were performed on the basis of the Sanchez-Lacombe lattice fluid theory and the new combinatorial rules for block copolymer according to the experimental results on the pressure-induced compat...The present calculations were performed on the basis of the Sanchez-Lacombe lattice fluid theory and the new combinatorial rules for block copolymer according to the experimental results on the pressure-induced compatibility in poly(ethylene oxide) (PEO) and poly(ethylene ox-ide-b-dimethylsiloxane) (P(EO-b-DMS)) mixtures with UCST behavior. The study on enthalpy, combinatorial entropy, vacancy entropy and Gibbs energy upon mixture shows that San-chez-Lacombe fluid theory and the new combinatorial rules could describe the pressure-induced compatibility (PIC) of polymer mixtures with UCST behavior well.展开更多
Hepatocellular carcinoma(HCC)is a life-threatening disease for which there is no effective treatment currently.Novel theranostics simultaneously having excellent imaging and therapeutic functions are highly desired in...Hepatocellular carcinoma(HCC)is a life-threatening disease for which there is no effective treatment currently.Novel theranostics simultaneously having excellent imaging and therapeutic functions are highly desired in cancer therapy.Herein,we develop the sialic acid(SA)modified polymeric micelles at an upper critical solution temperature(UCST)of 43℃(sialic acid-poly(ethylene glycol)-poly(acrylamide-co-acrylonitrile),SA-PEG-p(AAm-co-AN)),which further encapsulated with doxorubicin(DOX)and Gd-CuS nanoparticles(Gd-CuS NPs)for chemo-photothermal treatment of HCC guided by magnetic resonance(MR)/photoacoustic(PA)dual-mode imaging.The resultant SA-PEG-p(AAm-co-AN)/DOX/Gd-CuS(SPDG)had an excellent photothermal conversion efficiency,enabling SPDG with an instantaneous release behavior of DOX under near-infrared(NIR)irradiation.This study also revealed that SPDG could actively target to HCC,which was due to that SA had a high affinity with E-selectin overexpressed at the tumor site.Moreover,benefiting from the HCC-targeted ability and NIR light-controlled on-demand delivery of DOX,SPDG showed a superior potential in MR/PA dual-mode imaging-guided chemo-photothermal treatment.Overall,our study reveals that the designed SPDG may be used as an ideal multifunctional nanoplatform for cancer theranostics.展开更多
A novel switchable luminescent thermometer based on thermo-responsive triblock copolymer poly(ethylene glycol)-bpoly(acrylamide-co-acrylonitrile-co-dimethylaminoethylmethacrylate)(PEO113-b-P(AAm264-co-AN112-co-DMA8)) ...A novel switchable luminescent thermometer based on thermo-responsive triblock copolymer poly(ethylene glycol)-bpoly(acrylamide-co-acrylonitrile-co-dimethylaminoethylmethacrylate)(PEO113-b-P(AAm264-co-AN112-co-DMA8)) and Eu-containing polyoxometalate (Eu-POM) was successfully constructed.The copolymer synthesized by RAFT exhibited a linear response to temperature variations in aqueous media,which was quite different from the uncharged copolymer P(AAm-co-AN) having a specific upper critical solution temperature (UCST).Eu-POM was surrounded around thermo-responsive blocks through electrostatic interactions,and its luminescence could be finely tuned due to the sensitivity of copolymer to the temperature variation.In cold water,POMs were trapped in highly hydrophobic cores,exhibiting an intense emission.With the upraising of temperature,the emission intensity presented a gradual decrease and showed a linear correlation with temperature.When the complex solution cooled down,the luminescence could also be perfectly restored.This temperature-luminescence correlation could be held for numerous trials,showing a potential application in thermometer.展开更多
The results of this study reveals not only the sensitivity of the compatibility of PS with SBR to the molecular weight (MW) of PS and temperature, but also some other interesting characteristics, i. e., unusual morpho...The results of this study reveals not only the sensitivity of the compatibility of PS with SBR to the molecular weight (MW) of PS and temperature, but also some other interesting characteristics, i. e., unusual morphology change during the process of mixing with increase in temperature of specimen preparation observed under optical microscope and double-peak UCST curves for three blends with PS of low MW from DSC data. Acording to the amount of inward shift of the component T_g's and the broadening of the transition regions, it may be said that this polymer pair is compatible only when the MW of PS is low, and even then there still exists micro-heterogeneity.展开更多
Temperature-responsive polymers have garnered significant attention due to their ability to respond to external stimuli.In this work,dual temperature-responsive block copolymers are synthesized via reversible addition...Temperature-responsive polymers have garnered significant attention due to their ability to respond to external stimuli.In this work,dual temperature-responsive block copolymers are synthesized via reversible addition-fragmentation chain transfer polymerization(RAFT)polymerization utilizing zwitterionic monomer methacryloyl ethyl sulfobetaine(SBMA) and N-isopropyl acrylamide(NIPAAm) as monomers.The thermal responsive behaviors can be easily modulated by incorporating additional hydrophobic monomer benzyl acrylate(BN) or hydrophilic monomer acrylic acid(AA),adjusting concentration or pH,or varying the degree of polymerization of the block chain segments.The cloud points of the copolymers are determined by UV-Vis spectrophotometry,and these copolymers exhibit both controlled upper and lower critical solu bility temperatures(LCST and UCST) in aqueous solution.This study analyzes and summarizes the influencing factors of dual temperature responsive block copolymers by exploring the effects of various conditions on the phase transition temperature of temperature-sensitive polymers to explore the relationship between their properties and environment and structure to make them more selective in terms of temperature application range and regulation laws.It is very interesting that the introduction of poly-acrylic acid(PAA) segments in the middle of di-block copolymer PSBMA_(55)-b-PNIPAAm_(80) to form PSBMA_(55)-b-PAA_(x)-b-PNIPAAm_(80) results in a reversal of temperature-responsive behaviors from 'U'(LCST UCST) type,while the copolymer PSBMA_(55)-b-P(NIPAAm_(80)-co-AA_(x)) not.This work provides a clue for tuning the phase transition behavior of polymers for manufacture of extreme smart materials.展开更多
基金financially supported by the National Natural Science Foundation of China(No.21374056)the Program for Changjiang Scholars and Innovative Research Team in Universities(IRT 14R33)+3 种基金the Natural Science Basic Research Plan in Shaanxi Province of China(NSBRP-SPC 2014JM2051)the Program of Introducing Talents of Discipline to Universities(B14041)Shaanxi Innovative Research Team for Key Science and Technology(2012KCT-21,2013KCT-17)the One Hundred Plan of Shaanxi Province
文摘A betaine-type styrene monomer with the quaternary ammonium-borate anion inner-salt pair was synthesized through the quatemization reaction and polymerized to afford the target polybetaine of poly（4-vinylbenzyl methyl-diethanol ammonium borate） （PVMAB）. The chemical structures of the monomer and polymer were well demonstrated with 1H-NMR and llB-NMR spectra analysis. The thermal-sensitive experiment showed that PVMAB in water afforded gradually well- defined sigmoidal transmittance-temperature （T-t） curves along with the increasing polymer concentration. However, the phase transition temperatures at the bottom of the S-shaped curves were always below l0 ~C due to the very weak zwitterionic association of the ammonium-borate inner-salt pairs. The UCST phase transition could also be tuned by changing the ethanol content in the ethanol/water mixture. And the cytotoxicity experiment demonstrated the good biomimetic property of PVMAB. This study enriches the toolbox of polybetaines by introducing the quaternary ammonium- borate anion zwitterionic pair in the repeat units, therefore broadens the scope of synthetic polybetaines.
基金supported by National Key R&D Program of China(No.2017YFD0200302)the National Natural Science Foundation of China(NSFC,No.2604085)。
文摘Water-soluble thermoresponsive polymers present either upper critical solution temperature(UCST) or lower critical solution tempe rature(LCST) depending on the location of their miscibility range with water at high temperatures or at low temperatures.Compared with LCST polymers,the water-soluble UCST polymers are still less explored until now.In this work three copolymers of P(AAm-co-GAA) were synthesized by copolymerizing two acrylamide monomers,acrylamide(AAm) and acrylamide functionalized with natural glycyrrhetinic acid(GAA),using reversible addition-fragmentation chain transfer(RAFT) polymerization.These copolymers exhibited the typical UCST thermoresponsive behavior,and their phase transition temperatures could be easily tuned to around 37℃ for potential biological applications.Moreover,the UCST of P(AAm-co-GAA) can be adjusted not only by the content of glycyrrhetinic acid(GA) and polymer concentrations,but also by the host-vip interactions between GA and cyclodextrins(β-and γ-CD).The suitable value of UCST and the biocompatible nature of GA and CDs may endow these copolymers with practical applications in biomedical chemistry.
基金supported by the start-up funding from Westlake University under Grant Number 041030150118 and the scientific research project of Westlake University“Theoretical Research and Demonstration Application of Complex Systems and Deep-Sea Technology(Phase I)”under Grant Number WU2025A006.
文摘Human life is not determined by mechanical fatalism or a single material factor;instead,based on the dualistic ontology and active force mechanism in the Unified Complex Systems Theory(UCST),it can be actively designed under the guidance of mind,in accordance with causal laws,and through systematic interactions.This study integrates the dualistic ontology of UCST,as well as the cooperative mechanism of active force(Fa)and passive force(Fp).Furthermore,by incorporating Master Jiqun’s philosophy of“life design”and the practical principle of“destiny establishment and transformation”from The Four Lessons of Liaofan Yuan,it constructs a three-dimensional framework for life design encompassing the dimensions of science,philosophy,and practice.The significance of this research lies in breaking through the predicament of materialism in the AI(artificial intelligence)era,explaining the autonomy and initiative of life,providing feasible pathways for life design,and ultimately achieving the in-depth integration of scientific rationality and the wisdom of traditional Eastern culture.
基金the financial supported from the National Natural Science Foundation of China(12304482)Guizhou Provincial Basic Research Program(Natural Science)ZK[2022]Major Project 029+1 种基金Fund Project of Guizhou Minzu University(4D Printing Smart Materials Technological Innovative Talents Team,GZMUZK[2023]CXTD01)the financial supported from the Guizhou Provincial Key Technology R&D Program[2020]4Y107。
文摘The development of hydrogels capable of emitting multicolor fluorescence presents a promising avenue for addressing concerns related to information leakage and distortion of sensitive data.The integration of multifactorinduced tunable fluorescence with a unique upper critical solution temperature(UCST)behavior in hydrogels significantly contributes to the development of multi-dimensional and multi-level information storage materials that can dynamically display information as well as offer a high level of security and protection for information.However,the fusion of these advantageous properties into hydrogels intended for information storage and display remains a considerable challenge.In this context,we introduce a novel three-dimensional(3D)fluorescent code-producing hydrogel array fabricated via vat photopolymerization(VP)3D printing,a technique offers a sustainable and efficient approach.This array unites the desired properties,capable of sequentially revealing concealed information through two distinct steps:(i)a heat-induced phase transition,and(ii)multicolor fluorescence triggered by ultraviolet(UV)/temperature exposure under specific conditions(i.e.,certain UV irradiation duration,heating time,and wavelength).The reversible transparency and reprogrammable fluorescence emission properties of these hydrogels are expected to significantly enhance the processes of information encryption and anti-counterfeiting.This advancement could potentially revolutionize the field of information security.
基金supported by the National Natural Science Foundation of China for Special(Grant Nos.50253002,50027001)General(Grant Nos.50073024,90101001,20074037)+3 种基金Major(Grant No.50290090)the Special Pro-Funds for Major State Basic Research Projects(Grant No.2002CCAD4000)the Special Funds for Major State Basic Researcb Projects(Grant No.G1999064800)the Fund for Distinguished Young Scholars of China(Grant No.59825113).
文摘The present calculations were performed on the basis of the Sanchez-Lacombe lattice fluid theory and the new combinatorial rules for block copolymer according to the experimental results on the pressure-induced compatibility in poly(ethylene oxide) (PEO) and poly(ethylene ox-ide-b-dimethylsiloxane) (P(EO-b-DMS)) mixtures with UCST behavior. The study on enthalpy, combinatorial entropy, vacancy entropy and Gibbs energy upon mixture shows that San-chez-Lacombe fluid theory and the new combinatorial rules could describe the pressure-induced compatibility (PIC) of polymer mixtures with UCST behavior well.
基金National Key Research and Development projects intergovernmental cooperation in science and technology of China(No.2018YFE0126900)Zhejiang Provincial Natural Science Foundation(Nos.LD21H300002,LY18H180005,and LQ21H180003).
文摘Hepatocellular carcinoma(HCC)is a life-threatening disease for which there is no effective treatment currently.Novel theranostics simultaneously having excellent imaging and therapeutic functions are highly desired in cancer therapy.Herein,we develop the sialic acid(SA)modified polymeric micelles at an upper critical solution temperature(UCST)of 43℃(sialic acid-poly(ethylene glycol)-poly(acrylamide-co-acrylonitrile),SA-PEG-p(AAm-co-AN)),which further encapsulated with doxorubicin(DOX)and Gd-CuS nanoparticles(Gd-CuS NPs)for chemo-photothermal treatment of HCC guided by magnetic resonance(MR)/photoacoustic(PA)dual-mode imaging.The resultant SA-PEG-p(AAm-co-AN)/DOX/Gd-CuS(SPDG)had an excellent photothermal conversion efficiency,enabling SPDG with an instantaneous release behavior of DOX under near-infrared(NIR)irradiation.This study also revealed that SPDG could actively target to HCC,which was due to that SA had a high affinity with E-selectin overexpressed at the tumor site.Moreover,benefiting from the HCC-targeted ability and NIR light-controlled on-demand delivery of DOX,SPDG showed a superior potential in MR/PA dual-mode imaging-guided chemo-photothermal treatment.Overall,our study reveals that the designed SPDG may be used as an ideal multifunctional nanoplatform for cancer theranostics.
基金financially supported by the National Natural Science Foundation of China (Nos. 51673002, 51873001, and 51833001)
文摘A novel switchable luminescent thermometer based on thermo-responsive triblock copolymer poly(ethylene glycol)-bpoly(acrylamide-co-acrylonitrile-co-dimethylaminoethylmethacrylate)(PEO113-b-P(AAm264-co-AN112-co-DMA8)) and Eu-containing polyoxometalate (Eu-POM) was successfully constructed.The copolymer synthesized by RAFT exhibited a linear response to temperature variations in aqueous media,which was quite different from the uncharged copolymer P(AAm-co-AN) having a specific upper critical solution temperature (UCST).Eu-POM was surrounded around thermo-responsive blocks through electrostatic interactions,and its luminescence could be finely tuned due to the sensitivity of copolymer to the temperature variation.In cold water,POMs were trapped in highly hydrophobic cores,exhibiting an intense emission.With the upraising of temperature,the emission intensity presented a gradual decrease and showed a linear correlation with temperature.When the complex solution cooled down,the luminescence could also be perfectly restored.This temperature-luminescence correlation could be held for numerous trials,showing a potential application in thermometer.
基金This work was supported by the Selected Research Program of Academia Sinica and National Natural Science Foundation of China.
文摘The results of this study reveals not only the sensitivity of the compatibility of PS with SBR to the molecular weight (MW) of PS and temperature, but also some other interesting characteristics, i. e., unusual morphology change during the process of mixing with increase in temperature of specimen preparation observed under optical microscope and double-peak UCST curves for three blends with PS of low MW from DSC data. Acording to the amount of inward shift of the component T_g's and the broadening of the transition regions, it may be said that this polymer pair is compatible only when the MW of PS is low, and even then there still exists micro-heterogeneity.
基金financially supported by the National Natural Science Foundation of China (No. 22271207)the Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD)。
文摘Temperature-responsive polymers have garnered significant attention due to their ability to respond to external stimuli.In this work,dual temperature-responsive block copolymers are synthesized via reversible addition-fragmentation chain transfer polymerization(RAFT)polymerization utilizing zwitterionic monomer methacryloyl ethyl sulfobetaine(SBMA) and N-isopropyl acrylamide(NIPAAm) as monomers.The thermal responsive behaviors can be easily modulated by incorporating additional hydrophobic monomer benzyl acrylate(BN) or hydrophilic monomer acrylic acid(AA),adjusting concentration or pH,or varying the degree of polymerization of the block chain segments.The cloud points of the copolymers are determined by UV-Vis spectrophotometry,and these copolymers exhibit both controlled upper and lower critical solu bility temperatures(LCST and UCST) in aqueous solution.This study analyzes and summarizes the influencing factors of dual temperature responsive block copolymers by exploring the effects of various conditions on the phase transition temperature of temperature-sensitive polymers to explore the relationship between their properties and environment and structure to make them more selective in terms of temperature application range and regulation laws.It is very interesting that the introduction of poly-acrylic acid(PAA) segments in the middle of di-block copolymer PSBMA_(55)-b-PNIPAAm_(80) to form PSBMA_(55)-b-PAA_(x)-b-PNIPAAm_(80) results in a reversal of temperature-responsive behaviors from 'U'(LCST UCST) type,while the copolymer PSBMA_(55)-b-P(NIPAAm_(80)-co-AA_(x)) not.This work provides a clue for tuning the phase transition behavior of polymers for manufacture of extreme smart materials.
