A H_(2)O_(2)-triggered stimulus response electrochemiluminescence(ECL)sensor for sensitive detection of cancer cells using mesoporous silica nanoparticles(MSNs)has been proposed.ECL signal-generating molecules(Ru(phen...A H_(2)O_(2)-triggered stimulus response electrochemiluminescence(ECL)sensor for sensitive detection of cancer cells using mesoporous silica nanoparticles(MSNs)has been proposed.ECL signal-generating molecules(Ru(phen)32+)were encap-sulated into phenylboronic acid group-functionalized MSNs(PBA-MSNs)porous and capped by polyhydroxy functioned Au nanoparticles(AuNPs)through the interaction of carbohydrate-boronic acid first.Brunauer-Emmett-Teller(BET)and transmission electron microscopy(TEM)were applied to characterize the materials.The proposed controlled release sensing platform shows approximately no leakage from the mesoporrs of MSNs after a long time of storage.Cancer cells are initially incubated with the functionalized MSNs and then treated with ascorbic acid to endogenously produce H_(2)O_(2).Arylboronic esters in the MSNs surface can be oxidized by the produced H_(2)O_(2),causing the releasing of the molecule from MSNs and increased ECL signal.This technique displayed an excellent measurement for the breast cancer cells’sensitive diagnosis with a detection limit of 208 cells/mL.The phenomenon suggests that this sensing platform may be potentially applied for breast cancer sensitive detection in the future.展开更多
Hydrogels show versatile properties and are of great interest in the fields of bioelectronics and tissue engineering.Understanding the dynamics of the water molecules trapped in the three-dimensional polymeric network...Hydrogels show versatile properties and are of great interest in the fields of bioelectronics and tissue engineering.Understanding the dynamics of the water molecules trapped in the three-dimensional polymeric networks of the hydrogels is crucial to elucidate their mechanical and swelling properties at the molecular level.In this report,the poly(DMAEMA-co-AA)hydrogels were synthesized and characterized by the macroscopic swelling measurements under different pH conditions.Furthermore,the microscopic structural dynamics of pH stimulus-responsive hydrogels were studied using FTIR and ultrafast IR spectroscopies from the viewpoint of the SCN-anionic solute as the local vibrational reporter.Ultrafast IR spectroscopic measurements showed the time constants of the vibrational population decay of SCN-were increased from 14±1 ps to 20±1 ps when the pH of the hydrogels varied from2.0 to 12.0.Rotational anisotropy measurements further revealed that the rotation of SCNanionic probe was restricted by the three-dimensional network formed in the hydrogels and the rotation of SCN-anionic probe cannot decay to zero especially at the pH of 7.0.These results are expected to provide a molecular-level understanding of the microscopic structure of the cross-linked polymeric network in the pH stimulus-responsive hydrogels.展开更多
Stimulus re s ponsive materials can provide a variety of desirable properties in one equipment unit,such as optoelectronic devices,data communications,actuators,memories,sensors and capacitors.However,it remains a lar...Stimulus re s ponsive materials can provide a variety of desirable properties in one equipment unit,such as optoelectronic devices,data communications,actuators,memories,sensors and capacitors.However,it remains a large challenge to design such stimulus responsive materials,especially functional materials having both dielectric switch and second harmonic generation(SHG).Here,a new stimuli-responsive switchable material [(CH_(3))_(3)N(CH_(2))_(2)Cl]_(2)]Mn(SCN)_(4)(H_(2)O)_(2)] was discovered as a potential secondharmonic generation(SHG) dielectric switch.It is worth noting that it has SHG characteristics before and after undergoing reversible high-temperature phase transitions.In this work,we successfully refined the tetramethylammonium cation to obtain a quasi-spherical cation,which is tetramethylchloroethylamine(TMCEM) cation.By substituting H with a halogen,the increased steric hindrance of the molecular makes energy barrier increased,resulting in the reversible high-temperature phase transition.At the same time,the interactions of quasi-spherical cations and [Mn(SCN)_(4)(H_(2)O)_(2)]^(2-) anions affect a noncentrosymmetric structure to induce the SHG effect.These findings provide a new approach to design novel functional switch materials.展开更多
The ability of organisms to adjust to environmental changes offers valuable insights into the development and creation of innovative smart systems. As requirements increase, the ability of smart materials to change th...The ability of organisms to adjust to environmental changes offers valuable insights into the development and creation of innovative smart systems. As requirements increase, the ability of smart materials to change their shapes has become a broader aim beyond their original capabilities. In contrast to conventional manufacturing methods, additive manufacturing (AM) skillfully combines precise three-dimensional structures and the intricate response mechanisms of biological organisms with smart materials. This combination enables the production of smart bionic structures with programmable shapes and features. Trends such as dynamic modulation, responsive- ness to multiple stimuli, and the integration of functions are emerging as significant in the development of smart bionic structures. This review first presents smart structures that nature has designed and built in various organ- isms, highlighting the relationship between the structural characteristics and patterns of deformation. The review then discusses how smart bionic structures developed using AM techniques respond to different stimuli. Addi- tionally, the potential uses of smart bionic structures in biomedicine, intelligent robotics, origami construction, and aerospace are discussed. Finally, the challenges and future prospects for smart bionic structures are exam- ined with the goal of offering innovative solutions for creating the next generation of smart systems through interdisciplinary research.展开更多
“Life”represents a distinctive attribute inherent to organisms in nature,evident in their capacity to actively adapt to changes in their environment.In contrast to the static and intricate constructs of additive man...“Life”represents a distinctive attribute inherent to organisms in nature,evident in their capacity to actively adapt to changes in their environment.In contrast to the static and intricate constructs of additive manufacturing(AM),the dynamic structure of 4D printing(4DP)adeptly integrates AM technology,responsive mechanisms,and external stimuli,imbuing it with a semblance of“life.”This fusion significantly broadens its functional applica-tions across biomedicine,actuators,and metamaterials.The escalating demand across diverse fields necessitates heightened criteria for 4DP,encompassing rapid response,multi-stimulus response,large shape change,and specific mechanical properties(e.g.,high strength,high modulus)capable of accommodating varying environ-mental conditions.In recent years,shape memory polymers(SMPs)have garnered increasing attention among 4DP researchers due to their ease of design and preprogramming at the molecular level,facilitating controlled transformations along predictable pathways.However,4DP of high-strength SMPs,as an indispensable part of the high-performance field,is full of challenges because the intrinsic properties of the raw materials are not well compatible with the printing principle and the printed configuration is not flexible enough.Consequently,this paper provides a concise overview of the response mechanisms and applications of five prominent high-strength SMPs utilized in 4DP:epoxy resin,poly(ether-ether-ketone),polyimide,polylactic acid,and polyurethane.Ad-ditionally,it delves into the associated challenges and prospects,offering researchers valuable insights into the potential value of high-strength SMPs within the domain of 4DP.展开更多
It has been challenging to achieve multi-photochromic systems without affecting the individual photoswitching properties of the constituent units. Herein, we present the design and synthesis of a new family of platinu...It has been challenging to achieve multi-photochromic systems without affecting the individual photoswitching properties of the constituent units. Herein, we present the design and synthesis of a new family of platinum-acetylide dendrimers containing up to twenty-one photochromic dithienylethene(DTE)units that exhibit both high photochromic efficiency and individual switching properties. Upon irradiation with ultraviolet(UV) and visible(vis) light, the resultant metallodendrimers display high conversion yield and good fatigue resistance. More interestingly, cyclization-cycloreversion kinetics revealed that the photochromic property of each DTE unit in these metallodendrimers is unaffected by its neighbor and the full ring-closure of up to twenty-one DTE units in one single dendrimer has been achieved.展开更多
Single chemotherapy is difficult to meet the needs of tumor cure. Photothermia combined with chemotherapy is anew and effective anti-tumor therapy. However, the drug loading of nanoparticles and increase in performanc...Single chemotherapy is difficult to meet the needs of tumor cure. Photothermia combined with chemotherapy is anew and effective anti-tumor therapy. However, the drug loading of nanoparticles and increase in performance of photothermalconversion limits the therapeutic effect of combination therapy. In this study, two-dimensional boron (boron, B) nanoparticles wereprepared by ultrasonic exfoliation, and copper sulfide (CuS) nanoparticles and doxorubicin (DOX) were grown on the surface ofthe nanoparticles to form B-CuS-DOX nanoparticles. B-CuS carrier has high DOX drug loading capacity (864mg/g) and goodphotothermal conversion performance (photothermal conversion efficiency at 808nm is 55.8%). At the same time, it can achievedrug release and good photothermal response at near infrared and pH. The nanoparticles designed in this study are expected toprovide an effective chemotherapy-photothermal therapy strategy for tumor therapy in vivo.展开更多
Anti-counterfeiting labels with various fluorescent colors are of great importance in information encryption-decryption,but are still limited to static information display.Therefore,it is urgent to develop new materia...Anti-counterfeiting labels with various fluorescent colors are of great importance in information encryption-decryption,but are still limited to static information display.Therefore,it is urgent to develop new materials and encryption-decryption logic for improving the security level of secret information.In this study,an organohydrogel made up of poly(N,N-dimethylacrylamide)(pDMA)hydrogel network and polyoctadecyl methacrylate(pSMA)organogel network that copolymerized with two fluorophores,6-acrylamidopicolinic acid moieties(6APA,fluorescent ligand)and spiropyran units(SPMA,photochromic monomer),was prepared by a two-step interpenetrating method.As UV light of 365nm and 254nm can both cleave C_(spiro)-O bonds of SPMA,and the green fluorescence of 6APA-Tb^(3+) can only be excited by 254nm light,the organohydrogel displays yellow and red under the irradiation of 254nm and 365 nm,respectively.In addition to wavelength selectivity,these two fluorophores are thermal-responsive,leading to the fluorescence variation of the organohydrogel during heating process.As a result,secret information loaded on the organohydrogel can be decrypted by the irradiation of UV light,and the authenticity of the information can be further identified by thermal stimulation.Our fluorescent organohydrogel can act as an effective anti-counterfeiting label to improve the information security and protect the information from being cracked.展开更多
In this study, a novel H-bonded cholesteric polymer film responding to temperature and pH by changing the reflection color was fabricated. The H-bonded cholesteric polymer film was achieved by UV-photopolymerizing a c...In this study, a novel H-bonded cholesteric polymer film responding to temperature and pH by changing the reflection color was fabricated. The H-bonded cholesteric polymer film was achieved by UV-photopolymerizing a cholesteric liquid crystal （Ch-LC） monomers mixture containing a photopolymerizable chiral H-bonded assembly （PCHA）. The cholesteric polymer film based on PCHA can be thermally switched to reflect red color from the initial green/yellow color as temperature is increased, which is due to a change in helical pitch induced by the weakening of H-bonded interaction in the polymer film. Additionally, the selective reflection band （SRB） of the cholesteric polymer film in solution with pH 〉 7 showed an obvious red shift with increasing pH values. While the SRB of the cholesteric polymer film in solutions with pH = 7 and pH 〈 7 hardly changed. This pH sensitivity in solutions with pH 〉 7 could be explained by the breakage of H-bonds in the cholesteric polymer film and the structure changes induced by --OH- and --K＋ ions in the alkaline solution. In contrast, it couldn＇t happen in the neutral and acidic solutions. The cholesteric polymer film in this study can be used as optical/photonic papers, optical sensors and LCs displays, etc.展开更多
Deuteration of hydrogen-bonded phase transition crystals can increase the transition temperatures due to the isotope effect. But rare examples show the opposite trend that originates from the structural changes of the...Deuteration of hydrogen-bonded phase transition crystals can increase the transition temperatures due to the isotope effect. But rare examples show the opposite trend that originates from the structural changes of the hydrogen bond, known as the geometric H/D isotope effect. Herein, we report an organic crystal, diethylammonium hydrogen 1,4-terephthalate, exhibits a reversible structural phase transition and dielectric switching. Structural study shows the cations reside in channels formed by one-dimensional hydrogen-bonded anionic chains and undergo an order-disorder transition at around 206 K. The deuterated counterpart shows an elongation of the O…O hydrogen bond by about 0.005 A. This geometric isotope effect releases the internal pressure of the anionic host on the cation vips and results in a downward shift of the phase transition temperature by 10 K.展开更多
Boosting the effectiveness of cancer therapies by fine-tuning the tumor microenvironment has become a pivotal focus in modern cancer research.Nevertheless,the quest for impactful strategies in this regard is still ong...Boosting the effectiveness of cancer therapies by fine-tuning the tumor microenvironment has become a pivotal focus in modern cancer research.Nevertheless,the quest for impactful strategies in this regard is still ongoing.In this study,a drug-gated nanocomposite hydrogel was developed using polyglutamic acid-modified gold nanorods(AuNRs)and cisplatin(CDDP)to facilitate controlled drug release and augment localized combined antitumor effectiveness.CDDP not only serves as a cross-linking agent for creating the gel networks but also functions as a gating site for the controlled release of aPD-L1.This drug delivery system features a dual-action release mechanism,triggered by the endogenous chloride ions and enhanced by external near-infrared heating by AuNRs.Significantly,CDDP is clearly sensitized by this localized photothermal effect,which also results in tumor ablation.Additionally,the induction of immunogenic cell death through photothermal chemotherapy further potentiates the efficacy of aPD-L1-involved immune checkpoint blockade.The results demonstrated that this therapeutic gel scaffold has good antitumor effects that synergize with the effects of immune-mediated hyperthermic chemotherapy and show promising application of a local stimulus-responsive drug-delivery system.展开更多
To enhance the utilization of pesticides and reduce environmental risks,we constructed the magnetic recyclable and dual stimulus-responsive microspheres to achieve on-demand pesticide release.Magnetic multi-shell holl...To enhance the utilization of pesticides and reduce environmental risks,we constructed the magnetic recyclable and dual stimulus-responsive microspheres to achieve on-demand pesticide release.Magnetic multi-shell hollow mesoporous organosilicon nanoparticles(mMSN)were prepared by one-step hydrothermal method and loaded with pesticide avermectin(A@mMSN),afterward A@mMSN was coated with gelatin through emulsification and chemical cross-linking to prepare A@mMSN@G microspheres(21.5±9.7μm).After being absorbed by the pests,the gelatin layer was hydrolyzed with the neutral protease,and the disulfide bonds within mMSN framework were decomposed by glutathione(GSH),endowing A@mMSN@G microspheres with enzyme and GSH responsiveness to achieve sustained avermectin release till 7 days(about 3.5 times that of the commercial avermectin emulsion).Importantly,the A@mMSN@G microspheres containing Fe3O4 nanoparticles could be easily magnetically collected from soil with a recovery ratio of 63.7%,to reduce the environmental risks.With excellent biosafety,A@mMSN@G microspheres showed outstanding pest control effects till two weeks and the growth of cabbage was not affected by it.Therefore,based on the recyclability and dual stimulus-responsive controllable release,the fabricated A@mMSN@G microspheres have broad application potential in pesticide delivery.展开更多
Eliminating colloidal toxicity and enabling its intrinsic fluorescence in aggressive environmental conditions are the key challenges for commercializing hydrophobic cadmium based quantum dots(QD).Polyarylene ether nit...Eliminating colloidal toxicity and enabling its intrinsic fluorescence in aggressive environmental conditions are the key challenges for commercializing hydrophobic cadmium based quantum dots(QD).Polyarylene ether nitriles(PEN)are an example of super-engineering thermoplastics that possess a unique combination of thermal stability,intrinsic fluorescence,biocompatibility and distinct emulsion self-assembly feature.Herein,the co-self-assembly of amphiphilic PEN with hydrophobic CdSe@ZnS QD,confined in the three-dimensional(3D)oil-in-water emulsion droplets,has been explored tofabricate fluorescent microparticles(FMP).It was found that these FMP demonstrated good biocompatibility(cell viability above 90%),while exhibiting a fluorescence emission in aqueous solution that was retained(intensity retention ratio above 80%)within the whole pH range of 1-14,as well as,after being subjected to autoclaving at 120℃for 1 h.Interestingly,it was discovered that introduction of calcium ions in the emulsion self-assembly contributed to in-situ generation of phase changing nanoplates inside the FMP,which led to the photo-thermal modulated solid state fluorescence from drop-casted FMP film.Thanks to their versatile fluorescence,these FMP colloids were exploited as fluorescent probes for macrophages imaging,while micro-patterns with reversible changing of emission color were induced via thermal treatment and direct laser lithography.展开更多
Epilepsy is a common yet complex neurological disorder.Historically,antiseizure medications(ASMs)have faced challenges in crossing the blood-brain barrier(BBB)and targeting the epileptogenic zone,creating a bottleneck...Epilepsy is a common yet complex neurological disorder.Historically,antiseizure medications(ASMs)have faced challenges in crossing the blood-brain barrier(BBB)and targeting the epileptogenic zone,creating a bottleneck in seizure management.Certain nanomaterials can facilitate drug penetration through the BBB and enable stimulus-responsive drug release,thereby enhancing targeted and efficient drug utilization while reducing adverse reactions in other brain tissues and peripherally.This article reviews the current researches on stimulus-responsive nanosystems applicable in antiepileptic therapy,as well as nanotechnology applications that improve the brain delivery of ASMs.展开更多
Intelligent ion gels,which possess highly tunable mechanical,electrical,and stimulus‐responsive properties,have emerged as powerful candidates in the field of artificial intelligence,telemedicine,and health monitorin...Intelligent ion gels,which possess highly tunable mechanical,electrical,and stimulus‐responsive properties,have emerged as powerful candidates in the field of artificial intelligence,telemedicine,and health monitoring.To enrich the functionality of ion gels,it is critical to explore the link between the structure and function of ion gels.In this review,we provide an overview of the synthesis path and functional derivatives of ion gels.The conformational relationships of ion gels have been discussed,such as the effect of structure on electrical conductivity as well as sensing properties.From the perspective of stimulus response,the role of ion gels in areas such as bionic haptics,neural devices,artificial muscles,and intelligent displays has also been explored.It is possible that smart ion gels will open up a new horizon in the upcoming smart era,especially after the current challenges are resolved.展开更多
Luminescent materials exhibiting emission switching in the solid state have drawn much attention though there is still no clear design strategy for such materials. In this letter, we reported the crystallization induc...Luminescent materials exhibiting emission switching in the solid state have drawn much attention though there is still no clear design strategy for such materials. In this letter, we reported the crystallization induced emission enhancement (CIEE) of di(4-ethoxyphenyl)dibenzofulvene (1), and achieved switching its emission among four different colors through modulation of its molecular packing patterns. We have investigated its potential application as optical recording materials. The twisted conformations of CIEE compounds afford morphology dependent emission and facilitate tuning their emission through modulation of molecular packing patterns. Thus we provide a possible design strategy for solid stimulus responsive luminescent materials.展开更多
Self-assembly exists widely in natural living system and artificial synthetic material system.Administration of self-assemblies of artificial architectures in living cells can be used to explore the molecular physicoc...Self-assembly exists widely in natural living system and artificial synthetic material system.Administration of self-assemblies of artificial architectures in living cells can be used to explore the molecular physicochemical fundamentals and operating mechanisms of living system,and consequently promote the development of biomedicine.In order to mimic naturally occurring self-assemblies and realize controllable functions,great efforts have been devoted to constructing dynamic assembly of artificial architectures in living cells by responding to intracellular specific stimuli,which can be used to regulate morphology,behaviors and fate of living cells.This review highlights the recent progress on artificial self-assembly in living cells.The molecular fundamentals and characteristics of intracellular environment that can induce the self-assembly of artificial architectures are introduced,and the representative work on dynamic artificial self-assembly in living cells is sketched chronologically.Moreover,intracellular stimuli-mediated pathways of artificial assembly in living cells are categorized,biological effects caused by intracellular self-assembly are summarized,and biomedical applications focusing on therapy and imaging are described.In the end,the perspective and challenges of artificial self-assembly in living cells are fully discussed.It is believed that the grand advances on artificial self-assembly in living cells will contribute to elaborating the molecular mechanisms in cells,and further promoting the biologically and medically-related applications in the future.展开更多
基金supported by the National Science Foundation of China(Nos.21675028 and 21775026)the Program for Changjiang Scholars and Innovative Research Team in University(No.IRT15R11)+2 种基金the National Science Foundation of Fujian Province(No.2018J05018)the STS Key Project of Fujian Province(No.2017T3007)Provincial Health Technology Project of Fujian Province(No.2019-ZQN-93).
文摘A H_(2)O_(2)-triggered stimulus response electrochemiluminescence(ECL)sensor for sensitive detection of cancer cells using mesoporous silica nanoparticles(MSNs)has been proposed.ECL signal-generating molecules(Ru(phen)32+)were encap-sulated into phenylboronic acid group-functionalized MSNs(PBA-MSNs)porous and capped by polyhydroxy functioned Au nanoparticles(AuNPs)through the interaction of carbohydrate-boronic acid first.Brunauer-Emmett-Teller(BET)and transmission electron microscopy(TEM)were applied to characterize the materials.The proposed controlled release sensing platform shows approximately no leakage from the mesoporrs of MSNs after a long time of storage.Cancer cells are initially incubated with the functionalized MSNs and then treated with ascorbic acid to endogenously produce H_(2)O_(2).Arylboronic esters in the MSNs surface can be oxidized by the produced H_(2)O_(2),causing the releasing of the molecule from MSNs and increased ECL signal.This technique displayed an excellent measurement for the breast cancer cells’sensitive diagnosis with a detection limit of 208 cells/mL.The phenomenon suggests that this sensing platform may be potentially applied for breast cancer sensitive detection in the future.
基金supported by the National Natural Science Foundation of China(No.21873062)the Fundamental Research Funds for the Central Universities(GK202001009)+2 种基金the Natural Science Basis Research Plan in Shaanxi Province of China(No.2020JM-295)the 111 Project(B14041)Program for Changjiang Scholars and the Innovative Research Team in University(IRT-14R33)。
文摘Hydrogels show versatile properties and are of great interest in the fields of bioelectronics and tissue engineering.Understanding the dynamics of the water molecules trapped in the three-dimensional polymeric networks of the hydrogels is crucial to elucidate their mechanical and swelling properties at the molecular level.In this report,the poly(DMAEMA-co-AA)hydrogels were synthesized and characterized by the macroscopic swelling measurements under different pH conditions.Furthermore,the microscopic structural dynamics of pH stimulus-responsive hydrogels were studied using FTIR and ultrafast IR spectroscopies from the viewpoint of the SCN-anionic solute as the local vibrational reporter.Ultrafast IR spectroscopic measurements showed the time constants of the vibrational population decay of SCN-were increased from 14±1 ps to 20±1 ps when the pH of the hydrogels varied from2.0 to 12.0.Rotational anisotropy measurements further revealed that the rotation of SCNanionic probe was restricted by the three-dimensional network formed in the hydrogels and the rotation of SCN-anionic probe cannot decay to zero especially at the pH of 7.0.These results are expected to provide a molecular-level understanding of the microscopic structure of the cross-linked polymeric network in the pH stimulus-responsive hydrogels.
基金supported by the National Natural Science Foundation of China(Nos.21673038,21771037,21805033)Natural Science Foundation of Jiangsu Province(JSNSF,No.BK20170659)。
文摘Stimulus re s ponsive materials can provide a variety of desirable properties in one equipment unit,such as optoelectronic devices,data communications,actuators,memories,sensors and capacitors.However,it remains a large challenge to design such stimulus responsive materials,especially functional materials having both dielectric switch and second harmonic generation(SHG).Here,a new stimuli-responsive switchable material [(CH_(3))_(3)N(CH_(2))_(2)Cl]_(2)]Mn(SCN)_(4)(H_(2)O)_(2)] was discovered as a potential secondharmonic generation(SHG) dielectric switch.It is worth noting that it has SHG characteristics before and after undergoing reversible high-temperature phase transitions.In this work,we successfully refined the tetramethylammonium cation to obtain a quasi-spherical cation,which is tetramethylchloroethylamine(TMCEM) cation.By substituting H with a halogen,the increased steric hindrance of the molecular makes energy barrier increased,resulting in the reversible high-temperature phase transition.At the same time,the interactions of quasi-spherical cations and [Mn(SCN)_(4)(H_(2)O)_(2)]^(2-) anions affect a noncentrosymmetric structure to induce the SHG effect.These findings provide a new approach to design novel functional switch materials.
基金supported by National Natural Science Foundation of China(Grant Nos.52235006,52025053)National Key Research and Development Program of China(Grant No.2022YFB4600500).
文摘The ability of organisms to adjust to environmental changes offers valuable insights into the development and creation of innovative smart systems. As requirements increase, the ability of smart materials to change their shapes has become a broader aim beyond their original capabilities. In contrast to conventional manufacturing methods, additive manufacturing (AM) skillfully combines precise three-dimensional structures and the intricate response mechanisms of biological organisms with smart materials. This combination enables the production of smart bionic structures with programmable shapes and features. Trends such as dynamic modulation, responsive- ness to multiple stimuli, and the integration of functions are emerging as significant in the development of smart bionic structures. This review first presents smart structures that nature has designed and built in various organ- isms, highlighting the relationship between the structural characteristics and patterns of deformation. The review then discusses how smart bionic structures developed using AM techniques respond to different stimuli. Addi- tionally, the potential uses of smart bionic structures in biomedicine, intelligent robotics, origami construction, and aerospace are discussed. Finally, the challenges and future prospects for smart bionic structures are exam- ined with the goal of offering innovative solutions for creating the next generation of smart systems through interdisciplinary research.
基金supported by National Natural Science Foundation of China(Grant Nos.51935012,52005481)LICP Cooperation Foundation for Young Scholars(Grant No.HZJJ22-11)+1 种基金Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No.XDB0470303)Major Program of the Lanzhou Institute of Chemical Physics,CAS(Grant No.ZYFZFX-7).
文摘“Life”represents a distinctive attribute inherent to organisms in nature,evident in their capacity to actively adapt to changes in their environment.In contrast to the static and intricate constructs of additive manufacturing(AM),the dynamic structure of 4D printing(4DP)adeptly integrates AM technology,responsive mechanisms,and external stimuli,imbuing it with a semblance of“life.”This fusion significantly broadens its functional applica-tions across biomedicine,actuators,and metamaterials.The escalating demand across diverse fields necessitates heightened criteria for 4DP,encompassing rapid response,multi-stimulus response,large shape change,and specific mechanical properties(e.g.,high strength,high modulus)capable of accommodating varying environ-mental conditions.In recent years,shape memory polymers(SMPs)have garnered increasing attention among 4DP researchers due to their ease of design and preprogramming at the molecular level,facilitating controlled transformations along predictable pathways.However,4DP of high-strength SMPs,as an indispensable part of the high-performance field,is full of challenges because the intrinsic properties of the raw materials are not well compatible with the printing principle and the printed configuration is not flexible enough.Consequently,this paper provides a concise overview of the response mechanisms and applications of five prominent high-strength SMPs utilized in 4DP:epoxy resin,poly(ether-ether-ketone),polyimide,polylactic acid,and polyurethane.Ad-ditionally,it delves into the associated challenges and prospects,offering researchers valuable insights into the potential value of high-strength SMPs within the domain of 4DP.
基金supported by the National Natural Science Foundation of China (Nos. 11674101, 21873030, 91850202,and 21871092)the Fundamental Research Funds for the Central Universities。
文摘It has been challenging to achieve multi-photochromic systems without affecting the individual photoswitching properties of the constituent units. Herein, we present the design and synthesis of a new family of platinum-acetylide dendrimers containing up to twenty-one photochromic dithienylethene(DTE)units that exhibit both high photochromic efficiency and individual switching properties. Upon irradiation with ultraviolet(UV) and visible(vis) light, the resultant metallodendrimers display high conversion yield and good fatigue resistance. More interestingly, cyclization-cycloreversion kinetics revealed that the photochromic property of each DTE unit in these metallodendrimers is unaffected by its neighbor and the full ring-closure of up to twenty-one DTE units in one single dendrimer has been achieved.
文摘Single chemotherapy is difficult to meet the needs of tumor cure. Photothermia combined with chemotherapy is anew and effective anti-tumor therapy. However, the drug loading of nanoparticles and increase in performance of photothermalconversion limits the therapeutic effect of combination therapy. In this study, two-dimensional boron (boron, B) nanoparticles wereprepared by ultrasonic exfoliation, and copper sulfide (CuS) nanoparticles and doxorubicin (DOX) were grown on the surface ofthe nanoparticles to form B-CuS-DOX nanoparticles. B-CuS carrier has high DOX drug loading capacity (864mg/g) and goodphotothermal conversion performance (photothermal conversion efficiency at 808nm is 55.8%). At the same time, it can achievedrug release and good photothermal response at near infrared and pH. The nanoparticles designed in this study are expected toprovide an effective chemotherapy-photothermal therapy strategy for tumor therapy in vivo.
基金supported by the National Key R&D Program of China(No.2022YFB3204300)the National Natural Science Foundation of China(No.52103246)+1 种基金Zhejiang Provincial Natural Science Foundation,China(No.LQ22E030015)Natural Science Foundation of Ningbo,China(No.20221JCGY010301).
文摘Anti-counterfeiting labels with various fluorescent colors are of great importance in information encryption-decryption,but are still limited to static information display.Therefore,it is urgent to develop new materials and encryption-decryption logic for improving the security level of secret information.In this study,an organohydrogel made up of poly(N,N-dimethylacrylamide)(pDMA)hydrogel network and polyoctadecyl methacrylate(pSMA)organogel network that copolymerized with two fluorophores,6-acrylamidopicolinic acid moieties(6APA,fluorescent ligand)and spiropyran units(SPMA,photochromic monomer),was prepared by a two-step interpenetrating method.As UV light of 365nm and 254nm can both cleave C_(spiro)-O bonds of SPMA,and the green fluorescence of 6APA-Tb^(3+) can only be excited by 254nm light,the organohydrogel displays yellow and red under the irradiation of 254nm and 365 nm,respectively.In addition to wavelength selectivity,these two fluorophores are thermal-responsive,leading to the fluorescence variation of the organohydrogel during heating process.As a result,secret information loaded on the organohydrogel can be decrypted by the irradiation of UV light,and the authenticity of the information can be further identified by thermal stimulation.Our fluorescent organohydrogel can act as an effective anti-counterfeiting label to improve the information security and protect the information from being cracked.
基金supported by the National Natural Science Foundation of China (No. 50903004)
文摘In this study, a novel H-bonded cholesteric polymer film responding to temperature and pH by changing the reflection color was fabricated. The H-bonded cholesteric polymer film was achieved by UV-photopolymerizing a cholesteric liquid crystal （Ch-LC） monomers mixture containing a photopolymerizable chiral H-bonded assembly （PCHA）. The cholesteric polymer film based on PCHA can be thermally switched to reflect red color from the initial green/yellow color as temperature is increased, which is due to a change in helical pitch induced by the weakening of H-bonded interaction in the polymer film. Additionally, the selective reflection band （SRB） of the cholesteric polymer film in solution with pH 〉 7 showed an obvious red shift with increasing pH values. While the SRB of the cholesteric polymer film in solutions with pH = 7 and pH 〈 7 hardly changed. This pH sensitivity in solutions with pH 〉 7 could be explained by the breakage of H-bonds in the cholesteric polymer film and the structure changes induced by --OH- and --K＋ ions in the alkaline solution. In contrast, it couldn＇t happen in the neutral and acidic solutions. The cholesteric polymer film in this study can be used as optical/photonic papers, optical sensors and LCs displays, etc.
基金financially supported by the National Natural Science Foundation of China (Nos. 21875035 and 21991144)。
文摘Deuteration of hydrogen-bonded phase transition crystals can increase the transition temperatures due to the isotope effect. But rare examples show the opposite trend that originates from the structural changes of the hydrogen bond, known as the geometric H/D isotope effect. Herein, we report an organic crystal, diethylammonium hydrogen 1,4-terephthalate, exhibits a reversible structural phase transition and dielectric switching. Structural study shows the cations reside in channels formed by one-dimensional hydrogen-bonded anionic chains and undergo an order-disorder transition at around 206 K. The deuterated counterpart shows an elongation of the O…O hydrogen bond by about 0.005 A. This geometric isotope effect releases the internal pressure of the anionic host on the cation vips and results in a downward shift of the phase transition temperature by 10 K.
基金supported by the National Natural Science Foundation of China(Nos.52473127,22275046,22161142015)the National Key R&D Program of China(No.2020YFA0908500)+1 种基金the Hangzhou Leading Innovation and Entrepreneurship Team Project(No.TD2022001)the Interdisciplinary Research Project of Hangzhou Normal University(2025JCXK02).
文摘Boosting the effectiveness of cancer therapies by fine-tuning the tumor microenvironment has become a pivotal focus in modern cancer research.Nevertheless,the quest for impactful strategies in this regard is still ongoing.In this study,a drug-gated nanocomposite hydrogel was developed using polyglutamic acid-modified gold nanorods(AuNRs)and cisplatin(CDDP)to facilitate controlled drug release and augment localized combined antitumor effectiveness.CDDP not only serves as a cross-linking agent for creating the gel networks but also functions as a gating site for the controlled release of aPD-L1.This drug delivery system features a dual-action release mechanism,triggered by the endogenous chloride ions and enhanced by external near-infrared heating by AuNRs.Significantly,CDDP is clearly sensitized by this localized photothermal effect,which also results in tumor ablation.Additionally,the induction of immunogenic cell death through photothermal chemotherapy further potentiates the efficacy of aPD-L1-involved immune checkpoint blockade.The results demonstrated that this therapeutic gel scaffold has good antitumor effects that synergize with the effects of immune-mediated hyperthermic chemotherapy and show promising application of a local stimulus-responsive drug-delivery system.
基金supported by the Guangzhou Science and Technology Program Project(No.202206010187 and 2023B03J1332)the National Natural Science Foundation of China(No.22208115)+1 种基金the Fundamental Research Funds for the Central Universities(No.2023ZYGXZR041)the Young Elite Scientists Sponsorship Program by CAST(No.2022QNRC001).
文摘To enhance the utilization of pesticides and reduce environmental risks,we constructed the magnetic recyclable and dual stimulus-responsive microspheres to achieve on-demand pesticide release.Magnetic multi-shell hollow mesoporous organosilicon nanoparticles(mMSN)were prepared by one-step hydrothermal method and loaded with pesticide avermectin(A@mMSN),afterward A@mMSN was coated with gelatin through emulsification and chemical cross-linking to prepare A@mMSN@G microspheres(21.5±9.7μm).After being absorbed by the pests,the gelatin layer was hydrolyzed with the neutral protease,and the disulfide bonds within mMSN framework were decomposed by glutathione(GSH),endowing A@mMSN@G microspheres with enzyme and GSH responsiveness to achieve sustained avermectin release till 7 days(about 3.5 times that of the commercial avermectin emulsion).Importantly,the A@mMSN@G microspheres containing Fe3O4 nanoparticles could be easily magnetically collected from soil with a recovery ratio of 63.7%,to reduce the environmental risks.With excellent biosafety,A@mMSN@G microspheres showed outstanding pest control effects till two weeks and the growth of cabbage was not affected by it.Therefore,based on the recyclability and dual stimulus-responsive controllable release,the fabricated A@mMSN@G microspheres have broad application potential in pesticide delivery.
基金the National Natural Science Foundation of China(No.51403029)the Fundamental Research Funds for the Central Universities(No.ZYGX2019J026)+1 种基金Sichuan Science and Technology Program(No.2020YFG0100)International Science and Technology Cooperation Project from Chengdu municipal government(No.2019-GH02-00037-HZ).K.J.thanks Prof.Yanbo Li from the IoF of UESTC for his timely assistance in fluorescence lifetime measurement.
文摘Eliminating colloidal toxicity and enabling its intrinsic fluorescence in aggressive environmental conditions are the key challenges for commercializing hydrophobic cadmium based quantum dots(QD).Polyarylene ether nitriles(PEN)are an example of super-engineering thermoplastics that possess a unique combination of thermal stability,intrinsic fluorescence,biocompatibility and distinct emulsion self-assembly feature.Herein,the co-self-assembly of amphiphilic PEN with hydrophobic CdSe@ZnS QD,confined in the three-dimensional(3D)oil-in-water emulsion droplets,has been explored tofabricate fluorescent microparticles(FMP).It was found that these FMP demonstrated good biocompatibility(cell viability above 90%),while exhibiting a fluorescence emission in aqueous solution that was retained(intensity retention ratio above 80%)within the whole pH range of 1-14,as well as,after being subjected to autoclaving at 120℃for 1 h.Interestingly,it was discovered that introduction of calcium ions in the emulsion self-assembly contributed to in-situ generation of phase changing nanoplates inside the FMP,which led to the photo-thermal modulated solid state fluorescence from drop-casted FMP film.Thanks to their versatile fluorescence,these FMP colloids were exploited as fluorescent probes for macrophages imaging,while micro-patterns with reversible changing of emission color were induced via thermal treatment and direct laser lithography.
基金National Natural Science Foundation of China[81971598,82071456]Shanghai Academic Research Leader Program[21XD1420900]Shanghai Municipal Commission of Health Program[20224Z0002].
文摘Epilepsy is a common yet complex neurological disorder.Historically,antiseizure medications(ASMs)have faced challenges in crossing the blood-brain barrier(BBB)and targeting the epileptogenic zone,creating a bottleneck in seizure management.Certain nanomaterials can facilitate drug penetration through the BBB and enable stimulus-responsive drug release,thereby enhancing targeted and efficient drug utilization while reducing adverse reactions in other brain tissues and peripherally.This article reviews the current researches on stimulus-responsive nanosystems applicable in antiepileptic therapy,as well as nanotechnology applications that improve the brain delivery of ASMs.
基金support of the National Natural Science Foundation of China(Nos.52125205,U20A20166,and 52192614)the National Key R&D Program of China(Nos.2021YFB3200302 and 2021YFB3200304)+2 种基金the Natural Science Foundation of Beijing Municipality(Nos.Z180011 and 2222088)the Shenzhen Science and Technology Program(No.KQTD20170810105439418)the Fundamental Research Funds for the Central Universities.
文摘Intelligent ion gels,which possess highly tunable mechanical,electrical,and stimulus‐responsive properties,have emerged as powerful candidates in the field of artificial intelligence,telemedicine,and health monitoring.To enrich the functionality of ion gels,it is critical to explore the link between the structure and function of ion gels.In this review,we provide an overview of the synthesis path and functional derivatives of ion gels.The conformational relationships of ion gels have been discussed,such as the effect of structure on electrical conductivity as well as sensing properties.From the perspective of stimulus response,the role of ion gels in areas such as bionic haptics,neural devices,artificial muscles,and intelligent displays has also been explored.It is possible that smart ion gels will open up a new horizon in the upcoming smart era,especially after the current challenges are resolved.
基金the National Natural Science Foundation of China (51173018)the National Basic Research Program of China (973 program, 2013CB834704)
文摘Luminescent materials exhibiting emission switching in the solid state have drawn much attention though there is still no clear design strategy for such materials. In this letter, we reported the crystallization induced emission enhancement (CIEE) of di(4-ethoxyphenyl)dibenzofulvene (1), and achieved switching its emission among four different colors through modulation of its molecular packing patterns. We have investigated its potential application as optical recording materials. The twisted conformations of CIEE compounds afford morphology dependent emission and facilitate tuning their emission through modulation of molecular packing patterns. Thus we provide a possible design strategy for solid stimulus responsive luminescent materials.
基金supported in part by the National Natural Science Foundation of China(21621004,31971305,21905196)Tianjin Natural Science Foundation(Basic Research Plan,18JCJQJC47600,19JCQNJC01900)。
文摘Self-assembly exists widely in natural living system and artificial synthetic material system.Administration of self-assemblies of artificial architectures in living cells can be used to explore the molecular physicochemical fundamentals and operating mechanisms of living system,and consequently promote the development of biomedicine.In order to mimic naturally occurring self-assemblies and realize controllable functions,great efforts have been devoted to constructing dynamic assembly of artificial architectures in living cells by responding to intracellular specific stimuli,which can be used to regulate morphology,behaviors and fate of living cells.This review highlights the recent progress on artificial self-assembly in living cells.The molecular fundamentals and characteristics of intracellular environment that can induce the self-assembly of artificial architectures are introduced,and the representative work on dynamic artificial self-assembly in living cells is sketched chronologically.Moreover,intracellular stimuli-mediated pathways of artificial assembly in living cells are categorized,biological effects caused by intracellular self-assembly are summarized,and biomedical applications focusing on therapy and imaging are described.In the end,the perspective and challenges of artificial self-assembly in living cells are fully discussed.It is believed that the grand advances on artificial self-assembly in living cells will contribute to elaborating the molecular mechanisms in cells,and further promoting the biologically and medically-related applications in the future.
