Self-healing materials have been developed over the past decade with the recovery ability after damage.However,most researches focused on the self-healing process at three-dimension.Herein,we prepare monolayer self-he...Self-healing materials have been developed over the past decade with the recovery ability after damage.However,most researches focused on the self-healing process at three-dimension.Herein,we prepare monolayer self-healing hydrogen-bond-based supramolecular polymer film and explore the self-healing process at the two-dimensional limit.The healing process,which can be reversibly repeated for at least three times,is influenced by the temperature,the molecule-substrate interaction and the substrate roughness.In the application,the monolayer self-healing polymer film can be used to modify the SiO2 dielectric for copper phthalocyanine field effect transistor with improved mobility.This work will be valuable for developing two-dimensional functional self-healing materials in the future.展开更多
Chiral supramolecular assembly of π-conjugated luminophores provides a promising avenue for enhancing circularly polarized luminescence.In this study,we shed light on the impact of π-conjugation length on circularly...Chiral supramolecular assembly of π-conjugated luminophores provides a promising avenue for enhancing circularly polarized luminescence.In this study,we shed light on the impact of π-conjugation length on circularly polarized luminescent performance of the resulting supramolecular assemblies,by designing a tetra-cyanostilbene monomeric compound alongside two dicyanostilbene control compounds.These cyanostilbene-based compounds possess the ability to form chiral supramolecular polymers in toluene,driven by a synergistic combination of intermolecular hydrogen bonding and π-stacking interactions.The extended π π-aromatic skeleton brings bathochromic-shifted fluorescence and enhanced intermolecular stacking capability for the tetra-cyanostilbene compound.Consequently,chiral supramolecular assemblies formed by the tetra-cyanostilbene compound demonstrate a remarkable two-fold increase in g_(lum) values relative to the assemblies formed by the dicyanostilbene compounds.Overall,this study provides valuable insights into the relationship between-conjugation length and the circularly polarized luminescent performance of π-conjugatedsupramolecularassemblies.展开更多
Pillar[n]arenes are a novel class of macrocyclic hosts reported by Ogoshi and co-workers in 2008. Because of their rigid pillar structures, interesting host-guest properties and ease of modifications, pillar[n]arenes ...Pillar[n]arenes are a novel class of macrocyclic hosts reported by Ogoshi and co-workers in 2008. Because of their rigid pillar structures, interesting host-guest properties and ease of modifications, pillar[n]arenes have been developed rapidly in the field of functional materials and biomedicine. The modifications of pillar[n]arenes at different positions can give them varied characteristics. Functional groups can be introduced into one position of pillar[n]arenes without changing host-guest properties of pillar[n]arenes. A series of pillar[n]arene dimers, trimers, tetramers and metallacycles can be constructed by mono-functionalized pillar[n]arenes. In this review, two synthetic methods of mono-functionalized pillar[n]arenes are summarized and structures containing mono-functionalized pillar[n]arenes are described. Furthermore, the applications of mono-functionalized pillar[n]arenes in different fields (e.g., supramolecular polymers, sensors, molecular machines, catalysis, biological applications and light-harvesting systems) are also introduced. Hopefully, this article will be useful for researchers studying pillar[n]arenes, especially the mono-functionalized pillar[n]arenes.展开更多
A new method of light-powered dissipative supra-molecular polymerization is established,in which supramolecular polymerization is implemented in the far-from-equilibrium state.A bifunctional mono-mer containing two vi...A new method of light-powered dissipative supra-molecular polymerization is established,in which supramolecular polymerization is implemented in the far-from-equilibrium state.A bifunctional mono-mer containing two viologen moieties was designed.Upon inputting energy by light,the sys-tem was driven far from equilibrium,and the mono-mers were photoreduced and activated to form supramolecular polymers driven by 2∶1 host–guest complexation of the viologen cation radical and cucurbit[8]uril.As the system returned to equilibri-um,the supramolecular polymers depolymerized spontaneously by air oxidation.This method works in both linear and in cross-linked supramolecular polymerization.The strategy of light-powered dis-sipative supramolecular polymerization is anticipat-ed to have potential in the fabrication of functional supramolecular materials,especially in creating novel“living”materials.展开更多
Quantitatively establishing the correlation between nanoparticle size and fluorescence is essential for understanding the behavior and functionality of fluorescent nanoparticles(FNPs).However,such exploration focusing...Quantitatively establishing the correlation between nanoparticle size and fluorescence is essential for understanding the behavior and functionality of fluorescent nanoparticles(FNPs).However,such exploration focusing on organic FNPs has not been achieved to date.Herein,we employ the use of supramolecular polymeric FNPs prepared from tetraphenylethylene-based bis-ureidopyrimidinone monomers(bis-UPys)to relate the size to the fluorescence of organic nanoparticles.At an equal concentration of bis-UPys,a logarithmic relationship between them is built with a correlation coefficient higher than 0.96.Theoretical calculations indicate that variations in fluorescence intensity among FNPs of different sizes are attributed to the distinct molecular packing environments at the surface and within the interior of the nanoparticles.This leads to different nonradiative decay rates of the embedded and exposed bis-UPys and thereby changes the overall fluorescence quantum yield of nanoparticles due to their different specific surface areas.The established fluorescence intensity-size correlation possesses fine universality and reliability,and it is successfully utilized to estimate the sizes of other nanoparticles,including those in highly diluted dispersions of FNPs.This work paves a new way for the simple and real-time determination of nanoparticle sizes and offers an attractive paradigm to optimize nanoparticle functionalities by the size effect.展开更多
Constructing high strength pH sensitive supramolecular polymer hydrogel remains very challenging due to the unavoidable network swelling caused by ionization of acid or basic groups at a specified pH.In this work,we p...Constructing high strength pH sensitive supramolecular polymer hydrogel remains very challenging due to the unavoidable network swelling caused by ionization of acid or basic groups at a specified pH.In this work,we proposed a simple and very convenient approach to fabricate high strength pH responsive supramolecular polymer(SP) hydrogels by one-pot copolymerization of N-acryloyl glycinamide(NAGA) and 2-vinyl-4,6-diamino-1,3,5-triazine(VDT),two feature hydrogen bonding monomers.In these PNAGA-PVDT SP hydrogels obtained,the hydrogen bonding of NAGA was shown to play a dominant role in reinforcing strength,while the hydrogen bonding of diaminotriazine served as a pH sensitive moiety.At pH 3,the mechanical properties of PNAGA-PVDT hydrogels decreased to a different extent due to the breakup of hydrogen bonding;in contrast,the hydrogel resumed the original strength while pH was raised to 7.4 because of reconstruction of hydrogen bonding.Over the selected pH range,the PNAGA-PVDT hydrogels exhibited up to 1.25 MPa tensile strength,845% breaking strain,69 kPa Young's modulus and 21 MPa compressive strength.This novel high strength pH-responsive SP hydrogels may find applications in biomedical and industrial fields.展开更多
Stepwise energy transfer is ubiquitous in natural photosynthesis,which greatly promotes the widespread use of solar energy.Herein,we constructed a supramolecular light harvesting system based on sequential energy tran...Stepwise energy transfer is ubiquitous in natural photosynthesis,which greatly promotes the widespread use of solar energy.Herein,we constructed a supramolecular light harvesting system based on sequential energy transfer through the hierarchical self-assembly of M,which contains a cyanostilbene core flanked by two ureidopyrimidinone motifs,endowing itself with both aggregation-induced emission behavior and quadruple hydrogen bonding ability.The monomer M can self-assemble into hydrogen bonded polymers and then form supramolecular polymeric nanoparticles in water through a mini-emulsion process.The nanoparticles were further utilized to encapsulate the relay acceptor ESY and the final acceptor NDI to form a two-step FRET system.Tunable fluorescence including a white-light emission was successfully achieved.Our work not only shows a desirable way for the fabrication of efficient two-step light harvesting systems,but also shows great potential in tunable photoluminescent nanomaterials.展开更多
基金supported by National Program for Thousand Young Talents of China,the National Natural Science Foundation of China(Nos.51773041,21544001,21603038)Shanghai Committee of Science and Technology in China(No.18ZR1404900)Fudan University
文摘Self-healing materials have been developed over the past decade with the recovery ability after damage.However,most researches focused on the self-healing process at three-dimension.Herein,we prepare monolayer self-healing hydrogen-bond-based supramolecular polymer film and explore the self-healing process at the two-dimensional limit.The healing process,which can be reversibly repeated for at least three times,is influenced by the temperature,the molecule-substrate interaction and the substrate roughness.In the application,the monolayer self-healing polymer film can be used to modify the SiO2 dielectric for copper phthalocyanine field effect transistor with improved mobility.This work will be valuable for developing two-dimensional functional self-healing materials in the future.
基金supported by International Partnership Program of the Chinese Academy of Sciences(Grant No.123GJHZ2022064MI)the Collaborative Innovation Program of Hefei Science Center,CAS(No.2022HSC-CIP014)+1 种基金the Fundamental Research Funds for the Central Universities(YD2060002036)the Hospital Level Project of Shanghai Sixth People's Hospital in 2020(DY2020017).
文摘Chiral supramolecular assembly of π-conjugated luminophores provides a promising avenue for enhancing circularly polarized luminescence.In this study,we shed light on the impact of π-conjugation length on circularly polarized luminescent performance of the resulting supramolecular assemblies,by designing a tetra-cyanostilbene monomeric compound alongside two dicyanostilbene control compounds.These cyanostilbene-based compounds possess the ability to form chiral supramolecular polymers in toluene,driven by a synergistic combination of intermolecular hydrogen bonding and π-stacking interactions.The extended π π-aromatic skeleton brings bathochromic-shifted fluorescence and enhanced intermolecular stacking capability for the tetra-cyanostilbene compound.Consequently,chiral supramolecular assemblies formed by the tetra-cyanostilbene compound demonstrate a remarkable two-fold increase in g_(lum) values relative to the assemblies formed by the dicyanostilbene compounds.Overall,this study provides valuable insights into the relationship between-conjugation length and the circularly polarized luminescent performance of π-conjugatedsupramolecularassemblies.
基金the National Natural Science Foundation of China(No.22101043)the Fundamental Research Funds for the Central Universities(No.N2205013)and Northeastern University for financial support.
文摘Pillar[n]arenes are a novel class of macrocyclic hosts reported by Ogoshi and co-workers in 2008. Because of their rigid pillar structures, interesting host-guest properties and ease of modifications, pillar[n]arenes have been developed rapidly in the field of functional materials and biomedicine. The modifications of pillar[n]arenes at different positions can give them varied characteristics. Functional groups can be introduced into one position of pillar[n]arenes without changing host-guest properties of pillar[n]arenes. A series of pillar[n]arene dimers, trimers, tetramers and metallacycles can be constructed by mono-functionalized pillar[n]arenes. In this review, two synthetic methods of mono-functionalized pillar[n]arenes are summarized and structures containing mono-functionalized pillar[n]arenes are described. Furthermore, the applications of mono-functionalized pillar[n]arenes in different fields (e.g., supramolecular polymers, sensors, molecular machines, catalysis, biological applications and light-harvesting systems) are also introduced. Hopefully, this article will be useful for researchers studying pillar[n]arenes, especially the mono-functionalized pillar[n]arenes.
基金This work is supported financially by the National Natural Science Foundation of China(21434004,21890731,21821001,and 91527000)P.Z.is supported by the Na-tional Natural Science Foundation of China(21771103)the Natural Science Foundation of Jiangsu Province(BK20160639)。
文摘A new method of light-powered dissipative supra-molecular polymerization is established,in which supramolecular polymerization is implemented in the far-from-equilibrium state.A bifunctional mono-mer containing two viologen moieties was designed.Upon inputting energy by light,the sys-tem was driven far from equilibrium,and the mono-mers were photoreduced and activated to form supramolecular polymers driven by 2∶1 host–guest complexation of the viologen cation radical and cucurbit[8]uril.As the system returned to equilibri-um,the supramolecular polymers depolymerized spontaneously by air oxidation.This method works in both linear and in cross-linked supramolecular polymerization.The strategy of light-powered dis-sipative supramolecular polymerization is anticipat-ed to have potential in the fabrication of functional supramolecular materials,especially in creating novel“living”materials.
基金National Key R&D Program of China,Grant/Award Number:2022YFA1505900National Natural Science Foundation of China,Grant/Award Numbers:22105016,22173006+1 种基金Open Fund of Guangdong Provincial Key Laboratory of Luminescence,South China University of Technology,Grant/Award Number:2019B030301003Beijing Natural Science Foundation,Grant/Award Number:2222027。
文摘Quantitatively establishing the correlation between nanoparticle size and fluorescence is essential for understanding the behavior and functionality of fluorescent nanoparticles(FNPs).However,such exploration focusing on organic FNPs has not been achieved to date.Herein,we employ the use of supramolecular polymeric FNPs prepared from tetraphenylethylene-based bis-ureidopyrimidinone monomers(bis-UPys)to relate the size to the fluorescence of organic nanoparticles.At an equal concentration of bis-UPys,a logarithmic relationship between them is built with a correlation coefficient higher than 0.96.Theoretical calculations indicate that variations in fluorescence intensity among FNPs of different sizes are attributed to the distinct molecular packing environments at the surface and within the interior of the nanoparticles.This leads to different nonradiative decay rates of the embedded and exposed bis-UPys and thereby changes the overall fluorescence quantum yield of nanoparticles due to their different specific surface areas.The established fluorescence intensity-size correlation possesses fine universality and reliability,and it is successfully utilized to estimate the sizes of other nanoparticles,including those in highly diluted dispersions of FNPs.This work paves a new way for the simple and real-time determination of nanoparticle sizes and offers an attractive paradigm to optimize nanoparticle functionalities by the size effect.
基金supported by the National Natural Science Foundation of China(Grant No.51325305)National Key Research and Development Program(GrantNo.2016YFC1101301)Tianjin Municipal Natural Science Foundation(Grant Nos.13ZCZDSY00900,15JCZDJC38000)
文摘Constructing high strength pH sensitive supramolecular polymer hydrogel remains very challenging due to the unavoidable network swelling caused by ionization of acid or basic groups at a specified pH.In this work,we proposed a simple and very convenient approach to fabricate high strength pH responsive supramolecular polymer(SP) hydrogels by one-pot copolymerization of N-acryloyl glycinamide(NAGA) and 2-vinyl-4,6-diamino-1,3,5-triazine(VDT),two feature hydrogen bonding monomers.In these PNAGA-PVDT SP hydrogels obtained,the hydrogen bonding of NAGA was shown to play a dominant role in reinforcing strength,while the hydrogen bonding of diaminotriazine served as a pH sensitive moiety.At pH 3,the mechanical properties of PNAGA-PVDT hydrogels decreased to a different extent due to the breakup of hydrogen bonding;in contrast,the hydrogel resumed the original strength while pH was raised to 7.4 because of reconstruction of hydrogen bonding.Over the selected pH range,the PNAGA-PVDT hydrogels exhibited up to 1.25 MPa tensile strength,845% breaking strain,69 kPa Young's modulus and 21 MPa compressive strength.This novel high strength pH-responsive SP hydrogels may find applications in biomedical and industrial fields.
基金the financial support from the National Natural Science Foundation of China(No.21702020)We also acknowledge the analytical testing support from Analysis and Testing Center,NERC Biomass of Changzhou University.L.Z.acknowledges the Postgraduate Research&Practice Innovation Program of Jiangsu Province(No.KYCX22_3012).
文摘Stepwise energy transfer is ubiquitous in natural photosynthesis,which greatly promotes the widespread use of solar energy.Herein,we constructed a supramolecular light harvesting system based on sequential energy transfer through the hierarchical self-assembly of M,which contains a cyanostilbene core flanked by two ureidopyrimidinone motifs,endowing itself with both aggregation-induced emission behavior and quadruple hydrogen bonding ability.The monomer M can self-assemble into hydrogen bonded polymers and then form supramolecular polymeric nanoparticles in water through a mini-emulsion process.The nanoparticles were further utilized to encapsulate the relay acceptor ESY and the final acceptor NDI to form a two-step FRET system.Tunable fluorescence including a white-light emission was successfully achieved.Our work not only shows a desirable way for the fabrication of efficient two-step light harvesting systems,but also shows great potential in tunable photoluminescent nanomaterials.
