Topological supramolecular polymers are responsible for design of innovative materials with unique physical properties but remain a challenging task to prepare by means of supramolecular polymerization.In this contrib...Topological supramolecular polymers are responsible for design of innovative materials with unique physical properties but remain a challenging task to prepare by means of supramolecular polymerization.In this contribution,we present a novel method of region-confined amphiphilic supramolecular polymerization(RASP)in a controllable two-step self-organization pathway,which was certified by a new type of pyridine-oxadiazole alternating 48-membered macrocycles with structurally regional distribution of distinct self-assembling groups that can self-organize into circular supramolecular architectures.Meanwhile,water molecule plays a crucial role in RASP,and the water content in nonpolar solvent chloroform is sensitive to trigger controllable amphiphilic self-organization.Moreover,differing from the traditional rodlike micelles formed by self-assembly of linearly amphiphilic molecules,this approach of RASP exclusively gives rise to the formation of circularly assembled supramolecular polymers.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
We reported a type of strong and highly directional non-covalent interactions based on the dimerization of single-stranded helix to double-stranded helix that can achieve supramolecular polymerization, giving rise to ...We reported a type of strong and highly directional non-covalent interactions based on the dimerization of single-stranded helix to double-stranded helix that can achieve supramolecular polymerization, giving rise to the formation of linear supramolecular polymers.展开更多
Double-crossover-like(DXL)molecules are a series of DNA motifs containing two strands with identical or different sequences.These homo-or hetero-dimers can further polymerize into bulk structures through specific hydr...Double-crossover-like(DXL)molecules are a series of DNA motifs containing two strands with identical or different sequences.These homo-or hetero-dimers can further polymerize into bulk structures through specific hydrogen bonding between sticky ends.DXL molecules have high designability,predictivity and sequence robustness;and their supramolecular polymerization products would easily achieve controllable morphology.In addition,among all available DNA nanomotifs,DXL molecules are small in size so that the cost of DXL-based nanostructures is low.These properties together make DXL-based nanostructures good candidates for patterning,templating,information and matter storage,etc.Herein,we will discuss DXL motifs in terms of the detailed molecular design,and their supramolecular polymerization in various dimensions,and related applications.展开更多
The coordination geometry of d8 transition metal complexes has been successfully exploited as a tool to tune photophysical properties and self-assembly pathways of supramolecular polymerization processes,with a focus ...The coordination geometry of d8 transition metal complexes has been successfully exploited as a tool to tune photophysical properties and self-assembly pathways of supramolecular polymerization processes,with a focus being primarily placed on organic media.Expanding such controlled supramolecular and photophysical properties to assemblies in aqueous media by molecular design is,however,still challenging due to the difficulty in programming noncovalent interactions in water.Herein,we tackle this challenge by analyzing the aqueous self-assembly of amphiphilic Pt(II)complexes of different molecular geometry in order to control self-assembly and metal−metal interactions in aqueous media.To this end,we have designed two Pt(II)complexes,1 and 2,containing an identical oligophenyleneethynylene(OPE)-based aromatic scaffold that differ in the molecular geometry(linear vs V-shaped)imposed by ligand substitution and studied their comparative self-assembly behavior in aqueous media.Even though both molecules follow the isodesmic mechanism of self-assembly,their structural difference strongly influences the molecular packing in aqueous media,which in turn impacts the photophysical properties(i.e.absence or presence of MMLCT)and the self-assembly outcome.While the molecular geometry for 2 enforces short Pt…Pt contacts driven by an efficient face-to-face stacking of the OPE backbone,the antiparallel packing of 1 with slight translational offset does not allow the formation of short Pt…Pt contacts.Such a distinct interplay of interactions for 1 and 2 in aqueous media leads to significant differences in photoluminescence.展开更多
Integrating catalytic reactions with molecular assembly is a promising means of achieving controllable supramolecular polymerization.We report herein a novel and controllable method for in situ supramolecular polymeri...Integrating catalytic reactions with molecular assembly is a promising means of achieving controllable supramolecular polymerization.We report herein a novel and controllable method for in situ supramolecular polymerization via organometallic-catalyzed macromolecular metamorphosis.To this end,covalent polymers with polypentenamer backbones and pendant supramolecular motifs are designed and synthesized.By depolymerizing the polymers with Grubbs catalysts,the supramolecular motifs can be gradually released from the polymers to the solution.Supramolecular polymerization occurs when a critical concentration is reached.The supramolecular polymerization process was readily controlled by varying the rate of the depolymerization reaction.This work presents a novel approach that uses organometallic catalysis to transform covalent polymers into supramolecular polymers.It offers a new means of constructing complex molecular systems in a controllable manner.展开更多
This work confirms the new view of the initiation and propagation mechanism of the anionic polymerization previously proposed, based on the investigation of anionic bulk-polymerization of styrene and α-methyl styrene...This work confirms the new view of the initiation and propagation mechanism of the anionic polymerization previously proposed, based on the investigation of anionic bulk-polymerization of styrene and α-methyl styrene with the help of a self designed microflow device and characterized by GPC and in situ ^7Li NMR. It was found that n-BuLl tended to form the hexameric-aggregated structure and even to form the huge aggregated structure based on the former. These aggregations of initiators could directly initiate the anionic polymerization and form the su-pramolecule aggregations. The supramolecule aggregations inevitably blocked the diffusion of the monomers to the ion-pairs and resulted in a stationary-conversion platform. Then the aggregators were dissociated completely into equal binary-aggregated species, and the polymerization continued again rapidly before the termination. Tetrahy-drofuran （THF） acted as the electron donator, which could push the electron cloud to Li cation and make the aggre- gated ring of the active species rather loosened and facilitated the monomer to insert in. Therefore, a little THF can greatly promote the anionic polymerization. However, further addition of THF might block the channel between the ion-pairs and decrease the propagation rate. It was also found that the aggregated structure of the active species during the anionic polymerization only depends on the initiator aggregations which were formed before the polym-erization.展开更多
Natural adhesives have been widely replaced by industrial adhesives made from petroleum-based products.Compared with that of traditional natural adhesives,modern industrial adhesives show improved adhesion performance...Natural adhesives have been widely replaced by industrial adhesives made from petroleum-based products.Compared with that of traditional natural adhesives,modern industrial adhesives show improved adhesion performance.However,the drawbacks of modern adhesives,including toxicity and nonbiodegradability,drive the need for new and high-performance adhesive materials from renewable and biocompatible natural feedstock.In this study,a new family of acid-sugar adhesive materials exhibiting excellent and long-term adhesion effects was developed inspired by the concept of deep eutectic solvents(DESs).The supramolecular polymerization between natural sugars and acids gave rise to both strong cohesion and adhesion properties.Moreover,high resistance to organic solvents is an advantage of acid-sugar supramolecular adhesive materials.This study not only dramatically expands the applications of DESs but also sheds light on the development of supramolecular adhesive materials as promising alternatives to polymeric adhesives.展开更多
Supramolecular self-assembly in water based on non-covalent bonding is attracting major attention due to the potential of hydrogels and aqueous polymers in biomedical applications.Although supramolecular polymerizatio...Supramolecular self-assembly in water based on non-covalent bonding is attracting major attention due to the potential of hydrogels and aqueous polymers in biomedical applications.Although supramolecular polymerization in organic solvents is well established,the key design features,the assembly mechanisms in water and achieving control over the aggregate structures remain challenging.Here,we present the assembly and disassembly of geometrical isomers of a stiff-stilbene bis-urea amphiphile(SA)in pure water.A remarkable feature of this system is that the(E)-isomer forms supramolecular polymers in both pure water and organic solvents.Taking advantage of this unique property,the hydrophobic effect was studied by comparing the supramolecular assembly in both systems.The assembly process inwater follows an enthalpy-driven nucleation-elongation(cooperative)supramolecular polymerization mechanism with a standard Gibbs free energy(ΔG°=−53 kJ mol^(−1))double the value of the one found in toluene.We attributed this distinctive feature to the hydrophobic effect in water.Furthermore,we discovered an isomer-dependent assembly process,which can be used to control aggregation in aqueous media.Due to the substantial geometric difference between(E)-SA and(Z)-SA,we compared their assembly in water to study the influence of different driving forces involved in the process.The supramolecular polymerization of(E)-SA was cooperatively influenced by hydrogen bonding,π-stacking,and hydrophobic effects,whereas the assembly of(Z)-SAwasmainly driven by hydrophobic effects.As a result,the fiber length of(E)-SA in water is much longer than that of(Z)-SA,presenting opportunities for geometrical control of aggregation in aqueousmedia.展开更多
Our present study demonstrated and explored the solvent effects on the association mechanism of the supramolecular nanomaterials in a series of cyclo-tetrasiloxane-appended alkynylplatinum(II)terpyri-dine complexes.Th...Our present study demonstrated and explored the solvent effects on the association mechanism of the supramolecular nanomaterials in a series of cyclo-tetrasiloxane-appended alkynylplatinum(II)terpyri-dine complexes.Through the delicate balance of molecular interactions,some of these complexes were found to exhibit molecular association prop-erties,with possible morphological transformation in response to solvent polarities.展开更多
Supramolecular polymerization properties have been studied for a series of perylene bisimide(PBI)dyes containing identical hydrogen-bonding amide groups in imide positions but variable number or size of alkoxy substit...Supramolecular polymerization properties have been studied for a series of perylene bisimide(PBI)dyes containing identical hydrogen-bonding amide groups in imide positions but variable number or size of alkoxy substituents in bay-positions.展开更多
Polymerization-induced chiral self-assembly(PICSA)is an efficient strategy that not only allows the construction of the supramolecular chiral assemblies in a controlled manner but also can regulate the morphology in s...Polymerization-induced chiral self-assembly(PICSA)is an efficient strategy that not only allows the construction of the supramolecular chiral assemblies in a controlled manner but also can regulate the morphology in situ.Herein,a series of azobenzene-containing block copolymer(Azo-BCP)assemblies with tunable morphologies and supramolecular chirality were obtained through the PICSA strategy.The supramolecular chirality of Azo-BCP assemblies could be regulated by carbon dioxide(CO_(2))stimulus,and completely recovered by bubbling with Ar.A reversible morphology transformation and chiroptical switching process could also be achieved by the alternative 365 nm UV light irradiation and heatingcooling treatment.Moreover,the supramolecular chirality is thermo-responsive and a reversible chiral-achiral switching was successfully realized,which can be reversibly repeated for at least five times.This work provides a feasible strategy for constructing triple stimuli-responsive supramolecular chiral nano-objects in situ.展开更多
Understanding the precise molecular arrangement of chiral supramolecular polymers is essential not only to comprehend complex superstructures like proteins and DNA but also for the development of next-generation optoe...Understanding the precise molecular arrangement of chiral supramolecular polymers is essential not only to comprehend complex superstructures like proteins and DNA but also for the development of next-generation optoelectronic materials,including materials displaying high-performance circularly polarized luminescence(CPL).Herein,we report the first chiral supramolecular polymer systems based on hydrazone–pyridinium conjugates comprising alkyl chains of different lengths,which afforded control of the apparent supramolecular chirality.Although supramolecular chirality is governed basically by the remote chiral centers of alkyl chains,helicity inversion was achieved by controlling the conditions under which the hydrazone building blocks underwent aggregation(i.e.,solvent compositions or temperature).More importantly,the addition of water to the system led to aggregationinduced hydrazone deprotonation,which resulted in a completely different selfassembly behavior.Structural water molecules played an essential role,forming the assembly’s channel-like backbone,around which hydrazone molecules gathered as a result of hydrogen bonding interactions.Further co-assembly of an achiral hydrazone luminophore with the given supramolecular polymer system allowed the fabrication of a novel CPL-active hydrazone-based material exhibiting a high maximum value for the photoluminescence dissymmetry factor of -2.6×10^(-2).展开更多
Heavy metallic salts are capable to bind with proteins and cause detrimental fibrilization in living cells.Herein,we report a similar case of supramolecular polymerization and thus fibrilization from a liquid crystall...Heavy metallic salts are capable to bind with proteins and cause detrimental fibrilization in living cells.Herein,we report a similar case of supramolecular polymerization and thus fibrilization from a liquid crystalline(LC)block copolymer(BCP)initiated by heavy metallic salts.Analogous to the naturally-occurring process,LC BCP“monomers”could bind with metallic salts to form small aggregates,which functioned as seeds to trigger the subsequent supramolecular polymerization of the rest BCP monomers,to produce highly uniform supramolecular polymers.The lengths of the resultant supramolecular polymer fibrils were linearly proportional to the ratios between the BCP and the metallic salts,and largely influenced by the choice of metallic cations,as well as the counterions.Lastly,this method was used to polymerize two different diblock copolymer“monomers”to produce pentablock supramolecular polymers in a one-pot manner.展开更多
We proposed and demonstrated a kinetically interlocking multiple-units supramolecular polymer-ization strategy.Through rationally designed multi-ple-units monomers,the degree of polymerization(X w)detected was more th...We proposed and demonstrated a kinetically interlocking multiple-units supramolecular polymer-ization strategy.Through rationally designed multi-ple-units monomers,the degree of polymerization(X w)detected was more than 50 with a polydispersi-ty index of∼1.4.The prepared polymers were stable when diluted to 20μM or lower concentrations.展开更多
Based on block copolymer assisted topochemical polymerization,a new strategy for facilely producing robust nanoporous membranes with controlled incorporation of functional groups onto nanopores is developed.As exempli...Based on block copolymer assisted topochemical polymerization,a new strategy for facilely producing robust nanoporous membranes with controlled incorporation of functional groups onto nanopores is developed.As exemplified by preparing nanoporous polypyrrole decorated with amino acids,this strategy exhibits a high degree of freedom for tailoring the surface functionality in the created pores.展开更多
A simple and general strategy is described for preparing network supported catalyst through a one-pot synthetic procedure using supramolecular gel as template.This procedure directly attaches ligand to support during ...A simple and general strategy is described for preparing network supported catalyst through a one-pot synthetic procedure using supramolecular gel as template.This procedure directly attaches ligand to support during fabricating the support.Using this strategy,supported CuBr/di-（2-picolyl） amine catalyst with U-shaped fibrillar network was prepared and used in atom transfer radical polymerization of methyl methacrylate.XPS and SEM characterization of the catalyst revealed homogeneous distribution of ligand,sufficient reactive sites,adequate mechanical strength and macroporosity.The polymerization results demonstrated high activity and reusability of such catalyst.This strategy might be extended to other supported catalysts used in column reactors.展开更多
基金This work was supported by the National Natural Science Foundation of China(Nos.92156012,22071078)the Program for Jilin University Science and Technology Innovative Research Team(JLUSTIRT),China(No.2019TD-36).
文摘Topological supramolecular polymers are responsible for design of innovative materials with unique physical properties but remain a challenging task to prepare by means of supramolecular polymerization.In this contribution,we present a novel method of region-confined amphiphilic supramolecular polymerization(RASP)in a controllable two-step self-organization pathway,which was certified by a new type of pyridine-oxadiazole alternating 48-membered macrocycles with structurally regional distribution of distinct self-assembling groups that can self-organize into circular supramolecular architectures.Meanwhile,water molecule plays a crucial role in RASP,and the water content in nonpolar solvent chloroform is sensitive to trigger controllable amphiphilic self-organization.Moreover,differing from the traditional rodlike micelles formed by self-assembly of linearly amphiphilic molecules,this approach of RASP exclusively gives rise to the formation of circularly assembled supramolecular polymers.
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financially supported by the National Natural Science Foundation of China(Nos.21574054,21722403,and 21420102007)
文摘We reported a type of strong and highly directional non-covalent interactions based on the dimerization of single-stranded helix to double-stranded helix that can achieve supramolecular polymerization, giving rise to the formation of linear supramolecular polymers.
基金financially supported by NSF(Nos.CCF-2107393 and CCMI-2025187 to C.M.).
文摘Double-crossover-like(DXL)molecules are a series of DNA motifs containing two strands with identical or different sequences.These homo-or hetero-dimers can further polymerize into bulk structures through specific hydrogen bonding between sticky ends.DXL molecules have high designability,predictivity and sequence robustness;and their supramolecular polymerization products would easily achieve controllable morphology.In addition,among all available DNA nanomotifs,DXL molecules are small in size so that the cost of DXL-based nanostructures is low.These properties together make DXL-based nanostructures good candidates for patterning,templating,information and matter storage,etc.Herein,we will discuss DXL motifs in terms of the detailed molecular design,and their supramolecular polymerization in various dimensions,and related applications.
基金Deutsche Forschungsgemeinschaft(DFG,German Research Foundation)Project-ID 433682494-SFB 1459 Intelligent Matter)(T.D.and T.K.)。
文摘The coordination geometry of d8 transition metal complexes has been successfully exploited as a tool to tune photophysical properties and self-assembly pathways of supramolecular polymerization processes,with a focus being primarily placed on organic media.Expanding such controlled supramolecular and photophysical properties to assemblies in aqueous media by molecular design is,however,still challenging due to the difficulty in programming noncovalent interactions in water.Herein,we tackle this challenge by analyzing the aqueous self-assembly of amphiphilic Pt(II)complexes of different molecular geometry in order to control self-assembly and metal−metal interactions in aqueous media.To this end,we have designed two Pt(II)complexes,1 and 2,containing an identical oligophenyleneethynylene(OPE)-based aromatic scaffold that differ in the molecular geometry(linear vs V-shaped)imposed by ligand substitution and studied their comparative self-assembly behavior in aqueous media.Even though both molecules follow the isodesmic mechanism of self-assembly,their structural difference strongly influences the molecular packing in aqueous media,which in turn impacts the photophysical properties(i.e.absence or presence of MMLCT)and the self-assembly outcome.While the molecular geometry for 2 enforces short Pt…Pt contacts driven by an efficient face-to-face stacking of the OPE backbone,the antiparallel packing of 1 with slight translational offset does not allow the formation of short Pt…Pt contacts.Such a distinct interplay of interactions for 1 and 2 in aqueous media leads to significant differences in photoluminescence.
基金We gratefully acknowledge the financial support from National Key R&D Program of China(grant no.2021YFA1501600)National Natural Science Foundation of China(grant no.21901077)+2 种基金Natural Science Foundation of Guangdong Province(grant no.2016ZT06C322)Open Project of State Key Laboratory for Supramolecular Structure and Materials(grant no.SKLSSM2021012)the Research Fund Program of Guangdong Provincial Key Laboratory of Functional and Intelligent Hybrid Materials and Devices(grant no.2019B121203003).
文摘Integrating catalytic reactions with molecular assembly is a promising means of achieving controllable supramolecular polymerization.We report herein a novel and controllable method for in situ supramolecular polymerization via organometallic-catalyzed macromolecular metamorphosis.To this end,covalent polymers with polypentenamer backbones and pendant supramolecular motifs are designed and synthesized.By depolymerizing the polymers with Grubbs catalysts,the supramolecular motifs can be gradually released from the polymers to the solution.Supramolecular polymerization occurs when a critical concentration is reached.The supramolecular polymerization process was readily controlled by varying the rate of the depolymerization reaction.This work presents a novel approach that uses organometallic catalysis to transform covalent polymers into supramolecular polymers.It offers a new means of constructing complex molecular systems in a controllable manner.
基金Financial supports for this work from the Nature Science Foundation of China for the Major Program （No. 50933002）, the National High Technology Re-search and Development Program of China （863 Pro-gram, No. 2012AA040306） and Shanghai Leading Academic Discipline Project （No. B502） are gratefully acknowledged.
文摘This work confirms the new view of the initiation and propagation mechanism of the anionic polymerization previously proposed, based on the investigation of anionic bulk-polymerization of styrene and α-methyl styrene with the help of a self designed microflow device and characterized by GPC and in situ ^7Li NMR. It was found that n-BuLl tended to form the hexameric-aggregated structure and even to form the huge aggregated structure based on the former. These aggregations of initiators could directly initiate the anionic polymerization and form the su-pramolecule aggregations. The supramolecule aggregations inevitably blocked the diffusion of the monomers to the ion-pairs and resulted in a stationary-conversion platform. Then the aggregators were dissociated completely into equal binary-aggregated species, and the polymerization continued again rapidly before the termination. Tetrahy-drofuran （THF） acted as the electron donator, which could push the electron cloud to Li cation and make the aggre- gated ring of the active species rather loosened and facilitated the monomer to insert in. Therefore, a little THF can greatly promote the anionic polymerization. However, further addition of THF might block the channel between the ion-pairs and decrease the propagation rate. It was also found that the aggregated structure of the active species during the anionic polymerization only depends on the initiator aggregations which were formed before the polym-erization.
基金The authors gratefully acknowledge the National Natural Science Foundation of China(nos.21704024 and 21878326)the Huxiang Young Talent Program from Hunan Province(no.2018RS3036)the Fundamental Research Funds for the Central Universities from Hunan University,and the Training Program for Excellent Young Innovators of Changsha(no.kq1905049)for financial support.
文摘Natural adhesives have been widely replaced by industrial adhesives made from petroleum-based products.Compared with that of traditional natural adhesives,modern industrial adhesives show improved adhesion performance.However,the drawbacks of modern adhesives,including toxicity and nonbiodegradability,drive the need for new and high-performance adhesive materials from renewable and biocompatible natural feedstock.In this study,a new family of acid-sugar adhesive materials exhibiting excellent and long-term adhesion effects was developed inspired by the concept of deep eutectic solvents(DESs).The supramolecular polymerization between natural sugars and acids gave rise to both strong cohesion and adhesion properties.Moreover,high resistance to organic solvents is an advantage of acid-sugar supramolecular adhesive materials.This study not only dramatically expands the applications of DESs but also sheds light on the development of supramolecular adhesive materials as promising alternatives to polymeric adhesives.
基金Financial support from the Netherlands Organization for Scientific Research(NWO-CW)the European Research Council(ERC,advanced grant no.694345 to B.L.F.)+2 种基金the Dutch Ministry of Education,Culture and Science(Gravitation program no.024.001.035)the China Scholarship Council(CSC,no.201707040064 to F.X.)the Marie Skłodowska-Curie Actions(Individual Fellowships no.838280 to S.C.and no.793082 to L.P.)is gratefully acknowledged.
文摘Supramolecular self-assembly in water based on non-covalent bonding is attracting major attention due to the potential of hydrogels and aqueous polymers in biomedical applications.Although supramolecular polymerization in organic solvents is well established,the key design features,the assembly mechanisms in water and achieving control over the aggregate structures remain challenging.Here,we present the assembly and disassembly of geometrical isomers of a stiff-stilbene bis-urea amphiphile(SA)in pure water.A remarkable feature of this system is that the(E)-isomer forms supramolecular polymers in both pure water and organic solvents.Taking advantage of this unique property,the hydrophobic effect was studied by comparing the supramolecular assembly in both systems.The assembly process inwater follows an enthalpy-driven nucleation-elongation(cooperative)supramolecular polymerization mechanism with a standard Gibbs free energy(ΔG°=−53 kJ mol^(−1))double the value of the one found in toluene.We attributed this distinctive feature to the hydrophobic effect in water.Furthermore,we discovered an isomer-dependent assembly process,which can be used to control aggregation in aqueous media.Due to the substantial geometric difference between(E)-SA and(Z)-SA,we compared their assembly in water to study the influence of different driving forces involved in the process.The supramolecular polymerization of(E)-SA was cooperatively influenced by hydrogen bonding,π-stacking,and hydrophobic effects,whereas the assembly of(Z)-SAwasmainly driven by hydrophobic effects.As a result,the fiber length of(E)-SA in water is much longer than that of(Z)-SA,presenting opportunities for geometrical control of aggregation in aqueousmedia.
基金This work was also sup-ported by the University Grants Committee Areas of Excellence(AoE)Scheme(AoE/P-03/08)a General Research Fund(GRF)grant from the Research Grants Council of Hong Kong Special Administrative Region,P.R.China(HKU 17304715).
文摘Our present study demonstrated and explored the solvent effects on the association mechanism of the supramolecular nanomaterials in a series of cyclo-tetrasiloxane-appended alkynylplatinum(II)terpyri-dine complexes.Through the delicate balance of molecular interactions,some of these complexes were found to exhibit molecular association prop-erties,with possible morphological transformation in response to solvent polarities.
文摘Supramolecular polymerization properties have been studied for a series of perylene bisimide(PBI)dyes containing identical hydrogen-bonding amide groups in imide positions but variable number or size of alkoxy substituents in bay-positions.
基金financial support from the National Natural Science Foundation of China(Nos.92056111 and 21971180)Nature Science Key Basic Research of Jiangsu Province for Higher Education(No.19KJA360006)+1 种基金Postgraduate Research&Practice Innovation Program of Jiangsu Province(No.KYCX202655)the Priority Academic Program Development(PAPD)of Jiangsu Higher Education Institutions supported this work。
文摘Polymerization-induced chiral self-assembly(PICSA)is an efficient strategy that not only allows the construction of the supramolecular chiral assemblies in a controlled manner but also can regulate the morphology in situ.Herein,a series of azobenzene-containing block copolymer(Azo-BCP)assemblies with tunable morphologies and supramolecular chirality were obtained through the PICSA strategy.The supramolecular chirality of Azo-BCP assemblies could be regulated by carbon dioxide(CO_(2))stimulus,and completely recovered by bubbling with Ar.A reversible morphology transformation and chiroptical switching process could also be achieved by the alternative 365 nm UV light irradiation and heatingcooling treatment.Moreover,the supramolecular chirality is thermo-responsive and a reversible chiral-achiral switching was successfully realized,which can be reversibly repeated for at least five times.This work provides a feasible strategy for constructing triple stimuli-responsive supramolecular chiral nano-objects in situ.
基金National Research Foundation of Korea,Grant/Award Number:2012M3A7B4049677Nano Material Development Program,Grant/Award Number:2020R1A6A3A01100092+1 种基金Basic ScienceResearch ProgramInstitute forBasic Science,Grant/Award Number:IBS-R019-D1。
文摘Understanding the precise molecular arrangement of chiral supramolecular polymers is essential not only to comprehend complex superstructures like proteins and DNA but also for the development of next-generation optoelectronic materials,including materials displaying high-performance circularly polarized luminescence(CPL).Herein,we report the first chiral supramolecular polymer systems based on hydrazone–pyridinium conjugates comprising alkyl chains of different lengths,which afforded control of the apparent supramolecular chirality.Although supramolecular chirality is governed basically by the remote chiral centers of alkyl chains,helicity inversion was achieved by controlling the conditions under which the hydrazone building blocks underwent aggregation(i.e.,solvent compositions or temperature).More importantly,the addition of water to the system led to aggregationinduced hydrazone deprotonation,which resulted in a completely different selfassembly behavior.Structural water molecules played an essential role,forming the assembly’s channel-like backbone,around which hydrazone molecules gathered as a result of hydrogen bonding interactions.Further co-assembly of an achiral hydrazone luminophore with the given supramolecular polymer system allowed the fabrication of a novel CPL-active hydrazone-based material exhibiting a high maximum value for the photoluminescence dissymmetry factor of -2.6×10^(-2).
基金financially supported by the National Natural Science Foundation of China(Nos.51973019 and 22175024).
文摘Heavy metallic salts are capable to bind with proteins and cause detrimental fibrilization in living cells.Herein,we report a similar case of supramolecular polymerization and thus fibrilization from a liquid crystalline(LC)block copolymer(BCP)initiated by heavy metallic salts.Analogous to the naturally-occurring process,LC BCP“monomers”could bind with metallic salts to form small aggregates,which functioned as seeds to trigger the subsequent supramolecular polymerization of the rest BCP monomers,to produce highly uniform supramolecular polymers.The lengths of the resultant supramolecular polymer fibrils were linearly proportional to the ratios between the BCP and the metallic salts,and largely influenced by the choice of metallic cations,as well as the counterions.Lastly,this method was used to polymerize two different diblock copolymer“monomers”to produce pentablock supramolecular polymers in a one-pot manner.
基金This work was supported by the National Natural Science Foundation of China(No.21890731 and 21821001).
文摘We proposed and demonstrated a kinetically interlocking multiple-units supramolecular polymer-ization strategy.Through rationally designed multi-ple-units monomers,the degree of polymerization(X w)detected was more than 50 with a polydispersi-ty index of∼1.4.The prepared polymers were stable when diluted to 20μM or lower concentrations.
基金financial support from the Ministry of Science and Technology of the People's Republic of China(MOST,Nos.2017YFA0204501,2013CB834502)National Natural Science Foundation of China(NSFC,Nos.21773135,21473098 and 21421064)。
文摘Based on block copolymer assisted topochemical polymerization,a new strategy for facilely producing robust nanoporous membranes with controlled incorporation of functional groups onto nanopores is developed.As exemplified by preparing nanoporous polypyrrole decorated with amino acids,this strategy exhibits a high degree of freedom for tailoring the surface functionality in the created pores.
基金support from the National Natural Science Foundation of China(Nos.20574041 and 20874055)Hi-tech Research and Development Program(863 plan) of China(No.2009AA062903)
文摘A simple and general strategy is described for preparing network supported catalyst through a one-pot synthetic procedure using supramolecular gel as template.This procedure directly attaches ligand to support during fabricating the support.Using this strategy,supported CuBr/di-（2-picolyl） amine catalyst with U-shaped fibrillar network was prepared and used in atom transfer radical polymerization of methyl methacrylate.XPS and SEM characterization of the catalyst revealed homogeneous distribution of ligand,sufficient reactive sites,adequate mechanical strength and macroporosity.The polymerization results demonstrated high activity and reusability of such catalyst.This strategy might be extended to other supported catalysts used in column reactors.
