This study marks the birth of visible and selective click covalent assembly.It is achieved by amplifying orthogonal alkyne−azide click chemistry through interfacial multisite interactions between azide/alkyne function...This study marks the birth of visible and selective click covalent assembly.It is achieved by amplifying orthogonal alkyne−azide click chemistry through interfacial multisite interactions between azide/alkyne functionalized polymer hydrogels.Macroscopic assembly of hydrogels via host−guest chemistry or noncovalent interactions such as electrostatic interactions has been reported.Unlike macroscopic supramolecular assembly,here we report visible and selective“click”covalent assembly of hydrogels at the macroscale.LEGO-like hydrogels modified with alkyne and azide groups,respectively,can click together via the formation of covalent bonds.Monomer concentration-dependent assembly and selective covalent assembly have been studied.Notably,macroscopic gel assembly clearly elucidates click preferences and component selectivity not observed in the solution reactions of competing monomers.展开更多
Herein,we developed for the first time two carboxylic acid based intrinsic proton conductors(COOHCOF-1 and COOH-COF-2)via pre-assembly approach.The obtained COOH-COF-1 and COOH-COF-2 not only show outstanding chemical...Herein,we developed for the first time two carboxylic acid based intrinsic proton conductors(COOHCOF-1 and COOH-COF-2)via pre-assembly approach.The obtained COOH-COF-1 and COOH-COF-2 not only show outstanding chemical and thermal stabilities,but also exhibit superhigh intrinsic proton conductive behaviors.Especially,the intrinsic proton conductivity of COOH-COF-2 is up to 2.6×10^(−3) S/cm at 353 K and 98%RH,which is the highest value among all the reported acid functionalized COFs.This work lights up the way for the rational design of functional COFs with remarkably intrinsic proton conducting performance and related practical applications.展开更多
A core feature of two-dimensional covalent organic frameworks is crystallinity, but it remains challenging to gain their thin films with high crystallinity. Here, we presented growth of thin films of two-dimensional c...A core feature of two-dimensional covalent organic frameworks is crystallinity, but it remains challenging to gain their thin films with high crystallinity. Here, we presented growth of thin films of two-dimensional covalent organic frameworks with an average domain size of ~2.83 μm^(2) and maximum domain size of up to ~26.19 μm^(2) using amphiphilic glycine derivatives on water surface. We envisage that this work will inspire the growth of a wide variety of organic two-dimensional materials with high crystallinity and boost their structure property investigations.展开更多
Large-scale use of detergents to remove oil-fouling in industry continuously generates tremendous amounts of wastewater and thus leads to both economic and environmental problems.To develop recyclable oil-fouling remo...Large-scale use of detergents to remove oil-fouling in industry continuously generates tremendous amounts of wastewater and thus leads to both economic and environmental problems.To develop recyclable oil-fouling removal strategy is an appealing solution but a challenging task.Herein,a kind of dynamic imine-based surfactant has been constructed by 2-formylbenzenesulfonic acid sodium salt(FBSS)and linear amines(CnNH_(2),n=6,7,8,10,and 12).Owing to high interfacial activity and strong assembly ability,dynamic FBSS/C8NH_(2)system can remove oil-fouling on multiple substrates for at least 10 cycles,largely reducing the toxicity to ecosystem.At basic pH,the hierarchical assemblies(from vesicle to network and hollow sphere)are formed and boost surfactant molecule enrichment around oil-fouling,leading to highly efficient emulsification.When pH is changed to acidic condition,the surfactant molecules dissociate due to the breaking of imine bonds,and accordingly the emulsion is destroyed and the released oil droplets float to the top layer.After removing the oil-fouling and adjusting the solution back to basic pH,the surfactant assemblies are reconstructed and used for the next oil-fouling cleaning cycle.This study provides a recyclable,efficient and eco-friendly oil-fouling removal approach,satisfying the need of sustainable development.展开更多
To detect monoamine oxidase B(MAO-B), the level of which is one of the most important indicators of neurodegenerative diseases such as Parkinson's disease, a new type of cascade reaction based on the formation of ...To detect monoamine oxidase B(MAO-B), the level of which is one of the most important indicators of neurodegenerative diseases such as Parkinson's disease, a new type of cascade reaction based on the formation of coumarin was applied in this research. After the reaction with MAO-B, the protecting group of hydroxyl group in probes(DEAN-MA and DEAB-MA) was removed, and the fluorescence intensity significantly increased(l_(em) 456 nm) as the structure of coumarin was formed subsequently. The probes showed excellent sensitivity and selectivity to MAO-B. The detection limit of DEAN-MA and DEAB-MA were 0.6ng/mL and 0.2 ng/mL, respectively. We succeeded in detecting MAO-B in vitro and imaging it in human astrocyte(U87).展开更多
The quest for a general and facile way to regulate polymer self-assembled nanostructures with low-to high-order ergodicity is an eternal theme in soft nanoparticle fabrication. Here we present an unprecedented gas-bri...The quest for a general and facile way to regulate polymer self-assembled nanostructures with low-to high-order ergodicity is an eternal theme in soft nanoparticle fabrication. Here we present an unprecedented gas-bridging strategy that allows to use gas to direct polymer self-assembly in continuous and tunable manners. Such system comprises a partner of frustrated Lewis polymers with bulky Lewis acid and base groups. They can together “breathe in” external gases to form gas-bridged structures between the two complementary moieties, which drive their mutual complexation and assemble into polymer nanoparticles of diverse geometries and dimensionalities. This strategy is applicable to a broad family of gas substances including but not limited to carbon oxides, nitrogen oxides, sulfur oxides, and even olefins;moreover, tailoring gas types and levels can dictate distinct assembling evolutionary pathways and deformable behaviors among spherical, fibrous, polymersomal, tubesomal and cubosomal morphologies. We also discover that the gas-based bonding chemistry is the mechanistic basis underlying the phase transitional control and phase window regulation. This will open a new direction of making bespoke polymer nanostructures with gas.展开更多
Radical detection has attracted significant attention recently. Here we have developed a scaffold through covalent assembly principle（OR570）, which could facile applications in detection of oxidative radicals.The pr...Radical detection has attracted significant attention recently. Here we have developed a scaffold through covalent assembly principle（OR570）, which could facile applications in detection of oxidative radicals.The primary advantage of the assembly type probe lies at the turn-on fluorescence signal from a zero background and hence high fluorescence turn-on ratio for sensitive detection of weak signal.展开更多
In this paper, dynamic covalent bond has been employed to construct supra-amphiphile of carbohydrate for the first time. In neutral environment, the molecule was fabricated by reacting a hydrophobic building block bea...In this paper, dynamic covalent bond has been employed to construct supra-amphiphile of carbohydrate for the first time. In neutral environment, the molecule was fabricated by reacting a hydrophobic building block bearing benzoic aldehyde with a hydrophilic building block bearing hydrazine to form a sugar-containing supra-amphiphile based on acylhydrazone bond, The obtained azobenzene- galactopyranoside （Azo-Gal） supra-amphiphile self-assembled to fibrillar structure in water, which showed dual responses to UV light and pH.展开更多
Vectored non-covalent interactions—mainly hydrogen bonding and aromatic interactions—extensively contribute to(bio)-organic self-assembling processes and significantly impact the physicochemical properties of the as...Vectored non-covalent interactions—mainly hydrogen bonding and aromatic interactions—extensively contribute to(bio)-organic self-assembling processes and significantly impact the physicochemical properties of the associated superstructures.However,vectored non-covalent interaction-driven assembly occursmainly along one-dimensional(1D)or three-dimensional(3D)directions,and a two-dimensional(2D)orientation,especially that of multilayered,graphene-like assembly,has been reported less.In this present research,by introducing amino,hydroxyl,and phenyl moieties to the triazine skeleton,supramolecular layered assembly is achieved by vectored non-covalent interactions.The planar hydrogen bonding network results in high stability,with a thermal sustainability of up to about 330°C and a Young’s modulus of up to about 40 GPa.Upon introducing wrinkles by biased hydrogen bonding or aromatic interactions to disturb the planar organization,the stability attenuates.However,the intertwined aromatic interactions prompt a red edge excitation shift effect inside the assemblies,inducing broad-spectrum fluorescence covering nearly the entire visible light region(400–650 nm).We show that bionic,superhydrophobic,pillar-like arrays with contact angles of up to about 170°can be engineered by aromatic interactions using a physical vapor deposition approach,which cannot be realized through hydrogen bonding.Our findings show the feasibility of 2D assembly with engineerable properties by modulating vectored non-covalent interactions.展开更多
Binding of fluorescent molecules to the porous matrix through noncovalent interactions will synergistically expand their application spectrum. In this regard, we report an integrative self-assembly of molecule 1 with ...Binding of fluorescent molecules to the porous matrix through noncovalent interactions will synergistically expand their application spectrum. In this regard, we report an integrative self-assembly of molecule 1 with benzothiadizole and 9,9-dihexyl fluorene units, and covalent organic frameworks(COFs) via an emulsion-modulated polymerization process, within which molecules of 1 are able to interact with the scaffolds of COFs through CH-π interactions. Thus the π-πinteractions between the fluorescent molecules are largely suppressed, giving rise to their remarkable monomer-like optical properties. Of particular interest is that, given by the specific interaction between COFs and a nerve agent simulant diethyl chlorophosphite(DCP), these assembled composites show the ability of ultrasensitive detection of DCP with a detection limit of ~40 ppb. Moreover, the present integrative assembly strategy can be extended to encapsulate multiple fluorescent molecules, enabling the assemblies with white light emission. Our results highlight opportunities for the development of highly emissive porous materials by molecular selfassembly of fluorophores and molecular units of COFs.展开更多
Specific and dynamic biological interactions pave the blueprint of signal networks in cell. For example, a great variety of specific protein-ligand interactions define how intracellular signals flow. Taking advantage ...Specific and dynamic biological interactions pave the blueprint of signal networks in cell. For example, a great variety of specific protein-ligand interactions define how intracellular signals flow. Taking advantage of the specificity of these interactions, we postulate an "affinity-guided covalent conjugation" strategy to lock binding ligands through covalent reactions between the ligand and the receptor protein. The presence of a nucleophile close to the ligand binding site of a protein is sine qua none of this reaction. Specific noncovalent interaction of a ligand derivative(which contains an electrophile at a designed position) to the ligand binding site of the protein brings the electrophile to the close proximity of the nucleophile. Subsequently, a conjugation reaction spontaneously takes place between the nucleophile and the electrophile, and leads to an intermolecular covalent linkage. This strategy was first showcased in coiled coil peptides which include a cysteine mutation at a selected position. The short peptide sequence was used for covalent labeling of cell surface receptors. The same strategy was then used to guide the design of a set of protein Lego bricks for covalent assembly of protein complexes of unnatural geometry. We finally made "reactive peptides" for natural adaptor proteins that play significant roles in signal transduction. The peptides were designed to react with a single domain of the multidomain adaptor protein, delivered into the cytosol of neurons, and re-directed the intracellular signal of neuronal migration. The trilogy of protein labeling, assembly, and inhibition of intracellular signals, all through a specific covalent bond, fully demonstrated the generality and versatility of "affinity-guided covalent conjugation" in various applications.展开更多
基金Guangdong Provincial Pearl River Talents Program (No.2021ZT090195)Guangdong Basic and Applied Basic Research Foundation (No.2020A1515110777)Shenzhen Science,Technology and Innovation Committee (STIC)Shenzhen Key Laboratory Fund (No.ZDSYS20220507161600001)for the financial support for this work.
文摘This study marks the birth of visible and selective click covalent assembly.It is achieved by amplifying orthogonal alkyne−azide click chemistry through interfacial multisite interactions between azide/alkyne functionalized polymer hydrogels.Macroscopic assembly of hydrogels via host−guest chemistry or noncovalent interactions such as electrostatic interactions has been reported.Unlike macroscopic supramolecular assembly,here we report visible and selective“click”covalent assembly of hydrogels at the macroscale.LEGO-like hydrogels modified with alkyne and azide groups,respectively,can click together via the formation of covalent bonds.Monomer concentration-dependent assembly and selective covalent assembly have been studied.Notably,macroscopic gel assembly clearly elucidates click preferences and component selectivity not observed in the solution reactions of competing monomers.
基金supported by the National Natural Science Foundation of China(Nos.21978138 and 22035003)the Fundamental Research Funds for the Central Universities(Nankai University)the Haihe Laboratory of Sustainable Chemical Transformations(No.YYJC202101).
文摘Herein,we developed for the first time two carboxylic acid based intrinsic proton conductors(COOHCOF-1 and COOH-COF-2)via pre-assembly approach.The obtained COOH-COF-1 and COOH-COF-2 not only show outstanding chemical and thermal stabilities,but also exhibit superhigh intrinsic proton conductive behaviors.Especially,the intrinsic proton conductivity of COOH-COF-2 is up to 2.6×10^(−3) S/cm at 353 K and 98%RH,which is the highest value among all the reported acid functionalized COFs.This work lights up the way for the rational design of functional COFs with remarkably intrinsic proton conducting performance and related practical applications.
基金support from the National Natural Science Foundation of China(52061135103,52173296 and 51833011).
文摘A core feature of two-dimensional covalent organic frameworks is crystallinity, but it remains challenging to gain their thin films with high crystallinity. Here, we presented growth of thin films of two-dimensional covalent organic frameworks with an average domain size of ~2.83 μm^(2) and maximum domain size of up to ~26.19 μm^(2) using amphiphilic glycine derivatives on water surface. We envisage that this work will inspire the growth of a wide variety of organic two-dimensional materials with high crystallinity and boost their structure property investigations.
基金the National Natural Science Foundation of China(Nos.21988102,22072161,and 21773261)the Ministry of Science and Technology of the People’s Republic of China(No.2021YFA0716700).
文摘Large-scale use of detergents to remove oil-fouling in industry continuously generates tremendous amounts of wastewater and thus leads to both economic and environmental problems.To develop recyclable oil-fouling removal strategy is an appealing solution but a challenging task.Herein,a kind of dynamic imine-based surfactant has been constructed by 2-formylbenzenesulfonic acid sodium salt(FBSS)and linear amines(CnNH_(2),n=6,7,8,10,and 12).Owing to high interfacial activity and strong assembly ability,dynamic FBSS/C8NH_(2)system can remove oil-fouling on multiple substrates for at least 10 cycles,largely reducing the toxicity to ecosystem.At basic pH,the hierarchical assemblies(from vesicle to network and hollow sphere)are formed and boost surfactant molecule enrichment around oil-fouling,leading to highly efficient emulsification.When pH is changed to acidic condition,the surfactant molecules dissociate due to the breaking of imine bonds,and accordingly the emulsion is destroyed and the released oil droplets float to the top layer.After removing the oil-fouling and adjusting the solution back to basic pH,the surfactant assemblies are reconstructed and used for the next oil-fouling cleaning cycle.This study provides a recyclable,efficient and eco-friendly oil-fouling removal approach,satisfying the need of sustainable development.
基金financially supported by the National Natural Science Foundation of China (Nos. 21572147 and 21472131)
文摘To detect monoamine oxidase B(MAO-B), the level of which is one of the most important indicators of neurodegenerative diseases such as Parkinson's disease, a new type of cascade reaction based on the formation of coumarin was applied in this research. After the reaction with MAO-B, the protecting group of hydroxyl group in probes(DEAN-MA and DEAB-MA) was removed, and the fluorescence intensity significantly increased(l_(em) 456 nm) as the structure of coumarin was formed subsequently. The probes showed excellent sensitivity and selectivity to MAO-B. The detection limit of DEAN-MA and DEAB-MA were 0.6ng/mL and 0.2 ng/mL, respectively. We succeeded in detecting MAO-B in vitro and imaging it in human astrocyte(U87).
基金supported by the National Natural Science Foundation of China (21674022, 51703034)the National Defense Science and Technology Innovation Zone (163 Program)the Shanghai Rising-Star Program (19QA1400700)。
文摘The quest for a general and facile way to regulate polymer self-assembled nanostructures with low-to high-order ergodicity is an eternal theme in soft nanoparticle fabrication. Here we present an unprecedented gas-bridging strategy that allows to use gas to direct polymer self-assembly in continuous and tunable manners. Such system comprises a partner of frustrated Lewis polymers with bulky Lewis acid and base groups. They can together “breathe in” external gases to form gas-bridged structures between the two complementary moieties, which drive their mutual complexation and assemble into polymer nanoparticles of diverse geometries and dimensionalities. This strategy is applicable to a broad family of gas substances including but not limited to carbon oxides, nitrogen oxides, sulfur oxides, and even olefins;moreover, tailoring gas types and levels can dictate distinct assembling evolutionary pathways and deformable behaviors among spherical, fibrous, polymersomal, tubesomal and cubosomal morphologies. We also discover that the gas-based bonding chemistry is the mechanistic basis underlying the phase transitional control and phase window regulation. This will open a new direction of making bespoke polymer nanostructures with gas.
基金supported by the Fundamental Research Funds for the Central Universities (Nos. 1222201718004, WY1514053 and WY1516017)the National Natural Science Foundation of China (Nos. 21372080, 21572061, and 21236002)
文摘Radical detection has attracted significant attention recently. Here we have developed a scaffold through covalent assembly principle（OR570）, which could facile applications in detection of oxidative radicals.The primary advantage of the assembly type probe lies at the turn-on fluorescence signal from a zero background and hence high fluorescence turn-on ratio for sensitive detection of weak signal.
基金National Natural Science Foundation of China (Nos.91527305,21474020,91227203 and 51322306)the Innovation Program of the Shanghai Municipal Education Commission are acknowledged for their financial support
文摘In this paper, dynamic covalent bond has been employed to construct supra-amphiphile of carbohydrate for the first time. In neutral environment, the molecule was fabricated by reacting a hydrophobic building block bearing benzoic aldehyde with a hydrophilic building block bearing hydrazine to form a sugar-containing supra-amphiphile based on acylhydrazone bond, The obtained azobenzene- galactopyranoside （Azo-Gal） supra-amphiphile self-assembled to fibrillar structure in water, which showed dual responses to UV light and pH.
基金supported by the Fund for Creative Research Groups of National Natural Science Foundation of China (No. 51821093)the National Natural Science Foundation of China (Nos. 52175551, 52075484)(KT and DM)+2 种基金the National Key Research and Development Program (SQ2021YFE010405)(KT)Science Foundation Ireland (SFI) through awards Nos. 15/CDA/3491and 12/RC/2275_P2 (DT)computing resources at the SFI/Higher Education Authority Irish Center for High-End Computing (ICHEC)(SG and DT)
文摘Vectored non-covalent interactions—mainly hydrogen bonding and aromatic interactions—extensively contribute to(bio)-organic self-assembling processes and significantly impact the physicochemical properties of the associated superstructures.However,vectored non-covalent interaction-driven assembly occursmainly along one-dimensional(1D)or three-dimensional(3D)directions,and a two-dimensional(2D)orientation,especially that of multilayered,graphene-like assembly,has been reported less.In this present research,by introducing amino,hydroxyl,and phenyl moieties to the triazine skeleton,supramolecular layered assembly is achieved by vectored non-covalent interactions.The planar hydrogen bonding network results in high stability,with a thermal sustainability of up to about 330°C and a Young’s modulus of up to about 40 GPa.Upon introducing wrinkles by biased hydrogen bonding or aromatic interactions to disturb the planar organization,the stability attenuates.However,the intertwined aromatic interactions prompt a red edge excitation shift effect inside the assemblies,inducing broad-spectrum fluorescence covering nearly the entire visible light region(400–650 nm).We show that bionic,superhydrophobic,pillar-like arrays with contact angles of up to about 170°can be engineered by aromatic interactions using a physical vapor deposition approach,which cannot be realized through hydrogen bonding.Our findings show the feasibility of 2D assembly with engineerable properties by modulating vectored non-covalent interactions.
基金supported by the National Natural Science Foundation of China (21703120,21972076,51903140 and 21925604)China Postdoctoral Science Foundation (2019M662324)Taishan Scholars Program of Shandong Province (tsqn201812011)。
文摘Binding of fluorescent molecules to the porous matrix through noncovalent interactions will synergistically expand their application spectrum. In this regard, we report an integrative self-assembly of molecule 1 with benzothiadizole and 9,9-dihexyl fluorene units, and covalent organic frameworks(COFs) via an emulsion-modulated polymerization process, within which molecules of 1 are able to interact with the scaffolds of COFs through CH-π interactions. Thus the π-πinteractions between the fluorescent molecules are largely suppressed, giving rise to their remarkable monomer-like optical properties. Of particular interest is that, given by the specific interaction between COFs and a nerve agent simulant diethyl chlorophosphite(DCP), these assembled composites show the ability of ultrasensitive detection of DCP with a detection limit of ~40 ppb. Moreover, the present integrative assembly strategy can be extended to encapsulate multiple fluorescent molecules, enabling the assemblies with white light emission. Our results highlight opportunities for the development of highly emissive porous materials by molecular selfassembly of fluorophores and molecular units of COFs.
基金supported by the University Grants Committee of Hong Kong (ECS grant CUHK 404812, GRF grants 403711 and 404413, and Ao E/M-09/12)
文摘Specific and dynamic biological interactions pave the blueprint of signal networks in cell. For example, a great variety of specific protein-ligand interactions define how intracellular signals flow. Taking advantage of the specificity of these interactions, we postulate an "affinity-guided covalent conjugation" strategy to lock binding ligands through covalent reactions between the ligand and the receptor protein. The presence of a nucleophile close to the ligand binding site of a protein is sine qua none of this reaction. Specific noncovalent interaction of a ligand derivative(which contains an electrophile at a designed position) to the ligand binding site of the protein brings the electrophile to the close proximity of the nucleophile. Subsequently, a conjugation reaction spontaneously takes place between the nucleophile and the electrophile, and leads to an intermolecular covalent linkage. This strategy was first showcased in coiled coil peptides which include a cysteine mutation at a selected position. The short peptide sequence was used for covalent labeling of cell surface receptors. The same strategy was then used to guide the design of a set of protein Lego bricks for covalent assembly of protein complexes of unnatural geometry. We finally made "reactive peptides" for natural adaptor proteins that play significant roles in signal transduction. The peptides were designed to react with a single domain of the multidomain adaptor protein, delivered into the cytosol of neurons, and re-directed the intracellular signal of neuronal migration. The trilogy of protein labeling, assembly, and inhibition of intracellular signals, all through a specific covalent bond, fully demonstrated the generality and versatility of "affinity-guided covalent conjugation" in various applications.
