We provided a short review on the recent progresses in computer simulations of adsorption and self-assembly of amphiphilic molecules.Owing to the extensive applications of amphiphilic molecules,it is very important to...We provided a short review on the recent progresses in computer simulations of adsorption and self-assembly of amphiphilic molecules.Owing to the extensive applications of amphiphilic molecules,it is very important to understand thoroughly the effects of the detailed chemistry,solid surfaces and the degree of confinement on the aggregate morphologies and kinetics of self-assembly for amphiphilic systems.In this review we paid special attention on(i)morphologies of adsorbed surfactants on solid surfaces,(ii)self-assembly in confined systems,and(iii)kinetic processes involving amphiphilic molecules.展开更多
In this study,the benign target double terpyridine parts based amphiphilic ionic molecules(AIMs 1,2)and the reference single terpyridine segment included AIMs(AIMs 3,4)were synthesized through a multi-step method,and ...In this study,the benign target double terpyridine parts based amphiphilic ionic molecules(AIMs 1,2)and the reference single terpyridine segment included AIMs(AIMs 3,4)were synthesized through a multi-step method,and the molecular structures were fully characterized.The excellent anticorrosion of the target AIMs for copper surface in H_(2)SO_(4) solution was demonstrated by the electrochemistry analysis,which was more superior over those of the reference AIMs.The standard adsorption free energy changes of the target AIMs calculated by the adsorption isotherms were lower than -40 kJ·mol^(-1),suggesting an intensified chemical adsorption on metal surface.The molecular modeling and molecular dynamic computation of the studied AIMs were performed,demonstrating that the target AIMs exhibited lower highest occupied molecular orbital-lowest unoccupied molecular orbital energy gaps and greater adsorption energies than the reference ones.The chemical adsorption of the AIMs on metal surface was revealed by various spectroscopic methods including scanning electron microscopy,atomic force microscopy,Fourier transform infrared spectroscopy,attenuated total reflection infrared spectroscopy,Raman and X-ray diffraction.展开更多
Bilayer membranes self-assembled from amphiphilic molecules such as lipids, surfactants, and block copolymers are ubiquitous in biological and physiochemical systems. The shape and structure of bilayer membranes depen...Bilayer membranes self-assembled from amphiphilic molecules such as lipids, surfactants, and block copolymers are ubiquitous in biological and physiochemical systems. The shape and structure of bilayer membranes depend crucially on their mechanical properties such as surface tension, bending moduli, and line tension. Understanding how the molecular properties of the amphiphiles determine the structure and mechanics of the self-assembled bilayers requires a molecularly detailed theoretical framework. The self-consistent field theory provides such a theoretical framework, which is capable of accurately predicting the mechanical parameters of self-assembled bilayer membranes. In this mini review we summarize the formulation of the self-consistent field theory, as exemplified by a model system composed of flexible amphiphilic chains dissolved in hydrophilic polymeric solvents, and its application to the study of self-assembled bilayer membranes.展开更多
The construction of highly ordered organizations through self-assembly is one of the most popular phenomena both in natural and artificial environments.Amphiphilic molecules are the most commonly used building blocks ...The construction of highly ordered organizations through self-assembly is one of the most popular phenomena both in natural and artificial environments.Amphiphilic molecules are the most commonly used building blocks for the self-assembly,which are conventionally known as amphiphilic low molecular weight surfactants with polar heads and nonpolar tails,or amphiphilic block copolymers(BCPs)consisting of covalently bonded hydrophilic and hydrophobic block chains.Compared with single surfactant self-assembly system,binary amphiphiles co-assembly systems composing of both small mass surfactants and amphiphilic BCPs feature high flexibilities and versatilities in materials designing and structure regulation,ascribing to the vast possibilities of intermolecular interactions within the systems and facile component modulations during the assembly processes.The amphiphilic features of the two kinds of molecules endow them with similar self-assembly behaviors,while the unique and distinct characters of each kind of amphiphiles lead to various complex but highly diversified co-assembly systems.According to the roles of the surfactant played in the co-assembly system,in this review,we summarize the binary coassembly systems from three distinct types:1)the co-micellization system in which the surfactants are added into the BCPs assemblies as a self-assembly assistant;2)the co-emulsification system in which the surfactants work as an emulsion stabilizer to assist and confine the assembly of BCPs in 3D geometries;3)the co-templating system where the individual micelles of both surfactant and BCPs are hierarchically arranged and distributed to guide the formation of hierarchical nanomaterials.Following this,the major potential applications of the nanomaterials synthesized from the binary amphiphiles in biological field are described.Finally,we shortly discuss the current challenges and future perspectives of the binary amphiphiles selfassembly systems.展开更多
The structural precision of living supramolecular polymerization processes is dictated by nucleation control,conventionally achieved through kinetic trapping of monomers in metastable aggregates or inactive molecular ...The structural precision of living supramolecular polymerization processes is dictated by nucleation control,conventionally achieved through kinetic trapping of monomers in metastable aggregates or inactive molecular states.However,current strategies for living supramolecular polymerization,relying on bulk-phase kinetic trapping of monomers,homogenize assembly pathways and hinder hierarchical control.By leveraging the interfacial adsorption of amphiphilic molecules at the liquid-liquid interface,we engineered a self-limiting single-molecule film from PDIOH 1 that elevates the nucleation energy barrier,suppressing premature polymerization while enabling pathway-specific control over hierarchical self-assembly.The dynamic monolayer drives surface-catalyzed secondary nucleation at the liquid-liquid interface,programmably yielding epitaxially aligned 2D hierarchical architectures.Introducing interfacial seeds directs epitaxial growth of 2D hierarchical architectures with uniform shapes during living supramolecular polymerization.Remarkably,the excitation fluence-dependent transient absorption studies demonstrate that 2D hierarchical architectures exhibit a much larger exciton diffusion coefficient than that of disorganized fibers formed in the bulk solution.This work provides an interfacial strategy,enabling controllable assembly of 2D hierarchical materials via living supramolecular polymerization.展开更多
The preparation of multidimensional nano-and microstructures,in particular suprastructures with well-defined morphology and bright emissions,is a challenging task in supramolecular assembly.For this purpose,a new type...The preparation of multidimensional nano-and microstructures,in particular suprastructures with well-defined morphology and bright emissions,is a challenging task in supramolecular assembly.For this purpose,a new type of amphiphilic diplatinum complexes is presented as an excellent building block to assemble into highly phosphorescent nanofibers by supramolecular Pt…Pt interactions.These organoplatinum supramolecular fibers are further used as a pre-organized monomer reservior for the metal ion-triggered post-transformation into crystalline nanoneedles,nanorods,nanobunches,microplates,and microflowers with controllable morphology and bright phosphorescence.A reverse transformation of the obtained nanorods into nanofibers is demonstrated with the aid of ethylenediamine tetraacetic acid.In contrast,the direct treatment of diplatinum complexes with different metal ions fails to give well-defined nano and microstructures,suggestive of the pre-organized role of nanofibers for the morphological transformation.Preliminary applications of these nano-and suprastructures in sensing temperature and organic vapours by emission signal changes are demonstrated.In contrast to the conventional hierarchical assembly,the pre-organized monomer-reservoir strategy disclosed in this study offers a versatile method for the synthesis of organic nano and suprastructures with multidimensional morphology and controllable emission properties.展开更多
基金ZHANG XianRen acknowledges the support from the National Natural Science Foundation of China(20736005 and 20876004)
文摘We provided a short review on the recent progresses in computer simulations of adsorption and self-assembly of amphiphilic molecules.Owing to the extensive applications of amphiphilic molecules,it is very important to understand thoroughly the effects of the detailed chemistry,solid surfaces and the degree of confinement on the aggregate morphologies and kinetics of self-assembly for amphiphilic systems.In this review we paid special attention on(i)morphologies of adsorbed surfactants on solid surfaces,(ii)self-assembly in confined systems,and(iii)kinetic processes involving amphiphilic molecules.
基金the National Natural Science Foundation of China (21376282,21676035,21878029)Chongqing Science and Technology Commission (cstc2018jcyjAX0668)+2 种基金Shandong Province Natural Science Foundation (ZR2020QB18)China Postdoctoral Science Foundation (22012 T50762&2011 M501388)Graduate Student Research Innovation Project,Chongqing University (CYB18046)。
文摘In this study,the benign target double terpyridine parts based amphiphilic ionic molecules(AIMs 1,2)and the reference single terpyridine segment included AIMs(AIMs 3,4)were synthesized through a multi-step method,and the molecular structures were fully characterized.The excellent anticorrosion of the target AIMs for copper surface in H_(2)SO_(4) solution was demonstrated by the electrochemistry analysis,which was more superior over those of the reference AIMs.The standard adsorption free energy changes of the target AIMs calculated by the adsorption isotherms were lower than -40 kJ·mol^(-1),suggesting an intensified chemical adsorption on metal surface.The molecular modeling and molecular dynamic computation of the studied AIMs were performed,demonstrating that the target AIMs exhibited lower highest occupied molecular orbital-lowest unoccupied molecular orbital energy gaps and greater adsorption energies than the reference ones.The chemical adsorption of the AIMs on metal surface was revealed by various spectroscopic methods including scanning electron microscopy,atomic force microscopy,Fourier transform infrared spectroscopy,attenuated total reflection infrared spectroscopy,Raman and X-ray diffraction.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11421101 and 21274005)the Natural Sciences and Engineering Research Council(NSERC)of Canada
文摘Bilayer membranes self-assembled from amphiphilic molecules such as lipids, surfactants, and block copolymers are ubiquitous in biological and physiochemical systems. The shape and structure of bilayer membranes depend crucially on their mechanical properties such as surface tension, bending moduli, and line tension. Understanding how the molecular properties of the amphiphiles determine the structure and mechanics of the self-assembled bilayers requires a molecularly detailed theoretical framework. The self-consistent field theory provides such a theoretical framework, which is capable of accurately predicting the mechanical parameters of self-assembled bilayer membranes. In this mini review we summarize the formulation of the self-consistent field theory, as exemplified by a model system composed of flexible amphiphilic chains dissolved in hydrophilic polymeric solvents, and its application to the study of self-assembled bilayer membranes.
基金National Natural Science Foundation of China,Grant/Award Numbers:22005096,51621002,51972112National Key Research and Development Program of China,Grant/Award Number:2018YFC1105702+4 种基金Shanghai Sailing Program,Grant/Award Number:20YF1410100Shanghai Scientific and Technological Innovation Project,Grant/Award Number:19JC1411700Program of Shanghai Academic/Technology Research Leader,Grant/Award Number:18XD1401400Basic Research Program of Shanghai,Grant/Award Number:17JC1404702Leading Talents in Shanghai in 2018 and the 111 project,Grant/Award Number:B14018。
文摘The construction of highly ordered organizations through self-assembly is one of the most popular phenomena both in natural and artificial environments.Amphiphilic molecules are the most commonly used building blocks for the self-assembly,which are conventionally known as amphiphilic low molecular weight surfactants with polar heads and nonpolar tails,or amphiphilic block copolymers(BCPs)consisting of covalently bonded hydrophilic and hydrophobic block chains.Compared with single surfactant self-assembly system,binary amphiphiles co-assembly systems composing of both small mass surfactants and amphiphilic BCPs feature high flexibilities and versatilities in materials designing and structure regulation,ascribing to the vast possibilities of intermolecular interactions within the systems and facile component modulations during the assembly processes.The amphiphilic features of the two kinds of molecules endow them with similar self-assembly behaviors,while the unique and distinct characters of each kind of amphiphiles lead to various complex but highly diversified co-assembly systems.According to the roles of the surfactant played in the co-assembly system,in this review,we summarize the binary coassembly systems from three distinct types:1)the co-micellization system in which the surfactants are added into the BCPs assemblies as a self-assembly assistant;2)the co-emulsification system in which the surfactants work as an emulsion stabilizer to assist and confine the assembly of BCPs in 3D geometries;3)the co-templating system where the individual micelles of both surfactant and BCPs are hierarchically arranged and distributed to guide the formation of hierarchical nanomaterials.Following this,the major potential applications of the nanomaterials synthesized from the binary amphiphiles in biological field are described.Finally,we shortly discuss the current challenges and future perspectives of the binary amphiphiles selfassembly systems.
基金the Taishan Scholars Program(No.tsqn202306257)the Natural Science Foundation of Shandong Province(Nos.ZR2024YQ012,ZR2022YQ12,and ZR2024MB118)+1 种基金the National Natural Science Foundation of China(Nos.21972074 and 22106078)the Science,Education and Industry Integration of Basic Research Project of Qilu University of Technology(No.2023PY058).
文摘The structural precision of living supramolecular polymerization processes is dictated by nucleation control,conventionally achieved through kinetic trapping of monomers in metastable aggregates or inactive molecular states.However,current strategies for living supramolecular polymerization,relying on bulk-phase kinetic trapping of monomers,homogenize assembly pathways and hinder hierarchical control.By leveraging the interfacial adsorption of amphiphilic molecules at the liquid-liquid interface,we engineered a self-limiting single-molecule film from PDIOH 1 that elevates the nucleation energy barrier,suppressing premature polymerization while enabling pathway-specific control over hierarchical self-assembly.The dynamic monolayer drives surface-catalyzed secondary nucleation at the liquid-liquid interface,programmably yielding epitaxially aligned 2D hierarchical architectures.Introducing interfacial seeds directs epitaxial growth of 2D hierarchical architectures with uniform shapes during living supramolecular polymerization.Remarkably,the excitation fluence-dependent transient absorption studies demonstrate that 2D hierarchical architectures exhibit a much larger exciton diffusion coefficient than that of disorganized fibers formed in the bulk solution.This work provides an interfacial strategy,enabling controllable assembly of 2D hierarchical materials via living supramolecular polymerization.
基金supported by the National Science Fund for Distinguished Young Scholars(21925112)the National Natural Science Foundation of China(22090021,21601194,21872154)Beijing Natural Science Foundation(2191003)。
文摘The preparation of multidimensional nano-and microstructures,in particular suprastructures with well-defined morphology and bright emissions,is a challenging task in supramolecular assembly.For this purpose,a new type of amphiphilic diplatinum complexes is presented as an excellent building block to assemble into highly phosphorescent nanofibers by supramolecular Pt…Pt interactions.These organoplatinum supramolecular fibers are further used as a pre-organized monomer reservior for the metal ion-triggered post-transformation into crystalline nanoneedles,nanorods,nanobunches,microplates,and microflowers with controllable morphology and bright phosphorescence.A reverse transformation of the obtained nanorods into nanofibers is demonstrated with the aid of ethylenediamine tetraacetic acid.In contrast,the direct treatment of diplatinum complexes with different metal ions fails to give well-defined nano and microstructures,suggestive of the pre-organized role of nanofibers for the morphological transformation.Preliminary applications of these nano-and suprastructures in sensing temperature and organic vapours by emission signal changes are demonstrated.In contrast to the conventional hierarchical assembly,the pre-organized monomer-reservoir strategy disclosed in this study offers a versatile method for the synthesis of organic nano and suprastructures with multidimensional morphology and controllable emission properties.
