Polyelectrolytes(PEs)are polymers carrying ionizable groups along the chain backbone and play an important role in life and environmental sciences,industrial applications and other fields.Due to the complicated topolo...Polyelectrolytes(PEs)are polymers carrying ionizable groups along the chain backbone and play an important role in life and environmental sciences,industrial applications and other fields.Due to the complicated topological structure and electrostatic correlations of PEs,PEs exhibit very rich phase behavior and morphologies in both bulk and confined solutions.So far,many theories,simulations and machine learning approaches have been proposed to study the behavior of polyelectrolyte solutions,especially the intrinsic structure-property relationships.In this perspective,from a personal point of view,we present several recent trends in polyelectrolyte solutions.The main themes considered here are accelerated development of sequence-defined polyelectrolyte(SDPE)via artificial intelligence technology,liquid-liquid phase separation in bulk SDPE solutions,adsorption behaviors of SDPE in the vicinity of a single dielectric surface,and surface forces between two charged surfaces mediated by SDPE solutions.展开更多
Compared with spherical micelles,rod/worm-like micelles not only have extended blood circulation duration,but also exhibit favorable cellular uptake behavior,which is promising for next-generation nanomedicine and bio...Compared with spherical micelles,rod/worm-like micelles not only have extended blood circulation duration,but also exhibit favorable cellular uptake behavior,which is promising for next-generation nanomedicine and biomaterials.However,the controllable fabrication of narrowly dispersed nanorods in aqueous media is still challenging.Herein,the methodology of thermal annealing was developed for the fabrication of helical nanorods as well as a series of nanorods with different lengths.The thermal annealing process generally consisted of adding a percentage of organic solvent(10%(V/V)or 20%(V/V))to the digital micellar aqueous dispersion,followed by heating at 90℃for 1 h,then cooling naturally to room temperature,and dialyzing against water to remove the organic solvent.Right-handed helical nanorods were afforded by the treatment of 45 nm digital micelles in the presence of 10%(V/V)dioxane,while left-handed helical nanorods were obtained in the presence of 20%(V/V)dioxane.Meanwhile,the controlled growth of rod-like digital micelles was achieved after thermal annealing in the presence of different types of organic solvents,and the length of the annealed nanorods was correlated with the types of organic solvent.Furthermore,no matter the size of initial digital micelles,they all exhibited similar trend of rod growth in the presence of a certain amount of organic solvent,allowing for controllable formulation of narrowly dispersed nanorods.In addition,supramolecular self-assembly by amphiphilic dendritic oligourethane readily fabricated diverse uniform nanorods in aqueous media.Overall,this work provided an attractive methodology to fabricate uniform digital nanorods.展开更多
Multicomponent polymerizations have become powerful tools for the construction of sequence-defined polymers. Although the Passerini multicomponent reaction has been widely used in the synthesis of sequence-defined pol...Multicomponent polymerizations have become powerful tools for the construction of sequence-defined polymers. Although the Passerini multicomponent reaction has been widely used in the synthesis of sequence-defined polymers, the tandem usage of the Passerini multicomponent reaction and other multicomponent reactions in one-pot for the synthesis of sequence-defined polymers has not been developed until now. In this contribution, we report the tandem usage of the Passerini three-component reaction and the three-component amine-thiol-ene conjugation reaction in one pot for the synthesis of sequence-defined polymers. The Passerini reaction between methacrylic acid, adipaldehyde, and 2-isocyanobutanoate was carried out, affording a new molecule containing two alkene units. Subsequently, an amine and a thiolactone were added to the reaction system, whereupon the three-component amine-thiol-ene conjugating reaction occurred to yield a sequence-defined polymer. This method offers more rapid access to sequence-defined polymers with high molecular diversity and complexity.展开更多
Sequenced-defined oligomer has been emerged as one of the hot topics in polymer chemistry due to its capability of precisely controlling both chain length and monomer sequence.Recent efforts have focused on developmen...Sequenced-defined oligomer has been emerged as one of the hot topics in polymer chemistry due to its capability of precisely controlling both chain length and monomer sequence.Recent efforts have focused on development of synthetic methodologies using state-ofthe-art chemistry tools.However,investigating the impact of minor changes in monomer sequence on physical properties of these materials is still underdeveloped.Herein,four sequenced pentamers are synthesized by a reversible addition-fragmentation chain transfer(RAFT)single unit monomer insertion technique,in which a base pentamer possesses a relatively rigid backbone comprising of five cyclic monomer units.One of the cyclic units in this base pentamer is replaced by an acyclic monomer at different locations(the 1st,3rd and 5th unit)to produce three modified pentamers,which leads to a significant decrease of glass transition temperature(Tg)compared to the base pentamer.Meanwhile,the modified pentamers with identical primary structures but distinct monomer sequences also present different Tg values depending on the position of the acyclic monomer unit.The middle(3rd)position of the acyclic unit causes profound decrease of Tg due to its increased molecular flexibility.These synthetic pentamers have been demonstrated to be excellent oligomeric plasticizers to modulate thermal transitions of bulk polymer materials.展开更多
Due to various applications enabled by diverse morphologies of self-assembled sequence-defined polymers,controlling the self-assembly of synthetic peptidomimetics into designed morphologies has emerged as a promising ...Due to various applications enabled by diverse morphologies of self-assembled sequence-defined polymers,controlling the self-assembly of synthetic peptidomimetics into designed morphologies has emerged as a promising route for the development of bioinspired functional materials.Herein,we report morphological control over the assembly of a series of short peptoids,or poly-N-substituted glycines,that contain asymmetric hydrophobic domains.We demonstrate that the inherent flexibility of amphiphilic peptoid bilayers drives assembly polymorphism,resulting in the coexistence of nanosheets,twisted ribbons,and nanofibers—three distinct morphologies.By tuning peptoid molecular interactions through variations in sequence design,solution pH,and temperature,we demonstrate precise control over the twisting and folding of peptoid bilayers,enabling the formation of well-defined nanosheets and nanohelices.Molecular dynamics simulations further unravel how the introduction of asymmetric hydrophobic domains enables the flexibility of peptoid bilayers and results in peptoid assembly polymorphism.By tuning peptoid molecular interactions through heating,we further demonstrate the transformation of nanosheets into nanohelices.We envision that our mechanistic investigation of peptoid assembly polymorphism provides a strong foundation for leveraging peptoid sequences and chemistries to achieve controlled molecular interactions,driving the creation of biomimetic materials with tailored morphologies and functionalities.展开更多
基金supported by the National Natural Science Foundation of China(Nos.22273112 and 22203100).
文摘Polyelectrolytes(PEs)are polymers carrying ionizable groups along the chain backbone and play an important role in life and environmental sciences,industrial applications and other fields.Due to the complicated topological structure and electrostatic correlations of PEs,PEs exhibit very rich phase behavior and morphologies in both bulk and confined solutions.So far,many theories,simulations and machine learning approaches have been proposed to study the behavior of polyelectrolyte solutions,especially the intrinsic structure-property relationships.In this perspective,from a personal point of view,we present several recent trends in polyelectrolyte solutions.The main themes considered here are accelerated development of sequence-defined polyelectrolyte(SDPE)via artificial intelligence technology,liquid-liquid phase separation in bulk SDPE solutions,adsorption behaviors of SDPE in the vicinity of a single dielectric surface,and surface forces between two charged surfaces mediated by SDPE solutions.
基金financially supported by the National Key R&D Program of China(No.2020YFA0710700)the National Natural Science Foundation of China(Nos.52021002,52233009,U19A2094,52073270 and 51973071)。
文摘Compared with spherical micelles,rod/worm-like micelles not only have extended blood circulation duration,but also exhibit favorable cellular uptake behavior,which is promising for next-generation nanomedicine and biomaterials.However,the controllable fabrication of narrowly dispersed nanorods in aqueous media is still challenging.Herein,the methodology of thermal annealing was developed for the fabrication of helical nanorods as well as a series of nanorods with different lengths.The thermal annealing process generally consisted of adding a percentage of organic solvent(10%(V/V)or 20%(V/V))to the digital micellar aqueous dispersion,followed by heating at 90℃for 1 h,then cooling naturally to room temperature,and dialyzing against water to remove the organic solvent.Right-handed helical nanorods were afforded by the treatment of 45 nm digital micelles in the presence of 10%(V/V)dioxane,while left-handed helical nanorods were obtained in the presence of 20%(V/V)dioxane.Meanwhile,the controlled growth of rod-like digital micelles was achieved after thermal annealing in the presence of different types of organic solvents,and the length of the annealed nanorods was correlated with the types of organic solvent.Furthermore,no matter the size of initial digital micelles,they all exhibited similar trend of rod growth in the presence of a certain amount of organic solvent,allowing for controllable formulation of narrowly dispersed nanorods.In addition,supramolecular self-assembly by amphiphilic dendritic oligourethane readily fabricated diverse uniform nanorods in aqueous media.Overall,this work provided an attractive methodology to fabricate uniform digital nanorods.
基金supported by the National Natural Science Foundation of China(51273187,21374107)the Fundamental Research Funds for the Central Universities(WK2060200012)the Program for New Century Excellent Talents in Universities(NCET-11-0882)
文摘Multicomponent polymerizations have become powerful tools for the construction of sequence-defined polymers. Although the Passerini multicomponent reaction has been widely used in the synthesis of sequence-defined polymers, the tandem usage of the Passerini multicomponent reaction and other multicomponent reactions in one-pot for the synthesis of sequence-defined polymers has not been developed until now. In this contribution, we report the tandem usage of the Passerini three-component reaction and the three-component amine-thiol-ene conjugation reaction in one pot for the synthesis of sequence-defined polymers. The Passerini reaction between methacrylic acid, adipaldehyde, and 2-isocyanobutanoate was carried out, affording a new molecule containing two alkene units. Subsequently, an amine and a thiolactone were added to the reaction system, whereupon the three-component amine-thiol-ene conjugating reaction occurred to yield a sequence-defined polymer. This method offers more rapid access to sequence-defined polymers with high molecular diversity and complexity.
基金the Australian Research Council(ARC)and UNSW Sydney for the financial support under the schemes of Future Fellowship(No.FT160100095)and Startup Fund。
文摘Sequenced-defined oligomer has been emerged as one of the hot topics in polymer chemistry due to its capability of precisely controlling both chain length and monomer sequence.Recent efforts have focused on development of synthetic methodologies using state-ofthe-art chemistry tools.However,investigating the impact of minor changes in monomer sequence on physical properties of these materials is still underdeveloped.Herein,four sequenced pentamers are synthesized by a reversible addition-fragmentation chain transfer(RAFT)single unit monomer insertion technique,in which a base pentamer possesses a relatively rigid backbone comprising of five cyclic monomer units.One of the cyclic units in this base pentamer is replaced by an acyclic monomer at different locations(the 1st,3rd and 5th unit)to produce three modified pentamers,which leads to a significant decrease of glass transition temperature(Tg)compared to the base pentamer.Meanwhile,the modified pentamers with identical primary structures but distinct monomer sequences also present different Tg values depending on the position of the acyclic monomer unit.The middle(3rd)position of the acyclic unit causes profound decrease of Tg due to its increased molecular flexibility.These synthetic pentamers have been demonstrated to be excellent oligomeric plasticizers to modulate thermal transitions of bulk polymer materials.
基金supported by the US Department of Energy(DOE),Office of Science,Office of Basic Energy Sciences(BES)as part of the Energy Frontier Research Centers program:CSSAS-The Center for the Science of Synthesis Across Scales-under Award Number DE-SC0019288[FWP 72448 at Pacific Northwest National Laboratory(PNNL)]XRD work was conducted at the Advanced Light Source(ALS)of Lawrence Berkeley National Laboratory,which was supported by the Office of Science(No.DE-AC02-05CH11231)+1 种基金A portion of the AFM and S/TEM experiments were conducted at the Molecular Analysis Facility(MAF),a National Nanotechnology Coordinated Infrastructure(NNCI)site at the University of Washington,which is supported in part by funds from the National Science Foundation(Awards NNCI-2025489 and NNCI-1542101)PNNL is multi-program national laboratory operated for DOE by Battelle under Contracts No.DE-AC05-76RL01830.
文摘Due to various applications enabled by diverse morphologies of self-assembled sequence-defined polymers,controlling the self-assembly of synthetic peptidomimetics into designed morphologies has emerged as a promising route for the development of bioinspired functional materials.Herein,we report morphological control over the assembly of a series of short peptoids,or poly-N-substituted glycines,that contain asymmetric hydrophobic domains.We demonstrate that the inherent flexibility of amphiphilic peptoid bilayers drives assembly polymorphism,resulting in the coexistence of nanosheets,twisted ribbons,and nanofibers—three distinct morphologies.By tuning peptoid molecular interactions through variations in sequence design,solution pH,and temperature,we demonstrate precise control over the twisting and folding of peptoid bilayers,enabling the formation of well-defined nanosheets and nanohelices.Molecular dynamics simulations further unravel how the introduction of asymmetric hydrophobic domains enables the flexibility of peptoid bilayers and results in peptoid assembly polymorphism.By tuning peptoid molecular interactions through heating,we further demonstrate the transformation of nanosheets into nanohelices.We envision that our mechanistic investigation of peptoid assembly polymorphism provides a strong foundation for leveraging peptoid sequences and chemistries to achieve controlled molecular interactions,driving the creation of biomimetic materials with tailored morphologies and functionalities.
