Nanoporous polymers are extensively coated on various substrates to deliver optical,permselective,or other functions.However,it remains desired to fast produce uniform nanoporous polymer coatings on substrates with co...Nanoporous polymers are extensively coated on various substrates to deliver optical,permselective,or other functions.However,it remains desired to fast produce uniform nanoporous polymer coatings on substrates with complex surfaces.Herein,by manipulating the interactions between block copolymers and selective solvents,we prepare repairable nanoporous polymers on arbitrary substrates.This is realized by an extremely simple sequential coating process:sequential coating of block copolymers and their swelling agents on substrate surfaces.The swelling agents are comprised of two solvents that swell the constituent blocks of the copolymers to different degrees,rapidly producing polymer coatings with uniform,interconnected,sub-50 nm pores.This sequential coating process is able to conformally build nanoporous polymers on nonplanar substrates with large lateral sizes and complex surface features,and also to in situ repair defects arising during usages.We further demonstrate that the nanoporous coatings show excellent antireflective and membrane separation performances.This sequential coating process is dictated by polymer–solvent interactions,and is expected to find applications in diverse fields for its simplicity,adaptability,and the capability to produce well-defined nanoporosities.展开更多
The diagnostic efficacy of contemporary bioimaging technologies remains constrained by inherent limitations of conventional imaging agents,including suboptimal sensitivity,off-target biodistribution,and inherent cytot...The diagnostic efficacy of contemporary bioimaging technologies remains constrained by inherent limitations of conventional imaging agents,including suboptimal sensitivity,off-target biodistribution,and inherent cytotoxicity.These limitations have catalyzed the development of intelligent stimuli-responsive block copolymers-based bioimaging agents,which was engineered to dynamically respond to endogenous biochemical cues(e.g.,p H gradients,redox potential,enzyme activity,hypoxia environment) or exogenous physical triggers(e.g.,photoirradiation,thermal gradients,ultrasound(US)/magnetic stimuli).Through spatiotemporally controlled structural transformations,stimuli-responsive block copolymers enable precise contrast targeting,activatable signal amplification,and theranostic integration,thereby substantially enhancing signal-to-noise ratios of bioimaging and diagnostic specificity.Hence,this mini-review systematically examines molecular engineering principles for designing p H-,redox-,enzyme-,light-,thermo-,and US/magnetic-responsive polymers,with emphasis on structure-property relationships governing imaging performance modulation.Furthermore,we critically analyze emerging strategies for optical imaging,US synergies,and magnetic resonance imaging(MRI).Multimodal bioimaging has also been elaborated,which could overcome the inherent trade-offs between resolution,penetration depth,and functional specificity in single-modal approaches.By elucidating mechanistic insights and translational challenges,this mini-review aims to establish a design framework of stimuli-responsive block copolymersbased for high fidelity bioimaging agents and accelerate their clinical translation in precise diagnosis and therapy.展开更多
Switchable polymerization is emerging as a powerful tool to construct block copolymers directly from mixtures of monomers.However,current achievements typically iterate between two polymerization cycles to afford prod...Switchable polymerization is emerging as a powerful tool to construct block copolymers directly from mixtures of monomers.However,current achievements typically iterate between two polymerization cycles to afford products with fixed sequences and compositions.Herein,we report the triethylborane/1,8-diazabicyclo[5.4.0]undec-7-ene(Et_3B/DBU)pair-mediated four-component switchable polymerization of propylene oxide(PO),CO_(2),phthalic anhydride(PA),and racemic lactide(rac-LA),which enables the on-demand synthesis of four different block copolymers,i.e.,poly(propylene phthalate)-b-polylactide(PPE-b-PLA),PPE-b-PLA-b-poly(propylene carbonate)(PPC),PPE-b-PPC-b-PLA,and PPE-b-PPCb-poly(propylene oxide)(PPO),through rationally modulating the Lewis pair(LP)ratio.Core to this protocol is that increasing the loading of Et_(3)B accelerates the ring-opening of PO while impeding the reactivity of rac-LA,thus allowing for fine-tuning of the thermodynamic and kinetic of the switchable polymerization.Therefore,the four polymerization cycles involving PO/PA ring-opening copolymerization(ROCOP),PO/CO_(2) ROCOP,rac-LA ring-opening polymerization(ROP),and PO ROP can be connected and discriminated in precisely programmed manners.展开更多
Star-shaped six-arm polymers with hexaaza[2_(6)]orthoparacyclophane core and arms of block copolymers of poly-2-ethyl-5,6-dihydrooxazine with poly-2-isopropyl-5,6-dihydrooxazine were synthesized successfully using cat...Star-shaped six-arm polymers with hexaaza[2_(6)]orthoparacyclophane core and arms of block copolymers of poly-2-ethyl-5,6-dihydrooxazine with poly-2-isopropyl-5,6-dihydrooxazine were synthesized successfully using cationic ring-opening polymerization.The ratio of blocks,the order of their attachment to the core,and arm length were varied.Conformation of synthesized stars was determined by methods of molecular hydrodynamics and optics.It has been shown that star-shaped molecules were characterized by high intramolecular density,and the arm folding increased with their lengthening.The influence of the structure of block copolymers and their molar mass on the critical micelle concentration has been established.Complexes of synthesized star-shaped block copolymers with curcumin were obtained and the efficient binding of curcumin to polymer molecules was demonstrated.The behavior of the aqueous solutions of the prepared polymer stars and their complexes with curcumin was investigated by light scattering and turbidimetry methods.The influence of the structure and molar mass of star polymers on their thermoresponsiveness and the phase separation temperatures in aqueous solutions was analyzed.A slight increase in the phase separation temperature was found on passage from polymer solutions to solutions of polymer complexes with hydrophobic curcumin.展开更多
Some physical properties of the polyester-polyeher multiblock copolymers with Si-containing hard segment were further examined by a series of physical methods. Thehydrophobicity of the copolymers was improved with the...Some physical properties of the polyester-polyeher multiblock copolymers with Si-containing hard segment were further examined by a series of physical methods. Thehydrophobicity of the copolymers was improved with the incorporation of increasing amountof organosilicone, XPS test proved that silicon element was enriched at the surface of theSi-containing polyeser-polyether copolymers. It was also found that their heat resistanceand gas permeability for O_2 and N_2 were greatly improved. The study on semipermeabilityof films made of the Si-containing copolymers was also followed with interest.展开更多
A significant challenge in developing block copolymer photonic crystals is constructing low-symmetric ordered phases,which are essential for achieving a complete photonic band gap.Here,we propose a promising strategy ...A significant challenge in developing block copolymer photonic crystals is constructing low-symmetric ordered phases,which are essential for achieving a complete photonic band gap.Here,we propose a promising strategy to create low-symmetric ordered morphologies by incorporating shape-anisotropic rod-like side chains into block copolymers.Using dissipative particle dynamics simulations,we demonstrate that block copolymers with longer rod-like side chains can self-assemble into a hexagonally packed columnar phase characterized by a low-symmetric rectangular cross-section.Photonic band structure calculations reveal that this low-symmetric columnar phase can exhibit a complete photonic band gap,with the gap size dependent on the aspect ratio of the rectangular cross-sections of the columns.Our findings suggest an effective approach to constructing low-symmetric photonic crystals through the self-assembly of block copolymers with shape-anisotropic segments.展开更多
Colloidal molecules exhibit unique electronic,optical,and magnetic properties owing to their molecular-like configurations and coupling effects,making them promising building blocks for multifunctional materials.Howev...Colloidal molecules exhibit unique electronic,optical,and magnetic properties owing to their molecular-like configurations and coupling effects,making them promising building blocks for multifunctional materials.However,achieving precise and controllable assembly of isotropic nanoparticles with high yields remains a great challenge.In this study,we present a synergistic strategy that integrates molecular dynamics simulations with interpretable machine learning to develop a programmable assembly system based on block copolymers and DNA-functionalized nanoparticles.Our simulation results reveal that block copolymer modification facilitates stepwise control over surface phase separation and nanoparticle coassembly,thereby enhancing structural stability and efficiently suppressing disordered aggregation of atom-like nanoparticles.Furthermore,we demonstrated that precise,controllable,and programmable assembly of colloidal molecules can be achieved through rational DNA sequence design.SHapley Additive exPlanations(SHAP)analysis identified key structural descriptors that govern assembly outcomes and elucidated their underlying mechanistic roles.This work not only deepens the understanding of colloidal molecule assembly mechanisms but also lays a theoretical foundation for the rational design of functional colloidal architectures in nanomaterial science.展开更多
The self-assembly of block copolymers serves as an effective approach for fabricating various periodic ordered nanostructures. By employing self-consistent field theory (SCFT) to calculate the phase diagrams of block ...The self-assembly of block copolymers serves as an effective approach for fabricating various periodic ordered nanostructures. By employing self-consistent field theory (SCFT) to calculate the phase diagrams of block copolymers, one can accurately predict their self-assembly behaviors, thus providing guidance for the fabrication of various novel structures. However, SCFT is highly sensitive to initial conditions because it finds the free energy minima through an iterative process. Consequently, constructing phase diagrams using SCFT typically requires predefined candidate structures based on the experience of researchers. Such experience-dependent strategies often miss some structures and thus result in inaccurate phase diagrams. Recently, artificial intelligence (AI) techniques have demonstrated significant potential across diverse fields of science and technology. By leveraging AI methods, it is possible to reduce reliance on human experience, thereby constructing more robust and reliable phase diagrams. In this work, we demonstrate how to combine AI with SCFT to automatically search for self-assembled structures of block copolymers and construct phase diagrams. Our aim is to realize automatic construction of block copolymer phase diagrams while minimizing reliance on human prior knowledge.展开更多
Mechanochromic materials respond to external stimuli and provide early warnings of material damage.Perylene diimide(PDI)-based materials have attracted attention because of their outstanding fluorescence performance.H...Mechanochromic materials respond to external stimuli and provide early warnings of material damage.Perylene diimide(PDI)-based materials have attracted attention because of their outstanding fluorescence performance.However,the application of PDI in mechanochromism is limited by the difficulty for mechanical forces to disrupt the aggregation of PDI and its derivatives,as well as the fluorescence quenching caused by continuousπ-πstacking between PDI molecules.To eliminate the fluorescence quenching effect caused by the aggregation of PDI and broaden its application fields,polyhedral oligomeric silsesquioxane(POSS)-PDI-POSS(PPP)was screened as PDI doping.The photophysical properties of PPP in both monomeric and aggregated states in different solvents were studied.Then,PPP and styrene-butadiene-styrene block copolymer(SBS)were mixed to prepare the PPP/SBS film.The mechanochromic properties of PPP/SBS film were explored.The fluorescence emission spectra confirmed that when the PPP mass fraction increased to 0.30%,the PPP/SBS film exhibited mechanochromic behavior under uniaxial deformation due to the changes in the molecular packing.展开更多
Block copolymer(BCP) nanolithography offers potential beyond traditional photolithographic limits, yet reliably producing low-defect, perpendicular domains remains challenging. We introduce a microenvironmentdriven is...Block copolymer(BCP) nanolithography offers potential beyond traditional photolithographic limits, yet reliably producing low-defect, perpendicular domains remains challenging. We introduce a microenvironmentdriven isothermal annealing method for directed self-assembly of BCP thin films. By annealing films at stable temperature in a quasi-sealed, inert-gas chamber, our approach promotes highly uniform perpendicular lamellar nanopatterns over large areas, effectively mitigating environmental fluctuations and emulating solvent-vapor annealing without solvent exposure. Resulting BCP structures demonstrate enhanced spatial coherence and notably low defect density. Furthermore, we successfully transfer these nanopatterns into precise metal nano-line arrays,confirming the method's capability for high-fidelity pattern replication. This scalable, solvent-free technique provides a robust, reliable route for high-resolution nanopatterning in advanced semiconductor manufacturing.展开更多
Fouling resistance of ultrafiltration(UF) membranes is critical for their long-term usages in terms of stable performance, so convenient approaches to prepare fouling-resistant membranes are always anticipated. Herein...Fouling resistance of ultrafiltration(UF) membranes is critical for their long-term usages in terms of stable performance, so convenient approaches to prepare fouling-resistant membranes are always anticipated. Herein, we demonstrate the facile fabrication of antifouling polysulfone-block-poly(ethylene glycol)(PSF-b-PEG, SFEG)composite membranes. SFEG layer was coated onto macroporous supports and cavitated by immerging them in acetone/n-propanol following the mechanism of selective swelling induced pore generation. Thus-produced SFEG membranes possessed high permeance and excellent mechanical strength. Meanwhile, the structures and separation performances of the SFEG layers can be continuously tuned through simply changing swelling durations. More importantly, the hydrophilic PEG chains were spontaneously enriched onto the pore walls through swelling treatment, endowing intrinsic antifouling property to the SFEG membranes. Bovine serum albumin(BSA)/humic acid(HA) fouling tests proved the prominent fouling resistance of SFEG membranes, and the fouling resistance is expected to be long-standing because of the firm connection between PEG chains and PSF matrix by covalent bonding.展开更多
Conjugated block copolymers have gained increasing interests in recent years. Development of a novel method for facile synthesis of conjugated block copolymers with desired structures and functions is greatly desired....Conjugated block copolymers have gained increasing interests in recent years. Development of a novel method for facile synthesis of conjugated block copolymers with desired structures and functions is greatly desired. In this mini review, we summarized the recent advances in one-pot synthesis of conjugated block copolymers containing π-conjugated polythiophene and helical polyisocyanide segments by using a nickel（Ⅱ） complex as single catalyst. The sequential living polymerization of the two monomers proceeded in a controlled manner, affording expected block copolymers in high yields with controlled molecular weights（Mns） and narrow molecular weight distributions（Mw/Mns）. By using this method, a family of block copolymers with expected structure and tunable compositions can be facilely prepared. Introducing functional groups onto the pendant, these block copolymers can exhibit interesting self-assembly property, tunable light emission and multi-responsiveness.展开更多
A novel fluorinated triblock copolymer incorporating 2-ethylhexyl methacrylate （EHMA）, tert-butyl methacrylate （tBMA） and 1H,1H,2H,2H-perfluorodecyl acrylate （FA） （PEHMA-b-PtBMA-b-PFA） was first synthesized us...A novel fluorinated triblock copolymer incorporating 2-ethylhexyl methacrylate （EHMA）, tert-butyl methacrylate （tBMA） and 1H,1H,2H,2H-perfluorodecyl acrylate （FA） （PEHMA-b-PtBMA-b-PFA） was first synthesized using three successive reversible addition fragmentation chain transfer （RAFT） polymerization and the subsequent hydrolyzing at acidic condition. The as-fabricated triblock copolymer exhibited an interesting morphology evolution from the multi-compartment rod-like structure to spherical structure along with the addition of a selective solution. At the same time, a visible phase separation domain could be seen in the core area due to the existence of fluorocarbon segments. Furthermore, the self- assembly behavior of the triphilic copolymer at different pH was also verified by transmission electron microscopy, as well as the dynamic light scattering. These stimuli-responsive multi-compartment nanostructures may have potential applications in drug delivery.展开更多
Donor-acceptor （D-A） type fully conjugated block copolymer systems have been rarely reported due to the challenges in synthetic approaches to prepare well-defined low-polydispersity products. In this work, fully con...Donor-acceptor （D-A） type fully conjugated block copolymer systems have been rarely reported due to the challenges in synthetic approaches to prepare well-defined low-polydispersity products. In this work, fully conjugated block copolymers are synthesized in a one-pot reaction through Stille coupling polycondensation, by utilizing the end-functional polymer copolymerization method. End-functional P3HT are copolymerized with AA （2,7-dihromo-9-（heptadecan-9-yl）-9H- carbazole） and BB （4,7-bis（5-（trimethylstannyl）thiophen-2-yl）benzo[c][1,2,5]thiadiazole, TBT） type monomers, respectively. The orthogonal solubility between the very soluble P3HT donor and the insoluble PCDTBT acceptor block improves the purity of block copolymers as well as distinct nano-scale phase-separation compared with other reports on miscibility of donor and acceptor polymer block. Further purification via preparative GPC is carried out to remove the excess of unreacted P3HT and free PCDTBT as well as to achieve low polydispersity of block copolymers. The chemical structure of the P3HT- b-PCDTBT block copolymers are verified via IH-NMR, and further confirmed by FTIR spectra. The block copolymer shows broad absorption and moderate optical band gap of 1.8 eV. Furthermore, the fully conjugated block copolymer films exhibit significant fine structures, much smoother film morphology compared to P3HT/PCDTBT polymer blends. By adding a small amount of block copolymer P3HT-b-PCDTBT as a compatibilizer into the bulk-heterojunction of P3HT：PC61BM blends, polymer solar ceils with an 8% increase of short circuit current （Jse） and 10% increase of power conversion efficiency （PCE） are achieved owing to the improvement of the active-layer film morphology. To the best of our knowledge, this is the first report on donor-acceptor type fully conjugated block copolymer as an effective ternary additive in polymer： fullerene bulk heterojunction solar cells.展开更多
This feature article summarizes the synthesis of novel olefin block copolymers using fast syndiospecific living homo- and copolymerization of propylene, higher 1-alkene, and norbornene with ansa-fluorenylamidodimethyl...This feature article summarizes the synthesis of novel olefin block copolymers using fast syndiospecific living homo- and copolymerization of propylene, higher 1-alkene, and norbornene with ansa-fluorenylamidodimethyltitanium- based catalyst according to the authors＇ recent results. The catalytic synthesis of monodisperse polyolefin and olefin block copolymer was also described using this living system.展开更多
Controlled synthesis of amphiphilic block copolymer nanoparticles in a convenient way is an important and interest topic in polymer science. In this review, three formulations of polymerization-induced self-assembly t...Controlled synthesis of amphiphilic block copolymer nanoparticles in a convenient way is an important and interest topic in polymer science. In this review, three formulations of polymerization-induced self-assembly to in situ synthesize block copolymer nanoparticles are briefly introduced, which perform by reversible addition-fragmentation chain transfer （RAFT） polymerization under heterogeneous conditions, e.g., aqueous emulsion RAFT polymerization, dispersion RAFT polymerization and especially the recently proposed seeded RAFT polymerization. The latest developments in several selected areas on the synthesis of block copolymer nano-assemblies are highlighted.展开更多
pH-sensitive wettability of polystyrene-b-poly（4-vinylpyridine） （PS-b-P4VP） self assembled films, exhibiting superoleophobicity under water and hydrophilicity at low pH value, and oleophobicity under water and hyd...pH-sensitive wettability of polystyrene-b-poly（4-vinylpyridine） （PS-b-P4VP） self assembled films, exhibiting superoleophobicity under water and hydrophilicity at low pH value, and oleophobicity under water and hydrophobicity at neutral condition, has been realized. The wettability properties resulted from the surface topological and chemical transition, which were confirmed by in situ AFM measurements under water at different pH. At low pH, P4VP chains, which were confined in the hexagonal-packed nanodomains, got protonated into a swollen state, while at high pH, P4VP chains were deprotonated into a collapsed state. The reversible protonation/deprotonation procedure on the molecular scale leads to surface topological and chemical transition, thereby pH-sensitive wettability.展开更多
Block copolymer lithography is emerging as one of the leading technologies for patteming nanoscale dense features. In almost all potential applications of this technology, control over the orientation of cylindrical a...Block copolymer lithography is emerging as one of the leading technologies for patteming nanoscale dense features. In almost all potential applications of this technology, control over the orientation of cylindrical and lamellar domains is required for pattern transfer from the block copolymer film. This review highlights the state-of-art development of brushes to modify the substrates to control the assembly behaviors of block copolymers in films. Selected important contributions to the development of self-assembled monolayers, polymer brushes and mats, and chemically patterned brushes are discussed.展开更多
Structured block copolymer(BCP) particles have gained increasing attention due to their potential applications in separation,catalysis, controlled release, and other fields. Three-dimensional(3D) confined assembly has...Structured block copolymer(BCP) particles have gained increasing attention due to their potential applications in separation,catalysis, controlled release, and other fields. Three-dimensional(3D) confined assembly has been proved as a facile yet robust approach for generating BCP particles with controllable shapes and internal structures. In this feature article, we summarized the preparation of structured polymeric particles through 3D confined self-assembly of BCPs. The effects of interfacial interactions, degree of confinement,and additives on the shape and internal structure of BCP microparticles were comprehensively discussed. In addition, we highlighted the recent progress in using disassembly as a route to synthesize colloidal particles with unique structures. Two strategies were introduced in this part:(a) disassembling the discrete domains resulted in mesoporous microparticles;(b) disassembling the continuous domains led to the dissociation of microparticles into micelle-like nano-objects. The applications of the structured colloidal particles in photonic crystals,controlled release, and directed growth of inorganic materials were also presented. Finally, we discussed the current challenges and future opportunities in this promising area.展开更多
The self-assembly of block copolymer in solution has proven to be an effective strategy for building up a wide range of nanomaterials with diverse structures and applications.This paper reports a facile self-assembly ...The self-assembly of block copolymer in solution has proven to be an effective strategy for building up a wide range of nanomaterials with diverse structures and applications.This paper reports a facile self-assembly approach towards two-dimensional(2D)sandwich-like mesoporous nitrogen-doped carbon/reduced graphene oxide nanocomposites(denoted as mNC/rGO)with well-defined large mesopores.The strategy involves the synergistic self-assembly ofpolystyrene-block-poly(ethylene oxide)(PS-b-PEO)spherical micelles,m-phenylenediamine(mPD)monomers and GO in solution and the subsequent carbonization at 900~C.The resultant mNC/rGO nanosheets have an average pore size of 19 nm,a high specific surface of 812 m^(2)'g^(-1)and a nitrogen content of 2.2 wt%.As an oxygen reduction reaction(ORR)catalyst,the unique structural features render the metal-free nanosheets excellent electrocatalytic performance.In a 0.1 mol.L-~KOH alkaline medium,mNC/rGO exhibits a four-electron transfer pathway with a high half-wave-potential(El/2)of+0.77 V versus reversible hydrogen electrode(RHE)and a limiting current density(JL)of 5.2 mA'cm^(-2),which are well comparable with those of the commercial Pt/C catalysts.展开更多
基金support from National Science Foundation of China(22438005)the Natural Science Foundation of Jiangsu Province(BE2022056-3)is gratefully acknowledged.
文摘Nanoporous polymers are extensively coated on various substrates to deliver optical,permselective,or other functions.However,it remains desired to fast produce uniform nanoporous polymer coatings on substrates with complex surfaces.Herein,by manipulating the interactions between block copolymers and selective solvents,we prepare repairable nanoporous polymers on arbitrary substrates.This is realized by an extremely simple sequential coating process:sequential coating of block copolymers and their swelling agents on substrate surfaces.The swelling agents are comprised of two solvents that swell the constituent blocks of the copolymers to different degrees,rapidly producing polymer coatings with uniform,interconnected,sub-50 nm pores.This sequential coating process is able to conformally build nanoporous polymers on nonplanar substrates with large lateral sizes and complex surface features,and also to in situ repair defects arising during usages.We further demonstrate that the nanoporous coatings show excellent antireflective and membrane separation performances.This sequential coating process is dictated by polymer–solvent interactions,and is expected to find applications in diverse fields for its simplicity,adaptability,and the capability to produce well-defined nanoporosities.
基金supported by the National Natural Science Foundation of China (Nos.22208218,22078196,and 22278268)the Natural Science Foundation of Shanghai (No.22ZR1460400)Collaborative Innovation Center of Fragrance Flavour and Cosmetics,and Collaborative Innovation Project of Shanghai Institute of Technology (No.XTCX2023-07)。
文摘The diagnostic efficacy of contemporary bioimaging technologies remains constrained by inherent limitations of conventional imaging agents,including suboptimal sensitivity,off-target biodistribution,and inherent cytotoxicity.These limitations have catalyzed the development of intelligent stimuli-responsive block copolymers-based bioimaging agents,which was engineered to dynamically respond to endogenous biochemical cues(e.g.,p H gradients,redox potential,enzyme activity,hypoxia environment) or exogenous physical triggers(e.g.,photoirradiation,thermal gradients,ultrasound(US)/magnetic stimuli).Through spatiotemporally controlled structural transformations,stimuli-responsive block copolymers enable precise contrast targeting,activatable signal amplification,and theranostic integration,thereby substantially enhancing signal-to-noise ratios of bioimaging and diagnostic specificity.Hence,this mini-review systematically examines molecular engineering principles for designing p H-,redox-,enzyme-,light-,thermo-,and US/magnetic-responsive polymers,with emphasis on structure-property relationships governing imaging performance modulation.Furthermore,we critically analyze emerging strategies for optical imaging,US synergies,and magnetic resonance imaging(MRI).Multimodal bioimaging has also been elaborated,which could overcome the inherent trade-offs between resolution,penetration depth,and functional specificity in single-modal approaches.By elucidating mechanistic insights and translational challenges,this mini-review aims to establish a design framework of stimuli-responsive block copolymersbased for high fidelity bioimaging agents and accelerate their clinical translation in precise diagnosis and therapy.
基金financially supported by National Key R&D Program Young Scientists Project(No.2023YFC3903100)the National Natural Science Foundation of China(No.22322503)analytical and testing assistance from the Analysis and Testing Center of HUST。
文摘Switchable polymerization is emerging as a powerful tool to construct block copolymers directly from mixtures of monomers.However,current achievements typically iterate between two polymerization cycles to afford products with fixed sequences and compositions.Herein,we report the triethylborane/1,8-diazabicyclo[5.4.0]undec-7-ene(Et_3B/DBU)pair-mediated four-component switchable polymerization of propylene oxide(PO),CO_(2),phthalic anhydride(PA),and racemic lactide(rac-LA),which enables the on-demand synthesis of four different block copolymers,i.e.,poly(propylene phthalate)-b-polylactide(PPE-b-PLA),PPE-b-PLA-b-poly(propylene carbonate)(PPC),PPE-b-PPC-b-PLA,and PPE-b-PPCb-poly(propylene oxide)(PPO),through rationally modulating the Lewis pair(LP)ratio.Core to this protocol is that increasing the loading of Et_(3)B accelerates the ring-opening of PO while impeding the reactivity of rac-LA,thus allowing for fine-tuning of the thermodynamic and kinetic of the switchable polymerization.Therefore,the four polymerization cycles involving PO/PA ring-opening copolymerization(ROCOP),PO/CO_(2) ROCOP,rac-LA ring-opening polymerization(ROP),and PO ROP can be connected and discriminated in precisely programmed manners.
基金financially supported by the Russian Science Foundation(No.23-13-00205)。
文摘Star-shaped six-arm polymers with hexaaza[2_(6)]orthoparacyclophane core and arms of block copolymers of poly-2-ethyl-5,6-dihydrooxazine with poly-2-isopropyl-5,6-dihydrooxazine were synthesized successfully using cationic ring-opening polymerization.The ratio of blocks,the order of their attachment to the core,and arm length were varied.Conformation of synthesized stars was determined by methods of molecular hydrodynamics and optics.It has been shown that star-shaped molecules were characterized by high intramolecular density,and the arm folding increased with their lengthening.The influence of the structure of block copolymers and their molar mass on the critical micelle concentration has been established.Complexes of synthesized star-shaped block copolymers with curcumin were obtained and the efficient binding of curcumin to polymer molecules was demonstrated.The behavior of the aqueous solutions of the prepared polymer stars and their complexes with curcumin was investigated by light scattering and turbidimetry methods.The influence of the structure and molar mass of star polymers on their thermoresponsiveness and the phase separation temperatures in aqueous solutions was analyzed.A slight increase in the phase separation temperature was found on passage from polymer solutions to solutions of polymer complexes with hydrophobic curcumin.
文摘Some physical properties of the polyester-polyeher multiblock copolymers with Si-containing hard segment were further examined by a series of physical methods. Thehydrophobicity of the copolymers was improved with the incorporation of increasing amountof organosilicone, XPS test proved that silicon element was enriched at the surface of theSi-containing polyeser-polyether copolymers. It was also found that their heat resistanceand gas permeability for O_2 and N_2 were greatly improved. The study on semipermeabilityof films made of the Si-containing copolymers was also followed with interest.
基金financially supported by the National Key R&D Program of China(No.2022YFB3707300)the National Natural Science Foundation of China(Nos.22133002,22373089)the support from the Excellent Youth Foundation of Henan Scientific Committee(No.242300421032).
文摘A significant challenge in developing block copolymer photonic crystals is constructing low-symmetric ordered phases,which are essential for achieving a complete photonic band gap.Here,we propose a promising strategy to create low-symmetric ordered morphologies by incorporating shape-anisotropic rod-like side chains into block copolymers.Using dissipative particle dynamics simulations,we demonstrate that block copolymers with longer rod-like side chains can self-assemble into a hexagonally packed columnar phase characterized by a low-symmetric rectangular cross-section.Photonic band structure calculations reveal that this low-symmetric columnar phase can exhibit a complete photonic band gap,with the gap size dependent on the aspect ratio of the rectangular cross-sections of the columns.Our findings suggest an effective approach to constructing low-symmetric photonic crystals through the self-assembly of block copolymers with shape-anisotropic segments.
基金financially supported by the National Natural Science Foundation of China(Nos.92477118 and 22173045)the Postgraduate Research and Practice Innovation Program of Jiangsu Province(No.KYCX25_0188)。
文摘Colloidal molecules exhibit unique electronic,optical,and magnetic properties owing to their molecular-like configurations and coupling effects,making them promising building blocks for multifunctional materials.However,achieving precise and controllable assembly of isotropic nanoparticles with high yields remains a great challenge.In this study,we present a synergistic strategy that integrates molecular dynamics simulations with interpretable machine learning to develop a programmable assembly system based on block copolymers and DNA-functionalized nanoparticles.Our simulation results reveal that block copolymer modification facilitates stepwise control over surface phase separation and nanoparticle coassembly,thereby enhancing structural stability and efficiently suppressing disordered aggregation of atom-like nanoparticles.Furthermore,we demonstrated that precise,controllable,and programmable assembly of colloidal molecules can be achieved through rational DNA sequence design.SHapley Additive exPlanations(SHAP)analysis identified key structural descriptors that govern assembly outcomes and elucidated their underlying mechanistic roles.This work not only deepens the understanding of colloidal molecule assembly mechanisms but also lays a theoretical foundation for the rational design of functional colloidal architectures in nanomaterial science.
基金supported by the National Natural Science Foundation of China(Nos.52394272,22333002,22203018,22303017).
文摘The self-assembly of block copolymers serves as an effective approach for fabricating various periodic ordered nanostructures. By employing self-consistent field theory (SCFT) to calculate the phase diagrams of block copolymers, one can accurately predict their self-assembly behaviors, thus providing guidance for the fabrication of various novel structures. However, SCFT is highly sensitive to initial conditions because it finds the free energy minima through an iterative process. Consequently, constructing phase diagrams using SCFT typically requires predefined candidate structures based on the experience of researchers. Such experience-dependent strategies often miss some structures and thus result in inaccurate phase diagrams. Recently, artificial intelligence (AI) techniques have demonstrated significant potential across diverse fields of science and technology. By leveraging AI methods, it is possible to reduce reliance on human experience, thereby constructing more robust and reliable phase diagrams. In this work, we demonstrate how to combine AI with SCFT to automatically search for self-assembled structures of block copolymers and construct phase diagrams. Our aim is to realize automatic construction of block copolymer phase diagrams while minimizing reliance on human prior knowledge.
基金Yunfu 2023 Innovation Team Project,China(CYRC202305)。
文摘Mechanochromic materials respond to external stimuli and provide early warnings of material damage.Perylene diimide(PDI)-based materials have attracted attention because of their outstanding fluorescence performance.However,the application of PDI in mechanochromism is limited by the difficulty for mechanical forces to disrupt the aggregation of PDI and its derivatives,as well as the fluorescence quenching caused by continuousπ-πstacking between PDI molecules.To eliminate the fluorescence quenching effect caused by the aggregation of PDI and broaden its application fields,polyhedral oligomeric silsesquioxane(POSS)-PDI-POSS(PPP)was screened as PDI doping.The photophysical properties of PPP in both monomeric and aggregated states in different solvents were studied.Then,PPP and styrene-butadiene-styrene block copolymer(SBS)were mixed to prepare the PPP/SBS film.The mechanochromic properties of PPP/SBS film were explored.The fluorescence emission spectra confirmed that when the PPP mass fraction increased to 0.30%,the PPP/SBS film exhibited mechanochromic behavior under uniaxial deformation due to the changes in the molecular packing.
基金supported by the National Natural Science Foundation of China (Grant Nos.U20A20168 and 62404120)the National Key R&D Program (Grant No.2022YFB3204100)+2 种基金the Postdoctoral Fellowship Program of CPSF (Grant Nos.GZB20240335 and GZC20231216)the China Postdoctoral Science Foundation (Grant No.2025T180151)the Initiative Scientific Research Program of the School of Integrated Circuits,Tsinghua University。
文摘Block copolymer(BCP) nanolithography offers potential beyond traditional photolithographic limits, yet reliably producing low-defect, perpendicular domains remains challenging. We introduce a microenvironmentdriven isothermal annealing method for directed self-assembly of BCP thin films. By annealing films at stable temperature in a quasi-sealed, inert-gas chamber, our approach promotes highly uniform perpendicular lamellar nanopatterns over large areas, effectively mitigating environmental fluctuations and emulating solvent-vapor annealing without solvent exposure. Resulting BCP structures demonstrate enhanced spatial coherence and notably low defect density. Furthermore, we successfully transfer these nanopatterns into precise metal nano-line arrays,confirming the method's capability for high-fidelity pattern replication. This scalable, solvent-free technique provides a robust, reliable route for high-resolution nanopatterning in advanced semiconductor manufacturing.
基金Supported by the National Natural Science Foundation of China(21776126)the National Basic Research Program of China(2015CB655301)+1 种基金the Natural Science Foundation of Jiangsu Province(BK20150063)partially supported by the Open Fund of State Key Laboratory of Separation Membranes and Membrane Processes(M1-201702).
文摘Fouling resistance of ultrafiltration(UF) membranes is critical for their long-term usages in terms of stable performance, so convenient approaches to prepare fouling-resistant membranes are always anticipated. Herein, we demonstrate the facile fabrication of antifouling polysulfone-block-poly(ethylene glycol)(PSF-b-PEG, SFEG)composite membranes. SFEG layer was coated onto macroporous supports and cavitated by immerging them in acetone/n-propanol following the mechanism of selective swelling induced pore generation. Thus-produced SFEG membranes possessed high permeance and excellent mechanical strength. Meanwhile, the structures and separation performances of the SFEG layers can be continuously tuned through simply changing swelling durations. More importantly, the hydrophilic PEG chains were spontaneously enriched onto the pore walls through swelling treatment, endowing intrinsic antifouling property to the SFEG membranes. Bovine serum albumin(BSA)/humic acid(HA) fouling tests proved the prominent fouling resistance of SFEG membranes, and the fouling resistance is expected to be long-standing because of the firm connection between PEG chains and PSF matrix by covalent bonding.
基金financially supported by the National Natural Science Foundation of China(Nos.21622402,51673057 and 21574036)1000 plan Program for Young Talents of China
文摘Conjugated block copolymers have gained increasing interests in recent years. Development of a novel method for facile synthesis of conjugated block copolymers with desired structures and functions is greatly desired. In this mini review, we summarized the recent advances in one-pot synthesis of conjugated block copolymers containing π-conjugated polythiophene and helical polyisocyanide segments by using a nickel（Ⅱ） complex as single catalyst. The sequential living polymerization of the two monomers proceeded in a controlled manner, affording expected block copolymers in high yields with controlled molecular weights（Mns） and narrow molecular weight distributions（Mw/Mns）. By using this method, a family of block copolymers with expected structure and tunable compositions can be facilely prepared. Introducing functional groups onto the pendant, these block copolymers can exhibit interesting self-assembly property, tunable light emission and multi-responsiveness.
基金financially supported by the National Natural Science Foundation of China(Nos.51622301 and 51573046)Fundamental Research Funds for the Central Universities(Nos.B14018,WD1616010 and 222201717001)
文摘A novel fluorinated triblock copolymer incorporating 2-ethylhexyl methacrylate （EHMA）, tert-butyl methacrylate （tBMA） and 1H,1H,2H,2H-perfluorodecyl acrylate （FA） （PEHMA-b-PtBMA-b-PFA） was first synthesized using three successive reversible addition fragmentation chain transfer （RAFT） polymerization and the subsequent hydrolyzing at acidic condition. The as-fabricated triblock copolymer exhibited an interesting morphology evolution from the multi-compartment rod-like structure to spherical structure along with the addition of a selective solution. At the same time, a visible phase separation domain could be seen in the core area due to the existence of fluorocarbon segments. Furthermore, the self- assembly behavior of the triphilic copolymer at different pH was also verified by transmission electron microscopy, as well as the dynamic light scattering. These stimuli-responsive multi-compartment nanostructures may have potential applications in drug delivery.
基金financially supported by the National Natural Science Foundation of China(No.21304047)Natural Science Foundation of Jiangsu Province(No.13KJB430017)+1 种基金Research Fund for the Doctoral Program of Higher Education(No.20133221120015)Synergetic Innovation Center for Organic Electronics and Information Displays
文摘Donor-acceptor （D-A） type fully conjugated block copolymer systems have been rarely reported due to the challenges in synthetic approaches to prepare well-defined low-polydispersity products. In this work, fully conjugated block copolymers are synthesized in a one-pot reaction through Stille coupling polycondensation, by utilizing the end-functional polymer copolymerization method. End-functional P3HT are copolymerized with AA （2,7-dihromo-9-（heptadecan-9-yl）-9H- carbazole） and BB （4,7-bis（5-（trimethylstannyl）thiophen-2-yl）benzo[c][1,2,5]thiadiazole, TBT） type monomers, respectively. The orthogonal solubility between the very soluble P3HT donor and the insoluble PCDTBT acceptor block improves the purity of block copolymers as well as distinct nano-scale phase-separation compared with other reports on miscibility of donor and acceptor polymer block. Further purification via preparative GPC is carried out to remove the excess of unreacted P3HT and free PCDTBT as well as to achieve low polydispersity of block copolymers. The chemical structure of the P3HT- b-PCDTBT block copolymers are verified via IH-NMR, and further confirmed by FTIR spectra. The block copolymer shows broad absorption and moderate optical band gap of 1.8 eV. Furthermore, the fully conjugated block copolymer films exhibit significant fine structures, much smoother film morphology compared to P3HT/PCDTBT polymer blends. By adding a small amount of block copolymer P3HT-b-PCDTBT as a compatibilizer into the bulk-heterojunction of P3HT：PC61BM blends, polymer solar ceils with an 8% increase of short circuit current （Jse） and 10% increase of power conversion efficiency （PCE） are achieved owing to the improvement of the active-layer film morphology. To the best of our knowledge, this is the first report on donor-acceptor type fully conjugated block copolymer as an effective ternary additive in polymer： fullerene bulk heterojunction solar cells.
文摘This feature article summarizes the synthesis of novel olefin block copolymers using fast syndiospecific living homo- and copolymerization of propylene, higher 1-alkene, and norbornene with ansa-fluorenylamidodimethyltitanium- based catalyst according to the authors＇ recent results. The catalytic synthesis of monodisperse polyolefin and olefin block copolymer was also described using this living system.
基金financially supported by the National Science Foundation for Distinguished Young Scholars(No.21525419)the National Natural Science Foundation of China(Nos.21274066 and 21474054)the National Key Research and Development Program of China(No.2016YFA0202503)
文摘Controlled synthesis of amphiphilic block copolymer nanoparticles in a convenient way is an important and interest topic in polymer science. In this review, three formulations of polymerization-induced self-assembly to in situ synthesize block copolymer nanoparticles are briefly introduced, which perform by reversible addition-fragmentation chain transfer （RAFT） polymerization under heterogeneous conditions, e.g., aqueous emulsion RAFT polymerization, dispersion RAFT polymerization and especially the recently proposed seeded RAFT polymerization. The latest developments in several selected areas on the synthesis of block copolymer nano-assemblies are highlighted.
基金financially supported by the National Natural Science Foundation of China(No.21204002)Specialized Research Fund for the Doctoral Program of Higher Education(No.20111102120050)+1 种基金Program for New Century Excellent Talents in Universities(2010)the Fundamental Research Funds for the Central Universities
文摘pH-sensitive wettability of polystyrene-b-poly（4-vinylpyridine） （PS-b-P4VP） self assembled films, exhibiting superoleophobicity under water and hydrophilicity at low pH value, and oleophobicity under water and hydrophobicity at neutral condition, has been realized. The wettability properties resulted from the surface topological and chemical transition, which were confirmed by in situ AFM measurements under water at different pH. At low pH, P4VP chains, which were confined in the hexagonal-packed nanodomains, got protonated into a swollen state, while at high pH, P4VP chains were deprotonated into a collapsed state. The reversible protonation/deprotonation procedure on the molecular scale leads to surface topological and chemical transition, thereby pH-sensitive wettability.
基金financially supported by the National Natural Science Foundation of China(Nos.51173181 and 51373166)“The Hundred Talents Program”from the Chinese Academy of Sciences and the International S&T Cooperation Program from Department of Science and Technology of Jilin Province(No.20160414032GH)
文摘Block copolymer lithography is emerging as one of the leading technologies for patteming nanoscale dense features. In almost all potential applications of this technology, control over the orientation of cylindrical and lamellar domains is required for pattern transfer from the block copolymer film. This review highlights the state-of-art development of brushes to modify the substrates to control the assembly behaviors of block copolymers in films. Selected important contributions to the development of self-assembled monolayers, polymer brushes and mats, and chemically patterned brushes are discussed.
基金financially supported by the National Natural Science Foundation of China (Nos. 51525302 and 51811540404)Program for HUST Academic Frontier Youth Team (No. 2015-01)the Fundamental Research Funds for the Central Universities (No. 2019kfyXJJS077)
文摘Structured block copolymer(BCP) particles have gained increasing attention due to their potential applications in separation,catalysis, controlled release, and other fields. Three-dimensional(3D) confined assembly has been proved as a facile yet robust approach for generating BCP particles with controllable shapes and internal structures. In this feature article, we summarized the preparation of structured polymeric particles through 3D confined self-assembly of BCPs. The effects of interfacial interactions, degree of confinement,and additives on the shape and internal structure of BCP microparticles were comprehensively discussed. In addition, we highlighted the recent progress in using disassembly as a route to synthesize colloidal particles with unique structures. Two strategies were introduced in this part:(a) disassembling the discrete domains resulted in mesoporous microparticles;(b) disassembling the continuous domains led to the dissociation of microparticles into micelle-like nano-objects. The applications of the structured colloidal particles in photonic crystals,controlled release, and directed growth of inorganic materials were also presented. Finally, we discussed the current challenges and future opportunities in this promising area.
基金financially supported by the National Natural Science Foundation of China(Nos.51573091,21774076,21320102006 and 91527304)Program of the Shanghai Committee of Science and Technology(Nos.17JC1403200 and 16JC1400703)Program for Shanghai Eastern Scholar
文摘The self-assembly of block copolymer in solution has proven to be an effective strategy for building up a wide range of nanomaterials with diverse structures and applications.This paper reports a facile self-assembly approach towards two-dimensional(2D)sandwich-like mesoporous nitrogen-doped carbon/reduced graphene oxide nanocomposites(denoted as mNC/rGO)with well-defined large mesopores.The strategy involves the synergistic self-assembly ofpolystyrene-block-poly(ethylene oxide)(PS-b-PEO)spherical micelles,m-phenylenediamine(mPD)monomers and GO in solution and the subsequent carbonization at 900~C.The resultant mNC/rGO nanosheets have an average pore size of 19 nm,a high specific surface of 812 m^(2)'g^(-1)and a nitrogen content of 2.2 wt%.As an oxygen reduction reaction(ORR)catalyst,the unique structural features render the metal-free nanosheets excellent electrocatalytic performance.In a 0.1 mol.L-~KOH alkaline medium,mNC/rGO exhibits a four-electron transfer pathway with a high half-wave-potential(El/2)of+0.77 V versus reversible hydrogen electrode(RHE)and a limiting current density(JL)of 5.2 mA'cm^(-2),which are well comparable with those of the commercial Pt/C catalysts.
