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Chinese Journal of Chemistry 2021年第7期39卷 1819-1824页

作者： Xin Luo Zesheng An Institute of Nanochemistry and Nanobiology College of Environmental and Chemical EngineeringShanghai UniversityShanghai200444 China State Key Laboratory of Supramolecular Structure and Materials College of ChemistryJilin UniversityChangchunJilin130012 China

Main observation and conclusion polymerization-induced self-assembly(PISA)is an effective method to prepare block copolymer(BCP)particles with various ***,BCPs with inverse bicontinuous phase structure have been rarel... 详细信息

关键词： Block copolymers Inverse bicontinuous phase Mesophases polymerization-induced self-assembly RAFT polymerization

Sequence structure controllable polymerization-induced self-assembly

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Science China Chemistry 2024年第1期67卷 390-397页

作者： Zi-Xuan Chang Ren-Man Zhu Chun-Yan Hong Wen-Jian Zhang Department of Polymer Science and Engineering University of Science and Technology of ChinaHefei 230026China Institute of Physical Science and Information Technology Anhui UniversityHefei 230601China Key Laboratory of Environment-Friendly Polymeric Materials of Anhui Province Anhui UniversityHefei 230601China

polymerization-induced self-assembly(PISA)combines synthesis and self-assembly of artificial polymers in one-pot,which brings us one step closer to emulating ***,the reported PISA formulations primarily focus on developing nano-objects with new chemical compositions and rarely on structural regulation of polymers with specific ***,sequence structure controllable polymerization-induced self-assembly(SCPISA)is reported by using 7-(2-methacryloyloxyethoxy)-4-methylcoumarin(CMA)as a *** the copolymerization of 2-hydroxyethyl methacrylate(HEMA)and CMA,controlled incorporation of CMA units into the polymer chains can be realized by programmable light/heat ***-based P(HEMA-co-CMA)copolymers with the same composition but different sequence structures generate a range of ***,the morphologies of the resultant nano-objects can also be controlled by regulating the feed molar ratio of CMA and HEMA,which is similar to the conventional PISA,but the synthesis procedure is obviously simplified in *** versatility of the methodology is further demonstrated by the fabrication of different functional nano-objects with sequence structure-dependent morphologies in SCPISA systems with different functional monomers.

关键词： polymerization-induced self-assembly sequence-controlled polymers PET-RAFT polymerization

Enzyme-assisted Photoinitiated polymerization-induced self-assembly in Continuous Flow Reactors with Oxygen Tolerance

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Chinese Journal of Polymer Science 2021年第9期39卷 1127-1137页

作者： Wei-Bin Cai Dong-Dong Liu Ying Chen Li Zhang Jian-Bo Tan Department of Polymeric Materials and Engineering School of Materials and EnergyGuangdong University of TechnologyGuangzhou 510006China Guangdong Provincial Key Laboratory of Functional Soft Condensed Matter Guangzhou 510006China

polymerization-induced self-assembly(PISA)is an emerging method for the preparation of block copolymer nano-objects at high ***,most PISA formulations have oxygen inhibition problems and inert atmospheres(***,nitrogen)are usually ***,the large-scale preparation of block copolymer nano-objects at room temperature is ***,we report an enzyme-assisted photoinitiated polymerization-induced self-assembly(photo-PISA)in continuous flow reactors with oxygen *** addition of glucose oxidase(GOx)and glucose into the reaction mixture can consume oxygen efficiently and constantly,allow the flow photo-PISA to be performed under open-air *** kinetics indicated that only a small amount of GOx(0.5 μmol/L)was needed to achieve the oxygen *** copolymer nano-objects with different morphologies can be prepared by varying reaction conditions including the degree of polymerization(DP)of core-forming block,monomer concentration,reaction temperature,and solvent *** expect this study will provide a facile platform for the large-scale production of block copolymer nano-objects with different morphologies at room temperature.

关键词： polymerization-induced self-assembly Reversible addition-fragmentation chain transfer(RAFT)polymerization Photoinitiation Oxygen tolerance

Effect of Butyl α-Hydroxymethyl Acrylate Monomer Structure on the Morphology Produced via Aqueous Emulsion polymerization-induced self-assembly

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Chinese Journal of Polymer Science 2020年第1期38卷 9-16,I0005页

作者： Shou-Kuo Man Xiao Wang Jin-Wen Zheng Ze-Sheng An Institute of Nanochemistry and Nanobiology College of Environmental and Chemical EngineeringShanghai UniversityShanghai200444China State Key Laboratory of Supramolecular Structure and Materials College of ChemistryJilin UniversityChangchun 130012China

polymerization-induced self-assembly(PISA) is an efficient and versatile method to afford polymeric nano-objects with polymorphic morphologies. Compared to dispersion PISA syntheses based on soluble monomers, the vast majority of emulsion PISA formulations using insoluble monomers leads to kinetically-trapped spheres. Herein, we present aqueous emulsion PISA formulations generating worms and vesicles besides spheres. Two monomers with different butyl groups, n-butyl(n BHMA) and tert-butyl(t BHMA) α-hydroxymethyl acrylate, and thus possessing different water solubilities were synthesized via Baylis-Hillman reaction. Photoinitiated aqueous emulsion polymerizations of n BHMA and t BHMA employing poly(ethylene glycol) macromolecular chain transfer agents(macro-CTAs, PEG45-CTA, and PEG113-CTA) at 40 °C were systematically investigated to evaluate the effect of monomer structure and solubility on the morphology of the generated block copolymer nano-objects. Higher order morphologies including worms and vesicles were readily accessed for t BHMA, which has a higher water solubility than that of n BHMA. This study proves that plasticization of the core-forming block by water plays a key role in enhancing chain mobility required for morphological transition in emulsion PISA.

关键词： Block copolymer α-Hydroxymethyl acrylate RAFT emulsion polymerization polymerization-induced self-assembly

Preparation of pH-and reductive-responsive prodrug nanoparticles via polymerization-induced self-assembly

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Science China Chemistry 2018年第9期61卷 1159-1166页

作者： Miao Chen Wei-Guo Zhang Jia-Wei Li Chun-Yan Hong Wen-Jian Zhang Ye-Zi You CAS Key Laboratory of Soft Matter Chemistry Department of Polymer Science and Engineering University of Science and Technology of China Hefei 230026 China The First Affiliated Hospital of Xinxiang Medical University Xinxiang 453100 China

pH-and reductive-responsive prodrug nanoparticles are constructed via a highly efficient strategy, polymerization-induced selfassembly(PISA). First, reversible addition-fragmentation chain transfer(RAFT) polymerization of 2-(diisopropylamino) ethyl methacrylate(DIPEMA) and camptothecin prodrug monomer(CPTM) using biocompatible poly(N-(2-hydroxypropyl) methacrylamide)(PHPMA-CPDB) as the macro RAFT agent is carried out, forming prodrug diblock copolymer PHPMA-P(DIPEMA-co-CPTM). Then, simultaneous fulfillment of polymerization, self-assembly, and drug encapsulation are achieved via RAFT dispersion polymerization of benzyl methacrylate(Bz MA) using the PHPMA-P(DIPEMA-co-CPTM) as the macro RAFT agent. The prodrug nanoparticles have three layers, the biocompatible shell(PHPMA), the drug-conjugated middle layer(P(DIPEMA-co-CPTM)) and the PBz MA core, and relatively high concentration(250 mg/g). The prodrug nanoparticles can respond to two stimuli(reductive and acidic conditions). Due to reductive microenvironment of cytosol, the cleavage of the conjugated camptothecin(CPT) within the prodrug nanoparticles could be effectively triggered. p H-induced hydrophobic/hydrophilic transition of the PDIPEMA chains results in faster diffusion of GSH into the CPTM units, thus accelerated release of CPT is observed in mild acidic and reductive conditions. Cell viability assays show that the prodrug nanoparticles exhibit well performance of intracellular drug delivery and good anticancer activity.

关键词： polymerization-induced self-assembly pH-responsive reductive-responsive drug delivery

Synchronous Synthesis of Polymeric Vesicles with Controllable Size and Low-Polydispersity by polymerization-induced self-assembly

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Chinese Journal of Chemistry 2022年第4期40卷 453-459页

作者： Ren-Man Zhu Cheng-Lin Yang Zi-Xuan Chang Cai-Yuan Pan Wen-Jian Zhang Chun-Yan Hong CAS Key Laboratory of Soft Matter Chemistry Department of Polymer Science and EngineeringUniversity of Science and Technology of ChinaHefeiAnhui 230026China Institute of Physical Science and Information Technology Anhui UniversityHefeiAnhui 230601China

Comprehensive Summary The size and size distribution of polymeric nanoparticles have great impact on their physicochemical and biological ***-induced self-assembly(PISA)has been demonstrated to be an efficient method to fabricate various polymeric nanoparticles,among which polymeric vesicles have attracted great interest due to their unique hollow structure.

关键词： polymerization-induced self-assembly RAFT dispersion polymerization Vesicles Block copolymers Nanoparticles

High-performance nano-splitters containing aggregation-induced emission luminogens for stereoselective crystallization obtained via polymerization-induced self-assembly

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Aggregate

Aggregate 2021年第6期2卷 109-115页

作者： Bowen Li Na Li Zhaoxu Wang Xichong Ye Jie Zhang Xinhua Wan Beijing National Laboratory for Molecular Sciences Key Laboratory of Polymer Chemistry and Physics of Ministry of EducationCollege of Chemistry and Molecular EngineeringPeking UniversityBeijingChina

Collecting both enantiomorphs with high optical purity and yield in a single crystallization process can be achieved by adding aggregated polymeric“tailor-made”additives,known as *** preparation and large addition amount have hindered the practical application of such amazing ***,we report the first nano-splitters containing aggregation-induced emission luminogens prepared via polymerization-induced self-assembly of block copolymer,poly[(S)-2-(tert-butoxycarbonylamino)-6-(methacrylamido)hexanoic acid]-b-polystyrene,followed by the removal of tert-butoxycarbonyl *** added into the supersaturated solution of racemic amino acids(a.a.)with seeds,the fluorescent labeled nano-assemblies enantioselectivity dyed the crystals of *** enabled the separation from colorless *** in terms of fluorescent *** enantiomers were obtained with high optical purity and yield(e.g.,R-asparagine monohydrate,>99 ee%;S-asparagine monohydrate,∼94 ee%;88%total yield).Owing to a low detection limit of fluorescence,the addition amount was reduced to 0.03 wt%without remarkably compromising the ee values of both *** to the low addition amount and efficient synthesis,the output–input ratio was increased greatly.

关键词： aggregation-induced emission(AIE) chiral conglomerate polymerization-induced self-assembly RAFT stereoseparation

Principles and Characteristics of polymerization-induced self-assembly with Various polymerization Techniques

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CCS Chemistry 2021年第4期3卷 2104-2125页

作者： Erik Jan Cornel Jinhui Jiang Shuai Chen Jianzhong Du Department of Polymeric Materials School of Materials Science and EngineeringKey Laboratory of Advanced Civil Engineering Materials of Ministry of EducationTongji UniversityShanghai 201804 Department of Orthopedics Shanghai Tenth People’s HospitalTongji University School of MedicineShanghai 200072

A chemical reaction that drives a physical polymer selfassembly process,namely,polymerization-induced self-assembly(PISA),combines block copolymer synthesis and nanoparticle formation efficiently at high polymer *** nanoparticlemorphologies such as spheres,worms,and vesicles can be prepared readily in polar and *** has been well developed in combination with reversible addition-fragmentation chain transfer(RAFT)***,developments with other polymerization methods are also *** this report,first,we discuss the general principles of RAFT-PISA and the nanoparticles generated from this ***,new insights into polymer nucleation and subsequent morphological evolution are ***,PISA formulations that use other polymerization methods[atom transfer radical polymerization(ATRP),nitroxide-mediated polymerization(NMP),ring-opening metathesis polymerization(ROMP),and ring-opening polymerization(ROP)of N-carboxyanhydrides(NCAs)]are summarized in ***,more exotic PISA formulations are emphasized:these are based on organotelluriummediated living radical polymerization(TERP),living anionic polymerization(LAP),addition-fragmentation chain transfer(AFCT)polymerization,reversible complexation-mediated polymerization(RCMP),and cobalt-mediated radical polymerization(CMRP),or utilize a comonomer that undergoes radical ringopening polymerization(rROP).This reviewis concluded with a perspective on the status and potential of PISA.

关键词： polymerization-induced self-assembly block copolymers nanoparticles dispersion polymerization emulsion polymerization

Reversible CO_(2)-, Photo-and Thermo-Triple Responsive Supramolecular Chirality of Azo-containing Block Copolymer Assemblies Prepared by polymerization-induced Chiral self-assembly

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Chinese Journal of Polymer Science 2022年第1期40卷 56-66页

作者： Ya-Jing Sun Xiao-Xiao Cheng Teng-Fei Miao Hao-Tian Ma Wei Zhang Xiu-Lin Zhu Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application State and Local Joint Engineering Laboratory for Novel Functional Polymeric MaterialsCollege of ChemistryChemical Engineering and Materials ScienceSoochow UniversitySuzhou Industrial ParkSuzhou 215123China

polymerization-induced chiral self-assembly(PICSA)is an efficient strategy that not only allows the construction of the supramolecular chiral assemblies in a controlled manner but also can regulate the morphology in ***,a series of azobenzene-containing block copolymer(Azo-BCP)assemblies with tunable morphologies and supramolecular chirality were obtained through the PICSA *** supramolecular chirality of Azo-BCP assemblies could be regulated by carbon dioxide(CO_(2))stimulus,and completely recovered by bubbling with Ar.A reversible morphology transformation and chiroptical switching process could also be achieved by the alternative 365 nm UV light irradiation and heatingcooling ***,the supramolecular chirality is thermo-responsive and a reversible chiral-achiral switching was successfully realized,which can be reversibly repeated for at least five *** work provides a feasible strategy for constructing triple stimuli-responsive supramolecular chiral nano-objects in situ.

关键词： Supramolecular chirality polymerization-induced self-assembly Azobenzene CO_(2)responsiveness

Synthesis of New Hybrid Morphologies via Nitroxide-mediated polymerization-induced self-assembly of Block Copolymers at the Surface of Silica Particles

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Synthesis of New Hybrid Morphologies via Nitroxide-mediated ...