JOURNAL OF POLYMER RESEARCH
·
2022
·Vol. 29
·期 4
·1-9
·
IF 3.061
Zhang Andong,Hao Jingyi,Hou Sen,Shi Ge,He Yanjie,Cui Zhe,Liu Minying,Qiao Xiaoguang,Fu Peng,Pang Xinchang
Aggregation-induced emission (AIE) has already been applied for in-situ monitoring living radical polymerization process. Here we utilized functionalized monomer TPEE as fluoresce probes for the in-situ monitoring of photo-induced RAFT-PISA process. Hydrophilic POEGA macro chain transfer agent (Macro-CTA) was first prepared with light sensitive CTA 4-Cyanopentanoic acid dithiobenzoate, and (2-(4-vinylphenyl)ethene-1,1,2-triyl)tribenzene (TPEE) was copolymerized with styrene to form the hydrophobic block under UV irradiation. The growth of hydrophobic block induced the self-assembly of polymer chains and the emission signal could be observed by naked eyes afterwards. The PL intensity increased with the increase of particle size, as well as the monomer conversion and molecular weight, owing to the enhancement of AIE monomer in the self-assembly latex particles. This no-invasive and facile approach to in-situ visualization and continuously monitoring of the photo-induced RAFT-PISA process might be helpful for both scientific research and commercial application.
研究领域:
高分子化学
·
材料科学
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DOI
高影响因子
Soft Matter
·
2023
·Vol. 19
·期 25
·4651-4659
·
IF 3.4
Xi Zhao,Jiani Peng,Liangliang Shi,Guoxiang Wang,Yong Gao
The preparation of mixed-shell polymeric nanoparticles (MSPNs) and their stabilized non-aqueous Pickering emulsions was described in this study. Poly(methyl methacrylate)–poly(4-vinylpyridine) (PMMA–P4VP) diblock copolymer nanoparticles with different morphologies including spheres, worms and vesicles were first prepared via reversible addition-fragmentation chain transfer-based polymerization induced self-assembly in toluene. C18 alkyl chains were subsequently grafted onto the surfaces of the as-prepared PMMA–P4VP nanoparticles, affording C18/PMMA–P4VP MSPNs with P4VP blocks as the core and C18/PMMA chains as the mixed shells. MSPNs were utilized as Pickering emulsifiers to prepare non-aqueous Pickering emulsions, where [Bmim][PF6] and toluene oils were selected. Two kinds of different Pickering emulsions, [Bmim][PF6]-in-toluene and toluene-in-[Bmim][PF6], could be formed, depending on the initial location of MSPNs. However, neither of them could be generated when PMMA–P4VP diblock copolymer nanoparticles were adopted as Pickering emulsifiers, indicating MSPNs were better than diblock copolymer nanoparticle precursors in the aspect of stabilizing oil–oil interfaces. The formation mechanisms of different kinds of Pickering emulsions were unraveled in this study.
研究领域:
材料科学
·
化学工程
·
胶体科学
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产品关联
DOI
PubMed
高影响因子
Polymer Chemistry
·
2016
·Vol. 7
·期 22
·3756-3765
·
IF 5.687
Mingguang Yu,Jianbo Tan,Jianwen Yang,Zhaohua Zeng
In a common RAFT dispersion polymerization induced self-assembly (PISA) formulation, R-type macro-RAFT agents with a solvophilic chain attached at the leaving group side are normally used to mediate the polymerization, meanwhile Z-type macro-RAFT agents with a solvophilic chain attached at the Z-group side are seldom employed. In this paper, we have tried to use a Z-type macro-RAFT agent (mPEG113-BTPA) to mediate RAFT dispersion polymerization of styrene, and found that the process exhibited a poorer PISA tendency and weaker molecular weight control. In comparison, we have conducted the same process mediated with an R-type macro-RAFT agent (mPEG113-DDMAT), and found that the formulation exhibited a typical PISA process, and nanoparticles were produced in situ. Further experiments suggest that the location of RAFT groups plays a key role for the PISA process in RAFT dispersion polymerization. The RAFT groups will be embedded in the produced particles when an R-type macro-RAFT agent is employed, but locate on the particle surface in the case of the Z-type macro-RAFT agent. We have tried to employ the RAFT groups on the surface of the mPEG113-BTPA stabilized particles to modify the particle surface, and successfully removed the solvophilic block via breaking the RAFT group, and generated the poly(dimethylacrylamide) block by surface-initiated RAFT polymerization. Based on the above mechanism perspective, we have designed a preliminary experiment, and found that well-defined monodisperse nanospheres could be prepared by heterogeneous RAFT dispersion polymerization mediated with a Z-type macro-RAFT agent-based block copolymer which was synthesized via pre-polymerization of styrene in 1,4-dioxane mediated with mPEG113-BTPA.
研究领域:
高分子化学
·
胶体与界面科学
·
纳米材料
·
可控自由基聚合
·
自组装
·
药物递送系统
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DOI
高影响因子
CHINESE JOURNAL OF POLYMER SCIENCE
·
2019
·Vol. 38
·期 1
·9-16
·
IF 2.804
Man Shou-Kuo,Wang Xiao,Zheng Jin-Wen,An Ze-Sheng
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, PEG 45 -CTA, and PEG 113 -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.
研究领域:
材料科学
·
化学
✓ 已验证
产品关联
DOI
高影响因子
Polymer Chemistry
·
2017
·Vol. 8
·期 41
·6407-6415
·
IF 5.375
Ke Wang,Yixin Wang,Wangqing Zhang
Diblock copolymer nano-assemblies of poly(2-hydroxypropyl methacrylate-b-benzyl methacrylate) (PHPMA-b-PBzMA) were synthesized by initiators for continuous activator regeneration atom transfer radical polymerization (ICAR ATRP) using the CuIIBr2/tris(pyridin-2-ylmethyl)-amine (TPMA) complex as a catalyst under dispersion conditions and were compared with those obtained by RAFT dispersion polymerization. It is found that these two kinds of polymerizations afford good control, as indicated by the linearly increasing molecular weight with monomer conversion and the narrow molecular weight distribution, whereas the ICAR ATRP runs a little faster than RAFT. In the two cases of dispersion polymerization, the morphologies of the PHPMA-b-PBzMA nano-assemblies are similar to each other and change from spheres to wormlike aggregates with block extension, whereas the size of the nano-assemblies by ICAR ATRP is usually larger than those obtained by RAFT. The degree of polymerization (DP) of the poly(2-hydroxypropyl methacrylate) and poly(benzyl methacrylate) blocks affecting the size and/or morphology of the PHPMA-b-PBzMA nano-assemblies is investigated, and the reason for the larger size of the PHPMA-b-PBzMA nano-assemblies by ICAR ATRP is discussed.
研究领域:
高分子化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
POLYMER
·
2021
·
IF 4.43
Jia-Wei Li,Miao Chen,Jie-Mei Zhou,Cai-Yuan Pan,Wen-Jian Zhang,Chun-Yan Hong
Polymerization-induced self-assembly (PISA) is an efficient and robust strategy to fabricate polymeric nano-objects. PISA enables us to prepare polymeric nano-objects in situ during the course of polymerization in concentrated solution (up to 50% w/w), making industrial production of polymeric assemblies in large-scale possible. In this work, reversible addition-fragmentation chain transfer (RAFT) dispersion copolymerization of styrene (St) and N-methacryloxysuccinimide (NMAS) was conducted with poly(2-hydroxyethyl acrylate) (PHEA) as a macro-chain transfer agent (macro-CTA) in methanol. Compared with the PHEA-mediated alcoholic dispersion polymerization of St, RAFT dispersion copolymerization of St and NMAS promoted morphology transition of nano-objects to form higher order morphologies (such as worms and vesicles). Moreover, the introduction of NMAS units into the solvophobic blocks provided functional handles for post-PISA modification of the resultant nano-objects via the active ester-amine reaction. The reaction of 1,6-hexanediamine with NMAS units in P(St- co -NMAS) blocks was conducted to afford cross-linked nano-objects with robust structural stability.
研究领域:
高分子化学
·
材料科学
✓ 已验证
DOI
高影响因子
Polymer Chemistry
·
2017
·Vol. 8
·期 8
·1315-1327
·
IF 5.375
Jianbo Tan,Dongdong Liu,Yuhao Bai,Chundong Huang,Xueliang Li,Jun He,Qin Xu,Xuechao Zhang,Li Zhang
A poly(glycerol monomethacrylate) (PGMA) chain transfer agent is used for aqueous reversible addition–fragmentation chain transfer (RAFT) dispersion polymerization of 2-hydroxypropyl methacrylate (HPMA) via photoinitiation or thermal initiation. Kinetic studies showed that the rate of polymerization of photo-PISA was much faster than that of thermally initiated PISA, both at the homogeneous polymerization stage and the heterogeneous polymerization stage. The effect of light intensity on photo-PISA was investigated, which showed that increasing light intensity led to faster polymerization behavior. In virtue of the temperature-insensitive property of the photoinitiator, the sole effect of reaction temperature on PISA was studied in detail for the first time. Transmission electron microscopy (TEM) measurements indicated that higher reaction temperature facilitated the formation of higher order morphologies. Finally, a one-pot photoinitiated polymerization was conducted in water to prepare diblock copolymer nano-objects with different morphologies (spheres, worms, and vesicles).
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
Polymer Chemistry
·
2017
·Vol. 8
·期 44
·6853-6864
·
IF 5.375
Jianbo Tan,Jun He,Xueliang Li,Qin Xu,Chundong Huang,Dongdong Liu,Li Zhang
A series of well-defined all-acrylic poly(hydroxyethyl acrylate)-poly(isobornyl acrylate) (PHEA-PIBOA) diblock copolymer nano-objects were prepared by photoinitiated polymerization-induced self-assembly (photo-PISA) of isobornyl acrylate in ethanol/water at 40 °C using poly(hydroxyethyl acrylate)-based macromolecular chain transfer agents (macro-CTAs). Polymerizations proceeded rapidly upon exposure to visible light irradiation (λmax = 405 nm, 0.46 mW cm−2) with high monomer conversion being achieved within 30 min. Gel permeation chromatography (GPC) demonstrated that good control was maintained throughout the photo-PISA process, and the final block copolymers exhibited relatively low polydispersities (Mw/Mn ≤ 1.55). By virtue of the high Tg value of PIBOA, a diverse set of block copolymer nano-objects having different morphologies (e.g. spheres, worms, and vesicles) were prepared and characterized by conventional transmission electron microscopy (TEM). Two phase diagrams were constructed by varying the DP of the PIBOA block or monomer concentration or the DP of the PHEA macro-CTA. Worm-like micelles were prepared by monitoring the viscosity of the reaction mixture in a proof-of-concept experiment. Finally, poly(acrylic acid) (PAA) and poly(2-(dimethylamino)ethyl acrylate) (PDMAEA) macro-CTAs were also utilized to mediate the photo-PISA process, demonstrating the versatility of this method.
研究领域:
材料科学
·
高分子化学
✓ 已验证
产品关联
DOI
高影响因子
Polymer Chemistry
·
2016
·Vol. 7
·期 13
·2372-2380
·
IF 5.687
Jianbo Tan,Yuhao Bai,Xuechao Zhang,Li Zhang
The photoinitiated polymerization-induced self-assembly (photo-PISA) of 2-hydroxypropyl methacrylate (HPMA) is conducted in water by using poly(poly(ethylene glycol) methyl ether methacrylate) (PPEGMA) based macro-RAFT agents. Polymerizations were carried out at room temperature via exposure to visible light irradiation, and quantitative monomer conversions (>99%) were achieved within 30 min of visible light irradiation. A remarkably diverse set of complex morphologies (spheres, worms, and vesicles) have been prepared by aqueous photo-PISA under mild conditions (water medium, room temperature, and visible light). The morphology of nano-objects can be tuned by changing the reaction parameters (e.g. degree of polymerization, solids concentration), and two detailed phase diagrams were constructed. The polymerization can be activated or deactivated by a simple “ON/OFF” switch of the light source. A thermo-responsive behavior of PPEGMA14-PHPMA200 nanoparticles prepared at 15% w/w was investigated by changing the temperature from 25 °C to 4 °C.
研究领域:
材料科学
·
化学工程
·
高分子化学
✓ 已验证
产品关联
DOI
高影响因子
MACROMOLECULES
·
2025
·
IF 5.2
Guangran Shao,Fuyang Hu,Xiaohua Tong,Ming Yuan,Boyi Song,Wangqing Zhang
Polymer membranes are used in a wide range of categories such as gas separation, CO2 catalysis, and wastewater treatment. The preparation method exerts a crucial influence on the structure and properties of the membrane. In this work, three block copolymer nanoassemblies have been initially prepared by reversible addition–fragmentation chain transfer (RAFT) dispersion polymerization via polymerization-induced self-assembly (PISA), and then they are used to prepare block copolymer nanoassembly membranes by fusion of the block copolymer nanoassemblies with different morphologies, such as nanospheres, vesicles, and worms. The block copolymer nanoassembly membranes have many particle interfaces inside, which are different from the block copolymer membranes prepared by casting a polymer solution. Consequently, the mechanical property of the block copolymer nanoassembly membrane is inferior to that of the block copolymer membranes. Heating the block copolymer nanoassembly membrane above the glass transition temperature (Tg) of the block copolymer can promote interparticle fusion and therefore increase its mechanical strength. It is found that the typical membrane formed by block copolymer worms has a much higher CO2 permeability than the block copolymer membrane (754 vs 287 Barrer), suggesting less fusion of block copolymer worms to lead particle interfaces during membrane formation. The present study reveals how the polymer particle morphology affects the structure and properties of the block copolymer nanoassembly membranes, and this is believed to be useful for designing polymer membranes.
研究领域:
高分子科学
·
材料工程
·
化学工程
·
纳米技术
·
膜科学
✓ 已验证
产品关联
DOI
高影响因子
ANALYTICAL CHEMISTRY
·
2019
·
IF 6.35
Wei Li,Qi Zhang,Yijia Wang,Yanyan Ma,Zhanchen Guo,Zhen Liu
Molecularly imprinted polymers (MIPs) and aptamers, as effective mimics of antibodies, can overcome only some drawbacks of antibodies. Since they have their own advantages and disadvantages, the combination of MIPs with aptamers could be an ideal solution to produce hybrid alternatives with improved properties and desirable features. Although quite a few attempts have been made in this direction, a facile and controllable approach for the preparation of aptamer–MIP hybrids still remains lacking. Herein, we present a new approach for facile and controllable preparation of aptamer–MIP hybrids for high-specificity and high-affinity recognition toward proteins. An aptamer that can bind the glycoprotein alkaline phosphatase (ALP) with relative weak affinity and specificity was used as a ligand, and controllable oriented surface imprinting was carried out with an in-water self-polymerization system of dopamine. A thin layer of polydopamine was formed to cover the template to an appropriate thickness. After removing the template from the polymer, an aptamer–MIP hybrid with apparently improved affinity and specificity toward ALP was obtained, giving cross-reactivity of 3.2–5.6% and a dissociation constant of 1.5 nM. With this aptamer–MIP hybrid, a plasmonic immunosandwich assay (PISA) was developed. Reliable detection of ALP in human serum by the PISA was demonstrated.
研究领域:
生物材料
·
分析化学
·
生物技术
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Polymer Chemistry
·
2024
·
IF 4.1
Huangbing Xu,Teng Qiu,Haotian Shi,Xiaoqian Tian,Xiaoyu Li,Longhai Guo
RAFT-mediated polymerization-induced self-assembly (RAFT-PISA) has been undergoing fast development currently, promoting research toward more diverse morphologies and more cutting-edge applications. Herein, we demonstrate a polymerization-pH tailored RAFT-PISA (pH-PISA) process, which can conveniently harvest abundant nano/micro-scale morphologies using popular monomers N,N-dimethylacrylamide (DMAA) and diacetone acrylamide (DAAM). The process proceeded through ordinary RAFT dispersion polymerization in an aqueous medium but under different pH conditions. With the use of pH-sensitive bi-carboxylic acid-capped trithiocarbonate as the chain transfer agent (CTA), it was found that the PISA of propagating amphiphilic ABA triblock copolymers was highly affected by the different ionization of the CTA. When the polymerization pH was adjusted to 2.5, an especially wide spectrum of morphologies was detected, including spheres, worms, lamellae, single or double-head tadpoles, vesicle strings and large spheres with surface protrusions. However, the diversity in morphology gradually declined when the polymerization pH was increased to 6 or 8. Diverse structures with same monomer compositions provide an ideal model to explore the influence of particle morphology on ice recrystallization inhibition (IRI) activities. The variations in mean largest grain sizes (MLGS) and growth rates of a single ice crystal were related to packing parameters (P), bridging the interface geometry of the packing of amphiphilic molecules and ice-controlling activities.
研究领域:
高分子化学
·
材料科学
·
胶体与表面化学
·
低温生物学
✓ 已验证
产品关联
DOI
高影响因子