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COLLOID AND POLYMER SCIENCE · 2016 ·Vol. 294 ·期 4 ·767-776 · IF 1.89

Poor solvent as a nucleating agent to induce poly(ε-caprolactone) ultrathin film crystallization on poly(vinylpyrrolidone) substrate

Guo Caixia,Huo Hong

The poor solvent (hexanol)-induced crystallization of poly(ε-caprolactone) (PCL) ultrathin film on poly(vinylpyrrolidone) (PVPY) substrate is studied by using atomic force microscopy (AFM). PCL single crystals with screw dislocations melt and wet on PVPY substrate, forming a PCL ultrathin film with continuously changed film thickness. The effect of film thickness on the PCL crystallization morphology is directly observed by using the wetted PCL ultrathin film. Morphology transition from compact seaweed (CS) to fractal dendrite (FD) occurs with the decrease of the film thickness. A lot of dispersed FDs appear when PCL ultrathin film recrystallizes in the presence of minute amount of hexanol. We denote it as a “multi-nuclei” phenomenon. The content of residual hexanol is regulated by changing sample drying time under vacuum or sample melting temperature. Results show that the condition to obtain the highest nuclei density (or crystal density) is that the sample is dried under vacuum at room temperature for 24 h during sample preparation and melts at 200 °C for 10 min before recrystallization. If hexanol evaporates completely, the large area of FD grows continuously and no multi-nuclei phenomenon occurs. The interaction between PCL and PVPY substrate is excluded as the reason of the induction of multi-nuclei phenomenon. PVPY which blended in the PCL ultrathin film during the sample preparation is immiscible with PCL and inhibits the nucleation and crystallization of PCL. In this work, poor solvent provides us a new method to find nucleating agent for polymer thin films.

研究领域: 高分子科学 · 材料化学 · 表面科学 · 结晶学 · 纳米材料
✓ 已验证 DOI 高影响因子
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Journal of Tissue Engineering and Regenerative Medicine · 2022 ·Vol. 16 ·期 12 ·1163-1172 · IF 4.323

Nanofibrous polytetrafluoroethylene/poly(ε-caprolactone) membrane with hierarchical structures for vascular patch

Yulu Liu,Ya Liu,Zhiyuan Bai,Dongfang Wang,Yiyang Xu,Qian Li

With the prevalence of cardiovascular diseases, developing cardiovascular supplements is becoming increasingly urgent. The ability of cells to rapidly adhere and proliferate to achieve endothelialization is extremely important for vascular grafts. In this work, we electrospun polytetrafluoroethylene (PTFE) nanofibrous membranes and used induced crystallization to manufacture poly(ε-caprolactone) (PCL) shish-kebab microstructures on PTFE nanofibers to overcome the inertness of PTFE, and promote cell adhesion and proliferation. PCL lamella periodically grew on the surface of PTFE nanofibers yielding a hierarchical structure, which improved the biocompatibility and mechanical properties of the PTFE nanofibrous membrane. The deposition of PCL lamella improved the hydrophilicity of electrospun PTFE nanofibers membrane, leading to good cell proliferation and adhesion. Also, due to the surface inertness of the substrate material PTFE, this PTFE/PCL composite film has good anti-platelet adhesion properties. Furthermore, cell proliferation could be regulated by controlling the integrity of the PCL crystal network. The vascular patch showed similar mechanical properties to natural blood vessels, providing a new strategy for vascular tissue engineering.

研究领域: 生物医学工程 · 组织工程 · 材料科学 · 心血管病学 · 再生医学 · 生物材料 · 纳米技术
✓ 已验证 DOI 高影响因子
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Polymer Chemistry · 2017 ·Vol. 8 ·期 21 ·3261-3270 · IF 5.375

Schizophrenic poly(ε-caprolactone)s: synthesis, self-assembly and fluorescent decoration

Jun Zhang,Yan Xiao,Xueli Luo,Lianlei Wen,Andreas Heise,Meidong Lang

Double hydrophilic block copolymers (DHBCs) based on poly(ε-caprolactone)s, poly(6-acetoxyl-ε-caprolactone)-b-poly(4-N-piperilactone) (PCCL-b-PPIL), were synthesized via ring-opening polymerization and deprotection. The self-assembly behaviour of these block copolymers in aqueous solutions was thoroughly explored via a combination of UV-vis spectroscopy, zeta potential measurement, 1H NMR spectroscopy, dynamic light scattering (DLS) and transmission electron microscopy (TEM). It was observed that “schizophrenic” aggregations were formed and triggered by pH, i.e., the copolymers could self-assemble into PCCL-core micelles at acidic pH and PPIL-core micelles at alkaline pH. In addition, pendant groups in each block of copolymers facilitated further chemical modification with fluorescent dyes such as 1-(hydroxymethyl)pyrene and FITC. The fluorescence properties of pyrene-functionalized copolymers were closely related to their aggregate morphology, which could be adjusted simply by altering the environmental pH values. Meanwhile, it is expected that this novel type of degradable schizophrenic block copolymer holds potential application in stimuli-responsive fluorescent probes.

研究领域: 高分子化学 · 纳米医学 · 生物材料 · 药物递送 · 分子影像 · 刺激响应系统
✓ 已验证 DOI 高影响因子
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Journal of Macromolecular Science Part A-Pure and Applied Chemistry · 2013 · IF 0.807

Poly(glycidyl methacrylate)-block-poly(ϵ-caprolactone)- block-poly(glycidyl methacrylate) Triblock Copolymer: Synthesis and Use as Mesoporous Silica Porogen

Weiwei Xun,Yulin Yi,Chongyin Zhang,Sixun Zheng

In this contribution, we reported the preparation of mesoporous silica with a reactive block copolymer as the porogen via sol-gel process. Firstly, poly(glycidyl methacrylate)-block-poly(ϵ-caprolactone)-block-poly(glycidyl methacrylate) triblock copolymer (PGMA-b-PCL-b-PGMA) was synthesized with the combination of ring-opening polymerization (ROP) and reversible addition-fragmentation chain transfer (RAFT) polymerization. Thereafter, the triblock copolymer was functionalized via its reaction with 3-aminopropyltriethoxysilane (APTES) to afford a new reactive block copolymer bearing triethoxysilane moieties. The latter was employed to perform the inter-component sol-gel reactions with tetraethoxysilane (TEOS) to obtain the organic-inorganic composites with various compositions. The organic-inorganic composites were subsequently used as the precursors to obtain the mesoporous silica materials via pyrolysis at elevated temperatures. The surface-area Brunauer-Emmett-Teller (BET) measurements indicate that the materials of mesoporous silica with adjustable porosity have been successfully obtained.

研究领域: 高分子化学 · 纳米材料 · 生物医用材料 · 多孔材料 · 药物递送系统
✓ 已验证 DOI 高影响因子
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Polymer Chemistry · 2018 ·Vol. 9 ·期 28 ·3931-3943 · IF 4.927

Synthesis of aromatic-doped polycaprolactone with tunable degradation behavior

Yawei Sun,Qiuyan Wang,Shuying Zhang,Hao Li,Jinli Zhang,Daqing Li,Wei Li

A novel aromatic-doped polycaprolactone (Aro-PCL) material was synthesized through a facile PCL aminolysis-condensation polymerization incorporating the aromatic moiety to PCL chain and assessed by focusing on the dynamic aggregation and crystalline microdomains associated with the in vitro degradation properties, mechanical performance and biocompatibility. Characterizations by FTIR, NMR, UV-vis, DSC, WAXD, SAXS, POM, etc. illustrated that the incorporated aromatic and amine segments facilitated the formation of many low-oriented crystalline domains along the aliphatic chains. The results indicated that the evolution of mechanical performance is significantly associated with the chemical structure and the crystallization behavior of polymers. The Aro-PCL films possessed fast degradation rate, excellent biocompatibility and improved mechanical performance including augmented elongation at break, elastic modulus and radial strength. In particular, the Aro-PCL polymer films showed decrease in molecular weight at the beginning of hydrolytic degradation while maintaining mechanical support and stable mass. The Aro-PCL polymer has promising applications as a degradable biomaterial.

研究领域: 材料科学 · 高分子化学 · 生物医学工程 · 生物材料
✓ 已验证 DOI 高影响因子
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JOURNAL OF ALLOYS AND COMPOUNDS · 2022 · IF 6.371

In situ synthesis of MAPbX3 perovskite quantum dot-polycaprolactone composites for fluorescent 3D printing filament

Yun Tang,Ben Liu,Hudie Yuan,Yalou Xin,Xiaohu Ren,Qiang Chen,Hongfeng Yin

The development of functionalized polymer-based filament enables the fused deposition modeling (FDM) 3D-printed materials or structures with a wide range of unique functions. This work explores the use of MAPbX 3 (MA = CH 3 NH 3 , X = Cl, Br, I or mixture of them) perovskite quantum dots (PQDs) by harnessing their unique optical properties for the development of fluorescent 3D printing filaments. Firstly, a one-pot strategy for scalable synthesis of MAPbX 3 PQDs-polycaprolactone (PCL) composite was proposed by in situ formation of PQDs in PCL matrix. To demonstrate the ability for the obtained PQDs-PCL composites to fabricate fluorescent filaments, the effects of filament functionalization on optical properties of PQDs, as well as thermal and mechanical properties of polymer matrix were then comprehensively studied. Owing to the good protective capability of PCL, the synthesized PQDs-PCL composites exhibit comparable PLQY and enhanced UV, water and thermal stability compared to that of pure PQDs. Moreover, high concentration of embedded PQDs in PQDs-PCL composites was obtained with decreasing amount of PCL. The aggregation of PQDs at high temperature combined with the poor interaction between PQDs and surrounding PCL matrix led to the decreased thermal transition temperature and reduced mechanical properties in PQDs-PCL composites relative to pure PCL. The glass transition temperature was found to decrease by 5.5 °C, while the mode of failure changed from plastic fracture for pure PCL to brittle fracture for the highest concentration of PQDs in PCL tested. Consequently, PQD-PCL composites were further processed into fluorescent filaments and further fluorescent objects or structures via 3D printing. Green LED and white LED devices were realized by the combination of UV LED chip with 3D printed MAPbBr 3 PQD-PCL thin-film, and blue LED chip with MAPbBr 3 PQD-PCL thin-film and K 2 SiF 6 :Mn 4+ phosphor, respectively, demonstrating that the PQDs-functionalized 3D printing filaments have great potential in fields of optoelectronic application .

研究领域: 材料科学 · 高分子化学 · 纳米光学 · 增材制造 · 光电功能材料
✓ 已验证 DOI 高影响因子
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APPLIED CLAY SCIENCE · 2017 · IF 3.101

Poly(ε-caprolactone) filled with polydopamine-coated high aspect ratio layered double hydroxide: Simultaneous enhancement of mechanical and barrier properties

Long Mao,Yuejun Liu,Huiqing Wu,Jianhong Chen,Jin Yao

Inspired by the versatile adhesion capability of marine adhesive proteins, core-shell structured polydopamine-coated layered double hydroxide (LDH@PDA) were prepared successfully by in-situ growing PDA on the surface of MgAl-LDH with a high aspect ratio . LDH@PDA/poly(ε-caprolactone) (PCL) nanocomposites were prepared by blending LDH@PDA and pure PCL via solution casting method to obtain homogeneous films. The results of thermal analysis confirmed that LDH@PDA can act as a nucleating agent . And thermal stability of nanocomposites was improved due to core-shell structured LDH@PDA. With incorporation of as low as 1   wt% of LDH@PDA, a 20% increase in tensile strength (41.1   MPa), 26% increase in elongation at break (772%) and 26% reduction in the oxygen relative permeability were achieved. The improvement in the mechanical and gas barrier properties of nanocomposites at low filler loading was attributed to the strong interfacial interaction of LDH@PDA wtih the PCL matrix.

研究领域: 高分子材料 · 纳米复合材料 · 生物医用材料 · 材料科学 · 表面改性 · 气体阻隔 · 力学性能
✓ 已验证 DOI 高影响因子
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2019 · IF 6.361

Synthesis of poly(amide-thioether) with tunable hydrophilicity via thiolactone chemistry and its application in oil-in-oil emulsions

Zhengzhou Su,Chunmei Li,Jiaojun Tan,Ying Xue,Guoxian Zhang,Yumin Yang,Qiuyu Zhang

Oil-in-oil emulsions are ideal systems for water-sensitive reactions such as polymerizations and catalytic reactions , which has received extensive attention in recent years. The application of oil-in-oil emulsions has been developed slowly due to the limited types of surfactants and complicated synthesis process. Herein, we proposed a simple method to prepare poly(amide-thioether)-based surfactant for oil-in-oil emulsions via taking advantage of single-pot multicomponent and click characters of thiolactone chemistry. Using a combination of alkyl amine and acrylamide thiolactone, the aminolysis of thiolctone occurred first, generating thiol group in-situ, and then the generated thiol group would sequentially react with the double bonds of acrylamide to form polythioether in the presence of amine. The hydrophobicity of the surfactant could be effectively adjusted by the chain length of the alkyl amine and thus this polymer could serve as a promising surfactant for oil-in-oil emulsion. Notably, the emulsion types could be switched by changing the chain length of the alkyl amine. In addition, the effects of surfactant loading, volume ratio of oil phases, oil types on the size and stability of oil-in-oil emulsions were further investigated. It was demonstrated that the oil-in-oil emulsion stabilized by poly(amide-thioether)s kept stable after more than five months. Besides, we preliminarily explored the application of the oil-in-oil emulsion to prepare closed cell foam and porous particles via photo-initiated thiol-ene polymerization. It is believed that this super-stable oil-in-oil emulsion could offer more possibilities for highly potential water-sensitive systems.

研究领域: 高分子化学 · 胶体与界面科学 · 材料科学 · 化学工程 · 软物质物理
✓ 已验证 DOI 高影响因子
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Polymer Chemistry · 2012 ·Vol. 4 ·期 5 ·1430-1438 · IF 5.321

pH-sensitive nanoparticles prepared from amphiphilic and biodegradable methoxy poly(ethylene glycol)-block-(polycaprolactone-graft-poly(methacrylic acid)) for oral drug delivery

Longlong Chang,Jinjian Liu,Jianhua Zhang,Liandong Deng,Anjie Dong

A novel pH-sensitive, amphiphilic and biodegradable copolymer brush, methoxy poly(ethylene glycol)-block-(polycaprolactone-graft-poly(methacrylic acid)) (mPEG-b-(PCL-g-PMAA)), was developed for NPs for the oral delivery of hydrophobic drugs. The copolymer brush was synthesized by combining ring-opening polymerization (ROP) and atom transfer radical polymerization (ATRP), followed by selective hydrolysis. The structure and composition of the copolymer and its precursors were characterized by 1H-NMR, FT-IR and GPC. The critical micelle concentrations (CMC) of mPEG-b-(PCL-g-PMAA) in aqueous medium were determined to be 6.8 × 10−4 and 9.6 × 10−4 mg mL−1. The copolymer could self-assemble into NPs in aqueous solution with an average size of 104–129 nm, determined by DLS. The morphology of the NPs was spherical, as observed by TEM. The zeta potentials of the NPs were about −25 mV, measured by zeta potential measurements. Ibuprofen (IBU), a poorly water-soluble drug, was chosen as the model drug and encapsulated into the core of the NPs via a nano-precipitation method. The drug loading content (DLC) of the NPs prepared from mPEG-b-(PCL-g-PMAA) reached about 13%, with a drug loading efficiency (DLE) of above 75%. The in vitro release behavior of IBU from the NPs was pH-dependent. Typically, at pH 3.0 (0.01 M), the cumulative release percentage of IBU was about 40% over 12 h, whereas at pH 7.4 (0.01 M), more than 95% was released within 12 h for NPs prepared from mPEG113-b-(PCL91-g-PMAA155). The MTT assay indicated that blank NPs prepared from mPEG-b-(PCL-g-PMAA) did not show significant toxicity against NCL-H460 cells. These results indicated that this new type of pH-dependent polymeric NPs prepared from mPEG-b-(PCL-g-PMAA) has great potential to be used as a drug carrier for the oral administration of hydrophobic drugs.

研究领域: 药剂学 · 高分子科学 · 纳米医学 · 药物递送系统 · 生物材料 · 药代动力学 · 分子药理学
✓ 已验证 DOI 高影响因子
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MICROPOROUS AND MESOPOROUS MATERIALS · 2015 · IF 3.453

Conjugated polymer and spirolactam rhodamine-B derivative co-functionalized mesoporous silica nanoparticles as the scaffold for the FRET-based ratiometric sensing of mercury (II) ions

Lijuan Feng,Jie Sha,Yao He,Shaopeng Chen,Bingxin Liu,Haixia Zhang,Changli Lü

A novel fluorescence resonance energy transfer (FRET)-based ratiometric nanosensor is reported for toxic Hg 2+ ions detection. Poly(p-phenylenevinylene) (PPV) chain was encapsulated into the pores of mesoporous silica nanoparticles (MSNs) by ion-exchange and in situ polymerization , and used as the energy-transfer donor. A spirolactam rhodamine-B derivative (SRhB), as an ion recognition element and energy-transfer acceptor, was embedded in the pores of MSNs to form PPV@MSN@SRhB as the nanosensor . The presence of Hg 2+ in the dispersion solution of nanoparticles can induce the ring-opening reaction of the SRhB moieties and lead to the occurrence of FRET process , affording the nanoparticle system a ratiometric sensor for Hg 2+ ions. The nanoparticle sensor can selectively detect Hg 2+ ions with a detection limit of 200 nM (ca. 40 ppb). It has been found that the fabricated FRET-based scaffold with the conjugated polymer as a donor exhibited high environmental stability and was more preferred for the accurate ratiometric sensing . Moreover, the FRET-based ratiometric nanosensor can be applicable in a relatively wide pH range (pH = 5–8) in solution.

研究领域: 分析化学 · 纳米生物技术 · 环境毒理学 · 分子传感 · 材料科学
✓ 已验证 DOI 高影响因子
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Journal of Macromolecular Science Part B-Physics · 2019 · IF 1.204

Preparation and Characterization of Nanocomposite Scaffolds Based on Polycaprolactone-Polyethylene Glycol/Methylene Diphenyl Diisocyanate/Diethylene Glycol and Nano-Bioactive Glass

Xiaofei Li,Jianjun Fang,Hua Yan,Wenjuan Liu,Yunhui Zhao,Tianlong Huang,Jiale Cui,Yun Yang,Zhihua Zhou

Designing and fabricating nanocomposite scaffolds based on biodegradable polymers and bioactive materials are an important topic in the area of bone regeneration. A novel nanocomposite scaffold composed of polyurethane (BPU) and nano-bioactive glass (NBAG) was prepared. The effects of the NBAG content on the properties of the BPU/NBAG composite scaffolds, including the morphologies, porosity and compressive strength, were investigated. The BPU/NBAG composite scaffolds showed an interconnected pore structure with the pore size ranging from 50 to 500 μm for all samples. The porosity percent and swelling ability decreased with increasing NBAG content; however, the compressive strength was enhanced.

研究领域: 生物材料学 · 组织工程 · 高分子科学 · 再生医学 · 生物医学工程 · 纳米医学
✓ 已验证 DOI 高影响因子
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Journal of Macromolecular Science Part B-Physics · 2021 · IF 1.504

Preparation and Characterization of Poly(l-lactide-co-glycolide-co-ε-caprolactone) Porous Microspheres

Chao Zhang,Zhihua Zhou,Wenjuan Liu,Tianlong Huang,Yanmin Zhao,Ping Chen,Ziwei Zhou,Dan Wang,Meiling Yi,Jianjun Fang

Porous microspheres have interconnecting external and internal pore structure resulting in enormous specific surface area and have drawn attention for drug delivery. In this work, poly(l-lactide-co-glycolide-co-ε-caprolactone) (PLLGC) porous microspheres were prepared by a combined solvent evaporation and particle leaching method using gelatin as a porogen. The effects of preparation parameters on the morphologies of the porous microspheres were studied. The resultant microspheres showed porous surfaces and a three-dimensional internal network structure with interconnecting pores. The porous microsphere size decreased with increasing stirring speed and decreasing PLLGC concentration. There were fewer micropores on the surfaces of the microspheres with increasing temperature. The number of the pores and pore size on the surface of the microspheres increased with increasing gelatin content. By appropriate control of these factors (stirring speed 300 rpm, PLLGC solution concentration 1.0 wt%, temperature 0 °C, and gelatin concentration 7.5 wt%), a suitable porous microsphere, with a mean diameter of 200 μm, was prepared as a potential drug delivery agent.

研究领域: 材料科学 · 高分子科学 · 药剂技术 · 生物医学工程 · 药物递送系统
✓ 已验证 DOI 高影响因子
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