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GREEN CHEMISTRY · 2021 ·Vol. 23 ·期 16 ·5911-5923 · IF 10.182

High-performance 3D printing UV-curable resins derived from soybean oil and gallic acid

Guoqiang Zhu,Jinshuai Zhang,Jia Huang,Xixi Yu,Jianwen Cheng,Qianqian Shang,Yun Hu,Chengguo Liu,Lihong Hu,Yonghong Zhou

Developing sustainable 3D printing materials has attained intensive interest due to the rapid growth of the 3D printing industry and the concerns on depletion of fossil resources and environmental pollution. In this work, a novel biobased UV-curable oligomer (GMAESO) was firstly synthesized from epoxidized soybean oil (ESO) and gallic acid (GA) via a ‘green’ one pot method. The obtained biobased oligomer possessed a biobased content of 82.9%. By co-photopolymerization of the obtained oligomer with a hydroxyethyl methacrylate (HEMA) diluent, a series of UV-curable materials were prepared, and their properties as well as curing behaviors were investigated. Notably, the resulting GMAESO resins with high HEMA contents (50–60%) showed low viscosities (52–93 mPa s) and excellent thermal and mechanical properties (a Tg of 128–130 °C, Tp >430 °C, a tensile strength of 42.2–44.4 MPa, etc.) which were comparable or superior to a commercial product. Furthermore, the optimal resin (GMAESO with 50% HEMA) was used for digital light processing (DLP) 3D printing. The resin showed lower penetration depth (0.277 mm) than the commercial resin, thus different-structured objects with high resolution were successfully printed. In general, the developed bio-based UV-curable resins are very promising for application in the 3D printing industry.

研究领域: 材料科学 · 化学工程 · 可持续发展 · 3D打印技术
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COMPOSITES PART B-ENGINEERING · 2021 · IF 9.078

A novel UV-curable extravascular stent to prevent restenosis of venous grafts

Chun Dai,Tianshu Chu,Xiang Li,Hui Jiang,Tan Liu,Yang Zhou,Lei Gao,Cheng Shen,Jianjun Ge

The incidence of coronary heart disease is increasing yearly. Coronary artery bypass graft (CABG) is an important surgical method for the treatment of coronary heart disease. The vein grafts in CABG surgery mostly use saphenous vein, but restenosis of the graft frequently occurs, and has become an urgent clinical problem. In this study, we produced a UV-curable Hydroxyethyl Methacrylate (HEMA) gel containing Bletilla striata , and compared its tensile strength and expansibility to that of human vessels, showing that the film has good physical properties. Through cell experiments, we proved that film has no effect on cell proliferation, migration, apoptosis, and DNA damage. In addition, we placed the film under the skin of mice to measure inflammation-related cells and factors, and found that it did not trigger the body's immune response. After that, we designed a rat vein graft model to simulate the pathological changes of the vein graft vessel after CABG. The film had a good inhibitory effect on the restenosis of vein graft vessels in the rat model. Finally, analysis of the expression levels of proteins involved in the proliferation and migration indicated that the gel can effectively inhibit these processes in smooth muscle cells in the graft vein. In conclusion, this study has successfully produced a UV-curable HEMA gel containing B. striata that could effectively inhibit the restenosis of vein grafts.

研究领域: 心血管疾病 · 生物医学工程 · 材料科学 · 细胞生物学 · 药理学
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JOURNAL OF CONTROLLED RELEASE · 2023 · IF 10.8

Inducing in situ M2 macrophage polarization to promote the repair of bone defects via scaffold-mediated sustained delivery of luteolin

Yan Hu,Lixi Tang,Zheng Wang,Honghan Yan,Xinzeyu Yi,Huimin Wang,Liya Ma,Changying Yang,Jiabing Ran,Aixi Yu

Immunoregulation mediated bone tissue engineering (BTE) has demonstrated huge potential in promoting repair of critical-size bone defects (CSBDs). The trade-off between stable immunoregulation function and extended immunoregulation period has posed a great challenge to this strategy. Here, we reported a 3D porous biodegradable Poly(HEMA- co -3APBA)/LUT scaffold, in which reversible boronic acid ester bond was formed between the 3APBA moiety and the catechol moiety of luteolin (LUT). The boronic acid ester bond not only protected the bioactivity of LUT but also extended the release period of LUT. The rationale behind the phenomenon of sustained LUT release was explained using a classical transition state theory. In vitro/in vivo assays proved the immunoregulation function of the scaffold in inducing M 2 polarization of both M 0 and M 1 M φ . The crosstalk between the scaffold treated Raw 264.7 and BMSCs were also investigated through the in vitro co-culture assay. The results demonstrated that the scaffold could induce immunoregulation mediated osteogenic differentiation of BMSCs. In addition, CSBDs model of SD rats was also applied, and the corresponding data proved that the scaffold could accelerate new bone formation, therefore promoting repair of CSBDs. The as-prepared scaffold might be a promising candidate for repair of CSBDs in the future.

CAS / MDL: 52628-03-2
研究领域: 生物医学工程 · 组织工程 · 材料科学 · 免疫学 · 骨再生
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BIOCHEMICAL ENGINEERING JOURNAL · 2021 · IF 3.978

Low modification of PETase enhances its activity toward degrading PET: Effect of conjugate monomer property

Kun Chen,Mingqin Quan,Xiaoyan Dong,Qinghong Shi,Yan Sun

Polyethylene terephthalate is one of the most widely used synthetic plastics. The accumulation of abandoned PET has brought an environmental problem. A recently reported PET hydrolase , PETase, displays an efficient decomposition to PET. Herein, we synthesized four PETase conjugates by modifying four types of monomers onto PETase, which were hydrophobic tert-butyl methacrylate (TBMA), hydrophilic hydroxyethyl methacrylate (HEMA), positively charged 2-(dimethylamino)ethyl methacrylate (DMAEMA), and negatively charged methacrylic acid (MA). Despite the low modification with an average number of 3–5 monomers on each enzyme molecule, all the PETase conjugates exhibited improved enzyme activity , and thermal and pH stability. Particularly, the catalytic efficiency ( k cat / K m ) of TBMA-/DMAEMA-PETase toward bis-2(hydroxyethyl) terephthalate (BHET) increased 1.4 and 1.6-fold as compared with PETase. Characterizations by fluorescence and circular dichroism spectroscopy unraveled that the modification induced the structural transformations, including compact overall structure and opened substrate-binding pocket, which were in favor of the enhanced catalytic performance. Biodegradation against PET films by TBMA-/DMAEMA-PETase were 4.69 and 3.26-fold higher than PETase. The different catalytic performances of the enzyme conjugates for BHET and PET are considered due to the different interactions of the conjugates with the different substrates. The work demonstrated that the low modifications with hydrophobic and hydrophilic monomers were both effective in improving the catalytic performance toward PET degradation, especially for the hydrophobic and positively charged monomers.

研究领域: 生物技术 · 环境科学 · 酶学 · 材料科学
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COMPOSITES SCIENCE AND TECHNOLOGY · 2017 · IF 4.873

Post-functionalization of carboxylic polyethersulfone composite membranes

Chen Wang,Yuan Xu,Shudong Sun,Changsheng Zhao

Herein, a new and facile approach by in situ cross-linking polymerizationcoupled with a post-functionalization procedure was developed to prepare functional PES composite membranes to improve its over-all performance as hemodialysis membrane. In our strategy, poly(acrylate acid-co-2-hydroxyethyl methacrylate) P(AA-co-HEMA) as a macromonomer, was firstly synthesized by free radical copolymerization , then blended in PES solution and in situ cross-linked polymerization via the reaction of the hydroxy group of HEMA and the isocyanate group of 4,4′-diphenylmethane diisocyanate (MDI) to prepare the carboxylic membranes. To further enhance the hemocompatibility , the carboxylic membranes were post-functionalized by grafting sulfonic acid groups onto the membrane surfaces via a “grafting from” method. The chemical compositions and surface morphologies of the prepared membranes were investigated by ATR-FTIR, XPS , SEM and AFM . After introducing the functional groups, the surface hydrophilicity of the membranes was significantly improved, demonstrated by the reduced water contact angles (WCAs) and enhanced permeability. The decreased protein adsorptions and higher flux recovery ratios (F RR s) revealed that the modified membranes showed improved protein antifouling property. The improvement of hemocompatibility was confirmed by the inhibited platelet adhesion, prolonged clotting times , and suppressed blood-related complement activation. Moreover, the post-functionalized membranes also showed good cytocompatibility. In general, the in situ cross-linking technique is a suitable route in the field of membrane modification for its facile and easy operation; and the post-functionalization operation could endow the membranes with efficiently improved properties.

研究领域: 材料科学 · 化学工程 · 生物医学工程
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MICROCHEMICAL JOURNAL · 2019 · IF 3.206

Fluorescein-immobilized optical hydrogels: Synthesis and its application for detection of Hg2+

Zixiang Qu,Lizhen Wang,Shimin Fang,Dawei Qin,Jianhua Zhou,Geng Yang,Hongdong Duan

Hydrogels are attracting carriers for immobilization of small molecules due to their excellent properties, such as low optical background, recyclable and high loading ability. Several advantages will be found in designing optical sensors by utilizing hydrogels, such as the convenience for operation, the easiness to separate from media and the difficulties to introduce impurities to detection environment. As a fluorescein-based sensor for Hg 2+ , the N-(Fluorescein) lactam-N′-methylethylidene ( FLA ) was synthesized, and the structure confirmation process was finished by 1 H NMR, 13 C NMR, FT-IR and mass spectrometry. The interaction of FLA with various mental ions demonstrated the high selectivity to Hg 2+ , which was proved by UV–Vis and fluorescence spectrometry analysis. Meanwhile, the binding mode of FLA Hg 2+ was characterized by FT-IR, 1 H NMR and UV–Vis spectrophotometry . Then, counting FLA as functional monomer and MBA as crosslinker, different proportions of acrylamide (AAm), 2-hydroxyethyl methacrylate (HEMA) and methyl methacrylate (MMA) were copolymerized with FLA and N , N ′-methylenebisacrylamide (MBA) to prepare hydrogel sensors. The hydrogel sensor was characterized by colorimetry and swelling properties. At last, the prepared hydrogels is capable to respond to different colors of Hg 2+ in water or DMSO, and it can be reused after the treatment with ethylenediamine (EDA) solution.

CAS / MDL: 518-44-5
研究领域: 材料科学 · 分析化学 · 环境科学
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EUROPEAN POLYMER JOURNAL · 2021 · IF 4.598

Reinvestigation of the ring-opening polymerization of ε-caprolactone with 1,8-diazacyclo[5.4.0]undec-7-ene organocatalyst in bulk

Yang Chen,Jie Zhang,Wenhao Xiao,Anfu Chen,Zhixian Dong,Jinbao Xu,Wenhua Xu,Caihong Lei

1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU) was used as organocatalyst to reinvestigate the ring-opening polymerization (ROP) of ε -caprolactone (CL) with benzyl alcohol (BnOH) initiator in bulk at 90 °C considering the unsuccessful ROP of CL at RT in previously reported publications. Kinetic study indicates that the PCLs could be well-designed with a controlled/living character of polymerization. The use of functional initiators, such as 2-hydroxyethyl methacrylate (HEMA), propargyl alcohol (PGA), 6-azido-1-hexanol (AHA) and methoxy poly(ethylene glycol) (mPEG) leads to end-functionalized PCLs. Accordingly, the block copolymerization of CL with δ-valerolactone (VL), trimethylene carbonate (TMC) and lactide (LA) successfully proceeded to give PCL- b -PVL, PCL- b -PTMC and PCL- b -PLA copolymers. Finally, the reaction mechanism was studied with DFT calculations and NMR measurements.

研究领域: 高分子化学 · 材料科学 · 有机化学
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