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RSC Advances · 2015 ·Vol. 5 ·期 127 ·104907-104914 · IF 3.84

Self-repairing nonfouling polyurethane coatings via 3D-grafting of PEG-b-PHEMA-b-PMPC copolymer

Kunlin Chen,Shuxue Zhou,Limin Wu

Durability of nonfouling coatings is a critical problem to be solved for their practical application. In this paper, self-repairing nonfouling polyurethane (PU) coating was fabricated by spraying of a triblock copolymer of polyethylene glycol (PEG), 2-hydroxyethyl methacrylate (HEMA) and 2-methacryloyloxyethyl phosphorylcholine (MPC) on pre-cured acrylic-based PU coatings. The triblock copolymer was synthesized through living radical polymerization mediated by an atom transfer radical polymerization. Anchoring of the copolymer took place both on the surface and in the interior (namely, 3D-grafting) of PU coatings through the diffusion of the copolymer and subsequently the chemical reaction between the pendent hydroxyl group of the copolymer and the remaining isocyanate groups in the pre-cured PU coatings. This 3D grafting procedure is rather simple and favorable for large-area application. The 3D-grafted PU coating has higher hydrophilicity (water contact angle: 33°). In contrast, if the triblock copolymer was used as an additive in PU coatings, the hydrophilicity of the PU coating did not obviously change. The 3D-grafted PU coating effectively inhibited the adhesion of protein and human platelet cells due to the synergistic effect of PEG and MPC. Moreover, after the coatings were detached and mechanically damaged, the surfaces can restore their hydrophilicity and possess better long-term anti-fouling ability than the control surface-grafted coatings underwater.

研究领域: 材料科学 · 聚合物化学 · 生物医学工程
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Journal of Materials Chemistry B · 2019 ·Vol. 7 ·期 33 ·5078-5088 · IF 5.047

Fabrication of PMPC/PTM/PEGDA micropatterns onto polypropylene films behaving with dual functions of antifouling and antimicrobial activities

Liu Jiang,Wancheng Zhu,Huaming Qian,Changhao Wang,Yashao Chen,Peng Liu

Polymer materials with high biocompatibility and versatile functions are urgently required in the biomedical field. The hydrophobic surface and inert traits of polymer materials usually encounter severe biofouling and bacterial infection which hinder the potential application of polymers as biomedical materials. Although many antifouling or antimicrobial coatings have been developed for modification of biomedical devices/implants, few can simultaneously fulfill the requirements for antimicrobial and antifouling activities. Herein, we constructed bifunctional micropatterns with antifouling and antimicrobial properties onto polypropylene (PP) films using argon plasma activation treatment, photomask technique and UV-initiated graft polymerization method. Different sizes of PMPC/PTM/PEGDA micropatterns were fabricated on PP films to yield patterned PP–PMPC/PTM/PEGDA as evidenced by infrared (IR) spectroscopy, scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS), where PMPC is poly(2-methacryloyloxyethyl phosphorylcholine) for enhancement of hydrophilicity and biocompatibility, PTM is poly(methacryloyloxyethyltrimethylammonium chloride) for contribution to antimicrobial activity and PEGDA is poly(ethylene glycol diacrylate) as the crosslinker. The surface hydrophilicity of patterned PP–PMPC/PTM/PEGDA was characterized by the static water contact angle test. The results showed that the PP sample with a micropattern with the size of 5 μm exhibited the best hydrophilicity. For biological assays of patterned PP–PMPC/PTM/PEGDA, the micropattern size at 5 μm performed the best for both antiplatelet adhesion and antimicrobial activities. We anticipate that this work could provide a new method for building bifunctional biomedical materials to promote the application of PP in biomedical fields.

CAS / MDL: 7558-80-7
研究领域: 材料科学 · 生物医学工程
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Journal of Materials Chemistry B · 2022 ·Vol. 10 ·期 19 ·3759-3769 · IF 7.571

Rational design of dual-functional surfaces on polypropylene with antifouling and antibacterial performances via a micropatterning strategy

Liu Jiang,Niuniu Qin,Shunli Gu,Wancheng Zhu,Changhao Wang,Yashao Chen

The hydrophobicity and inertness of the polypropylene (PP) material surface usually lead to serious biofouling and bacterial infections, which hamper its potential application as a biomedical polymer. Many strategies have been developed to improve its antifouling or antibacterial properties, yet designing a surface to achieve both antifouling and antibacterial performances simultaneously remains a challenge. Herein, we construct a dual-function micropatterned PP surface with antifouling and antibacterial properties through plasma activation, photomask technology and ultraviolet light-induced graft polymerization. Based on the antifouling agent poly(2-methacryloyloxyethyl phosphate choline) (PMPC) and the antibacterial agent quaternized poly(N,N-dimethylamino)ethyl methacrylate (QPDMAEMA), two different micropatterning structures have been successfully prepared: PP-PMPC-QPDMAEMA in which QPDMAEMA is the micropattern and PMPC is the coating polymer, and PP-QPDMAEMA-PMPC in which PMPC is the micropattern and QPDMAEMA is the coating polymer. The composition, elemental distribution and surface morphology of PP-PMPC-QPDMAEMA and PP-QPDMAEMA-PMPC have been thoroughly characterized by Fourier transform infrared (FT-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM), respectively. Compared with pristine PP, the two types of micropatterned PP films exhibit good surface hydrophilicity as characterized by water contact angle measurements. The results of anti-protein adsorption, platelet adhesion and antibacterial evaluation showed that PP-PMPC-QPDMAEMA and PP-QPDMAEMA-PMPC had good anti-protein adsorption properties, especially for lysozyme (Lyz). They can effectively prevent platelet adhesion, and the anti-platelet adhesion performance of PP-QPDMAEMA-PMPC is slightly better than that of the PP-PMPC-QPDMAEMA sample. The sterilization rate of S. aureus and E. coli is as high as 95% for the two types of micropatterned PP films. Due to the rational design of micropatterns on the PP surface, the two classes of dual-functional PP materials realize both the resistance of protein and platelet adhesion, and the killing of bacteria at the same time. We anticipate that this work could provide a design strategy for the construction of multifunctional biomedical polymer materials.

CAS / MDL: 7558-80-7 25154-86-3
研究领域: 生物材料 · 表面工程 · 医学材料
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ACS Biomaterials Science & Engineering · 2020 · IF 4.152

Rational Design of PMPC/PDMC/PEGDA Hydrogel Micropatterns onto Polylactic Acid with Enhanced Biological Activity

Wancheng Zhu,Liu Jiang,Bulei Wang,Shunli Gu,Fenyan Hu,Changhao Wang,Yashao Chen

Polylactic acid (PLA) is one of the biodegradable materials that has been used in the areas of surgical healing lines, cancer treatment, and wound healing. However, the application of PLA is still rather limited due to its high hydrophobicity and poor antibacterial activity. In order to enhance the antifouling and antibacterial performances of PLA, here we modified the surface of PLA with various sizes of hydrogel micropatterns in negative or positive mode using plasma treatment, the photomask technique, and UV-graft polymerization. The hydrogel micropatterns consist of poly(ethylene glycol) diacrylate (PEGDA), poly(2-methacryloyloxyethylphosphorylcholine) (PMPC), and poly(methacryloyloxyethyltrimethylammonium chloride) (PDMC). Compared to PLA, the patterned PLA (PLA–PMPC/PDMC/PEGDA) shows obviously enhanced antifouling and antibacterial activities. For PLA–PMPC/PDMC/PEGDA with either positive or negative micropatterns, the antifouling and antibacterial properties are gradually increasing with decreasing the size of micropatterns. Compared with PLA–PMPC/PDMC/PEGDA bearing positive and negative micropatterns in the same size, the PLA–PMPC/PDMC/PEGDA with negative micropatterns exhibits slightly better biological activity and the PLA–PMPC/PDMC/PEGDA with 3 μm negative hydrogel micropatterns shows the best hydrophilicity, antifouling, and antibacterial properties. Combining the in vitro hemolysis assay, cytotoxicity, water absorption test, and degradation test results, it is suggested that the fabrication of hydrogel micropatterns onto the PLA surface could significantly improve biological activities of PLA. We expect that this work would provide a new strategy to potentially develop PLA as a promising wound dressing.

CAS / MDL: 26570-48-9
研究领域: 材料科学 · 生物医学工程 · 组织工程
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Journal of Biomedical Nanotechnology · 2017 ·Vol. 13 ·期 11 ·1500-1511 · IF 4.521

Comparison of Biomimetic Block Copolymer Micelles as Drug Carriers for Cancer Therapy

Liu Gongyan,Chen Xiaobing,Zhuang Weihua,Nie Yu,Zhang Kai,Yang Li,Wang Yunbing

Zwitterionic poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) is a promising alternative for poly(ethylene glycol) (PEG) as micelle shell-forming block. Three different PMPC-based polymeric micelles were designed and compared with PEGylated micelles. Cholesterol-conjugated and disulfide-modified poly(D, L-lactide)-SS-poly(2-methacryloyloxyethyl phosphorylcholine) (CPLA-SS-PMPC) micelles, cholesterol-conjugated CPLA-PMPC micelles without disulfides, and PLA-PMPC micelles without cholesterol-conjugation were compared to PLA-PEG micelles. These PMPC-based micelles showed better hydrophilicity and less protein adsorption. In cellular uptake evaluation, PMPC-based micelles exhibited much better cellular uptake than that of the PLA-PEG, which might reflect strong interaction between the biomimetic PMPC surface and the cellular membrane. In addition, although there was no statistical difference in cellular internalization behavior among these three PMPC-based micelles, the anticancer activity of paclitaxel (PTX)-loaded CPLA-SS-PMPC micelles was significantly higher than those of the other two kinds of micelles. This superiority was attributed to the rapid release of the anticancer drug under the redox environment inside cancer cells.

研究领域: 生物材料学 · 药剂学 · 肿瘤学
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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS · 2025 · IF 5.4

Bioinspired catechol/APTES interlayer for constructing zwitterionic PMPC coating on PVDF membranes with superior antifouling performance

Shaohua Li,Zhenyu Xi,Songchen Xie,Guanlun Jiang,Xinmiao Zhang

Membrane fouling significantly impairs separation performance and durability. To address this, a bioinspired intermediate layer of dopamine methacrylamide (DMA) and (3-aminopropyl)triethoxysilane (APTES) was developed to enhance the grafting of poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) onto polyvinylidene fluoride (PVDF) membranes via surface-initiated polymerization. The incorporation of this intermediate layer enabled complete surface wetting of the zwitterionic monomer MPC, increasing the availability of reactive sites and yielding a grafting ratio of 183.4 μg/cm 2 , compared to 10.3 μg/cm 2 for unmodified PVDF surfaces. Furthermore, the DMA/APTES layer may undergo cross-linking through the addition of Fe 3+ , leading to an increase in the chemical stability of the coating when exposed to extreme pH conditions. The PMPC-modified membrane (PVDF-DMA-APTES-Fe-PMPC) exhibited marked superhydrophilicity, with a static water contact angle of 16.0° that rapidly dropped to 0° within 10 s. This hydrophilic transformation significantly reduced protein adsorption, lowering bovine serum albumin (BSA) accumulation to 19.3 μg/cm 2 , in contrast to 197.5 μg/cm 2 observed on pristine PVDF. Antibacterial assays further revealed a 1.6 log 10 reduction in Escherichia coli after 12 h of incubation, indicating effective resistance to bacterial adhesion. In filtration performance, the modified membrane maintained a high pure water flux of 336.3 LMH in the first cycle, coupled with excellent antifouling durability. This study showcases a versatile approach for modifying hydrophobic polymeric membranes, highlighting their possible applications in purifying protein−wasted water.

研究领域: 材料科学 · 膜技术 · 表面工程 · 环境工程 · 高分子化学 · 生物界面科学
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Advanced Materials Interfaces · 2019 ·Vol. 6 ·期 12 ·1900180 · IF 4.713

Articular Cartilage-Inspired Surface Functionalization for Enhanced Lubrication

Yixin Wang,Yulong Sun,Yanhong Gu,Hongyu Zhang

Natural articular cartilage has excellent superlubrication property, and it is attributed to the hydration lubrication mechanism of the charged biomacromolecules which extend from the cartilage surface to form a brush-like layer. In this study, a bioinspired brush-like polyelectrolyte, namely poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC), is grafted onto the SiO 2 wafer and polystyrene (PS) microsphere via surface-initiated polymerization to enhance the lubrication performance. The characterization of Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, water contact angle, and scanning electron microscopy demonstrates that the PMPC polymer brushes are successfully modified onto the substrates. Furthermore, the lubrication test performed using atomic force microscope, with the PMPC-grafted SiO 2 wafer and PMPC-grafted PS microsphere as the contact tribopair, shows that the PMPC-functionalized surfaces significantly reduce friction coefficient under different test conditions. The tenacious water hydration shells formed surrounding the zwitterionic charges of PMPC polymer brushes are responsible for the reduced friction coefficient, which could support high pressures without being squeezed out under loading. In summary, the articular cartilage-inspired surface functionalization method can be used to modify various substrates for enhanced lubrication.

研究领域: 生物材料学 · 摩擦学
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MACROMOLECULES · 2021 · IF 5.985

Superlubricity Achieved with Zwitterionic Brushes in Diverse Conditions Induced by Shear Actions

Shaofei Feng,Yuhong Liu,Jinjin Li,Shizhu Wen

Polymer brushes are known to have excellent lubricity when grafted on surfaces in water. In this study, poly(2-(methacryloyloxy)-ethyl phosphorylcholine) (PMPC) has been successfully grafted on a silica wafer through a surface-initiated atom transfer radical polymerization (SI-ATRP) method. The microscale friction properties between a silica probe and PMPC brushes were studied by atomic force microscopy (AFM). The PMPC molecules are gradually transferred from the substrate to the silica probe induced by shear actions in the initial friction process, causing the frictional force to gradually reduce with increasing sliding distance. The robust superlubricity with a friction coefficient of 0.006 was finally achieved after enough PMPC molecules had transferred onto the probe, which was attributed to the formation of a uniform hydration layer after the running-in process. The effects of PMPC brush thickness and ion types on friction and normal forces were also examined. This work may help us develop various surface modifications for lubrication enhancement by shear actions.

研究领域: 材料科学 · 表面化学 · 摩擦学
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Biosurface and Biotribology · 2020 ·Vol. 6 ·期 3 ·82-86 · IF 0

Synthesis of articular cartilage-inspired branched polyelectrolyte polymer for enhanced lubrication

Yixin Wang,Li Wan,Yulong Sun,Hongyu Zhang

The superlubrication property of articular cartilage is attributed to the hydration lubrication mechanism. This involves the complexation of biomacromolecules with phosphatidylcholine lipids to form a lubricating boundary layer on the surface. Based on this mechanism, a branched polyelectrolyte polymer – PEI-PMPC was synthesised in this study to enhance lubrication via tert-butyl hydroperoxide-initiated grafting polymerisation of 2-methacryloyloxyethyl phosphorylcholine (MPC) onto polyethyleneimine (PEI) with various molecular weights. Following the characterisation of the polymer using nuclear magnetic resonance, a series of tribological tests were performed under different normal loads and different scan rates. The results showed that the PEI-PMPC polyelectrolyte polymer in aqueous solution could effectively reduce the friction coefficient and wear generation between the polyethylene ball and the silica wafer. Additionally, an improvement in the lubrication performance was detected for the PEI-PMPC polyelectrolyte polymer when high molecular weight PEI was used during the reaction, which was attributed to the formation of the hydration shells surrounding the zwitterionic charges of PMPC and the viscosity of the polymer. In conclusion, the PEI-PMPC polyelectrolyte polymer developed herein was characterised by enhanced lubrication, and may be potentially used for biomedical applications such as intra-articular injection to restore joint lubrication.

研究领域: 生物材料学 · 摩擦学 · 高分子化学
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MATERIALS CHEMISTRY AND PHYSICS · 2023 · IF 4.6

Construction of ZnONRs-PDA/PMPC nanocomposites on the surface of magnesium alloy with enhanced corrosion resistance and antibacterial performances

Fenyan Hu,Minting Du,Ruiqi Liang,Wancheng Zhu,Mengke Peng,Hao Xiang,Changhao Wang,Yashao Chen

Magnesium alloy (MgA) with satisfactory biodegradability and excellent mechanical properties has been widely applied in new degradable medical implant materials , especially cardiovascular scaffold materials. However, fast degradation and limited biological activities always restrict the application of MgA. Herein, we have constructed multi-functional inorganic-organic nanocomposites (ZnONRs-PDA/PMPC) onto the surface of micro-arc oxidation pretreated magnesium alloys (MgA-MgO), where ZnO nanorods (ZnONRs) were grown by a microwave-assisted hydrothermal method , and polydopamine/poly(2-methacryloyloxyethyl phosphorylcholine) (PDA/PMPC) films were prepared by a co-deposition strategy. The morphology and composition of MgA-MgO-ZnONRs-PDA/PMPC were characterized by field emission-scanning electron microscopy (FE-SEM), Fourier transform infrared spectroscopy (FT-IR) and X-ray diffraction (XRD), and so on. The MgA-MgO-ZnONRs-PDA/PMPC exhibited good hydrophilic property with a water contact angle of 37.4° and improved the corrosion resistance performance with decreasing the corrosion current density ( i corr ) by 3 orders of magnitude compared with pristine MgA. Moreover, the MgA-MgO-ZnONRs-PDA/PMPC showed good anti-platelet adhesion performance and excellent antibacterial activities with bactericidal rates of 98.1% against S. aureus and 96.2% against E. coli . This work provides an easy and effective method to fabricate a multi-functional nanocomposite with excellent corrosion resistance and biological activities that would facilitate the potential applications of MgA in biomedical fields.

研究领域: 生物医学工程 · 材料科学
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MACROMOLECULAR RAPID COMMUNICATIONS · 2021 ·Vol. 43 ·期 5 ·2100776 · IF 5.734

Super-Hydrophilic Zwitterionic Polymer Surface Modification Facilitates Liquid Transportation of Microfluidic Sweat Sensors

Fanfan Fu,Jilei Wang,Yurong Tan,Jing Yu

The transportation of sweat in an epidermal sweat sensor is critical for the monitoring of biochemical compositions of human sweat. However, it is still a challenge to engineer microfluidic devices with super-wetting channels for such epidermal sweat sensors. Herein, a zwitterionic poly (2-methacryloyloxyethyl phosphorylcholine) (PMPC) modified microfluidic device with super-wetting and good liquid transport ability via an azo coupling reaction of PMPC onto the surface of polydimethylsiloxane microfluidic devices is reported. The obtained PMPC-modified microfluidic device can be integrated with flexible electrochemical sensor to measure the ion compositions of human sweat in real-time. The super-hydrophilic zwitterionic polymer surface modification can greatly facilitate the transportation of body fluids in microfluidic sensors for the detection of various biomarkers. Such microfluidic sensors have great potential for next-generation personalized healthcare.

CAS / MDL: 63148-65-2
研究领域: 生物医学工程 · 材料科学 · 传感器技术
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Advanced Healthcare Materials · 2022 ·Vol. 11 ·期 13 ·2200090 · IF 11.092

Bioinspired Polysaccharide-Derived Zwitterionic Brush-like Copolymer as an Injectable Biolubricant for Arthritis Treatment

Qinyu Yue,Lele Lei,Ya Gu,Ruijin Chen,Mingming Zhang,Haikuan Yu,Shang Li,Luming Yang,Yixin Zhang,Xiaoduo Zhao,Qiangbing Wei,Shuanhong Ma,Licheng Zhang,Peifu Tang,Feng Zhou

Developing highly efficient and biocompatible biolubricants for arthritis treatment is extraordinarily demanded. Herein, inspired by the efficient lubrication of synovial joints, a paradigm that combines natural polysaccharide (chitosan) with zwitterionic poly[2-(methacryloyloxy) ethyl phosphorylcholine] (PMPC), to design a series of brush-like Chitosan- g -PMPC copolymers with highly efficient biological lubrication and good biocompatibility is presented. The Chitosan- g -PMPC copolymers are prepared via facile one-step graft polymerization in aqueous medium without using any toxic catalysts and organic solvents. The as-prepared Chitosan- g -PMPC copolymers exhibit very low coefficient of friction ( μ < 0.01) on Ti 6 Al 4 V alloy substrate in both pure water and biological fluids. The superior lubrication is attributed primarily to the hydrated feature of PMPC side chains, interface adsorption of copolymer as well as to the hydrodynamic effect. In vivo experiments confirm that Chitosan- g -PMPC can alleviate the swelling symptom of arthritis and protect the bone and cartilage from destruction. Due to their facile preparation, distinctive lubrication properties, and good biocompatibility, Chitosan- g -PMPC copolymers represent a new type of biomimetic lubricants derived from natural biopolymer for promising arthritis treatment and artificial joint lubrication.

CAS / MDL: 9012-76-4
研究领域: 生物材料 · 聚合物科学 · 生物医学工程 · 骨科
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