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PROGRESS IN ORGANIC COATINGS · 2020 · IF 4.469

Facile method for covalent-bonding coating of crosslinked silicone layer onto poly(ester-urethane) surface to improve tensile properties and hemocompatibility

Jinwei Teng,Xuejie Wang,Jing Xu,Tingting Hu,Zhaosheng Hou,Yifan Liu

In this paper, a facile method was provided to prepare covalent-bonding coating of crosslinked silicone (CLS) layer onto the poly(ester-urethane) (PEU) surface for improving its properties. The PEU containing well-ordered hard segments was prepared by the direct chain extension of poly(ε-caprolactone) with diurethane diisocyanate (HBH), and the PEU films were acquired via solvent evaporation. The CLS layer was covalently coated onto the film surface by a three-step chemical treatment: the -NCO groups were first introduced onto the PEU film surface by chemical treatment of the film with hexamethylene diisocyanate; the free N CO groups were subsequently coupled with the N H 2 groups of γ-aminopropyltriethoxysilane to fix the active alkoxysilane groups on the surface; finally, the alkoxysilane groups self-crosslinked to produce a CLS coating on the PEU surface (PEU-Si). FT-IR, XPS and SEM were used to characterize the modified surface. The studies on physicochemical properties of the films manifested that the PEU-Si film exhibited higher thermal stability, excellent tensile properties (broken elongation: 1389 %; ultimate strength: 41.6 MPa), and slower in vitro hydrolytic degradation (only 16.0 % weight loss after 18 months of degradation) than PEU film. The hemocompatibility evaluation of film surface was performed by protein adsorption and platelet adhesion measurements, and the results showed that the CLS-coated surface strongly inhibited protein adsorption (2.92 μg/cm 2 ) and platelet adhesion (2,129 platelets/mm 2 ). The PEU-Si exhibited excellent tensile properties, slow degradability, and superior surface hemocompatibility, indicating promise as a long-term implant.

研究领域: 材料科学 · 生物医学工程
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JOURNAL OF BIOMATERIALS SCIENCE-POLYMER EDITION · 2019 · IF 2.121

Synthesis and properties of biodegradable poly(ester-urethane)s based on poly(ε-caprolactone) and aliphatic diurethane diisocyanate for long-term implant application: effect of uniform-size hard segment content

Li Zhang,Chunxia Zhang,Wenwen Zhang,Honghong Zhang,Zhaosheng Hou

In this article, a series of medical poly(ester-urethane)s (PEUs) with varying uniform-size hard segment content were prepared via one-step chain extension of poly(ε-caprolactone)s with aliphatic urethane diisocyanate, and the corresponding films were obtained by solvent evaporation technique. The chemical structures of polymers were confirmed by 1H NMR, FT-IR and GPC. The effect of uniform-size hard segment content on the physicochemical properties of PEU films, including thermal properties, mechanical properties, crystallization behavior, water-swelling behavior and in vitro degradability, was extensively researched. The PEU films exhibiting similar thermal transition and thermal stability indicated that the uniform-size hard segment content had little effect on the thermal properties. Two obvious glass transition temperatures observed in DSC curves manifested a microphase separation structure, which endowed the PEU films excellent mechanical properties with ultimate stress of 34.6–51.2 MPa and strain at break of 898–1485%. And with the increase of uniform-size hard segment content, the initial modulus and ultimate stress increased, while the strain at break decreased. Due to the compact physical-linking network structure formed by the denser hydrogen bonds, the PEU films exhibited low water-swellability of less than 1.5 wt% and low degradation rate in vitro. The weight loss of the PEU films in degradation test was less than 1 wt% at the first four months and the time of films becoming fragments was more than 15 months. Cytotoxicity test of film extracts was conducted with L929 mouse fibroblasts, and the relative growth rate approached or exceeded 75%, indicating an acceptable cytocompatibility. For the excellent mechanical properties, slow biodegradability, non-toxic degradation products and adequate cytocompatibility, the PEUs containing uniform-size hard segments possess a high potential to be applied as long-term implant biomaterials.

研究领域: 材料科学 · 生物医学工程
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Journal of Materials Chemistry B · 2023 ·Vol. 11 ·期 25 ·5846-5855 · IF 7

Enhanced hemocompatibility and antibacterial activity of biodegradable poly(ester-urethane) modified with quercetin and phosphorylcholine for durable blood-contacting applications

Tiantian Hao,Guangliang Niu,Hao Zhang,Yuzheng Zhu,Chunxia Zhang,Fanzhao Kong,Jing Xu,Zhaosheng Hou

This work developed innovative poly(ester-urethane) materials double-modified by quercetin (QC) and phosphorylcholine (PC) with improved antibacterial activity and hemocompatibility. The functional monomer of PC-diol was first synthesized via a click reaction between 2-methacryloyloxyethyl phosphorylcholine and α-thioglycerol; the NCO-terminated prepolymer was subsequently prepared by a one-pot condensation method of PC-diol, poly(ε-caprolactone) diol, and excess isophorone diisocyanate; finally, the prepolymer was chain-extended with QC to produce the linear products (PEU-PQs). 1H NMR, FT-IR, and XPS techniques confirmed the successful introduction of PC and QC, and the in-depth characterization of the cast PEU-PQ films was carried out. Although a low crystallinity was demonstrated by XRD and thermal analysis, the films exhibited excellent tensile stress and stretchability due to the interchain multiple hydrogen bonds. The introduction of PC groups enhanced the surface hydrophilicity, water absorption, and the in vitro hydrolytic degradation rate of the film materials. Inhibition zone tests presented that the QC-based PEU-PQs had effective antibacterial activity against E. coli and S. aureus. The biological evaluations of the materials were performed in vitro by protein absorption, platelet adhesion, and cytotoxic test and in vivo by subcutaneous implantation, which demonstrated superior surface hemocompatibility and biocompatibility. Collectively, the PEU-PQ biomaterials hold a prospective application in durable blood-contacting devices.

研究领域: 生物材料 · 生物医学工程 · 材料科学
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ACS Applied Materials & Interfaces · 2013 · IF 5.008

In Vitro Constitution of Esophageal Muscle Tissue with Endocyclic and Exolongitudinal Patterns

Changfeng Gong,Lei Hou,Yabin Zhu,Jingjing Lv,Yuxin Liu,Lin Luo

Smooth muscle tissue is the main functional structure of the esophagus and comprises of the endocircular and exolongitudinal muscle layers. To construct a tissue engineered smooth muscle by mimicking the esophageal muscle tissue, we have designed a silicon wafer where a daughter mold was prepared using soft PDMS. The daughter mold was, in turn, casted with poly(ester urethane) (PU) solution to fabricate the tissue scaffolds. The casted PU scaffolds were available in two configurations. Prototype 1 (P1) have microchannels of 100 μm width and discontinuous channel wall with gaps of 30 μm at regular intervals. Prototype 2 (P2) have microchannels of 200 μm width and continuous channel walls. The wall thickness and depth of the microchannels are 30 μm. A tubular scaffold with micropattern P1 in the lumen and micropattern P2 on the exterior was fabricated with the aim of regenerating muscle tissue with endocircular and exolongitudinal muscle architecture. After grafting with natural silk fibroin (SF), the PU micropatterned scaffold demonstrated the ability to promote smooth muscle cell (SMC) growth and differentiation; differentiation is believed to contribute to maintain the contractile function of SMCs. Results from the preliminary in vivo test revealed that the tubular scaffold patterned with microchannels is capable of supporting esophageal muscle regeneration.

研究领域: 生物医学工程 · 组织工程 · 再生医学
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Materials Science & Engineering C-Materials for Biological Applications · 2019 · IF 4.959

Facile preparation of medical segmented poly(ester-urethane) containing uniformly sized hard segments and phosphorylcholine groups for improved hemocompatibility

Zhaosheng Hou,Jun Xu,Jinwei Teng,Qi Jia,Xuejie Wang

In order to improve the hemocompatibility of durable medical-grade polyurethane, a novel series of segmented poly(ester-urethane)s containing uniformly sized hard segments and phosphorylcholine (PC) groups on the side chains (SPU-PCs) was prepared by a facile method. The 2-methacryloyloxyethyl phosphorylcholine (MPC) was first reacted with α-thioglycerol by Michael addition to give a diol compound (MPC-diol), then the SPU-PCs with various PC content were prepared by a one-step chain extension of the mixture of MPC-diol and poly(ε-caprolactone) diol (PCL-diol) with aliphatic diurethane diisocyanates (HBH). The chemical structures of MPC-diol and SPU-PCs were confirmed by 1 H NMR and FT-IR, and the influences of PC content on the physicochemical properties of the SPU-PC films were studied. The introduction of PC groups enhanced the degree of micro-phase separation and improved the hydrolytic degradation of the films. Due to the denser hydrogen bonds formed in the uniformly sized hard segments, the films exhibited favorable tensile properties and a slow hydrolytic degradation rate. The results of water contact angle and XPS analysis indicated that the PC groups on the flexible side chains were concentrated on the surface after contact with water. The surface hemocompatibility of the films was evaluated by testing the protein adsorption and platelet adhesion, and the results revealed that the films surfaces could dramatically suppress the protein adsorption and platelet adhesion. The PC-containing polyurethane films possessed outstanding tensile properties, low degradation rate and good surface hemocompatibility, implying their great potential for use as long-term implant or blood-contacting devices.

CAS / MDL: 68-12-2
研究领域: 材料科学 · 生物医学工程 · 高分子化学
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Biomed Research International · 2013 · IF 0

Engineered Hypopharynx from Coculture of Epithelial Cells and Fibroblasts Using Poly(ester urethane) as Substratum

Zhisen Shen,Jingjing Chen,Cheng Kang,Changfeng Gong,Yabin Zhu

Porous polymeric scaffolds have been much investigated and applied in the field of tissue engineering research. Poly(ester urethane) (PEU) scaffolds, comprising pores of 1–20 μm in diameter on one surface and ≥200 μm on the opposite surface and in bulk, were fabricated using phase separation method for hypopharyngeal tissue engineering. The scaffolds were grafted with silk fibroin (SF) generated from natural silkworm cocoon to enhance the scaffold’s hydrophilicity and further improve cytocompatibility to both primary epithelial cells (ECs) and fibroblasts of human hypopharynx tissue. Coculture of ECs and fibroblasts was conducted on the SF-grafted PEU scaffold (PEU-SF) to evaluate its in vitro cytocompatibility. After co-culture for 14 days, ECs were lined on the scaffold surface while fibroblasts were distributed in scaffold bulk. The results of in vivo investigation showed that PEU porous scaffold possessed good biocompatibility after it was grafted by silk fibroin. SF grafting improved the cell/tissue infiltration into scaffold bulk. Thus, PEU-SF porous scaffold is expected to be a good candidate to support the hypopharynx regeneration.

CAS / MDL: 30525-89-4 111-30-8
研究领域: 组织工程 · 生物医用材料 · 再生医学
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Polymers · 2018 ·Vol. 10 ·期 10 ·1125 · IF 2.935

A Mild Method for Surface-Grafting PEG Onto Segmented Poly(Ester-Urethane) Film with High Grafting Density for Biomedical Purpose

Lulu Liu,Yuanyuan Gao,Juan Zhao,Litong Yuan,Chenglin Li,Zhaojun Liu,Zhaosheng Hou

In the paper, poly(ethylene glycol) (PEG) was grafted on the surface of poly(ester-urethane) (SPEU) film with high grafting density for biomedical purposes. The PEG-surface-grafted SPEU (SPEU-PEG) was prepared by a three-step chemical treatment under mild-reaction conditions. Firstly, the SPEU film surface was treated with 1,6-hexanediisocyanate to introduce -NCO groups on the surface with high density (5.28 × 10−7mol/cm2) by allophanate reaction; subsequently, the -NCO groups attached to SPEU surface were coupled with one of -NH2groups of tris(2-aminoethyl)amine via condensation reaction to immobilize -NH2on the surface; finally, PEG with different molecular weight was grafted on the SPEU surface through Michael addition between terminal C = C bond of monoallyloxy PEG and -NH2group on the film surface. The chemical structure and modified surface were characterized by FT-IR,1H NMR, X-ray photoelectron spectroscopy (XPS), and water contact angle. The SPEU-PEGs displaying much lower water contact angles (23.9–21.8°) than SPEU (80.5°) indicated that the hydrophilic PEG chains improved the surface hydrophilicity significantly. The SPEU-PEG films possessed outstanding mechanical properties with strain at break of 866–884% and ultimate stress of 35.5–36.4 MPa, which were slightly lower than those of parent film, verifying that the chemical treatments had minimum deterioration on the mechanical properties of the substrate. The bovine serum albumin adsorption and platelet adhesion tests revealed that SPEU-PEGs had improved resistance to protein adsorption (3.02–2.78 μg/cm2) and possessed good resistance to platelet adhesion (781–697 per mm2), indicating good surface hemocompatibility. In addition, due to the high grafting density, the molecular weight of surface-grafted PEG had marginal effect on the surface hydrophilicity and hemocompatibility.Keywords:segmented poly(ester-urethane);poly(ethylene glycol);surface grafting;chemical treatment;high grafting density;hemocompatibility

研究领域: 生物医学工程 · 材料科学 · 表面化学
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Materials Science & Engineering C-Materials for Biological Applications · 2019 · IF 4.959

A mild method for surface-grafting MPC onto poly(ester-urethane) based on aliphatic diurethane diisocyanate with high grafting efficiency

Xiaolong Liu,Bing Yang,Zhaosheng Hou,Na Zhang,Yuanyuan Gao

The aim of this work is to provide a new kind of polyurethane with improved surface blood compatibility for long-term blood-contacting biomaterials. In the study, an aliphatic poly(ester-urethane) (H-PEU) with uniform-size hard segments was synthesized by one-step chain extension of poly(ε-caprolactone) (PCL) with diurethane diisocyanate (HBH), and biomimetic phosphorylcholine (PC) groups were immobilized onto the film surface with high grafting efficiency by three-step chemical treatments under mild reaction conditions. The H-PEU film was firstly treated with 1,6-hexanediisocyanate (HDI) to introduce -NCO groups on the surface (H-PEU-NCO) through an allophanate reaction; the -NCO groups were then coupled via a condensation reaction with one of -NH 2 groups of tris(2-aminoethyl)amine (TAEA) to immobilize -NH 2 on the surface (H-PEU-NH 2 ); finally, the double bond of 2-methacryloyloxyethyl phosphorylcholine (MPC) reacted with -NH 2 by Michael addition reaction to obtain MPC-grafted H-PEU (H-PEU-MPC). The modified surfaces were characterized by Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). The results verified that MPC was successfully grafted onto H-PEU surface with high grafting density. The blank and modified films showed similar crystallization behaviors, thermal stabilities and mechanical properties, indicating that the chemical treatments had minimum influence on the physicochemical properties of the substrate. The H-PEU-MPC displaying a much lower water contact angle (~15.2°) than H-PEU (80.3°) meant that the hydrophilic PC functional groups improved the surface hydrophilicity significantly. The surface blood compatibility was examined by bovine serum albumin adsorption and platelet adhesion tests, and the results revealed that H-PEU-MPC had improved resistance to protein adsorption and platelet adhesion capacity. The MPC-grafted H-PEU film possessed outstanding mechanical properties (ultimate stress: 36.1 MPa; strain at break: 883%), low protein adsorption quantity (1.33 μg/cm 2 ) and good anti-platelet adhesion capacity (582 ± 16 per mm 2 ), implying its high potential to be applied as biomaterials for vascular grafts, subcutaneously implanted devices or other blood-contacting devices.

CAS / MDL: 110-63-4 7719-12-2
研究领域: 生物材料 · 表面化学 · 生物医学工程 · 材料科学
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