生物可降解医用聚氨酯及其应用

生物可降解医用聚氨酯由于其优良的生物相容性、降解性、功能化修饰和力学性能可调控等优点,逐渐引起研究者的关注,尤其在药物传递和组织工程支架等方面可望具有广阔的应用前景。结合本课题组开展的工作,本文综述了生物可降解医用聚氨酯材料在结构、功能化设计及医学应用上的研究进展,并展望了其在医学材料中的发展前景。     

PEG含量对水性可降解聚氨酯性能的影响简

本文采用“预聚-乳化法”合成了软段为聚（ε-己内酯）（PCL）和聚乙二醇（PEG）,硬段为异佛尔酮二异氰酸酯（IPDI）和小分子扩链剂的无毒水性可降解聚氨酯（PCLPU）,通过红外光谱（FTIR）和差示扫描量热（DSC）曲线分析、偏光显微镜（PLM）观察以及相对分子质量、水接触角和降解失重测定,研究了PEG含量对聚氨酯微相分离程度、软段结晶性能和降解行为的影响。发现随着PEG含量的增加,PCLPU的微相分离程度增加,软段PCL的结晶受到阻碍。材料的亲水性和结晶性对PCLPU的降解影响明显,当PEG和PCL比例（PCLPU50）适当时,所获得的亲水性、酯基含量以及结晶程度均适中,这时材料的降解速率最快。细胞毒性测试表明PCLPU降解液质量浓度低于1 mg/mL时,细胞生长正常。此类水性无毒可降解聚氨酯将在生物工程领域具有广阔的应用前景。     

PEG含量对水性可降解聚氨酯性能的影响

本文采用"预聚-乳化法"合成了软段为聚(ε-己内酯)(PCL)和聚乙二醇(PEG),硬段为异佛尔酮二异氰酸酯(IPDI)和小分子扩链剂的无毒水性可降解聚氨酯(PCLPU),通过红外光谱(FTIR)和差示扫描量热(DSC)曲线分析、偏光显微镜(PLM)观察以及相对分子质量、水接触角和降解失重测定,研究了PEG含量对聚氨酯微相分离程度、软段结晶性能和降解行为的影响。发现随着PEG含量的增加,PCLPU的微相分离程度增加,软段PCL的结晶受到阻碍。材料的亲水性和结晶性对PCLPU的降解影响明显,当PEG和PCL比例(PCLPU50)适当时,所获得的亲水性、酯基含量以及结晶程度均适中,这时材料的降解速率最快。细胞毒性测试表明PCLPU降解液质量浓度低于1mg/mL时,细胞生长正常。此类水性无毒可降解聚氨酯将在生物工程领域具有广阔的应用前景。     

Synthesis and phase behavior of polyurethanes end-capped with fluorinated phosphatidylcholine head groups

A series of fluorinated phosphatidylcholine polyurethane macromolecular additives were synthesized by solution polymerization using methylenebis(phylene isocyanates)(MDI) and 1,4-butanediol(BDO) as hard segments,a new phoshporycholine,2-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluoro-10-(2-hydroxyethoxy)decyloxy) ethyl phosphorycholine (HDFOPC) as end-capper,and four polydiols,poly(tetramethylene glycol)s(PTMG),polydimethylsiloxane(PDMS), poly(1,6-hexyl-1,5-pentylcarbonate)(PHPC) and poly(propylene glycol)(PPG) as soft segments,respectively.The chemical structures of the synthesized polyurethanes were characterized by ~1H-NMR and FTIR.DSC and DMA were employed to study the phase behavior of these novel polyurethanes due to their great influences on the surface properties,and hence their interactions with bio-systems.The results showed that phase separation of the fluorinated phosphatidylcholine end-capped polyurethanes was increased in comparison with that of normal polyurethanes.The effect of fluorinated phosphatidylcholine end-capped groups on the phase behavior was further demonstrated by analyzing the degree of hydrogen-bonding between hard and soft segments.     

Preparation and characterization of controlled heparin release waterborne polyurethane coating systems

In this study, to improve hemocompatibility of biomedical materials, a waterborne polyurethane (WPU)/heparin release coating system (WPU/heparin) is fabricated via simply blending biodegradable WPU emulsions with heparin aqueous solutions. The surface compositions and hydrophilicity of these WPU/heparin blend coatings are characterized by attenuated total reflectance infrared spectroscopy (ATR-FTIR) and water contact angle measurements. These WPU/heparin blend coatings show effectively controlled release of heparin, as determined by the toluidine blue method. Furthermore, the biocompatibility and anticoagulant activity of these blend coatings are evaluated based on the protein adsorption, platelet adhesion, activated partial thromboplastin time (APTT), thrombin time (TT), hemolysis, and cytotoxicity. The results indicate that better hemocompatibility and cytocompatilibity are obtained due to blending heparin into this waterborne polyurethane. Thus, the WPU/heparin blend coating system is expected to be valuable for various biomedical applications.     

硅烷化聚氨酯复合催化剂的研究

以聚丙二醇、TDI、N-正丁基-γ-氨丙基三甲氧基硅烷和蒙脱土为主要原料,采用原位聚合方法研究了蒙脱土和有机铋化合物对环境友好和储存稳定的硅烷化聚氨酯催化作用.通过滴定法测试了反应体系中异氰酸根(NCO)含量的变化,发现蒙脱土可以催化NCO与OH的反应,且与有机铋化合物具有协同效应,利用在线红外分析仪证实了蒙脱土的催化...     

Effect of trastuzumab on the micellization properties,endocytic pathways and antitumor activities of polyurethane-based drug delivery system

Polyurethane micelles (PM)-based nanovehicles have shown great potential in targeted delivery of therapeutics and diagnostics into tumors.However,the pathways of PMs entering cancer cells and the action mechanism of targeting ligands have yet to be understood.In this contribution,the actively-targeted PM were developed using trastuzumab as a model targeting group.It was found that PM were mainly taken up by SKOV-3 tumor cells via a micropinocytosis process,while the incorporation of trastuzumab to PM enabled a receptor-mediated endocytosis of nanocarriers in cancer cells,leading to more efficient cell entry and enhanced anticancer efficacy of chemotherapeutic drugs both in vitro and in vivo.This study is advantageous to the understanding of the action mechanism of trastuzumab,and significant for the construction of improved formulations for targeted delivery and precise therapy.     

The degradation and biocompatibility of waterborne biodegradable polyurethanes for tissue engineering

To better investigate the degradation and biocompatibility of waterborne biodegradable polyurethanes for tissue engineering, a series of new waterborne biodegradable polyurethanes (PEGPUs) with low degree of crosslinking was synthesized using IPDI, BDO and L-lysine as hard segments, PCL and PEG as soft segment. The bulk structures and properties of the prepared polyurethanes were characterized by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), tensile mechanical tests and water contact angle (WCA) measurements. The degree of microphase separation was slightly improved because of the lowered crosslinking degree of these PEGPUs in comparison with the high cross-linking degree samples, leading to good mechanical properties, as indicated by DSC and stress-strain data. Moreover, biodegradability of the polyurethanes was evaluated in phosphate buffer solutions (PBS) under different pH values and enzymatic solution at pH 7.4 through weight loss monitoring. The results suggested that the degradation of these PEGPUs was closely related to their bulk and surface properties. And the degradation products didn’t show apparent inhibition effect against fibroblasts in vitro. These studies demonstrated that the waterborne biodegradable polyurethanes could find potential use in soft tissue engineering and tissue regeneration.     

生物医用磷脂化聚氨酯的设计、制备与性能

聚氨酯因其具有优异的力学性能和良好的生物相容性广泛地应用于医疗领域.但医用聚氨酯常常会引起蛋白吸附、血小板激活、凝血、血栓和补体激活等不良生物学反应,使其应用受到限制.仿生物膜的磷脂表面被认为是和人体最亲和的表面,聚氨酯磷脂化是提高医用聚氨酯材料生物相容性的非常有效的手段之一.近年来国内外课题组在生物医用磷脂化聚氨酯的设计、制备与生物相容性等方面开展了大量的工作,取得了重要的研究进展.本文综述了磷脂改进医用聚氨酯的最新研究成果,指出含氟磷脂化聚氨酯和可降解的磷脂聚氨酯因其优异的性能,代表了该领域的发展方向并具有重要的应用前景.