Electrospinning of novel biodegradable poly(ester urethane)s and poly(ester urethane urea)s for soft tissue-engineering applications

The development of biomimetic highly-porous scaffolds is essential for successful tissue engineering. Segmented poly(ester urethane)s and poly(ester urethane urea)s have been infrequently used for the fabrication of electrospun nanofibrous tissues, which is surprising because these polymers represent a very large variety of materials with tailored properties. This study reports the preparation of new electrospun elastomeric polyurethane scaffolds. Two novel segmented polyurethanes (SPU), synthesized from poly(ε-caprolactone) diol, 1,6-hexamethylene diisocyanate, and diester-diphenol or diurea-diol chain extenders, were used (Caracciolo et al. in J Mater Sci Mater Med 20:145–155, 2009). The spinnability and the morphology of the electrospun SPU scaffolds were investigated and discussed. The electrospinning parameters such as solution properties (polymer concentration and solvent) and processing parameters (applied electric field, needle to collector distance and solution flow rate) were optimized to achieve smooth, uniform bead-free fibers with diameter (~700 nm) mimicking the protein fibers of native extracellular matrix (ECM). The obtained elastomeric polyurethane scaffolds could be appropriate for soft tissue-engineering applications.     

Lens epithelial cell response to atmospheric pressure plasma modified poly(methylmethacrylate) surfaces

Selective control of cellular response to polymeric biomaterials is an important consideration for many ocular implant applications. In particular, there is often a need to have one surface of an ophthalmic implant capable of promoting cell attachment while the other needs to be resistant to this effect. In this study, an atmospheric pressure dielectric barrier discharge (DBD) has been used to modify the surface region of poly(methyl methacrylate) (PMMA), a well established ocular biomaterial, with the aim of promoting a controlled response to human lens epithelial cells (LEC) cultured thereon. The DBD plasma discharge environment has also been employed to chemically graft a layer of poly(ethylene glycol) methyl ether methacrylate (PEGMA) onto the PMMA and the response to LEC likewise determined. Two different molecular weights of PEGMA, namely 1000 and 2000 MW were used in these experiments. The LEC response to DBD treated polystyrene (PS) samples has also been examined as a positive control and to help to further elucidate the nature of the modified surfaces. The LEC adhered and proliferated readily on the DBD treated PMMA and PS surfaces when compared to the pristine polymer samples which showed little or no cell response. The PMMA and PS surfaces that had been DBD grafted with the PEGMA₁₀₀₀ layer were found to have some adhered cells. However, on closer inspection, these cells were clearly on the verge of detaching. In the case of the PEGMA₂₀₀₀ grafted surfaces no cells were observed indicating that the higher molecular weight PEGMA has been able to attain a surface conformation that is capable of resisting cell attachment in vitro.     

Anti-microbial and anti-corrosive poly (ester amide urethane) siloxane modified ZnO hybrid coatings from Thevetia peruviana seed oil

The utilization of renewable resources for the development of organic coatings is a viable means of creating alternatives to petroleum-based chemicals which are not eco-friendly. This paper reports the synthesis of polyesteramide–urethane–silica–zinc oxide hybrid coatings from Thevetia peruviana seed oil (TPSO). The periphery of ZnO nano-particles is modified with 3-aminopropyltrimethoxysilane to prepare silica grafted ZnO composite particles. The TPSO based polyesteramide was reacted with 4,4′-diisocyanatodicyclohexylmethane in presence of siloxane modified ZnO to obtain –NCO terminated polyesteramide–urethane–silica ZnO prepolymer. These hybrid pre-polymers were casted on tin foil and cured under atmospheric moisture to obtain eco-friendly, moisture cured polyesteramide–urethanes–silica–zinc oxide hybrid coating films. The synthesized polyester and polyurethane formation was confirmed by using FT-IR and NMR spectroscopic techniques. The resultant hybrid coating films were characterized by using FT-IR, TGA, DSC, SEM, corrosion resistance and microbial resistance. Results confirm that with increase of siloxane modified ZnO content in the polyurethane matrix thermal stability, glass transition temperature and corrosion resistance improved. The antibacterial activity shows that the hybrid films exhibit excellent resistance towards Escherichia coli and Staphylococcus aureus. The salt spray test on coated panel samples show good corrosion resistance properties.     

聚乙二醇改性聚乳酸的合成与性能表征

以外消旋乳酸(D,L-LA)和不同数均分子量(Mn)的聚乙二醇(PEG)为原料,通过熔融缩聚法,合成了系列聚乳酸聚乙二醇(PLEG)。最佳工艺条件为:以(Sn(Oct)2)为催化剂,m(Sn(Oct)2)为0.8%,n(PEG)∶n(D,L-LA)=1∶600,聚合温度170℃,压力0.096 MPa条件下,反应8h。用特性粘度测试、FT-IR、XRD、接触角等对其进行表征,实验结果表明系列PLEG中PLEG-800接触角为63°,表明其亲水性能最好;PEG-800和乳酸共聚合成的PLEG的粘均分子量最大,可达48997,与PDLLA相比,结晶度有较大提高,亲水性得到改善。     

聚氨酯酰亚胺-聚酰亚胺嵌段共聚物制备炭膜

利用傅立叶变换红外光谱(FTIR)跟踪不同温度下聚氨酯酰亚胺(Poly-urethane-imide.PUI)-聚酰亚胺(polyirnide,PI)共聚物(PUI-PI)的热解反应过程,扫描电镜(SEM)表征所制炭膜的结构形貌,N2吸附仪测定计算微孔炭膜的表面积和微孔体积,结合不同PI-PUI体系的炭化收缩率、微孔炭膜水通量的分析,研究了南PI-PUI制备微孔炭膜时不同嵌段的热稳定性及其梯度炭化成孔特性.结果显示:氨基甲酸酯基团在200℃～300℃温间分解,酰亚胺基团在500℃～700℃温间热解,分别为炭膜贡献了大孔和微孔;PUI前驱体的加入能有效降低炭膜的收缩率;外加炭黑对减少炭膜的收缩也有一定的作用,并能显著提高炭膜的微孔体积和总孔体积.     

Novel reverse thermoresponsive injectable poly(ether carbonate)s

The water solutions of polymers displaying reverse thermal gelation (RTG), such as poly(ethylene oxide)/poly(propylene oxide)/poly(ethylene oxide) triblocks, exhibit a pronounced viscosity increase as temperature rises, within a very narrow temperature interval. Unfortunately, the viscosity increase attained by these solutions is not large enough, resulting in systems displaying limited stability and short residence times. This paper introduces a new family of reverse thermoresponsive alternating [A-B] _n block copolymers, comprising poly(ethylene oxide) (PEO), and poly(propylene oxide) (PPO) chains, using phosgene as the molecule connecting both components. The effect of various compositional and structural parameters on both the C _i (minimal gelation concentration) and T _i (minimal gelation temperature) of these systems was investigated. The copolymers were characterized by GPC, ¹H-NMR, FT-IR, and DSC and the rheological behavior of the water solutions was studied using a Brookfield viscometer. The water systems were also studied by dynamic light scattering (DLS) and fluorescence spectroscopy. The copolymers developed exhibited clearly superior rheological properties, when compared to existing RTG-displaying PEO–PPO–PEO triblocks. For example, while the viscosity of a 15% water solution of the commercially available Pluronic F-127 achieved 5000 Pa.s, at 37 °C, poly(ether carbonate) water solutions (15%) attained viscosities between 25 000 and 150 000 Pa.s.     

聚碳酸亚丙酯/聚甲基丙烯酸甲酯复合材料热降解动力学研究

利用溶液共混法制备聚碳酸亚丙酯/聚甲基丙烯酸甲酯(PPC/PMMA)复合材料,采用热重分析法研究PPC/PMMA热性能,结果表明PMMA的加入可以有效提高PPC的热稳定性能。以多升温速率法对PPC/PMMA热降解动力学进行研究,利用Friedman法、Kissinger法、Flynn-Wall-Ozawa法、Coats—Redfem方法对热降解动力学数据进行分析,确定PPC/PMMA热分解反应机理函数为Avrami-Erofeev方程,遵循一种热降解机理。     

Compositional study and cytotoxicity of biodegradable poly(ester urethane)s consisting of poly[(R)-3-hydroxybutyrate] and poly(ethylene glycol)

Biodegradable PHB–PEG multi-block polyurethane copolymers comprising PHB blocks (M_n: 1100, 1740 and 3240) and PEG blocks (M_n: 1960, 3250, 4150 or 7950) were synthesized followed by characterization by GPC, ¹H NMR, and FT-IR. The PHB contents ranged from 9 to 62% by weight. The copolymers displayed improved thermal stabilities compared with their respective precursors. The morphological structures of the copolymers were studied by FT-IR, DSC and XRD. FT-IR revealed the existence of amorphous and crystalline phases of PHB. Both DSC and XRD analyses showed that separate crystalline phases are formed by PEG and PHB blocks in the copolymers. Upon annealing, the melting transition temperature (T_m), melting enthalpy (ΔH_m) and the fractional crystallinity (X_c) of the PEG block increased when the length of PEG incorporated into the copolymer increased. These values were higher when the PHB block length is shorter as the shorter PHB chain does not disrupt the crystallization of PEG as much as the longer PHB chain. A similar disruptive effect on the crystallization of PHB segments was observed by varying PEG chain lengths but the effect is less pronounced compared with the PEG segments. A comparison of the swelling properties of the poly(ester urethane)s showed that the length and crystalline properties of the PHB block significantly affects the water uptake properties of the copolymers. The crystalline properties and the water uptake capacities of the copolymers could be fine-tuned by consideration of the length of the PHB and PEG block incorporated. The results of the cytotoxicity tests demonstrated that the poly(PHB/PEG) urethanes were non-cytotoxic and could potentially be used for biomedical purposes.     

复合型聚醚聚氨酯固体电解质的制备及交流阻抗分析

合成了1种线性聚醚聚氨酯,并以此聚合物为基体加入O/Li=16(摩尔比)的锂盐,分别掺入纳米SiO2、纳米TiO2制备了两类复合聚合物固体电解质(CSPE).在室温下,纳米SiO2复合型聚合物固体电解质的电导率最大,达到6.40×10-6S/cm.通过红外光谱、热分析及交流阻抗等手段研究了电解质本体,以及掺入无机氧化物粒子之后其质量分数与离子电导率之间的关系.结果表明,纳米SiO2质量分数达到15%,纳米TiO2质量分数达到25%时,离子电导率最大.在室温下,加入纳米SiO2比加入纳米TiO2的离子电导率要高;但随着温度的升高,这种差距越来越小.     

Alkaline hydrolysis of modified poly(l-lactide) monolayers

In this work, hydrolysis of biodegradable poly(l-lactide) (l-PLA) and copolymers of l-lactide (l-LA) and (benzyloxycarbonyl) methyl mophorline-2,5-dione (BMD) was investigated at the air/water interface. In order to improve the hydrophilicity of l-PLA, small amounts of BMD were copolymerized with l-LA. NaOH was used to adjust the pH of the subphase water. Under the conditions studied here, polymer monolayers showed much faster hydrolysis as either a subphase pH or the concentration of BMD in the copolymer is increased. This result was explained by increasing numbers of base attack sites per unit area and increasing hydrophilicity.     

Electrical conductivity of modified poly(vinyl chloride)

Chemical modification of poly(vinyl chloride) (PVC) by dehydrochlorination with ethanolic KOH is found to yield modified PVC with conjugated polyene sequence. The semiconducting nature of ethoxide-modified PVC is illustrated with temperature dependence of conductivity (σ). The relative ratios (r) of conductivity,σ _modifiedpvc /σ _{unmodifiedpvc} , are greater than unity in the temperature range 50° to 180°C,r being maximum in the vicinity of glass-transition temperature (T _g).T _g inferred from conductivity-temperature profiles is found to be greater for modified PVC relative to unmodified PVC, which is explicable in terms of restricted free rotation limiting segmental motion. For comparison with the conductivity andT _g of ethoxide-modified PVC, LiCl-modified PVC and (aniline + S₂O ₈ ²⁻ )-modified PVC have also been studied.     

Biomechanical studies on aliphatic physically crosslinked poly(urethane urea) for blood contact applications

Hydrophobic and physically crosslinked (virtually crosslinked through hydrogen bonding) aliphatic poly(urethane urea)s were developed and characterized for its biomechanical properties. The aging under induced-stress (bend samples) condition reveals resistance of poly(urethane urea) to environmental stress corrosion cracking (ESC) in hydrolytic media, Ringer's solution and phosphate buffered saline at 50 degrees C. The strain-induced (20% tensile strain) and aged polymer in hydrolytic enzyme medium, papain and in buffer reveals increase of elastic modulus in papain enzyme and papain buffer. The increase of elastic modulus is attributed to unidirectional reorganisation of chains under continually strained conditions. The polymer exposed in boiling alcoholic potassium hydroxide solution (accelerated hydrolytic chemical degradation) reveals no degradation. A comparative evaluation of poly(ether urethane urea)s reveals inferior properties. Poly(ether urethane urea)s polymer undergo hydrolytic degradation in boiling alcoholic potassium hydroxide solution. The candidate poly(urethane urea) HFL 18-PUU is more promising elastomer for long-term biomechanically sensitive blood contact applications such as heart valve and blood pump diaphragm of left ventricular assist device.     

可降解聚碳酸亚丙酯马来酸酯载药微球的制备

采用阴离子配位聚合方法,合成了二氧化碳(CO2),环氧丙烷(PO)与马来酸酐(MA)的三元共聚物,聚碳酸亚丙酯马来酸酯 (PPCMA).采用复相乳液(W/O/W)溶剂挥发法制备了包裹水溶性模型药物葡萄糖(glucose)的可降解微球,并研究了壁材与囊心的比例、稳定剂明胶浓度、搅拌速率等因素对微球性能的影响.当v(PPCMA)∶v(glucose)=1∶2,gelatin质量分数为0.2%,第1次乳化搅拌速率为400r/min,第2次乳化搅拌速率为500r/min时,得到粒径较小、载药量和包封率分别为26.1%和76.1%的载药微球.     

Efficient TCO-free organic solar cells with modified poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) anodes

Organic photovoltaic cells (OPVs) with a highly conductive poly 3,4-ethylenedioxythiophene:poly styrenesulfonate (PEDOT:PSS) layer as an anode and that were modified with the addition of some organic solvents such as sorbitol (So), dimethyl sulfoxide (DMSO), N-methyl-pyrrolidone (NMP), dimethylformamide (DMF), and ethylene glycol (EG) were fabricated without the use of transparent conducting oxide (TCO). The conductivity of the PEDOT:PSS film that was modified with each additive was enhanced by three orders of magnitude. According to the atomic force microscopy (AFM) study, the conductivity enhancement might have been related to the better connections between the conducting PEDOT chains. The TCO-free solar cells with a modified PEDOT:PSS layer and an active layer composed of poly (3-hexylthiophene) (P3HT) and phenyl [6, 6] C61 butyric acid methyl ester (PCBM) performed as well as the indium-tin-oxide (ITO)-based organic solar cells. The power conversion efficiency (PCE) of the organic solar cells with a DMSO-, So + DMSO-, and EG-modified PEDOT:PSS layer reached 3.51, 3.64, and 3.77%, respectively, under an illumination of AM 1.5 (100 mW/cm2).     

Thermo-mechanical properties of poly(vinylidene fluoride) modified graphite/poly(methyl methacrylate) nano composites

Poly(methyl methacrylate) (PMMA) nano composites were synthesized by melt compounding technique. Different graphite loadings were investigated, including some treated with poly(vinylidene fluoride) (PVDF). A homogeneous dispersion of graphite throughout the PMMA matrix was observed under microscopic analysis. Thermo-gravimetric analysis showed the incorporation of graphite resulted in improvement of thermal stability of neat PMMA. Dynamic mechanical thermal analysis also showed a significant improvement in the storage modulus over the temperature range of 25–150 °C. Coating the graphite with a small amount of PVDF was found to further extend the improvement in the modulus of the PMMA nano composite at 1 wt.% graphite loading.     

Wettability of poly(methyl methacrylate) surfaces in dental use

Poly(methyl methacrylate) is widely used in dentistry. In contact with water, there is an increase in the polar surface free energy from 9.5 to 21 mJ m^–2. Various other surface modification treatments have been examined (chemical treatment, gold deposition and flaming), which also bring about a surface polar component increase and thus produce a better wettability in contact with water or saliva. The water modification seems to be the best treatment.     

不饱和超支化聚(酰胺-酯)改性PVC研究

对不饱和超支化聚(酰胺-酯)(HBP)与聚氯乙烯(PVC)共混体系的力学性能和相形态结构进行了研究。研究结果表明,在聚氯乙烯中加入不饱和超支化聚(酰胺-酯)可以有效提高共混体系的拉伸强度,并且在100g PVC中加入3g HBP时共混体系的拉伸强度出现最大值,抗冲强度基本不变。扫描电子显微镜(SEM)研究结果证明了HBP和PVC相容性较好,且与测得的力学结果相一致。同时,利用氢键形成机理对其结果进行了解释。