Block and Graft Copolymers of Poly(ethylene glycol) and Poly(dimethylsiloxane) for Blood Contacting Biomedical Materials Applications

The incorporation of both hydrophobic and hydrophilic groups into a synthetic polymer is a potent way of controlling its surface and interfacial properties. With this end result in mind, we describe herein the synthesis and characterization of poly(dimethylsiloxane-b-ethyleneoxide) block copolymers (PDMS-b-PEO) and poly(dimethylsiloxane-g-ethyleneoxide) grafted copolymers (PDMS-g-PEO). These amphiphillic copolymers were also investigated as surface modifying agents for passifying hydrophobic polymer surfaces in blood contacting applications. Specifically, the various (PDMS-b-PEO) and (PDMS-g-PEO) copolymers were coated onto poly(styrene-divinylbenzene) microspheres by their physical adsorption from solution. These surfaces were then evaluated for blood contacting applications utilizing a fibrinogen and thrombin protocol. In particular, the binding of fibrinogen and the functionality of the surface bound fibrinogen on an otherwise hydrophobic surface (polystyrene) was investigated. As the conversion of fibrinogen to fibrin is facilitated by thrombin, the aggregation of the copolymer-coated hydrophobic microspheres was followed using an optical method after the sequential exposure of the microspheres to fibrinogen and then to thrombin. We were able to determine how the adsorbed copolymers affected the functionality of the bound fibrinogen at an interface. Our hypothesis is that the hydrophobic siloxane units of the copolymers will be in close proximity to the polystyrene surface and that the PEO will extend out from the surface and therefore render the synthetic polymer system hemocompatible. Following the fibrinogen and thrombin protocol and determining the fibrinogen-dependent aggregation, the results show that the PDMS-b-PEO copolymers (having a PEO content from 4.6 to 11.5 weight %) were similar in terms of particle aggregation when compared to the pure polystyrene microspheres (blank) or to the microspheres that were coated with a linear PDMS homopolymer. By comparison, the PDMS-g-PEO copolymers (having a PEO content from 58 to 80 weight %) were seen to reduce the fibrinogen functionality on the microsphere system surface. Thus the data indicate that the PDMS-g-PEO copolymers can behave like molecular brushes that are able to pacify the surface of the hydrophobic polystyrene microspheres. A somewhat unexpected observation was that for the copolymer system having a low PEO content the fibrinogen-dependent aggregation of the otherwise hydrophobic microspheres was observed to increase relative to the pure microspheres (blank). It is clear from the findings of this investigation that the surface packing and molecular orientation of both the adsorbed copolymer and also of the fibrinogen are important factors that govern the properties and applications of blood contacting biomaterials.     

不同PEG含量对PLA/PEG共混物结晶动力学的影响

采用溶液共混法制备了一系列不同配比的聚乳酸(PLA)/聚乙二醇(PEG)共混物。通过偏光显微镜(POM)、扫描电镜(SEM)和差式扫描量热仪(DSC)研究了不同PEG含量的PLA/PEG共混物在不同结晶温度下,聚乳酸的晶体形貌、球晶生长速率及热力学性能。研究发现,PEG能够显著提高聚乳酸球晶的生长速率。当PEG含量为60%时,PLA/PEG共混物中聚乳酸球晶的生长速率最快,达到23.6μm/min,比纯聚乳酸的最快球晶生长速率(0.5μm/min)高47倍。但是,当PEG含量高于60%时,聚乳酸球晶的生长速率有所降低。同时,PLA/PEG共混物中聚乳酸球晶速率随结晶温度变化的取向,均向低温移动。另外,PLA/PEG共混物中聚乳酸球晶呈现环状花纹。DSC测试结果表明,随着PEG含量的增加,PLA/PEG共混物的玻璃化转变温度明显降低。     

Poly(ethylene naphthalate) formation 1. transesterification of dimethylnaphthalate with ethylene glycol

The transesterification of dimethyl naphthalate (DMN) with ethylene glycol (EG) was kinetically investigated in the presence of various catalysts at 185 °C. The transesterification was assumed to obey first-order kinetics with respect to DMN and EG, and a rate equation was derived. The rate constant of transesterification which calculated from the quantity of methanol distilled from the reaction vessel was used to evaluate each metal compound in its activity. The first-order dependence on the catalyst concentration is valid below a critical concentration which was found to be dependent on the catalyst type. The order of decreasing catalytic activity of various metal ions was found to be: Pb Zn > Co > Mg > Ni Sb. But in the case of highly basic metal salts, the rate constants were found to be extremely large at the initial stage of the reaction, and then rapidly decreased with the progress of the reaction. Effects of reaction temperature were also discussed. The activation energies for zinc acetate and lead acetate were 97.84 and 97.2 KJ/mol, respectively, which were calculated from Arrhenius equation.     

聚乙二醇中共轭烯炔化合物的合成

发展了一种在聚乙二醇介质中末端炔烃与缺电子炔烃选择性生成共轭烯炔化合物的方法。在三苯基膦氯化钯(2mol%)、溴化亚铜(4mol%)、PEG-400(1.0g)和氮气的作用下,1mmol末端炔烃与0.5mmol缺电子炔烃可以顺利地发生交叉偶联反应选择性生成相应的共轭烯炔化合物,该反应产率较高,对环境友好,且催化体系可以适当地重复使用。     

单甲氧基聚乙二醇氨基的制备

通过两步反应制备了相对分子质量(简称分子量)为5 000的单甲氧基聚乙二醇氨基(m PEG5k-EDA)。首先以单甲氧基聚乙二醇5 000(m PEG5k)和对甲苯磺酰氯(p-Ts Cl)为原料,反应得到活性中间体m PEG5k-OTs,然后通过与乙二胺的亲核取代反应获得目标产物,并通过正交实验确定了最佳反应条件:m PEG5k-OTs与乙二胺的摩尔比为1∶25、反应温度为80℃和反应时间为24 h。产物和中间体的结构通过IR和1HNMR进行表征,并通过SDS-PAGE碘染色法检测产物分子量的变化情况。结果表明,通过该方法能简便快捷地制备m PEG5k-EDA,在最优实验条件下,目标产物的总收率高达76.8%,且SDS-PAGE检测表明,产物纯度较高,不含交联副产物。     

Crystallization Kinetics and Hydrophilicity Improvement of Biodegradable Poly(butylene succinate) in its Miscible Blends with Poly(ethylene oxide)

The spherulitic morphology and growth, overall isothermal crystallization kinetics and hydrophilicity of PBSU were investigated by POM, DSC and WCA measurements in its miscible blends with PEO. The Hoffman‐Lauritzen equation was employed to analyze the spherulitic growth rates of neat and blended PBSU, which show a crystallization regime transition between regime II and III. The overall crystallization rates of PBSU decreased with increasing crystallization temperature, regardless of blend composition, while the crystallization mechanism does not change. A significant improvement in the hydrophilicity of PBSU can be achieved by blending with different weight fractions of PEO, which may be essential for the practical application of PBSU/PEO blends.

     

Synthesis and Characterization of Poly(ethylene glycol) grafted Poly(ε-Caprolactone)

Summary A new graft copolymer, poly(ε-caprolactone) (PCL) grafted with poly(ethylene glycol) (PEG), was prepared by one-pot synthesis of ε-caprolactone and modified PEG. Aluminium isopropoxide or potassium tert-butoxide was used as a catalyst for the ring-opening polymerization. Polymerization using potassium tert-butoxide as a catalyst showed very effective graft reaction of PEG onto poly(ε-caprolactone). A slight decrease in the melting temperature was observed with the increase of the PEG graft frequency. Interestingly, considerable changes were observed on the surface property by the introducing PEG side chains compared to that of PCL homopolymer. Measurements of water contact angle showed that the hydrophilic surface of the polymer could be obtained even at a low graft frequency of PEG.     

Poly(butylene terephthalate)/poly(ethylene glycol) blends with compatibilizers

Polymer blend systems offer a versatile approach for tailoring the properties of polymer materials for specific applications. In this study, we investigated the compatibility of polybutylene terephthalate (PBT) and poly(ethylene glycol) (PEG) blends processed using a twin-screw extruder, with the aim of enhancing their compatibility. Phthalic anhydride (PAn) and phthalic acid (PAc) were used as potential compatibilizers at different concentrations to improve interfacial interactions between PBT and PEG. Blend morphologies were characterized using scanning electron microscopy, which revealed improved interfacial compatibility and reduced phase separation with the incorporation of small amounts of PAn and PAc. Differential scanning calorimetry analysis indicated changes in the melting temperature (T_m) and glass transition temperature (T_g) of the blends owing to the compatibilizing effects of PAn and PAc. Dynamic mechanical analysis further corroborated the influence of the compatibilizers on the T_g and viscoelastic behavior. Thermogravimetric analysis demonstrated enhanced thermal stability with the addition of either PAn or PAc. Rheological measurements indicated an increase in complex viscosity with increasing compatibilizer content, indicating improved compatibility. The degradation point (T_d) of PBT/PEG blend increased from 158 to 200 and 319°C with the incorporation of 5 phr PAn and 2 phr PAc, respectively. Mechanical properties, including tensile strength, Young's modulus, and Izod impact strength, were evaluated. For instance, the tensile strength of PBT/PEG blend was enhanced from 43.5 to 48.7 and 49.7 MPa by incorporating 5 phr PAn and 2 phr PAc, respectively. However, the impact strength of PBT/PEG blend increased from 3.0 to 4.3 and 4.2 kJ/m² with the addition of 1 phr PAn and 1 phr PAc, respectively. The findings demonstrated that adding 5 phr PAn or 2 phr PAc to the PBT/PEG blends was advantageous, achieving a harmony of performance benefits and compromises. Rheological observations contributed significantly to the mechanical and thermal properties. Overall, the study highlights the significance of utilizing PAn and PAc as effective compatibilizers for enhancing the properties of PBT/PEG blends, making them potential candidates for various applications.     

聚乙二醇中咪唑与芳基硼酸的N-芳基化反应

N-芳基咪唑类化合物是一类非常重要的结构单元,常见于药物、农药以及生物分子中,因此寻找新的合成N-芳基咪唑类物质的方法成为有机合成化学家关注的热点问题之一。在绿色化学的倡导下,研究发展了一个促进咪唑类底物与芳基硼酸N-芳基化反应的催化体系,它是以Cu_2O(10%)为催化剂,以聚乙二醇400为反应介质,在室温下反应。研究结果表明,该催化体系适用于咪唑类底物与各种具有不同取代基的芳基硼酸的N-芳基化反应,为N-芳基咪唑类化合物提供一个简单、有效、绿色的合成方法。     

二甲基丙烯酸聚乙二醇酯的RAFT交联聚合行为

采用差示扫描量热(DSC)和动态力学分析(DMA)方法研究二甲基丙烯酸聚乙二醇酯(PEGDMA)的可逆加成-断裂链转移(RAFT)自由基交联聚合,探索了交联单体双键间链段长度和链柔性对RAFT交联聚合动力学及其交联结构的影响.实验发现,随着双键间乙二醇单元数由4增加到9,聚合速率加快,当乙二醇单元数由9增加到14,聚合速率不增反降,这种行为是交联网络密度减小后增长自由基浓度下降和悬挂双键反应活性增加共同作用的结果;双键间链段柔性的增加使RAFT交联聚合速率加快:随双键间链段长度增加,交联网络密度和玻璃化转变温度降低,交联网络的均匀性得到改善.     

聚丁二酸乙二醇酯合成的研究进展

综述了直接酯化聚合法、丁二酸酐开环聚合法、酯交换聚合法、耦合反应法合成聚丁二酸乙二醇酯(PES)的国内外研究进展,着重介绍了丁二酸和乙二醇酯化聚合法合成PES的催化剂和工艺的研究现状,并展望了PES及其合成工艺的发展前景。     

Hydrolytic Degradation of Aliphatic Polyesters Copolymerized with Poly(ethylene glycol)s

Poly(1,4-butanediol succinate) copolymers were prepared by melt polycondensation of succinic acid and 1,4-butanediol with 10–50mol% (in feed) of poly(ethylene glycol) (PEG), where molecular weight (MW) of PEG is 200–2000. The reduced specific viscosity of the copolymers increased with incorporation of the PEG component, but a higher PEG content in the copolymers reduced it. The temperature of melting (T_m) and crystallinity decreased with increasing PEG content. T_m depression of the copolymers followed approximately Flory’s equation, suggesting that these are random type copolymers. Tensile strength and elongation decreased with increasing MW and content of PEG. The weight loss of copolymer films in a buffer solution with or without lipase at 37°C, as well as water absorption, increased with increasing PEG content, implying that higher water absorption contributes to hydrolytic degradation of the films. However, the weight loss of copolymers with PEG of lower MW increased greatly in spite of lower water absorption, demonstrating that hydrolytic degradation is influenced by the concentration of degradable ester linkages between succinic acid and PEG segments rather than water absorption. © of SCI.     

Poly(ethylene glycol) electrolyte gels prepared by condensation reaction

Poly(ethylene glycol) electrolyte gels were prepared by condensation reaction in the presence of tetraethoxysilane. Differential scanning calorimetry and X‐ray diffraction spectroscopy were used to investigate the thermal transition behavior and crystalline structure of polymer gels prepared. Both formation of crosslinks and incorporation of salts or plasticizers reduced the development of crystalline structure of poly(ethylene glycol)s. Cyclic voltammetric and ion‐conducting behaviors of polymer gels were analyzed using potentiostat and impedance spectroscopy, and those were also considerably affected by the crosslinking density of polymers and the concentration of electrolyte salt or plasticizers incorporated. Poly(ethylene glycol) gels possessing certain levels of electrolyte salt and plasticizer were expected to have applications of solid electrolytes for lithium polymer secondary batteries. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 948–956, 2002     

Characterization of Native Cellulose/Poly(ethylene glycol) Films

Water molecules retained in native cellulose gels obtained from Acetobacter xylinum (AX) were displaced by poly(ethylene glycol)s (PEG) of different molecular weight. The so obtained native cellulose/PEG material, characterized in film form by differential scanning calorimetry, dynamic mechanical thermal analysis and wide angle X‐ray scattering, revealed that strong interactions occur between PEG and cellulose and that the polymer mixture is in the rubbery state at ambient temperature. Moreover, it could be dyed in supercritical carbon dioxide by disperse dyes, thus exhibiting typically lipophilic properties and suitability to be employed as a biocompatible support for lipophilic active species.     

Injectable gel: Poly(ethylene glycol)-sebacic acid polyester

In order to develop an injectable material for drug delivery that has both formulation advantages of a sol-to-gel transition system and minimal burst release of a drug, a soft thermogel of poly(ethylene glycol)-sebacic acid polyester was synthesized. The polymer aqueous solution (25 wt%) undergoes ‘clear sol-to-gel’ transition as the temperature increases from 5 to 65 °C. The drug can be mixed in a low viscous sol state at low temperature (<15 °C). In particular, the thermogel is soft enough to be injected through a 21-gauge syringe needle even as a gel state. The model hydrophilic drug, FITC-dextran (molecular weight: 40,000 Da), was released from the gel over 24 h. The biodegradable poly(ethylene glycol)-sebacic acid polyester soft thermogel is believed to be promising for the hydrophilic drug delivery where an initial burst of a drug might be a concern.     

聚乙二醇增塑聚乳酸的等温结晶动力学研究

采用DSC方法对聚乙二醇(PEG)增塑聚乳酸的等温结晶动力学进行了研究。结果表明,PEG的加入提高了聚乳酸的结晶速度,在相同结晶温度下,随着PEG摩尔质量的增大,结晶速率增大,结晶活化能先减小后增大。不同摩尔质量PEG增塑PLA的结晶成核机理和生长方式一样。     

聚乙二醇接枝炭黑纳米导电复合材料气敏性研究

以聚乙二醇接枝炭黑(PEG—g—CB)为导电粒子，不同相对分子质量的聚乙二醇(PEG)为基体，制备了PEG／PEG—g—CB纳米导电高分子复合材料，并研究了其气敏性能。结果发现，该复合材料在PEG极性溶剂蒸汽中电阻响应快，而在非极性溶剂蒸气中电阻几乎不改变；PEG的晶相结构以及CB的接枝与否对响应重复性有很大影响。     

PEI、PEG修饰的SPIONs的制备及其在不同磁场强度下的磁共振对比

以乙酰丙酮铁(Fe(acac)_3)为铁源,聚乙二醇(PEG-1000)为溶剂、还原剂,聚乙烯亚胺(PEI)为修饰剂,采用高温热分解法制备PEI/PEG修饰的氧化铁纳米粒子(PEI/PEG-SPIONs)。采用X-射线衍射(XRD)、透射电镜(TEM)、热重分析仪(TGA)、傅里叶变换红外光谱仪(FT-IR)、纳米粒度与zeta电位分析仪、磁性能测试、磁共振成像(MRI)对样品进行表征。结果表明:PEI/PEG-SPIONs中含有Fe_3O_4晶相,形成了分散良好的球形粒子,没有团聚且有很高的结晶度,平均粒径为10.5±2.0 nm;PEI和PEG均修饰在了氧化铁纳米粒子的表面,使氧化铁纳米粒子具有良好的水分散性和生物相容性;具备优异的超顺磁性以及较高饱和磁化强度;MRI分析得知,电泳粒度为23.5 nm的PEI/PEG-SPIONs在3T和7T磁场强度下测得r2值分别为101.12 mM~(-1)S~(-1)和142.99 mM~(-1)S~(-1),均表现出较高的T2弛豫率。     

Poly(ethylene glycol)‐containing cationic hydrogels with lipophilic character

Not much effort has been focused towards the development of hydrogels that swell in nonpolar solvents. We have synthesized a new set of polyelectrolyte hydrogels and demonstrated their ability to absorb a less‐polar or nonpolar organic solvent, as well as their ability to resist gel‐collapse in a predominantly nonpolar medium. The hydrogels were prepared by free radical polymerization of different molar ratios of poly(ethylene glycol) methyl ether acrylate and (3‐(methacryloylamino)propyl)‐trimethyl ammonium chloride as comonomers in an aqueous medium. Their swelling behavior in organic solvents was studied by varying the dielectric constant of the swelling medium including mixed‐solvent systems. Besides a high degree of swelling (up to 200 times) in polar solvents, some of the hydrogels also exhibited moderate swelling (up to 15 times) in less‐polar organic solvents. Hydrogels samples with high cationic content showed drastic change in swelling extent in some of the mixed‐solvent systems. It was also interesting to note that the retention of significant swelling in dimethyl sulphoxide–toluene mixture with even 90% toluene content for some compositions. These polyelectrolyte hydrogels with improved lipophilicity opens up greater opportunities for the development of even superior soft materials through proper structural optimizations that would successfully function for a wider range of solvents. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39873.