聚乙二醇/聚己内酯三嵌段共聚物的合成与表征

以甲苯二异氰酸酯 (TDI)为偶联剂 ,合成了聚乙二醇 (PEG) /聚己内酯 (PCL)两亲性三嵌段共聚物 (PEG-b-PCL -b -PEG ,PECL) ,采用IR、1 H-NMR、DSC和WAXD分析和研究了PECL的结构与性能。实验结果表明 ,PECL的结构和组成与设计相一致 ,结晶度和熔点均低于均聚物 ,且随着PECL中PCL嵌段含量的增加 ,PCL嵌段熔点升高。透射电镜照片显示PECL纳米粒呈核 /壳结构的球形。     

Enzymatic Late-Stage Halogenation of Peptides

The late-stage site-selective derivatisation of peptides has many potential applications in structure-activity relationship studies and postsynthetic modification or conjugation of bioactive compounds. The development of orthogonal methods for C−H functionalisation is crucial for such peptide derivatisation. Among them, biocatalytic methods are increasingly attracting attention. Tryptophan halogenases emerged as valuable catalysts to functionalise tryptophan (Trp), while direct enzyme-catalysed halogenation of synthetic peptides is yet unprecedented. Here, it is reported that the Trp 6-halogenase Thal accepts a wide range of amides and peptides containing a Trp moiety. Increasing the sequence length and reaction optimisation made bromination of pentapeptides feasible with good turnovers and a broad sequence scope, while regioselectivity turned out to be sequence dependent. Comparison of X-ray single crystal structures of Thal in complex with d -Trp and a dipeptide revealed a significantly altered binding mode for the peptide. The viability of this bioorthogonal approach was exemplified by halogenation of a cyclic RGD peptide.     

Block copolymers of styrene containing oligomeric esters of terephthalic acids

A new generation of block copolymers were synthesized starting with depolymerized PET by glycolysis with some oligomeric diols. α,ω‐Dihydroxy poly(dimethyl siloxane)s, hexylene glycol, poly(ethylene oxide)glycols, and ethylene glycol were used as diols. The dihydroxy‐terminated depolymerization products containing a terephthalyl group and oligomeric diols were used to prepare a diradicalic macroinitiator (MI). These MIs were used to polymerize the styrene monomer. The new block copolymers obtained were characterized by physical and chemical methods and mechanical and thermal analyses. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 648–653, 2000     

聚乙二醇/聚(β-羟基丁酸酯)两嵌段共聚物的合成及表征

为改进聚(β-羟基丁酸酯)(PHB)的结晶性和亲水性,通过聚乙二醇单甲醚(MPEG)的端酰氯基团和聚(β-羟基丁酸酯)的端羟基基团的官能团反应,制备了聚乙二醇/聚(β-羟基丁酸酯)两嵌段共聚物。通过红外光谱、核磁、X射线衍射、差热分析和凝胶渗透色谱等手段,证明制备了嵌段共聚物。吸水实验表明,材料的亲水性得到了明显的改善。     

亲水性PET共混材料的制备及性能研究

以机械共混法制备亲水性聚对苯二甲酸乙二醇酯(PET)共混材料,并通过接触角测定仪、差示扫描量热仪(DSC)和电子万能材料试验机等对共混材料的亲水性能、热性能和力学性能等进行研究与分析。结果表明,亲水处理剂聚乙二醇(PEG)、聚丙烯酸钠(PAAS)、聚乙烯吡咯烷酮(PVP)均能改善PET的亲水性能,影响PET的结晶性能,但亲水处理剂对PET的力学性能影响较小,其中PET/PEG共混材料的亲水性最优;随着PEG含量的增加,PET/PEG共混材料的亲水性先逐渐增强,当PEG含量高于5%后,共混材料的亲水性变化很小;且PET的结晶度随着PEG的加入呈现先增大后减小的趋势。     

聚乙二醇/聚(β-羟基丁酸酯)/聚乙二醇三嵌段共聚物的合成与表征

为改进聚(β-羟基丁酸酯)(PHB)的结晶性和亲水性,通过聚乙二醇单甲醚(MPEG)的端酰氯基团和聚(β-羟基丁酸酯)的端羟基基团的官能团反应,制备了聚乙二醇/聚(β-羟基丁酸酯)/聚乙二醇三嵌段共聚物。通过红外光谱、核磁、X-射线衍射、差热分析和凝胶渗透色谱等手段,证明制备了嵌段共聚物。吸水实验表明,材料的亲水性得到了明显的改善。     

聚乙烯醇/聚乙二醇复合材料的热塑加工性能

通过热塑加工方法制备了增塑改性聚乙烯醇(mPVA)/聚乙二醇(PEG)复合材料,研究了PEG相对分子质量和含量对mPVA/PEG复合材料热性能、热塑加工性能,转矩流变性能和力学性能的影响.结果表明:加入适量PEG可降低mPVA的熔点,表明PEG对mPVA有一定的增塑作用;随着PEG用量的增加,mPVA的熔体流动速率增大...     

Effect of poly(ethylene glycol) on the solid‐state polymerization of poly(ethylene terephthalate)

Poly(ethylene glycol) (PEG) and end‐capped poly(ethylene glycol) (poly(ethylene glycol) dimethyl ether (PEGDME)) of number average molecular weight 1000 g mol^?1 was melt blended with poly(ethylene terephthalate) (PET) oligomer. NMR, DSC and WAXS techniques characterized the structure and morphology of the blends. Both these samples show reduction in T_g and similar crystallization behavior. Solid‐state polymerization (SSP) was performed on these blend samples using Sb₂O₃ as catalyst under reduced pressure at temperatures below the melting point of the samples. Inherent viscosity data indicate that for the blend sample with PEG there is enhancement of SSP rate, while for the sample with PEGDME the SSP rate is suppressed. NMR data showed that PEG is incorporated into the PET chain, while PEGDME does not react with PET. Copyright © 2005 Society of Chemical Industry     

聚乙二醇二酸(2-羟甲基-3,5,6-三甲基吡嗪)酯的合成

以二环己基碳二亚胺(DCCI)为缩合剂,用聚乙二醇-2000-二酸来修饰2 羟甲基 3,5,6 三甲基吡嗪,产率69%。通过熔点、IR和1HNMR对产物进行了表征,熔点为45～48℃;红外特征吸收为1747cm-1(CO),1254cm-1(C—O—C);1HNMR为1 9(—CH3,3H,s),2 2(—CH3,6H,s),4 2(—CH2—,2H,s),3 6(—OCH2—,multi-H,s)。     

Mixed poly(methyl methacrylate)/poly(ethylene glycol) brushes: Study of switching behavior in selective solvent

The mixed polymer brushes composed of two incompatible polymers, poly(methyl methacrylate) and poly(ethylene glycol), were successfully synthesized via a sequential grafting to method, which was confirmed by water‐contact angle and ellipsometric measurements. The resulted mixed polymer brushes could undergo conformational rearrangements upon exposure to different selective solvents, and then the lateral segregation in nonselective solvent and perpendicular segregation in selective solvent happened. As a result, the mixed polymer brushes exhibited the ripple morphology and dimple morphology in corresponding solvent, respectively, and which led to changes in water‐contact angle and surface composition as a function of bulk composition of the mixed polymer brushes. Moreover, the switching properties as the surface composition, wettability and topographical images could occur in a controlled and reversible fashion. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

聚对苯二甲酸乙二醇酯合成催化剂研究进展

探讨了各类锑系催化剂、钛系催化剂(包括乙二醇钛)等不同类型的催化剂在聚酯缩聚反应中的催化性能研究的最新成果,指出在各种类型催化剂中,由于具有作为催化剂时不会带入多余的杂质进入反应体系等优点,乙二醇锑和乙二醇钛的应用前景较为广阔。     

Biodegradable polymer blends of poly(lactic acid) and poly(ethylene glycol)

Poly(lactic acid) (PLA) and poly(ethylene glycol) (PEG) were melt-blended and extruded into films in the PLA/PEG ratios of 100/0, 90/10, 70/30, 50/50, and 30/70. It was concluded from the differential scanning calorimetry and dynamic mechanical analysis results that PLA/PEG blends range from miscible to partially miscible, depending on the concentration. Below 50% PEG content the PEG plasticized the PLA, yielding higher elongations and lower modulus values. Above 50% PEG content the blend morphology was driven by the increasing crystallinity of PEG, resulting in an increase in modulus and a corresponding decrease in elongation at break. The tensile strength was found to decrease in a linear fashion with increasing PEG content. Results obtained from enzymatic degradation show that the weight loss for all of the blends was significantly greater than that for the pure PLA. When the PEG content was 30% or lower, weight loss was found to be primarily due to enzymatic degradation of the PLA. Above 30% PEG content, the weight loss was found to be mainly due to the dissolution of PEG. During hydrolytic degradation, for PLA/PEG blends up to 30% PEG, weight loss occurs as a combination of degradation of PLA and dissolution of PEG. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1495–1505, 1997     

HT／Surlyn／PEG复合成核剂对PET结晶性能的影响

研究了水滑石(HT)/离子键聚合物(Surlyn)/聚乙二醇(PEG)复合成核剂对聚对苯二甲酸乙二醇酯(PET)非等温结晶性能的影响。通过正交实验选择最佳复合成核剂配方。差示扫描量热分析表明,HT/Surlyn/PEG复合成核剂各组分与PET的质量比为0．5/3/3/100时,PET的结晶温度提高,半结晶时间明显减少,说明PET的成核能力提高,结晶能力增强,结晶速率加快；同时,结晶放热焓和熔融吸热焓增加,说明PET的结晶度得到提高。     

异端基遥爪聚乙二醇的合成

采用3种新式引发剂,即2-(苄氧基）乙醇钾、2-(四氢-2H-吡喃-2-氧基)乙醇钾、单丙烯基乙二醇钾引发环氧乙烷阴离子开环聚合,反应条件为25 ℃、48 h、醇与萘钾摩尔比例1∶1,得到3种异端基遥爪聚乙二醇。以2-(苄氧基）乙醇钾引发聚合所得产物为起始物,经一系列反应,得到两种两端均为活性基团的异端基遥爪聚乙二醇,这种方法具有普适性。通过1HNMR及GPC手段,表征了产物的结构、分子量及分子量分布。结果表明可以得到高产率、分子量可控且分布窄的异端基遥爪聚乙二醇。     

Characterization and comparison of diblock and triblock amphiphilic copolymers of poly(δ‐valerolactone)

Three types of pegylated amphiphilic copolymers of poly(δ‐valerolactone) (PVL) were copolymerized with methoxy poly(ethylene glycol) (MePEG) and poly(ethylene glycol) (PEG₄₀₀₀ and PEG_10,000), respectively. Pegylation of PVL allowed copolymers possessing amphiphilic property and efficiently self‐assembled to form micelles with a low critical micelle concentration (CMC) in the range of 10^?7–10^?8M. The average molecular weight of copolymers was in the range of 10,000–20,000 Da, and the polydispersity of copolymers was about 1.7–1.8. Higher mobility of low molecular weight PEG (i.e., MePEG and PEG₄₀₀₀) than high molecular weight PEG_10,000 allowed valerolactone ring opening more efficient in terms of PVL/MePEG and PVL/PEG₄₀₀₀ copolymers possessing longer chain length in hydrophobic domain. Pegylated PVL with low CMC and triblock structure was preferred to encapsulate drug during micelle formation. Although all of these amphiphilic copolymers exhibited controlled release character, the micelles formed by triblock copolymer possessed a more stable core‐shell conformation than that by diblock copolymer, and resulted in the release of drug from triblock micelles slower than that from diblock micelles. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1836–1841, 2006     

阴离子表面活性剂对聚乙二醇水溶液粘度的影响

测定了聚乙二醇（PEG）在十二烷基硫酸钠（SDS）和琥珀酸双-2-乙己酯磺酸钠（AOT）水溶液中的粘度,讨论了SDS和AOT在水溶液中聚集形态的差异对PEG与SDS和AOT相互作用的不同影响,结果表明：PEG-SDS与PEG-AOT体系粘度均明显增加,而PEG-SDS与PEG-AOT体系粘度变化机制不同,根本原因是表面活性剂在高分子溶液中聚集行为不同,SDS分子在PEG链上聚集,形成类胶束,使高分子链带电,表现出聚电解质的粘度行为;PEG链吸附于AOT囊泡,不同PEG链对囊泡的吸附可能造成高分子链更加伸展,PEG特性粘数增大,使溶液粘度上升。     

Effect of self‐nucleation on the crystallization of segmented copolymer poly(ether ester)

The effect of self‐nucleation on the nonisothermal and isothermal crystallization behaviors of the segmented copolymer poly(ether ester), based on poly(ethylene glycol) as the soft segment and poly(ethylene terephthalate) as the hard segment was investigated by means of differential scanning calorimetry (DSC) and depolarization polarized light (DPL) techniques, respectively. The results demonstrated that self‐nucleation could enhance the crystallization rate in both cases. The experimental conditions of the self‐nucleation procedure studied by DSC were discussed in detail. The isothermal crystallization was analyzed by the Avrami equation, and the Avrami parameters were dependent on the melting temperature. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 498–504, 2001     

Improved processability and performance of biomedical devices with poly(lactic acid)/poly(ethylene glycol) blends

To improve the processability of micropolymer‐based devices used for biomedical applications, poly(lactic acid) (PLA) was melt‐blended with poly(ethylene glycol)s (PEGs) of different molecular weights (MWs; weight‐average MWs = 200, 800, 2000, and 4000; these PEGS are referred to as PEG200, PEG800, PEG2000, and PEG4000, respectively, in this article). The thermal properties, mechanical properties, and rheological properties of the PLA and the PLA–PEG blends were investigated. The tensile samples’ morphologies showed that the low‐MW PEGs filled molds well. The rheological properties confirmed that the low‐MW PEGs decreased the complex viscosity, and improved the processability. With decreasing PEG MW, the PLA glass‐transition temperature decreased. The nanoindenter data show that the addition of PEG decreased the modulus and hardness of PLA. The morphologies of the tensile samples showed that with increasing PEG MW, the thicknesses of the core layers increased gradually. The elongation at break was improved by approximately 247% with the addition of PEG200. Such methods can produce easily processed biological materials for producing biomedical products. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45194.     

Effect of antioxidant contained in poly(ethylene glycol) on cell fusion

The effect of antioxidants contained in poly(ethylene glycol) (PEG) on cell fusion was studied using L929 cells in the monolayer state. Hydroquinone monomethyl ether (HQME), 2-mercaptobenzimidazole (MB), butyl hydroxyanisole (BHA) and 2,6-di-(t-butyl)-4-methylphenol (BHT) were chosen from the antioxidants that have currently been used to protect commercially available PEG from oxidation. Cell culture was conducted in 40% w/w aqueous solution of PEG with a molecular weight of 3000 in the presence of different concentrations of antioxidants. BHA clearly enhanced membrane fusion of L929 cells with increasing concentration in PEG solution, whereas HQME, MB and BHT had no significant effect on cell fusion. The enhancement of cell fusion by BHA might be ascribed to balanced hydrophobicity and high water solubility in comparison with the other three antioxidants.     

Properties of Poly(vinyl chloride)/poly(ethylene oxide)/polyaniline Conductive Films: The Effect of Poly(ethylene glycol) Diglycidyl Ether

The effect of polyaniline and poly(ethylene glycol) diglycidyl ether on tensile properties, morphology, thermal degradation, and electrical conductivity of poly(vinyl chloride)/poly(ethylene oxide)/polyaniline conductive films was studied. The poly(vinyl chloride)/poly(ethylene oxide)/polyaniline conductive films were prepared using a solution casting technique at room temperature until a homogeneous solution was produced. Poly(vinyl chloride)/poly(ethylene oxide)/polyaniline/poly(ethylene glycol) diglycidyl ether conductive films exhibit higher electrical properties, tensile strength, modulus of elasticity but lower final decomposition temperature than poly(vinyl chloride)/poly(ethylene oxide)/polyaniline conductive films. Scanning electron microscopy morphology showed that the polyaniline more widely dispersed in the poly(vinyl chloride)/poly(ethylene oxide) blends with the addition of poly(ethylene glycol) diglycidyl ether as surface modifier.