Preparation of collagen‐immobilized poly(ethylene glycol)/poly(2‐hydroxyethyl methacrylate) interpenetrating network hydrogels for potential application of artificial cornea

To enhance the mechanical strength of poly(ethylene glycol)(PEG) gels and to provide functional groups for surface modification, we prepared interpenetrating (IPN) hydrogels by incorporating poly(2‐hydroxyethyl methacrylate)(PHEMA) inside PEG hydrogels. Formation of IPN hydrogels was confirmed by measuring the weight percent gain of the hydrogels after incorporation of PHEMA, as well as by ATR/FTIR analysis. Synthesis of IPN hydrogels with a high PHEMA content resulted in optically transparent and extensively crosslinked hydrogels with a lower water content and a 6 ～ 8‐fold improvement in mechanical properties than PEG hydrogels. Incorporation of less than 90 wt % PHEMA resulted in opaque hydrogels due to phase separation between water and PHEMA. To overcome the poor cell adhesion properties of the IPN hydrogels, collagen was covalently grafted to the surface of IPN hydrogels via carbamate linkages to hydroxyl groups in PHEMA. Resultant IPN hydrogels were proven to be noncytotoxic and cell adhesion study revealed that collagen immobilization resulted in a significant improvement of cell adhesion and spreading on the IPN hydrogel surfaces. The resultant IPN hydrogels were noncytotoxic, and a cell adhesion study revealed that collagen immobilization improved cell adhesion and spreading on the IPN hydrogel surfaces significantly. These results indicate that PEG/PHEMA IPN hydrogels are highly promising biomaterials that can be used in artificial corneas and a variety of other load‐bearing tissue engineering applications. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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     

Synthesis and characterization of novel block copolymer from trans‐4‐hydroxy‐L‐proline and poly(ethylene glycol)

A series of novel ABA‐type block copolymers were synthesized by polymerization of trans‐4‐hydroxy‐L ‐proline (HyP) in the presence of various molecular weight poly(ethylene glycol)s (PEGs), a bifunctional OH‐terminated PEG using stannous octoate as catalyst. The optimal reaction conditions for the synthesis of the copolymers were obtained with 5 wt % stannous octoate at 140°C under vacuum (20 mmHg) for 24 h. The synthesized copolymers were characterized by IR spectroohotometry, proton nuclear magnetic resonance, differential scanning calorimetry, and Ubbelohde viscometer. The glass transition temperature (T_g) of the copolymers shifted to significantly higher temperature with increasing the number average degree of polymerization and HyP/PEO molar ratio. In contrast, the melting temperature (T_m) decreased with increasing the HyP/PEO molar ratio. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1581–1587, 2001     

Relationship between the crystallization behavior of poly(ethylene glycol) and stereocomplex crystallization of poly(L‐lactic acid)/poly(D‐lactic acid)

Poly(l ‐lactic acid) (PLLA) is a good biomedical polymer material with wide applications. The addition of poly(ethylene glycol) (PEG) as a plasticizer and the formation of stereocomplex crystals (SCs) have been proved to be effective methods for improving the crystallization of PLLA, which will promote its heat resistance. In this work, the crystallization behavior of PEG and PLLA/poly(d ‐lactic acid) (PDLA) in PLLA/PDLA/PEG and PEG‐b‐PLLA/PEG‐b‐PDLA blends has been investigated using differential scanning calorimetry, polarized optical microscopy and X‐ray diffraction. Both SCs and homocrystals (HCs) were observed in blends with asymmetric mass ratio of PLLA/PDLA, while exclusively SCs were observed in blends with approximately equal mass ratio of PLLA/PDLA. The crystallization of PEG was only observed for the symmetric blends of PLLA_39k/PDLA_35k/PEG_2k, PLLA_39k/PDLA_35k/PEG_5k, PLLA_69k/PDLA_96k/PEG_5k and PEG‐b‐PLLA_31k/PEG‐b‐PDLA_27k, where the mass ratio of PLLA/PDLA was approximately 1/1. The results demonstrated that the formation of exclusively SCs would facilitate the crystallization of PEG, while the existence of both HCs and SCs could restrict the crystallization of PEG. The crystallization of PEG is related to the crystallinity of PLLA and PDLA, which will be promoted by the formation of SCs. © 2017 Society of Chemical Industry     

Synthesis and characterization of fluorocarbon‐containing,hydrophobically associative poly(acrylic acid‐co‐Rf‐poly(ethylene glycol) macromonomer)

Fluorocarbon‐ or hydrocarbon‐end‐capped poly(ethylene glycol) (PEG) macromonomers were prepared with coupling methods. Several factors affecting the synthesis were studied, and the optimal condition was ascertained. The critical micelle concentrations of these macromonomers were determined with the fluorescence method. Novel fluorocarbon‐containing, hydrophobically modified, alkali‐soluble copolymers were made by the copolymerization of fluorocarbon‐ or hydrocarbon‐alkyl‐end‐capped PEG macromonomers with acrylic acid in an organic solvent. The effects of the macromonomer contents, polymerization conditions, spacer, temperature, shear rate, pH, and addition of salt and various surfactants on the solution viscosity were preliminarily investigated. A very strong hydrophobic association was found for these copolymer solutions. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1035–1047, 2002; DOI 10.1002/app.10393     

Synthesis and characterization of poly(L‐lactide)‐poly(ethylene glycol) multiblock copolymers

Poly(L‐lactide)‐poly(ethylene glycol) multiblock copolymers with predetermined block lengths were synthesized by polycondensation of PLA diols and PEG diacids. The reaction was carried out under mild conditions, using dicyclohexylcarbodiimide as the coupling agent and dimethylaminopyridine as the catalyst. The resulting copolymers were characterized by various analytical techniques, such as GPC, viscometry, ¹H‐NMR, FTIR, DSC, X‐ray diffractometry, and contact angle measurement. The results indicated that these copolymers presented outstanding properties pertinent to biomedical use, including better miscibility between the two components, low crystallinity, and hydrophilicity. Moreover, the properties of the copolymers can be modulated by adjusting the block length of the two components or the reaction conditions. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1729–1736, 2002; DOI 10.1002/app.10580     

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     

The effect of poly(ethylene glycol) mixed with poly(l‐lactic acid) on the crystallization characteristics and properties of their blends

The non‐isothermal and isothermal crystallizations of extruded poly(l ‐lactic acid) (PLLA) blends with 10, 20 and 30 wt% poly(ethylene glycol) (PEG) were investigated with differential scanning calorimetry. The formation of α‐form crystals in the blend films was verified using X‐ray diffraction and an increase in crystallinity indexes using Fourier transformation infrared spectroscopy. Crystallization and melting temperatures and crystallinity of PLLA increased with decreasing cooling rate (CR) and showed higher values for the blends. Although PLLA crystallized during both cooling and heating, after incorporation of PEG and with CR = 2 °C min^?1 its crystallization was completed during cooling. Increasingly distinct with CR, a small peak appeared on the lower temperature flank of the PLLA melting curve in the blends. A three‐dimensional nucleation process with increasing contribution from nuclei growth at higher CR was verified from Avrami analysis, whereas Kissinger's method showed that the diluent effect of 10 and 20 wt% PEG in PLLA decreased the effective energy barrier. During isothermal crystallization, crystallization half‐time increased with temperature (T_ic) for the blends, decreased with PEG content and was lower than that of pure PLLA. In addition, the Avrami rate constants were significantly higher than those of pure PLLA, at the lower T_ic. Different crystal morphologies in the PLLA phase were formed, melting in a broader and slightly higher T_m range than pure PLLA. The crystallization activation energy of PLLA decreased by 56% after the addition of 10 wt% PEG, increasing though with PEG content. Finally, PEG/PLLA blends presented improved flexibility and hydrophilicity. © 2019 Society of Chemical Industry     

Gamma radiation synthesis and swelling properties of hydrogels based on poly(ethylene glycol)/methacrylic acid (MAc) mixtures

In this work, gamma radiation was used to prepare hydrophilic hydrogels based on different mass ratios of poly(ethylene glycol) (PEG) and methacrylic acid (MAc) monomer. The thermal stability of hydrogels was characterized thermogravimetric analysis (TGA). The effect of temperature and pH, as external environments, on the equilibrium swelling of PEG/MAc hydrogels was also studied. The results showed that the gel fraction of PEG/MAc hydrogels is lower than that of PMAc hydrogel, in which the gel fraction of PMAc hydrogel was decreased greatly with increasing the mass ratio of PEG polymer in the initial solutions. The results showed that PEG/MAc hydrogels reached the equilibrium swelling state in water after 6 hours. It was found that the equilibrium swelling of PEG/MAc hydrogels displayed a transition change within the temperature range 30–40°C. This change in equilibrium swelling was illustrated by differential scanning calorimetry (DSC). However, it was observed that the equilibrium swelling of PEG/MAc hydrogels increases progressively with increasing the pH value from 4 up to 8. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Porous poly(ethylene glycol)–polyurethane hydrogels as potential biomaterials

We report the synthesis of porous poly(ethylene glycol)–polyurethane (PEG‐PU) hydrogels using PEG‐4000 as a soft segment and 4,4′‐methylenebis(cyclohexylisocyanate) as a hard segment. The degree of swelling in the hydrogels could be controlled by varying the amount of crosslinking agent, namely 1,2,6‐hexanetriol. Structural characterization of the hydrogels was performed using solid‐state ¹³C NMR and Fourier transform infrared spectroscopy. Wide‐angle X‐ray diffraction studies revealed the existence of crystalline domains of PEG and small‐angle X‐ray scattering studies showed the presence of lamellar microstructures. For generating a porous structure in the hydrogels, cryogenic treatment with lyophilization was used. Scanning electron microscopy and three‐dimensional micro‐computed tomography imaging of the hydrogels indicated the presence of interconnected pores. The mechanical strength of the hydrogels and xerogels was measured using dynamic mechanical analysis. The observed dynamic storage moduli (E′) for the equilibrium swollen and dry gels were found to be 0.15 and 4.2 MPa, respectively. Interestingly, the porous PEG‐PU xerogel also showed E′ of 5.6 MPa indicating a similar mechanical strength upon incorporating porosity into the gel matrix. Finally, preliminary cytocompatibility studies showed the ability of cells to proliferate in the hydrogels. These gels show promise for applications as scaffolds and implants in tissue engineering. © 2014 Society of Chemical Industry     

Synthesis and surface properties of polystyrene‐graft‐poly(ethylene glycol) copolymers

Polystyrene‐graft‐poly(ethylene glycol) copolymers (PS‐g‐PEG) were successfully synthesized using the “grafting‐through” method. The graft copolymers and the surface properties of their coats were characterized by 1 H‐NMR, gel permeation chromatography (GPC), differential scanning calorimetry (DSC), transmission electron microscopy (TEM), X‐ray photoelectron spectroscopy (XPS), static contact angle measurement, and atomic force microscopy (AFM). Both DSC and TEM indicated that the graft copolymers had a microphase separated structure. AFM showed the microphase separated structure also occurred at the coat surface, especially at high PEG content, which could also be indirectly confirmed by the XPS and contact angle results. The formation mechanism of the microphase separated structure was discussed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1458–1465, 2007     

ABA triblock copolymers from poly(p‐dioxanone) and poly(ethylene glycol)

Poly(p‐dioxanone)–poly(ethylene glycol)–poly(p‐dioxanone) ABA triblock copolymers (PEDO) were synthesized by ring‐opening polymerization from p‐dioxanone using poly(ethylene glycol) (PEG) with different molecular weights as macroinitiators in N₂ atmosphere. The copolymer was characterized by ¹H NMR spectroscope. The thermal behavior, crystallization, and thermal stability of these copolymers were investigated by differential scanning calorimetry and thermogravimetric measurements. The water absorption of these copolymers was also measured. The results indicated that the content and length of PEG chain have a greater effect on the properties of copolymers. This kind of biodegradable copolymer will find a potential application in biomedical materials. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:1092–1097, 2006     

Biodegradability of poly(ethylene terephthalate) copolymers with poly(ethylene glycol)s and poly(tetramethylene glycol)

Poly(ethylene terephthalate) copolymers were prepared by melt polycondensation of dimethyl terephthalate and excess ethylene glycol with 10–40mol% (in feed) of poly(ethylene glycol) (E) and poly(tetramethylene glycol) (B), with molecular weight (MW) of E and B 200–7500 and 1000, respectively. The reduced specific viscosity of copolymers increased with increasing MW and content of polyglycol comonomer. The temperature of melting (T_m), cold crystallization and glass transition (T_g) decreased with the copolymerization. T_m depression of copolymers suggested that the E series copolymers are the block type at higher content of the comonomer. T_g was decreased below room temperature by the copolymerization, which affected the crystallinity and the density of copolymer films. Water absorption increased with increasing content of comonomer, and the increase was much higher for E1000 series films than B1000 series films. The biodegradability was estimated by weight loss of copolymer films in buffer solution with and without a lipase at 37°C. The weight loss was enhanced a little by the presence of a lipase, and increased abruptly at higher comonomer content, which was correlated to the water absorption and the concentration of ester linkages between PET and PEG segments. The weight loss of B series films was much lower than that of E series films. The abrupt increase of the weight loss by alkaline hydrolysis is almost consistent with that by biodegradation.     

Synthesis and characterization of multi‐block copolymers containing poly [(3‐hydroxybutyrate)‐co‐(3‐hydroxyvalerate)] and poly(ethylene glycol)

Various problems, including high crystallinity, high melting temperature, poor thermal stability, hydrophobicity and brittleness, have impeded many practical applications of poly[(3‐hydroxybutyrate)‐co‐(3‐hydroxyvalerate)] (PHBV) as an environmentally friendly material and biomedical material. In the work reported here, multi‐block copolymers containing PHBV and poly(ethylene glycol) (PHBV‐b‐PEG) were synthesized with telechelic hydroxylated PHBV as a hard and hydrophobic segment, PEG as a soft and hydrophilic segment and 1,6‐hexamethylene diisocyanate as a coupling reagent to solve the problems mentioned above. PHBV and PEG blocks in PHBV‐b‐PEG formed separate crystalline phases with lower crystallinity levels and lower melting temperatures than those of phases formed in the precursors. The crystallite dimensions of the two blocks in PHBV‐b‐PEG were smaller than those of the corresponding precursors. Compared to values for the original PHBV, the maximum decomposition temperature of the PHBV block in PHBV‐b‐PEG was 16.0 °C higher and the water contact angle was 9° lower. In addition, the elongation at break was 2.8% for a pure PHBV fiber but 20.9% for a PHBV/PHBV‐b‐PEG fiber with a PHBV‐b‐PEG content of 30%. PHBV‐b‐PEGs can overcome some of the disadvantages of pure PHBV; it is possible that PHBV might be a good candidate for the formulation of environmentally friendly materials and biomedical materials. Copyright © 2010 Society of Chemical Industry     

单端马来酰亚胺基功能化聚乙二醇的制备

以PEG2000为初始原料,通过与小分子的反应,将其一端羟基保留,得到NH2-PEG2000-OH,然后将NH2-PEG2000-OH与6-(马来酰亚胺基)己酸琥珀酰亚胺酯反应,得到单端马来酰亚胺基修饰的聚乙二醇(Mal-(CH2)5-CONH-PEG2000-OH)。经过1H NMR验证,结果表明,通过这条合成路线能够成功得到单端马来酰亚胺基功能化的聚乙二醇。     

Synthesis and characterization of star‐shaped poly(ethylene glycol)‐block‐poly(L‐lactic acid) copolymers by melt polycondensation

Compared with linear diblock or triblock poly(ethylene glycol)‐block‐poly(L ‐lactic acid) copolymer (PEG‐b‐PLLA), star‐shaped PEG‐b‐PLLA (sPEG‐b‐PLLA) copolymers exhibit smaller hydrodynamic radius and lower viscosity and are expected to display peculiar morphologies, thermal properties, and degradation profiles. Compared with the synthesis routine of PEG‐b‐PLLA form lactide and PEG, the traditional synthesis routine from LA and PEG were suffered by the low reaction efficiency, low purity, lower molecular weight, and wide molecular weight distribution. In this article, multiarm sPEG‐b‐PLLA copolymer was prepared from multiarm sPEG and L ‐lactic acid (LLA using an improved method of melt polycondensation, in which two types of sPEG, that is, sPEG₁ (four arm, Mn = 4300) and sPEG₂ (three arm, Mn = 3200) were chosen as the core. It was found the molecular weight of sPEG‐b‐PLLA could be strongly affected by the purity of LLA and sPEGs, and the purification technology of vacuum dewater and vacuum distillation could help to remove most of the impurities in commercial available LLA. The polymers, including sPEG and sPEG‐b‐PLLA with varied core (sPEG₁ and sPEG₂) and LLA/sPEG feeding ratios, were characterized and confirmed by ¹H‐NMR and ¹³C‐NMR spectroscopy, Fourier transform infrared spectroscopy (FT‐IR) and gel permeation chromatography, which showed that the terminal hydroxyl group in each arm of sPEGs had reacted with LLA to form sPEG‐b‐PLLA copolymers with fairly narrow molecular weight distribution. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and hydrophilicity of poly(butylene 2,6‐naphthalate)/poly(ethylene glycol) copolymers

Poly(butylene 2,6‐naphthalate) (PBN)/poly(ethylene glycol) (PEG) copolymers were synthesized by the two‐step melt copolymerization process of dimethyl‐2,6‐naphthalenedicarboxylate (2,6‐NDC) with 1,4‐butanediol (BD) and PEG. The copolymers produced had different PEG molecular weights and contents. The structures, thermal properties, and hydrophilicities of these copolymers were studied by ¹H NMR, DSC, TGA, and by contact angle and moisture content measurements. In particular, the intrinsic viscosities of PBN/PEG copolymers increased with increasing PEG molecular weights, but the melting temperatures (T_m)_, the cold crystallization temperatures (T_cc)_, and the heat of fusion (ΔH_f) values of PBN/PEG copolymers decreased on increasing PEG contents or molecular weights. The thermal stabilities of the copolymers were unaffected by PEG content or molecular weight. Hydrophilicities as determined by contact angle and moisture content measurements were found to be significantly increased on increasing PEG contents and molecular weights. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2677–2683, 2006     

Imparting recognition sites in poly(HEMA) for two compounds through molecular imprinting

So far, molecularly imprinted polymers (MIPs) have been synthesized and evaluated as selective matrices for single components. It may be possible to impart multiple recognition sites in MIPs, which could be used as elements capable of binding more than one component. Such systems could advantageously be used in the design of sensors having the ability to sense more than one compound at a time. This communication discusses such a possibility by imprinting sites for two model compounds, namely, salicylic acid and hydrocortisone in poly(2‐hydroxy ethyl methacrylate). © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1823–1826, 1999     

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。     

Surface modification of poly(ethylene terephthalate) film by coating with poly(ethylene glycol)‐grafted polystyrene

The poly(ethylene glycol) (PEG)‐grafted styrene (St) copolymer, which was formed as a nanosphere, was used as an agent to modify the surface of poly(ethylene terephthalate) (PET) film. The graft copolymer was dissolved into chloroform and coated onto the PET film by dip–coating method. The coated amount depends on the content ratios of PEG and St, the solution concentration, and the coating cycles. The graft copolymers having a low molecular weight of PEG‐ or St‐rich content was fairly stable on washing in sodium dodecyl sulfate (SDS) aqueous solution. It was confirmed that the PET surface easily altered its surface property by the coating of the graft copolymers. The contact angles of the films coated with the graft copolymers were very high (ca. 105–120°). The coated film has good antistatic electric property, which agreed with PEG content. The best condition of coating is a one‐cycle coating of 1% (w/v) graft copolymer solution. The coated surface had water‐repellency and antistatic electric property at the same time. The graft copolymer consisted of a PEG macromonomer; St was successfully coated onto PET surfaces, and the desirable properties of both of PEG macromonomer and PSt were exhibited as a novel function of the coated PE film. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1524–1530, 1999