Facile synthesis and detailed characterization of photo-polymerizable and biocompatible poly(ethylene glycol) dimethacrylates (PEGDM) and their hydrogels are described. Combined analyses of 1H NMR and MALDI-TOF MS confirmed the formation of prepolymers of high purity and narrow mass distribution (PD < 1.02). A systematic investigation into the structure and mechanical properties of PEGDM hydrogels was performed to characterize the relationships between the network structure and gel properties. Small-angle neutron scattering was used to characterize the structural features of hydrogels with respect to their semidilute solution precursors. A well-defined structural length scale (correlation length) manifested as a maximum in the scattering intensity was observed for hydrogels derived from high molecular mass PEGDMs and/or high oligomer mass fractions. Hydrogels derived from lower molecular mass PEGDMs and/or low oligomer mass fractions exhibited multiple correlation lengths suggesting the formation of inhomogeneous gel structures. The shear moduli, determined from uniaxial compression measurement, showed that the gel structures correlate well with the gel mechanical properties. 相似文献
Poly(ethylene glycol) diacrylate/polyvinyl alcohol(PEGDA/PVA) hydrogels were prepared from PEGDA and PVA as precurors by means of single UV radiation(UV ra.), UV radiation followed by high energy electron beam irradiation(Irra.), UV radiation followed by freeze-thawing(FT) or UV ra. and Irra. followed by FT, respectively. 2-Hydroxy-1-[4-(hydroxyethoxy)phenyl]-2-methyl-1-propanone(Irgacure 2959) was used as a photoinitiator. The effects of the various methods on the swelling and mechanical properties of the hydrogels were investigated. The results show that hydrogels made by UV ra. plus high energy electron beam irradiation followed by FT showed a higher crosslinking density and a larger tensile strength than those made by the other methods. 相似文献
Summary: Branched poly(L -lactide)-poly(ethylene glycol) (PLLA-PEG) block copolymers were synthesized from trifunctional PLLA and amine functionalized methoxy poly(ethylene glycol)s. The copolymers in water formed hydrogels that showed thermo-responsive behavior. The hydrogels underwent a gel to sol transition with increasing temperature as determined with the vial tilting method and oscillatory rheology. For all copolymers, the transition temperature increased with increasing copolymer concentration. The transition temperature of corresponding branched copolymers also increased with increasing PEG molecular weight, and surprisingly decreased with increasing molecular weight of the PLLA branches. In general, the gel-sol transition is explained by disruption of micellar or aggregate interactions because of partial dehydration and shrinkage of the PEG chains. An increase in the molecular weight of the PLLA branches led to the formation of micelles and aggregates as observed with DLS at low concentrations. It is speculated that the non-uniform size distribution and possible crystallization of longer PLLA blocks may have a negative effect on the formation of micellar packing upon gelation, allowing the disruption of micellar or aggregate interactions to occur at lower temperatures. The transition temperature of the gels could be tuned closely to body temperature by varying the concentration of the solution or the molecular weight of the PEG block and the PLLA blocks, which implies that these polymers may be used as injectable systems for in-situ gel formation. 相似文献
In the rapidly evolving multidisciplinary field of polymer therapeutics, tailored polymer structures represent the key constituent to explore and harvest the potential of bioactive macromolecular hybrid structures. In light of the recent developments for anticancer drug conjugates, multifunctional polymers are becoming ever more relevant as drug carriers. However, the potentially best suited polymer, poly(ethylene glycol) (PEG), is unfavorable owing to its limited functionality. Therefore, multifunctional linear copolymers (mf‐PEGs) based on ethylene oxide (EO) and appropriate epoxide comonomers are attracting increased attention. Precisely engineered via living anionic polymerization and defined with state‐of‐the‐art characterization techniques—for example real‐time 1H NMR spectroscopy monitoring of the EO polymerization kinetics—this emerging class of polymers embodies a powerful platform for bio‐ and drug conjugation. 相似文献
Poly(ethylene glycol) (PEG)‐interlocked hydrogels were prepared by linking the PEG with α‐cyclodextrins (α‐CDs) threaded onto a PEG chain having ester linkages at the terminals (hydrolyzable polyrotaxane). These hydrogels were examined to clarify the effect of ionic strength of phosphate buffers, pH, and the addition of ethanol on erosion time in relation to inclusion states of α‐CDs with the ester linkages. The most characteristic phenomenon of the hydrogel erosion was observed in an ethanol/PBS cosolvent system: the time to reach the complete erosion time was shortened with decreasing water content. NMR analysis revealed that the ester linkages were exposed to the aqueous environment due to the aggregation of α‐CDs. These results suggest that the movement of α‐CDs in the polyrotaxanes from the terminal ester region to the another region gives the ester linkages a chance to interact with water.
Poly(ethylene glycol) (PEG) blends photo-curable and thermal activated shape-memory polymers (SMPs), with different activation temperature (Tswitch), have been synthesized and characterized. PEG blends with different molecular weights were chain-end functionalized with isocyanate ethyl methacrylate and photo-cured with UV lamp. Degree of cross-linking of the blend network, determined by gel content measurement, resulted as higher than 95%. The thermal and thermomechanical properties of these SMPs PEG blends were characterized by differential scanning calorimetry and dynamic mechanical analysis. The shape-memory properties of the networks were quantified using thermomechanical three-point bending experiments and showed strain fixity rates higher than 99% and a minimum strain recovery ratio of 82%. 相似文献
A series of multiblock poly(ether urethane)s comprising poly(ethylene glycol) (PEG), and poly(propylene glycol) (PPG) segments were synthesized. Their aqueous solutions exhibited thermogelling behavior at critical gelation concentrations (CGC) ranging from 8 to 12 wt%. The composition and structural information of the copolymers were studied by GPC and 1H NMR. The critical micellization concentration (CMC) and thermodynamic parameters for micelle formation were determined at different temperatures. The temperature response of the copolymer solutions were studied and found to be associated with the composition of the copolymers. 相似文献
Poly(ethylene glycol) (PEG)‐based films, nanotubes, and nanotube arrays were successfully made using layer‐by‐layer (LbL) assembly ion‐containing PEO derivatives on porous templates and planar substrates. PEG nanotubes are challenging to produce because PEG dissolves into solutions and solvents used during nanotube processing, but our techniques circumvent the issue. Nanotube dimensions were verified using microscopy and the average observed diameter was 155 nm. The PEG‐based structures showed remarkable stability in water, salt water, and sodium hydroxide solution.
Summary: A methacrylate‐functionalized poly(ethylene glycol) macromonomer was copolymerized at the surface of methacrylate‐derivatized maghemite nanoparticles. After silylation of the magnetic core with methacryloxypropyltrimethoxysilane, two grafting procedures based on either a direct copolymerization reaction in water or an inverse emulsion polymerization were compared. A direct copolymerization led to low polymer surface amounts, whereas an inverse emulsion process allowed nanocomposite particles containing up to 90 wt.‐% polymer to be obtained.
TEM picture of maghemite‐PEG hybrid particles. 相似文献
Block copolymers were synthesized by ring‐opening polymerization of L ‐lactide or D ‐lactide in the presence of mono‐ or dihydroxyl poly(ethylene glycol), using zinc metal as catalyst. The resulting copolymers were characterized by various techniques, namely 1H NMR spectroscopy, differential scanning calorimetry (DSC), X‐ray diffractometry, and Raman spectrometry. The composition of the copolymers was designed such that they were water soluble. Bioresorbable hydrogels were prepared from aqueous solutions containing both poly(L ‐lactide)/poly(ethylene glycol) and poly(D ‐lactide)/poly(ethylene glycol) block copolymers. Rheological studies confirmed the formation of hydrogels resulting from stereocomplexation between poly(L ‐lactide) and poly(D ‐lactide) blocks.
Ring‐opening polymerization of L (D )‐lactide in the presence of dihydroxyl PEG using zinc powder as catalyst. 相似文献
A novel method of producing a poly(ethylene glycol) (PEG)-based gradient matrix that varies gradually in thickness from 0 to 500 A over a distance of 5-20 mm is presented. The gradient matrix is graft copolymerized from a mixture of PEG methacrylates onto organic thin films providing free radical polymerization sites initiated by UV irradiation at 254 nm. The films used as grafting platforms consist of either a spin-coated cycloolefin polymer or a self-assembled monolayer on planar gold. The thickness/irradiation gradient is realized by means of a moving shutter that slowly uncovers the modified gold substrate. The structural and functional characteristics of the gradient matrix are investigated with respect to thickness profile, degree of carboxylation, and subsequent immobilization of two model proteins of different sizes and shapes. These characteristics are studied with ellipsometry and infrared reflection-absorption microscopy using a grazing angle objective. It is revealed that the relatively small carboxylation agent used offers homogeneous activation throughout the gradient, even in the thick areas, whereas the diffusion/interpenetration and subsequent immobilization of large proteins is partially hindered. This is crucial information in biosensor design that can be easily obtained from a gradient experiment on a single sample. Moreover, the partially hindered protein interpenetration, the marginal swelling upon hydration, and the unspecific nature of the graft polymerization suggest a matrix growth mechanism that favors the formation of a bushlike polymer structure with a certain degree of cross linking. 相似文献
The effect of added poly(ethylene glycol) monolaurate (PEGML) on the formation and properties of lecithin organogels composed of polymer-like micelles was studied by the methods of dynamic rheology and the Fourier transform IR spectroscopy. It was established that the addition of even small amounts of PEGML causes a significant decrease in viscosity, whereas the elastic properties of organogels remained almost unchanged. The analysis of the scaling dependences indicated that the formation mechanism of polymer-like lecithin micelles remained also unchanged. Spectral studies revealed that the PEGML molecules affect intermolecular hydrogen bonding during their incorporation into micelles, thus stabilizing micellar structure. This effect is caused by the partial dehydration of the lecithin polar region. This leads to a decrease in the number of hydrogen bonds or their weakening and, as a result, to the disintegration of polymer-like lecithin micelles into shorter micellar aggregates. 相似文献
