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1.
A wide variety of cells usually integrate and respond to the microscale environment, such as soluble protein factors, extracellular matrix proteins, and contacts with neighboring cells. To gain insight into cellular microenvironment design, we investigated two-dimensional microarray formation of endothelial cells on a micropatterned poly(ethylene glycol) (PEG)-brushed surface, based on the relationship between PEG chain density and cellular attachment. The patterned substrates consisted of two regions: the PEG surface that acts as a cell-resistant layer and the exposed substrate surface that promotes protein or cell adsorption. A PEG-brushed layer was constructed on a gold substrate using PEG with a mercapto group at the end of the chain. The density of the PEG-brushed layer increased substantially with repetitive adsorption/rinse cycles of PEG on the gold substrate, allowing marked reduction of nonspecific protein adsorption. These repeated adsorption/rinse cycles were further regulated by using longer (5 kDa) and shorter (2 kDa) PEG to construct PEG layers with different chain density, and subsequent micropatterning was achieved by plasma etching through a micropatterned metal mask. The effects of PEG chain density on pattern formation of cell attachment were determined on micropatterning of endothelial cells. The results indicated that cell pattern formation was strongly dependent on the PEG chain density and on the extent of protein adsorption. Notably, a PEG chain density high enough to inhibit outgrowth of endothelial cells from the cell-adhering region in the horizontal direction could be obtained only by employing formation of a short filler layer of PEG in the preconstructed longer PEG-brushed layer, which prevented nonspecific protein adsorption almost completely. In this way, a completely micropatterned array of endothelial cells with long-term viability was obtained. This clearly indicated the importance of a short underbrushed PEG layer in minimizing nonspecific protein adsorption for long-term maintenance of the active cell pattern. The strategy for cell patterning presented here can be employed in tissue engineering to study cell-cell and cell-surface interactions. It is also applicable for high-throughput screening and clinical diagnostics, as well as interfacing cellular and microfabricated components of biomedical microsystems.  相似文献   

2.
A series of novel vegetable oil‐based interpenetrating polymer networks (IPNs) have been successfully prepared: on one hand, methacrylated camelina oil (MCO) and a polyethyleneglycol dimethacrylate (PEG, MW 750 g/mol) and on the other hand, diglycidylether of bisphenol A (DER), in various blend ratios (75/25, 50/50, and 25/75 wt). Hence the appealing innovative direction of the current work was to build oil‐based poly(methacrylate) network using PEG macromonomer which is able to modulate adequately the crosslinking degree of the oil‐based network. These innovative combinations of cross‐linkable resins in terms of flexible methacrylate network based on camelina oil (CO) and PEG and a rigid epoxy (DER) were simultaneously polymerized using two independent non‐interfering curing reactions: free‐radical process for MCO and anionic polymerization of epoxy resin in the presence of a tertiary amine. The effect of the IPNs composition compositional characteristics on the reactivity of methacrylate or epoxy groups was studied using differential scanning calorimetry. The influence of the MCO‐PEG bio‐based polymer on the system properties was evaluated after curing by dynamic mechanical and thermogravimetric analyses. In addition mechanical and morphological studies were also carried out. The results suggested that blending of MCO and DER gave synergistic effects on the overall properties of the developed oil‐based IPNs and a dependence on the methacrylate/epoxy ratio was clearly noticed. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

3.
Semi-interpenetrating polymer networks (semi-IPNs) of poly(ethylene glycol) (PEG) in poly(trimethylolpropane triacrylate) (TMPTA) were synthesized from PEG melts in neat TMPTA monomer, using PEG of molecular weights from 4000 to 100,000 g/mol. Differential scanning calorimetry and transmission electron microscopy were used to examine phase separation occurring during network formation. The degree of phase separation was observed to depend upon the rate of PEG aggregation relative to the rate of network formation during TMPTA polymerization. Higher molecular weight PEG and acrylate-functionalized PEG formed more phase-mixed networks compared to lower molecular weight PEG; acetatefunctionalized PEG showed no difference from unmodified PEG in the extent of phase mixing. For networks that demonstrated phase separation, the PEG was observed to be in two states: some being phase mixed and solvent inextractable, and some being phase separated and solvent extractable. Phase-mixed networks could be obtained from this thermodynamically incompatible polymer pair utilizing rapid photopolymerization systems to overcome PEG phase aggregation and kinetically entrap the PEG in a nonequilibrium phase-mixed state. These mixed-phase semi-IPNs of PEG and TMPTA may be useful in biological applications where the presence of PEG is desired throughout the bulk matrix rather than as a surface graft to reduce biological interactions. © 1994 John Wiley & Sons, Inc.  相似文献   

4.
A mechanochemical system which works by complexation between a poly(methacrylic acid) (PMAA) network and poly(ethylene glycol) (PEG) was studied. A PMAA membrane swollen with an aqueous PEG solution, to which a load 100 times the weight of the membrane was attached, contracts by over 90% of its length when heated from 10°C to 60°C. The work per contraction was 5 × 10?3 cal/g of membrane. The temperature at which the mechanochemical system undergoes a specified contraction can be regulated by the PEG concentration of the swelling fluid. The sign of the temperature coefficient of the membrane dimension can be reversed by addition of a small amount of ethanol to the swelling solution of PEG. A simple method for calculating the stability constant and thermodynamic parameters for the complexation is outlined.  相似文献   

5.
Bacterial cellulose (BC)/poly(ethylene glycol) (PEG) composite was prepared by immersing wet BC pellicle in PEG aqueous solution followed by freeze-drying process. The product looks like a foam structure. The morphology of BC/PEG composite was examined by scanning electron microscope (SEM) and compared with pristine BC. SEM images showed that PEG molecules was not only coated on the BC fibrils surface but also penetrated into BC fiber networks. It has very well interconnected porous network structure and large aspect surface. The composite was also characterized by Fourier transform infrared spectrum, X-ray diffraction, thermogravimetric analysis (TGA) and tensile test. It was found that the presence of PEG affected the preferential orientation of the (1[`1]0 1\bar{1}0 ) plane during the drying process of BC pellicle, which in turn decrease the crystallinity of dried BC. The TGA result showed that the thermal stability was improved from 263 to 293 °C, which might be associated with strong interaction between BC and PEG. Tensile test results indicate that the Young’s modulus and tensile strength tend to decrease. Biocompatibility of composite was preliminarily evaluated by cell adhesion studies using 3T3 fibroblast cells. The cells incubated with BC/PEG scaffolds for 48 h were capable of forming cell adhesion and proliferation, which showed much better biocompatibility than the pure BC. The prepared BC/PEG scaffolds can be used for wound dressing or tissue-engineering scaffolds.  相似文献   

6.
 We have applied the PFG NMR technique to investigate the translational mobility in the PVP-PEG system as a function of composition and temperature at the stages of PVP-PEG complex formation, its swelling, and dissolution in excess of liquid PEG. It has been found that the variations of the spin-echo attenuation with PEG content, water amount, and temperature reflect the different stages. The first two stages are characterized by a distribution of the self-diffusion coefficients of PEG involved in the network. The dissolution shows two diffusion coefficients; the fast one is attributed to PEG molecules, the slow one to the associates of PEG and PVP. The temperature dependencies can be described by an Arrhenius law with an activation energy depending on the composition of the blend. The concentration dependence of the PEG self-diffusion coefficients in the blend occurred to be independent of the molecular weight of PVP. The results are discussed in terms of the Mackie-Meares model. Received: 23 August 2000 Accepted: 19 October 2000  相似文献   

7.
Hydroxyapatite (HAp) is a raw material used to fabricate scaffolds. Scaffolds are required to be porous to facilitate nutrient flow and vascularization. This study aims to produce porous HAp ceramics with macropores (>200 μm) and bioactivity and tune their macropore size. Polyethylene glycol (PEG) with molecular weights of 400, 3,400, and 8,300 was used to generate macropores. The macropore size increased as the molecular weight of PEG increased. In this method, emulsions were formed by hydrophobic PEG binding HAp nanoparticles during chemical syntheses. Water foams, as a core of the emulsion, were transformed into steam, and the steam expanded under heat treatment. Macropores were generated by the evaporation of the steam and consolidation of HAp nanoparticles. The difference in the molecular weight of PEG did not affect cell adhesion to the porous HAp ceramics. Cells adhered well to and spread widely on the HAp ceramics regardless of macropore size.  相似文献   

8.
Novel environmentally friendly poly(hydroxybutyrate-co-hydroxyvalerate) and poly(ethylene glycol) (PHBV/PEG) copolymer networks were synthesized through free-radical solution polymerization with PHBV diacrylate (PHBVDA) and polyethylene glycol diacrylate (PEGDA) as macromers. The molecular structure of PHBV/PEG copolymer network was characterized by Fourier transform infrared (FT-IR) and 1H nuclear magnetic resonance (1H NMR). The morphology of the PHBV/PEG copolymer network was characterized by polarization optical microscopy. Thermal energy storage properties, thermal reliability and thermal stability were investigated by differential scanning calorimetry (DSC) and thermogravimetric analysis. The results indicated that the PHBV/PEG copolymer network hindered the growth of PEG crystalline segments or PHBV segments. PHBV/PEG copolymer network had a higher latent heat enthalpy, which didn’t reduce with the components of PHBV increased. Moreover, PHBV/PEG copolymer network still had good thermal stability even at 300 °C. These results suggested that such environmentally friendly copolymer network would have wide applications in phase change energy storage materials.  相似文献   

9.
In order to prepare the advanced cellulosic super-absorbent polymer with high grafting level, we tried the novel ultrasound wave assisting polyethylene glycol (PEG) pre-treatment method to decrease the crystallinity and increase the accessibility of cellulose fiber. The effects of ultrasonification assisting PEG method on the crystallinity and swelling capacity of cellulose fiber were investigated. To optimize the experimental condition, the Taguchi method was employed in the treatment process. The influence factors such as ultrasonic wave power, ultrasonic wave time and PEG molecular weight relative to the crystallinity of cellulose fiber were studied systematically. The degree of crystallinity of cellulose fiber was measured by wide-angle X-ray diffraction (WAXD). The morphology of cellulose fiber was observed by environment scanning electron microscopy (ESEM). The effects of pre-treatment variables on the water absorbency and water retention values of cellulose fiber were also investigated. The research results revealed that, under the optimal experimental condition (ultrasonic powder, 500 W; ultrasonic time, 150 s; PEG molecular weight, 600 g/mol), the crystallinity of cellulose fiber decreased from 72.16 to 42.95%. Accordingly, the absorbency of cellulose fiber increased from 1.436 to 2.063 g/g, and the water retention value increased from 47.21 to 113.4%. However, the morphology of cellulose fiber did not change thoroughly compared with the original cellulose fiber. It can be hypothesized that the original inter- and intra-macromolecular hydrogen bonds in cellulose network were weakened, resulting from the high level dispersion of PEG within cellulose network without breaking the surface morphology of fiber.  相似文献   

10.
The sol–gel transition mechanism of a thermoreversible hydrogel composed of a copolymer comprising poly(N-isopropylacrylamide) and poly(ethylene glycol) (PNIPAAm–PEG) was studied by NMR. The 1H– and 13C–NMR spectra measured on a PNIPAAm–PEG solution in 99.9% D2O showed a remarkable line width broadening of the PNIPAAm block of more than that of the PEG block, during thermally induced hydrogel formation. This result suggested that the mobility of the PNIPAAm block is more restricted than that of the PEG block during gelation. A crosslinked polymer network formation was ascertained by a sudden reduction in the spin-lattice relaxation time (T1) of the residual HDO proton during gelation. The temperature dependency of the T1 values for the PNIPAAm and PEG blocks revealed that the microscopic condition of the PNIPAAm block in water was drastically changed during gelation, while that of the PEG block was unchanged. The experimental results from NMR supported the following gelation mechanism; that an aggregation of PNIPAAm blocks in the separate copolymers caused by hydrophobic interaction forms crosslinking points to give an infinite three-dimensional network structure. The hydrated PEG chains in the copolymers provide the network with a swelling property in water, and prevent the aggregation from causing a macroscopic phase separation.  相似文献   

11.
Co-immobilization of enzymes and microorganism is an effective way to enable cells to use nonmetabolizable substrates and accelerate reaction rate of overall process. Herein, a facile strategy to separately co-immobilize β-glucosidase (BG) and yeast cells on non-woven fabrics was developed. The BG was firstly in situ entrapped into poly(ethylene glycol) (PEG) network grafted on non-woven fabrics by visible light induced living/controlled graft polymerization. Then re-graft polymerization was performed on the as-formed BG loaded layer by taking advantage of living-grafting polymerization on its surface to in situ encapsulate yeast cells into the second PEG network layer. This layered structure of co-immobilization avoided possible interference between enzyme and cells. Viability assay of yeast cells demonstrated that most of cells were viable after immobilization. While immobilized BG showed decreased Vmax compared to free BG, indicating that entrapping BG into inner PEG network layer restricted its accessibility with substrates. This co-immobilization sheet could successfully convert cellobiose to ethanol and a maximum of 98.6% bioethanol yield can be obtained after 48 h of simultaneous saccharification and fermentation (SSF). The co-immobilization sheet showed excellent reusability and could still reach more than 60% of original ethanol yield after reusing for 7 batches. Compared with the mixed co-immobilization, the sequential layered immobilization in this system showed better stability and higher ethanol yield.  相似文献   

12.
We here describe new double network (DN) hydrogels with excellent mechanical strength and high sensitivity to pH changes. The first polymer network has a bottle brush structure and is formed from oligo‐monomers of poly(ethylene glycol) methyl ether methacrylate (PEGMA). Poly(acrylic acid) (PAA) is used as the second network. This double network features strong intermolecular interactions between the neutral poly(ethylene glycol) (PEG) side chains of PPEGMA and the non‐ionized carboxylic acid groups of the PAA second network. When immersed in solutions with a pH below ~4 the DN hydrogels have a low swelling ratio and are opaque as a result of solvent‐polymer phase separation driven by the formation of dense hydrogen‐bonded clusters. The compression strength (~8 MPa) is at least 14 times higher than the analogous single networks. When immersed in solutions with a pH >4, the hydrogels are transparent and exhibit a high swelling ratio with a compression strength of ~1 MPa. The PEG side chain length can be readily controlled without greatly altering the overall DN topology by choosing PEGMA monomers having different PEG side chain lengths. Longer PEG side branches give higher compression and tensile strengths at pH <4 when hydrogen bonded clusters form. The robust nature of these DN gels over a wide pH range may be useful for applications such as artificial muscles and controlled release devices. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012  相似文献   

13.
Poly(N-isopropylacrylamide) (PNIPA) hydrogels with varied degree of crosslinking (DC) were synthesized by using poly(ethylene glycol) (PEG) as an additive. A phase separated ("macroporous") morphology was formed when using PEG contents of > or = 20 wt.-%. Temperature-dependent degrees of swelling had been measured, and average mesh sizes of the swollen polymer network had been calculated. The loading of the hydrogels with labelled dextrans with various molar masses and bovine serum albumin (BSA)-via swelling of the shrunken gel in a cold solution-and their subsequent unloading-via immersion in hot water-were studied in detail. The loading efficiencies were close to zero for PNIPA prepared at PEG contents of < or = 10 wt.-%, and they increased sharply to about 100% for PNIPA prepared with PEG contents of > or = 20 wt.-%. A complete unloading was achieved as well. For macroporous PNIPA prepared at 40 wt.-% PEG content, the loading efficiency was a function of the DC, and the "cut-off" observed as a function of dextran or protein size correlated with the mesh size of the hydrogel. The function of these "smart" hydrogels can be explained by the temperature-induced "pumping" of the solution into the gel bulk via the permanent pores, along with an uptake into the adjacent hydrogel network. Those materials could be used as matrices for the efficient and reversible immobilization of (bio)macromolecules.  相似文献   

14.
谭福能  何媛媛  隋卫平 《应用化学》2014,31(12):1399-1404
将壳聚糖改性为(2-羟基-3-丁氧基)丙基 羟丙基壳聚糖(2-H-3-B-P-HPCS),并以(2-羟基-3-丁氧基)丙基-羟丙基壳聚糖和聚乙二醇(PEG)为原料制备(2-羟基-3-丁氧基)丙基-羟丙基壳聚糖/聚乙二醇互穿网络凝胶,研究了(2-羟基-3-丁氧基)丙基-羟丙基壳聚糖浓度、聚乙二醇的用量、交联剂戊二醛用量、反应温度对该凝胶溶胀性能的影响。 通过红外光谱分析和扫描电子显微镜的方法比较了壳聚糖、(2-羟基-3-丁氧基)丙基-羟丙基壳聚糖和(2-羟基-3-丁氧基)丙基-羟丙基壳聚糖/聚乙二醇互穿网络凝胶结构和形态上的不同。 以阿昔洛韦为模型药物研究了其释药性能。 结果表明,该凝胶均具有良好的溶胀性、pH敏感性和药物缓释作用,有望用作新型的药物载体。  相似文献   

15.
A potential new photosensitizer based on a dissymmetric porphyrin derivative bearing a thiol group was synthesized. 5-[4-(11-Mercaptoundecyloxy)-phenyl-10,15,20-triphenylporphyrin (PR-SH) was used to functionalize gold nanoparticles in order to obtain a potential drug delivery system. Water-soluble multifunctional gold nanoparticles GNP-PR/PEG were prepared using the Brust–Schiffrin methodology, by immobilization of both a thiolated polyethylene glycol (PEG) and the porphyrin thiol compound (PR-SH). The nanoparticles were fully characterized by transmission electron microscopy and 1H nuclear magnetic resonance spectroscopy, UV/Vis absorption spectroscopy, and X-ray photoelectron spectroscopy. Furthermore, the ability of GNP-PR/PEGs to induce singlet oxygen production was analyzed to demonstrate the activity of the photosensitizer. Cytotoxicity experiments showed the nanoparticles are nontoxic. Finally, cellular uptake experiments demonstrated that the functionalized gold nanoparticles are internalized. Therefore, this colloid can be considered to be a novel nanosystem that could potentially be suitable as an intracellular drug delivery system of photosensitizers for photodynamic therapy.  相似文献   

16.
徐军 《高分子科学》2014,32(9):1234-1242
The poly(ethylene glycol) (PEG, with Mw 2000)-urea inclusion compound (IC) crystallized at high temperature region showed two typical orientations, flat-on and edge-on crystals. 2D-XRD and polarized FTIR spectroscopy revealed that the PEG chains within urea channels were perpendicular to the substrate in fiat-on oriented crystals, while PEG chain axes were parallel to the substrate and lay along the growth direction in the edge-on crystals. FT1R absorption bands of PEG in the ICs are sensitive to orientation of the crystals. A scheme of PEG chain packing in the urea IC channel was proposed, which could explain the orientation of the crystal nucleus causing the two types of morphologies. Furthermore, functioning of PEG2000 chain end with analine had significantly influence on the morphology and orientation of the inclusion compound crystals, due to the defects caused by large terminal groups included in the urea channel.  相似文献   

17.
Electrostatic interactions within a semi‐interpenetrating network (semi‐IPN) gel can control the postsynthesis loading, long‐term retention, and subsequent release of small‐molecule cationic antibiotics. Here, electrostatic charge is introduced into an otherwise neutral gel [poly(ethylene glycol) (PEG)] by physically entrapping high‐molecular‐weight poly(acrylic acid) (PAA). The network structure is characterized by small‐angle neutron scattering. PEG/PAA semi‐IPN gels absorb over 40 times more antibiotic than PAA‐free PEG gels. Subsequent soaking in physiological buffer (pH 7.4; 0.15 M NaCl) releases the loaded antibiotics for periods as long as 30 days. The loaded gels elute antibiotics with diffusivities of 4.46 × 10?8 cm2/s (amikacin) and 2.08 × 10?8 cm2/s (colistin), which are two orders of magnitude less than those in pure PEG gels where diffusion is controlled purely by gel tortuosity. The release and hindered diffusion can be understood based on the partial shielding of the charged groups within the loaded gel, and they have a significant effect on the antimicrobial properties of these gels. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 64–72  相似文献   

18.
The synthesis and characterization of novel tricomponent networks consisting of well‐defined poly(ethylene glycol) (PEG) and poly(dimethylsiloxane) (PDMS) strands crosslinked and reinforced by poly(pentamethylcyclopentasiloxane) (PD5) domains are described. Network synthesis occurred by dissolving α,ω‐diallyl PEG and α,ω‐divinyl PDMS prepolymers in a common solvent (toluene), introducing a stoichiometric excess of pentamethylcyclopentasiloxane (D5H) to the charge, inducing the cohydrosilation of the prepolymers by Karstedt's catalyst and completing network formation by the addition of water. Water in the presence of the Pt‐based catalyst oxidizes the SiH groups of D5H to SiOH functions that immediately polycondense and bring about crosslinking. The progress of cohydrosilation and polycondensation was followed by monitoring the disappearance of the SiH and SiOH functions by Fourier transform infrared spectroscopy. Because cohydrosilation and polycondensation are essentially quantitative, overall network composition can be controlled by calculating the stoichiometry of the three network constituents. The very low quantities of extractable (sol) fractions corroborate efficient crosslinking. The networks swell in both water and hexanes. Differential scanning calorimetry showed three thermal transitions assigned, respectively, to PEG (melting temperature: 46–60 °C depending on composition), PDMS [glass‐transition temperature (Tg) = ~?121 °C], and PD5 (Tg = ~?159 °C) and indicated a phase‐separated tricomponent nanoarchitecture. The low Tg of the PD5 phase is unprecedented. The strength and elongation of PEG/PD5/PDMS networks can be controlled by overall network composition. The synthesis of networks exhibiting sufficient mechanical properties (tensile stress: 2–5 MPa, elongation: 100–800%) for various possible applications has been demonstrated. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3093–3102, 2002  相似文献   

19.
Poly(ethylene glycol) (PEG)-coated capillaries exhibit unique properties in nonaqueous electrolytes. Immobilized PEG interacts significantly with different cations present in nonaqueous electrolytes. This can induce a positive surface charge on PEG-coated capillaries and results in an adjustable anodic electroosmotic flow (EOF) in nonaqueous electrolytes whereas a reduced cathodic EOF is observed in aqueous electrolytes. The EOF can reversibly be adjusted by the variation of the electrolyte constitution, namely the type of the solvent used and the nature and concentration of background cations. In methanol and especially in acetonitrile electrolytes the magnitude and also the direction of EOF is strongly dependent on the water content. Using different alkali metal cations, the EOF can be increased, reduced, or even reversed depending on the nature of the cation. The directed manipulation of EOF in methanolic electrolytes using PEG-coated capillaries was applied for optimization of nonaqueous capillary electrophoretic separations of acidic compounds with regard to reproducibility, resolution, and analysis time.  相似文献   

20.
Summary: Poly(ethylene glycol) (PEG) networks were synthesized by γ‐irradiation. The crystalline behavior of PEG was investigated by differential scanning calorimetry (DSC) and wide‐angle X‐ray diffraction (WAXD). It was shown that the crystallinity of PEG is dramatically lower in the cross‐linked networks than in pure PEG. When the molecular weight of PEG in the networks decreased to 1 000, it could not crystallize at all. Moreover, we also found that the melting temperature of PEG is greatly affected by the presence of a cross‐linked network.

The DSC curves of PEG ( = 1 500) and the corresponding cross‐linked PEG.  相似文献   


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