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1.
以不同臂(Arm)数的星形聚氧化乙烯(PEO)为对象,系统地研究了其在不同温度下结晶的晶体冰花图案.实验中采用的星形PEO样品,其臂数分别为3,4和8(3-arm-PEO,4-arm-PEO和8-arm-PEO)且每臂的分子量均为5000,线形PEO其分子量为5000.显然,随着星形PEO分子臂数的增加,分子拓扑形状的各向异性不断减小.在单层片晶冰花图案研究中发现,随着结晶温度逐渐向平衡熔点靠近,这些PEO样品的结晶冰花图案具有从树枝状晶体转变为海藻状晶体,然后转变为非规整的紧凑形晶体,最后变成多面晶体的变化规律.对细节的分析进一步表明,随着星形PEO分子臂数的增加,由于分子的各向异性减小,导致冰花状晶体的各向异性程度不断减弱,因此从树枝状晶体到海藻状晶体和从树枝状晶体到多面晶体的转变温度也都逐渐降低.将这些转变温度对臂数作图获得的一张形态相图(morphology diagram)说明了星形PEO结晶图案的分子形状依赖性,也阐明了冰花图案形成的大分子拓扑形状效应.  相似文献   

2.
Poly(N-isopropylacrylamide) (PIPAAm) of controlled molecular weight was densely grafted onto glass capillary lumenal surfaces using surface-initiated atom transfer radical polymerization (ATRP). Temperature-dependent changes of these thermoresponsive brush surfaces with hydrophobic steroids were investigated by exploiting thermoresponsive aqueous wettability changes of the polymer-modified surfaces in microfluidic systems. IPAAm was polymerized on ATRP initiator-immobilized glass surfaces using CuCl/CuCl(2)/tris(dimethylaminoethyl)amine (Me(6)TREN) as an ATRP catalyst in water at 25 degrees C. PIPAAm graft layer thickness and its homogeneity on glass surfaces are controlled by changing ATRP reaction time. Aqueous wettability changes of PIPAAm-grafted surfaces responses drastically changed to both grafted polymer layer thickness and temperature, especially at lower temperatures. Temperature-responsive surface properties of these PIPAAm brushes within capillary inner wall surfaces were then investigated using capillary chromatography. Effective interaction of hydrophobic steroids with dehydrated, hydrophobized PIPAAm-grafted capillary surfaces was observed above 30 degrees C without any column packing materials. Steroid elution behavior from PIPAAm-grafted capillaries contrasted sharply with that from PIPAAm hydrogel-grafted porous monolithic silica capillaries prepared by electron beam (EB) irradiation wherein significant peak broadening was observed at high-temperature regardless of sample hydrophobicity factors (log P values), indicating multistep separation modes in coated monolithic silica capillaries. In conclusion, thermoresponsive polymer-grafted capillary inner wall surfaces prepared by ATRP exhibit useful temperature-dependent surface property alterations effective to regulate interactions with biomolecules without requirements for separation bed packing materials within the capillary lumen.  相似文献   

3.
Dense, ultrathin networks of isocyanate terminated star-shaped poly(ethylene oxide) (PEO) molecules, cross-linked at their chain ends via urea groups, were shown to be extremely resistant to unspecific adsorption of proteins while at the same time suitable for easy biocompatible modification. Application by spin coating offers a simple procedure for the preparation of minimally interacting surfaces that are functionalized by suitable linker groups to immobilize proteins in their native conformations. These coatings form a versatile basis for biofunctional and biomimetic surfaces. We have demonstrated their advantageous properties by using single-molecule fluorescence microscopy to study immobilized proteins under destabilizing conditions. Biotinylated ribonuclease H (RNase H) was labeled with a fluorescence resonance energy transfer (FRET) pair of fluorescent dyes and attached to the surface by a biotin-streptavidin linkage. FRET analysis demonstrated completely reversible denaturation/renaturation behavior upon exposure of the surface-immobilized proteins to 6 M guanidinium chloride (GdmCl) followed by washing in buffer. A comparison with bovine serum albumin (BSA) coated surfaces and linear PEO brush surfaces yielded superior performance in terms of chemical stability, inertness and noninteracting nature of the star-polymer derived films.  相似文献   

4.
This paper describes the synthesis of a novel amphiphilic AB2 triarm star-shaped copolymer with A = non-toxic and biocompatible hydrophilic poly(ethylene oxide) (PEO) and B = biodegradable and hydrophobic poly(ε-caprolactone) (PCL). A series of AB2 triarm star-shaped copolymers with different molecular-weights for the PCL block were successfully synthesized by a three-step procedure. α-Methoxy-ω-epoxy-poly(ethylene oxide) (PEO-epoxide) was first synthesized by the nucleophilic substitution of α-methoxy-ω-hydroxy-poly(ethylene oxide) (MPEO) on epichlorohydrin. In a second step, the α-methoxy-ω,ω′-dihydroxy-poly(ethylene oxide) (PEO(OH)2) macroinitiator was prepared by the selective hydrolysis of the ω-epoxy end-group of the PEO-epoxide chain. Finally, PEO(OH)2 was used as a macroinitiator for the ring-opening polymerization (ROP) of ε-caprolactone (εCL) catalyzed by tin octoaote (Sn(Oct)2). PEO-epoxide, PEO(OH)2 and the AB2 triarm star-shaped copolymers were assessed by 1H NMR spectroscopy, size exclusion chromatography (SEC) and MALDI-TOF. The behavior of the AB2 triarm star-shaped copolymer in aqueous solution was studied by dynamic light scattering (DLS) and transmission electron microscopy (TEM).  相似文献   

5.
Surfaces coated with poly(ethylene oxide) containing nonionic polymers are of interest in medical applications due to, among other things, the low adsorption of proteins on such surfaces. In this paper we have studied the interfacial properties of surfaces coated with PEO by measuring the forces acting between two such surfaces in water and across a protein solution as well as between one such surface and a surface carrying adsorbed proteins. One type of surface coating was a graft copolymer of poly(ethylene imine) and poly(ethylene oxide) where the cationic poly(ethylene imine) group anchored the polymer to negatively charged mica surfaces. Three different ways to prepare this coating was used and compared. It was found that this coating was not stable in the presence of lysozyme, a small positively charged protein, when the PEO graft density was low. The other type of coating was obtained by adsorbing ethyl(hydroxyethyl)-cellulose onto hydrophobised mica surfaces. The driving force for adsorption is in this case the hydrophobic interaction between nonpolar segments of the polymer and the surface. The EHEC coating was stable in the presence of lysozyme and the interactions between adsorbed layers of lysozyme and EHEC coated surfaces are purely repulsive due to long-range steric forces.  相似文献   

6.
We covalently immobilized poly(ethylene oxide) (PEO) chains onto a fluorinated ethylene propylene copolymer (FEP) surface. On the FEP surface, aldehyde groups were first deposited by plasma polymerization of acetaldehyde or acrolein. Then, amino‐PEO chains were immobilized through Schiff base formation, which was followed by reduction stabilization with sodium cyanoborohydride. The PEO‐grafted polymer surfaces thus prepared were characterized by X‐ray photoelectron spectroscopy (XPS), atomic force microscopy, contact‐angle measurements, and protein adsorption. The dramatic increase in the C O intensity of the high‐resolution XPS C 1s spectrum, together with an overall increase in oxygen content, indicated the successful attachment of PEO chains onto the acetaldehyde plasma surfaces. The amount of grafted PEO chains depended on the superfacial density of the plasma‐generated aldehyde groups. The grafted monoamino‐PEO chains formed a brushlike structure on the polymer surface, whereas the bisamino‐PEO chains predominately adopted a looplike conformation. The PEO surface had a regular morphology with greater roughness than the aldehyde surface underneath. Surface hydrophilicity increased with the grafting of PEO. Also, the bisamino‐PEO‐grafted surface had slightly higher surface hydrophilicity than its monoamino‐PEO counterpart. These PEO coatings reduced fibrinogen adsorption by 43% compared with the substrate FEP surface. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2323–2332, 2000  相似文献   

7.
Catechol and spiropyran functional groups were conjugated to a polymer backbone, allowing immobilization on polystyrene beads (PS beads). The final product was capable of stably reproducing the optical properties of spiropyran. Through the outstanding surface adhesion properties of the catechol functional group, spiropyran was immobilized on PS beads. Switchable photoluminescence in the spiropyran coated PS bead surfaces was observed depending on irradiation with either UV or visible light. The surfaces of the PS beads were morphologically examined by field emission scanning electron microscopy and X‐ray photoelectron spectroscopy was used for characterization of the constituent atoms. Furthermore, UV–Vis and fluorescence spectroscopy were used to confirm conversion between the spiropyran (SP) and merocyanine (MC) forms through UV or visible light irradiation on SP, while fluorescent images for both SP and MC were studied using confocal laser scanning microscopy. The confocal images of the SP‐PS beads system onto MDAMB‐231 cells under UV and visible light indicate the cellular uptake by emerging color within the cytoplasm. Advancing study, the remaining catechol groups can confers adhesive properties, given by contact angle data of various coated surfaces film. These stimuli‐responsive coatings are compatible as drawing switchable photochromic material on versatile substrate shown in confocal images of propylene film. Overall, this great water solubility and biocompatibility PS beads system also showed potential as cell bio‐imaging light stimuli responsive material, and the benefits of this system can also possibly address coat able advanced material for a wide range of surface light sensor applications. Copyright © 2017 John Wiley & Sons, Ltd.  相似文献   

8.
Polyacrylamide/polyethylene oxide (PAAm/PEO) controlled release matrices were designed to obtain a better control over the concentration of indole‐3‐butyric acid (IBA). PAAm/PEO incorporated IBA was prepared by exposing aqueous solutions of PEO, PAAm, crosslinking agent N,N′‐methylene‐bisacrylamide, and IBA mixtures to electron beam irradiation. PAAm/PEO copolymer structural property relationships that affect its controlled release behavior were determined. Analysis of the results obtained indicated that it is possible to optimize IBA controlled release by adjusting the dimensions and crosslinking degree of the copolymer as well as the concentration of the incorporated IBA. The crosslinking degree of the copolymer can be controlled by governing the irradiation dose, polymer blend composition and/or the amount of crosslinking agent. IBA release rates have been investigated as a function of environmental conditions, such as the changes in pH and temperature to determine the factors, which mostly contribute to the release of IBA. The effect of PAAm/PEO–IBA matrix on the average height of corn (Zea mayz) plant was investigated. The results obtained, revealed that PAAm/PEO‐IBA systems have a capability to deliver IBA slowly and continuously. As a result, the development of root and vegetative systems of Zea mayz plant was greatly promoted. Copyright © 2004 John Wiley & Sons, Ltd.  相似文献   

9.
This article reviews surface grafting of star-shaped PEO. The use of star-shaped polymers is compared to linear PEO chains regarding the layer preparation and the ability of the resulting surfaces to resist protein adsorption. We then focus on the use of end-functionalized, star-shaped, PEO-based prepolymers that are able to form covalent crosslinks and functional polymer networks on the substrate. Examples are given for specific protein adsorption as well as for cell adhesion on such layers by covalent embedding of biofunctional molecules. The possibility of coating biomedically relevant polymer substrates in three-dimensional geometries is discussed and examples are shown for poly(ethylene terephthalate) monofilament constructs.  相似文献   

10.
Regenerated cellulose (RC) membranes which have pH modulated permeability have been prepared by anchoring the hydroxyl groups on the membrane surface with 2‐bromoisobutyryl bromide, followed by grafting with acrylic acid (AA) using atom transfer radical polymerization (ATRP). The obtained membranes were analyzed by X‐ray photoelectron spectroscopy (XPS), Fourier transform infrared attenuated total reflection spectrometer (ATR‐FTIR), scanning electron microscopy (SEM), TGA and the results showed that AA had been grafted onto the membrane surfaces successfully. Then the pH modulated permeability properties were tested by water flux measurement. All results show that the pH modulated permeability properties of a RC membrane can be obtained by surface‐initiated ATRP. Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   

11.
A new kind of binary hydrogels composed of poly(dimethylaminoethylmethacrylate) (PDMAEMA) and poly(ethylene oxide) (PEO) with varying weight average molecular weights ((M)w = 5 × 104, 1 × 105 and 2.5 × 106) were prepared by y-irradiation technology. The properties of PDMAEMA/PEO hydrogels obtained were evaluated in terms of gel fraction, gel strength, thermal characterization and swelling behavior. The gel strength and swelling degree of the hydrogels could be improved obviously after adding PEO into the PDMAEMA system, while the degree of improvement decreased with increasing (M)w of PEO. The temperature sensitivity of PDMAEMA/PEO was retained only in the sample with PEO of (M)w = 5 × 104, and the pH sensitivity was retained in samples with PEO of (M)w = 5 × 104 and 1 × 105. When DMAEMA/PEO mixtures containing PEO of (M)w = 5 × 104 were irradiated, the main reaction could be the cross-linking of DMAEMA, and the linear PEO molecular chains could penetrate into the cross-linked network of PDMAEMA. With increasing Mw of PEO, some side reactions were induced, such as grafting of DMAEMA onto PEO molecules, the scission or cross-linking of PEO.  相似文献   

12.
We compare two routes for creating protein adsorption-resistant self-assembled monolayers (SAMs) by chemical modification of silicon surfaces with poly(ethylene oxide) (PEO) oligomeric derivatives. The first route involves the assembly of 2-methyl[(polyethyleneoxy)propyl]trichlorosilane (Cl3SiMPEO) films onto oxidized silicon surfaces (OH-SiO(x)) either by a liquid-phase process at room temperature or by a gas-phase process at 423 K, producing Si-O-Si bonds between the substrate and the organic layer. The second pathway makes use of the assembly of poly(ethylene glycol methyl ether) (MPEG) films onto hydrogen-passivated silicon surfaces (H-Si) using a liquid-phase process at 353 or 423 K, leading to the formation of Si-O-C bonds between the substrate and the organic layer. Structural investigation by X-ray reflectometry (XRR) reveals that the thickness and surface densities of the grafted PEO monolayers strongly depend on experimental conditions such as temperature and grafting time. Atomic force microscopy (AFM) shows that very smooth and homogeneous monolayers can be obtained with average roughnesses close to those measured on the corresponding bare substrates. Finally, the antifouling properties of the modified silicon surfaces were evaluated by X-ray photoelectron spectroscopy (XPS), using a membrane protein (P.69 antigen) as model protein. Both types of PEO monolayers exhibit excellent protein repellency, as soon as the grafting density is equal to or higher than 1.7 chains/nm2.  相似文献   

13.
Three well-defined diblock copolymers of poly(methyl methacrylate-b-methacrylic acid)(P(MMA-b-MAA))were synthesized using atom transfer radical polymerization method and varying poly(methacrylic acid)(PMAA)chain lengths. These copolymers were blended with PVC to fabricate porous membranes via phase inversion process.Membrane morphologies were observed by scanning electron microscopy(SEM),and chemical composition changes of the membrane surfaces were measured by X-ray photoelectron spectroscopy(XPS).Static and dynamic protein adsorption experiments were used to evaluate antifouling properties of the blend membranes.It was found that,the blend membranes containing longer PMAA arm length showed lower static protein adsorption,higher water permeation flux and better protein solution flux recovery.  相似文献   

14.
Cleavable amphiphilic triblock surfactants with methoxypolyethylene oxide (PEO) side‐chains attached to polybutadiene (PBD) center blocks by ester linkages were synthesized. The PEO–PBD–PEO triblocks were adsorbed on hydrophobic silicon wafers and covalently stabilized by γ‐irradiation. The PEO side‐chains were then cleaved from the PBD backbones by acid hydrolysis. Decoration of the immobilized centerblocks with β‐cyclodextrin allowed direct imaging by standard atomic force microscopy techniques. Widely varied surface coverage, layer morphology and distributions of the PBD centerblocks were observed on surfaces coated with different triblock concentrations and PEO:PBD ratios. Surfaces coated from 1 mg/mL solutions of triblocks (near the critical aggregation concentration (CAC), 0.28–0.53 mg/mL) were sparsely coated, and triblocks containing 75–85% PEO exhibited negligible surface coverage, possibly due to poor adsorption or facile desorption during rinsing. Dense surface packings, albeit some with evident defects sufficiently large to allow for protein adsorption, were produced from 10 mg/mL triblock solutions (an order of magnitude above the CAC). This proof‐of‐concept report describes a method that may be useful in optimizing surface coatings on model substrates, and thus lend insight into optimization of coating conditions for economical production of non‐fouling triblock‐based PEO coatings on clinically relevant biomedical materials. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   

15.
The biocompatibility and substrate diffusion limiting properties for a range of diamond like carbon (DLC) coated microporous polycarbonate and DLC coated dialysis (haemodialysis) membranes have been studied. This characterisation builds upon previous findings where DLC coated membranes imparted enhanced enzyme electrode performance. In this study electrode linear ranges have been extended from 10 mM glucose for a 0.01 μm pore size membrane to 160 mM. These findings correlated with the duration of DLC deposition and associated reductions in permeability for glucose. Permeability coefficient ratios for both microporous and dialysis membranes were also found to be important with low glucose/O2 permeability ratios imparting extensions in glucose linear response range. DLC coated membranes employed within enzyme electrodes have also been shown to exhibit enhanced haemocompatibility as determined by both sensitivity change and surface deposition of blood components examined by scanning electron microscopy. Correlations are made between the reduced losses in sensor response to biofouling/ working electrode passivation processes, and extended linear ranges that DLC coated membranes may impart to enzyme electrode performance. Particular reference is made to the determination of glucose levels within whole blood.  相似文献   

16.
A hydroxyl-coated CdSe nanocrystal (CdSe-OH) and a CdSe-polymer nanocomposite were synthesized and used as the electron acceptors in polymer solar cells (PSCs). The CdSe-polymer composite was prepared via atom transfer radical polymerization (ATRP) of N-vinylcarbazole on functionalized CdSe quantum dots. Physical properties and photovoltaic characteristics of the CdSe-poly(N-vinylcarbazole) (CdSe-PVK) nanocomposite have been investigated. Thermogravimetric analysis (TGA) results displayed higher thermal stability for CdSe-PVK nanohybrid in comparison with the linear-type PVK polymer. Differential scanning calorimetry (DSC) studies indicated that CdSe-PVK had a lower glass-transition temperature (Tg) in comparison with PVK due to the branch effect of the star-shaped polymer hybrid. Cyclic voltammetric (CV) measurements were performed to obtain HOMO and LUMO values of PVK and CdSe-PVK. TEM and SEM micrographs exhibited CdSe nanoparticles were well coated with PVK polymer. Both CdSe-OH and CdSe-PVK were blended with poly(3-hexylthiophene) (P3HT) and used as the active layer in bulk heterojunction solar cells. Polymer solar cell based on CdSe-PVK as acceptor revealed that the photovoltaic properties can be significantly improved when PVK polymer chains were grafted on surfaces of CdSe nanocrystals. In comparison with the P3HT:CdSe-OH system, PSC based on P3HT:CdSe-PVK showed an improved power conversion efficiency (0.02% vs. 0.001%). Film topography studied by AFM further confirmed the better device performance was due to the enhanced compatibility between P3HT and CdSe-PVK.  相似文献   

17.
This paper reports a novel enzyme‐immobilization method for the direct electron transfer (DET) reaction of ascorbate oxidase from Acremonium sp. HI‐25 (ASOM). ASOM was adsorbed onto a gold electrode modified with a self‐assembled monolayer (SAM) of alkanethiol derivatives and immobilized by a cationic polymer membrane and anionic ω‐carboxyalkanethiol combined system. The redox responses of the immobilized ASOM were investigated by cyclic voltammetry. We found that the DET reaction of ASOM was facilitated by this novel immobilization. On the other hand, the redox responses of poly(ethylene oxide) (PEO)‐modified ASOMs were also investigated. ASOM was modified with two types of PEO which possess straight chain‐shaped (PEO2000) or comb‐shaped conformation (PM67). As a result, the DET reactions of PEO‐modified ASOMs were also facilitated by this immobilization method. We concluded that this immobilization method is effective for promoting the DET reaction of ASOMs.  相似文献   

18.
The silica coating has attracted much attention because of its superior corrosion resistance with almost no harm to human health and to the environment. In this study, a two layered silica film was tried to get an enhanced corrosion resistance. The silica film was prepared on the hairline finish 304 stainless steel surfaces by-a-spray- and subsequent-dip-coating process. The spray coating solution was prepared by mixing sodium silicate solution, silica colloid, tetraethyl orthosilicate (TEOS), methyltriethoxysilane (MTES), ethanol, and distilled water. Then the solution was sprayed onto the stainless steel surface, and was dried and heat treated. The dip coating solution was prepared by a simple mixing of TEOS and acidic water into ethanol, and the prior spray coated sample was dipped into the solution. The outer dip coated layer was intended to cover spray coated rough and porous layer and hence to enhance the corrosion resistance. A homogeneous and crack free surface was successfully obtained after the dip coating. The prepared silica film was characterized using scanning electron microscopy, potentiodynamic polarization scan, and electrochemical impedance spectroscopy. The two layered film showed an enhanced corrosion resistance. The enhancement was attributed to a protecting effect of the dip coated layer where the diffusion of ionic species was successfully impeded.  相似文献   

19.
Poly(ethylene oxide) (PEO)–clay (montmorillonite, hectorite, and laponite) nanocomposites were prepared by a melting intercalation procedure induced by microwave irradiation. The influence of parameters such as the time of irradiation, power, amount and relative ratio of the reagents, and relative humidity was investigated. X-ray diffraction, differential scanning calorimetry, elemental microanalysis, Fourier transform infrared, and scanning electron microscopy techniques were applied to characterize the resulting nanocomposites. Techniques involving impedance spectroscopy, thermoelectric power, and electrical polarization in the solid state were used to characterize the electrical properties of the nanocomposites. The electrical behavior of these PEO–silicate nanocomposites, including those containing an excess of alkaline metal salts in comparison with that of similar systems prepared by alternative procedures such as direct intercalation from polymer solutions or melting intercalation, was also examined. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 3249–3263, 2003  相似文献   

20.
A biocompatible needle-type glucose sensor with a 3-electrode configuration was constructed. A platinum-electroplated carbon stick was used as the working electrode, Ag/AgCl as the reference electrode, and a disposable hypodermic needle made of stainless steel as the counter electrode. A Nafion membrane, an immobilized glucose oxidase (GOD) membrane, and a biocompatible membrane with diffusion-limiting effect were coated successively onto the working electrode. The sensor showed a rapid response (< 120 s in batch operation), good reproducibility (RE < 3%), good stability (over 36 h in control serum), a wide dynamic range (5-600 mg/dL glucose), and superior biocompatibility. It was used to determine glucose in serum. The data obtained from the sensor showed good agreement with that from a clinical autoanalyzer (R > 0.95).  相似文献   

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