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1.
Temperature- and pH-sensitive poly(N-isopropylacrylamide)?Cco-acrylic acid (pNIPAm-co-AAc) microgels were deposited on glass substrates coated with polyelectrolyte multilayers composed of the polycation poly(allylamine hydrochloride) (PAH) and the polyanion poly(sodium 4-styrenesulfonate) (PSS). The microgel density and structure of the resultant films were investigated as a function of: (1) the number of PAH/PSS layers (layer thickness); (2) the charge on the outer layer of the polyelectrolyte multilayer film; and (3) the pH of microgel deposition solution. The resultant films were studied by differential interference contrast optical microscopy, atomic force microscopy, and scanning electron microscopy. It was found that the coverage of the microgels on the surface was a complex function of the pH of the deposition solution, the charge on the outer layer of the polyelectrolyte thin film and the PAH/PSS layer thickness; although it appears that microgel charge plays the biggest role in determining the resultant surface coverage.  相似文献   

2.
An efficient method for characterizing wetting properties of heterogeneous surfaces produced by sequential adsorption of polyelectrolytes was developed. Three types of polyelectrolytes were used: polyallylamine hydrochloride (PAH), polyethyleneimine (PEI), both of a cationic type, and polysodium 4-styrenesulfonate (PSS), of an anionic type. Multilayer films were prepared by 'layer-by-layer' (LbL) deposition technique. Natural ruby mica, glass, titanium foil and silicon wafers were used as the support material for PE films. Wetting of polyelectrolyte films was determined experimentally by contact angle measurements, using technique of direct image analysis of shape of sessile drops. Periodic oscillations in contact angle values were observed for multilayers terminated by polycation and polyanion, respectively, and the variations in contact angle values strongly depended on the conditions of adsorption and multilayer treatment after deposition. Therefore, the influence of ionic strength of polyelectrolyte solution used for deposition on wetting of multilayer films was considered and also the effect of conditioning in different environments was investigated. It is usually assumed that film properties and stability strongly depend on the first layer which is used to anchor a multilayer at the surface of support material. To investigate influence of the first layer, PAH/PSS films were compared with more complex ones having PEI as the first layer with a sequence of PSS/PAH deposited on top of it.  相似文献   

3.
Prussian blue (PB) nanoparticles were immobilized in polyelectrolyte (PE) multilayers of various compositions and thickness. Films containing nanoparticles and poly(allylamine hydrochloride) (PAH) were formed using the layer-by-layer adsorption method. A layer of branched poly(ethyleneimine) (PEI) was used to anchor the multilayer structure at the surface of a gold electrode. The films exhibited electroactive properties, increasing with the number of deposited PB layers. The properties of PEI/(PB/PAH) n multilayers were then compared with the ones containing additionally the conductive polymer poly(3,4-ethylenedioxythiophene)–poly(styrenesulfonate) (PEDOT:PSS). We found that the addition of the conductive, water-soluble polymer enhances the electroactive properties of the multilayer films. It also increased sensitivity of the multilayer-covered electrodes for electrochemical detection of hydrogen peroxide.  相似文献   

4.
Application of polyelectrolyte multilayer (PEM) capsules as vehicles for the controlled delivery of substances, such as drugs, genes, pesticides, cosmetics, and foodstuffs, requires a sound understanding of the permeability of the capsules. We report the results of a detailed investigation into probing capsule permeability via a molecular beacon (MB) approach. This method involves preparing MB-functionalized bimodal mesoporous silica (BMSMB) particles, encapsulating the BMSMB particles within the PEM film to be probed, and then incubating the encapsulated BMSMB particles with DNA target sequences of different lengths. Permeation of the DNA targets through the capsule shell causes the immobilized MBs to open due to hybridization of the DNA targets with the complementary loop region of the MBs, resulting in an increase in the MB fluorescence. The assay conditions (BMSMB particle concentration, MB loading within the BMS particles, DNA target concentration, DNA target size, pH, sodium chloride concentration) where the MB-DNA sensing process is effective were first examined. The permeability of DNA through poly(sodium 4-styrenesulfonate) (PSS)/poly(allylamine hydrochloride) (PAH) multilayer films, with and without a poly(ethyleneimine) (PEI) precursor layer, was then investigated. The permeation of the DNA targets decreases considerably as the thickness of the PEM film encapsulating the BMSMB particles increases. Furthermore, the presence of a PEI precursor layer gives rise to less permeable PSS/PAH multilayers. The diffusion coefficients calculated for the DNA targets through the PEM capsules range from 10-19 to 10-18 m2 s-1. This investigation demonstrates that the MB approach to measuring permeability is an important new tool for the characterization of PEM capsules and is expected to be applicable for probing the permeability of other systems, such as membranes, liposomes, and emulsions.  相似文献   

5.
6.
The Layer-by-layer deposition of positively and negatively charged macromolecular species is an ideal method for constructing thin films incorporating biological molecules. We investigate the adsorption of fibronectin onto polyelectrolyte multilayer (PEM) films using optical waveguide lightmode spectroscopy (OWLS) and atomic force microscopy (AFM). PEM films are formed by adsorption onto Si(Ti)O2 from alternately introduced flowing solutions of anionic poly(sodium 4-styrenesulfonate) (PSS) and cationic poly(allylamine hydrochloride) (PAH). Using OWLS, we find the initial rate and overall extent offibronectin adsorption to be greatest on PEM films terminated with a PAH layer. The polarizability density of the adsorbed protein layer, as measured by its refractive index, is virtually identical on both PAH- and PSS-terminated films; the higher adsorbed density on the PAH-terminated film is due to an adsorbed layer of roughly twice the thickness. The binding of monoclonal antibodies specific to the protein's cell binding site is considerably enhanced to fibronectin adsorbed to the PSS layer, indicating a more accessible adsorbed layer. With increased salt concentration, we find thicker PEM films but considerably thinner adsorbed fibronectin layers, owing to increased electrostatic screening. Using AFM, we find adsorbed fibronectin layers to contain clusters; these are more numerous and symmetric on the PSS-terminated film. By considering the electrostatic binding of a segmental model fibronectin molecule, we propose a picture of fibronectin adsorbed primarily in an end-on-oriented monolayer on a PAH-terminated film and as clusters plus side-on-oriented isolated molecules onto a PSS-terminated film.  相似文献   

7.
We report the investigation of surface forces between polyelectrolyte multilayers of poly(allylamine hydrochloride) (PAH) and poly(styrenesulfonate sodium salt) (PSS) assembled on mica surfaces during film buildup using a surface force apparatus. Up to four polyelectrolyte layers were prepared on each surface ex situ, and the surface interactions were measured in 10(-4) M KBr solutions. The film thickness under high compressive loads (above 2000 microN/m) increased linearly with the number of deposited layers. In all cases, the interaction between identical surfaces at large separations (>100 A from contact) was dominated by electrostatic double-layer repulsion. By fitting DLVO theory to the experimental force curves, the apparent double-layer potential of the interacting surfaces was calculated. At shorter separations, an additional non-DLVO repulsion was present due to polyelectrolyte chains extending some distance from the surface into solution, thus generating an electrosteric type of repulsion. Forces between dissimilar multilayers (i.e., one of the multilayers terminated with PSS and the other with PAH) were attractive at large separations (30-400 A) owing to a combination of electrostatic attraction and polyelectrolyte bridging.  相似文献   

8.
We have used anionic and cationic single-wall carbon nanotube polyelectrolytes (SWNT-PEs), prepared by the noncovalent adsorption of ionic naphthalene or pyrene derivatives on nanotube sidewalls, for the layer-by-layer self-assembly to prepare multilayers from carbon nanotubes with polycations, such as poly(diallyldimethylammonium) or poly(allylamine hydrochloride) (PDADMA or PAH, respectively), and polyanions (poly(styrenesulfonate), PSS). This is a general and powerful technique for the fabrication of thin carbon nanotube films of arbitrary composition and architecture and allows also an easy preparation of all-SWNT (SWNT/SWNT) multilayers. The multilayers were characterized with vis-near-IR spectroscopy, X-ray photoelectron spectroscopy (XPS), surface plasmon resonance (SPR) measurements, atomic force microscopy (AFM), and imaging ellipsometry. The charge compensation in multilayers is mainly intrinsic, which shows the electrostatic nature of the self-assembly process. The multilayer growth is linear after the initial layers, and in SWNT/polyelectrolyte films it can be greatly accelerated by increasing the ionic strength in the SWNT solution. However, SWNT/SWNT multilayers are much more inert to the effect of added electrolyte. In SWNT/SWNT multilayers, the adsorption results in the deposition of 1-3 theoretical nanotube monolayers per adsorbed layer, whereas the nominal SWNT layer thickness is 2-3 times higher in SWNT/polyelectrolyte films prepared with added electrolyte. AFM images show that the multilayers contain a random network of nanotube bundles lying on the surface. Flexible polyelectrolytes (e.g., PDADMA, PSS) probably surround the nanotubes and bind them together. On macroscopic scale, the surface roughness of the multilayers depends on the components and increases with the film thickness.  相似文献   

9.
Highly hydrated polyelectrolyte multilayers (PEMs) were fabricated by “layer by layer” (LBL) assembly of poly (diallyl dimethyl ammonium chloride) (PDADMAC) and poly (sodium 4‐styrene sulfonate) (PSS) in 0.5 M NaCl. Both thickness and hydration of the film were determined in situ as the multilayer was assembled by means of the quartz crystal microbalance with dissipation (QCM‐D) and the Spectroscopic Ellipsometry techniques combined in a single device. For PEMs of 17 total layers in water, a final thickness of up to 300 nm and a hydration of 69% were measured. The response towards the ionic strength was then studied by means of QCM‐D. PEMs of 17 layers, with PDADMAC as last layer, shrunk dramatically and lost water when exposed to aqueous NaCl solutions of increasing concentration. Indeed, a thickness variation up to 100 nm and reduction in the 50% of the water content were observed when the PEM was exposed to 1 M NaCl. On the contrary, PEMs where PSS appears on top showed no measurable change upon the variation in the ionic strength. This brings the possibility to control the responsive character of the PEMs simply by selecting the last polyelectrolyte layer (PDADMAC or PSS) deposited. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011  相似文献   

10.
Interactions between surfaces bearing multilayer films of poly(allylamine hydrochloride) (PAH) and poly(styrenesulfonate sodium salt) (PSS) were investigated across a range of aqueous KBr solutions. Three layer films (PAH/PSS/PAH) were preassembled on mica surfaces, and the resulting interactions were measured with the interferometric surface force apparatus (SFA). Increasing the ionic strength of the medium resulted in a progressive swelling of the multilayer films. Interactions in solutions containing more than 10(-3) M KBr were dominated by a long-ranged steric repulsion originating from compression of polyelectrolyte segments extending into solution. In 10(-1) M KBr, repeated measurements at the same contact position showed a considerable reduction of the range and the strength of the steric force, indicating a flattening of the film during initial approach. Furthermore, this flattening was irreversible on the time scale of the experiments, and measurements performed up to 72 h after the initial compression showed no signs of relaxation. These studies aid in understanding the dominant interactions between polyelectrolyte multilayers, including polyelectrolyte films deposited on colloidal particles, which is important for the preparation of colloidally stable nanoengineered particles.  相似文献   

11.
The heme protein cytochrome c (Cyt-c), immobilized on polyelectrolyte multilayers on a silver electrode, was studied by stationary and time-resolved surface-enhanced resonance Raman (SERR) spectroscopy to probe the redox site structure and the mechanism and dynamics of the potential-dependent interfacial processes. The layers were built up by sequential adsorption of polycations (poly[ethylene imine] (PEI); polyallylamine hydrochloride (PAH)) and polyanions (poly[styrene sulfonate] (PSS)). All multilayers terminated by PSS electrostatically bind Cyt-c. On PEI/PSS coatings, Cyt-c is peripherally bound and fully redox-active. Due to the interfacial potential drop, the apparent redox potential is lowered by 40 mV compared to that in solution. The rate constant for the heterogeneous electron transfer (ET) of ca. 0.1 s(-1) is consistent with electron tunneling through largely ordered PEI/PSS layers. ET is coupled to a reversible conformational transition of Cyt-c that involves a change of the coordination pattern of the heme. Additional (PAH/PSS) double layers cause a broadening of the redox transition and a drastic negative shift of the redox potential, which is attributed to the formation of PSS/Cyt-c complexes. It is concluded that Cyt-c can effectively compete with PAH for binding of PSS, resulting in a rearrangement of the layered structure and a penetration of the PSS-bound Cyt-c into the PAH/PSS double layers. This conclusion is consistent with SERR intensity and quartz microbalance measurements. ET was found to be overpotential-independent and faster than that for PEI/PSS coatings, which is interpreted in terms of specific PSS/Cyt-c complexes serving as gates for the heterogeneous ET.  相似文献   

12.
The growth, morphology, and interaction/adhesion properties of supported poly(sodium 4-styrenesulfonate)/poly(allylamine hydrochloride) (PSS/PAH) and DNA/PAH multilayers were investigated by means of surface plasmon resonance spectroscopy, atomic force microscope (AFM) imaging, and AFM-related force measurements. Multilayers were assembled on a prelayer of poly(ethylenimine) (PEI) both with and without drying. SPR results showed a linear growth of the assembly in the case of PSS/PAH multilayers and nonlinear growth for DNA/PAH multilayers. Measurements of forces acting between a bare glass sphere and a multilayer-coated surface indicated repulsive or attractive forces, depending on surface charge, which suggests that, on approach, electrostatic forces dominate. On separation, we observed large pull-off forces in the case of positively charged multilayers and weak pull-off forces in the case negatively charged multilayers. Multiple adhesions and plateau regions observed on separation were interpreted in terms of a bridging of multiple polymer chains between the glass particle and the multilayer and a stretching of the polyelectrolyte loops. The dependence of the pull-off force on the number of deposited layers shows regular oscillations.  相似文献   

13.
We report the influence of polyelectrolyte (PE) multilayer films prepared from poly(styrene sulfonate)-poly(acrylic acid) (PSS-PAA) blends, deposited in alternation with poly(allylamine hydrochloride) (PAH), on film wettability and the adsorption behavior of the protein immunoglobulin G (IgG). Variations in the chemical composition of the PAH/(PSS-PAA) multilayer films, controlled by the PSS/PAA blend ratio in the dipping solutions, were used to systematically control film thickness, surface morphology, surface wettability, and IgG adsorption. Spectroscopic ellipsometry measurements indicate that increasing the PSS content in the blend solutions results in a systematic decrease in film thickness. Increasing the PSS content in the blend solutions also leads to a reduction in film surface roughness (as measured by atomic force microscopy), with a corresponding increase in surface hydrophobicity. Advancing contact angles (theta) range from 7 degrees for PAH/PAA films through to 53 degrees for PAH/PSS films. X-ray photoelectron spectroscopy measurements indicate that the increase in film hydrophobicity is due to an increase in PSS concentration at the film surface. In addition, the influence of added electrolyte in the PE solutions was investigated. Adsorption from PE solutions containing added salt favors PSS adsorption and results in more hydrophobic films. The amount of IgG adsorbed on the multilayer films systematically increased on films assembled from blends with increasing PSS content, suggesting strong interactions between PSS in the multilayer films and IgG. Hence, multilayer films prepared from blended PE solutions can be used to tune film thickness and composition, as well as wetting and protein adsorption characteristics.  相似文献   

14.
Deposition of layer-by-layer polyelectrolyte multilayer (PEM) films has been a widely applied surface modification technique to improve the biocompatibility of biomaterials. The objective of this study was to investigate the impact of the deposition of poly(allylamine hydrochloride) (PAH) and poly(acrylic acid) (PAA) multilayer films on adhesion, growth and differentiation of osteoblasts-like MG63 cells. PAH and PAA were deposited sequentially onto tissue culture polystyrene at either pH 2.0 or pH 6.5 with 4-21 layers. While the MG63 cells attached poorly on the PAH/PAA multilayer films deposited at pH 2.0, while the cells adhered to the PEM films deposited at pH 6.5, depending on layer numbers. Cell adhesion, proliferation and osteogenic activities (alkaline phosphatase activity, expression of osteogenic marker genes and mineralization) were highest on the 4-layer PAH/PAA film and decreased with increasing layer numbers. On the other hand, the behavior of MG63 cells did not show any difference on the adjacent even and odd layers, except PEM4 and PEM5, i.e. the surface charges of the PAH/PAA multilayer films with over ten layers seem indifferent to osteoblastic functions. The results in this study suggested that the mechanical properties of PEM films may play a critical role in modulating the behavior of osteoblasts, providing guidance for application of PEM films to osteopaedic implants.  相似文献   

15.
The sensing sensitivity of wavelength interrogated surface plasmon resonance(WISPR) biosensor is improved by self-assembly of polyelectrolyte multilayer(PEM) film of poly(allylamine hydrochloride)(PAH)/ poly(sodium-p-styrenesulfonate)(PSS) on the Au film coated glass chip via the layer-by-layer(LBL) technique. The home-made WISPR with Krestchmann configuration consists of a tungsten-halogen lamp as a photon source and a charge coupled device(CCD) camera as the detector. The influence of PEM film thickness on the optical properties of WISPR biosensors was investigated theoretically and experimentally. In order to achieve higher sensing sensitivity, the PEM film thickness has to be designed as ca.14 nm at an Au layer thickness of 50 nm and an incidental angle of 11.8°. Furthermore, the PEM coated WISPR biosensor can serve as highly sensitive biosensor, in which the biotin-streptavidin is used as bioconjugate pair. After deposition of the PEM film of (biotin/PAH)(PSS/PAH)3, the modified WISPR biosensor is more sensitive to the low concentration(〈0.01 mg/mL) of streptavidin. And the sensing sensitivity can be further increased by one order of magnitude compared with that of the biotin/PAH coated WISPR biosensor. Thus, such low-cost, high-performance and efficient PEM-coated WISPR biosensors have great potentials in a diverse array of fields such as medical diagnostics, drug screening, food safety analysis, environmental monitoring, and homeland security.  相似文献   

16.
The functionalization of an organic polyethersulfone membrane (PES) was performed by alternating deposition of poly(allylamine hydrochloride) (PAH) and poly(sodium 4-styrene sulfonate) (PSS), leading to the formation of a polyelectrolyte multilayer film (PEM). The resulting assembly was characterized by tangential streaming potential measurements to determine the charge of the modified membranes as a function of the polyelectrolyte solution concentration and as a function of the immersion time of the membrane in the polyelectrolyte solutions. Then, the modified membranes were used to perform the ultrafiltration of aqueous solutions containing copper(II) ions. Different operating conditions were tested including: polyelectrolyte concentration, polyelectrolyte nature, thickness of the PEM film or pH of the Cu(2+) solutions. These filtration experiments demonstrated that it was possible to obtain a satisfactory retention of the copper ions (88%), thus proving that this type of assembly can be useful for the removal of copper ions from contaminated aqueous solutions.  相似文献   

17.
We report the synthesis of poly(acrylic acid-ran-vinylbenzyl acrylate) (PAArVBA), a photo-cross-linkable weak polyelectrolyte, and its incorporation into polyelectrolyte multilayer (PEM) films. PEM films assembled from PAArVBA and poly(allylamine hydrochloride) (PAH) are found to exhibit similar thickness trends with assembly pH as those previously reported for poly(acrylic acid) (PAA)/PAH multilayers. Swelling properties of the as-built and photo-cross-linked films are studied by in situ ellipsometry. Two-dimensional masking techniques are used to pattern regions of high and low swelling, as confirmed by atomic force microscopy (AFM), and to provide spatial control over the low-pH-induced microporosity transition exhibited by PAH/PAA PEMs. Films containing alternating blocks of PAH/PAArVBA bilayers and PAH/PAA bilayers were assembled, laterally photopatterned, and exposed to low-pH solution to generate nanoporosity leading to patterned Bragg reflectors, thereby demonstrating three-dimensional control over film structure in these weak PEM assemblies.  相似文献   

18.
We report on the binding of metal ions (Me(2+); Co(2+) and Cu(2+)) with weak polyelectrolyte multilayers (PEMs), as well as on catalytic activity of PEM-Me(2+) films for oxidation of toluene. Using several types of PEM films constructed using branched polyethyleneimine (BPEI) or quaterinized poly-4-vinylpyridines (QPVPs) as polycations and poly(acrylic acid) (PAA) or poly(styrene sulfonate) (PSS) as polyanions, we found that binding of Co(2+) and Cu(2+) ions with a PEM matrix can occur both through coordination to polycationic amino groups and/or ionic binding to polyacid groups. The amount of metal ions loaded within the film increased linearly with film thickness and was strongly dependent on polyelectrolyte type, film assembly pH, and fraction of permanent charge in polymer chains. Among various PEM-Me(2+) systems, BPEI/PAA-Co(2+) films assembled at pH 8.5 show the best catalytic performance, probably because of the preservation of high mobility of Co(2+) ions coordinated to amino groups of BPEI in these films. With BPEI/PAA-Co(2+) films, we demonstrated that films were highly permeable to reagents and reaction products within hundreds of nanometers of the film bulk; i.e., film catalytic activity increased linearly with layer number up to 30 bilayers and slowed for thicker films.  相似文献   

19.
The effect of solvent conditions on the growth of polyelectrolyte (PE) multilayer films comprising poly(allylamine hydrochloride) (PAH) and poly(styrenesulfonate sodium salt) (PSS) on planar substrates was investigated by means of surface plasmon resonance spectroscopy (SPRS), quartz crystal microbalance (QCM), and atomic force microscopy techniques. The solvent quality was varied by the addition of ethanol to the PE solutions used for deposition of the layers, thus tuning the relative strength of electrostatic and secondary intermolecular and intramolecular interactions. Experiments were performed with PE solutions both without added electrolyte and containing 0.5 M NaCl. Decreasing the solvent quality (i.e., increasing the amount of ethanol in the adsorption solution) resulted in a marked increase of both the multilayer film thickness and mass loading, as determined from the SPRS spectra and QCM frequency shifts, respectively. With the solution composition approaching the precipitation point, thick PAH/PSS films were formed due to the screening of the electrostatic intra- and interchain repulsions and enhanced hydrophobic interactions between the polyelectrolyte chains. However, the films formed from water/ethanol mixtures remained stable upon subsequent exposure to water or salt-containing solutions: no significant film desorption occurred after up to 24 h of exposure to water or 0.5 M NaCl solutions. In addition, the effect of postdeposition exposure to water/ethanol mixtures was investigated for PE multilayers assembled from aqueous solutions. In this case, the optical thickness of the films was determined during exposure to water/ethanol mixtures, and instead of swelling, the polyelectrolyte films collapse to the surface as a result of the unfavorable segment-solvent interactions.  相似文献   

20.
Multilayer films were assembled from a copolymer containing both weakly and strongly charged pendant groups, poly(4-styrenesulfonic acid-co-maleic acid) (PSSMA), deposited in alternation with poly(allylamine hydrochloride) (PAH). The strongly charged groups (styrene sulfonate, SS) are expected to form electrostatic linkages (to enhance film stability), while the weakly charged groups (maleic acid, MA) can alter multilayer film properties because they are responsive to external pH changes. In this study, we varied several assembly conditions such as pH, SS/MA ratio in PSSMA, and the ionic strength of the polyelectrolyte solutions. The multilayer films were also treated by immersion into pH 2 and 11 solutions after assembly. Quartz crystal microgravimetry and UV-visible spectrophotometry showed that the thickness of PSSMA/PAH multilayers decreases with increasing assembly pH regardless of whether salt was present in the polyelectrolyte solutions. When no salt was added, the multilayers are thinner, smoother, and grow less regularly. Atomic force microscopy images indicate that the presence of salt in polyelectrolyte solutions results in rougher surface morphologies, and this effect is especially significant in multilayers assembled at pH 2 and pH 11. When both polyelectrolytes are adsorbed at conditions where they are highly charged, salt was necessary to promote regular multilayer growth. Fourier transform infrared spectroscopy studies show that the carboxylic acids in the multilayers are essentially ionized when assembled from different pHs in 0.5 M sodium chloride solutions, whereas some carboxylic acids remain protonated in the multilayers assembled from solutions with no added salt. This resulted in different pH stability regimes when the multilayers were exposed to different pH solutions, post assembly.  相似文献   

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