Layer-by-layer assembled polyelectrolyte multilayer films of poly(acrylic acid) (PAA)/poly(allylamine hydrochloride) (PAH) have been successfully patterned by room-temperature imprinting using a Norland Optical Adhesives (NOA 63) polymer mold. The proper amount of water in the PAA/PAH multilayer film can decrease the viscosity of the film and facilitate the imprinting. Many factors, such as imprinting pressure, length of imprinting time, and the structure and size of the patterns in the polymer mold, can produce an influence on the final imprinted pattern structures on multilayer films. A high imprinting pressure of 100 bar and elongated imprinting time of several hours is needed to achieve a patterned PAA/PAH multilayer film with a feature size of several tens of micrometers. With a twice imprinting, grid structures can be successfully produced when a NOA 63 mold having line structures is used. Room-temperature imprinting by using polymer NOA 63 mold provides a facile way to fabricate layered polymeric films with various kinds of pattern structures. 相似文献
Summary: Polyelectrolyte multilayer films of poly(acrylic acid) (PAA)/poly(allylamine hydrochloride) (PAH) and PAH/poly(sodium 4‐styrenesulfonate) (PSS) based on electrostatic interactions as a driving force are patterned by room‐temperature nanoimprint lithography (RT‐NIL). Under an imprinting pressure of 40 bar for 8 min, well‐defined pattern structures with a line width of ≈330 nm and a separation of ≈413 nm are achieved. Meanwhile, hydrogen‐bonding‐directed multilayer films of poly(vinyl pyrrolidone) (PVPON)/poly(methyl acrylic acid) (PMAA) and poly(4‐vinylpyridine)/PAA can also be patterned in a similar way by RT‐NIL. The successful imprinting of these films originates from the high compressibility and fluidity of the layered polymeric films under high pressure.
SEM image of an imprinted (PAH/PAA)*20 film on silicon wafer. 相似文献
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
Polyelectrolyte multilayer (PEM) films have been recently applied to surface modification of biomaterials. Cellular interactions with PEM films consisted of weak polyelectrolytes are greatly affected by the conditions of polyelectrolyte deposition, such as pH of polyelectrolyte solution. Previous studies indicated that the adhesion of several types of mammalian cells to PAH/PAA multilayer films was hindered by low pH and high layer numbers. The objective of this study is to evaluate whether the hemocompatibility of polysulfone can be modulated by deposition of poly(allylamine hydrochloride) (PAH)/poly(acrylic acid) (PAA) multilayer films. PAH/PAA multilayer films with different layer numbers were assembled onto polysulfone at either pH 2.0 or pH 6.5. The number of platelet adhesion and the morphology of adherent platelets were determined to evaluate hemocompatibility of modified substrates. Compared to non-treat polysulfone, the PEM films developed at pH 2.0 decreased platelet adhesion, while those built at pH 6.5 enhanced platelet deposition. Platelet adhesion was found positively correlated to polyclonal antibodies binding to surface-bound fibrinogen. The extent of platelet spreading was increased with layer numbers of PEM films, suggesting that the adherent platelets on thick PEM films were prone to activation. In conclusion, PAH/PAA films with few layers developed at pH 2.0 possessed better hemocompatibility compared to other substrates. 相似文献
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
Superhydrophobic films mainly based on poly(allylamine hydrochloride) (PAH) and poly(acrylic acid) (PAA) polyelectrolyte multilayer have been deposited onto cleaned glass substrate by a layer-by-layer dip coating method. 3 bilayers of the PAH and PAA was directly coated onto the substrate as an underlying layer for subsequent coating. Desired surface roughness on the polyelectrolyte bilayers was created by etching the bilayers in hydrochloric acid solution so as to create the open pore having suitable size at the surface. Then, nanoparticles such as SiO2 and TiO2 of various sizes were deposited onto the etched polyelectrolyte bilayers. Finally, the surfaces were further modified with semifluorinated silane followed by cross-linking at 180 °C for 2 h to obtain desirable surface morphological features. The effect of etching time and addition of nanoparticles on surface morphology was investigated using an atomic force microscope (AFM). Wetting ability of the prepared film was determined by measuring water droplet contact angle using a goniometer. Adhesion between the superhydrophobic films and the substrate was evaluated by using a standard tape test method (D3359). The adhesion was improved by reducing the organic content in the films. 相似文献
Polyelectrolyte multilayer films were successfully assembled from each of the three charged derivatives of chitosan; N-[(2-hydroxyl-3-trimethylammonium)propyl]chitosan chloride (HTACC), N-succinyl chitosan (SCC) and N-sulfofurfuryl chitosan (SFC), paired with one of the two oppositely charged polyelectrolytes, poly(acrylic acid) (PAA) and poly(allylamine hydrochloride) (PAH) on surface-treated poly(ethylene terephthalate) (treated PET) substrates by alternate layer-by-layer adsorption. Surface coverage and wettability of the multilayer films were determined by AFM and water contact angle measurements, respectively. Analysis by quartz crystal balance with dissipation (QCM-D) has suggested that all multilayer films are relatively rigid and have a high water content associated within their structures, accounting for up to 85-90% (w/w) for films having 7-10 layers. In vitro cytocompatibility tests for the fibroblast-like L929 cell line revealed a slight dependency for cell adhesion and proliferation on the outermost layer. The multilayer film containing HTACC exhibited moderate antibacterial activity against E. coli and S. aureus. Bearing negative charges, the multilayer films terminating with SFC and having at least 10 layers were capable of suppressing the adsorption of plasma proteins and platelet adhesion at a comparable level to the multilayer film assembled from heparin, a well-known antithrombogenic polymer. 相似文献
We report on the influence of polyanion molecular weight on the growth and structure of multilayered thin films fabricated from poly(allylamine) (PAH) and well-defined, end-labeled poly(acrylic acid) (PAA) synthesized by atom transfer radical polymerization. We observed striking differences in the growth of PAH/PAA films fabricated using well-defined PAA compared to films fabricated using higher molecular weight, commercially available PAA. Past studies demonstrate that the thicknesses of PAH/PAA films increase as linear functions of the number of PAH and PAA layers deposited over a broad range of pH (e.g., from pH 2.5 to 4.5). We observed the thicknesses of films fabricated using solutions of PAH and PAA adjusted to pH 7.5 and 3.5, respectively, to increase in a nonlinear manner. Films fabricated using well-defined, low molecular weight samples of PAA under these conditions increased in thickness exponentially. Experiments using samples of PAA having substantially non-overlapping molecular weight distributions demonstrated a clear relationship between the molecular weight of PAA and rates of film growth. We also used confocal microscopy, in combination with fluorescently end-labeled samples of PAA, to characterize the location of PAA in these assemblies. The results of these experiments, when combined, support the general conclusion that PAA is able to penetrate or diffuse into these films over large distances during assembly. The mechanism of growth for these films thus appears similar to that recently reported for the exponential growth of films fabricated using a variety of biologically relevant polyelectrolytes. The use of living/controlled methods of polymerization to synthesize well-defined samples of PAA facilitates an interpretation of these differences in film behavior as arising largely from differences in polymer molecular weight and polydispersity. This work provides insight into the assembly and structure of a well-studied weak polyelectrolyte film system and illustrates the potential of living/controlled methods of polymerization to contribute to the characterization and understanding of the physical properties of these ionically cross-linked materials. 相似文献
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
This article describes the buildup of hydrogen bonded multilayer film of poly(2-vinylpyridine) (P2VP) and poly(acrylic acid) (PAA), and the influence of polymer molecular weight on the formation of microporous film by post-base treatment. The formation of a microporous film involved a two-step mechanism: the release of PAA from P2VP/PAA multilayer, and the reorganization of the remaining P2VP on the substrate. Fourier transform infrared spectroscopy (FT-IR) indicated that the release of PAA from hydrogen bonded multilayer was a rapid process, which was almost independent of the molecular weight of PAA. Furthermore, the molecular weight of P2VP had a great effect on micropore formation by immersing the P2VP/PAA multilayer in basic solution. The rate of micropore formation increased with increasing molecular weight. We anticipate that a comparative study on P2VP/PAA films containing high or low molecular weight polymer provides a way to control the surface morphology, and will be helpful and constructive for the forthcoming discussion about the formation of the microporous film. 相似文献
Porous thin films with memory for imprinted metals have been prepared by casting water-THF mixed solutions of a poly(vinyl chloride-co-acylic acid) / poly(propylene glycol) blend. When Cu2+ and Pb2+ ions are imprinted in the cast process, the films retain a memory for the original Cu2+ and Pb2+ ions. The imprinting processes can be thoroughly monitored by FT-IR spectroscopy. 相似文献
In this article we report the introduction of the cooperativity of various specific interactions combined with photo-cross-linking of the interlayers to yield binding sites that can realize better selectivity and imprinting efficiency of a surface molecularly imprinted LbL film (SMILbL), thus providing a new approach toward fabrication of nanostructured molecularly imprinted thin films. It involves preassembly of poly(acrylic acid) (PAA) conjugated of the theophylline residue template via a disulfide bridge, denoted as PAAtheo 15, in solution, and layer-by-layer (LbL) assembly of PAAtheo 15 and a positively charged photoreactive diazo resin (DAR) to form multilayer thin film with designed architecture. After photo-cross-linking of the film and template removal, binding sites specific to 7-(beta-hydroxyethyl)theophylline (Theo-ol) molecules are introduced within the film. Binding assay demonstrates that the SMILbL has a high selectivity of SMILbL to Theo-ol over caffeine. A control experiment demonstrates that the selectivity of SMILbL derives from nanostructured recognition sites among the layers. The imprinting amount per unit mass of the film can be 1 order of magnitude larger than that of the conventional bulk molecular imprinting systems. As this concept of construction SMILbL can be easily extended to the other molecules by the following similar protocol: its applications in building many other different molecular recognition systems are greatly anticipated. 相似文献
Polyelectrolyte multilayer thin films were prepared via the alternate deposition of poly(allylamine hydrochloride) (PAH) and a blend of poly(acrylic acid) (PAA) and poly(styrenesulfonate) (PSS). When the pH of the blend solution was 3.5, the presence of PAA in this solution significantly increased the total film thickness. With only 10 wt % PAA in the blend adsorption solution, a large increase in film thickness was observed (92 nm cf. 18 nm). It was also demonstrated that the total amount of PSS adsorbed was enhanced by the presence of PAA in the blend solution, showing that the blend solution composition influenced that of the multilayer films. Thin films prepared with nanoblended layers also showed improved pH stability, because they exhibited reduced film rearrangement upon exposure to acidic conditions (pH = 2.5). 相似文献
We report the use of copolymers synthesized with specific block ratios of weakly and strongly charged groups for the preparation of stable, pH-responsive multilayers. In this study, we utilized reversible addition-fragmentation chain transfer (RAFT) polymerization in the synthesis of novel pH-sensitive copolymers comprising block domains of acrylic acid (AA) and styrene sulfonate (SS) groups. The PAA x- b-SS y copolymers, containing 37%, 55%, and 73% of AA groups by mass (denoted as PAA 37- b-SS 63, PAA 55- b-SS 45, and PAA 73- b-SS 27, respectively), were utilized to perform stepwise multilayer assembly in alternation with poly(allylamine hydrochloride), PAH. The ratio of AA to SS groups, and the effect of the pH of both anionic and cationic adsorption solutions, on multilayer properties, were investigated using ellipsometry and atomic force microscopy. The presence of SS moieties in the PAA x- b-SS y copolymers, regardless of the precise composition, lead to films with a relatively consistent thickness. Exposure of these multilayers to acidic conditions postassembly revealed that these multilayers do not exhibit the characteristic large swelling that occurs with PAA/PAH films. The film stability was attributed to the presence of strongly charged SS groups. PAA x- b-SS y/PAH films were also formed on particle substrates under various adsorption conditions. Microelectrophoresis measurements revealed that the surface charge and isoelectric point of these core-shell particles are dependent on assembly pH and the proportion of AA groups in PAA x- b-SS y. These core-shell particles can be used as precursors to hollow capsules that incorporate weak polyelectrolyte functionality. The role of AA groups in determining the growth profile of these capsules was also examined. The multilayer films prepared may find applications in areas where pH-responsive films are required but large film swelling is unfavorable. 相似文献
Polyelectrolyte multilayer thin films were prepared by an alternate deposition of poly(allylamine hydrochloride) (PAH) and anionic polysaccharides {carboxymethylcellulose (CMC) and alginic acid (AGA)} on the surface of a gold (Au) disk electrode, and the binding of ferricyanide [Fe(CN)(6)](3)(-) and hexaammine ruthenium ions [Ru(NH(3))(6)](3+) to the films was evaluated. Poly(acrylic acid) (PAA) was also employed as a reference polyanion bearing carboxylate side chains. A quartz-crystal microbalance study showed that PAH-CMC and PAH-AGA multilayer films grow exponentially as the number of depositions increases. The thicknesses of five bilayers of (PAH-CMC)(5) and (PAH-AGA)(5) films were estimated to be 150 +/- 20 and 90 +/- 15 nm, respectively, in the dry state. The PAH/polysaccharide multilayer film-coated Au electrodes exhibited a redox response to the [Fe(CN)(6)](3)(-) ion dissolved in solution, irrespective of the sign of the surface charge of the film, suggesting the high permeability of the films to the [Fe(CN)(6)](3)(-) ion. In contrast, the PAH-PAA film-coated Au electrodes exhibited a redox response only when the outermost surface of the film was covered with a positively charged PAH layer. However, the permeation of the [Ru(NH(3))(6)](3+) cation was severely suppressed for all of the multilayer films. It was possible to confine the [Fe(CN)(6)](3)(-) ion in the films by immersing the film-coated electrodes in a 1 mM [Fe(CN)(6)](3)(-) solution for 15 min. Thus, the [Fe(CN)(6)](3)(-)-confined electrodes exhibited a cyclic voltammetric response in the [Fe(CN)(6)](3)(-) ion-free buffer solution. The loading of the [Fe(CN)(6)](3)(-) ion in the films was higher when the surface charge of the film was positive and increased with increasing film thickness. It was also found that the [Fe(CN)(6)](3)(-) ion confined in the films serves as an electrocatalyst that oxidizes ascorbic acid in solution. 相似文献
The layer-by-layer (LbL) assembly of salt-containing nonstoichiometric polyelectrolyte complexes (PECs) with oppositely charged uncomplexed polyelectrolyte for the fabrication of dewetting-induced porous polymeric films has been systematically investigated. Salt-containing poly(allylamine hydrochloride) (PAH) and poly(acrylic acid) (PAA) complexes (noted as PAH-PAA) with a molar excess of PAH were LbL assembled with polyanion poly(sodium 4-styrenesulfonate) (PSS) to produce PSS/PAH-PAA films. The structure of the PAH-PAA complexes is dependent on the concentration of NaCl added to their aqueous dispersions, which can be used to tailor the structure of the LbL-assembled PSS/PAH-PAA films. Porous PSS/PAH-PAA films are fabricated when salt-containing PAH-PAA complexes with a large amount of added NaCl are used for LbL assembly with PSS. In-situ and ex-situ atomic force microscopy measurements disclose that the dewetting process composed of pore nucleation and pore growth steps leads to the formation of pores in the LbL-assembled PSS/PAH-PAA films. The present study provides a facile way to fabricate porous polymeric films by dewetting LbL-assembled polymeric films comprising salt-containing PECs. 相似文献
We report characterization of pH-dependent behavior in polyelectrolyte multilayers (PEMs) fabricated from poly(allylamine) (PAH) and low molecular weight poly(acrylic acid) (PAA) synthesized by living/controlled polymerization. Exposure of these films to solutions of low pH (e.g. pH 2.0-3.2) resulted in transformations from films that were smooth and uniform to films with porous morphologies, as characterized by scanning electron microscopy (SEM). We observed large differences in both the extent of this transformation and the sizes of the pores that resulted compared to films fabricated using higher molecular weight PAA used in past studies. Whereas transformations reported in past studies generally lead to pores with sizes in the range of 0.3-2 μm, we observed larger-scale transformations and films with cell-like internal structures comprised of networks of closed pores, interconnected pores, and through-pores with sizes as large as 10-15 μm depending on pH and the manner in which the films were incubated. Films fabricated using fluorescently end-labeled samples of PAA permitted real-time imaging of changes in internal structure using confocal microscopy (LSCM). The results of these studies also revealed large differences in the nature of these transformations when films were placed in contact with surfaces as opposed to when dipped into aqueous solutions. Our results reveal approaches that can be used to fabricate films with large pores (e.g., pores with sizes on the order of 10-15 μm) and suggest methods that could potentially be used to generate PEMs having controlled gradients in pore size. 相似文献
Ultrathin multilayer films of two lanthanide polyoxometalates (LPOMs), K(17)[Eu(P(2)W(17)O(61))(2)] (EPW) and K(13)[Eu(SiW(11)O(39))(2)] (ESW), and poly(allylamine hydrochloride) (PAH) have been prepared by layer-by-layer self-assembly from dilute aqueous solutions. UV-vis spectroscopy and ellipsometry respectively show that the absorbance values at characteristic wavelengths and the thicknesses of the multilayer films increase linearly with the number of LPOM/PAH bilayers, suggesting that the deposition process is linear and highly reproducible from layer to layer. Average thicknesses of ca. 3.4 and 2.4 nm were determined for the EPW/PAH and ESW/PAH bilayers by ellipsometry, respectively. In addition, scanning electron microscopy (SEM) and atomic force microscopy (AFM) images provide the surface morphology of the LPOM/PAH films, indicating that the film surface is relatively uniform and smooth. The photoluminescent properties of these films have also been investigated by fluorescence spectroscopy. The LPOM/PAH multilayer film has a good thermal stability as shown by UV-vis, X-ray photoelectron, and fluorescence spectra. 相似文献
A new patterning approach using polymer-on-polymer stamping (POPS) has been developed to fabricate polymer-colloid templates for controlling selective cell attachment. In this paper, a polyamine surface patterned onto a poly(acrylic acid)/poly(allylamine hydrochloride) (PAA/PAH) cell resistant multilayer platform serves as a template for the deposition of close- or loose-packed colloidal particles. Peptides containing the RGD adhesion sequence were used to modify the PAH/colloid surface for specific cell attachment. Cell behavior was studied by varying colloidal packing array density, pattern geometry, and surface chemistry. It was found that loose-packed RGD-modified colloidal arrays enhance cell adhesion, as observed through the development of focal adhesion contacts and orientation of actin stress fibers, but close-packed colloidal arrays induce a rounded and nonadhesive cell morphology and yield a smaller number of attached cells. On loose-packed arrays, cells adjust their shapes to the pattern geometry when the stripe width is smaller than 50 microm and increase their extent of attachment when the concentration of surface RGD peptides is increased. This new biomaterials system allows the examination of cell behavior as a function of RGD surface distribution on the molecular to micrometer scale and reveals cellular response to different surface roughnesses. 相似文献