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1.
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   

2.
The fabrication of smart films with reversible wettability enabled by the stimulus-induced morphology changes has attracted growing interest but remains a challenge. Here we report a smart film that can reversibly changes its wettability between transparent hydrophobicity to translucent superhydrophobicity through the humidity-induced wrinkling/de-wrinkling process. The film was fabricated by depositing hydrophobic SiO2 nanoparticles (NPs) on poly(acrylic acid) (PAA)/poly(allylamine hydrochloride) (PAH) films, followed by partially exfoliating the films from the underlying substrates. The partially exfoliated PAA/PAH film can reversibly wrinkle and de-wrinkle when being alternately subjected to humid and dry environments. The deposition of hydrophobic SiO2 NPs on the wrinkling PAA/PAH film does not hinder the humidity-enabled wrin-kling/de-wrinkling ability of the composite film. The hydrophobic SiO2 NPs and the underlying humidity-wrinkling PAA/PAH film enable the composite film to spontaneously change from hydrophobic and transparent to superhydrophobic and translucent with the rise of environmental humidity.  相似文献   

3.
Liquid cell atomic force microscopy (LC-AFM) is used to image self-assembled polyelectrolyte films eliminating any drying effects on the film structure. Weak/weak and strong/weak polyelectrolyte films are formed by the alternated deposition of poly(acrylic acid) [PAA]/poly(allylamine hydrochloride) [PAH], and poly(sodium 4-styrene sulfonate) [PSS]/PAH, respectively, forming a granular surface structure. Number and area of grains (GN, GA) are used to characterize the surface of these films during their build up process. We show that hydrophilic PAA increases GA and decreases GN, while these parameters follow an opposite behavior with PSS. In both cases, GA and GN always have a simple inverse relationship, and then grain surface coverage (GS=GNGA) is nearly constant and independent of polyelectrolyte nature and the substrates used here, but also in the published data as well. The drying of the weak/weak film was also imaged after natural and forced solvent evaporation, and the surface structure is strongly affected, although the GS values keep roughly the same value found for wet films. The set of these results indicates that GS may be considered as a constant parameter during the build-up for the self-nascent assembled polyelectrolytes. The granular structure is still maintained after glucose oxidase adsorption on these films with comparable GS values.  相似文献   

4.
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   

5.
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   

6.
Janus magnetic nanoparticles (~20 nm) were prepared by grafting either polystyrene sodium sulfonate (PSSNa) or polydimethylamino ethylmethacrylate (PDMAEMA) to the exposed surfaces of negatively charged poly(acrylic acid) (PAA)-coated magnetite nanoparticles adsorbed onto positively charged silica beads. Individually dispersed Janus nanoparticles were obtained by repulsion from the beads on reversal of the silica surface charge when the solution pH was increased. Controlled aggregation of the Janus nanoparticles was observed at low pH values, with the formation of stable clusters of approximately 2-4 times the initial size of the particles. Cluster formation was reversed, and individually dispersed nanoparticles recovered, by restoring the pH to high values. At intermediate pH values, PSSNa Janus nanoparticles showed moderate clustering, while PDMAEMA Janus nanoparticles aggregated uncontrollably due to dipolar interactions. The size of the stable clusters could be controlled by increasing the molecular weight of the grafted polymer, or by decreasing the magnetic nanoparticle surface availability for grafting, both of which yielded larger cluster sizes. The addition of small amounts of PAA-coated magnetic nanoparticles to the Janus nanoparticle suspension resulted in a further increase in the final cluster size. Monte Carlo simulation results compared favorably with experimental observations and showed the formation of small, elongated clusters similar in structure to those observed in cryo-TEM images.  相似文献   

7.
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   

8.
Abstract

Electrostatically layered aluminosilicate nanocomposites have been prepared by the sequential deposition of poly(allylamine hydrochloride)/poly(acrylic acid)/poly(allylamine hydrochloride)/saponite (PAH/PAA/PAH/saponite)10 on poly(ethylene terephtalate) (PET) film. Exfoliated saponite nanoplatelets were obtained by extensive shaking, sonication, and centrifugation of a water suspension. To minimize permeability and improve the mechanical integrity, cross‐linking of composite films was carried out at different temperatures. The formation of amide linkage induced through heating was observed by Fourier Transform Infrared (FT‐IR) and x‐ray photoelectron spectroscopy (XPS). The cross‐linking of nanocomposites (PAH/PAA/PAH/saponite)10 showed 60% decrease in permeability of oxygen when compared with the pristine PET substrate film. In contrast, water permeability of the nanocomposite membrane was not affected by heating temperature and deposition cycles.  相似文献   

9.
The model catalysts of ZrO(2)-supported Au nanoparticles have been prepared by deposition of Au atoms onto the surfaces of thin ZrO(2) films with different morphologies. The adsorption and thermal stability of Au nanoparticles on thin ZrO(2) films have been investigated using synchrotron radiation photoemission spectroscopy (SRPES) and X-ray photoelectron spectroscopy (XPS). The thin ZrO(2) films were prepared by two different methods, giving rise to different morphologies. The first method utilized wet chemical impregnation to synthesize the thin ZrO(2) film through the procedure of first spin-coating a zirconium ethoxide (Zr(OC(2)H(5))(4)) precursor onto a SiO(2)/Si(100) substrate at room temperature followed by calcination at 773 K for 12 h. Scanning electron microscopy (SEM) investigations indicate that highly porous "sponge-like nanostructures" were obtained in this case. The second method was epitaxial growth of a ZrO(2)(111) film through vacuum evaporation of Zr metal onto Pt(111) in 1 × 10(-6) Torr of oxygen at 550 K followed by annealing at 1000 K. The structural analysis with low energy electron diffraction (LEED) of this film exhibits good long-range ordering. It has been found that Au forms smaller particles on the porous ZrO(2) film as compared to those on the ordered ZrO(2)(111) film at a given coverage. Thermal annealing experiments demonstrate that Au particles are more thermally stable on the porous ZrO(2) surface than on the ZrO(2)(111) surface, although on both surfaces, Au particles experience significant sintering at elevated temperatures. In addition, by annealing the surfaces to 1100 K, Au particles desorb completely from ZrO(2)(111) but not from porous ZrO(2). The enhanced thermal stability for Au on porous ZrO(2) can be attributed to the stronger interaction of the adsorbed Au with the defects and the hindered migration or coalescence resulting from the porous structures.  相似文献   

10.
For the first time to the knowledge of the authors, well-defined and stable lignin model surfaces have been utilized as substrates in polyelectrolyte adsorption studies. The adsorption of polyallylamine (PAH), poly(acrylic acid) (PAA), and polyelectrolyte complexes (PECs) was monitored using quartz crystal microgravimetry with dissipation (QCM-D). The PECs were prepared by mixing PAH and PAA at different ratios and sequences, creating both cationic and anionic PECs with different charge levels. The adsorption experiments were performed in 1 and 10 mM sodium chloride solutions at pH 5 and 7.5. The highest adsorption of PAH and cationic PECs was found at pH 7.5, where the slightly negatively charged nature of the lignin substrate is more pronounced, governing electrostatic attraction of oppositely charged polymeric substances. An increase in the adsorption was further found when the electrolyte concentration was increased. In comparison, both PAA and the anionic PEC showed remarkably high adsorption to the lignin model film. The adsorption of PAA was further studied on silica and was found to be relatively low even at high electrolyte concentrations. This indicated that the high PAA adsorption on the lignin films was not induced by a decreased solubility of the anionic polyelectrolyte. The high levels of adsorption on lignin model surfaces found both for PAA and the anionic PAA-PAH polyelectrolyte complex points to the presence of strong nonionic interactions in these systems.  相似文献   

11.
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   

12.
利用含氟疏水基团的梯度分布,结合草莓形纳米SiO2粒子提供的双重粗糙表面,制备了具有类"荷叶效应"的超疏水涂膜,水接触角达(174.2±2)°,滞后角几乎接近0°.通过原子力显微镜、扫描电镜和水接触角的测试对膜表面形貌及疏水性能进行了表征;探讨了其表面微观结构与表面疏水性能的关系.草莓形复合粒子在膜表面的无规则排列赋予涂膜表面不同等级的粗糙度,使水滴与涂膜表面接触时能够形成高的空气捕捉率,这种微观结构与疏水基团的梯度分布相结合,赋予了含氟硅丙烯酸酯乳液涂膜表面超疏水性能.  相似文献   

13.
A new copolymer (PAA-PEG2000) has been designed, consisting of a negatively charged poly(acrylic acid) (PAA) backbone to which poly(ethylene glycol) (PEG) side chains with a molecular weight of about 2 kDa were grafted in a molecular ratio of 3:10. It readily adsorbs to positively charged surfaces and may be considered to be the anionic counterpart of PEG-grafted poly(l-lysine) (PLL-PEG), which was first described by Kenausis et al. and is widely used to render negatively charged surfaces protein-resistant. The synthesis of PAA-PEG2000 can be carried out in aqueous solution at room temperature and does not require any sophisticated techniques such as handling in an inert gas atmosphere. Using ellipsometry and infrared reflection absorption spectroscopy (IRRAS), the film structure has been carefully analyzed for copolymer adsorption onto three different positively charged surfaces, namely, thin layers of poly(allylamine) (PAH), poly(ethyleneimine) (PEI) and (3-aminopropyl)triethoxysilane (APTES). Besides the film thickness, the conformation of the PEG chains and their orientation with respect to the surface normal appear to be important parameters for the protein resistance of the films. Although PAA-PEG2000 adsorbed to PAH and PEI renders the surfaces inert, only partial protein resistance has been observed if the copolymer is deposited on APTES. In a model application, we have generated heterogeneous surfaces composed of isolated small Au nanoparticles (AuNP's) embedded in a protein-resistant layer of PAA-PEG2000 and demonstrated that the AuNP's can serve as adsorption sites for single protein species. In the future, these nanopatterned surfaces may be used for the investigation of isolated proteins.  相似文献   

14.
A stable inorganic-organic hybrid multilayer film with homogeneous and dense inorganic nanoparticle deposition was constructed by coating ZrO2 nanoparticles with poly(4-sodium styrenesulfonate) (PSS) and irradiating multilayer film assembled from PSS-coated ZrO2 nanoparticles and a diazo-resin (DR).  相似文献   

15.
Polyelectrolyte multilayers (PEMs) formed at interfaces between aqueous solutions and thermotropic (water-immiscible) liquid crystals (LCs) offer the basis of a new method to tailor the nanometer-scale structure and chemical functionality of these interfaces. Toward this end, we report a study that compares the growth of PEMs formed at mobile and deformable interfaces defined by LCs relative to growth observed at model (rigid) solid surfaces. Experiments aimed at determining if polyelectrolytes such as poly(sodium-4-styrenesulfonate) (PSS) can partition from the aqueous phase into the bulk of the LC yielded no evidence of such partitioning. Whereas measurements of the growth of PEMs formed from poly(allylamine hydrochloride) (PAH) and PSS at the aqueous-LC interface revealed growth characteristics similar to those measured at both hydrophobic and hydrophilic interfaces of solids, the growth of PEMs from PAH and poly(acrylic acid) (PAA) at the aqueous-LC interface was found to differ substantially from the solids investigated: (i) the linear growth of PEMs of PAH/PAA that was measured at the aqueous-LC interface under conditions that did not lead to the growth of PEMs at the interface of octadecyltrichlorosilane (OTS)-treated glass (a hydrophobic solid surface), and (ii) in comparison to the growth of PEMs of PAH/PAA at the surface of glass (a hydrophilic charged surface), a higher rate of growth was observed at the aqueous-LC interface. The finding that the growth rate of PEMs of PAH/PAA at aqueous-LC interfaces is greater than on solid surfaces is supported by additional measurements of growth as a function of pH. Finally, the pH-triggered reorganization of PAH/PAA PEMs supported at the aqueous-LC interface led to changes in the order and optical properties of the LC. These data are discussed in light of the nature of aqueous-LC interfaces, including the mobility and deformability of the interface and recent measurements of the zeta-potentials of aqueous-LC interfaces.  相似文献   

16.
Multilayer thin films were constructed on polystyrene colloidal particles by depositing alternating layers of poly(allylamine hydrochloride) (PAH) at pH 7.5 and varying composition blends of poly(acrylic acid) (PAA) and poly(styrenesulfonate) (PSS) at pH 3.5. Following the deposition of each layer, microelectrophoresis experiments showed alternating zeta-potentials, suggesting the formation of multilayered films on the particles. Scanning and transmission electron microscopy were used to examine the surface morphology of the colloidal particles, with homogeneous surface coatings apparent for films deposited from PAA/PSS blend solutions containing up to 90 wt % PAA. The colloidal stability of these particles is greater than those coated with individual PAH and PAA layers. In the case of the blend PAA/PSS = 25:75 wt %, up to 20 layers were assembled without compromising the colloidal stability of the dispersion. The results demonstrate that the deposition of layers from PE blend solutions containing a strong and weak PE can be used as a facile method for controlling the surface properties and hence the colloidal stability of core-shell particles, as well as the thickness and morphology of the coatings. Control of these parameters is important for subsequent processing and application of these particles in controlled delivery, photonics, catalytic, and separation applications.  相似文献   

17.
Layer-by-layer (LBL) polyelectrolyte films were constructed from poly(L-glutamic acid) (PGA) and poly(L-aspartic acid) (PAA) as polyanions, and from poly(L-lysine) (PLL) as the polycation. The terminating layer of the films was always PLL. According to attenuated total reflection Fourier transform infrared measurements, the PGA/PLL and PAA/PLL films, despite their chemical similarity, had largely different secondary structures. Extended beta-sheets dominated the PGA/PLL films, while alpha-helices and intramolecular beta-sheets dominated the PAA/PLL films. The secondary structure of the polyelectrolyte film affected the adsorption of human serum albumin (HSA) as well. HSA preserved its native secondary structure on the PGA/PLL film, but it became largely deformed on PAA/PLL films. Both PGA and PAA were able to extrude to a certain extent the other polyanion from the films, but the structural consequences were different. Adding PAA to a (PGA/PLL)5-PGA film resulted in a simple exchange and incorporation: PGA/PLL and PAA/PLL complexes coexisted with their unaltered secondary structures in the mixed film. The incorporation of PGA into a (PAA/PLL)5-PAA film was up to 50% and caused additional beta-structure increase in the secondary structure of the film. The proportions of the two polyanions were roughly the same on the surfaces and in the interiors of the films, indicating practically free diffusion for both polyanions. The abundance of PAA/PLL and PGA/PLL domains on the film surfaces was monitored by the analysis of the amide I region of the infrared spectrum of a reporter molecule, HSA, adsorbed onto the three-component polyelectrolyte films.  相似文献   

18.
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   

19.
The adsorption of the cationic surfactant, hexadecyl trimethyl ammonium bromide, C16TAB, onto model cellulose surfaces, prepared by Langmuir-Blodgett deposition as thin films, has been investigated by neutron reflectivity. Comparison between the adsorption of C16TAB onto hydrophilic silica, a hydrophobic cellulose surface, and a regenerated (hydrophilic) cellulose surface is made. Adsorption onto the hydrophilic silica and onto the hydrophilic cellulose surfaces is similar, and is in the form of surface aggregates. In contrast, the adsorption onto the hydrophobic cellulose surface is lower and in the form of a monolayer. The impact of the surfactant adsorption and the in situ surface regeneration on the structure of the cellulose thin films and the nature of solvent penetration into the cellulose films are also investigated. For the hydrophobic cellulose surface, intermixing between the cellulose and surfactant occurs, whereas there is little penetration of surfactant into the hydrophilic cellulose surface. Measurements show that solvent exchange between the partially hydrated cellulose film and the solution is slow on the time scale of the measurements.  相似文献   

20.
以铝片为基底, 经电化学腐蚀和沸水处理制备了多级微纳米结构; 通过气相沉积和涂油分别制备了超疏水表面、 疏水超润滑(slippery)表面和亲水slippery表面; 探究了表面不同的特殊浸润性(超亲水、 超疏水、 疏水slippery和亲水slippery)对液滴凝结的影响. 结果表明, 超亲水表面的液滴凝结属于膜状冷凝, 超疏水表面和slippery表面的液滴凝结均属于滴状冷凝. 超疏水表面液滴合并时, 合并的液滴会不定向弹离表面. 疏水slippery表面和亲水slippery表面由于表面浸润性的不同导致液滴成核密度和液滴合并的差异, 亲水slippery表面凝结液滴的最大体积远大于疏水slippery表面凝结液滴的最大体积. 4种表面的雾气收集效率由大到小依次为亲水slippery表面>疏水slippery表面>超亲水表面>超疏水表面.  相似文献   

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