pH-responsive copolymer films by surface-catalyzed growth

We have engineered a new class of pH-responsive polymer films on gold surfaces by first developing a controlled, surface-catalyzed polymerization to prepare a copolymer film consistent with poly(methylene-co-ethyl acetate) and subsequently hydrolyzing the ester side chains to varying extents to yield carboxylic acids (denoted as PM-CO2H). When pH is increased, the acid groups become deprotonated or charged, dramatically increasing their water solubility and greatly altering the film properties. The carboxylic acid content within the copolymer film can be adjusted by changing the monomer concentration ratio used in the polymerization process or the length of time for the hydrolysis. We have designed PM-CO2H films to consist predominately (>95%) of polymethylene (PM) so that the film is hydrophobic in the uncharged state and, thereby, exhibits an extremely large pH-induced response in barrier properties once ionized. The effect of polymer composition on pH response was investigated by electrochemical impedance spectroscopy (EIS), reflectance-absorption infrared spectroscopy (RAIRS), and contact angle measurements. At a 1%-4% molar acid content, the copolymer film exhibits a 5 orders of magnitude change in its resistance to ion transport over 2-3 pH units. The pH at which this response begins can be tailored from pH 5 to pH 10 by decreasing the acid content in the film from 4% to 1%.     

A general method to determine ionization constants of responsive polymer thin films

A general method has been developed to determine the ionization constants of polymer thin films based on the stimuli-responsiveness of the polymer. Robust polymer films were fabricated on silicon wafers and gold slides using perfluorophenyl azide (PFPA) as the coupling agent. The ionization constants were measured by a number of techniques including ellipsometry, dynamic contact angle goniometry, and surface plasmon resonance imaging (SPRi). Using poly(4-vinylpyridine) (P4VP) as the model system, P4VP thin films were fabricated and the ionization constants of the films were measured taking advantage of the pH responsive property of the polymer. The pK(a) determined by ellipsometry, ~4.0, reflects the swelling of the polymer film in response to pH. The pK(a) value calculated from the dynamic contact angle measurements, ~5.0, relies on the change in hydrophilicity/hydrophobicity of the films as the polymer undergoes protonation/deprotonation. The pK(a) value measured by SPRi, ~4.9, monitors in situ the change of refractive index of the polymer thin film as it swells upon protonation. This was the first example where SPRi was used to measure the ionization constants of polymers.     

Water-in-model oil emulsions studied by small-angle neutron scattering: interfacial film thickness and composition

The ever-increasing worldwide demand for energy has led to the upgrading of heavy crude oil and asphaltene-rich feedstocks becoming viable refining options for the petroleum industry. Traditional problems associated with these feedstocks, particularly stable water-in-petroleum emulsions, are drawing increasing attention. Despite considerable research on the interfacial assembly of asphaltenes, resins, and naphthenic acids, much about the resulting interfacial films is not well understood. Here, we describe the use of small-angle neutron scattering (SANS) to elucidate interfacial film properties from model emulsion systems. Modeling the SANS data with both a polydisperse core/shell form factor as well as a thin sheet approximation, we have deduced the film thickness and the asphaltenic composition within the stabilizing interfacial films of water-in-model oil emulsions prepared in toluene, decalin, and 1-methylnaphthalene. Film thicknesses were found to be 100-110 A with little deviation among the three solvents. By contrast, asphaltene composition in the film varied significantly, with decalin leading to the most asphaltene-rich films (30% by volume of the film), while emulsions made in toluene and methylnaphthalene resulted in lower asphaltenic contents (12-15%). Through centrifugation and dilatational rheology, we found that trends of decreasing water resolution (i.e., increasing emulsion stability) and increasing long-time dilatational elasticity corresponded with increasing asphaltene composition in the film. In addition to the asphaltenic composition of the films, here we also deduce the film solvent and water content. Our analyses indicate that 1:1 (O/W) emulsions prepared with 3% (w/w) asphaltenes in toluene and 1 wt % NaCl aqueous solutions at pH 7 and pH 10 resulted in 80-90 A thick films, interfacial areas around 2600-3100 cm (2)/mL, and films that were roughly 25% (v/v) asphaltenic, 60-70% toluene, and 8-12% water. The increased asphaltene and water film composition at pH 10 versus pH 7, along with unique dynamic interfacial tension profiles, suggested that the protonation state of carboxylic moieties within asphaltenes impacts the final film properties. This was further supported when we characterized similar asphaltenic emulsions that also contained 9-anthracence carboxylic acid (ACA). Addition of this aromatic acid led to slightly thinner films (70-80 A) that were characteristically more aqueous (up to 20% by volume) and 5-6% (v/v) ACA. This unique in situ characterization (deduced entirely from SANS data from emulsion samples) of the entire film composition calls for further investigation regarding the role this film-based water plays in emulsion stability.     

Electrokinetics of a poly(N-isopropylacrylamid-co-carboxyacrylamid) soft thin film: evidence of diffuse segment distribution in the swollen state

Streaming current measurements were performed on poly(N-isopropylacrylamid-co-carboxyacrylamid) (PNiPAAM-co-carboxyAAM) soft thin films over a broad range of pH and salt concentration (pH 2.5-10, 0.1-10 mM KCl) at a constant temperature of 22 °C. The films are negatively charged because of the ionization of the carboxylic acid groups in the repeat unit of the copolymer. For a given salt concentration, the absolute value of the streaming current exhibits an unconventional, nonmonotonous dependence on pH with the presence of a maximum at pH ～6.4. This maximum is most pronounced at low electrolyte concentration and gradually disappears with increasing salinity. Complementary ellipsometry data further reveal that the average film thickness increases by a factor of ～2.2 with increasing pH over the whole range of salt concentration examined. The larger the solution salt concentration, the lower the pH value where expansion of the hydrogel layer starts to take place. The dependence of film thickness on pH and electrolyte concentration remarkably follows that obtained for surface conductivity. The streaming current and surface conductivity results could be consistently interpreted on a quantitative basis using the theory we previously derived for the electrokinetics of charged diffuse (heterogeneous) soft thin films complemented here by the derivation of a general expression for the surface conductivity of such systems. In particular, the maximum in streaming current versus pH is unambiguously attributed to the presence of an interphasial gradient in polymer segment density following the heterogeneous expansion of the chains within the film upon swelling with increasing pH. A quantitative inspection of the data further suggests that pK values of ionogenic groups in the film as derived from the streaming current and surface conductivity data differ by ～0.9 pH unit. Such a difference is attributed to the impact of position-dependent hydrophobicity across the film on the degree of ionization of carboxylic sites.     

Modification of indium-tin oxide electrodes with thiophene copolymer thin films: optimizing electron transfer to solution probe molecules

We describe the modification of indium-tin oxide (ITO) electrodes via the chemisorption and electropolymerization of 6-{2,3-dihydrothieno[3,4-b]-1.4-dioxyn-2-yl methoxy}hexanoic acid (EDOTCA) and the electrochemical co-polymerization of 3,4-ethylenedioxythiophene (EDOT) and EDOTCA to form ultrathin films that optimize electron-transfer rates to solution probe molecules. ITO electrodes were first activated using brief exposure to strong haloacids, to remove the top approximately 8 nm of the electrode surface, followed by immediate immersion into a 50:50 EDOT/EDOTCA co-monomer solution. Potential step electrodeposition for brief deposition times was used to grow copolymer films of thickness 10-100 nm. The composition of these copolymer films was characterized by solution depletion studies of the monomers and atomic force microscopy (AFM), X-ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy (reflection-absorption infrared spectroscopy (RAIRS)) of the product films. The spectroscopic data suggest that the composition of the copolymer approaches 80% EDOTCA when electropolymerization occurs from concentrated (10 mM) solutions. AFM characterization shows that electrodeposited poly(EDOT)/poly(EDOTCA) (PEDOT/PEDOTCA) films are quite smooth, with texturing on the nanometer scale. RAIRS studies indicate that these films consist of a combination of EDOTCA units with noninteracting -COOH groups and adjacent hydrogen-bonded -COOH groups. The EDOTCA-containing polymer chains appear to grow as columnar clusters from specific regions, oriented nearly vertically to the substrate plane. As they grow, these columnar clusters overlap to form a nearly continuous redox active polymer film. ITO activation and formation of these copolymer films enhances the electroactive fraction of the electrode surface relative to a nonactivated, unmodified "blocked" ITO electrode. Outer-sphere solution redox probes (dimethylferrocene) give standard rate coefficients, kS > or = 0.4 cm.s-1, at 10 nm thick copolymer films of PEDOT/PEDOTCA, which is 3 orders of magnitude greater than that on the unmodified ITO surface and approaches the values for kS seen on clean gold surfaces.     

Effects of copolymer concentration and chain length on the pH-responsive behavior of diblock copolymer micellar films

The pH-responsive behavior of adsorbed diblock copolymer films of PDMA-PDEA (poly(2-(dimethylamino)ethyl methacrylate)-block-poly(2-(diethylamino)ethyl methacrylate)) on silica has been characterized using a quartz crystal microbalance with dissipation monitoring (QCM-D), an optical reflectometer (OR) and an atomic force microscope (AFM). The copolymer was adsorbed at pH 9 from various copolymer concentrations; QCM-D measurements indicate that the level of desorption when rinsed at pH 9 depends on the initial copolymer concentration. The adsorbed films produced at pH 9 generally have low charge densities; adjusting the solution pH to 4 results in a significant protonation of the constituent copolymers and a related interfacial structural change for the copolymer film. OR studies show no significant change during pH cycling, while QCM-D measurements indicate that the adsorbed mass and dissipation alter dramatically in response to the solution pH. The difference between the QCM-D adsorbed masses and dissipation values at pH 4 and 9 were found to be dependent on the initial copolymer concentration. This is due to differences in the initial conformations within the adsorbed copolymer layers at pH 9. The effect of the PDMA chain length on the pH-responsive behavior has also been studied; both the QCM-D adsorbed mass and dissipation of PDMA54-PDEA24 (shorter PDMA block) at pH 4 and 9 were observed to be greater than those of PDMA9X-PDEA2Y (longer PDMA block). This suggests that the normal extension of the adsorbed PDMA54-PDEA24 copolymer films is more significant than that of the PDMA9X-PDEA2Y films on silica.     

Response mechanism of novel polyaniline composite conductimetric pH sensors and the effects of polymer binder, surfactant and film thickness on sensor sensitivity

This paper reports on investigations into the response mechanism of novel polyaniline composition conductimetric pH sensors and the effects of polymer binder, surfactant and film thickness on this response. It was revealed through X-ray photoelectron spectroscopy, focussed ion beam milling and impedance spectroscopy that the response mechanism was due to the deprotonation of the polymer backbone nitrogen atoms located on the uppermost surface level of the functional material particles. The equivalent circuits for the sensing layer were modelled using the Cole-Cole model for a range of pH environments. The optimum sensing layer composition was determined to contain less than 50 wt.% polymer binder with 5 wt.% surfactant. This composition was determined by examining the effects of both binder and surfactant on the electrical characteristics and sensor response of the composite films. The thickness of the sensing layer was found to have no discernable response on the sensing characteristics of the conductimetric pH sensors.     

pH-Induced antireflection coatings derived from hydrogen-bonding-directed multilayer films

Hydrogen-bonding-directed layer-by-layer assembled films, based on polystyrene-block-poly(acrylic acid) (PS-b-PAA) block copolymer micelles and poly(4-vinylpyridine) (P4VP), were successfully fabricated in methanol. Varying the PAA content in the PS-b-PAA micelles afforded control over the film growth properties, especially the multilayer film thickness. Interestingly, antireflection films with refractive indices that could be tuned between 1.58 and 1.28 were obtained by treatment with an aqueous HCl solution (pH 2.27), and the transmittance obtained was as high as 98.4%. In acid solution, the pyridine group was protonated, destroying the hydrogen bonding between P4VP and PAA. A concomitant pH-induced polymer reorganization in the multilayers resulted in a porous honeycomb-like texture on the substrate.     

Layer‐by‐layer assembly of weak‐strong copolymer polyelectrolytes: A route to morphological control of thin films

Multilayer films were assembled from a strong polyelectrolyte (poly(diallyldimethylammonium chloride), PDADMAC) and a copolymer containing both strongly charged styrene sulfonate moieties and weakly charged maleic acid moieties (poly(4‐styrenesulfonic acid‐co‐maleic acid), PSSMA). Growth of PSSMA/PDADMAC multilayers was linear, as characterized by UV‐vis spectroscopy and quartz crystal microgravimetry. The influence of both the pH of the PSSMA adsorption solutions and the ratio of SS:MA in the PSSMA on multilayer properties was investigated. Fourier transform infrared spectroscopy results showed that the ionization of carboxylic acid groups in PSSMA/PDADMAC multilayers did not vary significantly with changes in the PSSMA assembly pH. However, the multilayers showed different thicknesses, surface morphologies, and stability to post‐assembly pH treatment. We also demonstrate that PSSMA/PDADMAC multilayers are significantly more stable than PSSMA/PAH multilayers after post‐assembly pH treatment (i.e. the films remain intact when exposed to pH extremes). In addition, the surface morphology of two films (PSSMA 1:1 assembled at pH 5.8, post‐treated at pH 2 and PSSMA 3:1 assembled at pH 5.8, post‐treated at pH 11) changed significantly when the films were exposed to solutions of different pH and, in the former case, this change in film morphology was reversible. The porous morphology after treatment at pH 2 could be reversed to give a significantly smoother film after subsequent exposure to water for 24 h. Our results demonstrate that by the rational choice of the assembly pH of PSSMA, stable and pH‐responsive films can be obtained via the sequential assembly of PSSMA and PDADMAC. These films have potential in controlled release applications where film stability and pH‐responsive behavior are essential. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4341‐4351, 2007     

Interfacial reactions in confinement: kinetics and temperature dependence of the surface hydrolysis of polystyrene-block-poly(tert-butyl acrylate) thin films

The effect of confinement on the kinetics of the surface hydrolysis of polystyrene-block-poly(tert-butyl acrylate) (PS(n)-b-PtBA(m)) thin films on oxidized silicon substrates in 3 M aqueous hydrochloric acid was systematically investigated. As shown by X-ray photoelectron spectroscopy (XPS) and contact angle measurements, a skin layer of acid-sensitive PtBA is present on the surface of PS(n)-b-PtBA(m) films, consistent with the lower surface tension of PtBA compared to that of PS. The thickness of the skin layer was determined by angle-dependent XPS as approximately 8 nm for PS(690)-b-PtBA(1210). Tapping mode atomic force microscopy showed an increasing surface coverage of swollen poly(acrylic acid)-rich globules with increasing hydrolysis time. Using ex situ Fourier transform infrared spectroscopy, the reaction kinetics was determined quantitatively as a function of temperature, polymer film thickness, thermal pretreatment of the films, and block copolymer composition. The initial stages of the hydrolysis can be described as a pseudo-first-order reaction under all conditions investigated. The corresponding rate constants were found to be 2 orders of magnitude lower than those reported for the hydrolysis of tert-butyl acetate in solution and depended linearly on the fraction of PtBA exposed at the surface. However, the polymer film thickness, thermal pretreatment of the films, block copolymer composition, and local composition did not affect the rate constants. The negative value of the activation entropy (DeltaS(298)++ = -103 J/mol K), determined according to the Arrhenius equation and transition state theory, indicates that the tightness of the transition state is more pronounced in the PS(n)-b-PtBA(m) film compared to reactions in solution. Thus, the spatial constraints due to the incorporation of the reactive ester groups in thin polymer films are responsible for the observed reduced reactivity.     

An investigation of anodic film formation on electrodeposited ruthenium by potential sweep techniques

Potential sweep techniques were used to investigate the anodic behaviour of reduced ruthenium surfaces, prepared by electrodeposition on gold-plated substrates, as a function of sweep rate, temperature and pH. The most important factor appeared to be pH as this strongly influenced the oxide layer thickness and both the number and location of the peaks on the voltammogram. The formation of thin oxide films on ruthenium at intermediate pH values (3.5–9.5) is attributed to the growth of a compact amorphous film with significant metal-oxygen-metal bridging in the structure. Heavier oxide growth in strong acid is attributed to protonation of the oxide lattice resulting in the formation of a more porous anodic film. Thicker oxide growth in strong base is attributed to the growth of a higher (+6) oxide under these conditions. The effects of both sweep rate and temperature on anodic behaviour in strong acid are attributed to activation-controlled rearrangement of the oxide film.     

Polyelectrolyte complex films derived from polyethyleneoxide-maleic acid copolymer and chitosan: preparation and characterization

Polyelectrolyte complex films were prepared with polyethyleneoxide-maleic acid copolymer and chitosan using a casting/solvent evaporation method. The films were examined in terms of their IR spectra, surface and cross-section morphologies, cytotoxicity, and swelling behavior at different pH levels. To assess the potential of these films as a biomedical device, the profiles of the release of model drug from the CS/PEOMA films were examined at pH 4.8. The surface morphology of the films was quite smooth and uniform, and the cross-sectional morphology was dense and homogeneous. The swelling behaviors of CS/PEOMA films were found to depend on the pH of the solution as well as on the CS/PEOMA composition. Drug release from different CS/PEOMA films at pH 4.8 was found to be dependent on film composition. The results showed the potential applicability of CS/PEOMA film as a drug delivery vehicle.     

pH sensor based on polyaniline and aniline–anthranilic acid copolymer films using quartz crystal microbalance and electronic absorption spectroscopy

The pH sensitivity based on conducting polyaniline (PANI) and copolymer of aniline and o‐anthranilic acid (AA) films were studied using quartz crystal microbalance (QCM) technique and UV–Vis spectroscopy. The sensor was constructed from these polymer films coated on the electrode of the QCM. The resonant frequency changes as a function of pH in the range of 2–12 were measured. These changes are quantitative indication of the degree of dedoping or redoping of the polymer films upon the subsequent exposure of the electrode to 0.25 M sulfuric acid and different pH solutions. There are two linear regressions between the frequency change and pH with two different and opposite slopes in the regions from 2 to 9 and 9 to 12. The pH sensitivity of the copolymer film was found to be less than using the PANI film. Thin films of PANI and copolymer, which were chemically polymerized in a sulfuric acid solution, were deposited onto the inner walls of the quartz cuvettes. The UV–Vis absorption spectra of these films were measured in different pH solutions. Relations between the maximum absorption and its wavelength versus pH were constructed. The copolymer film shows some advantages over the PANI film. The difference between the PANI and copolymer films as pH sensors using the QCM and electronic absorption extends from the determination of pK_a for both films. Copyright © 2008 John Wiley & Sons, Ltd.     

Reversible activation of diblock copolymer monolayers at the interface by pH modulation, 1: Lateral chain density and conformation

This study focuses on the design of chemically regulated surfaces that allow for reversible control of the interactions between biological matter (cells and proteins) and planar substrates. As a tunable interlayer, we use a monolayer of a near-monodisperse poly[2-(dimethylamino)ethyl methacrylate-block-methyl methacrylate] (PDMAEMA-PMMA) diblock copolymer. Owing to the relatively large fraction (50%) of the hydrophobic PMMA block, this copolymer forms a stable Langmuir monolayer at the air/water interface. Both in situ and ex situ film balance experiments suggest that the hydrophilic PDMAEMA block adsorbs to the air/water interface in its uncharged state (pH 8.5), but stretches into the subphase in its charged state (pH 5.5). Optimization of the preparation protocols enables us to fabricate stable, homogeneous diblock copolymer films on hydrophobized substrates via Langmuir-Schaefer transfer at well-defined lateral chain densities. Ellipsometry and X-ray reflectivity studies of the transferred films confirm that the film thickness can be systematically regulated by the lateral chain densities. The transferred copolymer films remain stable in water for about a week, suggesting that they are promising materials for the creation of pH-controlled solid substrates for the support of biological matter such as proteins and cells.     

Electrochemical Properties of an Osmium(II) Copolymer Film and Its Electrocatalytic Ability Towards the Oxidation of Ascorbic Acid in Acidic and Neutral pH

Copolymerization of an osmium(II) functionalized pyrrole moiety, osmium‐bis‐N,N'‐(2,2′‐bipyridyl)‐N‐(pyridine‐4‐ylmethyl‐(8‐pyrrole‐1yl–octyl)‐amine)chloride ( I ) with 3‐methylthiophene was carried out. The resulting conducting polymer film exhibited a clear redox couple associated with the Os^3+/2+ response and the familiar conducting polymer backbone signature. The effect of film thickness upon the redox properties of the copolymer was investigated in organic electrolyte solutions. Scanning electron micrographs (SEM) along with energy dispersive X‐ray (EDX) spectra of the copolymerized films were undertaken, both after formation and redox cycling in neutral buffer solution. These clearly show that electrolyte is incorporated into the polymer film upon redox cycling through the Os^3+/2+ redox system. The Os^3+/2+ response associated with the copolymer was seen to be significantly altered in the presence of ascorbic acid both in acidic and neutral pH buffer solutions. This pointed to an electrocatalytic reaction between the ascorbic acid and the Os³⁺ form of the copolymer. Under acidic conditions the copolymer film exhibited a sensitivity of 1.76 (±0.05) μA/mM with a limit of detection (LOD) of 1.45 μM for ascorbic acid. Under neutral pH conditions the copolymer exhibited a sensitivity of 19.26 (±1.05) μA/mM with a limit of detection (LOD) of 1.28 μM for ascorbic acid.     

Characterizing the pH-responsive behavior of thin films of diblock copolymer micelles at the silica/aqueous solution interface

The pH-responsive behavior of cationic diblock poly(2-(dimethylamino)ethyl methacrylate)-block-poly(2-(diethylamino)ethyl methacrylate) copolymer micelles adsorbed at the silica/aqueous solution interface has been characterized. The micellar morphology of this copolymer, initially adsorbed at pH 9, can be dramatically altered by lowering the solution pH. The original micelle-like morphology of the adsorbed copolymer chains at pH 9 completely disappears as the pH is decreased to 4, and a brush-like layer structure is produced. This change results from protonation of the copolymer chains: the subsequent electrostatic repulsions within the film drive the copolymer chains to expand into the aqueous phase. Returning the solution pH from 4 to 9 causes this brush-like layer to collapse, with atomic force microscopy images suggesting degradation of the film. Hence, the pH-responsive behavior of the copolymer film exhibits irreversible morphological changes. Measurements of the adsorbed/desorbed amounts of the copolymer film were conducted using both a quartz crystal microbalance with dissipation monitoring (QCM-D) and optical reflectometry (OR). After an initial rinse at both pH values, the OR adsorbed mass becomes almost constant during subsequent pH cycling, whereas the corresponding QCM-D adsorbed mass changes significantly but reversibly in response to the solution pH. Since the QCM-D measures a bound mass that moves in tandem with the surface, the discrepancy with the OR data is due to changes in the amount of bound water in the copolymer film as a result of the pH-induced changes in surface morphology. The larger effective mass observed at pH 4 suggests that the brush-like layer contains much more entrapped water than the micellar films at pH 9. The pH dependence of the contact angle of the adsorbed film is consistent with the changes observed using the other techniques, regardless of whether the solution pH is altered in situ or the aqueous solution is completely replaced. In fact, comparison of these two approaches provides direct evidence of the exposure of adsorbed micelle core blocks to the solution during pH cycling and the concomitant impact upon all the other measurements.     

普鲁士蓝膜修饰电极的电化学阻抗谱

测量了应用电化学方法制备的不同厚度的普鲁士蓝膜修饰电极的循环伏安行为与电化学阻抗谱.由所得到的循环伏安图讨论了普鲁士蓝修饰膜的氧化还原过程,并对相关的Nyquist图进行了解析,提出了相应的等效电路.在此基础上计算出较薄膜中普鲁士蓝/普鲁士白电化学反应的表观速率常数和表观扩散系数,讨论了膜厚度对电荷扩散的影响.当膜相对较薄时,电极过程主要由动力学过程控制;当膜达到一定厚度时,电荷在膜中的扩散速率受到限制,电极过程由动力学过程和电荷扩散过程共同控制,证实了文献报导的普鲁士蓝膜修饰电极为多层空间分布电荷传递模型.     

Characterization of maleic acid/anhydride copolymer films by low-rate dynamic liquid-fluid contact angle measurements using axisymmetric drop shape analysis

Thin films of alternating maleic acid/anhydride copolymers (poly(octadecene-alt-maleic acid/anhydride), POMA; poly(propene-alt-maleic acid/anhydride), PPMA; poly(styrene-alt-maleic acid/anhydride), PSMA) were studied to unravel the influence of the comonomer characteristics in the backbone on the surface-energetic properties of the copolymer films in the dry state and in contact with aqueous solutions. Water contact angle measurements revealed a graduation of the wettability of the dry hydrolyzed and annealed copolymer films that was dependent on the comonomer unit. It ranged from moderately hydrophilic (PPMA, annealed gamma(sv) = 39.9 mJ/m2) to very hydrophobic (POMA, annealed, gamma(sv) = 18.4 mJ/m2) surfaces. Liquid-fluid contact angle measurements using captive air bubbles were performed in different aqueous media (pure water, phosphate-buffered saline, and 10(-)(3) M KCl of two different pH values (pH = 3 and pH = 10) to study the copolymer films in their hydrated states relevant for biointerfacial phenomena. It was found that the graduation of the wettability of the copolymer films in the dry state is overall maintained upon immersion in aqueous solutions. The dependence of the wettability on the pH value of the aqueous medium could be related to the (de)protonation of the carboxylic groups.     

Swelling–shrinking behavior of hydrated noncross‐linked copolymer films in response to photoreversible isomerizaton and metal complexation of spiropyran units of the copolymers

The copolymer of hydroxypropyl methacrylate (HPMA) and photochromic spiropyran methacrylate (SPMA) has been synthesized. The films of the copolymer (P(HPMA‐SPMA)) in a hydrated state showed reversible swelling–shrinking behavior in response to photoreversible isomerization and metal complexation of SPMA units in spite of covalently noncross‐linked copolymers. In addition, the protonated open form of the SPMA units of the copolymer was possibly stabilized thermodynamically by the HPMA units from ultraviolet–visible absorption measurement of the hydrated P(HPMA‐SPMA) film. On the other hand, the difference in color of the hydrated films between P(HPMA‐AABMA) and P(NIPMA‐AABMA), which was a copolymer of N‐isopropyl methacryl amide (NIPMA) and azobenzene methacrylate (AABMA) as a pH indicator, was suggestive of the interference of the proximal hydroxyl groups of the immobilized HPMA units with protonation of the AABMA units. The HPMA units of the copolymers also contributed to improvement of thermodynamic stability of the metal complexes with the SPMA units. Copyright © 2013 John Wiley & Sons, Ltd.     

Fabrication of polyelectrolyte multilayer films comprising nanoblended layers

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).