Polyelectrolyte blend multilayer films: surface morphology, wettability, and protein adsorption characteristics

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.     

含二氮杂萘酮结构聚醚砜酮膜的微波等离子体处理研究

含二氮杂萘酮结构型聚醚砜酮(ＰＰＥＳＫ)是近年来本研究组开发成功的新型耐高温聚合物[1].该聚合物具有优异的力学性能和突出的耐热性,玻璃化转变温度(Ｔｇ)为265～305℃(随砜酮比不同而变化),其结构式如下:ＯＮＮＯＳＯＯＯＮＮＯＣＯ　　研究表明,用ＰＰＥＳＫ制成的气体分离膜对Ｏ2/Ｎ2、ＣＯ2/Ｎ2有良好的气体渗透性和透过选择性[2,3],但由于其亲水性不高进而限制了它在纳滤膜和反渗透膜等方面的应用,因此有必要对其进行改性.目前,常用的膜及膜材料改性的方法有磺化、氯甲基化季胺化、接枝等化学改性和低温等离子体与辐射等物理改性.其…     

A novel method to introduce durable hydrophilicity onto hydrophobic polymer surface by plasma treatment

We have examined a novel method to fabricate a durable hydrophilic surface of hydrophobic polymeric materials modified by plasma treatment. The method involves a trapping of maleic anhydride-containing polymer onto poly(ethylene naphthalate) (PEN) by a plasma-induced crosslinking reaction of PEN followed by hydrolysis of maleic anhydride moiety to generate hydrophilic carboxyl groups on the PEN surface. In fact, the PEN film surface thus treated has shown an effective stability of wettability based on the water contact angle measurement.     

Optical Spectra of Polygermane/Mesoporous Silica Nanocomposites

Summary: The monitoring of poly(di-n-hexylgermane) (PDHG) optical spectra in a variety of structures ranging from a bulk film to a nanosize polymer confined into a nanopore of SBA-15 was performed using the fluorescence and fluorescence excitation spectra in the temperature range from 5 to 240 K as well as the absorption and FTIR spectra at room temperature. The observed data were compared with those obtained for poly(di-n-hexylsilane). It was shown that PDHG film absorption and fluorescence spectra strongly depend on the polymer thickness and consist of a number of bands which were assigned to centers with different amount of trans- and gauche- conformers of the polymer chains. Conformations of the polymer chains found in a thin film and in a 10 nm pore are similar while differing from the conformations of a thick film. Optical spectra of the confined PDHG are blue-shifted relative to those of a thin film. The PDHG polymer chain conformation becomes disordered with the decrease of the polymer film thickness and the nanopore size from 10 to 6 nm.     

Characteristics of a surface plasmon resonance sensor combined with a poly(vinyl chloride) film-based ionophore technique for metal ion analyses.

The characteristics of a surface plasmon resonance (SPR) sensor prepared by coating a metal film evaporated on a prism with a polymer film containing tetra-n-butyl thiuram disulfide (TBTDS) were studied. The differences in the sensitivity, selectivity, and detection limit for a Zn2+ ion of the SPR sensor were reported as a function of the thickness of the polymer film, the kind of a metal film, and the kind of a polymer film. The thinner was the polymer film, the higher was the sensitivity, and the lower was the detection limit. The Ag film gave to the SPR sensor higher sensitivity than the Au film. TBTDS contained in the poly(vinyl chloride) (PVC) film slightly improved the selectivity toward the Zn2+ ion. A non-conditioned poly(methyl methacrylate) (PMMA) film containing TBTDS gave a lower detection limit of 1.0 x 10(-6) mol/l, which is similar to that obtained by using an ion selective electrode (ISE) method, than the PVC film. The PVC film, however, gave higher concentration resolution than the PMMA film.     

电场极化调控聚(3-己基噻吩)薄膜润湿性

本文首次采用电场极化技术精确控制共轭聚合物P₃HT薄膜表面的润湿性,通过调节极化条件,成功实现了对P₃HT薄膜表面润湿性的精确控制,薄膜表面水接触角可以实现从疏水性到亲水性的转变.通过光谱学、形貌学及接触角等表征手段,详细研究了电场极化作用下共轭聚合物分子取向聚集形态及作用机理.该工作不但扩展了共轭聚合物薄膜材料的应用范围,也为分子形态学的研究奠定了基础.     

Facile measurement of polymer film thickness ranging from nanometer to micrometer scale using atomic force microscopy

As many properties of polymer thin films critically depend on their thickness, a convenient and cost‐effective method for precise measurement of film thickness in a wide range is highly desirable. Here, we present a method which enables polymer film thickness, ranging from nanometer to micrometer scale, to be facilely determined by measuring the height of an artificially created film step on smooth substrates with atomic force microscopy (AFM). Three polymeric films (polystyrene, poly(methyl methacrylate) and poly(styrene–ethylene/butylene–styrene) films), spin‐coated on either mica or quartz substrate with thickness ranging from 5.7 nm to 4.4 µm, were employed to demonstrate the procedure and feasibility of our method. The proposed method is particularly suitable for thicker polymer films, thus complementing the traditional AFM ‘tip‐scratch’ method which is generally limited to polymer films of no more than 100 nm thickness. Copyright © 2010 John Wiley & Sons, Ltd.     

Azobenzene-containing monolayer with photoswitchable wettability

A compact monolayer containing azobenzene has been prepared on silicon substrates. The elaboration route consisted of covalent grafting of freshly synthesized azobenzene moieties onto an isocyanate-functionalized self-assembled monolayer (SAM). The highly packed and ordered isocyanate-functionalized SAM and the azobenzene-functionalized SAM were monitored and characterized by contact angle measurements and X-ray reflectivity (XR). Photoswitching of the wettability of the film induced by the reversible cis-trans isomerization of the azobenzene chromophores is experimentally shown from water and olive oil contact angle measurements.     

二元聚合物刷体系相分离的计算机模拟

利用耗散粒子动力学(DPD)方法研究了二元聚合物刷体系的相分离行为. 发现组分间相容性的差别对膜厚的影响很小, 对纵向相分离结构中相区尺寸的影响则较大. 溶剂质量对控制聚合物刷膜的厚度和密度具有决定作用, 同时对层状膜结构也具有调控作用. 结果表明, 通过控制环境条件, 二元聚合物刷膜材料在快速且可逆地调节表面润湿性方面具有潜在的应用价值.     

Fabrication of flexible gold films with periodic sub-micrometer roughness and their wettability control by modification of SAM

Flexible honeycomb gold films supported by polymer sheets are fabricated by using polystyrene particle monolayers. The surfaces of the flexible gold films are covered with self-assembled monolayers (SAMs) of hydrophobic or hydrophilic thiol compounds, and the wettability of the modified surface is evaluated by measurements of the contact angles of water droplets. The contact angle of the film covered with hydrophobic SAM is ca. 150 degrees, which is greater than the value of 112 degrees for a flat gold surface, while the values for hydrophilic SAM are below 10 degrees.     

Monitoring the hygrothermal response of poly(vinyl methyl ether) submicron films using AFM

Films with submicron thickness of the thermoresponsive polymer poly(vinyl methyl ether) (PVME) are prepared by spin-coating and measured with AFM. The change of film thickness, work of adhesion (WOA), and modulus of elasticity (MOE) are monitored below and above the lower critical solution temperature (LCST) in controlled atmosphere. The film thickness decreases above the LCST at high relative humidity, but not at low humidity. Simultaneously, the MOE increases by 3 orders of magnitude due to conformational transition. The WOA shows a hysteretic behavior due to changes in surface wettability and film compressive strength. Hygrothermal cycling is found to facilitate the relaxation of initially arrested entanglements. The proposed hypothesis of hygrothermally induced partial disentanglement is further supported with cyclic DSC measurements of concentrated aqueous PVME solutions. This work is an important contribution to understand the local and macroscopic behavior of thermoresponsive polymers in dry and humidified atmosphere.     

Reversible photoswitchable wettability in noncovalently assembled multilayered films

Reversible and irreversible photoinduced changes in surface wettability were observed in noncovalently assembled multilayered films. The multilayered films studied were fabricated from a self-assembled monolayer (SAM) consisting of 4-(10-mercaptodecyloxy)pyridine-2,6-dicarboxylic acid on gold, Cu(II) ions complexed to the pyridine head group of the SAM, and either cis- (film 1) or trans- (film 2) stilbene-4,4'-dicarboxylic acid complexed to the Cu(II) ions. Irradiation of film 1 at wavelengths corresponding to the absorption band of the cis-stilbene isomer resulted in an irreversible chemical change and an irreversible increase in wettability, as indicated by surface contact angle and grazing incidence IR measurements. However, no evidence for cis-/trans-photoisomerization was observed. Films 3 and 4, similar to films 1 and 2 in that they consist of an underlying SAM, an intermediate layer consisting of Cu(II) ions, and either cis- or trans-stilbene-4,4'-dicarboxylic acid as the capping ligand, were fabricated with a mixed SAM that contained both 4-(10-mercaptodecyloxy)pyridine-2,6-dicarboxylic acid and 4-tert-butylbenzenethiol. Irradiation of these films at wavelengths corresponding to stilbene isomer absorption bands resulted in reversible cis- to trans- (film 3) and trans- to cis- (film 4) photoisomerization and reversible switching of the surface wettability between a low wetting state (cis-stilbene) and a high wetting state (trans-stilbene). The difference in observed behavior between films 1 and 2 and films 3 and 4 is attributed to the greater surface spacing afforded by the mixed monolayer, which allows greater conformational flexibility and lowers the steric barriers to isomerization.     

Entrapment of photosystem I within self-assembled films

We have developed a process to incorporate an integral membrane protein, Photosystem I (PSI), into an organic thin film at an electrode surface and thereby insulate the protein complex on the surface while mimicking its natural environment. The PSI complex, which is primarily more hydrophobic on the exterior than interior, is hydrophobically confined in vivo within the thylakoid membrane. To mimic the thylakoid membrane and entrap PSI on an electrode, we have designed a series of steps using a thin self-assembled monolayer (SAM) to adsorb and orient PSI followed by exposures to longer-chained methyl-terminated alkanethiols that place exchange with components of the original SAM in the interprotein domains. In this process, PSI is first adsorbed onto a HOC(6)S/Au substrate through a short exposure to a dilute solution of the protein to achieve a protein coverage of approximately 25%. The PSI/HOC(6)S/Au substrate is then placed into a solution containing one of various longer-chained alkanethiols including C(22)SH or C(18)OC(19)SH. Changes in thickness, interfacial capacitance, infrared spectra, and surface wettability were used to assess the extent of backfilling by the long-chained thiols. The coverage of the protein layer and the solvent used for backfilling affected the rate and quality of the SAM formed in the interprotein regions. After exposure of the PSI layer to solvents containing alkanethiols, there was only minor loss of protein on the surface and no real change in protein secondary structure as evidenced by reflectance absorption infrared spectroscopy.     

Atmospheric-Pressure Plasma Reduction of Metal Cation-Containing Polymer Films to Produce Electrically Conductive Nanocomposites by an Electrodiffusion Mechanism

We describe an atmospheric-pressure plasma process for the reduction of metal cation-containing polymer films to form electrically conductive patterns. Thin films of poly(acrylic) acid (PAA) containing silver ions (Ag⁺) were prepared by mixing the polymer with silver nitrate (AgNO₃) in solution to produce a cross-linked precipitate, homogenizing, and depositing onto a substrate by doctor’s blade. Exposing the Ag–PAA films to a scanning microplasma resulted in reduction of the bulk dispersed Ag⁺ in a desired pattern at the film surface. The processed films were characterized by scanning electron microscopy, energy dispersive spectroscopy, thermogravimetric analysis, and current–voltage measurements. The resistances of the patterned features were found to depend on the thickness of the films, the microplasma scan rate, residual solvent in the film, and electric field created between the microplasma and the substrate. Together these results show that the formation of conductive features occurs via an electrodiffusion process where Ag⁺ diffuses from the film bulk to the surface to be reduced by the microplasma.     

Adsorption of hydrophobically modified poly(acrylamide)-co-(acrylic acid) on an amino-functionalized surface and its response to the external solvent environment

The adsorption of hydrophobically modified poly(acrylamide)-co-(acrylic acid), designated as PAM-C14-AA (x%) (x = 5, 10, 20, representing the mole percent of acrylic acid units), at an amino-functionalized silicon surface was studied. The effect of polymer charge density was determined by varying the acrylic acid content of the copolymer. Characteristics of the adsorbed layer were evaluated by atomic force microscopy, water contact angle measurements, and X-ray photoelectron spectroscopy. The results showed that the adsorption behavior of PAM-C14-AA (x%) is influenced by the balance among the electrostatic, hydrogen-bonding, and hydrophobic interactions. Adjusting the solution pH and polymer charge density significantly affects the morphology and thickness of the adsorbed film. Furthermore, it was found that the adsorbed PAM-C14-AA undergoes conformational rearrangements when the surface is wetted by selected organic solvents. The resultant morphology and wettability of the films indicated that the different affinities of the solvents for different segments of PAM-C14-AA (x%) can be considered to be the possible cause of the conformational rearrangements of adsorbed polymer.     

Correlation between wetting properties and electrical performance of solution processed PEDOT:PSS/CNT nano-composite thin films

Nano-composite thin films of poly(3,4-ethylenedioxythiophene) poly(styrene-sulfonate) (PEDOT:PSS) with different loading concentrations of multi-walled carbon nanotubes (MWCNT) were deposited on glass substrates using inkjet printing and spin coating techniques. The surface energy of the substrate was modified using an oxygen plasma to achieve different degrees of wetting by the composite solution. We show that the electrical properties strongly depend on the wetting of the substrate and by controlling the wettability, the conductivity of the nano-composite samples can be improved. Based on polymer conductivity, the electrical conductivity of the composite film can be improved or degraded by orders of magnitude with the incorporation of the same concentration of MWCNT. Moreover, electrical measurements show strong correlation between the conductivity of the carbon nanotube network and the resulting nano-composite films. The dependence of electrical properties on the wettability and the conductivity of the composite components could explain the diversity in the electrical behaviour reported in the literature for PEDOT:PSS/MWCNT nano-composite thin films.

Internal Architecture of Zwitterionic Polymer Brushes Regulates Nonfouling Properties

In this work, we study how film thickness and chain packing density affect the protein‐resistant properties of polymer brushes in complex media. Polymer brushes based on dual‐functional poly(carboxybetaine acrylamide) (pCB) were prepared via surface‐initiated photoiniferter‐mediated polymerization. By adjusting UV radiation time and solvent polarity, pCB films with different thicknesses can be achieved and characterized using an ellipsometer. The packing density of pCB polymer chains is directly related to the swelling ratio of swollen to collapsed film thicknesses. Results showed that the dry film thickness alone, used often in the literature, is not sufficient to correlate with nonfouling properties and the chain packing density must be considered for the design of nonfouling surface coatings.     

Effet parasite en ellipsométrie

When measured by ellipsometry, the thickness of a polymer (PolyDiMethylSiloxane: PDMS) microscopic film deposited on a solid substrate (silicon wafer) is shown to depend upon the exposure time and the size of the light spot. We measured experimentally the thinning of such films. This effect can be a non-negligible source of error in the determination of microscopic liquid film thickness. To explain our results, we propose the existence of a Marangoni effect which is due to a local overheating produced by light absorption in the substrate.     

DNA在氨基功能化偶氮苯自组装膜表面的固定

采用简单快速的方法制备出将DNA固定在其表面的单分子层敏感膜.首先采用表面自组装技术将硅氧烷基偶氮苯衍生物H2NAzoCONHC3Si(OCH3)3(APDA-N-TMSPBA)组装在硅表面,在详细考察单分子层薄膜的化学结构、表面浸润性和分子表面形貌之后,又通过紫外吸收光谱(UV)在位考察了硅氧烷基偶氮苯衍生物的光学异构特性.在DNA在自组装薄膜固定后,X光电子能谱仪(XPS)结果显示出现了明显的磷元素信号,表明DNA分子可以成功固定在自组装膜表面.     

Crystalline morphology evolution in PCL thin films

The transition of crystalline morphology is revealed in poly(?‐caprolactone) (PCL) thin films as the polymer film thickness changes from hundreds of nanometers to several nanometers. The PCL can crystallize into spherulites, dense‐branching morphology (DBM), or dendrites, depending on the polymer film thickness. It was found that when the polymer film thickness approaches 2Rg (radius of gyration of polymer), there is a remarkable change in crystalline morphology. Under this condition, the polymer crystallization is a diffusion‐controlled process. When the value of polymer film thickness closes to Rg, PCL cannot crystallize, and a dewetting phenomenon will take place. Moreover, polymer morphology can be controlled by varying supercooling. The effect of molecular weight on polymer morphology has been investigated. The main factors that affected pattern formation in nonequilibrium crystallization are also discussed. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1303–1309, 2005