Adsorption behaviors of methanol, ethanol, n-butanol, n-hexanol and n-octanol on mica surface studied by atomic force microscopy

The adsorption behavior of methanol, ethanol, n-butanol, n-hexanol and n-octanol on mica surface was investigated by atomic force microscopy. All these alcohols have formed homogeneous films with different characteristics. Upright standing bilayer structure was formed on methanol adsorbed mica surface. For ethanol, bilayer structure and monolayer one were simultaneously formed, while for n-butanol and n-hexanol, rough films were observed. What was formed for n-octanol? Close-packed flat film was observed on n-octanol adsorbed mica substrate, the film was assumed to be a tilted monolayer. The possible adsorption model for each alcohol molecule was proposed according to its adsorption behavior.

Co-assembly of ferrocene-terminated and alkylthiophene thiols on gold and its redox chemistry modulated by surfactant adsorption

Coadsorption of ferrocene-terminated alkanethiols (FcCO(2)(CH2)(8)SH, Fc=(mu(5)-C5H5)Fe(mu(5)-C5H4)) with alkylthiophene thiols (2-mercapto-3-n-octylthiophene) yields stable, electroactive self-assembled monolayers on gold. The resulting mixed monolayer provides an energetically favorable hydrophobic surface for the adsorption of the surfactant aggregates in aqueous solution. The adsorptions have been characterized via their effect on the redox properties of ferrocenyl alkanethiols immobilized as minority components in the monolayers and on the interfacial capacitance of the electrode. Surfactant adsorption causes a decrease in the overall capacitance at the electrode and dramatically shifts the redox potential for ferrocene oxidation in a positive or negative direction depending on the identity of the surfactant employed. A structural model is proposed in which the alkane chains of the adsorbed surfactants interdigitate with those of the underlying self-assembled monolayer, leading to the formation of a hybrid bilayer membrane.

Fabrication and characterization of DNA/QPVP-Os redox-active multilayer film

Calf thymus DNA was immobilized on functionalized glassy carbon, gold and quartz substrates, respectively, by the layer-by-layer (LBL) assembly method with a polycation QPVP-Os, a quaternized poly(4-vinylpyridine) partially complexed with osmium bis(2,2'-bipyridine) as counterions. UV-visible absorption and surface plasmon resonance spectroscopy (SPR) showed that the resulting film was uniform with the average thickness 3.4 nm for one bilayer. Cyclic voltammetry (CV) showed that the total surface coverage of the polycations increases as each QPVP-Os/DNA bilayer added to the electrode surface, but the surface formal potential of Os-centered redox reaction shifts negatively, which is mainly attributed to the intercalation of redox-active complex to DNA chain. The electron transfer kinetics of electroactive QPVP-Os in the multilayer film was investigated by electrochemical impedance experiment for the first time. The permeability of Fe(CN)(6)(3-) in the solution into the multilayer film depends on the number of bilayers in the film. It is worth noting that when the multilayer film is up to 4 bilayers, the CV curves of the multilayer films display the typical characteristic of a microelectrode array.

Vacuum-deposited submonolayer thin films of a three-ring bent-core compound

Submonolayer thin films of a three-ring bent-core (that is, banana-shaped) compound, m-bis(4-n-octyloxystyryl)benzene (m-OSB), were prepared by the vacuum-deposition method, and their morphologies, structures, and phase behavior were investigated by atomic force microscopy (AFM) and transmission electron microscopy (TEM). The films have island shapes ranging from compact elliptic or circular patterns at low temperatures (below 40 degreesC) to branched patterns at high temperatures (above 60 degreesC). This shape evolution is contrary to the prediction based on the traditional diffusion-limited aggregation (DLA) theory. AFM observations revealed that two different mechanisms governed the film growth, in which the compact islands were formed via a dewetting-like behavior, while the branched islands diffusion-mediated. It is suggested m-OSB forms a two-dimensional, liquid crystal at the low-temperature substrate that is responsible for the unusual formation of compact islands. All of the monolayer islands are unstable and apt to transform to slender bilayer crystals at room temperature. This phase transition results from the peculiar molecular shape and packing of the bent-core molecules and is interpreted as escaping from macroscopic net polarization by the formation of an antiferroelectric alignment.

Electrochemical biosensors based on advanced bioimmobilization matrices

Biosensors have experienced rapid, extensive development. To maintain the bioactivity of biomolecules and to give the electrochemical output signal required, appropriate bioimmobilization matrices for biomolecules are critical.In this review, we describe some advanced membrane materials (including hydrogels, sol-gel-derived organic-inorganic composites and lipid membranes), introduce electrochemical biosensors based on bioimmobilization materials and describe their performance.Biosensors operating in extreme conditions and displaying direct electron transfer with electrodes based on these advanced membrane materials are attractive. Recent developments in nanomaterials include biosensors, so we emphasize the intersection of nanomaterials with advanced membrane materials in biosensors.

Stabilization of polymer bilayers by introducing crosslinking at the interface

Bisphenol A solid epoxy serves as an effective reaction compatibilizer to the bisphenol A polycarbonate (PC)/PMMA bilayer systems. Addition of epoxy to the bottom PMMA layer can retard or even prevent the dewetting of PC films by introducing crosslinking between both components at the interface. This is the first investigation of polymer bilayers stabilized by chemical reactions.

The interaction of recombinant Pseudomonas aeruginosa exotoxin A with DNA and mimic biomembrane investigated by surface plasmon resonance and electrochemical methods

Based on the multidomain structure of Pseudomonas aeruginosa exotoxin A, a fusion protein termed rPEA has been constructed, which is expected to serve as a gene carrier in vitro. The expression and purification of rPEA are described. The basal properties of rPEA as a gene carrier are evaluated by investigating its interaction with plasmid DNA and mimic biomembrane by surface plasmon resonance (SPR) and electrochemical methods. rPEA is proved to be able to bind with plasmid DNA with high affinity. It can also interact with lipid membrane and increase permeability of the membrane, so the probe molecules can easily reach the gold surface and exhibit the electrochemical response.

Surface and interface morphology of polystyrene/poly(methyl methacrylate) thin-film blends and bilayers

The surface and interface morphologies of polystyrene (PS)/poly(methyl methacrylate) (PMMA) thin-film blends and bilayers were investigated by means of atomic force microscopy (AFM) and X-ray photoelectron spectroscopy. Spin-coating a drop of a PS solution directly onto a PMMA bottom layer from a common solvent for both polymers yielded lateral domains that exhibited a well-defined topographical structure. Two common solvents were used in this study. The structure of the films changed progressively as the concentration of the PS solution was varied. The formation of the blend morphology could be explained by the difference in the solubility of the two polymers in the solvent and the dewetting of PS-rich domains from the PMMA-rich phase. Films of the PS/PMMA blend and bilayer were annealed at temperatures above their glass-transition temperatures for up to 70 h. All samples investigated with AFM were covered with PS droplets of various size distributions. Moreover, we investigated the evolution of the annealed PS/PMMA thin-film blend and bilayer and gave a proper explanation for the formation of a relatively complicated interface inside a larger PS droplet.

Direct electrochemistry and surface plasmon resonance characterization of alternate layer-by-layer self-assembled DNA-myoglobin thin films on chemically modified gold surfaces

Alternate layer-by-layer (L-by-L) polyion adsorption onto gold electrodes coated with chemisorbed cysteamine gave stable, electroactive multilayer films containing calf thymus double stranded DNA (CT ds-DNA) and myoglobin (Mb). Direct, quasi-reversible electron exchange between gold electrodes and proteins involved the Mb heme Fe2+/Fe3+ redox couple. The formation of L-by-L (DNA/Mb), films was characterized by both in situ surface plasmon resonance (SPR) monitoring and cyclic voltammetry (CV). The effective thickness of DNA and Mb monolayers in the (DNA/Mb)l bilayer were 1.0 +/- 0.1 and 2.5 +/- 0.1 mn, corresponding to the surface coverage of similar to65% and similar to89% of its full packed monolayer, respectively. A linear increase of film thickness with increasing number of layers was confirmed by SPR characterizations. At pH 5.5, the electroactive Mb in films are those closest to the electrode surface; additional protein layers did not communicate with the electrode. CV studies showed that electrical communication might occur through hopping conduction via the electrode/base pair/Mb channel, thanks to the DNA-Mb interaction. After the uptake of Zn2+, a special electrochemical behavior, where MbFe(2+) acts as a DNA-binding reduction catalyst in the Zn2+-DNA/Mb assembly, takes place.

Selective penetration of liquid-phase organic probe molecules into SAM of 2-mercapto-3-n-octylthiophene

An inherently disorganized self-assembled monolayer (SAM) of 2-mercapto-3-n-octylthiophene (MOT) has been formed on a gold bead electrode from its dilute ethanolic solution. The disorganization of the monolayer is attributed to the loose packing of the aliphatic chains of the MOT adsorbates, which results from a large difference in dimension/or cross-sectional area between the head (thiophene thiolate) and the tail (alkane chain) groups. Electrochemical measurements including ac impedance spectroscopy and metal underpotential deposition have shown that the monolayer is almost pinhole free. However, the MOT SAM can be penetrated by an organic probe molecule with affinity for the alkane chain part of the monolayer. Some typical probe molecules with different size and hydrophilicity have been employed to assess the permselectivity of the monolayer. Measurement results demonstrate that the ability of the employed probe molecules to penetrate into the monoalyer is mainly dominated by their hydrophilicity/or hydrophobicity. The results presented here suggest the potential application of MOT monoalyer to effectively modify the electrode surface for several research areas such as electrochemical sensors, electrocatalysis, electroanalysis, and supported hybrid bilayer membranes.

A dinuclear aluminum 8-hydroxyquinoline complex with high electron mobility for organic light-emitting diodes

A dinuclear aluminum 8-hydroxyquinoline complex (DAlq(3)) with improved electron mobility was designed for organic light-emitting diodes. The electron mobility in DAlq(3) was determined via transient electroluminescence (EL) from bilayer devices with structure of indium tin oxide (ITO)/N,N-'-di(naphthalene-1-yl)-N,N-'-diphenyl-benzidine (NPB)/DAlq(3)/Mg:Ag. It was found that the electron mobility in DAlq(3) is between 3.7-8.4x10(-6) cm(2)/Vs at electric fields ranging between 1.2x10(6) and 4.0x10(6) V/cm, which is a factor of two higher than that in Alq(3). The DAlq(3) also shows a higher EL efficiency of 2.2 cd/A (1.2 Lm/W), as compared to Alq(3) with an EL efficiency of 2.0 cd/A (1.0 Lm/W), which is attributed to more balanced electron and hole recombination due to the improved electron mobility of DAlq(3).

Bright electroluminescence from a new conjugated dendrimer

Photoluminescence and electroluminescence from a new conjugated dendrimer consisting of three distyrylbenzene units linked by a central nitrogen atom as core and meta-linked biphenyl units as dendrons were investigated. Bright electroluminescence was realized by using bilayer devices with blurred interface, which were fabricated by sequentially spin-coating a neat dendrimer and a dendrimer doped with 2-(4-biphenyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (PBD). By optimizing the concentration of PBD, the maximum brightness and EL quantum efficiency reach 4100 cd/m(2) and 0.10%, respectively.

Lipid membrane immobilized horseradish peroxidase biosensor for amperometric determination of hydrogen peroxide

Stable films of didodecyldimethylammonium bromide (DDAB, a synthetic lipid) and horseradish peroxidase (HRP) were made by casting the mixture of the aqueous vesicle of DDAB and HRP onto the glassy carbon (GC) electrode. The direct electron transfer between electrode and HRP immobilized in lipid film has been demonstrated. The lipid films were used to supply a biological environment resembling biomembrane on the surface of the electrode. A pair of redox peaks attributed to the direct redox reaction of HRP were observed in the phosphate buffer solution (pH 5.5). The cathodic peak current increased dramatically while anodic peak decreased by addition of small amount H2O2. The pH effect on amperometric response to H2O2 was studied. The biosensor also exhibited fast response (5 s), good stability and reproducibility.

Conformation change of horseradish peroxidase in lipid membrane

The electrochemical behavior of horseradish peroxidase (HRP) in the dimyristoyl phosphatidylcholine (DMPC) bilayer on the glassy carbon (GC) electrode was studied by cyclic voltammetry. The direct electron transfer of HRP was observed in the DMPC bilayer. Only a small cathodic peak was observed for HRP on the bare GC electrode. The electron transfer of HRP in the DMPC membrane is facilitated by DMPC membrane. UV-Vis and circular dichroism (CD) spectroscopy were used to study the interaction between HRP and DMPC membrane. On binding to the DMPC membrane the secondary structure of HRP remains unchanged while there is a substantial change in the conformation of the heme active site. Tapping mode atomic force microscopy (AFM) was first applied for the investigation on the structure of HRP adsorbed on supported phospholipid bilayer on the mica and on the bare mica. HRP molecules adsorb and aggregate on the mica without DMPC bilayer. The aggregation indicates an attractive interaction among the adsorbed molecules. The molecules are randomly distributed in the DMPC bilayer. The adsorption of HRP in the DMPC bilayer changes drastically the domains and defects in the DMPC bilayer due to a strong interaction between HRP and DMPC films.

Electrochemical and Raman studies of the biointeraction between Escherichia coli and mannose in polydiacetylene derivative supported on the self-assembled monolayers of octadecanethiol on a gold electrode

Here, we describe a new method to study the biointeraction between Escherichia coli and mannose by using supramolecular assemblies composed of polydiacetylene supported on the self-assembled monolayer of octadecanethiol on a gold electrode. These prepared bilayer materials simply are an excellent protosystem to study a range of important sensor-related issues. The experimental results from UV-vis spectroscopy, resonance Raman spectroscopy, and electrochemistry confirm that the specific interactions between E. coli and mannose can cause conformational changes of the polydiacetylene backbone rather than simple nonspecific adsorption. Moreover, the direct electrochemical detection by polydiacetylene supramolecular assemblies not only opens a new path for the use of these membranes in the area of biosensor development but also offers new possibilities for diagnostic applications and screening for binding ligands.