Self-assembled monolayer growth of octanol on mica: Atomic force microscopy and Fourier-transform infrared spectroscopy studies

The growth kinetics of self-assembled monolayers formed by exposing freshly cleaved mica to octanol solution has been studied by atomic force microscopy (AFM) and Fourier-transform infrared spectroscopy (FTIR). AFM images of samples immersed in octanol for varying exposure times showed that before forming a complete monolayer the octanol molecules aggregated in the form of small islands on the mica surface. With the proceeding of immersion, these islands gradually grew and merged into larger patches. Finally, a close-packed film with uniform appearance and few defects was formed. The thickness of the final film showed 0.8 nm in height, which corresponded to the 40degrees tilt molecular conformation of the octanol monolayer. The growth mechanisms consisted of nucleation, growth, and coalescence of the submonolayer films. The growth process was also confirmed by FTIR. And the surface coverage of the submonolayer islands estimated from AFM images and FTIR spectra as a function of immersion time was quite consistent.

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.

Synthesis, characterization and fabrication on a glassy carbon electrode of a tetra-iron substituted sandwich-type pentadecatungstodiarsenate heteropolyanion

A novel sandwich-type compound, Na-12[Fe-4(H2O)(2)(As2W15O56)2].41H(2)O, has been synthesized. The compound was well-characterized by means of IR, UV-vis, W-183 NMR and elemental analyses. The compound crystallizes in the triclinic, P (1) over bar symmetry group. The structure of the compound is similar to that of Na-16[M-4(H2O)(2)(As2W15O56)(2)].nH(2)O (M = Cu, Zn, Co, Ni, Mn, Cd), and consists of an oxo-aqua tetranuclear iron core, [(Fe4O14)-O-III(H2O)(2)], sandwiched by two trivacant alpha-Wells-Dawson structural moieties, alpha-[As2W15O56]. Redoxelectrochemistry of the compound has been studied in buffer solutions at pH = 4.7 using polarography and cyclic voltammetry ( CV). The compound exhibited four one-electron couples associated with the Fe(III) center followed by three four-electron redox processes attributed to the tungsten-oxo framework. The compound-containing monolayer and multilayer films have been fabricated on a 4-aminobenzoic acid modified glassy carbon electrode surface by alternating deposition with a quaternized poly(4-vinylpyridine) partially complexed with [Os(bpy)(2)Cl](2+/-). CV, X-ray photoelectron spectroscopy (XPS), UV-vis spectroscopy and atomic force microscopy (AFM) have been used to characterize the multilayer films.

Multifunctional organic-inorganic multilayer films of tris(2,2 '-bipyridine)ruthenium and decatungstate

A new multifunctional multilayer films consisting of tris(2,2'-bipyridyl)ruthenium(II) (Rubpy) and sodium decatungstate (W-10) have been prepared by the layer-by-layer (LbL) self-assembly method on ITO substrate. X-ray photoelectron spectra (XPS) confirmed the existence of W10 and Rubpy. Cyclic voltammetry (CV) and UV-Vis spectroscopy demonstrated the uniform assembly of (W-10/Rubpy) multilayer films. The multilayer films possess electrocatalytic activities on the reduction of iodate and oxidation of oxalate. Moreover, the films exhibited electrochemiluminescence (ECL) with tripropylamine (abbreviated as TPA) as the coreactant and the ECL response was proportional to the number of (W-10/Rubpy) layers. These characteristics of the multilayer films might find potential applications in the field of sensors and materials fields.

Lanthanide complex/polymer composite optical resin with intense narrow band emission, high transparency and good mechanical performance

Novel composite resins possessing good luminescent properties have been synthesized through a free radical copolymerization of styrene, alpha-methylacrylic acid and the binary or ternary complexes of lanthanide ions (Eu3+ and Tb3+). These polymer-based composite resins not only possess good transparency and mechanical performance but also exhibit an intense narrow band emission of lanthanide complexes under UV excitation. We characterized the molecular structure, physical and mechanical performance, and luminescent properties of the composite resins. Spectra investigations indicate that alpha-methyl-acrylic acid act as both solubilizer and ligand. Photoluminescence measurements indicate that the lanthanide complexes show superior emission lines and higher intensities in the resin matrix than in the corresponding pure complex powders, which can be attributed to the restriction of molecular motion of complexes by the polymer chain networks and the exclusion of water molecules from the complex. We also found that the luminescence intensity decreased with increasing content of alpha-methylacrylic acid in the copolymer system. The lifetime of the lanthanide complexes also lengthened when they were incorporated in the polymer matrix. In addition, we found that the relationships between emission intensity and Tb (Eu) content exhibit some extent of concentration quenching.

Molecular construction of oriented crystalline NaMnF3 and KMnF3 with perovskite structures at room temperature

In this work. we report the fabrication of high-quality (101)-oriented orthorhombic NaMnF3 and (100)-oriented cubic KMnF3 perovskites via an organic monolayer template at room temperature. The controlled crystallization under the organic monolayer template is explained in terms of the electrostatic interactions and beneficial lattice matching between the organic template and the ions undergoing nucleation. The present study is of great importance in the preparation of oriented perovskite materials as well as in the understanding of the mechanism for organic-template-directed crystallization.

LB films of 2-n-heptadecanoylbenzoic-rare earth and their luminescence properties

Several ultrathin luminescent Langmuir-Blodgett (LB) films have been prepared by using the subphase containing the rare earth ions (Eu3+, Tb3-). The effect of the rare earth ions on the monolayer of 2-n-heptadecanoylbenzoic acid (HBA) was investigated. IR and UV spectra showed the rare earth ions were bound to the carboxylic acid head groups and the coordination took place between the polar head group and the rare earth ions. The layer structure of the LB films was demonstrated by low-angle X-ray diffraction. UV absorbance intensity increases linearly with the number of LB films layers, which indicate that the LB films are homogeneously deposited. The LB films can give off strong fluorescence. and the signal can be detected from a single layer. The characteristic luminescence behaviors of LB films have been discussed compared with those of the complexes.

Luminescence properties of LB films based on heteropolytungstate of rare earth

In this work, the LB films based on heteropolytungstate of Dy and Sm have been prepared. The X-ray diffraction shows the LB films have a highly ordered lamella structure. The luminescence characteristics of the LB films were studied. The charge transfer bands of LB films are in higher energies than those of the corresponding solids. It is noticed that the yellow to blue intensity ratio (Y:B) of Dy3+ in the LB films is different from that of the solid. The differences in the spectra show that the Dy3+ site symmetry in LB film was changed due to the interaction between the surfactant and the polyanions. The differences could also be found in the luminescence spectra of the LB films of Sm complex.

Preparation and luminescence properties of LB films based on 4-hexadecyloxybenzoic terbium

LB films of 4-hexadecyloxybenzoic-terbium by using the subphase containing Tb3+ were prepared. The monolayer behavior of 4-hexadecyloxybenzoic acid (HOBA) on the subphase containing rare earth ions was studied. IR and UV spectra show that the rare earth ions were bound to carboxylic acid head groups and the coordination took place between the polar head group and the rare earth ions. The luminescence spectra show that the LB films have the fine luminescence properties, and the LB films emit strong luminescence under UV light irradiation.

Effect of alkyl group length on the conductivity in the 2,3,7,8,12,13,17,18-octakis(alkyl-thio)tetraazaporphyrins and redox properties of the metallooctakis(hexyl-thio)tetraazaporphyrins

A series of 2,3,7,8,12,13,17,18-octakis(alkyl-thio)tetraazaporphyrins (H(2)OATTAP) with different alkyl chain lengths have been synthesized. Cyclic voltammetry and differential pulse voltammetry have been used to investigate the effect of the controlled lengths of the eight peripheral thioether tails on the redox behavior of the molecules. The electrochemical reduction of octakis(hexyl-thio)tetraazaporphyrins, MOHTTAP (where M = Cu, Ni), was studied in 1,2-dichloroethane at a platinum electrode. The Cu derivative was oxidized in one single-electron-transfer step to yield a pi-cation radical and reduced in three single-electron-transfer steps to yield a pi-anion radical, dianion and trianion, respectively. For the Ni derivative, electron transfer reactions involving both the central metal atom and the macrocyclic ring were observed. Electron transfer pathways are proposed based upon voltammetric and in situ spectroelectrochemical results.

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.

Infrared spectrum of 2-octadecyl-7,7,8,8-tetracyanoquinodimethane

Infrared spectrum of 2-octadecyl-7,7,8,8-tetracyanoquinodimethane was dealt with 2nd-derivative and deconvolution methods. It was first discovered that the band near 2849 cm(-1) assigned to the CH2 Symmetric stretching mode splited into two bands and this splitting might result from the coexistence of two kinds of conformations of CH2 in the hydrocarbon chain.

Effective energy transfer and luminescence of LB films based on europium-substituted heteropolytungstate

The europium-substituted heteropolytungstate K13Eu(SiW11O39)(2) was successfully assembled into two lipids by LB technique for the first time. X-ray diffraction has shown a well defined lamellar for the LB films. The LB films have been characterized by fluorescence spectra and the characteristic luminescence behaviors were discussed. The ligand-metal charge transfer band could be observed in the spectra of the LB films, which could not be found in that of heteropolytungstate solid. The results of fluorescence spectra indicate the energy could be effectively transferred from ligands to the Eu3+ ions in the LB films and the luminescence efficiency was increased greatly. The influences of various lipids on the luminescence of polyoxometalates were investigated. The various interactions between monolayer and polyanions have different effect on the luminescence properties of europium-substituted heteropolytungstate.

Preparation and characterization of ordered yttrium arachidate multilayer

The behavior of arachidic acid on the surface of YCI3 aqueous subphase was studied by LB and Brewster angle microscopy techniques. The results showed that the pre-compressing time and the pH of the subphase played an important role in the forming of the monolayer. The monolayer on the subphase surface was irreversible. If the monolayer was compressed into wrinkles, the monolayer could not become uniform again. The optimum transferring conditions were selected and the ordered yttrium arachidate multilayer with a long spacing of 4.96 nm and a tilt angle of 28.5degrees of the three alkyl chains from the surface normal was fabricated and characterized.