Self-assembled monolayer of polyoxometalate on gold surfaces: Quartz crystal microbalance, electrochemistry, and in-situ scanning tunneling microscopy study

A new kind of inorganic self-assembled monolayer (SAM) was prepared by spontaneous adsorption of polyoxometalate anion, AsMo11VO404-, onto a gold surface from acidic aqueous solution. The adsorption process, structure, and electrochemical properties of the AsMo11VO404- SAM were investigated by quartz crystal microbalance (QCM), electrochemistry, and scanning tunneling microscopy (STM). The QCM data suggested that the self-assembling process could be described in terms of the Langmuir adsorption model, providing the value of the free energy of adsorption at -20 KJ mol(-1). The maximum surface coverage of the AsMo11VO404- SAM on gold surface was determined from the QCM data to be 1.7 x 10(-10) mol cm(-2), corresponding to a close-packed monolayer of AsMo11VO404- anion. The analysis of the voltammograms of the AsMo11VO404- SAM on gold electrode showed three pairs of reversible peaks with an equal surface coverage of 1.78 x 10(-10) mol cm(-2) for each of the peaks, and the value was agreed well with the QCM data. In-situ STM image demonstrated that the AsMo11VO404- SAM was very uniform and no aggregates or multilayer could be observed. Furthermore, the high-resolution STM images revealed that the AsMo11VO404- SAM on Au(lll) surface was composed of square unit cells with a lattice space of 10-11 Angstrom at +0.7 V (vs Ag\AgCl). The value was quite close to the diameter of AsMo11VO404- anion obtained from X-ray crystallographic study. The surface coverage of the AsMo11VO404- SAM on gold electrode estimated from the STM image was around 1.8 x 10(-10) mol cm(-2), which was consistent with the QCM and electrochemical results.

Study of ferric oxide nanoparticles-tris-(2,4-di-t-amylphenoxy)-(8-quinolinolyl) copper phthalocyanine composite LB film

The ferric oxide nanoparticles-tris-(2,4-di-t-amylphenoxy)-(8-quinolinolyl) copper phthalocyanine (CuPcA(2)) composite ultrathin film was obtained by LB (Langmuir-Blodgett) technique. Structure of the composite LB film was characterized by X-ray photoelectron spectra, transmission electron microscopy, infrared spectra and visible spectra. Gas sensitivity measurements indicate that the composite LB film is sensitive to 100-200 ppm C2H5OH at room temperature. (C) 2000 Elsevier Science S.A. All rights reserved.

Investigation into self-assembled monolayers of a polyether dendron thiol: Chemisorption, kinetics, and patterned surface

Different sizes of Frechet-type dendrons with a thiol group at the focal point were synthesized, well characterized, and used as building blocks for the preparation of self-assembled monolayers (SAMs) on metal surfaces. From the studies of the kinetic process of dendron thiol self-assembling on gold, it is shown that the dendron thiol assembling proceeds with different adsorption rates depending on the assembly time. In contrast to normal alkanethiols forming highly molecular structures on metal surfaces, the SAMs of polyether dendron form patterned surfaces with nanometer-sized features and in long-range order. It is found that the patterned stripes are closely related to the size of the dendron, and the patterned stripes can be improved by thermal annealing.

Preparation, structure, and properties of three-dimensional ordered alpha-Fe2O3 nanoparticulate film

alpha-Fe2O3 nanoparticulate films could be formed on the surface of alpha-Fe2O3 hydrosol after aging of the hydrosol or by compressing of the nanoparticles on the sol surface, in. which a three-dimensional ordered structure was constructed by the Langmuir-Blodgett; technique and colloid chemical methods. The structure of the LB film was characterized by AFM, TEM, XPS, and UV-vis spectra and small-angle X-ray diffraction. Gas-sensing measurement shows that the LB film has good sensitivity to alcohols at room temperature,

Self-assembled monolayer growth of phospholipids on hydrophobic surface toward mimetic biomembranes: Scanning probe microscopy study

Atomic force microscopy (AFM) and lateral force microscopy (LFM) were used simultaneously to analyze a model membrane bilayer structure consisting of a phospholipid outer monolayer deposited onto organosilane-derivatized mica surfaces, which were constructed by using painting and self-assembly methods. The phospholipid used as outer monolayer was dimyristoylphosphatidylcholine (DMPC). The hydrocarbon-covered substrate that formed the inner half bilayer was composed of a self-assembly monolayer (SAM) of octadecyltrichloroorganosilane (OTS) on mica. SAMs of DMPC were formed by exposing hydrophobic mica to a solution of DMPC in decane/isobutanol and subsequently immersing into pure water. AFM images of samples immersed in solution for varying exposure times showed that before forming a complete monolayer the molecules aggregated into dense islands (2.2-2.6 nm high) on the surface. The islands had a compact and rounded morphology. LFM, coupled with topographic data obtained with the atomic force mode, had made possible the distinction between DMPC and OTS. The rate constant of DMPC growth was calculated. This is the first systematic study of the SAM formation of DMPC by AFM and LFM imaging. It reveals more direct information about the film morphology than previous studies with conventional surface analytical techniques such as infrared spectroscopy, X-ray, or fluorescence microscopy.

掺杂态聚苯胺LB膜的制备与性质

掺杂樟脑磺酸的聚苯胺在纯水表面可以形成稳定的单分子层 ,采用Langmuir Blodgett技术可以将其较好地转移到氟化钙基片上制成薄膜.对其LB膜的红外和紫外 可见 近红外光谱研究表明 ,在膜的压缩或转移过程中有少量的樟脑磺酸分子发生脱掺杂的现象.并且该LB膜在室温下对乙醇有较好的气敏性.

Assembly of alternating polycation and DNA multilayer films by electrostatic layer-by-layer adsorption

The assembly of alternating DNA and positively charged poly(dimethyldiallylammonium chloride) (PDDA) multilayer films by electrostatic layer-by-layer adsorption has been studied. The real-time surface plasmon resonance (BIAcore) technique was used to characterize and monitor the formation of multilayer films in solution in real time continuously. Electrochemical impedance spectroscopy (EIS) and UV-vis absorbance measurements were also used to study the film assembly, and linear film growth was observed. All the results indicate that the uniform multilayer can be obtained on the poly(ethylenimine)- (PEI-) coated substrate surface. The kinetics of the adsorption of DNA on PDDA surface was also studied by the real-time BIAcore technique; the observed rate constant was calculated using a Langmuir model (k(obs) = (1.28 +/- 0.08) x 10(-2) s(-1).

Molecular orientation of copper phthalocyanine in thin films and their gas-sensing properties

Copper phthalocyanine derivative Langmuir-Blodgett (LB) films were prepared by vertical dipping and horizontal lifting methods. Molecular orientation of copper phthalocyanine derivative in thin films was studied by polarized UV-Vis spectra. The relationship between the molecular orientation of copper phthalocyanine in LB films and their gas-sensing properties was investigated.

A novel method for preparing ordered SnO2/TiO2 alternate nanoparticulate films

A novel method using LB films as precursors to prepare pure inorganic ordered film with periodic structure was developed. Surfactant-stabilized SnO2 nanoparticulate organosols and TiO2 nanoparticulate organosols were prepared and used as spreading solutions. Using LB technique, the good film-forming ability of the surfactant-stabilized SnO2 nanoparticles and TiO2 nanoparticles was confirmed by the determination of the pi -A isotherms. The surfactant-stabilized SnO2 and TiO2 nanoparticulate monolayers were fabricated on the water surface and then were transferred to solid substrates (CaF2, quartz, silicon, and so on) alternately, layer-by-layer. Then the as-deposited alternate LB film was treated at different temperatures. The as-deposited alternate LB film and the treated film were characterized by Fourier transform infrared spectroscopy, UV visible spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The results indicate that our method was successful. The as-deposited alternate LB film formed a periodic structure with a long spacing of 6.5 nm that was composed of SnO2 nanoparticles, TiO2 nanoparticles, and arachidic acid. The treated film composed of SnO2 nanoparticles and TiO2 nanoparticles formed a pure inorganic periodic structure with an ordered distance of 5.4 nm. (C) 2001 Academic Press.

Simple preparation method of multilayer polymer films containing Pd nanoparticles

A simple route to the fabrication of multilayer films containing Pd nanoparticles is described. Following layer-by-layer assembly of PdCl42- and polycation, QPVP-Os (a quaternized poly(4-vinylpyridine) complexed with [Os(bpy)(2)Cl](2+/+)), on 4-aminobenzoic acid-modified glassy carbon electrodes, the three-dimensional Pd nanoparticle multilayer films are directly formed on electrode surfaces via electrochemical reduction of PdCl42- sandwiched between polymers. The growth of PdCl42- is easy on electrode surfaces by electrostatic interaction, and the assembly processes are monitored by cyclic voltammetry and UV-vis spectroscopy. The depth profile analyses by X-ray photoelectron spectroscopy verify the constant composition of the Pd nanoparticle multilayer films. Atomic force microscopy proves that the as-prepared Pd nanoparticles are uniformly distributed with an average particle diameter of 3-7 mn. The resulting Pd nanoparticle multilayer-modified electrode possesses high catalytic activity for the reduction of dissolved oxygen and oxidation of hydrazine compounds in aqueous solution.

Study on polymer micelles of hydrophobically modified ethyl hydroxyethyl cellulose using single-molecule force spectroscopy

Individual hydrophobically modified ethyl hydroxyethyl cellulose (HM-EHEC) molecules under different conditions were elongated using a new atomic force microscope (AFM) based technique-single-molecule force spectroscopy (SMFS). The critical concentration of HM-EHEC for micelle-like clusters at a solid/liquid interface was around 0.8 wt %, which is lower than that in solution. The different mechanical properties of HM-EHEC below and above the critical concentration were displayed on force-extension curves. Through a comparison with unmodified hydroxyethyl cellulose, substituent-induced effects on nanomechanical features of HM-EHEC were investigated. Because of hydrophobic interactions and cooperative binding with the polymer, surfactants such as sodium dodecyl sulfate (SDS) dramatically influence the elastic properties of HM-EHEC below the critical concentration, and further addition of SDS reduces the interactions between the hydrophobic groups and the surfactant.

Formation of a self-assembled monolayer of 2-mercapto-3-n-octylthiophene on gold

Monolayer assembly of 2-mercapto-3-n-octylthiophene (MOT) having a relatively large headgroup onto gold surface from its dilute ethanolic solutions has been investigated by electrochemistry. An electrochemical capacitance measurement on the permeability of the monolayer to aqueous ions, as compared with its alkanethiol counterpart [CH3(CH2)(9)SH (DT)] with a similar molecular length, shows that the self-assembled monolayers (SAMs) of MOT can be penetrated by aqueous ions to some extent. Furthermore, organic molecular probes, such as dopamine, can sufficiently diffuse into the monolayer because a diffusion-limited current peak is observed when the dopamine oxidation reaction takes place, showing that the monolayer is loosely packed or dominated by defects. But the results of electron transfer to aqueous redox probes (including voltammetry in Fe(CN)(6)(3-/4-) solutions and electrochemical ac impedance spectrum) confirm that the monolayer can passivate the gold electrode surface effectively for its very low ratio of pinhole defects. Moreover, a heterogeneous patching process involving addition of the surfactants into the SAMs provides a mixed or hybrid membrane that has superior passivating properties. These studies show that the MOT monolayer on the electrode can provide an excellent barrier for hydrated ionic probe penetration but cannot resist the organic species penetration effectively. The unusual properties of the SAMs are attributed to the entity of the relatively large thiophene moiety between the carbon chain and the thiol group.

Study of the mechanism for controlled crystallization of BaF2 under two kinds of monolayers

Controlled crystallization of BaF2 under two different kinds of monolayers, octadecylamine [CH3(CH2)(17)NH2] and hexadecanol [CH3(CH2)(14)CH2OH], has been studied by using x-ray diffraction (XRD) and scanning electron microscope. It was found that the monolayer headgroup, the degree of ionization of the headgroup, etc., had a complicated effect on the selectivity of monolayers for crystal and on the morphology and orientation of crystals grown under the compressed monolayers. At pH = 7.0, XRD analysis showed that (100)-oriented BaF2 crystals were formed under the octadecylamine monolayer, while several kinds of crystals were found under the hexadecanol monolayer. In comparison, at pH = 8.5, both (100)-oriented BaF2 and (111)-oriented Ba(NO3)(2) crystals were obtained under the monolayer of octadecylamine. However, crystals formed under hexadecanol monolayer consist of BaF2, Ba(NO3)(2), etc. The detailed mechanism for crystallization was discussed in terms of the specific interaction and lattice matching between the monolayer headgroup and the nucleating species.

Controlled nucleation and growth of surface-confined gold nanoparticles on a (3-aminopropyl)trimethoxysilane-modified class slide: A strategy for SPR substrates

The thickness of the gold film and its morphology, including the surface roughness, are very important for getting a good, reproducible response in the SPR technique. Here, we report a novel alternative approach for preparing SPR-active substrates that is completely solution-based. Our strategy is based on self-assembly of the gold colloid monolayer on a (3-aminopropyl)trimethoxysilane-modified glass slide, followed by electroless gold plating. Using this method, the thickness of films can be easily controlled at the nanometer scale by setting the plating time in the same conditions. Surface roughness and morphology of gold films can be modified by both tuning the size of gold nanoparticles and agitation during the plating. Surface evolution of the Au film was followed in real time by UV-vis spectroscopy and in situ SPRS. To assess the surface roughness and electrochemical stability of the Au films, atomic force microscopy and cyclic voltammetry were used. In addition, the stability of the gold adhesion is demonstrated by three methods. The as-prepared Au films on substrates are reproducible and stable, which allows them to be used as electrodes for electrochemical experiments and as platforms for studying SAMs.

Study of elastic modulus and yield strength of polymer thin films using atomic force microscopy

Nanometer-scale elastic moduli and yield strengths of polycarbonate (PC) and polystyrene (PS) thin films were measured with atomic force microscopy (AFM) indentation measurements. By analysis of the AFM indentation force curves with the method by Oliver and Pharr, Young's moduli of PC and PS thin films could be obtained as 2.2 +/- 0.1 and 2.6 +/- 0.1 GPa, respectively, which agree well with the literature values. By fitting Johnson's conical spherical cavity model to the measured plastic zone sizes, we obtained yield strengths of 141.2 MPa for PC thin films and 178.7 MPa for PS thin films, which are similar to2 times the values expected from the literature. We propose that it is due to the AFM indentation being asymmetric, which was not accounted for in Johnson's model. A correction factor, epsilon, of similar to0.72 was introduced to rescale the plastic zone size, whereupon good agreement between theory and experiment was achieved.