Single-molecule spectroscopy studies of microenvironmental acidity in silicate thin films

Single-molecule (SM) spectroscopic methods were employed to study single site variations in the acidity properties of sol-gel-derived silicate films. The pH-sensitive dye Carboxy SNARF-1 (C.SNARF-1) was used to sense film acidity. Its concentration in the films was maintained at nanomolar levels to allow for SMs to be spectroscopically interrogated. The ratio of C.SNARF-1 fluorescence at 580 nm (protonated form) and 640 nm (deprotonated form) was used to characterize local film pH. SM data were acquired both for "untreated" films and for those treated by immersion for either 1 or 8 h in phosphate solutions of different pH. The SM results prove that the spectral variability observed is dominated by static variations in the local matrix acidity. Shorter immersion times lead to relatively broad histograms and broad "titration" curves, providing clear evidence for kinetic limitations to access of certain film environments by the immersion solutions. Films subjected to longer immersion times generally exhibit narrower histograms. Particularly narrow distributions were obtained for films treated near pH 8-9, while much broader histograms were produced near pH 7. These results are attributed to the buffering effects of surface silanols near pH 9 and enhanced pH sensitivity of the dye near pH 7.     

Physical insights into the photoactivated Ullmann coupling process producing highly conjugated oligothiophene films on a copper substrate

This paper describes the details of surface reactions producing >100-nm-thick conjugated polymer films. When 2,5-diiodothiophene films deposited on copper are irradiated with UV at room temperature in Ar environments, oligothiophene films are synthesized. The average conjugation length of the produced film varies from approximately 7 to 3-4 as the film thickness increases from approximately 100 to approximately 500 nm. The X-ray photoelectron spectroscopy analysis of the produced films reveals evidence for the formation of organo-copper intermediate species at the copper-monomer film interface and their diffusion from the copper surface into the monomer film during the photochemical process. A one-dimensional diffusion-reaction model is presented to explain the formation, diffusion, and reaction of organo-copper intermediates in the multilayer film during the photochemical reaction. The model simulation results qualitatively explain the decrease of the Ullmann coupling contribution in the photochemical reaction with the film thickness.     

Optical Viscometry of Spinning Sol Coatings

Optical interferometric monitoring of spin coating (optospinography) has allowed close observation of the temporal evolution of a thin silicate sol film (typically at 2000 rpm, 100 Hz data acquisition). The kinematic viscosity data obtained, using a simple analytical model, are validated with those from a mineral oil standard, with agreement well within the experimental uncertainties. For spin coating in open air, the influence of variations in refractive index, rheological properties and air flow are discussed. Inflections in the temporal evolution of the optical thickness of silicate sol films are analyzed, which indicate the usefulness of optospinography, particularly when applied in the proximity of the rotation axis and evaporation is minimized, to monitor time variations in the kinematic viscosity of these sols during spin coating.     

Electropolymerization of polypyrrole, modified with germanium, on a passivated titanium electrode in aqueous nitrate solution: new results on catalytic reduction of protons and dissolved oxygen

Conductive polypyrrole (PPy) films and PPy films containing Ge microparticles were synthesized by anodic oxidation of pyrrole in acidic nitrate solutions using a bare passivated titanium electrode. Well-adhering black PPy films were obtained both under galvanostatic and potentiodynamic polarization. After the formation of the PPy film, during the first anodic cycle, an increase of the anodic deposition current with the number of cycles was observed, revealing the increase of conductivity of the growing film. The variations of the electrode surface area were estimated by impedance spectroscopy measurements. The kinetics of the PPy film formation is controlled by diffusion of the Py monomer in the solution. The diffusion coefficient, estimated by two different methods, was ca. 2×10^–6 cm² s^–1. The reduction rate of oxygen and protons at the Ti/PPy/Ge electrodes depends on how the Ge microparticles are incorporated in the PPy film. Optimum conditions for this incorporation are realized with thin PPy films and high Ge loading. Thermogravimetric analysis shows that the PPy film containing Ge microparticles is more thermally stable than the blank PPy film. Electronic Publication     

An ensemble and single-molecule fluorescence microscopy investigation of phase-separated monolayer films stained with Nile Red

Phase-separated Langmuir-Blodgett monolayer films prepared from mixtures of arachidic acid (C19H39COOH) and perfluorotetradecanoic acid (C13F27COOH) were stained via spin-casting with the polarity sensitive phenoxazine dye Nile Red, and characterized using a combination of ensemble and single-molecule fluorescence microscopy measurements. Ensemble fluorescence microscopy and spectromicroscopy showed that Nile Red preferentially associated with the hydrogenated domains of the phase-separated films, and was strongly fluorescent in these areas of the film. These measurements, in conjunction with single-molecule fluorescence imaging experiments, also indicated that a small sub-population of dye molecules localizes on the perfluorinated regions of the sample, but that this sub-population is spectroscopically indistinguishable from that associated with the hydrogenated domains. The relative importance of selective dye adsorption and local polarity sensitivity of Nile Red for staining applications in phase-separated LB films as well as in cellular environments is discussed in context of the experimental results.     

Scanning electrochemical microscopy study of laccase within a sol-gel processed silicate film

The enzyme p-diphenol:dioxygen oxidoreductase (laccase, EC 1.10.3.2) was isolated from Cerrena unicolor fungus and embedded in a sol-gel film obtained by acidic condensation of TMOS. The gel was cast to thin films on glass. The laccase-containing silicate films were inspected by confocal laser scanning microscopy (CLSM), scanning force microscopy (SFM) and scanning electrochemical microscopy (SECM). CLSM images in the reflection mode showed aggregates within the silicate films. SECM images in the substrate-generation/tip-collection mode using 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonate) (ABTS) as electron donor for laccase showed that the position of aggregates coincides with increased enzymatic activity within the silicate film. The flux from individual aggregates was detected. SECM images in the redox competition mode confirmed the assignment and could exclude that topographic features observed by CLSM and SFM could be the reason for the image contrast. SFM images showed that the aggregates partially dissolve during prolonged exposure to aqueous buffer. The experimental setup allowed following one individual aggregate over time with all three microscopic techniques which enabled the collection of complementing information on morphology and catalytic activity as well as their development over time.     

Covalently networked monolayer-protected nanoparticle films

Covalently networked films of nanoparticles can be assembled on various substrates from functionalized monolayer-protected clusters (MPCs) via ester coupling reactions. Exposure of a specifically modified substrate to alternating solutions of 11-mercaptoundecanoic acid exchanged and 11-mercaptoundecanol exchanged MPCs, in the presence of ester coupling reagents, 1,3-dicyclohexylcarbodiimide and 4-(dimethylamino)pyridine, results in the formation of a multilayer film with ester bridges between individual nanoparticles. These films can be grown in a controlled manner to various thicknesses and exhibit certain properties that are consistent with films having other types of interparticle connectivity, including chemical vapor response behavior and quantized double layer charging. Ester coupling of MPCs into assembled films is a straightforward and highly versatile approach that results in robust films that can endure harsher chemical environments than other types of films. The stability of these covalent films is assessed and compared to other more traditional MPC film assemblies.     

Imaging nanostructures with scanning photoionization microscopy

We report detailed studies of local electronic properties in nanostructured thin metallic films using scanning photoionization microscopy. This novel form of microscopy combines the advantages of diffraction-limited optical excitation with the ability to detect both photons and low kinetic energy photoelectrons, permitting sensitive characterization of heterogeneous surfaces under vacuum conditions. Using this technique, correlated measurements of multiphoton photoemission cross section and optical penetration depth are reported for Au films supported on Pt. These results present a first step toward combining confocal fluorescence or Raman microscopy with time-resolved photoelectron imaging spectroscopy in complex metal film environments, which should be ideally suited to investigating local plasmonic effects in nanostructures.     

Raman imaging and Kelvin probe microscopy for the examination of the heterogeneity of doping in polycrystalline boron-doped diamond electrodes

The issue of the heterogeneity of boron doping in microcrystalline diamond films was addressed by four different methods: micro-Raman spectroscopy and Raman imaging, Kelvin probe force microscopy, conducting atomic force microscopy, and scanning electrochemical microscopy. The samples were commercially available films from Windsor Scientific, with an average boron concentration of about 5 x 10(20) cm(-3). In agreement with previous works, all of the methods showed that the boron uptake was nonuniform across the surface of the electrode. Two different types of regions were evidenced, with metallic or semiconducting properties that were characterized with different types of Raman spectra. The line shape of these spectra was strongly dependent on the excitation wavelength. Local variations in electroactivity were evidenced by the SECM curves, which are related to the electronic properties of the individual grains, which, in turn, are governed by the boron content of the individual crystallites. In this study, two different micro-Raman imaging techniques were used that reveal the grain structure of the films: the images constructed from the diamond line intensity perfectly reproduced the optical image obtained by illuminating the sample in reflection. The method also allows detection of the presence of nondiamond carbon, especially in the metallic parts of the samples. Other spectral features (intensity of the boron-related broad lines, as well as the frequency and width of the diamond line) were used to construct images. In every case, the grain structure of the film was revealed, as well as twinning within individual crystallites. All approaches revealed that no enhanced doping or boron depletion occurred at the grain boundaries.     

Synthesis and Properties of Composite Polyaniline–Nafion Films on Platinum

Information on the synthesis of a polyaniline film on platinum covered with a Nafion film is obtained. The effect of electrochemical conditions on the synthesis is studied. The relationship between these conditions and properties of obtained composite polyaniline–Nafion films is revealed. It is established that on platinum covered with a Nafion film in certain electrochemical conditions in a polyaniline solution there occurs the formation of a composite polyaniline–Nafion film. The polyaniline in the film mainly retains its individual properties. It is demonstrated that the mechanism of the synthesis of polyaniline in the composite film substantially differs from that in the case of the formation of a film on platinum.     

TEM investigation of formation mechanism of monocrystal-thick b-oriented pure silica zeolite MFI film

The first direct transmission electron microscopic (TEM) observation has been carried out on the continuous monocrystal-thick b-oriented pure silica zeolite MFI films produced by in situ crystallization. The self-supporting film samples for TEM study were fabricated by dissolving the steel substrate with acid. This TEM study is free of those artifacts that are typically associated with TEM sample preparations, and allows us to investigate the "true" structure and texture of a very large area of the film and at the same time to focus at will on each individual zeolite crystal in the film. Abundant TEM information including crystallographic orientation relationships among crystals in the film (both out-of-plane and in-plane), grain boundaries, and each crystal grain was obtained. This TEM investigation provides direct unambiguous new evidence to support the homogeneous nucleation mechanism, by which the films form through homogeneous nucleation and crystal growth in the bulk to form equal-sized disk-shape crystals, followed by self-assembly of these crystals onto the substrate to produce a two-dimensional close-packed structure. The last stage of the film formation involves simultaneous space-limited growth and rotation of the individual crystals to realize the in-plane crystallographic control within the film.     

Interaction of hydrogen with surfaces of silicates: single crystal vs. amorphous

We have studied how the formation of molecular hydrogen on silicates at low temperature is influenced by surface morphology. At low temperature (<30 K), the formation of molecular hydrogen occurs chiefly through weak physical adsorption processes. Morphology then plays a role in facilitating or hindering the formation of molecular hydrogen. We studied the formation of molecular hydrogen on a single crystal forsterite and on thin films of amorphous silicate of general composition (Fe(x)Mg((x-1)))(2)SiO(4), 0 < x < 1. The samples were studied ex situ by Atom Force Microscopy (AFM), and in situ using Thermal Programmed Desorption (TPD). The data were analysed using a rate equation model. The main outcome of the experiments is that TPD features of HD desorbing from an amorphous silicate after its formation are much wider than the ones from a single crystal; correspondingly typical energy barriers for diffusion and desorption of H, H(2) are larger as well. The results of our model can be used in chemical evolution codes of space environments, where both amorphous and crystalline silicates have been detected.     

Alginate-magnesium aluminum silicate films for buccal delivery of nicotine

Sodium alginate-magnesium aluminum silicate (SA-MAS) dispersions with nicotine (NCT) were prepared at different pHs and characterized for the particle size and zeta potential, NCT adsorbed by MAS, and flow behavior before film casting. The physicochemical properties, NCT content, in vitro bioadhesive property, and NCT release and permeation of the NCT-loaded SA-MAS films were investigated. This study showed that incorporation of NCT into the SA-MAS dispersions caused a change in particle size and flow behavior and that NCT could be adsorbed by MAS. The formation of protonated NCT at acidic and neutral pHs could interact with negatively charged MAS via an electrostatic force, resulting in the formation of NCT-MAS flocculates/complexes that could act as microreservoirs in the films. The NCT-loaded SA-MAS films prepared at pH 5 yielded the highest NCT content due to non-significant loss of NCT during drying. Moreover, pH of the preparation also affected the crystallinity and thermal properties of the films. The NCT release and permeation across the mucosal membrane of the films could be described using a matrix diffusion controlled mechanism. In addition, the NCT-loaded SA-MAS films also possessed a bioadhesive property for adhesion to the mucosal membrane. This finding suggests that the NCT-loaded SA-MAS films composed of numerous NCT-MAS complexes as microreservoirs demonstrated a strong potential for use as a buccal delivery system.     

Nanostructures of surfaces of silica films obtained by sol—gel method in the presence of organic additives

The dependence of the antireflection properties of film coatings deposited on the silicate glass obtained by sol—gel method in the presence of organic additives on the dimensions of nanostructures of the silica films was studied.     

Regularities of Electrochemical Formation and Properties of Oxide Films on Titanium–Iron Alloys

Regularities governing the formation and properties of oxide films on titanium–iron alloys containing 10, 20, 32, 45, 60, or 80 at. % Fe are studied by the voltammetry and chronoamperometry methods coupled with local measurements of activation potentials. Dependences of the oxide film thickness on potential are found. Activation potentials for samples with oxide films formed in air and at 5 V decrease with increasing iron content in alloys.     

Thin ORMOSIL Films with Different Organics

Structural, optical and electrical properties of silicate films modified by structure fragments containing different organic groups were studied. The ORMOSILs were produced by a cohydrolysis of tetraethoxysilane with different types of alkyl (aryl) substituted alkoxysilanes. Film structure and its evolution during heat treatment were studied by ellipsometry and IR spectroscopy. For methyl- and phenyl-modified silicate films the shrinkage is lower than for silicate ones in the range of annealing temperature from 200 to 500°C. The shrinkage of phenyl-modified silicate film is more than three times lower than of methyl- and trimethyl-modified ones. The presence of single or double C=C bonds in the organic chain leads to an increase in the film shrinkage due to the thermodestruction of the bond as it is confirmed by IR data. In the case of phenyl- and methyl-modified silicate films this process starts from 500°C and it is accompanied by abrupt film shrinkage. The dielectric constant and the loss tangent of methyl and phenyl groups decrease due to reduction of hydroxyl content and film density. Other groups are not effective due to their thermodestruction at lower temperatures.     

Zeolite Beta Formation from Clear Sols: Silicate Speciation,Particle Formation and Crystallization Monitored by Complementary Analysis Methods

The formation of silicate nanoaggregates (NAs) at the very early stages of precursor sols and zeolite beta crystallization from silicate nanoparticles (NPs) are investigated in detail using a combination of different analysis methods, including liquid‐state ²⁹Si, ²⁷Al, ¹⁴N, and ¹H NMR spectroscopy, mass spectrometry (MS), small‐angle X‐ray scattering (SAXS), X‐ray diffraction (XRD), and transmission electron microscopy at cryogenic temperatures (cryo‐TEM). Prior to hydrothermal treatment, silicate NAs are observed if the Si/OH ratio in the reaction mixture is greater than 1. Condensation of oligomers within the NAs then generates NPs. Aluminum doped into the synthesis mixtures is located exclusively in the NPs, and is found exclusively in a state that is fourfold connected to silicate, favoring their condensation and aggregation. These results are in agreement with general trends observed for other systems. Silicate NAs are essential intermediates for zeolite formation and are generated by the aggregation of hydrated oligomers, aluminate, and templating cations. Subsequent further intra‐nanoaggregate silicate condensation results in the formation of NPs. ¹H and ¹⁴N liquid NMR as well as diffusion ordered spectroscopy (DOSY) experiments provide evidence for weakly restricted rotational and translational mobility of the organic template within NAs as a consequence of specific silicate–template interactions. NAs thus appear as key species in clear sols, and their presence in the precursor sol favors silicate condensation and further crystallization, promoted either by increasing the Si/OH ratio or by heating.     

Dependence of electrochemical properties of vanadium oxide films on their nano- and microstructures

Platelet- and fibrillar-structured V2O5 films have been prepared by solution methods, and their electrochemical Li+ intercalation properties have been studied. Platelet film consists of 20-30 nm sized V2O5 particles with random orientation, whereas fibrillar film is comprised of randomly oriented fibers though most of them protrude from the substrate surface. These platelet- and fibrillar-structured films exhibit relatively larger surface area and shorter diffusion path for Li+ intercalation than plain thin film structure. The processing methods, the discharge capacity, and cyclic performance of these films are compared with those of the conventional plain structured film.     

Stability and disintegration of ultrathin heptane films in water: molecular dynamics simulations

Molecular dynamics simulations of ultrathin heptane films (less than 5 nm in thickness) in water were conducted to study their stability and disintegration behavior. The density distributions of heptane and water molecules across the film were determined for different equilibrium film thicknesses ranging from 1.5 to 4 nm. The potential energy of the system was computed as a function of the heptane number fraction, and the results were employed to determine the excess energy of mixing of heptane in water. The diffusion coefficients of heptane and water obtained from the MD simulations were also compared with experimental data. A good agreement was found between the heptane self-diffusivity obtained from the MD simulations and its literature reported value. Following an analysis of the equilibrium properties of the heptane films and associated structures, we performed simulations where the shapes of the heptane films were initially perturbed. Different perturbations of these ultrathin films led to formation of various associated structures, including cylindrical rodlike heptane droplets, films with holes, and intact films. The different shapes are formed in systems with the same heptane/water composition. An analysis of this behavior is presented showing the possibility of multiple associated structures with similar total energy in these highly confined systems.     

Polymer films on electrodes: Part III. Digital simulation model for cyclic voltammetry of electroactive polymer film and electrochemistry of poly(vinylferrocene) on platinum

The electrochemistry of electrodeposited poly(vinylferrocene) (PVF) and poly(vinylferrocene acrylonitrile) (PVFAN) films on platinum electrodes was studied in acetonitrile solutions using perchlorate or p-toluenesulfonate as the counter ion by cyclic voltammetry. A model is proposed for the cyclic voltammetric behavior of polymeric films on electrode surfaces. The model incorporates non-equivalent redox sites with interconversion between such sites, electron-transfer kinetics at substrate/film interface and diffusion within the film. Parameters are obtained which yield a good fit to the experimental results.