Thin films of functionalized amorphous silica for immunosensors application

Within the framework of the development of an optical immunosensor, the sol-gel process has been used to prepare a thin film of amorphous silica, deposited by spin coating on a gold-coated glass slide, and possessing chemically active functional groups (SH, NH₂...). After activation of the sol-gel film in aqueous buffers by a bifunctional coupling agent, biological molecules such as antibodies could be covalently bonded on or inside the sol-gel film. Therefore, the behavior in aqueous solutions of the functionalized silica thin films has been analysed by Surface Plasmon Resonance (SPR) and guided wave propagation. Results show a modification of the thickness and of the refractive index of the silica film. Pore size range has been deduced by the infiltration of different molecular weight dextran molecules diluted in water into the sol-gel material. Immunosassays have demonstrated biological activity of antibodies which are covalently linked to or entraped in the sol-gel film.     

Mesoporous hybrid thin films: the physics and chemistry beneath

Mesoporous films containing organic or biological functions within an organised array of cavities are produced by combining sol-gel, self-assembly of supramolecular templates and surface chemistry. This paper reviews the essential physics and chemical concepts behind the synthesis of these complex multifunctional materials.     

Electrochemical and spectroscopic characterization of surface sol-gel processes

(3-Mercaptopropyl)trimethoxysilane (MTS) forms a unique film on a platinum substrate by self-assembly and sol-gel cross-linking. The gelating and drying states of the self-assembled MTS sol-gel films were probed by use of electrochemical and spectroscopic methods. The thiol moiety was the only active group within the sol-gel network. Gold nanoparticles were employed to detect the availability of the thiol group and their interaction further indicated the physicochemical states of the sol-gel inner structure. It was found that the thiol groups in the open porous MTS aerogel matrix were accessible to the gold nanoparticles while thiol groups in the compact MTS xerogel network were not accessible to the gold nanoparticles. The characteristics of the sol-gel matrix change with time because of its own irreversible gelating and drying process. The present work provides direct evidence of gold nanoparticle binding with thiol groups within the sol-gel structures and explains the different permeability of "aerogel" and "xerogel" films of MTS on the basis of electrochemical and spectroscopic results. Two endogenous species, hydrogen peroxide and ascorbic acid, were used to test the permeability of the self-assembled sol-gel film in different states. The MTS xerogel film on the platinum electrode was extremely selective against ascorbic acid while maintaining high sensitivity to hydrogen peroxide in contrast to the relatively high permeability of ascorbic acid in the MTS aerogel film. This study showed the potential of the MTS sol-gel film as a nanoporous material in biosensor development.     

Matrix Effects on Selective Chemical Sensing by Sol-Gel Entrapped Complexing Agents

Changes in the selectivity of molecular recognition systems on sol-gel entrapment are reported. Thermodynamic effects are exemplified by studies of the metal-ion complexing agent Eriochrome Cyanine R (ECR). In aqueous solution this binds strongly and selectively to Al3+, whereas in a TMOS-based sol-gel matrix it is selective for Cu3+. Thermodynamic effects, due to restricted translational freedom of water molecules or different solvent structure and isolation of ligands, can explain these observations. Effects of entrapment on molecular recognition by a large conformationally flexible molecule have been studied using a tris-terminated PAMAM dendrimer. The dendrimer conformation and its complexation with Cu2+ changes on entrapment, and binding of aromatic carboxylic acids such as ibuprofen can be detected by changes in visible absorption and surface plasmon resonance using spun films of the sol-gel composite. These effects show that in addition to providing a porous entrapment matrix of good optical quality, sol-gels may be used to alter the binding characteristics of the entrapped receptors.     

Patterned Deposition of Sol-Gel Thin Films Using an Airbrush

ABSTRACT

In this article, we present a method to pattern glass substrates with sol-gel derived thin films. This method is based on the aerosol deposition of sol-gel precursor solutions using an inexpensive, commercially available airbrush. The technique was demonstrated using Cy5-doped sol-gel thin films for the creation of wavelength conversion devices. The films deposited were mechanically and chemically rigid, and patterns could be achieved with a resolution limit of approximately 250 μm. Constructing channel waveguides was also attempted using both zirconium- and titanium-based sol-gel thin films. Deposited thin films of these materials showed graininess that limited the ability to couple light into the films and increased the observed scatter. However, light was successfully coupled into the titanium-based sol-gel film using small lens-like structures created on the glass surface.     

Fluorescence spectroscopic study of dip coated sol-gel thin film internal environment using fluorescent probes Hoechst33258 and Pyranine

The characterization of physicochemical properties of the internal environment of sol-gel thin films is required for understanding and designing applications in optical biosensors. We have investigated the dip coated tetraethyl-orthosilicate (TEOS) derived sol-gel thin films deposited on microscopic glass cover slips using molar ratio (water or ethanol / TEOS) R=32 using fluorescence spectroscopic measurements (emission, lifetime and anisotropy) on entrapped fluorescent probes. The effect of water and/or ethanol was studied as a function of storage (60 days) using fluorescent probes Hoechst 33258 (H258) and Pyranine (PY). Distribution of fluorescent probes in thin film was studied using confocal microscope. Emission maxima of H258 entrapped thin films from sol prepared using water as solvent showed emission maximum at 503 nm indicating the presence of water like environment which did not change during storage. On the contrary, PY entrapped thin films depicted emission bands at 434 nm and 513 nm, characteristics of ethanol and water respectively, up to the first few weeks and then the band at 434 nm prevailed (60 days), suggesting heterogeneous internal environment. Thin films from sol prepared using ethanol as solvent showed presence of ethanol through out storage. Fluorescence lifetime data of these probes in both sol-gel and thin films also suggested presence of heterogeneous internal environment. Thin films prepared from sol-gel using water as solvent suggested release of ethanol in the pores during hydrolysis and condensation reaction, which were clearly indicated by PY. The effect of sodium phosphate buffer was also studied in sol-gel and thin films. The results of these measurements showed that both the probes H258 and PY could be used effectively in monitoring the physicochemical properties of internal environment of thin films and sol-gel as a function of storage.     

Biological sensing using transmission surface plasmon resonance spectroscopy

Ultrathin gold island films evaporated on transparent substrates offer promising transducers for chemical and biological sensing in the transmission surface plasmon resonance (T-SPR) mode. In the present work, the applicability of T-SPR-based systems to biosensing is demonstrated, using a well-established biological model system. Au island films were evaporated on polystyrene slides and modified with a biotinylated monolayer via a multistep surface reaction, the latter assisted by the good adhesion of metal islands to polystyrene. The biotin-derivatized Au island film was then used as a biological recognition surface for selective sensing of avidin binding, distinguishing between specific and nonspecific binding to the substrate. Transduction of the binding event into an optical signal was achieved by T-SPR spectroscopy, using plasmon intensity measurements, rather than wavelength change, for maximal sensitivity and convenience. T-SPR spectroscopy of Au island films is shown to be an effective tool for monitoring the binding of biological molecules to receptor layers on the Au surface and a promising approach to label-free optical biosensing.     

Silica-stabilized gold island films for transmission localized surface plasmon sensing

Ultrathin gold films prepared by evaporation of sub-percolation layers (typically up to 10 nm nominal thickness) onto transparent substrates form arrays of well-defined metal islands. Such films display a characteristic surface plasmon (SP) absorption band, conveniently measured by transmission spectroscopy. The SP band intensity and position are sensitive to the film morphology (island shape and inter-island separation) and the effective dielectric constant of the surrounding medium. The latter has been exploited for chemical and biological sensing in the transmission localized surface plasmon resonance (T-LSPR) mode. A major concern in the development of T-LSPR sensors based on Au island films is instability, manifested as change in the SP absorbance following immersion in organic solvents and aqueous solutions. The latter may present a problem in the use of Au island-based transducers for biological sensing, usually carried out in aqueous media. Here, we describe a facile method for stabilizing Au island films while maintaining a high sensitivity of the SP absorbance to analyte binding. Stabilization is achieved by coating the Au islands with an ultrathin silica layer, ca. 1.5 nm thick, deposited by a sol-gel procedure on an intermediate mercaptosilane monolayer. The silica coating is prepared using a modified literature procedure, where a change in the reaction conditions from room temperature to 90 degrees C shortened the deposition time from days to hours. The system was characterized by UV-vis spectroscopy, ellipsometry, XPS, HRSEM, AFM, and cyclic voltammetry. The ultrathin silica coating stabilizes the optical properties of the Au island films toward immersion in water, phosphate buffer saline (PBS), and various organic solvents, thus providing proper conditions where the optical response is sensitive only to changes in the effective dielectric constant of the immediate environment. The silica layer is thin enough to afford high T-LSPR sensitivity, while the hydroxyl groups on its surface enable chemical modification for binding of receptor molecules. The use of silica-encapsulated Au island films as a stable and effective platform for T-LSPR sensing is demonstrated.     

Selected-area sol-gel deposition of barium strontium titanate thin films on thermally oxidized silicon through mediation of self-assembled monolayers

Self-assembled monolayers (SAMs) of octadecyltrichlorosilane (OTS) and mercapto ethanol were used to modify the surface functionality of platinum/titanium or platinum/tantalum bilayer patterns on thermally oxidized silicon wafers. The attachment of OTS to the exposed oxide region made it hydrophobic, while the anchoring of mercapto ethanol to the bilayer pattern turned it hydrophilic. This patterned hydrophobicity and hydrophilicity was exploited to preferentially deposit barium strontium titanate (BST) thin films on the patterned bilayers from an aqueous sol-gel solution. The combination of the SAMs and the sol-gel film formation method allowed direct patterned deposition of BST thin films, which could be useful for on-chip electronic applications. Wet oxygen annealing at 50 °C was sufficient to stabilize the deposited sol-gel coating without adversely affecting the functionality of the OTS, thus permitting multiple dip-coatings to obtain patterned films of a desired thickness. Heat treatment at 750 °C allowed densification and conversion of the sol-gel coatings to perovskite BST films.     

Immobilization of lactate dehydrogenase on tetraethylorthosilicate-derived sol-gel films for application to lactate biosensor

Tetraethylorthosilicate (TEOS)-derived sol-gel films were utilized for the immobilization of lactate dehydrogenase (LDH) by physical adsorption and sol-gel/LDH/sol-gel sandwich configuration. An attempt was made to ascertain the optimum pH and temperature for the immobilized LDH. It was shown that TEOS-derived sol-gel films containing physically adsorbed LDH exhibited linearity from 0.5 to 4 mM, whereas those containing LDH in sandwich configuration showed linearity from 0.5 to 3 mM l-lactate. These sol-gel films, immobilized with LDH, were found to be stable for about 4 weeks at 4–10°C.     

Ultraviolet-Laser-Induced Crystallization of Sol-Gel Derived Indium Oxide Films

Modification of sol-gel derived indium oxide thin films using ultraviolet lasers was investigated. Irradiation by an ArF excimer (6.4 eV) and the fourth harmonic generation of a Nd : YAG laser (4.7 eV) was found to be effective in crystallization with a loss of hydroxyl groups and a decrease in the sheet resistance of the sol-gel films. Transparent crystalline indium oxide films were successfully obtained by 6.4 eV laser irradiation at fluences below 20 mJ/(cm2·shot), whereas degradation of the films was induced by a relatively high-fluence beam.     

Highly selective molecular recognition and high throughput detection of melamine based on molecularly imprinted sol-gel film

Multimode reader has been generally applied in immunoassay, and in the proposed paper, the 96 well micro-plate was modified with molecularly imprinted melamine sol-gel film, based on which the highly selective and high throughput detection of melamine was achieved. Melamine was imprinted into silica sol-gel films directly using phenyltrimethoxysilane and methyltrimethoxysilane as functionalized organosilicon precursors. The binding characteristic of the imprinted film to melamine was evaluated by equilibrium binding experiments and the morphology was studied by scanning electronic microscope (SEM). Scatchard analysis was carried out to estimate the binding parameters of the imprinted film. The proposed method exhibited excellent selectivity because of specific recognition of MM by molecularly imprinted film. Under the optimum conditions, the chemiluminescence (CL) intensity had a linear relationship against the concentration of melamine over the range of 0.1-50 μg mL⁻¹ with a lower detection limit of 0.02 μg mL⁻¹.     

Photophysical properties of [60]fullerenes and phthalocyanines embedded in ordered mesoporous silica films annealed at various temperatures

The photophysical properties of fullerene and/or phthalocyanine dyes embedded in ordered mesoporous silica films and the influence of annealing temperature on the nature of the immobilized dye molecules has been investigated using photoluminescence (PL) and diffuse reflectance (DR) studies. The PL and DR studies show that fullerene (C60) and/or zinc phthalocyanine (ZnPc) molecules incorporated into transparent mesoporous silica films, via either sol-gel or grafting routes, exist predominantly in monomeric form. Careful choice of annealing temperature, between 25 and 225 degrees C, can further enhance monomeric dispersion. For C60-containing films, monomeric dispersion of fullerene was observed for annealing temperatures up to 175 degrees C for sol-gel derived films and 225 degrees C for grafted films. Both sol-gel and grafted ZnPc-containing films showed evidence of monodispersed phthalocyanine for annealing temperatures up to 225 degrees C. In general, annealing temperatures in the range 125-175 degrees C were found to yield optimal monodispersion of the dye molecules. When both C60 and ZnPc were incorporated into the silica films, no evidence of interaction between the dyes, i.e., charge-transfer transitions or the formation of fullerene/phthalocyanine charge-transfer complexes, was observed. This suggests that embedded fullerene and phthalocyanine molecules may be used for the preparation of solid-state optical limiters, based on reverse saturable absorption, where monomeric dispersion of the dye molecules is important.     

Processing and characterization of Pb(Mg,Nb)O3-PbTiO3 thin films from metal alkoxide-derived gels

The sol-gel processing is one of promising methods to fabricate well-derived integrated thin films at relatively low temperature. Ferroelectric niobates films do afford the possibilities for adding the values by the hybridization with semiconductor and/or electro-optic systems. The molecular level designing of the precursor solution was stressed as well as the control of key processing factors. The advantages of this sol-gel have been extended to prepare the ferroelectric Pb(Mg, Nb)O₃-PbTiO₃ solid solution films integrated on Si wafers. The crystallization of the films with desired crystal structure could be promoted by the controlled partial hydrolysis of designed alkoxide solution in the intermediate state and the pre-heated treatment of alkoxide-derived films in flow of water vapor and oxygen gas mixture.     

Low Dielectric Constant Organosilicate Films Prepared by Sol-Gel and Templating Methods

Low dielectric constant organosilicate films with controllable microstructure have been successfully synthesized by multiple-step sol-gel process and templating method, which are the two basic methods to establish porous network in the films. Ultra-low dielectric constant (k) of around 2.0 can be achieved for both films. The microstructure such as porosity, pore interconnection and pore size of the two types of the films have been studied and compared. It has been found that the sol-gel films have a higher level of porosity comparing to the templating films to obtain the same k value. The sol-gel film has a majority of closed pores with pore size around 5 nm. The templating film has a closed pore structure with pore size around 10 nm. Preliminary results present a very positive prospective for intermetal dielectric applications.     

牛血清白蛋白在超薄纳米二氧化钛膜表面的印迹与吸附

基于溶胶凝胶分子印迹方法,以溶胶二氧化钛TiO2为基质印迹了牛血清白蛋白分子。用1%的NaOH溶液可有效地除去纳米TiO2印迹膜中的模板分子。采用石英晶体微天平现场技术,研究了牛血清白蛋白在超薄纳米TiO2膜表面的吸附行为。研究表明,牛血清白蛋白在印迹膜和非印迹膜上的吸附量都随溶液浓度增加而增大,印迹膜具有吸附的特异性和可再生性,其吸附量是非印迹膜的3~5倍;在非印迹膜上的吸附符合Langmuir吸附模型,而在印迹膜上的吸附符合allosteric吸附模型;牛血清白蛋白在非印迹膜上的吸附量先随pH升高而增大,当pH为5左右时达到最大值,随后吸附量又随pH的增大而减小;而在印迹膜上其吸附量仅随pH增大而增大。     

Strength of interactions between immobilized dye molecules and sol-gel matrices

In this paper we present a new theory to re-examine the immobilization technique of dye doped sol-gel films, define the strength and types of possible bonds between the immobilized molecule and sol-gel glass, and show that the immobilized molecule is not free inside the pores as was previously thought. Immobilizing three different pH sensitive dyes with different size and functional groups inside the same sol-gel films revealed important information about the nature of the interaction between the doped molecule and the sol-gel matrix. The samples were characterized by means of ultraviolet-visible spectrophotometer (UV-VIS), thermal gravimetric analysis (TGA), mercury porosimetry (MP), nuclear magnetic resonance spectroscopy ((29)Si NMR) and field-emission environmental scanning electron microscopy (ESEM-FEG). It was found that the doped molecule itself has a great effect on the strength and types of the bonds. A number of factors were identified, such as number and types of the functional groups, overall charge, size, pK(a) and number of the silanol groups which surround the immobilized molecule. These results were confirmed by the successful immobilization of bromocresol green (BCG) after a completely polymerized sol-gel was made. The sol-gel consisted of 50% tetraethoxysilane (TEOS) and 50% methyltriethoxysilane (MTEOS) (w/w). Moreover, the effect of the immobilized molecule on the structure of the sol-gel was studied by means of a leaky waveguide (LW) mode for doped films made before and after polymerization of the sol-gel.     

Chemistry-Crystallization-Microstructure Relations of Sol-Gel Derived Lanthanum Modified Lead Titanate Thin Films

Lanthanum modified lead titanate thin films have been obtained by the deposition of sol-gel solutions onto platinized (100) silicon substrates. Crystallization of perovskite films was achieved by thermal treatments at 650°C with slow or rapid heatings. Lead oxide excesses were used in the precursor solutions to counterbalance the lead losses produced during the thermal treatment. Rapid heatings and large excesses of lead produce a preferred orientation of the films. These films have more homogeneous and denser microstructures than slow heated films without lead excess.     

Preparation of thick silica films in the presence of poly(acrylic acid) by using electrophoretic sol-gel deposition

Thick silica films were fabricated by electrophoretic sol-gel deposition of silica particles on a stainless steel sheet. Using sols prepared by the sol-gel method with poly(acrylic acid) (PAA) films of ca. 25 m in thickness were prepared with no cracks. The films were shown to be agglomerates of monodispersed silica particles with PAA. The size of the silica particles decreased with an increase in the added amount of PAA. The deposited weight was considerably larger for the films with PAA than that of the films without PAA.     

A Generic Technique for Coating Doped Sol-Gel Films onto the Inside of Tubes for Use as Colorimetric Sensors

Sol-gel thin films have been doped with bromophenol blue and eriochrome cyanine RC for measuring pH and Cu⁺⁺ in solution respectively. The films were coated inside glass tubes by a novel method. Films doped with bromophenol blue responded to pH changes from pH 3 to 8. They were stable to variations in temperature from 20°C to 40°C. The sensing films have been subjected to leaching studies in different pH buffer solutions. Copper ions in solution have been measured to a minimum concentration of 0.6 ppm by eriochrome immobilised in sol-gel films. The interferences of other metal ions were also studied. Doped sol-gel films coated onto the inside of test tubes offer a simple, none-invasive, reusable and fast optical chemical sensing technique for the measurement of colour by spectroscopy or colorimetry.