Tuning the Photo-Luminescence Properties of WO3 Layers by the Adjustment of Layer Formation Conditions.

In this research we have applied sol-gel synthesis for the deposition of tungsten (VI) oxide (WO3) layers using two different reductants (ethanol and propanol) and applying different dipping times. WO3 samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier Transform Infrared spectroscopy (FTIR), photoluminescence (PL) and time-resolved photoluminescence decay methods. Photoelectrochemical (PEC) behaviour of synthesized coatings was investigated using cyclic voltammetry in the dark and under illumination. Formation of different structures in differently prepared samples was revealed and significant differences in the PL spectra and PEC performance of the samples were observed. The results showed that reductant used in the synthesis and dipping time strongly influenced photo-electrochemical properties of the coatings. Correlation between the morphology, PL and PEC behaviour has been explained.

Application of ZnO Nanorods Based Whispering Gallery Mode Resonator in Optical Immunosensors.

In this research a whispering gallery mode (WGM) resonator based on vertically oriented ZnO nanorods, which were formed on silicon surface (silicon/ZnO-NRs), has been applied in the design of optical immunosensor that was dedicated for the determination of grapevine virus A-type (GVA) proteins. Vertically oriented ZnO-NRs were grown on silicon substrates by atmospheric pressure metal organic chemical vapor deposition (APMOCVD) and the silicon/ZnO-NRs structures formed were characterized by structural and optical methods. Optical characterization demonstrates that silicon/ZnO-NRs-based structures can act as 'whispering gallery mode' (WGM) resonator where quasi-whispering gallery modes (quasi-WGMs) are generated. These quasi-WGMs were experimentally observed in the visible and infrared ranges of the photoluminescence spectra. In order to design an immuno-sensing system the anti-GVA antibodies were immobilized on the surface of silicon/ZnO-NRs and in this way silicon/ZnO-NRs/anti-GVA structure was formed. The immobilization of anti-GVA antibodies and then the interaction of silicon/ZnO-NRs/anti-GVA structure with GVA proteins (GVA-antigens) resulted in an opposite shifts of the WGMs peaks in the visible range of the photoluminescence spectra observed as a defect-related photoluminescence emission of ZnO-NRs. Here designed silicon/ZnO-NRs/anti-GVA immuno-sensing structure demonstrates the sensitivity towards GVA-antigens in the concentration range of 1-200 ng/ml. Bioanalytical applicability of the silicon/ZnO-NRs-based structures in the WGMs registration mode is discussed.

Evaluation of affinity sensor response kinetics towards dimeric ligands linked with spacers of different rigidity: Immobilized recombinant granulocyte colony-stimulating factor based synthetic receptor binding with genetically engineered dimeric analyte derivatives.

The modelling of protein-protein binding kinetics is important for the development of affinity-sensors and the prediction of signaling protein based drug efficiency. Therefore, in this research we have evaluated the binding kinetics of several genetically designed protein models: (i) three different ligands based on granulocyte colony-stimulating factor GCSF homo-dimeric derivatives linked by differed by linkers of different length and flexibility; (ii) an antibody-like receptor (GCSF-R) based on two GCSF-receptor sites immobilized to Fc domains, which are common parts of protein structures forming antibodies. Genetically engineered GCSF-R is similar to an antibody because it, like the antibody, has two binding sites, which both selectively bind with GCSF ligands. To design the affinity sensor model studied here, GCSF-R was immobilized on a thin gold layer via self-assembled monolayer conjugated with Protein-G. Binding kinetics between immobilized GCSF-R and all three different recombinant GCSF-based homo-dimeric derivatives were evaluated by total internal reflection ellipsometry. Association constants were determined by fitting mathematical models to the experimental data. It was clearly observed that both (i) affinity and (ii) binding kinetics depend on the length and flexibility of the linker that connects both domains of a GCSF-based ligand. The fastest association between immobilized GCSF-R and GCSF-based ligands was observed for ligands whose GCSF domains were interconnected by the longest and the most flexible linker. Here we present ellipsometry-based measurements and models of the interaction kinetics that advance the understanding of bidentate-receptor-based immunosensor action and enables us to predict the optimal linker structure for the design of GCSF-based medications.

TiO2-x/TiO2-Structure Based 'Self-Heated' Sensor for the Determination of Some Reducing Gases.

In this research we report the gas-sensing properties of TiO2-x/TiO2-based hetero-structure, which was 'self-heated' by current that at constant potential passed through the structure. Amperometric measurements were applied for the evaluation of sensor response towards ethanol, methanol, n-propanol and acetone gases/vapours. The sensitivity towards these gases was based on electrical resistance changes, which were determined by amperometric measurements of current at fixed voltage applied between Pt-based contacts/electrodes deposited on the TiO2-x/TiO2-based layer. X-ray diffraction (XRD) analysis revealed the formation of TiO2-x/TiO2-based hetero-structure, which is mainly based on Ti3O5/TiO2 formed during the hydro-thermal oxidation-based sensing-layer preparation process. Additionally, photoluminescence and time-resolved photoluminescence decay kinetics-based signals of this sensing structure revealed the presence of TiO2 mainly in the anatase phase in the TiO2-x/TiO2-based hetero-structure, which was formed at 400 °C annealing temperature. The evaluation of TiO2-x/TiO2-based gas-sensing layer was performed at several different temperatures (25 °C, 72 °C, 150 °C, 180 °C) and at these temperatures different sensitivity to the aforementioned gaseous materials was determined.

Electrochemical Deposition and Investigation of Poly-9,10-Phenanthrenequinone Layer.

In this research, a 9,10-phenanthrenequinone (PQ) was electrochemically polymerized on a graphite rod electrode using potential cycling. The electrode modified by poly-9,10-phenanthrenequinone (poly-PQ) was studied by means of cyclic voltammetry, electrochemical impedance spectroscopy, atomic force microscopy and scanning electron microscopy. The poly-PQ shows variations in growth pattern depending on the number of potential cycles for the initiation of polymerization. Formed poly-PQ layer demonstrates good electric conductivity, great degree of electrochemical capacitance and unique oxidation/reduction properties, which are suitable for broad technological applications, including applicability in biosensors, supercapacitors and in some other electrochemical systems.

Interaction mechanism between TiO2 nanostructures and bovine leukemia virus proteins in photoluminescence-based immunosensors.

In this research a mechanism of interaction between a semiconducting TiO2 layer and bovine leukemia virus protein gp51, applied in the design of photoluminescence-based immunosensors, is proposed and discussed. Protein gp51 was adsorbed on the surface of a nanostructured TiO2 thin film, formed on glass substrates (TiO2/glass). A photoluminescence (PL) peak shift from 517 nm to 499 nm was observed after modification of the TiO2/glass by adsorbed gp51 (gp51/TiO2/glass). After incubation of the gp51/TiO2/glass in a solution containing anti-gp51, a new structure (anti-gp51/gp51/TiO2/glass) was formed and the PL peak shifted backwards from 499 nm to 516 nm. The above-mentioned PL shifts are attributed to the variations in the self-trapped exciton energy level, which were induced by the changes of electrostatic interaction between the adsorbed gp51 and the negatively charged TiO2 surface. The strength of the electric field affecting the photoluminescence centers, was determined from variations between the PL-spectra of TiO2/glass, gp51/TiO2/glass and anti-gp51/gp51/TiO2/glass. The principle of how these electric field variations are induced has been predicted. The highlighted origin of the changes in the photoluminescence spectra of TiO2 after its protein modification reveals an understanding of the interaction mechanism between TiO2 and proteins that is the key issue responsible for biosensor performance.

ZnO films formed by atomic layer deposition as an optical biosensor platform for the detection of Grapevine virus A-type proteins.

Novel sensitive optical biosensor for determination of Grapevine virus A-type (GVA) proteins (GVA-antigens) has been designed. This biosensor was based on thin films of Zinc Oxide (ZnO) deposited by atomic layer deposition (ALD). The ZnO-based films have demonstrated favorable surface-structural properties for the direct immobilization of antibodies against GVA-antigens in order to form a biosensitive layer sensitive to GVA-antigens. The immobilization was confirmed by intensity changes in the main near band emission (NBE) peak of ZnO and by the formation of intense photoluminescence band, discovered in the visible range around 425nm, caused by the immobilized proteins. The GVA-antigen detection was performed by the evaluation of changes and behavior of a corresponding luminescence band. The sensitivity of as-formed label-free biosensor towards the GVA-antigens was determined in the range from 1pg/ml to 10ng/ml; in addition, the selectivity of biosensor was evaluated.