The molecularly dispersed V 2 O 5 /SiO 2 supported oxides were prepared by the incipient wetness impregnation of 2-propanol solutions of V-isopropoxide. The experimental maximum dispersion of surface vanadium oxide species on SiO 2 was achieved at ∼12 wt % V 2 O 5 (∼2.6 V atoms/nm 2 ). The surface structures of the molecularly dispersed V 2 O 5 /SiO 2 samples under various conditions were extensively investigated by in situ Raman, UVvis-NIR DRS and XANES spectroscopies. The combined characterization techniques revealed that in the dehydrated state only isolated VO 4 species are present on the silica surface up to monolayer coverage. Interestingly, the three-member siloxane rings on the silica surface appear to be the most favorable sites for anchoring the isolated, three-legged (SiO) 3 VdO species. Hydration dramatically changes the molecular structure of the surface vanadium oxide species. The specific structure of the hydrated surface vanadium oxide species is dependent on the degree of hydration. The molecular structure of the fully hydrated vanadium oxide species closely resembles V 2 O 5 ‚nH 2 O gels, rather than V 2 O 5 crystallites. The fully hydrated surface vanadium oxide species are proposed to be chain and/or two-dimensional polymers with highly distorted square-pyramidal VO 5 connected by V-OH-V bridges, which are stabilized on the silica surface by the sixth neighbor of Si-OH hydroxyls via Si-OH‚‚‚V hydrogen bonds. In analogy to the hydration process, alcoholysis occurs during methanol chemisorption, and similar molecular structures are proposed to interpret the interaction between methanol molecules and the surface vanadium oxide species on silica.

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The molecularly dispersed TiO 2 /SiO 2 supported oxides were prepared by the incipient wetness impregnation of 2-propanol solutions of titanium isopropoxide. Experimental monolayer dispersion of surface titanium oxide species on SiO 2 was reached at ∼4 Ti atoms/nm 2 with a two-step impregnation procedure. The surface structures of the molecularly dispersed TiO 2 /SiO 2 under various environments were extensively investigated by in-situ spectroscopic techniques (e.g., Raman, UV-vis-NIR DRS, and XANES) as well as XPS. The combined characterization techniques revealed the consumption of surface Si-OH groups and the formation of Ti-O-Si bridging bonds. In the dehydrated state, the surface Ti atoms in the 1% TiO 2 /SiO 2 sample (0.24 Ti atoms/nm 2 ) are predominantly found to be isolated TiO 4 units, whereas at maximum surface coverage (∼4 Ti atoms/nm 2 ), two-dimensional polymerized TiO 5 units are dominant on the silica surface. The in-situ spectroscopic studies demonstrated that the coordination and ligands of the surface Ti cations change upon hydration/dehydration as well as during methanol oxidation. Methanol oxidation showed that the molecularly dispersed surface titanium oxide species exhibit completely different catalytic behavior (predominantly redox products) compared to bulk titanium oxide (predominantly dehydration products). Furthermore, the TOF of the surface titanium oxide species is strongly dependent on their local structures and varies by 1 order of magnitude (isolated TiO 4 . polymerized TiO 5 ). These new results provide fundamental insights about molecular structure-reactivity/selectivity relationships of the molecularly dispersed TiO 2 /SiO 2 supported oxides.

UV−vis−NIR diffuse reflectance spectroscopy (DRS) was applied to study the local structures of V(V) cations on various oxide supports (Al2O3, ZrO2 TiO2, Nb2O5, CeO2, and SiO2) under hydrated and dehydrated conditions. The edge energy (E g) of the LMCT transitions of V(V) cations was used to elucidate the local structures of V(V) cations, and a correlation between the edge energy and the number of the covalent V−O−V bonds (CVB) around the central V(V) cations was established based on some V(V) reference compounds/oxides. For TiO2, Nb2O5, and CeO2 supported vanadia catalysts, the strong support absorption in the same region as the V(V) cations prevents a reliable determination of the local structure of the surface vanadium oxide species by either the LMCT band position or the edge energy. For Al2O3, ZrO2, and SiO2 supported vanadia catalysts, the average CVB number derived from the edge energy allows the assignment of the possible structure of the surface vanadium oxide species, which is a strong function of the support, environmental conditions, and vanadia surface density. The DRS results provide reliable information and new insights into the structural characteristics of the surface vanadium oxide species on these oxide supports under different environmental conditions.

We herein report the design of a novel semiconducting silicon nanowire field-effect transistor (SiNW-FET) biosensor array for ultrasensitive label-free and real-time detection of nucleic acids. Highly responsive SiNWs with narrow sizes and high surface-to-volume-ratios were "top-down" fabricated with a complementary metal oxide semiconductor compatible anisotropic self-stop etching technique. When SiNWs were covalently modified with DNA probes, the nanosensor showed highly sensitive concentration-dependent conductance change in response to specific target DNA sequences. This SiNW-FET nanosensor revealed ultrahigh sensitivity for rapid and reliable detection of 1 fM of target DNA and high specificity single-nucleotide polymorphism discrimination. As a proof-of-concept for multiplex detection with this small-size and mass producible sensor array, we demonstrated simultaneous selective detection of two pathogenic strain virus DNA sequences (H1N1 and H5N1) of avian influenza.

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Silicon nanowire (SiNW) field effect transistors (FETs) have emerged as powerful sensors for ultrasensitive, direct electrical readout, and label-free biological/chemical detection. The sensing mechanism of SiNW-FET can be understood in terms of the change in charge density at the SiNW surface after hybridization. So far, there have been limited systematic studies on fundamental factors related to device sensitivity to further make clear the overall effect on sensing sensitivity. Here, we present an analytical result for our triangle cross-section wire for predicting the sensitivity of nanowire surface-charge sensors. It was confirmed through sensing experiments that the back-gated SiNW-FET sensor had the highest percentage current response in the subthreshold regime and the sensor performance could be optimized in low buffer ionic strength and at moderate probe concentration. The optimized SiNW-FET nanosensor revealed ultrahigh sensitivity for rapid and reliable detection of target DNA with a detection limit of 0.1 fM and high specificity for single-nucleotide polymorphism discrimination. In our work, enhanced sensing of biological species by optimization of operating parameters and fundamental understanding for SiNW FET detection limit was obtained.

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