Sol–gel derived mesoporous Pt and Cr-doped WO<Subscript>3</Subscript> thin films: the role played by mesoporosity and metal doping in enhancing the gas sensing properties

Mesoporous Cr or Pt-doped WO₃ thin films to be employed as ammonia gas sensors were prepared by a fast one-step sol–gel procedure, based on the use of triblock copolymer as templating agent. The obtained films were constituted by aggregates of interconnected WO₃ nanocrystals (20–50 nm) separated by mesopores with dimensions ranging between 2 and 15 nm. The doping metals, Pt and Cr, resulted differently hosted in the WO₃ mesoporous matrix. Chromium is homogeneously dispersed in the oxide matrix, mainly as Cr(III) and Cr(V) centers, as revealed by EPR spectroscopy; instead platinum segregated as Pt (0) nanoparticles (4 nm) mainly included inside the WO₃ nanocrystals. The semiconductor layers containing Pt nanoclusters revealed, upon exposure to NH₃, remarkable electrical responses, much higher than Cr-doped and undoped layers, particularly at low ammonia concentration (6.2 ppm). This behavior was attributed to the presence of Pt nanoparticles segregated inside the semiconductor matrix, which act as catalysts of the N–H bond cleavage, decreasing the activation barrier in the ammonia dissociation. The role of the mesoporous structure in influencing the chemisorption and the gas diffusion in the WO₃ matrix appeared less decisive than the electronic differences between the two examined doping metals. The overall results suggest that a careful combination between mesoporous architecture and metal doping can really promote the electrical response of WO₃ toward ammonia.     

Biofunctionalization of anisotropic nanocrystalline semiconductor-magnetic heterostructures

Asymmetric binary nanocrystals (BNCs) formed by a spherical γ-Fe(2)O(3) magnetic domain epitaxially grown onto a lateral facet of a rodlike anatase TiO(2) nanorod have been functionalized with PEG-terminated phospholipids, resulting in a micellar system that enables the BNC dispersion in aqueous solution. The further processability of the obtained water-soluble BNC including PEG lipid micelles and their use in bioconjugation experiments has been successfully demonstrated by covalently binding to bovine serum albumin (BSA). The whole process has also been preliminarily performed on spherical iron oxide nanocrystals (NCs) and TiO(2) nanorods (NRs), which form single structural units in the heterostructures. Each step has been thoroughly monitored by using optical, structural, and electrophoretic techniques. In addition, an investigation of the magnetic behavior of the iron oxide NCs and BNCs, before and after incorporation into PEG lipid micelles and subsequently bioconjugation, has been carried out, revealing that the magnetic characteristics are mostly retained. The proposed approach to achieving water-soluble anisotropic BNCs and their bioconjugates has a large potential in catalysis and biomedicine and offers key functional building blocks for biosensor applications.     

Membrane morphology modifications induced by hydroquinones

We synthesize and characterize alkylthiohydroquinones (ATHs) in order to investigate their interactions with lipid model membranes, POPE and POPC. We observe the formation of structures with different morphologies, or curvature of the lipid bilayer, depending on pH and increasing temperature. We attribute their formation to changes in the balance charge/polarity induced by the ATHs. Mixtures of ATHs with POPE at pH 4 form two cubic phases, P4(3)32 and Im3m, that reach a maximum lattice size at 40 °C while under basic conditions these phases only expand upon heating from room temperature. The cubic phases coexist with lamellar or hexagonal phases and are associated with inhomogeneous distribution of the ATH molecules over the lipid matrix. The zwitterionic POPC does not form cubic phases but instead shows lamellar structures with no clear influence of the 2,6-BATH.     

Capillary filling in nanostructured porous silicon

An experimental study on the capillary filling of nanoporous silicon with different fluids is presented. Thin nanoporous membranes were obtained by electrochemical anodization, and the filling dynamics was measured by laser interferometry, taking advantage of the optical properties of the system, related with the small pore radius in comparison to light wavelength. This optical technique is relatively simple to implement and yields highly reproducible data. A fluid dynamic model for the filling process is also proposed including the main characteristics of the porous matrix (tortuosity, average hydraulic radius). The model was tested for different ambient pressures, porous layer morphology, and fluid properties. It was found that the model reproduces well the experimental data according to the different conditions. The predicted pore radii quantitatively agree with the image information from scanning electron microscopy. This technique can be readily used as nanofluidic sensor to determine fluid properties such as viscosity and surface tension of a small sample of liquid. Besides, the whole method can be suitable to characterize a porous matrix.     

Rapid acquisition of 1H and 19F NMR experiments for direct and competition ligand-based screening

Direct and competition ligand-based NMR experiments are often used in the screening of chemical fragment libraries against a protein target due to the high relative sensitivity of NMR for protein-binding events. A plethora of NMR methods has been proposed for this purpose. Two of these techniques are the (19)F T(2) filter and the (1)H selective T(2) filter experiments. Modifications of the pulse sequences of these experiments have resulted in a ～2-fold reduction in the experiment time thus allowing an increase in the screening throughput and making NMR an attractive technique for screening large compound collections.     

Influence of oxidation state of sulfur on the dissociation of [Tz-(CH2)n-S(O)m-(CH2)n-Tz + Na+] adducts generated by electrospray ionization (Tz = tetrazole ring; n = 2, 3; m= 0, 1, 2)

Sodium adducts of six organosulfur‐α,ω‐ditetrazole compounds (Tz‐(CH₂)_n‐S(O)_m‐(CH₂)_n‐Tz; where Tz = tetrazole ring; n = 2, 3; m = 0, 1, 2) were generated via electrospray ionization (ESI) and their fragmentation pattern assessed via collision‐induced dissociation (CID). Two main dissociation channels were observed: (a) losses of N₂ and HN₃ from the tetrazole rings; (b) cleavage of the C–S bond. The sulfoxides pass predominantly through the second fragmentation pathway, but for the sulfides and sulfones the tetrazole ring fragmentation occurs. Theoretical calculations at the B3LYP/6‐31 + G(d,p) level indicate that for all the adducts (sulfide, sulfoxide, and sulfone) the dissociation pathway that leads to product ions arising from loss of N₂ was the most exothermic. Based on these results and assumptions, it was postulated that the dissociation of the sulfoxide adducts occurs under kinetic control (N₂‐loss pathway via a much more energetic transition state). For the sulfide and sulfone adducts, on the other hand, the dissociation process takes place via a thermodynamically controlled process. Copyright © 2011 John Wiley & Sons, Ltd.     

BLUF Hydrogen network dynamics and UV/Vis spectra: A combined molecular dynamics and quantum chemical study

Blue light sensing using flavin (BLUF) protein photoreceptor domains change their hydrogen bond network after photoexcitation. To explore this phenomenon, BLUF domains from R. sphaeroides were simulated using Amber99 molecular dynamics (MD). Five starting configurations were considered, to study different BLUF proteins (AppA/BlrB), Trp conformations (“W_in”/“W_out”), structure determination (X‐ray/NMR), and finally, His protonation states. We found dependencies of the hydrogen bonds on almost all parameters. Our data show an especially strong correlation of the Trp position and hydrogen bonds involving Gln63. The latter is in some contradiction to earlier results (Obanayama et al., Photochem. Photobiol. 2008, 84 10031010). Possible origins and implications are discussed. Our calculations support conjectures that Gln63 is more flexible with Trp104 in W_in position. Using snapshots from MD and time‐dependent density functional theory, UV/vis spectra for the chromophore were determined, which account for molecular motion of the protein under ambient conditions. In accord with experiment, it is found that the UV/vis spectra of BLUF bound flavin are red‐shifted and thermally broadened for all calculated π → π* transitions, relative to gas phase flavin at T = 0 K. However, differences in the spectra between the various BLUF configurations cannot be resolved with the present approach. © 2012 Wiley Periodicals, Inc.     

A novel technique for simultaneous diagnosis and radioprotection by radioactive cerium oxide nanoparticles: study of cyclotron production of <Superscript>137m</Superscript>Ce

Application of nanoparticles in nuclear medicine has aimed to develop diagnosis and therapeutic techniques. Cerium oxide nanoparticles (CNPs) are expected to be useful for protection of healthy tissue from radiation-induced harm and could serve therapeutic function. Among a variety of cerium radioisotopes, ^137mCe (T _1/2 = 34.4 h, IT (99.22%), β⁺ (0.779%)) could be a novel candidate radionuclide in the field of diagnosis owing to its appropriate half-life, 99.91% natural abundance of target and its intense gamma line at 254.29 keV. In this study, ^137mCe excitation function via the ^natLa(p,3n) reaction was calculated by TALYS-1.2 and EMPIRE-3 codes. The excitation function calculations demonstrated that the ^natLa(p,3n)^137mCe reaction leads to the formation of the ^136/138Ce isotopic contamination in the 22–35 MeV energy range. Interestingly, the isotopic impurities of ^137mCe could serve radio protector function. Overall results indicate that the cyclotron produced ^137mCeO₂ nanoparticles by irradiation of a target encompassing lanthanum oxide nanoparticles could be a potent alternative for conventional diagnostic radionuclides with simultaneous radioprotection capacity.