Towards Visible Light Hydrogen Generation: Quantum Dot-Sensitization via Efficient Light Harvesting of Hybrid-TiO2

We report pronounced enhancement of photoelectrochemical hydrogen generation of a quantum dot-sensitized hybrid-TiO2 (QD/H-TiO2) electrode that is composed of a mesoporous TiO2 layer sandwiched by a double sided energy harvesting layer consisting of a surface-textured TiO2 inverse opals layer on the bottom and a patterned mesoporous TiO2 layer on the top. CdSe/H-TiO2 exhibits a maximum photocurrent density of similar to 16.2 mA/cm(2), which is 35% higher than that of the optimized control sample (CdSe/P25), achieved by matching of the bandgap of quantum dot-sensitization with the wavelength where light harvesting of H-TiO2 is observed. Furthermore, CdSe/H-TiO2 under filtered exposure conditions recorded current density of similar to 14.2 mA/cm(2), the greatest value in the visible range. The excellent performance of the quantum dot-sensitized H-TiO2 suggests that alteration of the photoelectrodes to suitable nanostructures with excellent light absorption may offer optimal strategies for attaining maximum efficiency in a variety of photoconversion systems.open3

Synthesis of iron-doped TiO2 nanoparticles by ball-milling process : the influence of process parameters on the structural, optical, magnetic, and photocatalytic properties

Titanium dioxide (TiO2) absorbs only a small fraction of incoming sunlight in the visible region thus limiting its photocatalytic efficiency and concomitant photocatalytic ability. The large-scale application of TiO2 nanoparticles has been limited due to the need of using an ultraviolet excitation source to achieve high photocatalytic activity. The inclusion of foreign chemical elements in the TiO2 lattice can tune its band gap resulting in an absorption edge red-shifted to lower energies enhancing the photocatalytic performance in the visible region of the electromagnetic spectrum. In this research work, TiO2 nanoparticles were doped with iron powder in a planetary ball-milling system using stainless steel balls. The correlation between milling rotation speeds with structural and morphologic characteristics, optical and magnetic properties, and photocatalytic abilities of bare and Fedoped TiO2 powders was studied and discussed.This work was partially financed by FCT-Fundacao para a Ciencia e Tecnologia-under the project PTDC/FIS/120412/2010: "Nanobased concepts for Innovative & Eco-sustainable constructive material's surfaces.

Pressure Load: The Main Factor for Altered Gene Expression in Right Ventricular Hypertrophy in Chronic Hypoxic Rats

BACKGROUND: The present study investigated whether changes in gene expression in the right ventricle following pulmonary hypertension can be attributed to hypoxia or pressure loading. METHODOLOGY/PRINCIPAL FINDINGS: To distinguish hypoxia from pressure-induced alterations, a group of rats underwent banding of the pulmonary trunk (PTB), sham operation, or the rats were exposed to normoxia or chronic, hypobaric hypoxia. Pressure measurements were performed and the right ventricle was analyzed by Affymetrix GeneChip, and selected genes were confirmed by quantitative PCR and immunoblotting. Right ventricular systolic blood pressure and right ventricle to body weight ratio were elevated in the PTB and the hypoxic rats. Expression of the same 172 genes was altered in the chronic hypoxic and PTB rats. Thus, gene expression of enzymes participating in fatty acid oxidation and the glycerol channel were downregulated. mRNA expression of aquaporin 7 was downregulated, but this was not the case for the protein expression. In contrast, monoamine oxidase A and tissue transglutaminase were upregulated both at gene and protein levels. 11 genes (e.g. insulin-like growth factor binding protein) were upregulated in the PTB experiment and downregulated in the hypoxic experiment, and 3 genes (e.g. c-kit tyrosine kinase) were downregulated in the PTB and upregulated in the hypoxic experiment. CONCLUSION/SIGNIFICANCE: Pressure load of the right ventricle induces a marked shift in the gene expression, which in case of the metabolic genes appears compensated at the protein level, while both expression of genes and proteins of importance for myocardial function and remodelling are altered by the increased pressure load of the right ventricle. These findings imply that treatment of pulmonary hypertension should also aim at reducing right ventricular pressure

Olfactory Interference during Inhibitory Backward Pairing in Honey Bees

Background: Restrained worker honey bees are a valuable model for studying the behavioral and neural bases of olfactory plasticity. The proboscis extension response (PER; the proboscis is the mouthpart of honey bees) is released in response to sucrose stimulation. If sucrose stimulation is preceded one or a few times by an odor (forward pairing), the bee will form a memory for this association, and subsequent presentations of the odor alone are sufficient to elicit the PER. However, backward pairing between the two stimuli (sucrose, then odor) has not been studied to any great extent in bees, although the vertebrate literature indicates that it elicits a form of inhibitory plasticity. Methodology/Principal Findings: If hungry bees are fed with sucrose, they will release a long lasting PER; however, this PER can be interrupted if an odor is presented 15 seconds (but not 7 or 30 seconds) after the sucrose (backward pairing). We refer to this previously unreported process as olfactory interference. Bees receiving this 15 second backward pairing show reduced performance after a subsequent single forward pairing (excitatory conditioning) trial. Analysis of the results supported a relationship between olfactory interference and a form of backward pairing-induced inhibitory learning/ memory. Injecting the drug cimetidine into the deutocerebrum impaired olfactory interference. Conclusions/Significance: Olfactory interference depends on the associative link between odor and PER, rather than between odor and sucrose. Furthermore, pairing an odor with sucrose can lead either to association of this odor to PER or t

Autoradiographic quantification of muscarinic cholinergic synaptic markers in bat, shrew, and rat brain

We employed radioligand binding autoradiography to determine the distributions of pre- and postsynaptic cholinergic radioligand binding sites in the brains of two species of bat, one species of shrew, and the rat. High affinity choline uptake sites were measured with [ 3 H]hemicholinium, and presynaptic cholinergic vesicles were identified with [ 3 H]vesamicol. Muscarinic cholinergic receptors were determined with [ 3 H]scopolamine. The distribution patterns of the three cholinergic markers were similar in all species examined, and identified known major cholinergic pathways on the basis of enrichments in both pre- and postsynaptic markers. In addition, there was excellent agreement, both within and across species, in the regional distributions of the two presynaptic cholinergic markers. Our results indicate that pharmacological identifiers of cholinergic pathways and synapses, including the cholinergic vesicle transport site, and the organizations of central nervous system cholinergic pathways are phylogenetically conserved among eutherian mammals.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/45409/1/11064_2004_Article_BF00971334.pd

Advanced photocatalysts: Pinning single atom co-catalysts on titania nanotubes

Single atom (SA) catalysis, over the last 10 years, has become a forefront in heterogeneous catalysis, electrocatalysis, and most recently also in photocatalysis. Most crucial when engineering a SA catalyst/support system is the creation of defined anchoring points on the support surface to stabilize reactive SA sites. Here, a so far unexplored but evidently very effective approach to trap and stabilize SAs on a broadly used photocatalyst platform is introduced. In self-organized anodic TiO2 nanotubes, a high degree of stress is incorporated in the amorphous oxide during nanotube growth. During crystallization (by thermal annealing), this leads to a high density of Ti3+-O-v, surface defects that are hardly present in other common titania nanostructures (as nanoparticles). These defects are highly effective for SA iridium trapping. Thus a SA-Ir photocatalyst with a higher photocatalytic activity than for any classic co-catalyst arrangement on the semiconductive substrate is obtained. Hence, a tool for SA trapping on titania-based back-contacted platforms is provided for wide application in electrochemistry and photoelectrochemistry. Moreover, it is shown that stably trapped SAs provide virtually all photocatalytic reactivity, with turnover frequencies in the order of 4 x 10(6) h(-1) in spite of representing only a small fraction of the initially loaded SAs.Web of Science3130art. no. 210284