Enhanced Lifetime Of Excitons In Nonepitaxial Au/cds Core/shell Nanocrystals

The ability of metal nanoparticles to capture light through plasmon excitations offers an opportunity for enhancing the optical absorption of plasmon-coupled semiconductor materials via energy transfer. This process, however, requires that the semiconductor component is electrically insulated to prevent a backward charge flow into metal and interfacial states, which causes a premature dissociation of excitons. Here we demonstrate that such an energy exchange can be achieved on the nanoscale by using nonepitaxial Au/CdS core/shell nanocomposites. These materials are fabricated via a multistep cation exchange reaction, which decouples metal and semiconductor phases leading to fewer interfacial defects. Ultrafast transient absorption measurements confirm that the lifetime of excitons in the CdS shell (tau approximate to 300 ps) is much longer than lifetimes of excitons in conventional, reduction-grown Au/CdS heteronanostructures. As a result, the energy of metal nanoparticles can be efficiently utilized by the semiconductor component without undergoing significant nonradiative energy losses, an important property for catalytic or photovoltaic applications. The reduced rate of exciton dissociation in the CdS domain of Au/CdS nanocomposites was attributed to the nonepitaxial nature of Au/CdS interfaces associated with low defect density and a high potential barrier of the interstitial phase

Diapause as escape strategy to exposure to toxicants: response of Brachionus calyciforus to arsenic

Invertebrate organisms commonly respond to environmental fluctuation by entering diapause. Production of diapause in monogonont rotifers involves a previous switch from asexual to partial sexual reproduction. Although zooplankton have been used in ecotoxicological assays, often their true vulnerability to toxicants is underestimated by not incorporating the sexual phase. We experimentally analyzed traits involved in sexual reproduction and diapause in the cyclically parthenogenetic freshwater rotifer, Brachionus calyciflorus, exposed to arsenic, a metalloid naturally found in high concentrations in desert zones, focusing on the effectiveness of diapause as an escape response in the face of an adverse condition. Addition of sublethal concentrations of arsenic modified the pattern of diapause observed in the rotifer: investment in diapause with arsenic addition peaked earlier and higher than in non-toxicant conditions, which suggests that sexual investment could be enhanced in highly stressed environmental conditions by increased responsiveness to stimulation. Nevertheless, eggs produced in large amount with arsenic, were mostly low quality, and healthy-looking eggs had lower hatching success, therefore it is unclear whether this pattern is optimum in an environment with arsenic, or if rather arsenic presence in water bodies disturbs the optimal allocation of offspring entering diapause. We observed high accumulation of arsenic in organisms exposed to constant concentration after several generations, which suggests that arsenic may be accumulated transgenerationally. The sexual phase in rotifers may be more sensitive to environmental conditions than the asexual one, therefore diapause attributes should be considered in ecotoxicological assessment because of its ecological and evolutionary implications on lakes biodiversity

Temperature-Dependent Permeability of the Ligand Shell of PbS Quantum Dots Probed by Electron Transfer to Benzoquinone

This paper describes an increase in the yield of collisionally gated photoinduced electron transfer (electron transfer events per collision) from oleate-capped PbS quantum dots (QDs) to benzoquinone (BQ) with increasing temperature (from 0 to 50 °C), due to increased permeability of the oleate adlayer of the QDs to BQ. The same changes in intermolecular structure of the adlayer that increase its permeability to BQ also increase its permeability to the solvent, toluene, resulting in a decrease in viscous drag and an apparent increase in the diffusion coefficient of the QDs, as measured by diffusion-ordered spectroscopy (DOSY) NMR. Comparison of NMR and transient absorption spectra of QDs capped with flexible oleate with those capped with rigid methylthiolate provides evidence that the temperature dependence of the permeability of the oleate ligand shell is due to formation of transient gaps in the adlayer through conformational fluctuations of the ligands

Cardiorespiratory capacity in children living at moderate altitude [Capacidad cardio-respiratoria de niños escolares que viven a moderada altitud]

Objective: To determine the cardiorespiratory capacity of school children living at moderate altitude. Patients and Method: 795 children (394 children and 401 girls) were selected from urban public schools in Arequipa, Peru at moderate altitude (2,320 m). Anthropometric variables (body mass, height, body fat percentage) and cardiorespiratory capacity were assessed using the Course Navette test, considering the following categories: Deficient, poor, fair, good, very good and excellent. Results: The results showed significant differences in all categories (p < 0.05). It was described that the median values of the poor and deficient categories in both gender were lower than what is considered acceptable (p <0.05). It was concluded that 19% of boys and 21% of girls showed low level of cardiorespiratory capacity and a low negative correlation with overweight (r = -0.20 to -0.22) and a moderate negative correlation with obesity (r = -0.39 to -0.42) were described for both genders. Conclusions: Low levels of cardiorespiratory capacity in boys and girls living at moderate altitude are observed, which is negatively correlated with excess body weight. The results suggest that 1 in 5 children are likely to suffer some type of cardiovascular event

Description of the Adsorption and Exciton Delocalizing Properties of <i>p</i>‑Substituted Thiophenols on CdSe Quantum Dots

This work describes the quantitative characterization of the interfacial chemical and electronic structure of CdSe quantum dots (QDs) coated in one of five <i>p</i>-substituted thiophenolates (X-TP, X = NH₂, CH₃O, CH₃, Cl, or NO₂), and the dependence of this structure on the <i>p</i>-substituent X. ¹H NMR spectra of mixtures of CdSe QDs and X-TPs yield the number of X-TPs bound to the surface of each QD. The binding data, in combination with the shift in the energy of the first excitonic peak of the QDs as a function of the surface coverage of X-TP and Raman and NMR analysis of the mixtures, indicate that X-TP binds to CdSe QDs in at least three modes, two modes that are responsible for exciton delocalization and a third mode that does not affect the excitonic energy. The first two modes involve displacement of OPA from the QD core, whereas the third mode forms cadmium–thiophenolate complexes that are not electronically coupled to the QD core. Fits to the data using the dual-mode binding model also yield the values of Δ<i>r</i>₁, the average radius of exciton delocalization due to binding of the X-TP in modes 1 and 2. A 3D parametrized particle-in-a-sphere model enables the conversion of the measured value of Δ<i>r</i>₁ for each X-TP to the height of the potential barrier that the ligand presents for tunneling of excitonic hole into the interfacial region. The height of this barrier increases from 0.3 to 0.9 eV as the substituent, X, becomes more electron-withdrawing