Long-range electronic-to-vibrational energy transfer from nanocrystals to their surrounding matrix environment

A radiationless transition process of long-range, resonance interconversion of electronic-to-vibrational energy transfer (EVET) is discovered between the band-gap excitation of nanocrystal quantum dots to matrix vibrational overtone modes using fluorescence lifetime measurements. A theoretical analysis based on long-range dipole-dipole nonadiabatic couplings, being distinct from the traditional adiabatic or "static-coupling" pictures, is given and is in qualitative agreement with experiments. EVET should be considered in matrix choices for near-infrared optoelectronic applications of nanocrystals.     

Imprinting of molecular recognition sites through electropolymerization of functionalized Au nanoparticles: development of an electrochemical TNT sensor based on pi-donor-acceptor interactions

Electrochemical sensors for the analysis of TNT with enhanced sensitivities are described. The enhanced sensitivities are achieved by tailoring pi-donor-acceptor interactions between TNT and pi-donor-modified electrodes or pi-donor-cross-linked Au nanoparticles linked to the electrode. In one configuration a p-aminothiophenolate monolayer-modified electrode leads to the analysis of TNT with a sensitivity corresponding to 17 ppb (74 nM). In the second configuration, the cross-linking of Au NPs by oligothioaniline bridges to the electrode yields a functionalized electrode that detects TNT with a sensitivity that corresponds to 460 ppt (2 nM). Most impressively, the imprinting of molecular TNT recognition sites into the pi-donor oligoaniline-cross-linked Au nanoparticles yields a functionalized electrode with a sensitivity that corresponds to 46 ppt (200 pM). The electrode reveals high selectivity, reusability, and stability.     

Separation/preconcentration of trace amounts of Cr, Cu and Pb in environmental samples by magnetic solid-phase extraction with Bismuthiol-II-immobilized magnetic nanoparticles and their determination by ICP-OES

A new method for separation/preconcentration of trace amounts of Cr, Cu and Pb in environmental samples by magnetic solid-phase extraction (SPE) with Bismuthiol-II-immobilized magnetic nanoparticles and their determination by ICP-OES has been developed. The separation of the target analytes from the aqueous solution containing the target analytes and Bismuthiol-II-immobilized magnetic nanoparticles was simply achieved by applying external magnetic field. Optimal experimental conditions including pH, sample volume, eluent concentration and volume and co-existing ions have been studied and established. Under the optimal experimental conditions, the detection limits for Cr, Cu and Pb with enrichment factors of 96, 95 and 87 were found to be 0.043, 0.058 and 0.085 ng mL⁻¹ and their relative standard deviations (R.S.D.s) were 3.5%, 4.6% and 3.7% (n = 5, C = 2 ng mL⁻¹), respectively. The method was validated with certified reference material (GBW50009-88) of environmental water sample and the analytical results coincided well with the certified values. Furthermore, the method was successfully applied to the determination of target analytes in river and lake water samples. Compared with established methods, the proposed method is characterized with high enrichment factor, fast separation and low detection limits.     

Phosphinoborane and Sulfidoborohydride as Chelating Ligands in Polyhydride Ruthenium Complexes: Agostic σ‐Borane versus Dihydroborate Coordination

A question of coordination mode : Two new borane compounds are prepared. They act as bifunctional ligands as illustrated by their reaction with ruthenium polyhydrides which leads to the formation of two complexes (see scheme) displaying either a δ‐agostic interaction of a η²‐B? H bond involving a trivalent boron atom or a dihydroborate ligation.

     

Three points method for searching the best least absolute deviations plane

In this paper a new method for estimation of optimal parameters of a best least absolute deviations plane is proposed, which is based on the fact that there always exists a best least absolute deviations plane passing through at least three different data points. The proposed method leads to a solution in finitely many steps. Moreover, a modification of the aforementioned method is proposed that is especially adjusted to the case of a large number of data and the need to estimate parameters in real time. Both methods are illustrated by numerical examples on the basis of simulated data and by one practical example from the field of robotics.     

A nonlinear symmetry breaking effect in shear cracks

Shear cracks propagation is a basic dynamical process that mediates interfacial failure. We develop a general weakly nonlinear elastic theory of shear cracks and show that these experience tensile-mode crack tip deformation, including possibly opening displacements, in agreement with Stephenson's prediction. We quantify this nonlinear symmetry breaking effect, under two-dimensional deformation conditions, by an explicit inequality in terms of the first and second order elastic constants in the quasi-static regime and by semi-analytic calculations in the fully dynamic regime. Our general results are applied to various materials. Finally, we discuss related works in the literature and note the potential relevance of elastic nonlinearities for various problem, including frictional sliding.     

Adsorption of sulfur dioxide by CoFe2O4 spinel ferrite nanoparticles and corresponding changes in magnetism

Adsorption of sulfur dioxide on 10 nm CoFe(2)O(4) spinel ferrite nanoparticles was examined. Adsorption loadings of sulfur dioxide at breakthrough conditions were determined to be approximately 0.62 mol/kg, which is significant given the 150 m(2)/g surface area of the nanoparticles. Adsorption proceeds through a chemisorption mechanism with sulfur dioxide forming a sulfate upon adsorption on the particle surface, which leads to a 23% decrease in the remnant magnetization, a 20% decrease in the saturation magnetization, and a 9% decrease in the coercivity of the magnetic nanoparticles. Adsorbent materials that provide a magnetic signal when adsorption occurs could have broad implications on adsorption-based separations.     

The singularity in weakly nonlinear fracture mechanics

Material failure by crack propagation essentially involves a concentration of large displacement-gradients near a crack's tip, even at scales where no irreversible deformation and energy dissipation occurs. This physical situation provides the motivation for a systematic gradient expansion of general nonlinear elastic constitutive laws that goes beyond the first order displacement-gradient expansion that is the basis for linear elastic fracture mechanics (LEFM). A weakly nonlinear fracture mechanics theory was recently developed by considering displacement-gradients up to second order. The theory predicts that, at scales within a dynamic lengthscale ℓ from a crack's tip, significant logr displacements and 1/r displacement-gradient contributions arise. Whereas in LEFM the 1/r singularity generates an unbalanced force and must be discarded, we show that this singularity not only exists but is also necessary in the weakly nonlinear theory. The theory generates no spurious forces and is consistent with the notion of the autonomy of the near-tip nonlinear region. The J-integral in the weakly nonlinear theory is also shown to be path-independent, taking the same value as the linear elastic J-integral. Thus, the weakly nonlinear theory retains the key tenets of fracture mechanics, while providing excellent quantitative agreement with measurements near the tip of single propagating cracks. As ℓ is consistent with lengthscales that appear in crack tip instabilities, we suggest that this theory may serve as a promising starting point for resolving open questions in fracture dynamics.