Cu<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Ni<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript> alloy nanoparticles embedded SiO<Subscript>2</Subscript> films: synthesis and structure

Cu–Ni fcc alloy nanoparticles (NPs) of tunable atomic ratios were generated in SiO₂ films. The films were prepared using the Cu(NO₃)₂ and Ni(NO₃)₂ co-doped inorganic–organic hybrid silica sols by single dipping. Transparent, crack-free, glassy SiO₂ films of 310 ± 10 nm in thickness embedded with high mol percent of Cu–Ni alloy NPs were yielded after annealing at 750 °C in 10% H₂-90% Ar atmosphere. Nominal compositions of the films were 20 mol% (Cu–Ni)-80 mol% SiO₂. Optical spectral study of the heat-treated films showed disappearance of Cu plasmon bands due to Cu–Ni alloy formation. Grazing incidence X-ray diffraction (GIXRD) studies revealed the formation of Cu–Ni alloy (2:1, 1:1 and 1:2) NPs inside the SiO₂ film. GIXRD showed a systematic shifting of the diffraction peaks with respect to the fcc Cu–Ni alloy composition, maintaining the nominal ratios. Transmission electron microscopy (TEM) studies of the representative Cu_0.5Ni_0.5-doped film showed existence of homogeneously dispersed Cu–Ni alloy NPs of average size 6.35 nm inside the SiO₂ matrix. The energy dispersive X-ray scattering (EDX) analysis of the individual NPs using the nano-probe (scanning TEM mode) confirmed the presence of both the Cu and Ni with the desired atomic ratio.     

Unitary parametrization of perturbations to tribimaximal neutrino mixing

Current experimental data on neutrino mixing are very well described by tribimaximal mixing. Accordingly, any phenomenological parametrization of the Maki-Nakagawa-Sakata-Pontecorvo matrix must build upon tribimaximal mixing. We propose one particularly natural parametrization, which we call "triminimal." The three small deviations of the Particle Data Group angles from their tribimaximal values, and the PDG phase, parametrize the triminimal mixing matrix. As an important example of the utility of this new parametrization, we present the simple resulting expressions for the flavor-mixing probabilities of atmospheric and astrophysical neutrinos. As no foreseeable experiment will be sensitive to more than second order in the small parameters, we expand these flavor probabilities to second order.     

Oxygen atom transfer promoted nitrate to nitric oxide transformation: a step-wise reduction of nitrate → nitrite → nitric oxide

Nitrate reductases (NRs) are molybdoenzymes that reduce nitrate (NO₃⁻) to nitrite (NO₂⁻) in both mammals and plants. In mammals, the salival microbes take part in the generation of the NO₂⁻ from NO₃⁻, which further produces nitric oxide (NO) either in acid-induced NO₂⁻ reduction or in the presence of nitrite reductases (NiRs). Here, we report a new approach of VCl₃ (V³⁺ ion source) induced step-wise reduction of NO₃⁻ in a Co^II-nitrato complex, [(12-TMC)Co^II(NO₃⁻)]⁺ (2,{Co^II–NO₃⁻}), to a Co^III–nitrosyl complex, [(12-TMC)Co^III(NO)]²⁺ (4,{CoNO}⁸), bearing an N-tetramethylated cyclam (TMC) ligand. The VCl₃ inspired reduction of NO₃⁻ to NO is believed to occur in two consecutive oxygen atom transfer (OAT) reactions, i.e., OAT-1 = NO₃⁻ → NO₂⁻ (r₁) and OAT-2 = NO₂⁻ → NO (r₂). In these OAT reactions, VCl₃ functions as an O-atom abstracting species, and the reaction of 2 with VCl₃ produces a Co^III-nitrosyl ({CoNO}⁸) with V^V-Oxo ({V^V O}³⁺) species, via a proposed Co^II-nitrito (3, {Co^II–NO₂⁻}) intermediate species. Further, in a separate experiment, we explored the reaction of isolated complex 3 with VCl₃, which showed the generation of 4 with V^V-Oxo, validating our proposed reaction sequences of OAT reactions. We ensured and characterized 3 using VCl₃ as a limiting reagent, as the second-order rate constant of OAT-2 (k₂^/) is found to be ∼1420 times faster than that of the OAT-1 (k₂) reaction. Binding constant (K_b) calculations also support our proposition of NO₃⁻ to NO transformation in two successive OAT reactions, as K_{b(Co^II–NO2⁻)} is higher than K_{b(Co^II–NO3⁻)}, hence the reaction moves in the forward direction (OAT-1). However, K_{b(Co^II–NO2⁻)} is comparable to K_b{CoNO}⁸, and therefore sequenced the second OAT reaction (OAT-2). Mechanistic investigations of these reactions using ¹⁵N-labeled-¹⁵NO₃⁻ and ¹⁵NO₂⁻ revealed that the N-atom in the {CoNO}⁸ is derived from NO₃⁻ ligand. This work highlights the first-ever report of VCl₃ induced step-wise NO₃⁻ reduction (NRs activity) followed by the OAT induced NO₂⁻ reduction and then the generation of Co-nitrosyl species {CoNO}⁸.

Single metal-induced reduction of NO₃⁻ → {NO₂⁻} → NO via oxygen atom transfer reaction.     

Synthesis and characterization of new O,O‐diethyl phosphorothioates derived from substituted tetrazolo[1,5‐a]quinolin‐ 4‐ylmethanol derivatives

A simple and convenient method is developed for the synthesis of new O,O‐diethyl O‐(substituted tetrazolo[1,5‐a]quinolin‐4‐yl)methyl phosphorothioates, which has been synthesized for the first time from tetrazolo[1,5‐a] quinolines via tetrazolo[1,5‐a]quinolin‐4‐ylmethanol derivatives. The structures of the all newly synthesized compounds were elucidated by analytical and spectral methods. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 20:436–441, 2009; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20570     

Supramolecular Barrel-Rosette Ion Channel Based on 3,5-Diaminobenzoic Acid for Cation-Anion Symport

The structural tropology and functions of natural cation-anion symporting channels have been continuously investigated due to their crucial role in regulating various physiological functions. To understand the physiological functions of the natural symporter channels, it is vital to develop small-molecule-based biomimicking systems that can provide mechanistic insights into the ion-binding sites and the ion-translocation pathways. Herein, we report a series of bis((R)-(−)-mandelic acid)-linked 3,5-diaminobenzoic acid based self-assembled ion channels with distinctive ion transport ability. Ion transport experiment across the lipid bilayer membrane revealed that compound 1 b exhibits the highest transport activity among the series, and it has interesting selective co-transporting functions, i.e., facilitates K⁺/ClO₄⁻ symport. Electrophysiology experiments confirmed the formation of supramolecular ion channels with an average diameter of 6.2±1 Å and single channel conductance of 57.3±1.9 pS. Selectivity studies of channel 1 b in a bilayer lipid membrane demonstrated a permeability ratio of , , and indicating the higher selectivity of the channel towards KClO₄ over KCl salt. A hexameric assembly of a trimeric rosette of 1 b was subjected to molecular dynamics simulations with different salts to understand the supramolecular channel formation and ion selectivity pattern.     

Floquet Transmission in Weyl/Multi-Weyl and Nodal-Line Semimetals through a Time-Periodic Potential Well

A quantum pumping protocol through which the quasiparticles of Weyl/multi-Weyl and nodal-line semimetals are subjected to a time-periodic rectangular potential well is considered. The presence of an oscillating potential of frequency ω creates equispaced Floquet side-bands with spacing $\hslash \omega$. As a result, a Fano resonance is observed when the difference in the Fermi energy (i.e., the energy of the incident quasiparticle), and the energy of one of the (quasi)bound state levels of the well, coincides with the energy of an integer number of photons (each carrying energy quantum $\hslash \omega$). Using the Floquet theory and the scattering matrix approach in the zero-temperature non-adiabatic pumping limit, characteristic Fano resonance patterns are found in the transmission coefficients. The inflection points in the pumped shot noise spectra also serve as a proxy for the corresponding Fano resonances. Therefore, the pumped shot noise is also numerically evaluated. Finally, the existence of the Fano resonance points is correlated to the (quasi)bound states of the well, by explicitly calculating the bound states of the static well (which are a subset of the bound states of the driven system). Since semimetals with anisotropic dispersions are considered, all the features observed depend on the orientation of the potential well.