Determination of preferential rare earth adatom adsorption geometries on Si(001)

The adsorption patterns of rare earth atoms on Si(001) were investigated using scanning tunneling microscopy measurements and density functional calculations. Stable configurations were systematically determined via calculation of binding energies of various adatom coverage and adsorption geometry. Competition between inter-adatom hybridization and Coulomb repulsion is the mechanism contributing to binding energy minima associated with commonly observed rare earth adsorption geometries. Comparison of stable configurations with experimental scanning tunneling microscopy images demonstrated accuracy of the theoretical models. This paves a way for the understanding of self-assembly of rare earth disilicide nanowires on vicinal Si(001) substrates.     

Dy3+ emission in M5(PO4)3F (M = Ca, Ba) phosphor

Ultrafine M₅(PO₄)₃F:Dy³⁺ (M = Ca, Ba) phosphors were prepared via combustion process using metal nitrates as precursors. The formation of crystalline phosphate was confirmed by X-ray diffraction pattern. The PL excitation spectra show the excitation peaks observed at 250 to 400 nm due to f → f transition of Dy³⁺ ion, which are useful for solid-state lighting purpose (mercury free excitation). The PL emission of Dy³⁺ ion by 348 nm excitation gave an emission at 489 nm (blue), 582 nm (yellow) and 675 nm (red). All the characteristics of BYR emissions like BGR indicate that Dy doped Ca₅(PO₄)₃F and Ba₅(PO₄)₃F phosphors are good candidates that can be applied in solid-state lighting phosphor (mercury free excited lamp phosphor) and white light LED.      

Potentiation of the cytotoxicity of the anticancer agent tirapazamine by benzotriazine N-oxides: the role of redox equilibria

Tirapazamine (3-amino-1,2,4-benzotriazine 1,4-dioxide), the lead bioreductive drug with selective toxicity for hypoxic cells in tumors, is thought to act by forming an active oxidizing radical of high one-electron reduction potential, E(1), when reduced by reductases. It has a dual mechanism of action, both generating DNA radicals, following its one-electron reduction and subsequently oxidizing these DNA radicals to form labile cations or hydrolyzable lactones through transferring an O atom, resulting in DNA strand breaks. These parallel secondary reactions have been proposed to be also initiated by its two-electron reduced metabolite, the 1-oxide. We have used pulse radiolysis to show that the benzotriazinyl radical of a highly soluble analogue of tirapazamine, the 3-(N,N-dimethyl-1,2-ethanediamine) analogue, is able to oxidize tirapazamine itself. We have found that both tirapazamine and the 1-oxides are in equilibrium with their respective benzotriazinyl radicals, with high concentrations of the more soluble 1-oxide maintaining a high concentration of the more reactive oxidizing radical of tirapazamine. The one-electron reduction potentials, E(1), of the 1-oxides and related compounds have been measured and, together with the E(1) values of tirapazamine and the 2-nitroimidazole radiosensitizer, misonidazole, are shown to predict the published percentages of electron transfer. This radical chemistry study gives an insight into the mechanisms of the potentiation of radical damage, reported for DNA, that underlies the hypoxic cytotoxicity of electron affinic compounds. The E(1) values of the benzotriazinyl radicals of the benzotriazine compounds govern the position of the redox equilibria, which determine the amount of initial radical damage. The E(1) values of the 1,4-dioxides and 1-oxide compounds govern the degree of potentiation of the initial radical damage once formed.     

Releasable luciferin-transporter conjugates: tools for the real-time analysis of cellular uptake and release

The design, synthesis, and evaluation of conjugates of arginine-rich transporters and luciferin are described that release luciferin only after entry into cells that are stably transfected with luciferase. Each molecule of free luciferin that is released after entry generates a photon that can be measured allowing for real-time quantification of uptake and release in cells. The process provides a method to assay uptake and release of free luciferin as a function of variations in the releasable linker and in the transporter.     

Structural,optical, and photoelectrochemical properties of nanosphere-like CdXZn1-XS synthesized by electrochemical route

Here, we present the effect of different Zn contents on the structural, morphological, and optical properties of Cd_XZn_1-XS thin films deposited by electrodeposition method on stainless steel and indium-doped tin oxide (ITO) glass substrates. Electrosynthesized Cd_XZn_1-XS thin films are characterized by using X-ray diffraction (XRD), UV-Vis spectrophotometer, field emission scanning electron microscope (FE-SEM), and surface wettability analysis. XRD pattern reveals that the Cd_XZn_1-XS thin films are polycrystalline in nature with hexagonal crystal structure. FE-SEM micrograph displays that these Cd_XZn_1-XS thin films exhibit the different sizes of sphere-like nanostructures by varying the X value. The optical absorption study indicates that drastic variation in band gap energy of Cd_XZn_1-XS thin films. In advance photovoltaic measurements, Cd_XZn_1-XS thin films are to be studied by forming the photoelectrochemical (PEC) cell having Cd_XZn_1-XS/0.5 M (Na₂SO₃)/C configuration. The efficiency values of Cd_XZn_1-XS are found to be 0.2, 0.35, 0.32, 0.25, and 0.23 % respectively at X content.

     

Charge state distribution studies of pure and oxygen mixed krypton ECR plasma – signature of isotope anomaly and gas mixing effect

We report the charge state distributions of the pure, 25% and 50% oxygen mixed krypton plasma to shed more light on the understanding of the gas mixing and the isotope anomaly [A. G. Drentje, Rev. Sci. Instrum. 63 (1992) 2875 and Y Kawai, D Meyer, A Nadzeyka, U Wolters and K Wiesemann, Plasma Sources Sci. Technol. 10 (2001) 451] in the electron cyclotron resonance (ECR) plasmas. The krypton plasma was produced using a 10 GHz all‐permanent‐magnet ECR ion source. The intensities of the highly abundant four isotopes, viz. ⁸²Kr (~11.58%), ⁸³Kr (~11.49%), ⁸⁴Kr (~57%) and ⁸⁶Kr (17.3%) up to ~ +14 charge state have been measured by extracting the ions from the plasma and analysing them in the mass and the energy using a large acceptance analyzer‐cum‐switching dipole magnet. The influence of the oxygen gas mixing on the isotopic krypton ion intensities is clearly evidenced beyond +9 charge state. With and without oxygen mixing, the charge state distribution of the krypton ECR plasma shows the isotope anomaly with unusual trends. The anomaly in the intensities of the isotopes having quite closer natural abundance, viz. ⁸²Kr, ⁸⁶Kr and ⁸³Kr, ⁸⁶Kr is prominent, whereas the intensity ratio of ⁸⁶Kr to ⁸⁴Kr shows a weak signature of it. The isotope anomaly tends to disappear with increasing oxygen mixing in the plasma. The observed trends in the intensities of the krypton isotopes do not follow the prediction of linear Landau wave damping in the plasma. Copyright © 2016 John Wiley & Sons, Ltd.     

Mechanical unfolding of ensemble biomolecular structures by shear force

Mechanical unfolding of biomolecular structures has been exclusively performed at the single-molecule level by single-molecule force spectroscopy (SMFS) techniques. Here we transformed sophisticated mechanical investigations on individual molecules into a simple platform suitable for molecular ensembles. By using shear flow inside a homogenizer tip, DNA secondary structures such as i-motifs are unfolded by shear force up to 50 pN at a 77 796 s⁻¹ shear rate. We found that the larger the molecules, the higher the exerted shear forces. This shear force approach revealed affinity between ligands and i-motif structures. It also demonstrated a mechano-click reaction in which a Cu(i) catalyzed azide–alkyne cycloaddition was modulated by shear force. We anticipate that this ensemble force spectroscopy method can investigate intra- and inter-molecular interactions with the throughput, accuracy, and robustness unparalleled to those of SMFS methods.

Shear force in a homogenizer mechanically unfolds an ensemble set of biomolecular structures.     

Ion-isotopic exchange reaction kinetics using Duolite ARA-9366B and Indion-AGR resins

Radiotracer isotopic technique as an effective analytical tool was used to study the kinetics of ion-isotopic exchange reactions in the nuclear- and nonnuclear-grade anion exchange resins Duolite ARA-9366B and Indion-AGR. On the basis of kinetic data, specific reaction rate (per minute), amount of ion exchanged (millimoles), initial rate of iodide ion exchange (millimoles per minute), and log K _d values were calculated for the two resins. It was observed that under identical experimental conditions of 35.0 °C, 1.000 g of ion exchange resins, and 0.002 mol/L of labeled iodide ion solution, the values calculated were 0.200 min^?1, 0.278 mmol, 0.056 mmol/min, and 9.6, respectively, for Duolite ARA-9366B resin, which were higher than 0.102 min^?1, 0.216 mmol, 0.022 mmol/min, and 5.7, respectively, for Indion-AGR resins. An identical trend was observed for the two resins during bromide ion-isotopic exchange reaction. The overall results indicate that under identical experimental conditions, Duolite ARA-9366B resins show superior performance than Indion-AGR resins. The results of the present experimental work have demonstrated that the radioanalytical technique used here can be successfully applied for the characterization of different ion exchange resins so as to evaluate their performance under various process parameters.