Counterion influence on the N–I–N halogen bond

A detailed investigation of the influence of counterions on the [N–I–N]⁺ halogen bond in solution, in the solid state and in silico is presented. Translational diffusion coefficients indicate close attachment of counterions to the cationic, three-center halogen bond in dichloromethane solution. Isotopic perturbation of equilibrium NMR studies performed on isotopologue mixtures of regioselectively deuterated and nondeuterated analogues of the model system showed that the counterion is incapable of altering the symmetry of the [N–I–N]⁺ halogen bond. This symmetry remains even in the presence of an unfavorable geometric restraint. A high preference for the symmetric geometry was found also in the solid state by single crystal X-ray crystallography. Molecular systems encompassing weakly coordinating counterions behave similarly to the corresponding silver(i) centered coordination complexes. In contrast, systems possessing moderately or strongly coordinating anions show a distinctly different behavior. Such silver(i) complexes are converted into multi-coordinate geometries with strong Ag–O bonds, whereas the iodine centered systems remain linear and lack direct charge transfer interaction with the counterion, as verified by ¹⁵N NMR and DFT computation. This suggests that the [N–I–N]⁺ halogen bond may not be satisfactorily described in terms of a pure coordination bond typical of transition metal complexes, but as a secondary bond with a substantial charge-transfer character.     

Laser desorption ionization time‐of‐flight mass spectrometric study of binary As‐Se glasses

Binary chalcogenide As‐Se glasses and their thin films are important for optics, computers, materials science and technological applications. To increase understanding of the properties of thin films fabricated by plasma deposition techniques, more information concerning the physics of plasma plume is needed. In this study the formation of clusters in plasma plume from different As‐Se glasses by laser desorption ionization (LDI) or laser ablation (LA) was studied by time‐of‐flight mass spectrometry (TOF MS) in positive and negative ion modes. Formation of a number of As_pSe_q singly charged clusters As₃Se (q = 1–5), AsSe (q = 1–3), As₂Se (q = 2–4), and As₃Se (q = 2–5) was found from As‐Se glasses with the molar ratio As:Se in the range from 1:2 to 7:3. The stoichiometry of the As_pSe_q clusters was determined via isotopic envelope analysis and computer modeling. The structure of the clusters is proposed and the relationship to the structure of the parent glasses, as also suggested by Raman scattering spectra, is discussed. Copyright © 2010 John Wiley & Sons, Ltd.     

Investigation of the Reaction of Gold(III) with 2‐[2‐(4‐Dimethylamino‐Phenyl)‐Vinyl]‐1,3,3‐Trimethyl‐3H‐Indolium. Application for Determination of Gold

A new, simple, rapid, sensitive, efficient and low‐cost spectrophotometric procedure for the determination of gold was developed. The method is based on the reaction of [AuCl₄]^? with 2‐[2‐(4‐dimethylaminophenyl)‐vinyl]‐1,3,3‐trimethyl‐3H‐indolium reagent to form a colored ion associate extractable by various organic solvents. The molar absorptivity of the ion associates is in the range (5.7–9.2) × 10⁴ L mol^?1 cm^?1 depending on the extractant. Butyl acetate was chosen as the extractant. The optimum reaction conditions were established: pH 2–4, concentration of the dye reagent (0.8–1.5) × 10^?4 mol L^?1. The determination of gold is not hindered even by a 1000‐fold concentration of Ni and Co; a 500‐fold concentration of Pb and Zn; a 100‐fold concentration of Bi, Cu, Cd, Pt, Rh and Ru; or a 20‐fold concentration of Ag. The established method was applied to the determination of gold in model samples and enriched polymetallic ores.     

Laser desorption/ionization and laser ablation synthesis of new selenium oxide compounds from selenium(IV) dioxide

Laser desorption/ionization (LDI) and/or laser ablation (LA) of selenium dioxide crystals or its mixtures with sodium peroxide were studied using a commercial matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometer. It was found that LDI and LA of selenium (IV) dioxide not only ionizes SeO(2), but also leads to the formation of several positively and negatively singly charged species: SeO(n) (+) (n = 0-2), Se(2) (+), SeO(n) (-) (n = 0-4), Se(2)O(n) (-) (n = 3-7), Se(3)O(n) (-) (n = 4-9), Se(4)O(n) (-) (n = 8-10). A rather high yield of selenium species in the positive ion mode, Se(m) (+) (m = 1-8) and Se(m)OH(+) (m = 3-7), was obtained by using the MALDI approach while the species detected in the negative ion mode, SeO(n) (-) (n = 0-4), Se(2)O(n) (-) (n = 3-7), Se(3)O(n) (-) (n = 4-9), and Se(4)O(n) (-) (n = 9, 10), were the same as those observed during LDI/LA of selenium dioxide. The addition of sodium peroxide to selenium dioxide with the aim of enhancing its oxidation and thus increasing the production of SeO(4) product resulted in extensive cationization of the species with sodium or potassium. The following positively and negatively charged species were identified: Se(+), Se(2) (+), Se(2)OH(+), Se(2)ONa(+), SeO(n) (-) (n = 0-3), and Se(2)O(n) (-) (n = 0, 1, 4). Also observed in mass spectra of such mixtures, various mixed sodium and/or potassium adducts with selenium oxide species, e.g. Se(2)O(4)K(2)Na(-), were identified. In all, 26 totally new species, Se(2)O(n) (-) (n = 3-6), Se(3)O(n) (-) (n = 4-9), Se(4)O(n) (-) (n = 8-10), Se(4)O(11)H(5) (-), Se(4)O(12)H(3) (-), Se(2)O(4)Na(-), Se(2)O(5)HNa(-), Se(2)O(5)HNa(2) (-), Se(3)O(6)K(2)Na(-), Se(3)O(6)K(2)Na(2) (-), Se(2)ONa(+), and Se(m)OH(+) (m = 3-7), were described for the first time. Also, for the first time, the formation of selenium(IV) diperoxide, O-O-Se-O-O or O(2)SeO(2), is described. The stoichiometries of the compounds generated were confirmed using isotopic pattern modeling.     

Principles of control for decoherence-free subsystems

Decoherence-free subsystems (DFSs) are a powerful means of protecting quantum information against noise with known symmetry properties. Although Hamiltonians that can implement a universal set of logic gates on DFS encoded qubits without ever leaving the protected subsystem theoretically exist, the natural Hamiltonians that are available in specific implementations do not necessarily have this property. Here we describe some of the principles that can be used in such cases to operate on encoded qubits without losing the protection offered by the DFSs. In particular, we show how dynamical decoupling can be used to control decoherence during the unavoidable excursions outside of the DFS. By means of cumulant expansions, we show how the fidelity of quantum gates implemented by this method on a simple two physical qubit DFS depends on the correlation time of the noise responsible for decoherence. We further show by means of numerical simulations how our previously introduced "strongly modulating pulses" for NMR quantum information processing can permit high-fidelity operations on multiple DFS encoded qubits in practice, provided that the rate at which the system can be modulated is fast compared to the correlation time of the noise. The principles thereby illustrated are expected to be broadly applicable to many implementations of quantum information processors based on DFS encoded qubits.     

Spherical and Clockwise Spherical Graphs

The main subject of our study are spherical (weakly spherical) graphs, i.e. connected graphs fulfilling the condition that in each interval to each vertex there is exactly one (at least one, respectively) antipodal vertex. Our analysis concerns properties of these graphs especially in connection with convexity and also with hypercube graphs. We deal e.g. with the problem under what conditions all intervals of a spherical graph induce hypercubes and find a new characterization of hypercubes: G is a hypercube if and only if G is spherical and bipartite.     

Characterization of a sapphire-epoxy coating for capillary electrophoresis

A new procedure for coating capillaries for capillary electrophoresis applying a sapphire (alumina) containing epoxy resin was developed. Coated capillaries showed considerably reduced electroosmotic flow, and decreased the adsorption of proteins to the internal wall of the capillary. Coating is transparent down to 195 nm and can be used with advantage to analyze different kinds of substances, such as small cations and/or anions, and proteins.