The rich crystal chemistry of the AMM′(PO4)2 morphotropic series: NaZnAl(PO4)2, the first Na representative with a new structure type

A novel phosphate, sodium zinc aluminium bis(phosphate), NaZnAl(PO₄)₂, was obtained under mild‐temperature hydrothermal conditions at 553 K. The crystal structure has been studied using single‐crystal X‐ray experimental data. The pseudo‐hexagonal phase NaZnAl(PO₄)₂ crystallizes in the monoclinic space group P2₁/c. Its unique crystal structure is based on a three‐dimensional (3D) framework built by Zn‐, Al‐ and P‐centred tetrahedra sharing vertices. Channels parallel to the [101] and [01] directions are limited by six‐ and eight‐membered windows, and incorporate Na atoms. The new compound is discussed as a member of the morphotropic series AMM′PO₄, where A = Na, K, Rb or NH₄, M = Cu, Ni, Co, Fe, Zn or Mg and M′ = Fe, Al or Ga. The title compound is the first Na representative within the series and is characterized by a 3D architecture of tetrahedra populated in an ordered manner by Zn²⁺, Al³⁺ and P⁵⁺ ions.     

On the nature of the lowest triplet excited state of the [Rh 2(1,3-diisocyanopropane)(4)]2+ ion

The nature of the ground state and the lowest triplet excited state of the [Rh(2)(1,3-diisocyanopropane)(4)](2+) ion have been investigated by the density functional theory. Two locally stable geometrical conformations are found on the potential energy surfaces of both the ground and excited states, corresponding to the eclipsed and twisted conformations, the eclipsed conformation being more stable and having the shorter Rh-Rh bond length. While the Rh-Rh distances of the two conformations differ by approximately 0.4 A, they shorten to the same value upon excitation ( approximately 3.1 A). The excited state originates from the d(z)()()2 (metal antibonding) to p(z)() (ligand-metal bonding) electronic transition. The Mayer Rh-Rh bond order increases from approximately 0.2 to more than 0.8 upon excitation, while the Rh-C(N) bond order shows a slight decrease. A topological bond path between the Rh atoms is found in both the ground and excited states, while the electron localization function (ELF) indicates weak Rh-Rh covalent bonding for the excited state only.     

Aqueous room temperature metal-catalyzed living radical polymerization of vinyl chloride

This paper describes the room-temperature living radical polymerization (LRP) of vinyl chloride in H2O/THF in the presence of Cu0 or CuI salts as catalysts, tren or PEI as ligands, and iodoform as initiator. The disproportionation reaction 2CuI + L --> Cu0 + CuII(L) is the crucial step, as it continuously provides the active species for both the initiation (Cu0) and the reversible termination step (CuII). Mn was found to increase linearly with conversion and is in good agreement with Mth, with the Mw/Mn being approximately 1.5.     

Enhancement of frequency modulation response time for polymer-dispersed liquid crystal

Through the ferroelectric nanoparticles of BaTiO₃ (BTO) doping, the response time for the frequency modulation of the polymer-dispersed liquid crystal (PDLC) was improved. The BTO-doped PDLC cells were prepared by polymerisation induced phase separation (PIPS) process using UV light. The capacitance of the PDLC composites was measured with an impedance analyzer in the frequency range of 100 Hz–1 MHz at 1 V. The dynamic signal for the response time of the PDLC devices was monitored through a digital oscilloscope. The electro-optical properties of the PDLC were found to strongly depend on the doped BTO concentration. The BTO doping caused a large increase in the capacitance. The dielectric constants were drastically decreased in the samples with rather low BTO doping ratio at a high frequency. No outstanding difference in the rising time of the LC was observed in the BTO-doped PDLC device, but the falling time was significantly decreased from 0.334 to 0.094 s. The present results imply that the nanoparticle-doping technology could improve the electro-optical performance of the PDLC requiring fast response and frequency modulation, such as optical modulators and PDLC-hybrid electroluminescence device for flexible electronic devices.     

Fluorescence-based Broad Dynamic Range Viscosity Probes

We introduce two new fluorescent viscosity probes, SYBR Green (SG) and PicoGreen (PG), that we have studied over a broad range of viscosity and in collagen solutions. In water, both dyes have low quantum yields and excited state lifetimes, while in viscous solvents or in complex with DNA both parameters dramatically (300–1000-fold) increase. We show that in log-log scale the dependence of the dyes’ quantum yield vs. viscosity is linear, the slope of which is sensitive to temperature. Application of SG and PG, as a fluorescence-based broad dynamic range viscosity probes, to the life sciences is discussed.     

Some Algebraic and Analytical Properties of Coquaternion Algebra

The aim of this work is to prove some basic properties of coquaternions and to find the zeros of polynomials involving coquaternionic elements. We also provide some expansions of hyperholomorphic function on coquaternion algebra by using Fueter polynomials.     

Bulk and surface structure and high-temperature thermoelectric properties of inverse clathrate-III in the Si-P-Te system

The creation of thermoelectric materials for waste heat recovery and direct solar energy conversion is a challenge that forces the development of compounds that combine appreciable thermoelectric figure‐of‐merit with high thermal and chemical stability. Here we propose a new candidate for high‐temperature thermoelectric materials, the type‐III Si_172?xP_xTe_y cationic clathrate, in which the framework is composed of partially ordered silicon and phosphorus atoms, whereas tellurium atoms occupy guest positions. We show that the utmost stability of this clathrate (up to 1500 K) in air is ensured by the formation of a nanosized layer of phosphorus‐doped silica on the surface, which prevents further oxidation and degradation. As‐cast (non‐optimized) Si‐P‐Te clathrates display rather high values of the thermoelectric figure‐of‐merit (ZT=0.24–0.36) in the temperature range of 700–1100 K. These ZT values are comparable to the best values achieved for the properly doped transition‐metal‐oxide materials. The methods of the thermoelectric efficiency optimization are discussed.     

Resonant optothermoacoustic detection: technique for measuring weak optical absorption by gases and micro-objects

We report a laser spectroscopy technique for detecting optical absorption in gases and micro-objects via linked thermal effects and by using a sharp mechanical resonance in a quartz crystal. The performance of this technique is studied using near-IR diode lasers and two gases, pure CO(2) and C(2)H(2) diluted in nitrogen. A 7.3 × 10(-8) cm(-1)W/(Hz)(1/2) noise equivalent sensitivity to absorption in gases is demonstrated. Based on experimental results, it was estimated that 10(-8) fractional absorption of optical radiation by a micro-object deposited on a thin transparent fiber can be detected.     

New representatives of the linear structure series containing empty Ga/Ge cubes in the Sm-Ga-Ge system

New ternary intermetallic compounds Sm₂Ga_7−xGe_x (x=5.2-6.1) and Sm₄Ga_11−xGe_x (x=5.76-8.75) were synthesized and their crystal structures were determined by X-ray powder diffraction at compositions Sm₂Ga_1.8Ge_5.2 and Sm₄Ga_5.24Ge_5.76. Sm₂Ga_1.8Ge_5.2 crystallizes with the Ce₂(Ga_0.1Ge_0.9)₇ type of structure (space group Cmce, Pearson code oS80-8.00, a=8.46216(13), b=8.15343(13), , Z=8), while Sm₄Ga_5.24Ge_5.76 exhibits a new structure (space group Cmmm, Pearson code oS52-22.00, a=4.21038(4), b=35.8075(3), , Z=2). Both structures are the members of the linear intergrowth structure series built up from segments of BaAl₄, AlB₂ and α-Po structure types. Their Ga/Ge networks contain characteristic empty cubes with one side capped by an atom subjected to an intrinsic displacive disorder. A model of Ga/Ge localization was suggested on the basis of crystal-chemical analysis.