AIPE-active green phosphorescent iridium(III) complex impregnated test strips for the vapor-phase detection of 2,4,6-trinitrotoluene (TNT)

Detection of explosives, especially trinitrotoluene (TNT), is of utmost importance due to its highly explosive nature and environmental hazard. Therefore, detection of TNT has been a matter of great concern to the scientific community worldwide. Herein, a new aggregation-induced phosphorescent emission (AIPE)-active iridium(III) bis(2-(2,4-difluorophenyl)pyridinato-NC2') (2-(2-pyridyl)benzimidazolato-N,N') complex FIrPyBiz] has been developed and serves as a molecular probe for the detection of TNT in the vapor phase, solid phase, and aqueous media. In addition, phosphorescent test strips have been constructed by impregnating Whatman filter paper with aggregates of FIrPyBiz for trace detection of TNT in contact mode, with detection limits in nanograms, by taking advantage of the excited state interaction of AIPE-active phosphorescent iridium(III) complex with that of TNT and the associated photophysical properties.

The CaO-SrO-CuO-O-2 system: Phase equilibria and thermodynamic properties at 1123 K

Phase relationships in the CaO-SrO-CuO system in pure oxygen at 1.01 x 10(5) Pa pressure were determined by equilibrating different compositions at 1123 K for similar to 120 h and analyzing the phases present in the quenched samples using X-ray diffraction (XRD), optical and scanning electron microscopy, and energy dispersive analysis of X-rays (EDAX). Four solid solution series were observed in the system, The CawSr1-wO monoxide solid solution with rock-salt structure was found to exhibit an asymmetric miscibility gap, The mixing properties of the monoxide system were deduced using a subregular solution model, For the (CaxSr1-x)(2)CuO3 series, a complete solid solution range with orthorhombic space group Immm was obtained. Calcium substituted for strontium up to 68 at. % in SrCuO2+delta and 51.5 at. % in Sr14Cu24O41-delta. The tie lines between the solid solutions were determined accurately, The activity-composition relations in (CaxSr1-x)(2)CuO3, CaySr1-yCuO2+delta, and (Ca2Sr1-z)(14)Cu24O41-delta solid solutions were determined from experimental tie lines. Activities in the (CaxSr1-x)(2)CuO3 and CaySr1-yCuO2+delta series were close to the predictions of the Temkin model, The behavior of the (CazSr1-(z))(14)Cu24O41-delta solid solution was more complex, with the activity of SrCu(24/14)O-(41-delta/14) exhibiting both positive and negative deviations from ideality. Gibbs energy of formation of the CaCuO2+delta metastable phase at 1123 K was deduced from an analysis of the phase diagram.

Mutagenic significance of proton acidities in methylated guanine and thymine bases and deoxynucleosides: A theoretical study

Proton changes have been advanced as being the key molecular basis for the mutagenecity of alkylated DNA bases and nucleosides, leading to questions as to which protons are involved and whether the protic changes are tautomeric shifts or abstractions. This semiempirical molecular orbital study seeks to clarify the issue by examining the various possibilities open for these protic changes in a number of methylated guanines and thymines and their deoxynucleosides. Proton shifts leading to tautomer formation are not predicted as being thermodynamically favourable in most cases. The most feasible proton abstractions are predicted to involve the Watson-Crick protons in all cases, which corroborates Watson-Crick proton loss as providing the key molecular basis for the induction of point mutations. The calculated proton acidities correlate well with experimental data. The gas-phase deprotonation enthalpies for a number of alkylated nucleosides are found to correlate linearly with the solvent-phase pK(a) values. The theoretically calculated enthalpies in a simulated aqueous solvent phase of the deprotonation reactions of various nucleic acid bases are also found to have good linear correlations with experimental pK(a) values. The consensus of these calculations is that O-6-alkyldeoxyguanosines, and O-2- and O-4-alkyldeoxythymidines would be mutagenic while N-7-alkyldeoxyguanosines would not be mutagenic (as experiment indicates). The untested N-3-methyldeoxyguanosine is predicted to be mutagenic. (C) 1997 Elsevier Science B.V.

High thermopower and ultra low thermal conductivity in Cd-based Zintl phase compounds

By combining first principles density functional theory and electronic as well as lattice Boltzmann transport calculations, we unravel the excellent thermoelectric properties of Zintl phase compounds ACd(2)Sb(2) (where, A = Ca, Ba, Sr). The calculated electronic structures of these compounds show charge carrier pockets and heavy light bands near the band edge, which lead to a large power factor. Furthermore, we report large Gruneisen parameters and low phonon group velocity indicating essential strong anharmonicity in these compounds, which resulted in low lattice thermal conductivity. The combination of low thermal conductivity and the excellent transport properties give a high ZT value of similar to 1.4-1.9 in CaCd2Sb2 and BaCd2Sb2 at moderate p and n-type doping. Our results indicate that well optimized Cd-based Zintl phase compounds have the potential to match the performance of conventional thermoelectric materials.

Multicomponent multiphase equilibria

A method has been developed for the computation of multicomponent multiphase equilibrium. This method is essentially a modification of White’s element potentials method. It has been found that if the search for equilibrium is confined to a physically significant zone, a solution of the equilibrium problem can be obtained even with a poor initial guess.

Modeling the solubilities of fatty acids in supercritical carbon dioxide

A thermodynamic model was developed for modeling the solubilities of fatty acids in supercritical carbon dioxide. The model combines the Peng-Robinson equation of state (EOS) with the two parameter van der Waal's mixing rules. The model is applied to predict the solubilities of various fatty acids. The two adjustable interaction parameters in the model are found to vary linearly with the chain length of the fatty acids. Thus this model can be used to predict the solubilities of various fatty acids in supercritical carbon dioxide. (C) 2003 Elsevier Science B.V. All rights reserved.

Comparative high pressure Raman studies on perfluorohexane and perfluoroheptane

High pressure Raman spectroscopic studies on perfluorohexane and perfluoroheptane have performed up to 12 GPa. Perfluorohexane under goes two pressure induced transitions: (1) liquid-solid transition at 1.6 GPa and (2) solid-solid transition at 8.2 GPa. On the contrary, perfluoroheptane under goes three phase transitions, they are as follows: (1) liquid-solid transition at 1.3 GPa, (2) intermediate solid I transition at 3 GPa, (3) solid II transition at 7 GPa. The change in slope (d omega/dP) shows that the solid I transition at 3.0 GPa could be the conversion of mid-gauche defect into trans conformers for perfluoroheptane. The pressure induced Raman spectra and the behavior of individual band with pressure shows that the solid phase comprises more than one conformer beyond crystallization. The intensity ratio for both the compounds shows that the high pressure phase beyond 8.2 and 7.0 GPa tends to have close packing with distorted all-trans conformers. (C) 2015 Elsevier B.V. All rights reserved.

Effect of Ni content on the diffusion-controlled growth of the product phases in the Cu(Ni)-Sn system

A strong influence of Ni content on the diffusion-controlled growth of the (Cu,Ni)(3)Sn and (Cu,Ni)(6)Sn-5 phases by coupling different Cu(Ni) alloys with Sn in the solid state is reported. The continuous increase in the thickness ratio of (Cu,Ni)(6)Sn-5 to (Cu,Ni)(3)Sn with the Ni content is explained by combined kinetic and thermodynamic arguments as follows: (i) The integrated interdiffusion coefficient does not change for the (Cu,Ni)(3)Sn phase up to 2.5 at.% Ni and decreases drastically for 5 at.% Ni. On the other hand, there is a continuous increase in the integrated interdiffusion coefficient for (Cu,Ni)(6)Sn-5 as a function of increasing Ni content. (ii) With the increase in Ni content, driving forces for the diffusion of components increase for both components in both phases but at different rates. However, the magnitude of these changes alone is not large enough to explain the high difference in the observed growth rate of the product phases because of Ni addition. (iv) Kirkendall marker experiments indicate that the Cu6Sn5 phase grows by diffusion of both Cu and Sn in the binary case. However, when Ni is added, the growth is by diffusion of Sn only. (v) Also, the observed grain refinement in the Cu6Sn5 phase with the addition of Ni suggests that the grain boundary diffusion of Sn may have an important role in the observed changes in the growth rate.

High-Temperature Phase Transition Studies in a Novel Fast Ion Conductor, Na2Cd(SO4)2, Probed by Raman Spectroscopy

Temperature-dependent Raman spectroscopic studies were carried out on Na2Cd(SO4)(2) from room temperature to 600 degrees C. We observe two transitions at around 280 and 565 degrees C. These transitions are driven by the change in the SO4 ion. On the basis of these studies, one can explain the changes in the conductivity data observed around 280 and 565 degrees C. At 280 degrees C, spontaneous tilting of the SO4 ion leads to restriction of Na+ mobility. Above 565 degrees C, the SO4 ion starts to rotate freely, leading to increased mobility of Na+ ion in the channel.

Phase Equilibria in the System $Al_{2}O_{3}-CaO-CoO$ and Gibbs Energy of Formation of $Ca_{3}CoAl_{4}O_{10}$

The floating-zone method with different growth ambiences has been used to selectively obtain hexagonal or orthorhombic DyMnO3 single crystals. The crystals were characterized by x-ray powder diffraction of ground specimens and a structure refinement as well as electron diffraction. We report magnetic susceptibility, magnetization and specific heat studies of this multiferroic compound in both the hexagonal and the orthorhombic structure. The hexagonal DyMnO3 shows magnetic ordering of Mn3+ (S = 2) spins on a triangular Mn lattice at T-N(Mn) = 57 K characterized by a cusp in the specific heat. This transition is not apparent in the magnetic susceptibility due to the frustration on the Mn triangular lattice and the dominating paramagnetic susceptibility of the Dy3+ (S = 9/2) spins. At T-N(Dy) = 3 K, a partial antiferromagnetic order of Dy moments has been observed. In comparison, the magnetic data for orthorhombic DyMnO3 display three transitions. The data broadly agree with results from earlier neutron diffraction experiments, which allows for the following assignment: a transition from an incommensurate antiferromagnetic ordering of Mn3+ spins at T-N(Mn) = 39 K, a lock-in transition at Tlock-in = 16 K and a second antiferromagnetic transition at T-N(Dy) = 5 K due to the ordering of Dy moments. Both the hexagonal and the orthorhombic crystals show magnetic anisotropy and complex magnetic properties due to 4f-4f and 4f-3d couplings.

Bridged systems via radical cyclization reactions. Stereospecific synthesis of chiral tricyclo[6.2.1.0(1,5)]undecanes

The application of radical-mediated cyclizations and annulations in organic synthesis has grown in importance steadily over the years to reach the present status where they are now routinely used in the strategy-level planning.2 The presence of a quaternary carbon atom is frequently encountered in terpenoid natural products, and it often creates a synthetic challenge when two or more quaternary carbon atoms are present in a contiguous manner.3 Even though creation of a quaternary carbon atom by employing a tertiary radical is very facile, creation of a quaternary carbon atom (or a spiro carbon atom) via radical addition onto a fully substituted olefinic carbon atom is not that common but of synthetic importance. For example, the primary radical derived from the bromide 1 failed to cyclize to generate the two vicinal quaternary carbon atoms and resulted in only the reduced product 2.4 The tricyclic carbon framework tricyclo[6.2.1.01,5]undecane (3) is present in a number of sesquiterpenoids e.g. zizzanes, prelacinanes, etc.5

Synthesis and Reactions of Binuclear Diolefin Rhodium(I) Compounds bridged by Nitrogen Heterocycles, Crystal Structure of Dichloro-Di-1,5-Cyclooctadiene(Mu-Pyrazine)-Dirhodium(I) [[Rh(1,5-C8h12)Cl]2(Mu-C4h4n2)]

Binuclear complexes of rhodium(I) of the type [(dien)(X)Rh(μ-N-N)Rh(X)(dien)] (dien = 1,5-cyclooctadiene or norbornadiene; N-N = pyrazine, 4,4′-bipyridine or Phenazine and X = Cl or Br) with bridging heterocycles have been isolated and their reactions with carbon monoxide, 2,2′-bipyridine and 1,10-phenanthroline investigated. The crystal structure of [(COD)(Cl)Rh(μ-pyrazine)Rh(Cl)(COD)] has been determined.

Esr study of (SO4)2- dynamics in relation to the ferroelectric phase transition in ammonium sulfate

Ferroelectric phase transition in ammonium sulfate has been studied by ESR of CrO43- radical substituting for SO42- ion in (NH4)2SO4. In addition to discontinuous changes at Tc, certain continuous changes are observed in ESR parameters of this probe below Tc, which reflect the role of the sulfate ion in the phase transition. A microscopic mechanism of the phase transition is proposed and discussed in terms of the change of orientation of the sulfate tetrahedron through a finite angle. The degree of the change of orientation below Tc is thought to be the possible order parameter of the phase transition.

NMR studies of phase transition in ammonium hydrogen bischloroacetate, NH4H(CH2ClCOOO)2

Proton second moment (M2) and spin-lattice relaxation time (T1) of Ammonium Hydrogen Bischloroacetate (ABCA) have been measured in the range 77-350 K. A value of 6.5 G2 has been observed for the second moment at room temperature, which is typical of NH4+ reorientation and also a second moment transition in the range 170-145 K indicates the freezing of NH4+ motion. The NMR signal disappears dicontinuously at 128 K. Proton spin-lattice relaxation time (T1) Vs temperature, yielded only one sharp miniumum of 1.9 msec which is again typical of NH4+ reorientation. A slope change at 250 K is also observed, prbably due to CH2 motion. Further, the FID signal disappears at 128 K. Thus the Tc appears to be 128 K (of two reported values 120 K and 128 K). Activation energies have been calculated and the mechanism of the phase transition is discussed.