Experimental and Theoretical Studies of Unusual Four-Membered Metallacycles from Reactions of Group 4 Metallocene Bis(trimethylsilyl)-acetylene Complexes with the Sulfurdiimide Me3SiN=S=NSiMe3

The use of the sulfurdiimide RN=S=NR' (R = R' = SiMe3, 3) in reactions with group 4 metallocene bis(trimethylsilyl)-acetylene complexes of the type [Cp2M(L (eta(2)-Me3Si-C2SiMe3)] (1: M = Ti, no L; 2: M = Zr, L = pyridine) has led to the formation of four-membered metallacycles 4M containing the group 4 metal, nitrogen and sulfur. DFT calculations performed on compound 4Ti indicate that this complex is best described as a sigma-complex with cyclic delocalisation of the ring electrons. Moreover, pseudo-Jahn-Teller distortion plays a significant role in stabilising this complex.

Variation of diffusivity with the cation radii in molten salts of superionic conductors containing iodine anion: A molecular dynamics study

A molecular dynamics study of the dependence of diffusivity of the cation on ionic radii in molten AgI is reported. We have employed modified Parinello-Rahman-Vashistha interionic pair potential proposed by Shimojo and Kobayashi.(1) Our results suggest that the diffusivity of the cation exhibits an increase followed by a decrease as the ionic radius is increased. Several structural and dynamical properties are reported.

Phalangopsidae crickets from the Indian Region (Orthoptera, Grylloidea), with the descriptions of new taxa, diagnoses for genera, and a key to Indian genera

The Indian region is presently the second region after the Neotropics in terms of diversity of phalangopsid crickets. Yet their study is impeded by the lack of necessary taxonomic tools for taxon identification. In the present paper, all generic diagnoses are clarified, using morphological and genitalic characters; female genitalia are described and illustrated for all genera with known females. New taxa are described from southern India: Kempiola flavipunctatus Desutter-Grandcolas n. sp., Opiliosina meridionalis Desutter-Grandcolas n. gen., n. sp., Phalangopsina bolivari Desutter-Grandcolas n. sp., P. chopardi Desutter-Grandcolas n. sp., P. gravelyi Desutter-Grandcolas n. sp., and Speluncasina Desutter-Grandcolas n. gen. The list of phalangopsid crickets from the Indian Region is updated, and a key to phalangopsid genera proposed. A lectotype and a paralectotype are designated to fix the name of Phalangopsina dubia (Bolivar, 1900). Opilionacris annandalei Chopard, 1928, previously transferred to the African genus Phaeophilacris Walker, 1871, is transferred to the genus Speluncasina Desutter-Grandcolas n. gen., while Larandopsis jharnae Bhowmik, 1981 and L. newguineae Bhowmik, 1981 described from New Guinea are transferred to the eneopterine genus Lebinthus Stal, 1877. Finally Luzaropsis confusa Chopard, 1969 is removed from its synonymy with L. ferruginea Walker, 1871.

Optical properties change with the addition and diffusion of Bi to As2S3 in the Bi/As2S3 bilayer thin film

The role of Bi layer (thickness similar to 7 nm) on As2S3 film was extensively studied for different optical applications in which Bi (top layer) as active and diffusing layer and As2S3 as barrier (matrix) layer. Bilayer thin films of Bi/As2S3 were prepared from Bi and As2S3 by thermal evaporation technique under high vacuum. The decrease of optical band gap with the addition of Bi to As2S3 has been explained on the basis of density of states and the increase in disorder in the system. It was found that the efficient changes of optical parameters (transmission, optical band gap, refraction) could be realized due to the photo induced diffusion activated by the focused 532 nm laser irradiation and formation of different bonds. The diffusion of Bi into As2S3 matrix increases the optical band gap producing photo bleaching effect. The changes were characterised by different experimental techniques. (C) 2012 Elsevier B.V. All rights reserved.

The curvature of the liquid-vapor reduced pressure curve and its relation with the critical region

For most fluids, there exist a maximum and a minimum in the curvature of the reduced vapor pressure curve, p(r) = p(r)(T-r) (with p(r) = p/p(c) and T-r = T/T-c, p(c) and T-c being the pressure and temperature at the critical point). By analyzing National Institute of Standards and Technology (NIST) data on the liquid-vapor coexistence curve for 105 fluids, we find that the maximum occurs in the reduced temperature range 0.5 <= T-r <= 0.8 while the minimum occurs in the reduced temperature range 0.980 <= T-r <= 0.995. Vapor pressure equations for which d(2)p(r)/dT(r)(2) diverges at the critical point present a minimum in their curvature. Therefore, the point of minimum curvature can be used as a marker for the critical region. By using the well-known Ambrose-Walton (AW) vapor pressure equation we obtain the reduced temperatures of the maximum and minimum curvature in terms of the Pitzer acentric factor. The AW predictions are checked against those obtained from NIST data. (C) 2013 Elsevier Ltd. All rights reserved.

Some Themes in Chemical Crystallography Pertinent to the Indian Contribution

It is particularly appropriate that the Journal of the Indian Institute of Science is bringing out a commemorative issue to mark the International Year of Crystallography 2014 (IYCr2014). India has had a strong crystallographic tradition, and the earliest work in what may be described as structural crystallography from this country is the work of K. Banerjee on the determination of the crystal structure of naphthalene in 1930. The Indian Institute of Science itself has played no small part in establishing and sustaining the subject of crystallography in this country. A large number of papers in this special issue are written by authors who have either have been trained in the Institute or who have some kind of professional association with this organization. In this article I will try to capture some unique features that characterize the intersection of the crystallographic and the chemical domains, mostly as they pertain to the Indian contribution to this subject. Crystallography is of course is as old as chemistry itself, and some would say it is even older. The relationships between chemistry and crystallography go back to much before the discovery of diffraction of X-rays by crystals.The discovery of polymorphism by Mitscherlisch in 1822, Haüy’s formulation of the molecule integrante, and the work of Fedorov and Groth on the identification of crystals from their morphology alone, are well known examples of such relationships.A very early article by Tutton speaks of “crystallo-chemical analysis”. In this article, I shall, however, be dealing with the interplay of chemistry and crystallography only in the post diffraction era, that is, after 1912. Much had been written and said about chemical crystallography, and even within the context of the present special issue, there is a review of chemical crystallography in India including some futuristic trends. This topic was also reviewed by Nangia in a special publication brought out by Indian Academy of Sciences in 2009,and by Desiraju in a special publication brought out by the Indian National Science Academy in 2010. A rather detailed account of crystallography in India appeared in 2007 in the newsletter of the International Union of Crystallography (IUCr) in which chemical crystallography was detailed. Since all these publications are fairly recent there is little need for me to attempt a comprehensive coverage of chemical crystallography in India in this short review

Contrast in luminescence characteristics (intense UV to bright visible light) of ZnO nanostructures with the variation in microstructure

We report the controlled variation of luminescence of ZnO nanostructures from intense ultraviolet to bright visible light. Deliberate addition of surfactants in the reaction medium not only leads to growth anisotropy of ZnO, but also alters the luminescence property. ZnO nanoclusters comprising of very fine particles with crystallite sizes approximate to 15-22nm were prepared in a non-aqueous medium, either from a single alcohol or from their mixtures. Introduction of the aqueous solution of the surfactant helps in altering the microstructure of ZnO nanostructure to nanorods, nanodumb-bells as well as the luminescence property. The as-prepared powder material is found to be well crystallized. Defects introduced by the surfactant in aqueous medium play an important role in substantial transition in the optical luminescence. Chromaticity coordinates were found to lie in the yellow region of color space. This gives an impression of white light emission from ZnO nanocrystals, when excited by a blue laser. Oxygen vacancy is described as the major defect responsible for visible light emission as quantified by X-ray photoelectron spectroscopy and Raman analysis.

Capacity of Gaussian Channels With Energy Harvesting and Processing Cost

Energy harvesting sensor nodes are gaining popularity due to their ability to improve the network life time and are becoming a preferred choice supporting green communication. In this paper, we focus on communicating reliably over an additive white Gaussian noise channel using such an energy harvesting sensor node. An important part of this paper involves appropriate modeling of energy harvesting, as done via various practical architectures. Our main result is the characterization of the Shannon capacity of the communication system. The key technical challenge involves dealing with the dynamic (and stochastic) nature of the (quadratic) cost of the input to the channel. As a corollary, we find close connections between the capacity achieving energy management policies and the queueing theoretic throughput optimal policies.

Cu-II-Azide Polynuclear Complexes of Three Different Building Clusters with the Same Schiff-Base Ligand: Synthesis, Structures, Magnetic Behavior, and Density Functional Theory Studies

Three copper-azido complexes Cu-4(N-3)(8)(L-1)(2)(MeOH)(2)](n) (1), Cu-4(N-3)(8)(L-1)(2)] (2), and Cu-5(N-3)(10)(L-1)(2)](n) (3) L-1 is the imine resulting from the condensation of pyridine-2-carboxaldehyde with 2-(2-pyridyl)ethylamine] have been synthesized using lower molar equivalents of the Schiff base ligand with Cu(NO3)(2)center dot 3H(2)O and an excess of NaN3. Single crystal X-ray structures show that the basic unit of the complexes 1 and 2 contains Cu-4(II) building blocks; however, they have distinct basic and overall structures due to a small change in the bridging mode of the peripheral pair of copper atoms in the linear tetranudear structures. Interestingly, these changes are the result of changing the solvent system (MeOH/H2O to EtOH/H2O) used for the synthesis, without changing the proportions of the components (metal to ligand ratio 2:1). Using even lower proportions of the ligand, another unique complex was isolated with Cu-5(II) building units, forming a two-dimensional complex (3). Magnetic susceptibility measurements over a wide range of temperature exhibit the presence of both antiferromagnetic (very weak) and ferromagnetic exchanges within the tetranuclear unit structures. Density functional theory calculations (using B3LYP functional, and two different basis sets) have been performed on the complexes 1 and 2 to provide a qualitative theoretical interpretation of their overall magnetic behavior.

Improved quasiparticle wave functions and mean field for G(0)W(0) calculations: Initialization with the COHSEX operator

The GW approximation to the electron self-energy has become a standard method for ab initio calculation of excited-state properties of condensed-matter systems. In many calculations, the G W self-energy operator, E, is taken to be diagonal in the density functional theory (DFT) Kohn-Sham basis within the G0 W0 scheme. However, there are known situations in which this diagonal Go Wo approximation starting from DFT is inadequate. We present two schemes to resolve such problems. The first, which we called sc-COHSEX-PG W, involves construction of an improved mean field using the static limit of GW, known as COHSEX (Coulomb hole and screened exchange), which is significantly simpler to treat than GW W. In this scheme, frequency-dependent self energy E(N), is constructed and taken to be diagonal in the COHSEX orbitals after the system is solved self-consistently within this formalism. The second method is called off diagonal-COHSEX G W (od-COHSEX-PG W). In this method, one does not self-consistently change the mean-field starting point but diagonalizes the COHSEX Hamiltonian within the Kohn-Sham basis to obtain quasiparticle wave functions and uses the resulting orbitals to construct the G W E in the diagonal form. We apply both methods to a molecular system, silane, and to two bulk systems, Si and Ge under pressure. For silane, both methods give good quasiparticle wave functions and energies. Both methods give good band gaps for bulk silicon and maintain good agreement with experiment. Further, the sc-COHSEX-PGW method solves the qualitatively incorrect DFT mean-field starting point (having a band overlap) in bulk Ge under pressure.

Combining data sets of satellite-retrieved products for basin-scale water balance study: 2. Evaluation on the Mississippi Basin and closure correction model

In this study, we applied the integration methodology developed in the companion paper by Aires (2014) by using real satellite observations over the Mississippi Basin. The methodology provides basin-scale estimates of the four water budget components (precipitation P, evapotranspiration E, water storage change Delta S, and runoff R) in a two-step process: the Simple Weighting (SW) integration and a Postprocessing Filtering (PF) that imposes the water budget closure. A comparison with in situ observations of P and E demonstrated that PF improved the estimation of both components. A Closure Correction Model (CCM) has been derived from the integrated product (SW+PF) that allows to correct each observation data set independently, unlike the SW+PF method which requires simultaneous estimates of the four components. The CCM allows to standardize the various data sets for each component and highly decrease the budget residual (P - E - Delta S - R). As a direct application, the CCM was combined with the water budget equation to reconstruct missing values in any component. Results of a Monte Carlo experiment with synthetic gaps demonstrated the good performances of the method, except for the runoff data that has a variability of the same order of magnitude as the budget residual. Similarly, we proposed a reconstruction of Delta S between 1990 and 2002 where no Gravity Recovery and Climate Experiment data are available. Unlike most of the studies dealing with the water budget closure at the basin scale, only satellite observations and in situ runoff measurements are used. Consequently, the integrated data sets are model independent and can be used for model calibration or validation.

Interaction of Sesbania mosaic virus (SeMV) RNA-dependent RNA polymerase (RdRp) with the p10 domain of polyprotein 2a and its implications in SeMV replication

Identification of viral encoded proteins that interact with RNA-dependent RNA polymerase (RdRp) is an important step towards unraveling the mechanism of replication. Sesbania mosaic virus (SeMV) RdRp was shown to interact strongly with p10 domain of polyprotein 2a and moderately with the protease domain. Mutational analysis suggested that the C-terminal disordered domain of RdRp is involved in the interaction with p10. Coexpression of full length RdRp and p10 resulted in formation of RdRp-p10 complex which showed significantly higher polymerase activity than RdRp alone. Interestingly, C Delta 43 RdRp also showed a similar increase in activity. Thus, p10 acts as a positive regulator of RdRp by interacting with the C-terminal disordered domain of RdRp. (C) 2014 The Authors. Published by Elsevier B.V.

Synthesis and crystal structure of copper (II) uracil ternary polymeric complex with 1,10-phenanthroline along with the Hirshfeld surface analysis of the metal binding sites for the uracil ligand

The study of models for ``metal-enzyme-substrate'' interaction has been a proactive area of research owing to its biological and pharmacological importance. In this regard the ternary copper uracil complex with 1,10-phenanthroline represents metal-enzyme-substrate system for DNA binding enzymes. The synthesis of the complex, followed by slow evaporation of the reaction mixture forms two concomitant solvatomorph crystals viz., {Cu(phen)(mu-ura)(H2O)](n)center dot H2O (1a)} and {Cu(phen)(mu-ura)(H2O)](n)center dot CH3OH (1b)}. Both complexes are structurally characterized, while elemental analysis, IR and EPR spectra were recorded for 1b (major product). In both complexes, uracil coordinates uniquely via N1 and N3 nitrogen atom acting as a bidentate bridging ligand forming a 1-D polymer. The two solvatomorphs were quantitatively analyzed for the differences with the aid of Hirshfeld surface analysis. (C) 2014 Elsevier B.V. All rights reserved.

Chaperone protein HYPK interacts with the first 17 amino acid region of Huntingtin and modulates mutant HTT-mediated aggregation and cytotoxicity

Huntington's disease is a polyglutamine expansion disorder, characterized by mutant HTT-mediated aggregate formation and cytotoxicity. Many reports suggests roles of N-terminal 17 amino acid domain of HTT (HTT-N17) towards subcellular localization, aggregate formation and subsequent pathogenicity induced by N-terminal HTT harboring polyQ stretch in pathogenic range. HYPK is a HTT-interacting chaperone which can reduce N-terminal mutant HTT-mediated aggregate formation and cytotoxicity in neuronal cell lines. However, how HYPK interacts with N-terminal fragment of HTT remained unknown. Here we report that specific interaction of HYPK with HTT-N17 is crucial for the chaperone activity of HYPK. Deletion of HTT-N17 leads to formation of tinier, SDS-soluble nuclear aggregates formed by N-terminal mutant HTT. The increased cytotoxicity imparted by these tiny aggregates might be contributed due to loss of interaction with HYPK. (C) 2014 Elsevier Inc. All rights reserved.