Ru(II)-CO complexes of thioarylazoimidazoles: Syntheses, structures, spectroscopy and DFT calculation

The complexes, cis-(CO)-trans-(Cl)-[Ru(SRaaiNR)(CO)(2)Cl-2] (2) and trans-(Cl)-[Ru(SRaaiNR)(CO)Cl-2] (3) (SRaaiNR = 1-alkyl-2-{(o-thioalkyl)phenylazo}imidazoles; R = Me (1a) and Et (1b)) have been synthesized and characterized. The structural confirmation is achieved by single crystal X-ray structure determinations. The complexes show Ru(III)/Ru(II) couple and ligand reductions. Electronic structure and spectral properties of the complexes have been explained with the DFT and TDDFT calculation. (C) 2009 Elsevier B.V. All rights reserved.

Kinetics of photocatalytic reduction of NO by CO with Pd2+-Ion-Substituted Nano-TiO2

The objective of the present study is to develop the reaction mechanism and kinetics of photoreduction of NO by CO. For this purpose, the reactions were conducted in the presence of Pd-ion-substituted nano-TiO2, Ti1-xPdxO2-delta, which was synthesized via a solution combustion method. The photocatalytic activity was investigated with unsubstituted TiO2, 1% Pd/TiO2(imp), and Ti1-xPdxO2-delta (where x = 0.05-0.3). No appreciable NO conversion was observed over unsubstituted TiO2, although, despite competitive adsorption of NO and CO on the Pd2+ sites, there was a significant reduction of NO over Ti1-xPdxO2-delta. The kinetic model showed that the enhanced catalytic activity is due to the NO photodissociation at the oxide-ion vacancy.

High-rate, Single-Symbol Decodable Distributed STBCs for Partially-Coherent Cooperative Networks

Space-time block codes (STBCs) that are single-symbol decodable (SSD) in a co-located multiple antenna setting need not be SSD in a distributed cooperative communication setting. A relay network with N relays and a single source-destination pair is called a partially-coherent relay channel (PCRC) if the destination has perfect channel state information (CSI) of an the channels and the relays have only the phase information of the source-to-relay channels. In our earlier work, we had derived a set of necessary and sufficient conditions for a distributed STBC (DSTBC) to be SSD for a PCRC. Using these conditions, in this paper we show that the possibility of channel phase compensation operation at the relay nodes using partial CSI at the relays increases the possible rate of SSD DSTBCs from 2/N when the relays do not have CSI to 1/2, which is independent of N. We also show that when a DSTBC is SSD for a PCRC, then arbitrary coordinate interleaving of the in-phase and quadrature-phase components of the variables does not disturb its SSD property. Using this property we are able to construct codes that are SSD and have higher rate than 2/N but giving full diversity only for signal constellations satisfying certain conditions.

OFDM Based Distributed Space Time Coding for Asynchronous Relay Networks

Recently Li and Xia have proposed a transmission scheme for wireless relay networks based on the Alamouti space time code and orthogonal frequency division multiplexing to combat the effect of timing errors at the relay nodes. This transmission scheme is amazingly simple and achieves a diversity order of two for any number of relays. Motivated by its simplicity, this scheme is extended to a more general transmission scheme that can achieve full cooperative diversity for any number of relays. The conditions on the distributed space time block code (DSTBC) structure that admit its application in the proposed transmission scheme are identified and it is pointed out that the recently proposed full diversity four group decodable DST-BCs from precoded co-ordinate interleaved orthogonal designs and extended Clifford algebras satisfy these conditions. It is then shown how differential encoding at the source can be combined with the proposed transmission scheme to arrive at a new transmission scheme that can achieve full cooperative diversity in asynchronous wireless relay networks with no channel information and also no timing error knowledge at the destination node. Finally, four group decodable distributed differential space time block codes applicable in this new transmission scheme for power of two number of relays are also provided.

On a Special Co-cycle Basis of Graphs

In this paper we consider the problems of computing a minimum co-cycle basis and a minimum weakly fundamental co-cycle basis of a directed graph G. A co-cycle in G corresponds to a vertex partition (S,V ∖ S) and a { − 1,0,1} edge incidence vector is associated with each co-cycle. The vector space over ℚ generated by these vectors is the co-cycle space of G. Alternately, the co-cycle space is the orthogonal complement of the cycle space of G. The minimum co-cycle basis problem asks for a set of co-cycles that span the co-cycle space of G and whose sum of weights is minimum. Weakly fundamental co-cycle bases are a special class of co-cycle bases, these form a natural superclass of strictly fundamental co-cycle bases and it is known that computing a minimum weight strictly fundamental co-cycle basis is NP-hard. We show that the co-cycle basis corresponding to the cuts of a Gomory-Hu tree of the underlying undirected graph of G is a minimum co-cycle basis of G and it is also weakly fundamental.

How Effective Is The Data On Co-Occurrence Of Domains In Multi-Domain Proteins In Prediction Of Protein-Protein Interactions?

We explore the fuse of information on co-occurrence of domains in multi-domain proteins in predicting protein-protein interactions. The basic premise of our work is the assumption that domains co-occurring in a polypeptide chain undergo either structural or functional interactions among themselves. In this study we use a template dataset of domains in multidomain proteins and predict protein-protein interactions in a target organism. We note that maximum number of correct predictions of interacting protein domain families (158) is made in S. cerevisiae when the dataset of closely related organisms is used as the template followed by the more diverse dataset of bacterial proteins (48) and a dataset of randomly chosen proteins (23). We conclude that use of multi-domain information from organisms closely-related to the target can aid prediction of interacting protein families.

Photocatalytic degradation of methyl methacrylate copolymers

The photolytic and photocatalytic degradation of the copolymers poly(methyl methacrylate-co-butyl methacrylate) (MMA–BMA), poly(methyl methacrylate-co-ethyl acrylate) (MMA–EA) and poly(methyl methacrylate-co-methacrylic acid) (MMA–MAA) have been carried out in solution in the presence of solution combustion synthesized TiO2 (CS TiO2) and commercial Degussa P-25 TiO2 (DP 25). The degradation rates of the copolymers were compared with the respective homopolymers. The copolymers and the homopolymers degraded randomly along the chain. The degradation rate was determined using continuous distribution kinetics. For all the polymers, CS TiO2 exhibited superior photo-activity compared to the uncatalysed and DP 25 systems, owing to its high surface hydroxyl content and high specific surface area. The time evolution of the hydroxyl and hydroperoxide stretching vibration in the Fourier transform-infrared (FT-IR) spectra of the copolymers indicated that the degradation rate follows the order MMA–MAA > MMA–EA > MMA–BMA. The same order is observed for the rate coefficients of photocatalytic degradation. The photodegradation rate coefficients were compared with the activation energy of pyrolytic degradation. In degradation by pyrolysis, it was observed that MMA–BMA was the least stable followed by MMA–EA and MMA–MAA. The observed contrast in the order of thermal stability compared to the photo-stability of these copolymers was attributed to the two different mechanisms governing the scission of the polymer and the evolution of the products.

Process-dependent magnetic properties of Co-doped ZnO in bulk and thin film form

Structural, optical and magnetic studies of Co-doped ZnO have been carried out for bulk as well as thin films. The magnetic studies revealed the superparamagnetic nature for low-temperature synthesized samples, indicating the presence of cobalt metallic clusters, and this is supported by the optical studies. For the high-temperature sintered samples one obtains paramagnetism. The optical studies reveal the presence of Co2+ ions in the tetrahedral sites indicating proper doping. Interestingly, the films deposited by laser ablation from the paramagnetic target showed room temperature ferromagnetism. It appears that the magnetic nature of this system is process dependent.

Three-dimensional hybrid networks based on aspartic acid

Three-dimensional achiral coordination polymers of the general formula M2(D, l-NHCH (COO)CH2COO)2·C4H4N2 where M = Ni and Co and pyrazine acts as the linker molecule have been prepared under hydrothermal conditions starting with [M(L-NHCH(COO)CH2COO)·3H2O] possessing a helical chain structure. A three-dimensional hybrid compound of the formula Pb2.5[N{CH(COO) CH2COO}22H2O] has also been prepared hydrothermally starting with aspartic acid and Pb(NO3)2. In this lead compound, where a secondary amine formed by the dimerisation of aspartic acid acts as the ligand, there is two-dimensional inorganic connectivity and one-dimensional organic connectivity.

One-dimensional zig-zag type coordination polymers of Ni(II) and Cu(II) containing 1,3-benzenedicarboxylate and 1,3-diaminopropane: Structural, spectral and thermal studies

Two coordination polymers [Ni(ipt)(dap)(2)](n) (1) and [Cu(ipt)(dap)H2O](n) center dot nH(2)O (2) with an overall one-dimensional arrangement and having isophthalate (ipt) as bridging moieties and chelating 1,3-diaminopropane (dap) as structure modulating units have been prepared and characterized by crystallographic, spectroscopic and thermo-analytical studies. Both have an overall one-dimensional zig-zag nature but with a distorted octahedral NiN4O2 chromophore for 1 and a distorted square pyramidal CuN2O3 chromophore for 2. Even though the ipt units are acting as bridging units through mono-dentatively coordinating carboxylate functions in both polymers, compound 1 has the carboxylate oxygen linkages at the trans positions, while in 2 the oxygen linkages occur at the cis positions leading to a different type of zig-zag arrangement. Relevant spectral and bonding parameters also could be evaluated for the compounds using UV-Vis and EPR spectra. Thermal stability and possible structural modifications on thermal treatment of the compounds were also investigated and the relevant thermodynamic and kinetic parameters evaluated from the thermal data. (C) 2007 Elsevier B.V. All rights reserved.

Understanding the folding process of synthetic polymers by small-molecule folding agents

Two acceptor containing polyimides PDI and NDI carrying pyromellitic diimide units and 1,4,5,8-naphthalene tetracarboxy diimide units, respectively, along with hexa(oxyethylene) (EO6) segments as linkers, were prepared from the corresponding dianhydrides and diamines. These polyimides were made to fold by interaction with specifically designed folding agents containing a dialkoxynaphtha-lene (DAN) donor linked to a carboxylic acid group. The alkali-metal counter-ion of the donor carboxylic acid upon complexation with the EO6 segment brings the DAN unit in the right location to induce a charge-transfer complex formation with acceptor units in the polymer backbone. This two-point interaction between the folding agent and the polymer backbone leads to a folding of the polymer chain, which was readily monitored by NMR titrations. The effect of various parameters, such as structures of the folding agent and polymer, and the solvent composition, on the folding propensities of the polymer was studied.

BER analysis of space-time block codes from generalized complex orthogonal designs for M-PSK

In this paper, we present an analysis for the bit error rate (BER) performance of space-time block codes (STBC) from generalized complex orthogonal designs for M-PSK modulation. In STBCs from complex orthogonal designs (COD), the norms of the column vectors are the same (e.g., Alamouti code). However, in generalized COD (GCOD), the norms of the column vectors may not necessarily be the same (e.g., the rate-3/5 and rate-7/11 codes by Su and Xia in [1]). STBCs from GCOD are of interest because of the high rates that they can achieve (in [2], it has been shown that the maximum achievable rate for STBCs from GCOD is bounded by 4/5). While the BER performance of STBCs: from COD (e.g., Alamouti code) can be simply obtained from existing analytical expressions for receive diversity with the same diversity order by appropriately scaling the SNR, this can not be done for STBCs from GCOD (because of the unequal norms of the column vectors). Our contribution in this paper is that we derive analytical expressions for the BER performance of any STBC from GCOD. Our BER analysis for the GCOD captures the performance of STBCs from COD as special cases. We validate our results with two STBCs from GCOD reported by Su and Xia in [1], for 5 and 6 transmit antennas (G(5) and G(6) in [1]) with rates 7/11 and 3/5, respectively.

Suppression of spinel formation to induce reversible thermal behavior in the layered double hydroxides (LDHs) of Co with Al, Fe, Ga, and In

The layered double hydroxides (LDHs) of Co with trivalent cations decompose irreversibly to yield oxides with the spinel structure. Spinel formation is aided by the oxidation of Co(II) to Co(III) in the ambient atmosphere. When the decomposition is carried out under N-2, the oxidation of Co(II) is suppressed, and the resulting oxide has the rock salt structure. Thus, the Co-Al-CO32-/Cl- LDHs yield oxides of the type Co1- Al-x(2x/3)rectangle O-x/3, which are highly metastable, given the large defect concentration. This defect oxide rapidly reverts back to the original hydroxide on soaking in a Na2CO3 solution. Interlayer NO3- anions, on the other hand, decompose generating a highly oxidizing atmosphere, whereby the Co-Al-NO3- LDH decomposes to form the spinel phase even in a N-2 atmosphere. The oxide with the defect rock salt structure formed by the thermal decomposition of the Co-Fe-CO32- LDH under N2, on soaking in a Na2CO3 solution, follows a different kinetic pathway and undergoes a solution transformation into the inverse spinel Co(Co, Fe)(2)O-4. Fe3+ has a low octahedral crystal field stabilization energy and therefore prefers the tetrahedral coordination offered by the structure of the inverse spinel rather than the octahedral coordination of the parent LDH. Similar considerations do not hold in the case of Ga- and In-containing LDHs, given the considerable barriers to the diffusion of M3+ (M=Ga, In) from octahedral to tetrahedral sites owing to their large size. Consequently, the In-containing oxide residue reverts back to the parent hydroxide, whereas this reconstruction is partial in the case of the Ga-containing oxide. These studies show that the reversible thermal behavior offers a competing kinetic pathway to spinel formation. Suppression of the latter induces the reversible behavior in an LDH that otherwise decomposes irreversibly to the spinel.

Hybrid moving block bootstrap for stochastic simulation of multi-site multi-season streamflows

The Hybrid approach introduced by the authors for at-site modeling of annual and periodic streamflows in earlier works is extended to simulate multi-site multi-season streamflows. It bears significance in integrated river basin planning studies. This hybrid model involves: (i) partial pre-whitening of standardized multi-season streamflows at each site using a parsimonious linear periodic model; (ii) contemporaneous resampling of the resulting residuals with an appropriate block size, using moving block bootstrap (non-parametric, NP) technique; and (iii) post-blackening the bootstrapped innovation series at each site, by adding the corresponding parametric model component for the site, to obtain generated streamflows at each of the sites. It gains significantly by effectively utilizing the merits of both parametric and NP models. It is able to reproduce various statistics, including the dependence relationships at both spatial and temporal levels without using any normalizing transformations and/or adjustment procedures. The potential of the hybrid model in reproducing a wide variety of statistics including the run characteristics, is demonstrated through an application for multi-site streamflow generation in the Upper Cauvery river basin, Southern India. (C) 2004 Elsevier B.V. All rights reserved.