Exploring the color of transition metal ions in irregular coordination geometries: new colored inorganic oxides based on the spiroffite structure, Zn2-xMxTe3O8 (M = Co, Ni, Cu)

We describe the synthesis, crystal structures, and optical absorption spectra of transition metal substituted spiroffite derivatives, Zn2-xMxTe3O8 (M-II = Co, Ni, Cu; 0 < x <= 1.0). The oxides are readily synthesized by solid state reaction of stoichiometric mixtures of the constituent binaries at 620 degrees C. Reitveld refinement of the crystal structures from powder X-ray diffraction (XRD) data shows that the Zn/MO6 octahedra are strongly distorted, as in the parent Zn2Te3O8 structure, consisting of five relatively short Zn/M-II-O bonds (1.898-2.236 angstrom) and one longer Zn/M-II-O bond (2.356-2.519 angstrom). We have interpreted the unique colors and the optical absorption/diffuse reflectance spectra of Zn2-xMxTe3O8 in the visible, in terms of the observed/irregular coordination geometry of the Zn/M-II-O chromophores. We could not however prepare the fully substituted M2Te3O8 (M-II = Co, Ni, Cu) by the direct solid state reaction method. Density Functional Theory (DFT) modeling of the electronic structure of both the parent and the transition metal substituted derivatives provides new insights into the bonding and the role of transition metals toward the origin of color in these materials. We believe that transition metal substituted spiroffites Zn2-xMxTe3O8 reported here suggest new directions for the development of colored inorganic materials/pigments featuring irregular/distorted oxygen coordination polyhedra around transition metal ions.

Periodic architecture for high performance shock absorbing composites

A novel composite architecture consisting of a periodic arrangement of closely-spaced spheres of a stiff material embedded in a soft matrix is proposed for extremely high damping and shock absorption capacity. Efficacy of this architecture is demonstrated by compression loading a composite, where multiple steel balls were stacked upon each other in a polydimethylsiloxane (PDMS) matrix, at a low strain-rate of 0.05 s(-1) and a very high strain-rate of >2400 s(-1). The balls slide over each other upon loading, and revert to their original position when the load is removed. Because of imposition of additional strains into the matrix via this reversible, constrained movement of the balls, the composite absorbs significantly larger energy and endures much lesser permanent damage than the monolithic PDMS during both quasi-static and impact loadings. During the impact loading, energy absorbed per unit weight for the composite was, 8 times larger than the monolithic PDMS.

A new 3D cadmium(II) coordination polymer having mu(4)-oxalato, mu-aquo and mu-chlorido bridges: crystal structure, solid state fluorescence and thermal behavior

A new 3D cadmium(II) coordination polymer, Cd(C2O4)(0.5)Cl(H2O)](n) (1) has been synthesized from a mixture of CdCl2. H2O and (NH4)(2)C2O4 in a slightly acidic pH. Its molecular structure was determined by single crystal X-ray diffraction which reveals that the new polymeric structure consists of simultaneous mu(4)-oxalato, mu-aquo, and mu-chlorido bridges between the metal centers, embedded in distorted pentagonal bipyramidal geometries. On thermal analysis compound exhibits high thermal stability up to 330 degrees C. Compound 1 also exhibits strong fluorescent emission. (c) 2013 Elsevier B.V. All rights reserved.

Solvent-templated supramolecular isomerism in 2D coordination polymer constructed by (Ni2CoII)-Co-II nodes and dicyanamido spacers: drastic change in magnetic behaviours

Two heterometallic coordination polymers (CPs) have been prepared using (NiL)-L-II](2)Co-II (where H2L = N,N'-bis(salicylidene)-1,3-propanediamine) as nodes and dicyanamido spacers by varying the solvent for synthesis. Structural characterizations revealed that methanol assisted the formation of a two-dimensional (4,4) connected rhombic grid network of (NiL)(2)Co(NCNCN)2](infinity) (1a) whereas relatively less polar acetonitrile afforded a different superstructure {(NiL)(2)Co(NCNCN)(2)]center dot CH3CN}(infinity) (1b) with a two-dimensional (4,4) connected square grid network. The presence of acetonitrile molecules in the structure of 1b seems to change the spatial orientation of the terminal metalloligands NiL] from pseudo-eclipsed in 1a to staggered-like in 1b around the central Co(II). These structural changes in the nodes together with the conformationally flexible dicyanamido spacers, which are cis coordinated to the Co(II) in both trinuclear units, led to the differences in the final 2D network. Variable-temperature magnetic susceptibility measurements revealed that this supramolecular isomerism led to a drastic transition from spin-frustrated antiferromagnetism for 1a to a dominant ferromagnetic behaviour for 1b. The geometrical differences in Ni2Co coordination clusters (CCs) which are scalene triangular in 1a but nearly linear in 1b, are held responsible for the changes of the magnetic properties. The DFT calculations of exchange interactions between metal centres provide a clear evidence of the role played by the fundamental geometrical factors on the nature and magnitude of the magnetic coupling in these pseudo-polymorphic CPs.

e-SURAKSHAK: A Cyber-Physical Healthcare System with Service Oriented Architecture

In this paper we present the design of ``e-SURAKSHAK,'' a novel cyber-physical health care management system of Wireless Embedded Internet Devices (WEIDs) that sense vital health parameters. The system is capable of sensing body temperature, heart rate, oxygen saturation level and also allows noninvasive blood pressure (NIBP) measurement. End to end internet connectivity is provided by using 6LoWPAN based wireless network that uses the 802.15.4 radio. A service oriented architecture (SOA) 1] is implemented to extract meaningful information and present it in an easy-to-understand form to the end-user instead of raw data made available by sensors. A central electronic database and health care management software are developed. Vital health parameters are measured and stored periodically in the database. Further, support for real-time measurement of health parameters is provided through a web based GUI. The system has been implemented completely and demonstrated with multiple users and multiple WEIDs.

DNA STRUCTURAL FEATURES AND ARCHITECTURE OF PROMOTER REGIONS PLAY A ROLE IN GENE RESPONSIVENESS OF S. CEREVISIAE

Gene expression is the most fundamental biological process, which is essential for phenotypic variation. It is regulated by various external (environment and evolution) and internal (genetic) factors. The level of gene expression depends on promoter architecture, along with other external factors. Presence of sequence motifs, such as transcription factor binding sites (TFBSs) and TATA-box, or DNA methylation in vertebrates has been implicated in the regulation of expression of some genes in eukaryotes, but a large number of genes lack these sequences. On the other hand, several experimental and computational studies have shown that promoter sequences possess some special structural properties, such as low stability, less bendability, low nucleosome occupancy, and more curvature, which are prevalent across all organisms. These structural features may play role in transcription initiation and regulation of gene expression. We have studied the relationship between the structural features of promoter DNA, promoter directionality and gene expression variability in S. cerevisiae. This relationship has been analyzed for seven different measures of gene expression variability, along with two different regulatory effect measures. We find that a few of the variability measures of gene expression are linked to DNA structural properties, nucleosome occupancy, TATA-box presence, and bidirectionality of promoter regions. Interestingly, gene responsiveness is most intimately correlated with DNA structural features and promoter architecture.

Template-free multicomponent coordination-driven self-assembly of Pd(II)/Pt(II) molecular cages

Recent years have seen a tremendous increase in the interest for constructing hollowed-out molecular frameworks, for their potential uses. Metal-ligand coordination-driven self-assembly has provided multitudes of opportunities in the formation of molecular architectures of desired shapes and sizes, with the help of the information already coded in the components. This article summarizes the recent developments in the construction of multicomponent molecular cages through this process, with a focus on the decreasing relevance of templates, and use of these systems in catalysis/host-guest chemistry.

Design of a Low Power 64 Point FFT Architecture for WLAN Applications

This paper presents a Radix-4(3) based FFT architecture suitable for OFDM based WLAN applications. The radix-4(3) parallel unrolled architecture presented here, uses a radix-4 butterfly unit which takes all four inputs in parallel and can selectively produce one out of the four outputs. A 64 point FFT processor based on the proposed architecture has been implemented in UMC 130nm 1P8M CMOS process with a maximum clock frequency of 100 MHz and area of 0.83mm(2). The proposed processor provides a throughput of four times the clock rate and can finish one 64 point FFT computation in 16 clock cycles. For IEEE 802.11a/g WLAN, the processor needs to be operated at a clock rate of 5 MHz with a power consumption of 2.27 mW which is 27% less than the previously reported low power implementations.

High Throughput, Low Latency, Memory Optimized 64K Point FFT Architecture using Novel Radix-4 Butterfly Unit

In this paper we propose a fully parallel 64K point radix-4(4) FFT processor. The radix-4(4) parallel unrolled architecture uses a novel radix-4 butterfly unit which takes all four inputs in parallel and can selectively produce one out of the four outputs. The radix-4(4) block can take all 256 inputs in parallel and can use the select control signals to generate one out of the 256 outputs. The resultant 64K point FFT processor shows significant reduction in intermediate memory but with increased hardware complexity. Compared to the state-of-art implementation 5], our architecture shows reduced latency with comparable throughput and area. The 64K point FFT architecture was synthesized using a 130nm CMOS technology which resulted in a throughput of 1.4 GSPS and latency of 47.7 mu s with a maximum clock frequency of 350MHz. When compared to 5], the latency is reduced by 303 mu s with 50.8% reduction in area.

Coordination of Reactive Power in Grid-Connected Wind Farms for Voltage Stability Enhancement

This paper studies the feasibility of utilizing the reactive power of grid-connected variable-speed wind generators to enhance the steady-state voltage stability margin of the system. Allowing wind generators to work at maximum reactive power limit may cause the system to operate near the steady-state stability limit, which is undesirable. This necessitates proper coordination of reactive power output of wind generators with other reactive power controllers in the grid. This paper presents a trust region framework for coordinating reactive output of wind generators-with other reactive sources for voltage stability enhancement. Case studies on 418-bus equivalent system of Indian southern grid indicates the effectiveness of proposed methodology in enhancing the steady-state voltage stability margin.

beta gamma-fused turn structures in sugar amino acid (SAA) containing cyclic tetrapeptides with alpha 3 delta architecture

The current manuscript describes conformational analysis of 15-membered cyclic tetrapeptides (CTPs), with alpha 3 delta architecture, containing sugar amino acids (SAA) having variation in the stereocenter at C5 carbon. Conformational analyses of both the series, in protected and deprotected forms, were carried out in DMSO-d(6) using various NMR techniques, supported by restrained MD calculations. It was intriguing to notice that the alpha 3 delta macrocycles got stabilized by both 10-membered beta-turn as well as a seven-membered gamma-turn, fused within the same macrocycle. The presence of fused sub-structures within a 15-membered macrocycle is rare to see. Also, the stereocenter variation at C5 did not affect the fused turn structures and exhibited similar conformations in both the series. The design becomes highly advantageous as fused reverse turn structures are occurring in the cyclic structure with minimalistic size macrocycle and this can be applied to develop suitable pharmacophores in the drug development process. (C) 2014 Elsevier Ltd. All rights reserved.

Salmonella methylglyoxal detoxification by STM3117-encoded lactoylglutathione lyase affects virulence in coordination with Salmonella pathogenicity island 2 and phagosomal acidification

Intracellular pathogens such as Salmonella enterica serovar Typhimurium (S. Typhimurium) manipulate their host cells through the interplay of various virulence factors. A multitude of such virulence factors are encoded on the genome of S. Typhimurium and are usually organized in pathogenicity islands. The virulence-associated genomic stretch of STM3117-3120 has structural features of pathogenicity islands and is present exclusively in non-typhoidal serovars of Salmonella. It encodes metabolic enzymes predicted to be involved in methylglyoxal metabolism. STM3117-encoded lactoylglutathione lyase significantly impacts the proliferation of intracellular Salmonella. The deletion mutant of STM3117 (Delta lgl) fails to grow in epithelial cells but hyper-replicates in macrophages. This difference in proliferation outcome was the consequence of failure to detoxify methylglyoxal by Delta lgl, which was also reflected in the form of oxidative DNA damage and upregulation of kefB in the mutant. Within macrophages, the toxicity of methylglyoxal adducts elicits the potassium efflux channel (KefB) in the mutant which subsequently modulates the acidification of mutant-containing vacuoles (MCVs). The perturbation in the pH of the MCV milieu and bacterial cytosol enhances the Salmonella pathogenicity island 2 translocation in Delta lgl, increasing its net growth within macrophages. In epithelial cells, however, the maturation of Delta lgl-containing vacuoles were affected as these non-phagocytic cells maintain less acidic vacuoles compared to those in macrophages. Remarkably, ectopic expression of Toll-like receptors 2 and 4 on epithelial cells partially restored the survival of Delta lgl. This study identified a novel metabolic enzyme in S. Typhimurium whose activity during intracellular infection within a given host cell type differentially affected the virulence of the bacteria.

Reduction in DNA topoisomerase I level affects growth, phenotype and nucleoid architecture of Mycobacterium smegmatis

The steady-state negative supercoiling of eubacterial genomes is maintained by the action of DNA topoisomerases. Topoisomerase distribution varies in different species of mycobacteria. While Mycobacterium tuberculosis (Mtb) contains a single type I (Topol) and a single type II (Gyrase) enzyme, Mycobacterium smegmatis (Msm) and other members harbour additional relaxases. Topol is essential for Mtb survival. However, the necessity of Topol or other relaxases in Msm has not been investigated. To recognize the importance of Topol for growth, physiology and gene expression of Msm, we have developed a conditional knock-down strain of Topol in Msm. The Topol-depleted strain exhibited extremely slow growth and drastic changes in phenotypic characteristics. The cessation of growth indicates the essential requirement of the enzyme for the organism in spite of having additional DNA relaxation enzymes in the cell. Notably, the imbalance in Topol level led to the altered expression of topology modulatory proteins, resulting in a diffused nucleoid architecture. Proteomic and transcript analysis of the mutant indicated reduced expression of the genes involved in central metabolic pathways and core DNA transaction processes. RNA polymerase (RNAP) distribution on the transcription units was affected in the Topol-depleted cells, suggesting global alteration in transcription. The study thus highlights the essential requirement of Topol in the maintenance of cellular phenotype, growth characteristics and gene expression in mycobacteria. A decrease in Topol level led to altered RNAP occupancy and impaired transcription elongation, causing severe downstream effects.

Novel architecture for anomalous strengthening of a particulate filled polymer matrix composite

We propose an architecture for dramatically enhancing the stress bearing and energy absorption capacities of a polymer based composite. Different weight fractions of iron oxide nano-particles (NPs) are mixed in a poly(dimethylesiloxane) (PDMS) matrix either uniformly or into several vertically aligned cylindrical pillars. These composites are compressed up to a strain of 60% at a strain rate of 0.01 s(-1) following which they are fully unloaded at the same rate. Load bearing and energy absorption capacities of the composite with uniform distribution of NPs increase by similar to 50% upon addition of 5 wt% of NPs; however, these properties monotonically decrease with further addition of NPs so much so that the load bearing capacity of the composite becomes 1/6th of PDMS upon addition of 20 wt% of NPs. On the contrary, stress at a strain of 60% and energy absorption capacity of the composites with pillar configuration monotonically increase with the weight fraction of NPs in the pillars wherein the load bearing capacity becomes 1.5 times of PDMS when the pillars consisted of 20 wt% of NPs. In situ mechanical testing of composites with pillars reveals outward bending of the pillars wherein the pillars and the PDMS in between two pillars, located along a radius, are significantly compressed. Reasoning based on effects of compressive hydrostatic stress and shape of fillers is developed to explain the observed anomalous strengthening of the composite with pillar architecture.