The generalized anomeric effect in the 1,3-thiazolidines: Evidence forboth sulphur and nitrogen as electron donors. Crystal structures of various N-acylthiazolidines including mercury(II) complexes. Possible relevance to penicillin action

Evidence for the generalized anomeric effect (GAE) in the N-acyl-1,3-thiazolidines, an important structural motif in the penicillins, was sought in the crystal structures of N-(4-nitrobenzoyl)-1,3-thiazolidine and its (2:1) complex with mercuric chloride, N-acetyl-2-phenyl-1,3-thiazolidine, and the (2:1) complex of N-benzoyl-1,3-thiazolidine with mercuric bromide. An inverse relationship was generally observed between the. C-2-N and C-2-S bond lengths of the thiazolidine ring, supporting the existence of the GAE. (Maximal bond length changes were similar to 0.04 angstrom for C-2-N-3, S-1-C-2, and similar to 0.08 angstrom for N-3-C-6.) Comparison with N-acylpyrrolidines and tetrahydrothiophenes indicates that both the nitrogen-to-sulphur and sulphur-to-nitrogen GAE's operate simultaneously in the 1,3-thiazolidines, the former being dominant. (This is analogous to the normal and exo-anomeric effects in pyranoses, and also leads to an interesting application of Baldwin's rules.) The nitrogen-to-sulphur GAE is generally enhanced in the mercury(II) complexes (presumably via coordination at the sulphur); a 'competition' between the GAE and the amide resonance of the N-acyl moiety is apparent. There is evidence for a 'push-pull' charge transfer between the thiazolidine moieties in the mercury(II) complexes, and for a 'back-donation' of charge from the bromine atoms to the thiazolidine moieties in the HgBr2 complex. (The sulphur atom appears to be sp(2) hybridised in the mercury(II) complexes, possibly for stereoelectronic reasons.) These results are apparently relevant to the mode of action of the penicillins. (c) 2006 Elsevier B.V. All rights reserved.

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.

Deformation dynamics of SS-316 Between 1023-K TO 1223-K In The Framework of Cottrell-Stokes Law

Kocks' formalism for analysing steady state deformation data for the case where Cottrell-Stokes law is valid is extended to incorporate possible back stresses from solution and/or precipitation hardening, and dependence of pre-exponential factor on the applied stress. A simple graphical procedure for exploiting these equations is demonstrated by analyzing tensile steady state data for a type 316 austentic stainless steel for the temperature range 1023 to 1223 K. In this instance, the computed back stress values turned out to be negative, a physically meaningless result. This shows that for SS 316, deformation in this temperature regime can not be interpreted in terms of a mechanism that obeys Cottrell-Stokes law.

Characterization of substrate UpA binding to RNase A--computer modelling and energetics approach.

In the past two decades RNase A has been the focus of diverse investigations in order to understand the nature of substrate binding and to know the mechanism of enzyme action. Although this system is reasonably well characterized from the view point of some of the binding sites, the details of interactions in the second base binding (B2) site is insufficient. Further, the nature of ligand-protein interaction is elucidated generally by studies on RNase A-substrate analog complexes (mainly with the help of X-ray crystallography). Hence, the details of interactions at atomic level arising due to substrates are inferred indirectly. In the present paper, the dinucleotide substrate UpA is fitted into the active site of RNase A Several possible substrate conformations are investigated and the binding modes have been selected based on Contact Criteria. Thus identified RNase A-UpA complexes are energy minimized in coordinate space and are analysed in terms of conformations, energetics and interactions. The best possible ligand conformations for binding to RNase A are identified by experimentally known interactions and by the energetics. Upon binding of UpA to RNase A the changes associated,with protein back bone, Side chains in general and at the binding sites in particular are described. Further, the detailed interactions between UpA and RNase A are characterized in terms of hydrogen bonds and energetics. An extensive study has helped in interpreting the diverse results obtained from a number of experiments and also in evaluating the extent of changes the protein and the substrate undergo in order to maximize their interactions.

DNA analysis indicates that Asian elephants are native to Borneo and are therefore a high priority for conservation

The origin of Borneo's elephants is controversial. Two competing hypotheses argue that they are either indigenous, tracing back to the Pleistocene, or were introduced, descending from elephants imported in the 16th-18th centuries. Taxonomically, they have either been classified as a unique subspecies or placed under the Indian or Sumatran subspecies. If shown to be a unique indigenous population, this would extend the natural species range of the Asian elephant by 1300 km, and therefore Borneo elephants would have much greater conservation importance than if they were a feral population. We compared DNA of Borneo elephants to that of elephants from across the range of the Asian elephant, using a fragment of mitochondrial DNA, including part of the hypervariable d-loop, and five autosomal microsatellite loci. We find that Borneo's elephants are genetically distinct, with molecular divergence indicative of a Pleistocene colonisation of Borneo and subsequent isolation. We reject the hypothesis that Borneo's elephants were introduced. The genetic divergence of Borneo elephants warrants their recognition as a separate evolutionary significant unit. Thus, interbreeding Borneo elephants with those from other populations would be contraindicated in ex situ conservation, and their genetic distinctiveness makes them one of the highest priority populations for Asian elephant conservation.

Climate forcing and response to idealized changes in surface latent and sensible heat

Land use and land cover changes affect the partitioning of latent and sensible heat, which impacts the broader climate system. Increased latent heat flux to the atmosphere has a local cooling influence known as `evaporative cooling', but this energy will be released back to the atmosphere wherever the water condenses. However, the extent to which local evaporative cooling provides a global cooling influence has not been well characterized. Here, we perform a highly idealized set of climate model simulations aimed at understanding the effects that changes in the balance between surface sensible and latent heating have on the global climate system. We find that globally adding a uniform 1 W m(-2) source of latent heat flux along with a uniform 1 W m(-2) sink of sensible heat leads to a decrease in global mean surface air temperature of 0.54 +/- 0.04 K. This occurs largely as a consequence of planetary albedo increases associated with an increase in low elevation cloudiness caused by increased evaporation. Thus, our model results indicate that, on average, when latent heating replaces sensible heating, global, and not merely local, surface temperatures decrease.

An Accurate Model for EESM and its Application to Analysis of CQI Feedback Schemes and Scheduling in LTE

The Effective Exponential SNR Mapping (EESM) is an indispensable tool for analyzing and simulating next generation orthogonal frequency division multiplexing (OFDM) based wireless systems. It converts the different gains of multiple subchannels, over which a codeword is transmitted, into a single effective flat-fading gain with the same codeword error rate. It facilitates link adaptation by helping each user to compute an accurate channel quality indicator (CQI), which is fed back to the base station to enable downlink rate adaptation and scheduling. However, the highly non-linear nature of EESM makes a performance analysis of adaptation and scheduling difficult; even the probability distribution of EESM is not known in closed-form. This paper shows that EESM can be accurately modeled as a lognormal random variable when the subchannel gains are Rayleigh distributed. The model is also valid when the subchannel gains are correlated in frequency or space. With some simplifying assumptions, the paper then develops a novel analysis of the performance of LTE's two CQI feedback schemes that use EESM to generate CQI. The comprehensive model and analysis quantify the joint effect of several critical components such as scheduler, multiple antenna mode, CQI feedback scheme, and EESM-based feedback averaging on the overall system throughput.

Usefulness of in Situ Single Crystal to Single Crystal Transformation (SCSC) Studies in Understanding the Temperature-Dependent Dimensionality Cross-over and Structural Reorganization in Copper-Containing Metal-Organic Frameworks (MOFs)

Two copper-containing compounds [Cu(3)(mu(3)-OH)(2)-(H(2)O)(2){(SO(3))-C(6)H(3)-(COO)(2)}(CH(3)COO)] , I, and [Cu(5)(mu(3)-OH)(2)(H(2)O)(6){(NO(2))-C(6)H(3)-(COO)(2)}(4)]center dot 5H(2)O, II, were prepared using sulphoisophthalic and nitroisophthalic acids. The removal of the coordinated water molecules in the compounds was investigated using in situ single crystal to single crystal (SCSC) transformation studies, temperature-dependent powder X-ray diffraction (PXRD), and thermogravimetric analysis (TGA). The efficacy of SCSC transformation studies were established by the observation of dimensionality cross-over from a two-dimensional (I) to a three-dimensional structure, Cu(6)(mu(3)-OH)(4){(SO(3))-C(6)H(3)-(COO)(2)}(2)(CH(3)COO)(2), Ia, during the removal of the coordinated water molecules. Compound H exhibited a structural reorganization forming Cu(5)(mu(2)-OH)(2){(NO(2))C(6)H(3)-(COO)(2))(4)], Ha, possessing trimeric (Cu(3)O(12)) and dimeric (Cu(2)O(8)) copper clusters. The PXRD studies indicate that the three-dimensional structure (Ia) is transient and unstable, reverting back to the more stable two-dimensional structure (I) on cooling to room temperature. Compound Ha appears to be more stable at room temperature. The rehydration/dehydration studies using a modified TGA setup suggest complete rehydration of the water molecules, indicating that the water molecules in both compounds are labile. A possible model for the observed changes in the structures has been proposed. Magnetic studies indicate changes in the exchanges between the copper centers in Ha, whereas no such behavior was observed in Ia.

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

Hall viscosity to entropy ratio in higher derivative theories

In this paper based on the basic principles of gauge/gravity duality we compute the hall viscosity to entropy ratio in the presence of various higher derivative corrections to the dual gravitational description embedded in an asymptotically AdS(4) space time. As the first step of our analysis, considering the back reaction we impose higher derivative corrections to the abelian gauge sector of the theory where we notice that the ratio indeed gets corrected at the leading order in the coupling. Considering the probe limit as a special case we compute this leading order correction over the fixed background of the charged black brane solution. Finally we consider higher derivative (R-2) correction to the gravity sector of the theory where we notice that the above ratio might get corrected at the sixth derivative level.

A Grid Simulator to Evaluate Control Performance of Grid-Connected Inverters

Grid simulators are used to test the control performance of grid-connected inverters under a wide range of grid disturbance conditions. In the present work, a three phase back-to-back connected inverter sharing a common dc bus has been programmed as a grid simulator. Three phase balanced disturbance voltages applied to three-phase balanced loads has been considered in the present work. The developed grid simulator can generate three phase balanced voltage sags, voltage swells, frequency deviations and phase jumps. The grid simulator uses a novel disturbance generation algorithm. The algorithm allows the user to reference the disturbance to any of the three phases at any desired phase angle. Further, the exit of the disturbance condition can be referenced to the desired phase angle of any phase by adjusting the duration of the disturbance. The grid simulator hardware has been tested with different loads – a linear purely resistive load, a non-linear diode-bridge load and a grid-connected inverter load.