Charge Density Analysis of a Pentaborate Ion in an Ammonium Borate: Toward the Understanding of Topological Features in Borate Minerals

Structural and charge density distribution studies have been carried out on a single crystal data of an ammonium borate, [C(10)H(26)N(4)][B(5)O(6)(OH)(4)](2), synthesized by solvothermal method. Further, the experimentally observed geometry is used for the theoretical charge density calculations using the B3LYP/6-31G** level of theory, and the results are compared with the experimental values. Topological analysis of charge density based on the Atoms in Molecules approach for B-O bonds exhibit mixed covalent/ionic character. Detailed analysis of the hydrogen bonds in the crystal structure in the ammonium borate provides insights into the understanding of the reaction pathways that net atomic charges and electrostatic potential isosurfaces also give additional such systems. could result in the formation of borate minerals. The input to evaluate chemical and physical properties in such systems.

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.

Understanding How the Brain Changes Its Mind: Microstimulation in the Macaque Frontal Eye Field Reveals How Saccade Plans Are Changed

Accumulator models that integrate incoming sensory information into motor plans provide a robust framework to understand decision making. However, their applicability to situations that demand a change of plan raises an interesting problem for the brain. This is because interruption of the current motor plan must occur by a competing motor plan, which is necessarily weaker in strength. To understand how changes of mind get expressed in behavior, we used a version of the double-step task called the redirect task, in which monkeys were trained to modify a saccade plan. We microstimulated the frontal eye fields during redirect behavior and systematically measured the deviation of the evoked saccade from the response field to causally track the changing saccade plan. Further, to identify the underlying mechanisms, eight different computational models of redirect behavior were assessed. It was observed that the model that included an independent, spatially specific inhibitory process, in addition to the two accumulators representing the preparatory processes of initial and final motor plans, best predicted the performance and the pattern of saccade deviation profile in the task. Such an inhibitory process suppressed the preparation of the initial motor plan, allowing the final motor plan to proceed unhindered. Thus, changes of mind are consistent with the notion of a spatially specific, inhibitory process that inhibits the current inappropriate plan, allowing expression of the new plan.

Understanding Aqueous Dispersibility of Graphene Oxide and Reduced Graphene Oxide through pK(a) Measurements

The chemistry underlying the aqueous dispersibility of graphene oxide (GO) and reduced graphene oxide (r-GO) is a key consideration in the design of solution processing techniques for the preparation of processable graphene sheets. Here, we use zeta potential measurements, pH titrations, and infrared spectroscopy to establish the chemistry underlying the aqueous dispersibility of GO and r-GO sheets at different values of pH. We show that r-GO sheets have ionizable groups with a single pK value (8.0) while GO sheets have groups that are more acidic (pK = 4.3), in addition to groups with pK values of 6.6 and 9.0. Infrared spectroscopy has been used to follow the sequence of ionization events. In both GO and r-GO sheets, it is ionization of the carboxylic groups that is primarily responsible for the build up of charge, but on GO sheets, the presence of phenolic and hydroxyl groups in close proximity to the carboxylic groups lowers the pK(a) value by stabilizing the carboxylate anion, resulting in superior water dispersibility.

Understanding the Magnetization Reversal in Six-Fold Anisotropic Hexagonal Networks

Isolated magnetic nanowires have been studied extensively and the magnetization reversal mechanism is well understood in these systems. But when these nanowires are joined together in different architectures, they behave differently and can give novel properties. Using this approach, one can engineer the network architectures to get artificial anisotropy. Here, we report six-fold anisotropy by joining the magnetic nanowires into hexagonal network. For this study, we also benchmark the widely used micromagnetic packages: OOMMF, Nmag, and LLG-simulator. Further, we propose a local hysteresis method by post processing the spatial magnetization information. With this approach we obtained the hysteresis of nanowires to understand the six-fold anisotropy and the reversal mechanism within the hexagonal networks.

The hazard potential of the western segment of the Makran subduction zone, northern Arabian Sea

Evaluating the hazard potential of the Makran subduction zone requires understanding the previous records of the large earthquakes and tsunamis. We address this problem by searching for earthquake and tectonic proxies along the Makran Coast and linking those observations with the available constraints on historical seismicity and the tell-tale characteristics of sea floor morphology. The earthquake of Mw 8.1 of 1945 and the consequent tsunami that originated on the eastern part of the Makran are the only historically known hazardous events in this region. The seismic status of the western part of the subduction zone outside the rupture area of the 1945 earthquake remains an enigma. The near-shore shallow stratigraphy of the central part of Makran near Chabahar shows evidence of seismically induced liquefaction that we attribute to the distant effects of the 1945 earthquake. The coastal sites further westward around Jask are remarkable for the absence of liquefaction features, at least at the shallow level. Although a negative evidence, this possibly implies that the western part of Makran Coast region may not have been impacted by near-field large earthquakes in the recent past-a fact also supported by the analysis of historical data. On the other hand, the elevated marine terraces on the western Makran and their uplift rates are indicative of comparable degree of long-term tectonic activity, at least around Chabahar. The offshore data suggest occurrences of recently active submarine slumps on the eastern part of the Makran, reflective of shaking events, owing to the great 1945 earthquake. The ocean floor morphologic features on the western segment, on the contrary, are much subdued and the prograding delta lobes on the shelf edge also remain intact. The coast on the western Makran, in general, shows indications of progradation and uplift. The various lines of evidence thus suggest that although the western segment is potentially seismogenic, large earthquakes have not occurred there in the recent past, at least during the last 600 years. The recurrence period of earthquakes may range up to 1,000 years or more, an assessment based on the age of the youngest dated coastal ridge. The long elapsed time points to the fact that the western segment may have accumulated sufficient slip to produce a major earthquake.

Crystal-structure analysis of cis-X-pro-containing peptidomimetics: understanding the steric interactions at cis X-pro amide bonds

Catch the twist: The cis Piv-Pro conformer (Piv=pivaloyl) of peptides is no longer inaccessible. Any cis X-Pro tertiary-amide-bond conformer can be stabilized in crystals of peptides by accommodating the unavoidable distortion of the dihedral angle of the peptide bond to the carbonyl group of the Pro residue (see picture), in this case through ni−1→πi* interactions. Steric clashes were not observed in the cis Piv-Pro rotamers studied.

A new approach for understanding ion transport in glasses; example of complex alkali diborate glasses containing lead, bismuth and tellurium oxides

Mechanism of ion transport in glasses continues to be incompletely understood. Several of the theoretical models in vogue fail to rationalize conductivity behaviour when d.c. and a.c. measurements are considered together. While they seem to involve the presence of at least two components in d.c. activation energy, experiments fail to reveal that feature. Further, only minor importance is given to the influence of structure of the glass on the ionic conductivity behaviour. In this paper, we have examined several general aspects of ion transport taking the example of ionically conducting glasses in pseudo binary, yNa(2)B(4)O(7)center dot(1-y) M (a) O (b) (with y = 0 center dot 25-0 center dot 79 and M (a) O (b) = PbO, TeO2 and Bi2O3) system of glasses which have also been recently characterized. Ion transport in them has been studied in detail. We have proposed that non-bridging oxygen (NBO) participation is crucial to the understanding of the observed conductivity behaviour. NBO-BO switching is projected as the first important step in ion transport and alkali ion jump is a subsequent event with a characteristically lower barrier which is, therefore, not observed in any study. All important observations in d.c. and a.c. transport in glasses are found consistent with this model.

Towards the understanding of formation of micro/nano holes of Ge/GeO2 through phase mapping

Here, we report for the first time a simple thermal oxidation strategy for the large area synthesis of Ge/GeO2 nanoholes from Ge and studied the luminescence of Ge/GeO2 and hole formation mechanism through phase and luminescence mapping. Photoluminescence mapping reveals that the emission in the visible range is only from the hole region, which provokes the necessity of the nanoholes. Such materials can also be used to convert ultraviolet to visible radiation for detection by conventional phototubes and to coat blue or ultraviolet diodes to obtain white light.

Relook into the historical progress and philosophy of Indian space exploration

A study of the history and philosophy of the contribution of India towards the exploration of space since antiquity provides interesting insights. The contributions are described during the three periods namely: (1) the ten millenniums from 10,000 BC with a twilight period up to 900 AD; (2) the ten centuries from 900 AD to 1900 AD; and (3) the ten decades from 1900 AD to 2000 AD; called mythological, medieval, and modern respectively. Some important events during the above periods provide a reference view of the progress. The Vedas during the mythological period and the Siddhantas during the medieval periods, which are based on astronomical observations, indicate that the Indian contribution preceded other cultures. But most Western historians ignore this fact time and again in spite of many proofs provided to the contrary. This chapter also shows that Indians had the proper scientific attitude of developing any physical theory through the triplet of mind, model, and measurements. It is this same triplet that forms the basis of the present day well known Kalman filter technique. Up to about 1500 BC the Indian contribution was leading but during foreign invasion and occupation it lagged and has been improving only after independence.

Assessing resilience and state-transition models with historical records of cheatgrass Bromus tectorum invasion in North American sagebrush-steppe

1. Resilience-based approaches are increasingly being called upon to inform ecosystem management, particularly in arid and semi-arid regions. This requires management frameworks that can assess ecosystem dynamics, both within and between alternative states, at relevant time scales. 2. We analysed long-term vegetation records from two representative sites in the North American sagebrush-steppe ecosystem, spanning nine decades, to determine if empirical patterns were consistent with resilience theory, and to determine if cheatgrass Bromus tectorum invasion led to thresholds as currently envisioned by expert-based state-and-transition models (STM). These data span the entire history of cheatgrass invasion at these sites and provide a unique opportunity to assess the impacts of biotic invasion on ecosystem resilience. 3. We used univariate and multivariate statistical tools to identify unique plant communities and document the magnitude, frequency and directionality of community transitions through time. Community transitions were characterized by 37-47% dissimilarity in species composition, they were not evenly distributed through time, their frequency was not correlated with precipitation, and they could not be readily attributed to fire or grazing. Instead, at both sites, the majority of community transitions occurred within an 8-10year period of increasing cheatgrass density, became infrequent after cheatgrass density peaked, and thereafter transition frequency declined. 4. Greater cheatgrass density, replacement of native species and indication of asymmetry in community transitions suggest that thresholds may have been exceeded in response to cheatgrass invasion at one site (more arid), but not at the other site (less arid). Asymmetry in the direction of community transitions also identified communities that were at-risk' of cheatgrass invasion, as well as potential restoration pathways for recovery of pre-invasion states. 5. Synthesis and applications. These results illustrate the complexities associated with threshold identification, and indicate that criteria describing the frequency, magnitude, directionality and temporal scale of community transitions may provide greater insight into resilience theory and its application for ecosystem management. These criteria are likely to vary across biogeographic regions that are susceptible to cheatgrass invasion, and necessitate more in-depth assessments of thresholds and alternative states, than currently available.

The problem of clear air turbulence: Changing perspectives in the understanding of the phenomenon

Due to rapid improvements in on-board instrumentation and atmospheric observation systems, in most cases, aircraft are able to steer clear of regions of adverse weather. However, they still encounter unexpected bumpy flight conditions in regions away from storms and clouds. This is the phenomenon of clear air turbulence (CAT), which has been a challenge to our understanding as well as efforts at prediction. While most of such cases result in mild discomfort, a few cases can be violent leading to serious injuries to passengers and damage to the aircraft. The underlying physical mechanisms have been sought to be explained in terms of fluid dynamic instabilities and waves in the atmosphere. The main mechanisms which have been proposed are: (i) Kelvin-Helmholtz instability of shear layers, (ii) waves generated from flow over mountains, (iii) inertia-gravity waves from clouds and other sources, (iv) spontaneous imbalance theory and (v) horizontal vortex tubes. This has also undergone a change over the years. We present an overview of the mechanisms proposed and their implications for prediction.