Spin State Selective Excitation of Single Quantum Transitions Using Multiple Quantum Spectroscopy- an Aid to Analyse Complex Proton NMR spectra of Oriented Molecules

NMR spectra of molecules oriented in liquid-crystalline matrix provide information on the structure and orientation of the molecules. Thermotropic liquid crystals used as an orienting media result in the spectra of spins that are generally strongly coupled. The number of allowed transitions increases rapidly with the increase in the number of interacting spins. Furthermore, the number of single quantum transitions required for analysis is highly redundant. In the present study, we have demonstrated that it is possible to separate the subspectra of a homonuclear dipolar coupled spin system on the basis of the spin states of the coupled heteronuclei by multiple quantum (MQ)−single quantum (SQ) correlation experiments. This significantly reduces the number of redundant transitions, thereby simplifying the analysis of the complex spectrum. The methodology has been demonstrated on the doubly 13C labeled acetonitrile aligned in the liquid-crystal matrix and has been applied to analyze the complex spectrum of an oriented six spin system.

Two-timescale Q-learning Algorithms with an Application to Routing in Networks

We propose two variants of the Q-learning algorithm that (both) use two timescales. One of these updates Q-values of all feasible state-action pairs at each instant while the other updates Q-values of states with actions chosen according to the ‘current ’ randomized policy updates. A sketch of convergence of the algorithms is shown. Finally, numerical experiments using the proposed algorithms for routing on different network topologies are presented and performance comparisons with the regular Q-learning algorithm are shown.

A Simultaneous Deterministic Perturbation Actor-Critic Algorithm with an Application to Optimal Mortgage Refinancing

We develop a simulation-based, two-timescale actor-critic algorithm for infinite horizon Markov decision processes with finite state and action spaces, with a discounted reward criterion. The algorithm is of the gradient ascent type and performs a search in the space of stationary randomized policies. The algorithm uses certain simultaneous deterministic perturbation stochastic approximation (SDPSA) gradient estimates for enhanced performance. We show an application of our algorithm on a problem of mortgage refinancing. Our algorithm obtains the optimal refinancing strategies in a computationally efficient manner

Mini Forest - An experiment to evaluate the adaptability of Western Ghats species for afforestation

Saplings of forty nine species of trees from Western Ghats forests were planted on a 1.5 hectare tract of Deccan plateau (in the campus of Indian Institute of Science, Bangalore) and their performance monitored for 23 years. The objective was to evaluate their adaptability to a habitat and conditions apparently alien to these species. The study was also meant to understand the linkages of these trees with the surrounding environment. Contrary to the belief that tree species are very sensitive to change of location and conditions, the introduced trees have grown as good as they would do in their native habitat and maintained their phenology. Further, they have grown in perfect harmony with trees native to the location. The results show that the introduced species are opportunistic and readily acclimatized and grew well overcoming the need for the edaphic and other factors that are believed to be responsible for their endemicity. Besides ex situ conservation, the creation of miniforest has other accrued ecosystem benefits. For instance, the ground water level has risen and the ambient temperature has come down by two degrees.

Representation of evidence: An approach to uncertainty handling in knowledge-based systems

Many knowledge based systems (KBS) transform a situation information into an appropriate decision using an in built knowledge base. As the knowledge in real world situation is often uncertain, the degree of truth of a proposition provides a measure of uncertainty in the underlying knowledge. This uncertainty can be evaluated by collecting `evidence' about the truth or falsehood of the proposition from multiple sources. In this paper we propose a simple framework for representing uncertainty in using the notion of an evidence space.

An approach to chiral amino acids via reductive amination of ketones: hydride reduction of 1-(S)-phenethyl amine derived Schiff bases of C-protected alpha-keto acids

Various 1-acyl-2,4,10-trioxaadamantanes were prepared from the corresponding 1-methoxycarbonyl derivatives, via conversion to the N-acylpiperidine derivatives followed by reaction with a Grignard reagent in refluxing THF. These alpha-keto orthoformates were converted to the corresponding imines with 1-(S)-phenethyl amine (TiCl4/Et3N/toluene/reflux), with the Schiff bases being reduced further with NaBH4 (MeOH/0 degrees C) into the corresponding 1-(S)-phenethyl amines (diastereomeric excess 91:9 by NMR). Hydrogenolysis of the phenethyl group (Pd-C/MeOH) finally led to the 1-(aminoalkyl)trioxaadamantanes, which are chiral C-protected alpha-amino acids, in excellent overall yields. (C) 2012 Elsevier Ltd. All rights reserved.

An approach to multi-temporal MODIS image analysis using image classification and segmentation

This paper discusses an approach for river mapping and flood evaluation based on multi-temporal time series analysis of satellite images utilizing pixel spectral information for image classification and region-based segmentation for extracting water-covered regions. Analysis of MODIS satellite images is applied in three stages: before flood, during flood and after flood. Water regions are extracted from the MODIS images using image classification (based on spectral information) and image segmentation (based on spatial information). Multi-temporal MODIS images from ``normal'' (non-flood) and flood time-periods are processed in two steps. In the first step, image classifiers such as Support Vector Machines (SVMs) and Artificial Neural Networks (ANNs) separate the image pixels into water and non-water groups based on their spectral features. The classified image is then segmented using spatial features of the water pixels to remove the misclassified water. From the results obtained, we evaluate the performance of the method and conclude that the use of image classification (SVM and ANN) and region-based image segmentation is an accurate and reliable approach for the extraction of water-covered regions. (c) 2012 COSPAR. Published by Elsevier Ltd. All rights reserved.

An Approach to seco-Prezizaane Sesquiterpenoids: Enantioselective Total Synthesis of (+)-1S-Minwanenone

A strategy of general applicability toward seco-prezizaane sesquiterpenes, from a chiral, tricyclic synthon, readily available via an enzymatic resolution step from the Diels-Alder adduct of cyclopentadiene and p-benzoquinone, has been devised. Our approach enables harnessing of the stereochemical proclivities of the norbornyl system to install the desired stereochemistry at the key stereogenic centers. Recourse to an interesting stratagem to realign a stereochemical divergence into stereoreconvergence forms the cornerstone of our successful approach. The first total synthesis of (+)-1S-minwanenone, a prototypical member of seco-prezizaane subclass, has been accomplished.

Ganga-Brahmaputra river discharge from Jason-2 radar altimetry: An update to the long-term satellite-derived estimates of continental freshwater forcing flux into the Bay of Bengal

This paper discusses the use of Jason-2 radar altimeter measurements to estimate the Ganga-Brahmaputra surface freshwater flux into the Bay of Bengal for the period mid-2008 to December 2011. A previous estimate was generated for 1993-2008 using TOPEX-Poseidon, ERS-2 and ENVISAT, and is now extended using Jason-2. To take full advantages of the new availability of in situ rating curves, the processing scheme is adapted and the adjustments of the methodology are discussed here. First, using a large sample of in situ river height measurements, we estimate the standard error of Jason-2-derived water levels over the Ganga and the Brahmaputra to be respectively of 0.28 m and 0.19 m, or less than similar to 4% of the annual peak-to-peak variations of these two rivers. Using the in situ rating curves between water levels and river discharges, we show that Jason-2 accurately infers Ganga and Brahmaputra instantaneous discharges for 2008-2011 with mean errors ranging from similar to 2180 m(3)/s (6.5%) over the Brahmaputra to similar to 1458 m(3)/s (13%) over the Ganga. The combined Ganga-Brahmaputra monthly discharges meet the requirements of acceptable accuracy (15-20%) with a mean error of similar to 16% for 2009-2011 and similar to 17% for 1993-2011. The Ganga-Brahmaputra monthly discharge at the river mouths is then presented, showing a marked interannual variability with a standard deviation of similar to 12500 m(3)/s, much larger than the data set uncertainty. Finally, using in situ sea surface salinity observations, we illustrate the possible impact of extreme continental freshwater discharge event on the northern Bay of Bengal as observed in 2008.

An algorithm to find all palindromic sequences in proteins

A palindrome is a set of characters that reads the same forwards and backwards. Since the discovery of palindromic peptide sequences two decades ago, little effort has been made to understand its structural, functional and evolutionary significance. Therefore, in view of this, an algorithm has been developed to identify all perfect palindromes (excluding the palindromic subset and tandem repeats) in a single protein sequence. The proposed algorithm does not impose any restriction on the number of residues to be given in the input sequence. This avant-garde algorithm will aid in the identification of palindromic peptide sequences of varying lengths in a single protein sequence.

An 8-to-1 bit 1-MS/s SAR ADC With VGA and Integrated Data Compression for Neural Recording

Low power consumption per channel and data rate minimization are two key challenges which need to be addressed in future generations of neural recording systems (NRS). Power consumption can be reduced by avoiding unnecessary processing whereas data rate is greatly decreased by sending spike time-stamps along with spike features as opposed to raw digitized data. Dynamic range in NRS can vary with time due to change in electrode-neuron distance or background noise, which demands adaptability. An analog-to-digital converter (ADC) is one of the most important blocks in a NRS. This paper presents an 8-bit SAR ADC in 0.13-mu m CMOS technology along with input and reference buffer. A novel energy efficient digital-to-analog converter switching scheme is proposed, which consumes 37% less energy than the present state-of-the-art. The use of a ping-pong input sampling scheme is emphasized for multichannel input to alleviate the bandwidth requirement of the input buffer. To reduce the data rate, the A/D process is only enabled through the in-built background noise rejection logic to ensure that the noise is not processed. The ADC resolution can be adjusted from 8 to 1 bit in 1-bit step based on the input dynamic range. The ADC consumes 8.8 mu W from 1 V supply at 1 MS/s speed. It achieves effective number of bits of 7.7 bits and FoM of 42.3 fJ/conversion-step.

Computational Study of the Migration of Rhenium from One Enantioface of an Olefin to the Other Facilitated by (C-H)center dot center dot center dot Re Interactions

The migration of a metal atom in a metal olefin complex from one pi face of the olefin to the opposite pi face has been rarely documented. Gladysz and co-workers showed that such a movement is indeed possible in monosubstituted chiral Re olefin complexes, resulting in diastereomerization. Interestingly, this isomerization occurred without dissociation, and on the basis of kinetic isotope effects, the involvement of a trans C-H bond was indicated. Either oxidative addition or an agostic interaction of the vinylic C-H(D) bond with the metal could account for the experimentally observed kinetic isotope effect. In this study we compute the free energy of activation for the migration of Re from one enantioface of the olefin to the other through various pathways. On the basis of DFT calculations at the B3LYP level we show that a trans (C-H)center dot center dot center dot Re interaction and trans C-H oxidative addition provide a nondissociative path for the diastereomerization. The trans (C-H)center dot center dot center dot Re interaction path is computed to be more favorable by 2.3 kcal mol(-1) than the oxidative addition path. While direct experimental evidence was not able to discount the migration of the metal through the formation of a eta(2)-arene complex (conducted tour mechanism), computational results at the B3LYP level show that it is energetically more expensive. Surprisingly, a similar analysis carried out at the M06 level computes a lower energy path for the conducted tour mechanism and is not consistent with the experimental isotope effects observed. Metal-(C-H) interactions and oxidative additions of the metal into C-H bonds are closely separated in energy and might contribute to unusual fluxional processes such as this diastereomerization.

Calibration Curve with Improved Limit of Detection for Cadmium in Soil: An Approach to Minimize the Matrix Effect in Laser-Induced Breakdown Spectroscopic Analysis

The present article describes a working or combined calibration curve in laser-induced breakdown spectroscopic analysis, which is the cumulative result of the calibration curves obtained from neutral and singly ionized atomic emission spectral lines. This working calibration curve reduces the effect of change in matrix between different zone soils and certified soil samples because it includes both the species' (neutral and singly ionized) concentration of the element of interest. The limit of detection using a working calibration curve is found better as compared to its constituent calibration curves (i.e., individual calibration curves). The quantitative results obtained using the working calibration curve is in better agreement with the result of inductively coupled plasma-atomic emission spectroscopy as compared to the result obtained using its constituent calibration curves.