Acid/Base Controlled Size Modulation of Capsular Phosphates, Hydroxide Encapsulation, Quantitative and Clean Extraction of Sulfate with Carbonate Capsules of a Tripodal Urea Receptor

A simple tris-(2-aminoethyl) amine based pentafluorophenyl substituted tripodal urea receptor L has been extensively studied as a versatile receptor for various anions. Combined H-1-NMR, Isothermal Titration Calorimetry (ITC) and single crystal X-ray diffraction studies reveal that mononegative anions like F-, OH- and H2PO4- are encapsulated into the pseudocapsular dimeric assemblies of L with 1 : 1 stoichiometry whereas dinegative anions like CO32-, SO42- and HPO42- form tight capsular dimeric assemblies of L with 1 : 2 stoichiometries. Single crystal X-ray diffraction study clearly depicts that the size of the dimer of H2PO4- encapsulated pseudocapsule is 13.8 angstrom whereas the size of the tight HPO42- encapsulated capsular assembly is only 9.9 angstrom. The charge dependent anion encapsulated capsular size modulation of phosphates has been demonstrated by simple acid/base treatment via solution state P-31-NMR and single crystal X-ray diffraction studies. L is also capable of encapsulating hydroxide in its C-3v-symmetric cavity that is achieved upon treating a DMSO solution of L with tetrabutylammonium (TBA) cyanide and characterized by single crystal X-ray diffraction study. To the best of our knowledge this is the first report on the encapsulation of hydroxide in a neutral synthetic receptor. The excellent property of L to quantitatively capture aerial CO2 in the form of CO32- capsules [L-2(CO3)][N(n-Bu)(4)](2) in basic DMSO solution has been utilized to study the liquid-liquid extraction of SO42- from water via anion exchange. Almost quantitative and clean extraction of SO42- from water (99% from extracted pure mass and > 95% shown gravimetrically) has been unambiguously demonstrated by NMR, FT-IR, EDX, XRD and PXRD studies. Selective SO42- extraction is also demonstrated even in the presence of H2PO4- and NO3-. On the other hand the mixtures of L and TBACl (to solubilize L in CHCl3) results impure sulfate extraction even when 1 : 1 L/TBACl is used. Similar impure SO42- extraction is also observed when organic layers containing [L(Cl)][N(n-Bu)(4)] are used as the extractant, obtained upon precipitating SO42- from the extracted mass, [L-2(SO4)][N(n-Bu)(4)](2) in the carbonate capsules method using aqueous BaCl2 solution.Department of Science and TechnologyCSIR, IndiaChemistr

On Graphical Models via Univariate Exponential Family Distributions

Undirected graphical models, or Markov networks, are a popular class of statistical models, used in a wide variety of applications. Popular instances of this class include Gaussian graphical models and Ising models. In many settings, however, it might not be clear which subclass of graphical models to use, particularly for non-Gaussian and non-categorical data. In this paper, we consider a general sub-class of graphical models where the node-wise conditional distributions arise from exponential families. This allows us to derive multivariate graphical model distributions from univariate exponential family distributions, such as the Poisson, negative binomial, and exponential distributions. Our key contributions include a class of M-estimators to fit these graphical model distributions; and rigorous statistical analysis showing that these M-estimators recover the true graphical model structure exactly, with high probability. We provide examples of genomic and proteomic networks learned via instances of our class of graphical models derived from Poisson and exponential distributions.Comment: Journal of Machine Learning Researc

Coreference detection of low quality objects

The problem of record linkage is a widely studied problem that aims to identify coreferent (i.e. duplicate) data in a structured data source. As indicated by Winkler, a solution to the record linkage problem is only possible if the error rate is sufficiently low. In other words, in order to succesfully deduplicate a database, the objects in the database must be of sufficient quality. However, this assumption is not always feasible. In this paper, it is investigated how merging of low quality objects into one high quality object can improve the process of record linkage. This general idea is illustrated in the context of strings comparison, where strings of low quality (i.e. with a high typographical error rate) are merged into a string of high quality by using an n-dimensional Levenshtein distance matrix and compute the optimal alignment between the dirty strings. Results are presented and possible refinements are proposed

Stable and Metastable vortex states and the first order transition across the peak effect region in weakly pinned 2H-NbSe_2

The peak effect in weakly pinned superconductors is accompanied by metastable vortex states. Each metastable vortex configuration is characterized by a different critical current density J_c, which mainly depends on the past thermomagnetic history of the superconductor. A recent model [G. Ravikumar, et al, Phys. Rev. B 61, R6479 (2000)] proposed to explain the history dependent J_c postulates a stable state of vortex lattice with a critical current density J_c^{st}, determined uniquely by the field and temperature. In this paper, we present evidence for the existence of the stable state of the vortex lattice in the peak effect region of 2H-NbSe_2. It is shown that this stable state can be reached from any metastable vortex state by cycling the applied field by a small amplitude. The minor magnetization loops obtained by repeated field cycling allow us to determine the pinning and "equilibrium" properties of the stable state of the vortex lattice at a given field and temperature unambiguously. The data imply the occurence of a first order phase transition from an ordered phase to a disordered vortex phase across the peak effect.Comment: 20 pages, 10 figures. Corresponding author: S. Ramakrishna

Minimum and maximum against k lies

A neat 1972 result of Pohl asserts that [3n/2]-2 comparisons are sufficient, and also necessary in the worst case, for finding both the minimum and the maximum of an n-element totally ordered set. The set is accessed via an oracle for pairwise comparisons. More recently, the problem has been studied in the context of the Renyi-Ulam liar games, where the oracle may give up to k false answers. For large k, an upper bound due to Aigner shows that (k+O(\sqrt{k}))n comparisons suffice. We improve on this by providing an algorithm with at most (k+1+C)n+O(k^3) comparisons for some constant C. The known lower bounds are of the form (k+1+c_k)n-D, for some constant D, where c_0=0.5, c_1=23/32=0.71875, and c_k=\Omega(2^{-5k/4}) as k goes to infinity.Comment: 11 pages, 3 figure

Comparison of History Effects in Magnetization in Weakly pinned Crystals of high-TcT_c and low-Tc_c Superconductors

A comparison of the history effects in weakly pinned single crystals of a high $T_c$ YBa$_2$Cu$_3$O$_{7 - \delta}$ (for H $\parallel$ c) and a low $T_c$ Ca$_3$Rh$_4$Sn$_{13}$, which show anomalous variations in critical current density $J_c(H)$ are presented via tracings of the minor magnetization hysteresis loops using a vibrating sample magnetometer. The sample histories focussed are, (i) the field cooled (FC), (ii) the zero field cooled (ZFC) and (iii) an isothermal reversal of field from the normal state. An understanding of the results in terms of the modulation in the plastic deformation of the elastic vortex solid and supercooling across order-disorder transition is sought.Comment: Presented in IWCC-200