The chemistry of ynol and thioynol ethers

Alkynyl ethers and alkynyl thioethers (‘ynol ethers’ and ‘thioynol ethers’) are appealing building-blocks in synthetic chemistry due to their ease of manipulation and predictable reactivity. Until recently however, their potential has remained underexploited due to difficulties in preparation and isolation. Although recent advances in synthetic chemistry have highlighted various applications for ynol ethers, the equivalent thioynol examples have been rather less exploited despite a unique and fascinating reactivity profile. Although superficially the chemistry of alkynyl ethers and their sulfide counterparts are similar, close examination of their chemistry reveals important differences which can be exploited by the synthetic chemist. This review will examine the preparation of both classes of compound and examine their reactivity to highlight their powerful synthetic applications. Particular focus will be made of thiynol ethers whose chemistry exhibits some fascinating differences compared to their oxygen counterparts and have immense untapped potential for synthetic chemistry

Structure and dielectric properties of polar fluids with extended dipoles: results from numerical simulations

The strengths and short-comings of the point-dipole model for polar fluids of spherical molecules are illustrated by considering the physically more relevant case of extended dipoles formed by two opposite charges $\pm q$ separated by a distance $d$ (dipole moment $\mu=q d$). Extensive Molecular Dynamics simulations on a high density dipolar fluid are used to analyse the dependence of the pair structure, dielectric constant \eps and dynamics as a function of the ratio $d/\sigma$ (\sig is the molecular diameter), for a fixed dipole moment $\mu$. The point dipole model is found to agree well with the extended dipole model up to d/\sig \simeq 0.3. Beyond that ratio, \eps shows a non-trivial variation with d/\sig. When d/\sig>0.6, a transition is observed towards a hexagonal columnar phase; the corresponding value of the dipole moment, \mu^2/\sig^3 k T=3, is found to be substantially lower than the value of the point dipole required to drive a similar transition.Comment: 10 pages, 11 figures; Paper submitted to Molecular Physic

Spectral Classification; Old and Contemporary

Beginning with a historical account of the spectral classification, its refinement through additional criteria is presented. The line strengths and ratios used in two dimensional classifications of each spectral class are described. A parallel classification scheme for metal-poor stars and the standards used for classification are presented. The extension of spectral classification beyond M to L and T and spectroscopic classification criteria relevant to these classes are described. Contemporary methods of classifications based upon different automated approaches are introduced.Comment: To be published in "Principles and Perspectives in Cosmochemistry" Lecture Notes on Kodai School on Synthesis of Elements in Stars: Ed Aruna Goswami & Eswar Reddy, Springer Verlag, 2009, 17 pages, 10 figure

T2{}^2K2{}^2: The Twitter Top-K Keywords Benchmark

Information retrieval from textual data focuses on the construction of vocabularies that contain weighted term tuples. Such vocabularies can then be exploited by various text analysis algorithms to extract new knowledge, e.g., top-k keywords, top-k documents, etc. Top-k keywords are casually used for various purposes, are often computed on-the-fly, and thus must be efficiently computed. To compare competing weighting schemes and database implementations, benchmarking is customary. To the best of our knowledge, no benchmark currently addresses these problems. Hence, in this paper, we present a top-k keywords benchmark, T${}^2$K${}^2$, which features a real tweet dataset and queries with various complexities and selectivities. T${}^2$K${}^2$ helps evaluate weighting schemes and database implementations in terms of computing performance. To illustrate T${}^2$K${}^2$'s relevance and genericity, we successfully performed tests on the TF-IDF and Okapi BM25 weighting schemes, on one hand, and on different relational (Oracle, PostgreSQL) and document-oriented (MongoDB) database implementations, on the other hand

Numerical elimination and moduli space of vacua

We propose a new computational method to understand the vacuum moduli space of (supersymmetric) field theories. By combining numerical algebraic geometry (NAG) and elimination theory, we develop a powerful, efficient, and parallelizable algorithm toextract important information such as the dimension, branch structure, Hilbert series and subsequent operator counting, as well as variation according to coupling constants and mass parameters. We illustrate this method on a host of examples from gauge theory, string theory, and algebraic geometry

Numerical Algebraic Geometry: A New Perspective on String and Gauge Theories

The interplay rich between algebraic geometry and string and gauge theories has recently been immensely aided by advances in computational algebra. However, these symbolic (Gr\"{o}bner) methods are severely limited by algorithmic issues such as exponential space complexity and being highly sequential. In this paper, we introduce a novel paradigm of numerical algebraic geometry which in a plethora of situations overcomes these short-comings. Its so-called 'embarrassing parallelizability' allows us to solve many problems and extract physical information which elude the symbolic methods. We describe the method and then use it to solve various problems arising from physics which could not be otherwise solved.Comment: 36 page

On directed information theory and Granger causality graphs

Directed information theory deals with communication channels with feedback. When applied to networks, a natural extension based on causal conditioning is needed. We show here that measures built from directed information theory in networks can be used to assess Granger causality graphs of stochastic processes. We show that directed information theory includes measures such as the transfer entropy, and that it is the adequate information theoretic framework needed for neuroscience applications, such as connectivity inference problems.Comment: accepted for publications, Journal of Computational Neuroscienc

Phylogeny of Prokaryotes and Chloroplasts Revealed by a Simple Composition Approach on All Protein Sequences from Complete Genomes Without Sequence Alignment

The complete genomes of living organisms have provided much information on their phylogenetic relationships. Similarly, the complete genomes of chloroplasts have helped to resolve the evolution of this organelle in photosynthetic eukaryotes. In this paper we propose an alternative method of phylogenetic analysis using compositional statistics for all protein sequences from complete genomes. This new method is conceptually simpler than and computationally as fast as the one proposed by Qi et al. (2004b) and Chu et al. (2004). The same data sets used in Qi et al. (2004b) and Chu et al. (2004) are analyzed using the new method. Our distance-based phylogenic tree of the 109 prokaryotes and eukaryotes agrees with the biologists tree of life based on 16S rRNA comparison in a predominant majority of basic branching and most lower taxa. Our phylogenetic analysis also shows that the chloroplast genomes are separated to two major clades corresponding to chlorophytes s.l. and rhodophytes s.l. The interrelationships among the chloroplasts are largely in agreement with the current understanding on chloroplast evolution

On finite monoids of cellular automata.

For any group G and set A, a cellular automaton over G and A is a transformation τ:AG→AGτ:AG→AG defined via a finite neighbourhood S⊆GS⊆G (called a memory set of ττ) and a local function μ:AS→Aμ:AS→A. In this paper, we assume that G and A are both finite and study various algebraic properties of the finite monoid CA(G,A)CA(G,A) consisting of all cellular automata over G and A. Let ICA(G;A)ICA(G;A) be the group of invertible cellular automata over G and A. In the first part, using information on the conjugacy classes of subgroups of G, we give a detailed description of the structure of ICA(G;A)ICA(G;A) in terms of direct and wreath products. In the second part, we study generating sets of CA(G;A)CA(G;A). In particular, we prove that CA(G,A)CA(G,A) cannot be generated by cellular automata with small memory set, and, when G is finite abelian, we determine the minimal size of a set V⊆CA(G;A)V⊆CA(G;A) such that CA(G;A)=⟨ICA(G;A)∪V⟩CA(G;A)=⟨ICA(G;A)∪V⟩