Application of the multi-standard methodology for calculating 1H NMR chemical shifts

Gauge including atomic orbitals (GIAO) (1)H NMR chemical shift calculations have been performed for 66 organic compounds at 72 different levels of theory using the multi-standard approach (MSTD) previously developed for (13)C NMR. This straightforward computational technique involves the combination of methanol and benzene as standards. The studied methodology has been shown to predict (1)H NMR chemical shifts efficiently at different levels of theory.     

Increasing the output length of zero‐error dispersers

Let $\cal{C}$ be a class of probability distributions over a finite set Ω. A function $D : \Omega \mapsto\{0,1\}^{m}$ is a disperser for $\cal{C}$ with entropy threshold $k$ and error $\epsilon$ if for any distribution X in $\cal{C}$ such that X gives positive probability to at least $2^{k}$ elements we have that the distribution $D(X)$ gives positive probability to at least $(1-\epsilon)2^{m}$ elements. A long line of research is devoted to giving explicit (that is polynomial time computable) dispersers (and related objects called “extractors”) for various classes of distributions while trying to maximize m as a function of k. For several interesting classes of distributions there are explicit constructions in the literature of zero‐error dispersers with “small” output length m. In this paper we develop a general technique to improve the output length of zero‐error dispersers. This strategy works for several classes of sources and is inspired by a transformation that improves the output length of extractors (which was given by Shaltiel (CCC'06; Proceedings of the 21st Annual IEEE Conference on Computational Complexity, (2006) 46–60.) building on earlier work by Gabizon, Raz and Shaltiel (SIAM J Comput 36 (2006) 1072–1094). Our techniques are different than those of Shaltiel (CCC'06; Proceedings of the 21st Annual IEEE Conference on Computational Complexity (2006) 46–60) and in particular give non‐trivial results in the errorless case. Using our approach we construct improved zero‐error 2‐source dispersers. More precisely, we show that for any constant $\delta >0$ there is a constant $\eta >0$ such that for sufficiently large n there is a poly‐time computable function $D :\{0,1\}^{n}\times\{0,1\}^{n}\mapsto\{0,1\}^{\eta n}$ such that for every two independent distributions $X_1,X_2$ over $\{0,1\}^{n}$ each with support size at least $2^{\delta n}$ , the output distribution $D(X_1,X_2)$ has full support. This improves the output length of previous constructions by Barak, Kindler, Shaltiel, Sudakov and Wigderson (Proceedings of the 37th Annual ACM Symposium on Theory of Computing (2005) 1–10) and has applications in Ramsey theory and in improved constructions of certain data structures from the work of Fiat and Naor [SIAM J Comput 22 (1993)]. We also use our techniques to give explicit constructions of zero‐error dispersers for bit‐fixing sources and affine sources over polynomially large fields. These constructions improve the best known explicit constructions due to Rao (unpublished data) and Gabizon and Raz [Combinatorica 28 (2008)] and achieve $m=\Omega(k)$ for bit‐fixing sources and $m=k-o(k)$ for affine sources over polynomial size fields. © 2011 Wiley Periodicals, Inc. Random Struct. Alg., 2011     

The singularity in weakly nonlinear fracture mechanics

Material failure by crack propagation essentially involves a concentration of large displacement-gradients near a crack's tip, even at scales where no irreversible deformation and energy dissipation occurs. This physical situation provides the motivation for a systematic gradient expansion of general nonlinear elastic constitutive laws that goes beyond the first order displacement-gradient expansion that is the basis for linear elastic fracture mechanics (LEFM). A weakly nonlinear fracture mechanics theory was recently developed by considering displacement-gradients up to second order. The theory predicts that, at scales within a dynamic lengthscale ℓ from a crack's tip, significant logr displacements and 1/r displacement-gradient contributions arise. Whereas in LEFM the 1/r singularity generates an unbalanced force and must be discarded, we show that this singularity not only exists but is also necessary in the weakly nonlinear theory. The theory generates no spurious forces and is consistent with the notion of the autonomy of the near-tip nonlinear region. The J-integral in the weakly nonlinear theory is also shown to be path-independent, taking the same value as the linear elastic J-integral. Thus, the weakly nonlinear theory retains the key tenets of fracture mechanics, while providing excellent quantitative agreement with measurements near the tip of single propagating cracks. As ℓ is consistent with lengthscales that appear in crack tip instabilities, we suggest that this theory may serve as a promising starting point for resolving open questions in fracture dynamics.     

Subtractive anodic stripping voltammetry with twin identical mercury-film electrodes differing in their convection transport during deposition

Subtractive anodic stripping voltammetry based on the use of different convection rates at the surface of two identical working electrodes during the deposition step is described. Twin mercury-film glassy-carbon disc electrodes, one rotated and one stationary, are used to demonstrate this technique. All background currents arising from nonconvective-dependent sources are effectively compensated. Deposition times of 3–5 min suffice for measuring heavy metal ions at sub-μg ml^-1 concentration levels.     

Determination of nitrate with a flow-injection system combining square-wave polarographic detection with on-line deaeration

The combination of a flow-injection system with square-wave polarography and on-line deaeration is applied to the determination of nitrate, utilizing the catalytic reaction between nitrate and uranyl ion. The method is simple, rapid (60 samples h^?1), sensitive and accurate, with a detection limit of 2 μM nitrate. The method has been applied to the determination of nitrate in drinking and river waters.     

Dynamic storage allocation with known durations

This paper is concerned with a new version of on-line storage allocation in which the durations of all processes are known at their arrival time. This version of the problem is motivated by applications in communication networks and has not been studied previously. We provide an on-line algorithm for the problem with a competitive ratio of O(min{log Δ,log τ}), where Δ is the ratio between the longest and shortest duration of a process, and τ is the maximum number of concurrent active processes that have different durations. For the special case where all durations are powers of two, the competitive ratio achieved is O(loglog Δ).     

Surface reconstruction of chiral glassy oligomers under the action of volatile organic compounds (VOCs)

The response of chiral polymers to volatile organic compounds (VOCs) was studied by atomic force microscopy. It was found that under the influence of toluene vapour, the focal conic domains on the surface of chiral polymer undergo remarkable reconstruction that is at least partially reversible. This opens new ways for building VOC sensors and using surface reconstruction in creating new surface patterns for nanotechnology.