OptDesign: extending optimizable k-dissimilarity selection to combinatorial library design

Optimizable k-dissimilarity (OptiSim) selection entails drawing a series of subsamples of size k from a population and choosing the "best" candidate from each such subsample for inclusion in the selection set. By varying the size of the subsample, one can control the balance between representativeness and diversity in the selection set obtained. In the original formulation, a uniform random sampling from among valid candidates was used to draw the subsamples from a single target population. Here we describe in detail two key modifications that serve to extend the OptiSim methodology to vector selection for interdependent variables, specifically as applied to the design of combinatorial sublibraries. The first modification involves pivoting between variables: subsamples are drawn from each reagent pool in turn, with the viability of each candidate being evaluated in isolation as well as in terms of the products it will produce from complementary reagents already selected. The filters applied may be static or dynamic in nature, with molecular weight and hydrophobicity being examples of the former and structural diversity with respect to reagents already selected being an example of the latter. The second key modification is adding the ability to bias the selection of candidate reagents for inclusion in the subsamples. Taken together, these modifications support the efficient generation of multiblock and other sparse matrix designs that are both representative and diverse, and for which "backfilling" of designs edited to remove undesirable reagents or products is straightforward. The method is intrinsically fast and efficient, since enumeration of the full combinatorial is not required- only those candidates actually considered for inclusion need be evaluated. Moreover, because the subsample selection step is separate from the diversity-based selection of the "best" candidate, incorporating such bias in favor of a competing criterion such as low price provides a "natural," nonparametric mechanism for generating designs that are likely to be "good" in a double-objective, Pareto sense.     

Two New Pseudoguaianolides from the Flowers of Parthenium hysterophorus

Chemical investigation on two samples of the flowers of Parthenium hysterophorus afforded two new pseudoguaianolides (one from each sample) together with several known constituents. The structures of the new compounds were established by extensive spectroscopic (1D‐ and 2D‐NMR) studies. The X‐ray crystallographic analysis of one of these compounds was also accomplished.     

A dual‐weighted trust‐region adaptive POD 4‐D Var applied to a finite‐volume shallow water equations model on the sphere

In this paper we study solutions of an inverse problem for a global shallow water model controlling its initial conditions specified from the 40‐yr ECMWF Re‐analysis (ERA‐40) data sets, in the presence of full or incomplete observations being assimilated in a time interval (window of assimilation) with or without background error covariance terms. As an extension of the work by Chen et al. (Int. J. Numer. Meth. Fluids 2009), we attempt to obtain a reduced order model of the above inverse problem, based on proper orthogonal decomposition (POD), referred to as POD 4D‐Var for a finite volume global shallow water equation model based on the Lin–Rood flux‐form semi‐Lagrangian semi‐implicit time integration scheme. Different approaches of POD implementation for the reduced inverse problem are compared, including a dual‐weighted method for snapshot selection coupled with a trust‐region POD adaptivity approach. Numerical results with various observational densities and background error covariance operator are also presented. The POD 4‐D Var model results combined with the trust‐region adaptivity exhibit similarity in terms of various error metrics to the full 4D Var results, but are obtained using a significantly lesser number of minimization iterations and require lesser CPU time. Based on our previous and current work, we conclude that POD 4‐D Var certainly warrants further studies, with promising potential of its extension to operational 3‐D numerical weather prediction models. Copyright © 2011 John Wiley & Sons, Ltd.     

Thermolysis studies on platinacycloalkane complexes

Thermal decomposition studies on platinacycloalkanes of the type Pt(CH₂)_mL₂ (where m = 6,7,8,10 and L₂ = dppp {1,3-bis(diphenylphosphino)propane}, dppe {1,2-bis(diphenylphosphino)ethane} or L = PPh₃, ^tBu₃P) are described. The results reveal that the organic product distribution depends on various factors such as the nature of ligand, the metal system, the mode of decomposition, the ring size and the temperature. Possible mechanistic pathways for the formation of various products are discussed. These platinacycloalkanes can be used as models for metallacycloalkane intermediates in catalytic reactions.     

X-ray difffraction studies on samarium up to one megabar pressure

Abstract

High—pressure crystal structure studies have been performed on Sm up to 100 GPa using synchrotron x-radiation and a diamond anvil cell. The structural sequence Sm-dhcp-fcc-dist.fcc has been confirmed. There is no evidence of any volume collapse. The bulk modulus and its pressure derivative have been determined (B₀ = 30.7 GPa, B₀’ = 2.5).     

Melting of lead and zinc to 60 kbar

The melting curves for lead and zinc were determined to 60 kbar. Our melting data for lead is in good agreement with that of Millet up to 22 kbar, beyond which Millet's values are significantly higher than ours. The melting curve for zinc is almost linear to 60 kbar and our values are lower than the values reported by other workers. The melting relationship proposed by Kennedy as well as the Lindemann law have been examined in the light of the new melting data for these two metals. A straight line can be fitted through the T_m vs ΔV/V₀ plots for zinc within the limits of experimental precision, but the data for lead shows a departure from the straight line fit. The lead melting curve is concave toward the T_m axis, as predicted by the Lindermann law and, in this respect, resembles previously studied Van der Waals solids.     

Ultrahigh pressure equation of state of CaS to 1.5 Mbar

Abstract

Energy Dispersive X-ray Diffraction (EDXD) was performed at room temperature to gather structural data on CaS between approximately 1.7 GPa to nearly 150GPa. In these experiments, CaS retained the B1 structure up to approximately 40 GPa above which it began to transform to the B2 structure. The B2 structure remained stable to the highest pressure reached, 149 GPa, where the relative volume V/V₀ was 0.490. Previous studies on CaS extended only up to 52 GPa, which is barely 10 GPa after the B1 phase changes to the B2 structure. Thus it was not possible to accurately extrapolate the equation of state (EOS) for the B2 phase region to significantly higher pressures. In the present study EOS data for CaS was collected to 150 GPa and no other structural change was observed. EOS parameters for the B1 and B2 phase regions agree well with values reported in the literature.     

Two-photon holographic recording in aluminosilicate glass containing silver particles

Recording of holographic gratings by 532-nm laser pulses in photochromic bulk aluminosilicate glass containing silver particles is demonstrated. A diffraction efficiency of 1.5% is achieved for readout at the same wavelength. The speed of grating formation as a function of pulse energy suggests that two-photon excitation is responsible for the recording. The light causes bleaching of an absorption peak near 417nm, which corresponds to the excitation of surface plasmons on the silver, and broad darkening throughout the visible to the near infrared. A likely mechanism for the photochromic effect is discussed.     

Synthesis, structure and some reactions of (C5Me4hex)2Ru2(CO)4

The synthesis of the new cyclopentadiene, C₅Me₄(hex)H is described and its reaction with Ru₃(CO)₁₂ to yield (C₅Me₄hex)₂Ru₂(CO)₄ (hex = n-hexyl) is reported. The X-ray crystal structure of the dimer confirms the structure with bridging and terminal CO groups. Reactions of the dimer to yield (C₅Me₄hex)Ru(CO)₂X (X = Cl, Br, I) are reported. IR, NMR and mass spectra are reported for all new compounds. The solubility of the dimer is found to be 10 times greater than that for (C₅Me₅)₂Ru₂(CO)₄.