A general treatment of solubility. 3. Principal component analysis (PCA) of the solubilities of diverse solutes in diverse solvents

A phenomenological study of solubility has been conducted using a combination of quantitative structure-property relationship (QSPR) and principal component analysis (PCA). A solubility database of 4540 experimental data points was used that utilized available experimental data into a matrix of 154 solvents times 397 solutes. Methodology in which QSPR and PCA are combined was developed to predict the missing values and to fill the data matrix. PCA on the resulting filled matrix, where solutes are observations and solvents are variables, shows 92.55% of coverage with three principal components. The corresponding transposed matrix, in which solvents are observations and solutes are variables, showed 62.96% of coverage with four principal components.     

Lewis Acid Assisted Nickel‐Catalyzed Cross‐Coupling of Aryl Methyl Ethers by C−O Bond‐Cleaving Alkylation: Prevention of Undesired β‐Hydride Elimination

In the presence of trialkylaluminum reagents, diverse aryl methyl ethers can be transformed into valuable products by C?O bond‐cleaving alkylation, for the first time without the limiting β‐hydride elimination. This new nickel‐catalyzed dealkoxylative alkylation method enables powerful orthogonal synthetic strategies for the transformation of a variety of naturally occurring and easily accessible anisole derivatives. The directing and/or activating properties of aromatic methoxy groups are utilized first, before they are replaced by alkyl chains in a subsequent coupling process.     

The asymptotically commuting bounded approximation property of Banach spaces

We introduce and study the asymptotically commuting bounded approximation property of Banach spaces. This property is, e.g., enjoyed by any dual space with the bounded approximation property. The principal result is the following: if a Banach space X has the asymptotically λ-commuting bounded approximation property, then X is saturated with locally λ-complemented separable subspaces enjoying the λ-commuting bounded approximation property.     

Selective ortho-Functionalization of Adamantylarenes Enabled by Dispersion and an Air-Stable Palladium(I) Dimer

Contrary to the general belief that Pd-catalyzed cross-coupling at sites of severe steric hindrance are disfavored, we herein show that the oxidative addition to C−Br ortho to an adamantyl group is as favored as the corresponding adamantyl-free system due to attractive dispersion forces. This enabled the development of a fully selective arylation and alkylation of C−Br ortho to an adamantyl group, even if challenged with competing non-hindered C−OTf or C−Cl sites. The method makes use of an air-stable Pd^I dimer and enables straightforward access to diversely substituted therapeutically important adamantylarenes in 5–30 min.     

The role of porosity in char combustion

A detailed study has been conducted on the nature of porosity developed during the combustion of chars prepared from different coals, and how this relates to the apparent reactivity of the char towards oxygen. An Illinois No. 6 coal char and a Wyodak coal char have been examined in both Zone I and Zone II conditions (intrinsic rate control and diffusional mass transfer zones, respectively). These results strongly suggest that there exists some amount of free volume in a char that has not been burned off. Such an unburned char does not reveal much porosity when standard nitrogen adsorption is applied, but rapidly develops such porosity upon burnoff. The free volume opens, but is not truly accessible to reactant gases. It appears likely, based upon the present results, that the only truly available surface for reaction exists in pores larger than 10–15 Å.     

On combustion in a closed rectangular channel with initial vorticity

This article examines the detailed combustion process in a theoretical model with applicability to combustion in a wave rotor or wave disc engine. The model comprises a single channel into which an initial loading of methane and air is admitted and ignited after all inlet and exit ports have been closed. Combustion takes place at constant volume. However, the initial gaseous mixture in the channel is not at rest. The initial opening and closing of the ports generates significant vorticity which influences the evolution of the combustion process. Numerical evaluations are provided for the detailed flame shape for simplified (one-step) chemistry and a simulation using the detailed 235-step San Diego scheme. Quantities examined are the evolution of vorticity, pressure fluctuations, mass consumption rate, flame surface area and the influences on combustion of adiabatic and non-adiabatic channel walls. Combustion regimes are identified and compared with simpler model studies (no initial flow). Pointwise quantities are examined to describe the various stages of burning in the channel. The focus of the study is directed towards quantities that influence overall burning rate and completeness of combustion.     

Efficient method of finding scaling exponents from finite-size Monte-Carlo simulations

Monte-Carlo simulations are routinely used for estimating the scaling exponents of complex systems. However, due to finite-size effects, determining the exponent values is often difficult and not reliable. Here, we present a novel technique of dealing with the problem of finite-size scaling. This new method allows not only to decrease the uncertainties of the scaling exponents, but makes it also possible to determine the exponents of the asymptotic corrections to the scaling laws. The efficiency of the technique is demonstrated by finding the scaling exponent of uncorrelated percolation cluster hulls.     

The Effect of TiO2 Catalyst on the NO Reduction by Barrier Discharge in Nitrogen

The study investigated NO reduction by N radicals produced by barrier discharge in nitrogen and the possible effect of TiO₂ catalyst on this reaction. The experiments for NO reduction were carried out at temperatures ranging from room temperature to 140 °C and at NO concentrations ranging from 200 to 800 ppm. The experimental results were described by a model which was based on six main reactions for the calculation of the NO and NO₂ concentrations. The analysis of model suggested two simple methods for the estimation of nitrogen radical production efficiency which in present study was 2 ppm/(J/L). The model also confirmed that N radicals are used very efficiently in the reduction of NO and this process can’t be improved by the catalyst. Nonetheless, experiments showed that the presence of TiO₂ catalyst improved the removal of NO. The experimental results can be explained by surface processes taking place with NO₂ with the help of other plasma produced nitrogen species.

     

Motional narrowing of broadband absorption of solvatochromic indicator Betaine 30

Temperature dependence of the absorption spectra of Betaine 30 (2,6-diphenyl-4-(2,4,6-triphenylpyridinio)-phenolate, widely known as Reichardt's dye) is compared with that of the broadband spectra of other dyes. The double value of the half-width (2 hwhm) of Betaine 30 absorption band between 10 and 293 K in a polymer decreases by 130±20 cm⁻¹, from 4220 to 4090 cm⁻¹. This unprecedented narrowing with increasing temperature is ascribed to hydrogen bond symmetrization due to thermally activated proton tunneling in a pigment-solvent complex. The averaging of charge distribution along the proton coordinate causes motional narrowing of inhomogeneous width.