Microwave-assisted synthesis of 1,3-dialkyl ethers of calix[4]arenes: application to the synthesis of cesium selective calix[4]crown-6 ionophores

Partial etherification of phenolic-OH groups of calix[4]arenes with various alkyl halides/tosylates and K₂CO₃ under microwave irradiation afforded 1,3-dialkoxycalix[4]arenes in their cone conformation only as predominant/sole product in good yields (71–85%). The protocol was found to be much superior to conventional heating both in terms of yield and reaction time. Some of the 1,3-dialkoxycalix[4]arenes were elaborated further to the syntheses of cesium selective calix[4]crown-6 ionophores.     

Solvent and Zn2+ Binding Effects on the Photo-physical Properties of (Dibenzoylmethanato)boron Difluoride

Absorption and emission spectroscopic studies of (dibenzoylmethanato)boron difluoride (1bf) in various polar and non-polar, protic and aprotic solvents are reported. The solvatochromic shifts of the spectral bands were examined in terms of solvent properties, including donor and acceptor numbers, followed by multilinear regression in which several solvent parameters were simultaneously analyzed. This π-conjugated positively charged system exhibits excellent solvatochromism. Variations in the electronic absorption spectral characteristics of 1bf were studied in solution in the presence of zinc perchlorate. Absorption spectral studies indicate stable complex formation between the zinc ion and 1bf in the ground state in aprotic dipolar benzonitrile rather than in protic polar solvent methanol. Zinc ion binding of 1bf was theoretically rationalized through frontier molecular orbital interaction.     

Synthesis of 3-keto-quinolines from enaminones,anilines and DMSO: Transition metal free one pot cascade

An efficient and transition metal-free approach for the synthesis of functionalized 3-ketoquinolines from readily available anilines, enaminones and DMSO in the presence of K₂S₂O₈ has been conducted. This one pot tandem reaction proceeds through [3+2+1] cycloaddition reaction involving DMSO, enaminones and amines. In this environmental benign approach, DMSO acts as both a one carbon source and the solvent. A broad range of variously substituted amines and enaminones are successfully employed in this one pot tandem process to access a broad range of substituted 3-ketoquinolines.     

The effect of the finite size of ions and Debye layer overspill on the screened Coulomb interactions between charged flat plates

Screened repulsion between uniformly charged plates with an intervening electrolyte is analyzed for strongly overlapped electrical double layers (EDL), accounting for the steric effect of ions and their expulsion from EDL edges into the surrounding solution. As a generalization of a study by Philipse et al. which does not account for these effects, an analytical expression is derived for the repulsion pressure in the limit of infinitely long plates with a zero-field assumption, which agrees closely with the corresponding numerical solution at low inter-plate separations. Our results show an augmented repulsive pressure for finite-sized ions at strong EDL overlaps. For plates with a finite lateral size, we demonstrate a further extended domain of low inter-plate gaps where the repulsion pressure increases with ion size due to a strong interplay between the steric interaction of ions and the EDL overspill phenomenon, considered earlier in a study by Ghosal & Sherwood limited to the linear Debye-Hückel regime (which cannot account for the steric effect of ions). This investigation on a simple model should enhance our understanding of the interaction between charged particles in electrophoresis, nanoscale self-assembly, active particles, and various other electrokinetic systems.     

Comparison of analytical techniques for purity evaluation of single-walled carbon nanotubes

We compare popular analytical techniques, including scanning and transmission electron microscopy (SEM and TEM), thermogravimetric analysis (TGA), and Raman and near-infrared (NIR) spectroscopy, for the evaluation of the purity of bulk quantities of single-walled carbon nanotubes (SWNTs). Despite their importance as imaging techniques, SEM and TEM are not capable of quantitatively evaluating the purity of typical inhomogeneous bulk SWNT samples because the image frame visualizes less than 1 pg of SWNT material; furthermore, there is no published algorithm to convert such images into numerical data. The TGA technique is capable of measuring the amount of metal catalyst in an SWNT sample, but does not provide an unambiguous separation between the content of SWNTs and carbonaceous impurities. We discuss the utilization of solution-phase near-infrared spectroscopy and solution-phase Raman spectroscopy to quantitatively compare arbitrary samples of bulk SWNT materials of different purities. The primary goal of this paper is to provide the chemical community with a realistic evaluation of current analytical tools for the purity evaluation of a bulk sample of SWNTs. The secondary goal is to draw attention to the growing crisis in the SWNT industry as a result of the lack of quality control and the misleading advertising by suppliers of this material.     

Solution NMR studies of supramolecular complexes of [60]- and [70]fullerenes with mono O-substituted calix[6]arene

Supramolecular complexation of [60]- and [70]fullerenes with 37-allyl-38,39,40,41,42-pentahydroxy-5,11,17,23,29,35-hexa(4-tert butyl)calix[6]arene (I) has been studied in CCl(4) medium by NMR spectrometric method. All of the complexes are found to be stable with 1:1 stoichiometry. Formation constants (K) of the above supramolecular complexes have been determined from systematic variation of NMR chemical shifts of specific protons of I in the presence of [60]- and [70]fullerenes. Trends in the K value suggest that [70]fullerene binds more strongly with I relative to [60]fullerene. Both PM3 and ab initio calculations reveal that the intermolecular interaction in the [70]fullerene/I complex proceeds through quite deep energy minima.     

Mobility-induced instability and pattern formation in a reaction-diffusion system

Ions undergoing a reaction-diffusion process are susceptible to electric field. We show that a constant external field may induce a kind of instability on the state stabilized by diffusion in a reaction-diffusion system giving rise to formation of pattern even when the diffusion coefficients of the reactants are equal. The origin of the pattern is due to the difference in mobilities of the two species and is thus markedly different from that of deformed Turing pattern in presence of the field. While this differential flow instability had been shown earlier to result in traveling waves, we realize in the context of stationary pattern formation in a typical reaction-diffusion-advective system. Our analysis is based on a numerical simulation of a generic model on a two-dimensional domain.     

Coupled solution of the species conservation equations using unstructured finite‐volume method

A coupled solver was developed to solve the species conservation equations on an unstructured mesh with implicit spatial as well as species‐to‐species coupling. First, the computational domain was decomposed into sub‐domains comprised of geometrically contiguous cells—a process similar to additive Schwarz decomposition. This was done using the binary spatial partitioning algorithm. Following this step, for each sub‐domain, the discretized equations were developed using the finite‐volume method, and solved using an iterative solver based on Krylov sub‐space iterations, that is, the pre‐conditioned generalized minimum residual solver. Overall (outer) iterations were then performed to treat explicitness at sub‐domain interfaces and nonlinearities in the governing equations. The solver is demonstrated for both two‐dimensional and three‐dimensional geometries for laminar methane–air flame calculations with 6 species and 2 reaction steps, and for catalytic methane–air combustion with 19 species and 24 reaction steps. It was found that the best performance is manifested for sub‐domain size of 2000 cells or more, the exact number depending on the problem at hand. The overall gain in computational efficiency was found to be a factor of 2–5 over the block (coupled) Gauss–Seidel procedure. All calculations were performed on a single processor machine. The largest calculations were performed for about 355 000 cells (4.6 million unknowns) and required 900 MB of peak runtime memory and 19 h of CPU on a single processor. Copyright © 2009 John Wiley & Sons, Ltd.