Effect of kosmotrope and chaotrope anions on rate and equilibria processes for the α-cyclodextrin catalysed reaction of 3-chloroperbenzoic acid with iodide

Solutes, ranging from small hydrophobic molecules to macromolecular structures such as proteins, are heavily influenced by the presence of salts, particularly the anionic component. It is well known that anions possessing a high charge density, such as sulfate, are able to reduce the solubility of these solutes, with this effect likely to be entropically driven and based on the influence the anions have on the structure of water. Other anions with a lower charge density, such as perchlorate, can have the opposite effect, improving solubility. The current consensus for the latter effect is that rather than being as a result of changes to water structure, it is due to specific binding of the anions to solute molecules, acting to reduce unfavourable interactions with the solvent. In this paper we report on how both sulfate and perchlorate influence binding and catalysis for the α-cyclodextrin mediated reaction of iodide with 3-chloroperbenzoic acid (MCPBA) for which the cyclodextrin–MCPBA complex is the catalytic species. Kinetic runs have been carried out over the temperature range 15–35 °C in dilute nitric acid and with added sulfate and perchlorate, allowing the calculation of enthalpies and entropies for the rate and equilibria processes involved in this system. We show that both sulfate and perchlorate demonstrate the expected Hofmeister behaviours, with sulfate acting to exclude the MCPBA from solution into the cyclodextrin cavity, thus increasing the amount of the catalytic species, whereas perchlorate acts to solubilise the MCPBA. Perchlorate has a complex range of effects, since as well as forming an association complex with cyclodextrin, the thermodynamic parameters indicate that it may also associate with MCPBA and the MCPBA–cyclodextrin complex. These associations may explain the catalysis that is observed with increasing perchlorate concentration. The effects observed in this study may be relevant to other binding processes in chemistry and biology.     

Heparin-cellulose-charcoal composites for drug detoxification prepared using room temperature ionic liquids

We report novel heparin-cellulose-charcoal composites prepared using room temperature ionic liquids (RTILs) to enhance the biocompatibility and blood compatibility of activated charcoal beads while decreasing the size of their active pores.     

Synthesis of organosoluble polyamides with bulky triaryl imidazole pendent group

New unsymmetrical diamine monomer containing triaryl imidazole pendent group,4-[4-(4,5-diphenyl-1H-imidazol-2-yl)phenoxy] -1,3-benzenediamine,was synthesized via aromatic substitution reaction of 1-chloro-2,4-dinitrobenzene with 4-(4,5- diphenyl-1H-imidazol-2-yl)phenol,followed by palladium-catalyzed hydrazine reduction.This new monomer was further confirmed by FT-IR,~1H NMR and ~(13)C NMR.Novel polyamides having pendant triaryl imidazole group were prepared by the phosphorylation polycondensation of fou...     

Spectroscopic studies on 2-[2-(4-methylquinolin-2-yl)hydrazono]-1,2-diphenylethanone molecule and its metal complexes

The electronic absorption spectra of a hydrazone: 2-[2-(4-methylquinolin-2-yl)hydrazono]-1,2-diphenylethanone (BHQ) derived from 2-hydrazino-4-methylquinoline and 1,2-diphenylethan-1,2-dione (benzil) have been studied in various solvents of different polarities. The dependence of the band shift Δύ on the solvent parameters viz. D, Z, E_T, DN, AN, α, β and π* was discussed. Also, the effect of pH on the free hydrazone and its Co(II), Ni(II) and Cu(II) complexes was studied spectrophotometrically in 75% (v/v) dioxane–water in order to determine the dissociation and stability constants. The stoichiometry of the formed complexes was determined by three different methods: Job's, mole ratio and slope ratio which indicate the formation of 1:2, M:L complexes for Co(II) and Cu(II) and 1:1, Ni(II):L. Beer's law is valid in the range 0.32–7.04 μg/mL depending on the type of the metal ion. The use of BHQ as an indicator via a spectrophotometric titration of Cu(II) and Ni(II) with EDTA was efficient.     

An inverse problem of identifying the time-dependent potential in a fourth-order pseudo-parabolic equation from additional condition

The aim of this work is to identify numerically, for the first time, the time-dependent potential coefficient in a fourth-order pseudo-parabolic equation with nonlocal initial data, nonlocal boundary conditions, and the boundary data as overdetermination condition. This problem emerges significantly in the modeling of various phenomena in physics and engineering. From literature we already know that this inverse problem has a unique solution. However, the problem is still ill-posed by being unstable to noise in the input data. For the numerical realization, we apply the quintic B-spline (QB-spline) collocation method for discretizing the pseudo-parabolic problem and the Tikhonov regularization for finding a stable and accurate solution. The resulting nonlinear minimization problem is solved using the MATLAB subroutine lsqnonlin. Moreover, the von Neumann stability analysis is also discussed.