Zeolite-mediated photochemical charge separation using a surface-entrapped ruthenium-polypyridyl complex

Employing the strategy of quaternization of the 2,2' N atoms of the conjugated bipyridine ligand 1,4-bis[2-(4'-methyl-2,2'-bipyrid-4-yl)ethenyl]benzene (L), a polypyridyl complex of ruthenium(II) was tethered on the surface of zeolite Y. Electrochemical and spectroscopic properties of the complex suggest that, upon visible photoexcitation of the MLCT band, the electron is localized on the conjugated ligand rather than the bipyridines. Electron transfer from the surface complex to bipyridinium ions (methyl viologen) within the zeolite was observed. Visible light photolysis of the ruthenium-zeolite solid ion-exchanged with diquat and suspended in a propyl viologen sulfonate solution led to permanent formation of the blue propyl viologen sulfonate radical ion in solution. The model that is proposed involves intrazeolitic charge transfer to ion-exchanged diquat followed by interfacial (zeolite to solution) electron transfer to propyl viologen sulfonate in solution. Because of the slow intramolecular back-electron-transfer reaction and the forward electron propagation via the ion-exchanged diquat, Ru(III) is formed. This Ru(III) complex formed on the zeolite is proposed to react rapidly with water in the presence of light, followed by reaction with the propyl viologen sulfonate, to form pyridones and regeneration of Ru(II), which then continues the photochemical process.     

A family of vanadate esters of monoionized and diionized aromatic 1,2-diols: synthesis,structure, and redox activity

The concerned diols (general abbreviation, H(2)L) are catechol (H(2)L(1)) and its 3,5-Bu(t)(2) derivative (H(2)L(2)). Esters of the type VO(xsal)(HL), 2, are obtained by reacting H(2)L with VO(xsal)(H(2)O) or VO(xsal)(OMe)(HOMe), where xsal(2-) is the diionized salicylaldimine of glycine (x = g), L-alanine (x = a), or L-valine (x = v). The reaction of VO(acac)(2) with H(2)L and the salicylaldimine (Hpsal) of 2-picolylamine has furnished VO(psal)(L), 3. In the structures of VO(gsal)(HL(1)), 2a, and VO(vsal)(HL(2)), 2f, the HL(-) ligand is O,O-chelated, the phenolic oxygen lying trans to the oxo oxygen atom. The xsal(2-) coligand has a folded structure and the conformation of 2f is exclusively endo. In both 2a and 2f the phenolic oxygen atom is strongly hydrogen bonded (O...O, 2.60 A) to a carboxylic oxygen atom of a neighboring molecule. In VO(psal)(L(2)).H(2)O, 3b, the diionized diol is O,O-chelated to the metal and the water molecule is hydrogen bonded to a phenoxidic oxygen atom (O.O, 2.84 A). The C-O and C-C distances in the V(diol) fragment reveal that 2 is a pure catecholate and 3 is a catecholate-semiquinonate hybrid. In solution each ester gives rise to a single (51)V NMR signal (no diastereoisomers), which generally shifts downfield with a decrease in the ester LMCT band energy. The V(V)/V(IV) and catecholate-semiquinonate reduction potentials lie near -0.75 and 0.35, and 1.10 and 0.70 V vs SCE for 2 and 3, respectively. Molecular oxygen reacts smoothly with 2 quantitatively furnishing the corresponding o-quinone, and in the presence of H(2)L the reaction becomes catalytic. In contrast, type 3 esters are inert to oxygen. The initial binding of O(2) to 2 is proposed to occur via hydrogen bonding with chelated HL(-).     

Synthesis of chiral 4-hydroxy-2,3-unsaturated carbonyl compounds from 3,4-epoxy alcohols by oxidation: application in the formal synthesis of macrosphelide A

An interesting transformation during the oxidation of 3,4-epoxy alcohols 1a-d, derived from the corresponding homoallylic alcohols, led to the formation of 4-hydroxy-2,3-unsaturated carbonyls 2a-d in very good yields. One of these products 2c was transformed into the functionalised carboxylic acid 5, an advanced stage intermediate from which the total synthesis of macrosphelide A has been reported.     

Amino Acid based cationic surfactants in aqueous solution: physicochemical study and application of supramolecular chirality in ketone reduction

The present study provides a molecular understanding of the origin of the chirality in aqueous micelles and its correlation with the proficiency of stereoselective ketone reduction. The effects of varied headgroup architecture on the surface-active properties as well as on other microstructural parameters were studied and correlated to the structural differences of these naturally occurring amino acid containing surfactants (1-4). Micropolarity sensed by pyrene showed that the micelles prepared using 1-4 are mostly hydrated; particularly large headgroup size surfactant produces more polar environment. A theoretical study was done to quantify the varied spatial dissymmetry for all four surfactants. Asymmetric reduction of prochiral ketones was carried out at the aqueous micellar interface of these chiral amphiphiles by exploiting the supramolecular chirality as evidenced from a circular dichroism study. The enantioselectivity of the reduction process is rationally improved through increase in spatial dissymmetry and steric constraint imposed at the micellar interface by the polar head of surfactants.     

Studies of carbazole-based polyarylates

A low temperature solution condensation method with pyridine as acceptor-catalytic reagent was applied to the synthesis of polyarylates from carbazole and bisphenol A/phenolphthalein. The polyarylates were classified with respect to their structure, thermal stability, and dielectric behavior.     

Determination of critical micelle concentration by hyper-rayleigh scattering

The critical micelle concentration (CMC) of several surfactants that contain an NLO chromophore, either at the hydrocarbon tail, or at the hydrophilic headgroup, or even as a counterion, was determined by hyper-Rayleigh scattering (HRS). In all cases, the HRS signal exhibited a similar variation with surfactant concentration, wherein the CMC is inferred from a rather unprecedented drop in the signal intensity. This drop is attributed to the formation of small pre-micellar aggregates, whose concentrations become negligible above CMC. In addition, a probe molecule, which upon protonation yielded a species with significantly enhanced HRS intensity, was developed and its utility for the determination of the CMC of simple fatty acids was demonstrated.     

Thermodynamics of silver—silver halide electrodes and thermodynamic solubility products of silver halides in glycerol + water mixtures at different temperatures

The standard potentials of silver—silver bromide and silver—silver iodide electrodes in glycerol+water mixtures containing 5, 10, 20 and 30 wt% glycerol were determined from electromotive force measurements of the cell Ag(s), AgX(s), KX(c)//KCl(c), AgCl(s), Ag(s), where X is Br or I, at seven different temperatures in the range 5–35°C. The standard potentials in each solvent are represented as a function of temperature. The standard thermodynamic functions for the electrode reactions, the primary medium effects of various solvents upon X⁻, and the standard thermodynamic quantities for the transfer of 1 g-ion of X⁻ from water to the respective glycerol + water media are evaluated and discussed in the light of ion—solvent interactions as well as the structural changes of the solvents. From the values of the Ag/Ag⁺ and Ag/AgX, X⁻ electrodes, the thermodynamic solubility product constants of silver chloride, silver bromide and silver iodide have been determined in glycerol + water solvent mixtures at different temperatures.     

Studies of vulcanization with tetramethylthiuram disulfide and sulfur vulcanization accelerated by tetramethylthiuram disulfide of styrene–butadiene rubber in presence and absence of dicumyl peroxide

The salient features of nonelemental sulfur vulcanization by tetramethylthiuram disulfide (TMTD) and elemental sulfur vulcanization promoted by TMTD both in presence and absence of ZnO and stearic acid have been studied. In stock containing TMTD, a higher rate constant value for dicumyl peroxide (DCP) decomposition was observed. TMTD decreases the crosslinking density due to DCP depending on its concentration. An entirely radical mechanism has been advanced in the absence of ZnO. ZnO or ZnO–stearic acid seems to alter the entire course of reaction. The rate of crosslinking increases in the presence of ZnO or ZnO–stearic acid. Moreover, crosslinks are formed additively (further supported from the activation energy data), and mixed crosslink formation has been confirmed by the methyl iodide test of the vulcanizates. Stearic acid has no effect on crosslink formation. An ionic chain mechanism has been postulated in the presence of ZnO, as suggested by British authors.     

Arsenic speciation in aqueous samples using a selective As(III)/As(V) preconcentration in combination with an automatable cryotrapping hydride generation procedure for monomethylarsonic acid and dimethylarsinic acid

Differentiation between As(III) and As(V) is accomplished using earlier developed selective preconcentration methods (carbamate and molybdate mediated (co)precipitation of As(III) and As(V) respectively) follewed by AAS detection of the (co)precipitates. Apart from this, separation of methylated arsenic species is performed by an automatable system comprising a continuous flow hydride generation unit in which monomethylarsonic acid (MMAA) and dimethylarsinic acid (DMAA) are converted into their corresponding volatile methylarsines, monomethylarsine (MMA) and dimethylarsine (DMA) respectively. These species are cryogenically trapped in a Teflon-line stainless stell U-tube packed with a gas chromatographic solid-phase and subsequently separated by selective volatilization. A novel gas drying technique by means of a Perma Pure dryer was applied successfully prior to trapping. Detection is by atomic absorption spectrometry (AAS). MMAA and DMAA are determined with absolute limits of detection of 0.2 and 0.5 ng, respectively. Investigation of the behaviour of the methylarsines in the system was conducted with synthesized⁷³As labeled methylated arsenic species. It was found that MMA is taken through the system quantitatively whereas DMA is recovered for about 85%. The opumized system combined with selective As(III)/As(V) preconcentration has been tested out for arsenic speciation of sediment interstitial water from the Chemiehaven at Rotterdam. The obtained concentrations are 28.5, 26.8 and 0.60 ng·ml^–1 for As(III), As(V) and MMAA, respectively, whereas the DMAA concentration was below 0.16 ng·ml^–1.