Reactivity Of Pph3 Toward Ruiiruiiicl(O2car)4 - Syntheses, Molecular-Structures, And Spectroscopic And Electrochemical Properties Of Ruiiruiii(Oh2)Cl(Mecn)(O2car)4(Pph3)2 And Ruii2(Oh2)(Mecn)2(O2car)4(Pph3)2

By the reaction of Ru2Cl(O2CAr)4 (1) and PPh3 in MeCN-H2O the diruthenium(II,III) and diruthenium(II) compounds of the type Ru2(OH2)Cl(MeCN)(O2CAr)4(PPh3)2 (2) and Ru2(OH2)(MeCN)2(O2CAr)4(PPh3)2 (3) were prepared and characterized by analytical, spectral, and electrochemical data (Ar is an aryl group, C6H4-p-X; X = H, OMe, Me, Cl, NO2). The molecular structure of Ru2(OH2)Cl(MeCN)(O2CC6H4-p-OMe)4(PPh3)2 was determined by X-ray crystallography. Crystal data are as follows: triclinic, P1BAR, a = 13.538 (5) angstrom, b = 15.650 (4) angstrom, c = 18.287 (7) angstrom, alpha = 101.39 (3)-degrees, beta = 105.99 (4)-degrees, gamma = 97.94 (3)-degrees, V = 3574 angstrom 3, Z = 2. The molecule is asymmetric, and the two ruthenium centers are clearly distinguishable. The Ru(III)-Ru(II), Ru(III)-(mu-OH2), and Ru(II)-(mu-OH2) distances and the Ru-(mu-OH2)-Ru angle in [{Ru(III)Cl(eta-1-O2CC6H4-p-OMe)(PPh3)}(mu-OH2)(mu-O2CC6H4-p-OMe)2{Ru(II)(MeCN)(eta-1-O2CC6H4-p-OMe)(PPh3)}] are 3.604 (1), 2.127 (8), and 2.141 (10) angstrom and 115.2 (5)-degrees, respectively. The compounds are paramagnetic and exhibit axial EPR spectra in the polycrystalline form. An intervalence transfer (IT) transition is observed in the range 900-960 nm in chloroform in these class II type trapped mixed-valence species 2. Compound 2 displays metal-centered one-electron reduction and oxidation processes near -0.4 and +0.6 V (vs SCE), respectively in CH2Cl2-TBAP. Compound 2 is unstable in solution phase and disproportionates to (mu-aquo)diruthenium(II) and (mu-oxo)diruthenium(III) complexes. The mechanistic aspects of the core conversion are discussed. The molecular structure of a diruthenium(II) compound, Ru2(OH2)(MeCN)2(O2CC6H4-p-NO2)4(PPh3)2.1.5CH2Cl2, was obtained by X-ray crystallography. The compound crystallizes in the space group P2(1)/c with a = 23.472 (6) angstrom, b = 14.303 (3) angstrom, c = 23.256 (7) angstrom, beta = 101.69 (2)-degrees, V = 7645 angstrom 3, and Z = 4. The Ru(II)-Ru(II) and two Ru(II)-(mu-OH2) distances and the Ru(II)-(mu-OH2)-Ru(II) angle in [{(PPh3)-(MeCN)(eta-1-O2CC6H4-p-NO2)Ru}2(mu-OH2)(mu-O2CC6H4-p-NO2)2] are 3.712 (1), 2.173 (9), and 2.162 (9) angstrom and 117.8 (4)-degrees, respectively. In both diruthenium(II,III) and diruthenium(II) compounds, each metal center has three facial ligands of varying pi-acidity and the aquo bridges are strongly hydrogen bonded with the eta-1-carboxylato facial ligands. The diruthenium(II) compounds are diamagnetic and exhibit characteristic H-1 NMR spectra in CDCl3. These compounds display two metal-centered one-electron oxidations near +0.3 and +1.0 V (vs SCE) in CH2Cl2-TBAP. The overall reaction between 1 and PPh3 in MeCN-H2O through the intermediacy of 2 is of the disproportionation type. The significant role of facial as well as bridging ligands in stabilizing the core structures is observed from electrochemical studies.

Bridging the Ruddlesden–Popper and the Dion–Jacobson series of layered perovskites: synthesis of layered oxides, A2–xLa2Ti3–xNbxO10(A = K, Rb), exhibiting ion exchange

Solid solutions of the formula, A2–xLa2Ti3–xNbxO10(A = K, Rb), exist for the range 0[less-than-or-eq]x[less-than-or-eq]1.0, bridging n= 3 members of the Ruddlesden–Popper series (A2La2Ti3O10) and the Dion–Jacobson series (ALa2Ti2NbO10). For 0[less-than-or-eq]x[less-than-or-eq]0.75, the phases possess body-centred structures characteristic of the Ruddlesden–Popper phases, while the x= 1 members are isostructural with KCa2Nb3O10(A = K) and CsCa2Nb3O10(A = Rb). Protonated derivatives, H2–xLa2Ti3–xNbxO10, which are prepared by ion exchange, retain the structural difference of the parent phases. A difference in the Brønsted acidity of the protonated derivatives revealed by intercalation experiments with organic bases seems to be related to this structural difference.

Consistency limits behavior of bentonites exposed to sea water

This article examines the changes in interparticle forces brought about on prolonged contact (1 year period) of a bentonite clay with artificial seawater. The study is undertaken with the purpose of identifying the physico-chemical factors that impart a nonswelling character to smectite clays deposited in marine environments. Results show that equilibration of the bentonite clay with artificial seawater (total pore salinity approximately 42 gL-1) for a 1 year period does not lead to any mineralogical changes in the clay specimens; however, their exchangeable cation positions become prominently dominated by magnesium ions. The consistency limits of the seawater-equilibrated bentonite was determined on stepwise leaching to lower salinities. The predominance of diffuse double-layer repulsion forces in the pore salt concentration range of 42 gL-1 to 1.1 gL-1 caused an increase in the liquid limits of the seawater-equilibrated bentonite specimens on reducing the salinity in the corresponding range (42 gL-1 to 1.1 gL-1). The attraction forces, however, prevail over the repulsion forces at salt concentrations <1.1 gL-1 and cause a decrease in liquid limit of the clay specimens with reduction in pore salinity, which is typical of nonswelling clays. The attraction forces cause aggregation of the clay unit layers into domains that break down on sodium saturation of the clay specimens. It is inferred that the physico-chemical factors responsible for the nonswelling character of the seawater-equilibrated bentonite specimens at pore salt concentrations below 1.1 gL-1 are inadequate to explain the nonswelling character of smectite-rich Ariake marine clays. The lower consistency limits of the Ariake marine clays in comparison to the nonswelling character, seawater-equilibrated bentonite specimens is attributed to a relative deficiency of interparticle forces in the Ariake marine clay.

Antiulcerogenic activity of Terminalia chebula fruit in experimentally induced ulcer in rats

Objective: The present study is to evaluate the antiulcer effect of hydroalcoholic (70%) extract of Terminalia chebula fruit. Materials and methods: Aspirin, ethanol and cold restraint stress-induced ulcer methods in rats were used for the study. The effects of the extract on gastric secretions, pH, total and free acidity using pylorus ligated methods were also evaluated. Results: Animals pretreated with doses of 200 and 500 mg/kg hydroalcoholic extract showed significant reduction in lesion index, total affected area and percentage of lesion in comparison with control group (P < 0.05 and P < 0.01) in the aspirin, ethanol and cold restraint stress-induced ulcer models. Similarly extracts increased mucus production in aspirin and ethanol-induced ulcer models. At doses of 200 and 500 mg/kg of T. chebula extract showed antisecretory activity in pylorus ligated model, which lead to a reduction in the gastric juice volume, free acidity, total acidity, and significantly increased gastric pH. Discussion and conclusion: These findings indicate that hydroalcoholic extract of the fruit T. chebula displays potential antiulcerogenic activity. This activity thus lends pharmacological credence to the suggested use of the plant as a natural remedy in the treatment or management of ulcer.

Soft-chemical routes to synthesis of solid oxide materials

We describe three different families of metal oxides, viz., (i) protonated layered perovskites, (ii) framework phosphates of NASICON and KTiOPO4 (KTP) structures and (iii) layered and three-dimensional oxides in the H-V-W-O system, synthesized by 'soft-chemical' routes involving respectively ion-exchange, redox deinteracalation and acid-leaching from appropriate parent oxides. Oxides of the first family, HyA2B3O10(A = La/Ca; B = Ti/Nb), exhibit variable Bronsted acidity and intercalation behaviour that depend on the interlayer structure. V2(PO4)3 prepared by oxidative deintercalation from Na3V2(PO4)3 is a new host material exhibiting reductive insertion of lithium/hydrogen, while K0.5Nb0.5 M0.5OPO4(M = Ti, V) are novel KTP-like materials exhibiting second harmonic generation of 1064 nm radiation. HxVxW1-xO3 for x = 0.125 and 0.33 possessing alpha-MoO3 and hexagonal WO3 structures, prepared by acid-leaching of LiVWO6, represent functionalized oxide materials exhibiting redox and acid-base intercalation reactivity.

Potential-distance relationships of clay-water systems considering the Stern theory

This paper deals with the use of Stem theory as applied to a clay-water electrolyte system, which is more realistic to understand the force system at micro level man the Gouy-Chapman theory. The influence of the Stern layer on potential-distance relationship has been presented quantitatively for certain specified clay-water systems and the results are compared with the Gouy-Chapman model. A detailed parametric study concerning the number of adsorption spots on the clay platelet, the thickness of the Stern layer, specific adsorption potential and the value of dielectric constant of the pore fluid in the Stern layer, was carried out. This study investigates that the potential obtained at any distance using the Stern theory is higher than that obtained by the Gouy-Chapman theory. The hydrated size of the ion is found to have a significant influence on the potential-distance relationship for a given clay, pore fluid characteristics and valence of the exchangeable ion.

The intercalation reaction of pyridine with manganese thiophosphate, MnPS3

The intercalation of pyridine in the layered manganese thiophosphate, MnPS3, has been examined in detail by a variety of techniques. The reaction is interesting since none of the anticipated changes in optical and electrical properties associated with intercalation of electron donating molecules is observed. The only notable change in the properties of the host lattice is in the nature of the low-temperature magnetic ordering; while MnPS3 orders antiferromagnetically below 78 K, the intercalated compound shows weak ferromagnetism probably due to a canted spin structure. Vibrational spectra clearly show that the intercalated species are pyridinium ions solvated by neutral pyridine molecules. The corresponding reduced sites of the host lattice, however, were never observed. The molecules in the solvation shell are exchangeable. Although the reaction appears to be topotactic and reversible, from XRD, a more detailed analysis of the products of deintercalation reveal that it is not so. The intercalation proceeds by an ion exchange/intercalation mechanism wherein the intercalated species are pyridinium ions solvated by neutral molecules with charge neutrality being preserved not by electron transfer but by a loss of Mn2+ ions from the lattice. The experimental evidence leading to this conclusion is discussed and it is shown that this model can account satisfactorily for the observed changes (or lack of it) in the optical, electrical, vibrational, and magnetic properties.

Laboratory studies on the volume change characteristics of kaolinite contaminated with sodium phosphate/sulfate

Reported distress to an industrial structure from phosphate/sulfate contamination of kaolinitic foundation soil at an industrial location in Southern India prompted this laboratory study. The study examines the short-term effect of sodium sulfate/phosphate contamination on the swell/compression characteristics of a commercial kaolinite. Experimental results showed that the unsaturated contaminated kaolinite specimens exhibited slightly higher swell potentials and lower compressions than the unsaturated uncontaminated kaolinite specimens. It is suggested that the larger double layer promoted by the increased exchangeable sodium ion concentration is responsible for the slightly higher swell potentials and lower compressions of the unsaturated contaminated kaolinite specimens.

Mechanisms controlling the undrained strength behavior of remolded Ariake marine clays

The soft clay of Ariake Bay, in western Kyushu, Japan covers several hundred square kilometers. Ariake clay consists of the principal clay minerals namely, smectite, illite, kaolinite and vermiculite, and other minerals in lesser quantity. The percentage of the principal clay, mineral can vary significantly. The percent clay, size fraction and the salt concentration can also vary significantly. In view of the importance of undrained shear strength in geotechnical engineering practice, its behavior has been studied with respect to variation in salt concentration. Basically, two mechanisms control the undrained strength in clays, namely (a) cohesion or undrained strength is due to the net interparticle attractive forces, or (b) cohesion is due to the viscous nature of the double layer water. Concept (a) operates primarily for kaolinitic soil, and concept (b) dominates primarily for montmorillonitic soils. In Ariake clay, different clay minerals with different exchangeable cations and varying ion concentration in the pore water and varying nonclay size fraction are present. In view of this while both concepts (a) and (b) can coexist and operate simultaneously, one of the mechanisms dominates. For Isahaya clay, concept (a), factors responsible for an increase in level of flocculation and attractive forces result in higher undrained strength. Increase in salt concentration increases the remolded undrained strength at any moisture content. For Kubota and Kawazoe clays, concept (b) factors responsible for an expansion of diffuse double layer thickness, resulting in higher viscous resistance, increase the undrained shear strength, that is, as concentration decreases, the undrained strength increases at any moisture content.The liquid limit of Isahaya,a clay increases with increase in ion concentration and a marginal decrease is seen for both Kubota and Kawazoe clays, and their behavior has been explained satisfactorily,.

Reaction of La2CuO4 with binary metal oxides in the solid state: Metathesis, addition, and redox metathesis pathways

Investigation of the reaction of La2CuO4 with several binary metal oxides in the solid state at elevated temperatures has revealed three different reaction pathways. Reaction of La2CuO4 with strongly acidic oxides such as Re2O7, MoO3, and V2O5 follows a metathesis route, yielding a mixture of products: La3ReO8/La2MoO6/LaVO4 and CuO. Oxides such as TiO2, MnO2, and RuO2 which are not so acidic yield addition products: La2CuMO6 (M = Ti, Mn, Ru). SnO2 is a special case which appears to follow a metathesis route, giving La2Sn2O7 pyrochlore and CuO, which on prolonged reaction transform to the layered perovskite La2CuSnO6. The reaction of La2CuO4 with lower valence oxides VO2 and MoO2, on the other hand, follows a novel redox metathesis route, yielding a mixture of LaVO4/LaCuO2 and La2MoO6/Cu, respectively. This result indicates that it is the redox reactivity involving V-IV + Cu-II --> V-V + Cu-I and Mo-IV + Cu-II --> Mo-VI + Cu-0, and not the acidity of the binary oxide, that controls the nature of the products formed in these cases. The general significance of these results toward the synthesis of complex metal oxides containing several metal atoms is discussed.

Swelling pressure of sodium montmorillonites

Determination of the swelling pressure of montmorillonitic clays is required in many situations concerned with stability problems of foundations, retaining walls, slope stability of embankments and excavations in expansive soils. Recently expansive soils such as bentonite have been used as a mixture backfill material, for example as backfill material for nuclear waste disposal systems, for which a knowledge of the swelling pressure is desirable. This is the pressure required to keep the clay-water system at the required void ratio when it is allowed to absorb water or electrolyte. If the pressure is less than the swelling pressure, volume expansion occurs; if the pressure is more than the swelling pressure, volume compression occurs. Because of isomorphous substitutions in the crystal lattice, in general the clay particles carry negative charges at the surfaces of the platelets. Exchangeable cations in the clay media are attracted to these negative charges, but this attraction is opposed by the tendency of ions to be distributed. As a result, an electric diffuse double layer is formed (Gouy, 1910).

The design and synthesis of redox core-alpha amino acid composites based on thiol-disulfide exchange mechanism and a comparative study of their zinc abstraction potential from [CCXX] boxes in proteins

The design and synthesis of agents that can abstract zinc from their [CCXX] (C=cysteine; X=cysteine/histidine) boxes by thioldisulfide exchange-having as control, the redox parities of the core sulfur ligands of the reagent and the enzyme, has been illustrated, and their efficiency demonstrated by monitoring the inhibition of the transcription of calf thymus DNA by E. coli RNA polymerase, which harbors two zinc atoms in their [CCXX] boxes of which one is exchangeable. Maximum inhibition possible with removal of the exchangeable zinc was seen with redox-sulfanilamide-glutamate composite. In sharp contrast, normal chelating agents (EDTA, phenanthroline) even in a thousand fold excess showed only marginal inhibition, thus supporting an exchange mechanism for the metal removal. (C) 2002 Elsevier Science Ltd. All rights reserved.

Kinetics of catalytic degradation of polycarbonate in benzene

The degradation kinetics of polycarbonate [poly(bisphenol A carbonate)] in benzene catalyzed by commercial (rutile) TiO2 (BET surface area = 11 m(2)/g), anatase TiO2 (156 m(2)/g), and 1 atom % Pt/TiO2 (111 m2/g), prepared by the solution combustion technique, was investigated at various temperatures (230-280 degreesC) and 50 atm. The time evolution of the molecular weight distribution (MWD) was determined by gel permeation chromatography (GPC) and modeled with continuous distribution kinetics to obtain the degradation rate coefficients. The rate coefficients for the catalytic degradation of polycarbonate increased by factors of 20, 3.5, and 1.3 compared to the rate coefficients for thermal degradation when catalyzed by nanosized TiO2 anatase, Pt/TiO2 anatase, and commercial TiO2, respectively, at 280 degreesC. The increased catalytic activity of combustion for synthesized TiO2 and 1% Pt/TiO2 might be due to the increased acidity and BET surface area. The activation energies, determined from the temperature dependencies of the rate coefficients, were 16.3, 21.5, and 39.1 kcal/mol for commercial TiO2, combustion-synthesized Pt/TiO2, and anatase TiO2, respectively.

Geotechnical Characterization of Some Indian Bentonites for their Use as Buffer Material in Geological Repository

The present study examines the geotechnical properties of Indian bentonite clays for their suitability as buffer material in deep geological repository for high-level nuclear wastes. The bentonite samples are characterized for index properties, compaction, hydraulic conductivity and swelling characteristics. Evaluation of geotechnical properties of the compacted bentonite-sand admixtures, from parts of NW India reveals swelling potentials and hydraulic conductivities in the range of 55 % - 108 % and 1.2 X 10 –10 cm/s to 5.42x 10 –11 cm/s respectively. Strong correlation was observed between ESP (exchangeable sodium percentage) and liquid limit/swell potential of tested specimens. Relatively less well-defined trends emerged between ESP and swell pressure/hydraulic conductivity. The Barmer-1 bentonite despite possessing relatively lower montmorillonite content of 68 %, developed higher Atterberg limit and swell potential, and exhibited comparable swelling pressure and hydraulic conductivity as other bentonites with higher montmorillonite contents (82 to 86 %). The desirable geotechnical properties of Barmer clay as a buffer material is attributed to its large ESP (63 %) and, EMDD (1.17 Mg/m3) attained at the experimental compactive stress(5 MPa).

Impact of Sulphate counter ion in the migration of sodium ion through soils

Laboratory advection-diffusion tests are performed on two regional soils-Brown Earth and Red Earth-in order to assess their capacity to control contaminant migration with synthetic contaminant solution of sodium sulphate with sodium concentration of 1000 mg/L. The test was designed to study the transport/attenuation behaviour of sodium in the presence of sulphate. Effective diffusion coefficient (De) that takes into consideration of attenuation processes is used. Cation exchange capacity is an important factor for the attenuation of cationic species. Monovalent sodium ion cannot usually replace other cations and the retention of sodium ion is very less. This is particularly true when chloride is anion is solution. However, sulphate is likely to play a role in the attenuation of sodium. Cation exchange capacity and type of exchangeable ions of soils are likely to play an important role. The effect of sulphate ions on the effective diffusion coefficient of sodium, in two different types of soils, of different cation exchange capacity has been studied. The effective diffusion coefficients of sodium ion for both the soils were calculated using Ogata Bank’s equation. It was shown that effective diffusion coefficient of sodium in the presence of sulphate is lower for Brown Earth than for Red Earth due to exchange of sodium with calcium ions from the exchangeable complex of clay. The soil with the higher cation exchange retained more sodium. Consequently, the breakthrough times and the number of pore volumes of sodium ion increase with the cation exchange capacity of soil.