A XANES study of the K-absorption edge of copper in some of its compounds and use of the same in the determination of bond length

XANES in the K-edge of copper in the systems CuO, Cu(OH)2, La2CuO4, Cu3AsO4 and CuOHF have been investigated and transitions have been assigned to the observed structures. The measurements have been used for calculating the first coordination bond distance in the above systems. It is observed that the values so determined agree fairly well with crystallographic values.

MNDO study of coupled strained hydrocarbons: Additivity of exocyclic C---C bond contraction induced by different ring systems

MNDO geometry optimizations were carried out on a series of symmetrically and unsymmetrically coupled strained ring hydrocarbons, R1-R1 and R1–R2 (R1=methyl, cyclopropyl, 1-bicyclo[1.1.0]butyl, 1-bicyclo[1.1.1]pentyl, prismyl, cubyl, 6-tricyclo [3.1.1.03,6]heptyl, and tetrahedryl groups; R2=methyl and cyclopropyl). The remarkable contraction of the C---C bond connecting the strained rings found experimentally in a few cases was reproduced correctly by the calculations. A linear correlation was found between the bond length shortening and the bond angle widening at the corresponding carbon atoms for all the structures considered. The reduction in C---C bond lengths due to various ring systems is additive. The additivity indicates that inter-ring interactions which effect the central bond length are absent and confirms the common electronic origin of bond contraction in these systems, viz. enhanced s-character in the exocyclic bonds of strained rings.

Antitumour activity of [1,2-di(cyclopentadienyl)-1,2-di(p-N,N-dimethylaminophenyl)-ethanediyl] titanium dichloride in xenografted Ehrlich's ascites tumour

The effects of a new titanocene compound with an ansa ligand in the cyclopentadienyl rings, the 1,2-di(cyclopentadienyl)-1,2-di(p-NNdimethylaminophenyl)-ethanediyl] titanium dichloride (TITANOCENE X), on the growth and differentiation of granulocyte-macrophage progenitor cells [colony-forming unit-granulocyte-macrophage (CFU-GM)] and Natural killer (NK) cell activity in Ehrlich's ascites tumour (EAT)-bearing mice were studied. Myelosuppression concomitant with increased numbers of spleen CFU-GM was observed in tumour-bearing mice. Treatment of these animals with TITANOCENE X (2.5-50mg/kg/day) produced an increase in myelopoicsis, in a dose-dependent manner, and reduced spleen colony formation. In addition, the treatment of EAT-bearing mice with 3 doses of 20 or 50 mg/kg TITANOCENE X restored to normal values the reduced Natural killer cell function observed during tumour growth. In parallel, TITANOCENE X prolonged, in a dose-dependent manner, the survival of mice inoculated with Ehrlich's ascites tumour. The highest dose of 50 mg/kg prolonged in 50% the survival time of EAT-bearing mice, compared to non-treated tumour-bearing controls. In comparison with previous results from our laboratory addressing the effects of titanocenes on haematopoiesis, we observed with TITANOCENE X a similar effective profile as for bis(cyclopentadienyl) dithiocyanate titanium(IV), being both less effective than di(cyclopentadienyl) dichloro titanium(IV), since the latter not only prolonged, but also increased the rate of survival. These differences in efficacy may be due to the nature of the ansa-cyclopentadienyl ligand used in TITANOCENE X, since the C, bridge between the two cyclopentadienyl groups will increase the hydrolytic stability by an organometallic chelate effect. Also, the introduction of two dimethylamino substituents increases the water solubility of TITANOCENE X when compared to titanocene dichloride itself (c) 2006 Elsevier B.V. All rights reserved.

The effect of dimethyl sulfoxide (DMSO) on dentin bonding and nanoleakage of etch-and-rinse adhesives

Objective The objective was to examine the effect of a solvent dimethyl sulfoxide (DMSO) on resin-dentin bond durability, as well as potential functional mechanisms behind the effect. Methods Microtensile bond strength (μTBS) was evaluated in extracted human teeth in two separate experiments. Dentin specimens were acid-etched and assigned to pre-treatment with 0.5 mM (0.004%) DMSO as additional primer for 30 s and to controls with water pre-treatment. Two-step etch-and-rinse adhesive (Scotchbond 1XT, 3M ESPE) was applied and resin composite build-ups were created. Specimens were immediately tested for μTBS or stored in artificial saliva for 6 and 12 months prior to testing. Additional immediate and 6-month specimens were examined for interfacial nanoleakage analysis under SEM. Matrix metalloproteinase (MMP) inhibition by DMSO was examined with gelatin zymography. Demineralized dentin disks were incubated in 100% DMSO to observe the optical clearing effect. Results The use of 0.5 mM DMSO had no effect on immediate bond strength or nanoleakage. In controls, μTBS decreased significantly after storage, but increased significantly in DMSO-treated group. The control group had significantly lower μTBS than DMSO-group after 6 and 12 months. DMSO also eliminated the increase in nanoleakage seen in controls. 5% and higher DMSO concentrations significantly inhibited the gelatinases. DMSO induced optical clearing effect demonstrating collagen dissociation. Significance DMSO as a solvent may be useful in improving the preservation of long-term dentin-adhesive bond strength. The effect may relate to dentinal enzyme inhibition or improved wetting of collagen by adhesives. The collagen dissociation required much higher DMSO concentrations than the 0.5 mM DMSO used for bonding. © 2013 Academy of Dental Materials.

Silica-based Nano-coating on Zirconia Surfaces Using Reactive Magnetron Sputtering: Effect on Chemical Adhesion of Resin Cements

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Infrared spectra of trichloroacetates of copper, calcium, strontium and barium

Infrared spectra of trichloroacetates of Cu, Ca, Sr and Ba were studied in order to investigate the effect of coordination on the vibration spectra of the ligand. The shifts of the antisymmetric and symmetric COO- stretching frequencies are explained on the basis of the type of co-ordination of the COO- group to the metal ion. From the spectra it is established that the coordination of the COO- group to metal is different for trichloroacetates and monochloroacetates.

Synthesis, antimicrobial, DNA-binding and photonuclease studies of Cobalt(III) and Nickel(II) Schiff base complexes

New metal complexes of the type M(nih)(L)](PF6)(n)center dot xAH(2)O and M(nih)(2)](PF6)center dot xH(2)O (where M = Co(III) or Ni(II), L = 1,10-phenanthroline (phen)/or 2,2' bipyridine (bpy), nih = 2-hydroxy-1-naphthaldehyde isonicotinoyl hydrazone, n = 2 or 1 and x = 3 or 2) have been synthesized and characterized by elemental analysis, magnetic, IR and H-1 NMR spectral data. The electronic and magnetic moment 2.97-3.07 B.M. data infers octahedral geometry for all the complexes. The IR data reveals that Schiff base (nih) form coordination bond with the metal ion through azomethine-nitrogen, phenolic-oxygen and carbonyl-oxygen in a tridentate fashion. In addition, DNA-binding properties of these six metal complexes were investigated using absorption spectroscopy, viscosity measurements and thermal denaturation methods. The results indicated that the nickel(II) complex strongly bind with calf-thymus DNA with intrinsic DNA binding constant K-b value of 4.9 x 10(4) M-1 for (3), 4.2 x 10(4) M-1 for (4), presumably via an intercalation mechanism compared to cobalt(III) complex with K-b value of 4.6 x 10(4) M-1 (1) and 4.1 x 10(4) M-1 (2). The DNA Photoclevage experiment shows that, the complexes act as effective DNA cleavage agent. (C) 2012 Elsevier B.V. All rights reserved.

A lattice dynamical treatment for the total potential energy of single-walled carbon nanotubes and its applications: relaxed equilibrium structure, elastic properties, and vibrational modes of ultra-narrow tubes

In this paper, we propose a lattice dynamic treatment for the total potential energy of single-walled carbon nanotubes (SWCNTs) which is, apart from a parameter for the nonlinear effects, extracted from the vibrational energy of the planar graphene sheet. The energetics, elasticity and lattice dynamics are treated in terms of the same set of force constants, independently of the tube structures. Based upon this proposal, we have investigated systematically the relaxed lattice configuration for narrow SWCNTs, the strain energy, the Young's modulus and Poisson ratio, and the lattice vibrational properties with respect to the relaxed equilibrium tubule structure. Our calculated results for various physical quantities are nicely in consistency with existing experimental measurements. In particular, we verified that the relaxation effect makes the bond length longer and the frequencies of various optical vibrational modes softer. Our calculation provides evidence that the Young's modulus of an armchair tube exceeds that of the planar graphene sheet, and that the large diameter limits of the Young's modulus and Poisson ratio are in agreement with the experimental values of graphite; the calculated radial breathing modes for ultra-narrow tubes with diameters ranging between 2 and 5 angstrom coincide with the experimental results and the existing ab initio calculations with satisfaction. For narrow tubes with a diameter of 20 angstrom, the calculated frequencies of optical modes in the tubule's tangential plane, as well as those of radial breathing modes, are also in good agreement with the experimental measurements. In addition, our calculation shows that various physical quantities of relaxed SWCNTs can actually be expanded in terms of the chiral angle defined for the corresponding ideal SWCNTs.

The PPh3 ligand modified Rh/SiO2 catalyst for hydroformylation of olefins

A novel family of hybrid catalyst with high turnover frequency (TOF) and high selectivity towards aldehydes for hydroformylation of olefins could be successfully approached through direct coordination with the PPh3 ligand to the highly dispersed Rh metal particle precursors. A further advantage is that the catalyst is easily prepared and recyclable. The results revealed that hydroformylation of olefins to aldehydes dominantly took place on the surface of PPh3 ligand modified Rh metal particles of the hybrid catalyst. It was found that the formation of chemical coordination bond between the Rh metal particles and the lone-pair electron of PPh3 was evident through the TG and P-31 NMR measurement. Moreover, the addition of PPh3 onto the Rh/SiO2 exert a significant influence on the adsorption state of reactant CO, H-2 and C2H4 on the PPh3-Rh/SiO2 sample, which probably lead to good catalytic performances for hydroformylation of olefins. (C) 2004 Elsevier B.V. All rights reserved.

Recyclable heterogeneous Rh/SiO2 catalyst enhanced by organic PPh3 ligand

Heterogeneous PPh3-Rh/SiO2 catalysts for hydroformylation of olefins, prepared by direct doping of phosphine onto the heterogeneous Rh/SiO2 precursor, exhibited high activity and selectivity towards aldehydes, which originated from chemical coordination bond between the phosphine and Rh metal nantoparticles on the SiO2 support.

Étude Pharmacologique de la Douleur Neuropathique Centrale à la suite d'une Hémorragie Intrathalamique induite chez le Rat.

La douleur neuropathique centrale post accident vasculaire cérébral est une condition débilitante dont le traitement s’avère souvent délicat et infructueux. Le but de ce projet était de reproduire cette condition chez le rat en injectant par stéréotaxie une solution de collagènase produisant une hémorragie localisée dans le noyau ventropostérolatéral du thalamus. Des tests comportementaux évaluant la coordination motrice, la sensibilité mécanique, au chaud et au froid étaient réalisés régulièrement afin d’établir la présence de douleur neuropathique puis les effets de l’administration de kétamine, d’amitriptyline, de gabapentine, et de carbamazepine étaient évalués. L’induction d’une hémorragie intrathalamique conduit à l’apparition d’allodynie mécanique bilatérale persistante ainsi que d’allodynie au froid transitoire chez certains sujets et ce sans modification de la coordination motrice. L’administration de kétamine à forte dose renverse l’allodynie mécanique mais est associée à une altération de la motricité. L’administration de gabapentine renverse également cette allodynie mécanique sans effet notable sur la coordination motrice. Les autres médicaments n’ont pas démontré d’effet significatif. L’évaluation histopathologique des cerveaux montre une lésion bien localisée dans la zone d’intérêt. Ces résultats montrent que l’injection intrathalamique de collagénase peut être utilisée comme un modèle fiable de douleur neuropathique centrale. Si la kétamine semble capable de soulager ce type de douleur, elle est associée à des effets indésirables. En revanche, la gabapentine serait une molécule prometteuse pour le traitement de cette condition. Le rôle des récepteurs NMDA et des canaux calciques voltage dépendants, cibles respectives de la kétamine et de la gabapentine dans le maintien de cette douleur mérite d’être précisé.

Synthesis and properties of d6 metal complexes of bidentate and tridentate ‘super donor’ ligands

La polyvalence de la réaction de couplage-croisé C-N a été explorée pour la synthèse de deux nouvelles classes de ligands: (i) des ligands bidentates neutres de type N^N et (ii) des ligands tridentates neutres de type N^N^N. Ces classes de ligands contiennent des N-hétérocycles aromatiques saturés qui sont couplés avec hexahydropyrimidopyrimidine (hpp). Les ligands forment de cycles à six chaînons sur la coordination du centre Ru(II). Ce fait est avantageux pour améliorer les propriétés photophysiques des complexes de polypyridyl de Ru(II). Les complexes de Ru(II) avec des ligands bidentés ont des émissions qui dépendent de la basicité relative des N-hétérocycles. Bien que ces complexes sont électrochimiquement et photophysiquement attrayant, le problème de la stereopurité ne peut être évité. Une conception soigneuse du type de ligand nous permet de synthétiser un ligand bis-bidentate qui est utile pour surmonter le problème de stereopurité. En raison de la spécialité du ligand bis-bidentate, son complexe diruthénium(II,II) présente une grande diastéréosélectivité sans séparation chirale. Alors que l'unité de hpp agit comme un nucléophile dans le mécanisme de C-N réaction de couplage croisé, il peut également agir en tant que groupe partant, lorsqu'il est activé avec un complexe de monoruthenium. Les complexes achiraux de Ru(II) avec les ligands tridentés présentent des meilleures propriétés photophysiques en comparason avec les prototypes [Ru(tpy)2]2+ (tpy = 2,2′: 6′, 2′′-terpyridine). L’introduction de deux unités de hpp dans les ligands tridentates rend le complexe de Ru(II) en tant que ‘absorbeur noir’ et comme ‘NIR émetteur’ (NIR = de l’anglais, Near Infra-Red). Cet effet est une conséquence d'une meilleure géométrie de coordination octaédrique autour de l'ion Ru(II) et de la forte donation sigma des unités hpp. Les complexes du Re(I) avec des ligands tridentates présentent un comportement redox intéressant et ils émettent dans le bleu. L'oxydation quasi-réversible du métal est contrôlée par la donation sigma des fragments hpp, tandis que la réduction du ligand est régie par la nature électronique du motif N-hétérocycle central du ligand lui-même. Cette thèse presente également l'auto-assemblage des métal-chromophores comme ‘métallo-ligands’ pour former des espèces supramoléculaires discretes utilisant des complexes neutres. Les synthèses et propriétés des métaux-chromophores précités et les supramolécules sont discutées.

Organotin Complexes of Alizarin and Purpurin

Five novel organotin complexes with the anthraquinone dyes alizarin (1,2-dihydroxyanthraquinone) and purpurin (1,2,4-trihydroxyanthraquinone) were synthesized and characterized by elemental analyses, FTIR and NMR spectroscopy ((1)H, (13)C and (119)Sn). The crystal and Molecular structures Of four complexes were determined by X-ray diffraction on single crystals: [Bu(2)Sn(aliz)(H(2)O)]center dot C(2)H(5)OH (A1 center dot EtO H), [Bu(2)Sn(aliz)(dmso)](2) (A3), [(Bu(2)Sn)(3)O(Hpurp)(2)] (P1) and [Bu(2)Sn(Hpurp)(dmso)](2) (P2), where H(2)aliz = alizarin and H(3)purp = purpurin. The coordination mode of the ligands is identical to that found in their Al/Ca complexes, where they act as dianionic tridentate ligands forming five and six-membered fused chelate rings. The coordination to the tin atoms occurs exclusively via the 1,2- phenolate oxygen and the adjacent quinoid oxygen atoms. The complexes A1, A3 and P1 are dimers with hepta-coordinated tin atoms in form of a slightly distorted pentagonal bipyramid. The trinuclear complex P2 contains two pentacoordinated and one heptacoordinated tin atoms.

Ion clustering in molecular dynamics simulations of sodium iodide solutions

Model systems of sodium iodide dissolved in dimethyl ether or 1,2-dimethoxyethane (glyme) were studied in order to investigate the structural and dynamic properties of ionic solutions in small and polymeric ethers. Full molecular dynamics simulations were performed at a range of different salt concentrations. An algorithm was designed which assigns ions to clusters and then calculates all the terms which contribute to ionic conductivity. In dilute solutions, free ions are the most common ionic species, followed by ion pairs. As the concentration increases, pairs become the most common species, with significant concentrations of clusters with 3 through 6 ions. Changing the solvent from dimethyl ether to glyme significantly decreases the ion clustering due to the chelate effect in which the two oxygens on a solvent stabilize an associated cation. The conductivity in stable systems is shown to be primarily the result of the movement of free ions and the relative movement of ions within neutral pairs. The Nernst-Einstein relation, commonly used in the discussion of polymer electrolytes, is shown to be inadequate to quantitatively describe conductivity in the model systems.

Synthesis and anti-corrosion performance of Adenine-L-Alanine ramification

In this paper, a new amino acid derivative, namely Adenine-L-Alanine ramification (ALAR) was synthesized and investigated as a green corrosion inhibitor for X80 pipeline steel in 0.1 mol/L hydrochloric acid solution using the weight loss, AC impedance, and polarization curve method. The structure of the derivative was characterized by IR and UV–vis spectrum. The weight loss and AC impedance found that the inhibition efficiency increased with the increase in concentration of the inhibitor but decreased with rise in temperature, the corrosion inhibition efficiency attains 91.26% in 8 × 10−2 g/L concentration at 30 °C. The polarization studies showed that the studied amino acid derivative can be used as a corrosion inhibitor. The surface of inhibited and uninhibited specimens was analyzed by scanning electron microscopy and the adsorption of the inhibitor on the mild steel surface obeys Langmuir adsorption isotherm. The quantum chemical descriptors such as the energy of highest occupied molecular orbital, energy of lowest unoccupied molecular orbital were calculated and the inhibition mechanism can be analyzed by the distribution of electrons. Analysis indicated that the inhibitor molecular and empty d orbital of metal forms the coordination bond, covers on the surface of metal, and prevents corrosion reaction.