Nickel complexes with tris(2-aminoethyl)amine (tren): [Ni-3(tren)(4)(H2O)(2)][Cr(ox)(3)](2)center dot 6H(2)O (ox = oxalate), {[Ni-2(tren)(3)][ClO4](4)center dot H2O}(n), and [Ni-2(tren)(2)(aepd)][ClO4](4)center dot 2H(2)O (aepd = N-(2-aminoethyl)pyrrolidi

Reaction of K-3[Cr(ox)(3)] (ox = oxalate) with nickel(II) and tris(2-aminoethyl)amine (tren) in aqueous solution resulted in isolation of the bimetallic assembly [Ni-3(tren)(4)(H2O)(2)][Cr(ox)(3)](2). 6H(2)O. The polymeric complex {[Ni-2(tren)(3)][ClO4](4). H2O}(n) has been prepared by reaction of nickel(II) perchlorate and tren in aqueous solution. From the same reaction mixture the complex [Ni-2(tren)(2)(aepd)][ClO4](4). 2H(2)O (aepd = N-(2-aminoethyl)pyrrolidine-3,4-diamine), in which a bridging tren ligand contains a carbon-carbon bond between two arms forming a substituted pyrrolidine, has been isolated. The complexes have been characterized by X-ray crystallography. The magnetic susceptibility (300-4.2 K) and magnetization data (2, 4 K, H = 0-5 T) for {[Ni-2(tren)(3)][ClO4](4). H2O}(n) (300 K , 4.23 mu(B)) exhibit evidence of weak antiferromagnetic coupling and zero field splitting (2J = -1.8 cm(-1); \ D\ = 2 cm(-1)) at low temperature. For [Ni-3(tren)(4)(H2O)(2)][Cr(ox)(3)](2). 6H(2)O the susceptibility data at 300 K are indicative of uncoupled nickel(II) and chromium(III) sites with zero-field splitting and intramolecular antiferromagnetic coupling predicted at low temperature.

Especiação de metais-traço em sedimentos de florestas de manguezais com Avicennia e Rhizophora

Speciation studies of Fe, Cr, Co, Ni and Cu on reactive fraction (adsorved on oxides, hydroxides, carbonates and clay minerals) and pyrite were performed in Avicennia schaueriana and Rhizophora mangle sediments from Amapá shoreline-Brazil. The soil under Avicennia showed a higher heavy metal concentration in reactive fraction than under Rhizophora. The soil under Rhizophora showed low heavy metal bioavailability, having an increasing association with pyrite across sediment section.

A new model for the population pharmacokinetics of didanosine in healthy subjects

Didanosine (ddI) is a component of highly active antiretroviral therapy drug combinations, used especially in resource-limited settings and in zidovudine-resistant patients. The population pharmacokinetics of ddI was evaluated in 48 healthy volunteers enrolled in two bioequivalence studies. These data, along with a set of co-variates, were the subject of a nonlinear mixed-effect modeling analysis using the NONMEM program. A two-compartment model with first order absorption (ADVAN3 TRANS3) was fitted to the serum ddI concentration data. Final pharmacokinetic parameters, expressed as functions of the co-variates gender and creatinine clearance (CL CR), were: oral clearance (CL = 55.1 + 240 x CL CR + 16.6 L/h for males and CL = 55.1 + 240 x CL CR for females), central volume (V2 = 9.8 L), intercompartmental clearance (Q = 40.9 L/h), peripheral volume (V3 = 62.7 + 22.9 L for males and V3 = 62.7 L for females), absorption rate constant (Ka = 1.51/h), and dissolution time of the tablet (D = 0.43 h). The intraindividual (residual) variability expressed as coefficient of variation was 13.0%, whereas the interindividual variability of CL, Q, V3, Ka, and D was 20.1, 75.8, 20.6, 18.9, and 38.2%, respectively. The relatively high (>30%) interindividual variability for some of these parameters, observed under the controlled experimental settings of bioequivalence trials in healthy volunteers, may result from genetic variability of the processes involved in ddI absorption and disposition.

Theoretical study of catalytic reactions of carbenes: haptotropic rearrangements and the Dötz reaction

En aquesta tesi s'han estudiat mecanismes de reaccions de cicloanulació en carbens de Fischer a través de mètodes teòrics, concretament fent servir el nivell de teoria B3LYP/(Wachters' basis / 6-31G**). Els alcoxi- i amino carbens de pentacarbonil crom, ja siguin vinílics o aromàtics, reaccionen amb acetilè per produir fenols, naftols o derivats ciclopentadiè o indè substituïts amb el Cr(CO)3 coordinat, d'una manera regioselectiva. L'objectiu d'aquest treball és discutir ambudes reaccions competitives particularment a la reacció de Dötz, la qual durant els darrers anys ha estat explorada experimentalment per W.D. Wulff, C.P. Casey, R. Aumann i J. Barluenga entre altres diferents propostes mecanístiques. A més K.H. Dötz va demostrar que la coordinació del Cr(CO)3, un cop l'anell ja està format, pot patir canvis haptotròpics, és a dir, la caminada del complex metàl·lic d'un anell a un altre -generalment almenys substituït- canviant la seva hapticitat (coordinació pi amb els membres de l'anell). Llavors, s'han estudiat les migracions haptotròpiques intramoleculars en petits hidrocarbons aromàtics policíclics amb l'objectiu d'analitzar les rutes de reacció per les quals aquestes reaccions es porten a terme

Metal cluster expansion by addition of low valent group 14 reagents: III. Reaction of bis[bis(trimethylsilyl)methyl]tin with M3(CO)12 or its derivatives (M = Fe, Ru, or Os): the crystal and molecular structures of M3(μ-SnR2)2(CO)10(R = CH(SiMe3)2; M = Ru or Os)

The stannylene [SnR2] (R = CH(SiMe3)2) reacts in different ways with the three dodecacarbonyls of the iron triad: [Fe3(CO)12] gives [Fe2(CO)8(μ-SnR2)], [Ru3(CO)12] gives the planar pentametallic cluster [Ru3(CO)10(μ-SnR2)2], for which a full structural analysis is reported, while [Os3(CO)12] fails to react. Different products are also obtained from three nitrile derivatives: [Fe3-(CO)11(MeCN)] gives [Fe2(CO)6(μ-SnR2)2], which has a structure significantly different from that of known Fe2Sn2 clusters, [Ru3(CO)10(MeCN)2] gives the pentametallic cluster described above, while [Os3(CO)10(MeCN)2] gives the isostructural osmium analogue, which shows the unusual feature of a CO group bridging two osmium atoms.

Direct probing of photoinduced electron transfer in a self- assembled biomimetic [2Fe2S]-hydrogenase complex using ultrafast vibrational spectroscopy

A pyridyl-functionalized diiron dithiolate complex, [μ-(4-pyCH2−NMI-S2)Fe2(CO)6] (3, py = pyridine(ligand), NMI = naphthalene monoimide) was synthesized and fully characterized. In the presence of zinc tetraphenylporphyrin (ZnTPP), a self-assembled 3·ZnTPP complex was readily formed in CH2Cl2 by the coordination of the pyridyl nitrogen to the porphyrin zinc center. Ultrafast photoinduced electron transfer from excited ZnTPP to complex 3 in the supramolecular assembly was observed in real time by monitoring the ν(CO) and ν(CO)NMI spectral changes with femtosecond time-resolved infrared (TRIR) spectroscopy. We have confirmed that photoinduced charge separation produced the monoreduced species by comparing the time-resolved IR spectra with the conventional IR spectra of 3•− generated by reversible electrochemical reduction. The lifetimes for the charge separation and charge recombination processes were found to be τCS = 40 ± 3 ps and τCR = 205 ± 14 ps, respectively. The charge recombination is much slower than that in an analogous covalent complex, demonstrating the potential of a supramolecular approach to extend the lifetime of the chargeseparated state in photocatalytic complexes. The observed vibrational frequency shifts provide a very sensitive probe of the delocalization of the electron-spin density over the different parts of the Fe2S2 complex. The TR and spectro-electrochemical IR spectra, electron paramagnetic resonance spectra, and density functional theory calculations all show that the spin density in 3•− is delocalized over the diiron core and the NMI bridge. This delocalization explains why the complex exhibits low catalytic dihydrogen production even though it features a very efficient photoinduced electron transfer. The ultrafast porphyrin-to-NMIS2−Fe2(CO)6 photoinduced electron transfer is the first reported example of a supramolecular Fe2S2-hydrogenase model studied by femtosecond TRIR spectroscopy. Our results show that TRIR spectroscopy is a powerful tool to investigate photoinduced electron transfer in potential dihydrogen-producing catalytic complexes, and that way to optimize their performance by rational approaches.

Simultaneous Determination of Ba, Cr, Mo (Group 1), and Cu, Fe, Ni, and Pb (Group 2) in Commercial Fuel Ethanol by Graphite Furnace AAS

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

Cyanide Compounds

Chapter 4, “Cyanide Compounds,” illustrates an explosively developing research theme in which the cyanide ligand is used as a linking agent for the designed assembly of polynuclear metal complexes. Syntheses of several basic building blocks, such as K3[Cr(CN)6],Cr(Me3tacn)(CN)3,K4[Mo(CN)8],Na[W(CO)5CN],K[CpFe(CO)(CN)2],[NEt4][Cp*Rh(CN)3],[Fe4(bpy)8(μ-CN)4][PF6]4,. are given here. These units may be used in several ways to construct polynuclear compounds. One approach involves a hexacyanometalate core decorated with peripheral metal centers, e.g., [{Cu(tpa)(CN)}6Fe][ClO4]8. or [Cr{CNNi(tetren)}6][ClO4]9. An octacyanometalate unit can lead to higher nuclearity condensed compounds, as in [Co{Co(MeOH)3}8(μ-CN)30{Mo(CN)3}6]. Alternatively, a cluster core may be substituted with cyano complexes as ligands, as in [PPh4]2[Fe4S4{NCW(CO)5}4]. If there are two cis cyano ligands on the building block, then quadrilateral or square structures often result, as in {CpFe(CO(μ-CN)2Cu(PCy3)}2 and [Fe2Cu2(bpy)6(μ-CN)4][PF6]4 However, if there are three adjacent cyano ligands, then cubic cages may be constructed as in [(CpCo)4(Cp*Rh)4(μ-CN)12][PF6]4.

Mineralogy micromorphology, and geochemistry at DSDP Site 89-585

At Site 585 of Deep Sea Drilling Project Leg 89 more than 500 m of volcaniclastic to argillaceous middle-Late Cretaceous sediments were recovered. Analyses by X-ray diffraction (bulk sediment and clay fraction), transmission electron microscopy, molecular and atomic absorption, and electron microprobe were done on Site 585 samples. We identify four successive stages and interpret them as the expression of environments evolving under successive influences: Stage 1, late Aptian to early Albian - subaerial and proximal volcanism, chiefly expressed by the presence of augite, analcite, olivine, celadonite, small and well-shaped transparent trioctahedral saponite, Al hydroxides, Na, Fe, Mg, and various trace elements (Mn, Ni, Cr, Co, Pb, V, Zn, Ti). Stage 2, early to middle Albian - submarine and less proximal volcanic influence, characterized by dioctahedral and hairy Mg-beidellites, a paucity of analcite and pyroxenes, the presence of Mg and K, and local alteration of Mg-smectites to Mg-chlorites. Stage 3, middle Albian to middle Campanian - early marine diagenesis, marked by the development of recrystallization from fleecy smectites to lathed ones (all of alkaline Si-rich Fe-beidellite types), by the development of opal CT and clinoptilolite, and by proximal to distal volcanic influences (Na parallel to Ti, K). Local events consist of the supply of reworked palygorskite during the Albian-Cenomanian, and the recurrence of proximal volcanic activity during the early Campanian. Stage 4, late Campanian to Maestrichtian - development of terrigenous supply resulting from the submersion of topographic barriers; this terrigenous supply is associated with minor diagenetic effects and is marked by a clay diversification (beidellite, illite, kaolinite, palygorskite), the rareness of clay recrystallizations, and the disappearance of volcanic markers.

Grain size, mineral and chemical compositions of modern deposits fron the northern Caspian Sea and the Volga River delta

Comprehensive investigations revealed that modern deposits in the northern Caspian Sea involve terrigenous sands and aleurites with admixture of detritus and intact bivalve shells, including coquina. Generally, these deposits overlay dark grayish viscous clays. Similar geological situation occurs in the Volga River delta; however, local deposits are much poorer in biogenic constituents. Illite prevails among clay minerals. In coarse aleurite fraction (0.100-0.050 mm) heavy transparent minerals are represented mostly by epidotes, while light minerals - mostly by quartz and feldspars. Sedimentary material in the Volga River delta is far from completely differentiated into fractions due to abundant terrigenous inflows. Comparatively better grading of sediments from the northern Caspian Sea is due to additional factors such as bottom currents and storms. When passing from the Volga River delta to the northern Caspian Sea, sediments are enriched in rare earth elements (except Eu), Ca, Au, Ni, Se, Ag, As, and Sr, but depleted in Na, Rb, Cs, K, Ba, Fe, Cr, Co, Sc, Br, Zr, ??, U, and Th. Concentrations of Zn remain almost unchanged. Sedimentation rates and types of recent deposits in the northern Caspian Sea are governed mainly by abundant runoff of the Volga River.

Concentrations of dissolved and particulate heavy metals in waters above the northwestern slope of the Paramushir Island (Sea of Okhotsk)

Distributions of Mn, Fe, Cu, Cd, Cr, Co and Ni in sea water are investigated (42 samples, dissolved and particulate forms) in the vicinity of the underwater gas vent field on the northwestern slope of the Paramushir Island. While regular background distributions of the elements occur in the shore zone, there is a column of elevated concentrations of particulate matter, particulate Mn, and dissolved Mn, Fe, Cu, Cd, Cr, Co and Ni that coincides with location of the gas plume. This column can be traced as high as 780 m above the bottom. High metal concentrations in water of the plume are attributable to physico-chemical concentration at the phase interface; the source of elevated mineral concentrations is obviously flux of dissolved minerals from interstitial waters, which extends to considerable distances in vertical direction.

High pressure studies on group VI metal hexacarbonyl molecular solids

Group VI metal hexacarbonyls, M(CO)6 (M = Cr, Mo and W), are of extreme importance as catalysts in industry and also of fundamental interest due to the established charge transfer mechanism between the carbon monoxide and the metal. They condense to molecular solids at ambient conditions retaining the octahedral (Oh) symmetry of gas phase and have been extensively investigated by previous workers to understand their fundamental chemical bonding and possible industrial applications. However little is known about their behavior at high pressures which is the focus of this dissertation. Metal hexacarbonyls were subjected to high pressures in Diamond-Anvil cells to understand the pressure effect on chemical bonding using Raman scattering in situ. The high-pressure results on each of the three metal hexacarbonyls are presented and are followed by a critical analysis of the entire family. The Raman study was conducted at pressures up to 45 GPa and X-ray up to 58 GPa. This is followed by a discussion on infra red spectra in conjunction with Raman and X-ray analysis to provide a rationale for polymerization. Finally the probable synthesis of extremely reactive species under high-pressures and as identified via Raman is discussed. The high-pressure Raman scattering, up to 30 GPa, demonstrated the absence of Π-backbonding. The disappearance of parental Raman spectra for (M = Cr, Mo and W) at 29.6, 23.3 and 22.2 GPa respectively was attributed to the total collapse of the Oh symmetry. This collapse under high-pressure lead to metal-mediated polymeric phase characterized by Raman active δ(OCO) feature, originating from intermolecular vibrational coupling in the parent sample. Further increase in pressures up to 45 GPa, did not affect this feature. The pressure quenched Raman spectra, revealed various chemical groups non-characteristic of the parent sample and adsorption of CO in addition to the characteristic δ(OCO) feature. The thus recorded Raman, complemented with the far and mid-infrared pressure quenched spectra, reveal the formation of novel metal-mediated polymers. The X-ray diffraction on W(CO)6 up to 58 GPa revealed the generation of amorphous polymeric pattern which was retained back to ambient conditions.

Probing the electronic delocalization in a cyclic pyrazine ruthenium cluster hexamer

[Ru(3)O(CH(3)COO)(6)(pz)(CO)](6) is a cyclic hexamer species encompassing six triangular ruthenium cluster centers bridged by pyrazine ligands. The electronic communication among the cluster units strongly depends on their oxidation states, and has been successfully probed by means of cyclic voltammetry and UV-vis spectroelectrochemistry. (C) 2010 Elsevier B.V. All rights reserved.

Influence of the bonding substrate in dental composite polymerization stress testing

Our objective was to compare the polymerization stress (sigma(pol)) of a series of composites obtained using poly(methyl methacrylate) (PMMA) or glass as bonding substrates, and to compare the results with those from in vitro microleakage of composite restorations. The tested hypothesis was that stress values obtained in a less rigid testing system (i.e. using PMMA) would show a better relationship with microleakage data. Five dental composites were tested: Filtek Z250 (FZ), Z100 (Z1), Concept (CO), Durafill (DU) and Heliomolar (HM). sigma(pol) was determined in 1 mm high specimens inserted between two rods (empty set = 5 mm) of either PMMA or glass. The composite elastic modulus (E) was obtained by three-point bending. sigma(pol) and E data were submitted to a one-way analysis of variance/Tukey test (alpha = 0.05). For the microleakage test (MI), bovine incisors received cylindrical cavities (empty set = 5 mm, h = 2 mm), which were restored in bulk. After storage for 24 h in water, specimens were subjected to dye penetration using AgNO(3) as tracer. Specimens were sectioned twice, perpendicularly, and microleakage was measured (in millimeters) under 20x magnification. Data from MI were submitted to the Kruskal-Wallis test. Means (SD) of sigma(pol) (MPa) using glass/PMMA were FZ: 7.5(1.8)(A)/2.5(0.2)(bc); Z1: 7.3(0.5)(A)/2.8(0.3)(ab); CO: 6.8(1.1)(A)/3.2(0.5)(a); DU: 4.5(0.7)(B)/2.0(0.2)(bc); HM: 3.5(0.2)(B)/2.3(0.3)(c). sigma(pol) obtained using PMMA rods were 34-67% lower than with glass. Means (SD) for tooth average/tooth maximum microleakage were FZ: 0.92(0.19)(B)/1.53(0.30)(a); Z1: 1.19(0.21)(A)/1.75(0.20)(a); CO: 1.26(0.25)(A)/1.78(0.24)(a); DU: 0.83(0.30)(B)/1.68(0.46)(a): HM: 0.81(0.27)(B)/1.64(0.54)(a). The tested hypothesis was confirmed, as the composites showed the same ordering both in the polymerization stress test using PMMA rods and in the microleakage test. (C) 2009 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Molybdenum Complexes Bearing the Tris(1-pyrazolyl)methanesulfonate Ligand: Synthesis, Characterization and Electrochemical Behaviour

The tris(1-pyrazolyl)methanesulfonate lithium salt Li(Tpms) [Tpms = SO3C(pz)(3)-] reacts with [Mo(CO)(6)] in NCMe heated at reflux to yield Li[Mo(Tpms)(CO)(3)] (1), which, upon crystallization from thf, forms the coordination polymer [Mo(Tpms)(CO)(2)(mu-CO)Li(thf)(2)](n) (2). Reaction of 1 with I-2, HBF4 or AgBF4 yields [Mo(Tpms)I(CO)(3)] (3), (Mo(Tpms)-H(CO)(3)] (5) or (Mo(Tpms)O-2](2)(mu-O) (7), respectively. The high-oxidation-state dinuclear complexes [{Mo(Tpms)O(mu-O)}(2)] (4) and [{Mo(tpms)OCl)(2)](mu-O) (6) are formed upon exposure to air of solutions of 3 and 5, respectively. Compounds 1-7, which appear to be the first tris(pyrazolyl)methanesulfonate complexes of molybdenum to be reported, were characterized by IR, H-1 and C-13 NMR spectroscopy, ESI-MS, elemental analysis, cyclic voltammetry and, in the cases of Li(Tpms) and compounds 2, 4.2CH(3)CN, 6.6CHCl(3) and 7, by X-ray diffraction analyses. Li(Tpms) forms a 1D polymeric structure (i.e., [Li(tpms)](n)} with Tpms as a tetradentate N2O2 chelating ligand that bridges two Li cations with distorted tetrahedral coordination. Compound 2 is a 1D coordination polymer in which Tpms acts as a bridging tetradentate N3O ligand and each Li(thf)(2)(+) moiety is coordinated by one bridging CO ligand and by the sulfonyl group of a contiguous monomeric unit. In 4, 6 and 7, the Tpms ligand is a tridentate chelator either in the NNO (in 4) or in the NNN (in 6 and 7) fashion. Complexes 1, 3 and 5 exhibit, by cyclic voltammetry, a single-electron oxidation at oxidation potential values that indicate that the Tpms ligand has an electron-donor character weaker than that of cyclopentadienyl.