Synthesis, spectral and thermal studies on dicarboxylate-bridged palladium(II) coordination polymers. Part II

The synthesis and thermal behavior of the new [Pd(fum)(bipy)] (n) center dot 2nH(2)O (1), [Pd(fum)(bpe)] (n) center dot nH(2)O (2) and [Pd(fum)(pz)] (n) center dot 3nH(2)O (3) {bipy = 4,4'-bipyridine, bpe = 1,2-bis(4-pyridyl)ethene and pz = pyrazine} fumarate complexes are described in this work as well their characterization by IR and (13)C CPMAS NMR spectroscopies. TG curves showed that the compounds released organic ligands and lattice water molecules in the temperature range of 46-491 A degrees C. In all the cases, metallic palladium was identified as the final residue.

A solid nickel(II) complex with methionine sulfoxide

Solid Ni(C(5)H(10)NO(3)S)(2) . 2H(2)O complex was prepared and characterized. Electronic absorption spectrum shows an octahedral geometry for the complex. Infrared spectroscopy analysis shows that the metal atom is coordinated to the ligand through (COO(-)) and (S = O) groups. Thermal analysis confirmed the composition of the complex and suggests that the water molecules are not coordinated to the metal ion. The complex shows extremely high solubility in water. (C) 2000 Elsevier B.V. S.A. All rights reserved.

Spectroscopic investigation of a new hybrid glass formed by the interaction between croconate ion and calcium polyphosphate

In this work, a new organic-inorganic hybrid material has been synthesized by the incorporation of croconate ion into a calcium polyphosphate coacervate. The hybrid so obtained was characterized by means of electronic and vibrational spectroscopies. The material is a homogeneous mixture described by a structural model, which includes helical chains of polyphosphate ions, where the calcium ion occupies the internal vacancies of the structure. The croconate ion appears to be occupying the regions outside the polymeric structure, surrounded by several water molecules. The electronic spectrum of the incorporated material shows a broad band peaking at the same wavelength region (363 nm) observed for the aqueous solution of croconate ion, and manifesting the Jahn-Teller effect as evidenced by the doublet structure of the band. The infrared spectrum is widely dominated by the absorption bands of the polyphosphate ion and the appearance of the carbonyl stretching band at ca. 1550 cm(-1) indicates the presence of croconate ion incorporated in the structure. The Raman spectrum of the material shows several vibrational bands related to the oxocarbon moiety; most of them are shifted in comparison with the free ion. These shifts can be understood in terms of strong hydrogen bonding interactions between water molecules and the oxocarbon moiety. The low temperature methodology proposed here can be well used in the preparation of new phosphate glasses containing organic moieties opening the route to an entirely new class of hybrid glasses. (c) 2004 Elsevier B.V All rights reserved.

Structure of human uropepsin at 2.45 angstrom resolution

The molecular structure of human uropepsin, an aspartic proteinase from the urine produced in the form of pepsinogen A in the gastric mucosa, has been determined by molecular replacement using human pepsin as the search model. Crystals belong to space group P2(1)2(1)2(1), with unit-cell parameters a = 50.99, b = 75.56, c = 89.90 Angstrom. Crystallographic refinement led to an R factor of 0.161 at 2.45 Angstrom resolution. The positions of 2437 non-H protein atoms in 326 residues have been determined and the model contains 143 water molecules. The structure is bilobal, consisting of two predominantly beta -sheet lobes which, as observed in other aspartic proteinases, are related by a pseudo-twofold axis. A model of the uropepsin-pepstatin complex has been constructed based on the high-resolution crystal structure of pepsin complexed with pepstatin.

Local Er(III) environment in luminescent titanosilicates prepared from microporous precursors

The local environment of Er3+ ions in microporous titanosilicate ETS-10 and in synthetic narsarsukite and glassy materials obtained by calcination of ETS-10 has been investigated by EXAFS, Raman and photoluminescence spectroscopies. Er L-III-edge EXAFS studies of Er3+-doped ETS-10 support the view that the exchanged Er3+ ions reside close to the (negatively charged) TiO6 octahedra. In ETS-10, Er3+ is partially bonded to framework oxygen atoms and hydration water molecules. The Er...Ti distance (3.3 Angstrom) is similar to the Na...Ti distances (3.15-3.20 Angstrom) reported previously for Na-ETS-10. Although the exact location of the ErO6 units within the host structure of Er3+-doped synthetic narsarsukite is still an open question, it is most likely that Er3+ substitutes Ti4+ rather than Na+ ions. EXAFS spectroscopy indicates that no significant clustering of erbium atoms occurs in the titanosilicate samples studied. Evidence for the insertion of Er3+ ions in the framework of narsarsukite has been obtained by Raman spectroscopy. This is indicated by the increasing full-width at half-maximum (FWHM) of the 775 cm(-1) peak and the increasing intensity of the anatase peaks as the erbium content increases. In addition, as the narsarsukite Er3+ content increases a band at ca. 515 cm(-1) firstly broadens and subsequently a new peak appears at ca. 507 cm(-1).Er3+-doped narsarsukite exhibits a characteristic local vibrational frequency, (h) over bar omega ca. 330 cm(-1), with an electron-phonon coupling, g ca. 0.2, which constitutes additional evidence for framework Er3+ insertion. The number of lines in the infrared emission spectrum of synthetic narsarsukite indicates the presence of two optically-active erbium centres with very similar local environments and an average I-4(13/2) lifetime of 7.8 +/- 0.2 ms.

THE B-FORM TO Z-FORM TRANSITION OF POLY(DG-M(5)DC) IS SENSITIVE TO NEUTRAL SOLUTES THROUGH AN OSMOTIC-STRESS

Several neutral solutes, ranging in size from methanol to a tetrasaccharide, stachyose, are shown to stabilize the left-handed Z form of the methylated polynucleotide poly(dG-m(5)dC). The action of these solutes is consistent with an osmotic stress, that is, with their effect on water chemical potentials coupled to a difference in the number of-associated water molecules between the B and Z conformations. The apparent difference in hydration between the two forms is, however, dependent on the particular solute used to probe the reaction. The effect of solutes is not consistent either with a direct binding of solute or with an indirect effect on electrostatics or ion binding through changes in the solution dielectric constant. The interplay of NaCl and neutral solute in modulating the B-Z transition suggests that salt also could be stabilizing the Z form through an osmotic stress.

Synthesis and X-ray structure of the dinuclear platinum(II) complex with saccharin {K[Pt(sac)(3)(H2O)] center dot H2O}(2): Studies on its antiproliferative activity in aqueous solution

Synthesis and X-ray structure of a dinuclear platinum(II) complex with the ligand saccharin(sac) are described. The structure shows two approximately square-planar platinum centers. Each platinum atom is coordinated to one water molecule and three N-bonded saccharinate ligands. The two centers are linked through two potassium atoms. Each potassium atom interacts with six oxygen atoms from hydration and coordinated water molecules and from carbonyl and sulfonate groups of the ligands. It is suggested that, in aqueous solution, the dimeric structure of the complex is dissociated and the monomeric species K[Pt(sac)(3)(H2O)] is formed. The complex was dissolved in water and submitted to in vitro cytotoxic analyses using HeLa cells (human cervix cancer). It was shown that the monomeric complex elicited a potent cytotoxic activity when compared to the vehicle-treated cells. The IC50 value for the monomeric complex is 6.8 mu M, a little bit higher than that obtained for cisplatin. (c) 2007 Elsevier B.V. All rights reserved.

Synthesis and some properties of hybrid gels of titanium oxide containing europium (III)

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Novel allosteric conformation of human HB revealed by the hydration and anion effects on O-2 binding

The effect of anions on the stability of different functional conformations of Hb is examined through the determination of the dependence of O-2 affinity on water activity (a(w)). The control of a(w) is effected by varying the sucrose osmolal concentration in the bathing solution according to the osmotic stress method. Thus, the hydration change following Hb oxygenation is determined as a function of Cl- and of DPG concentration. We find that only similar to 25 additional water molecules bind to human Hb during the deoxy-to-oxy conformation transition in the absence of anions, in contrast with similar to 72 that bind in the presence of more than 50 mM Cl- or more than 15 mu M DPG. We demonstrate that the increase in the hydration change linked with oxygenation is coupled with anion binding to the deoxy-Hb. Hence, we propose that the deoxy-Hb coexists in two allosteric conformations which depend on whether anion is bound or not: the tense T-state, with low oxygen affinity and anion bound, or a new allosteric P-state, with intermediate oxygen affinity and free of bound anions. The intrinsic oxygen affinity of this unforeseen P-state and the differential binding of Cl-, DPG, and H2O between states P and T and P and R are characteristics which are consistent with those expected for a putative intermediate allosteric state of Hb. These findings represent a new opportunity to explore the structure-function relationships of hemoglobin regulation.

Enhanced emission from Eu(III) beta-diketone complex combined with ether-type oxygen atoms of di-ureasil organic-inorganic hybrids

Organic-inorganic hybrids, named di-ureasils and described by polyether-based chains grafted to both ends to a siliceous backbone through urea cross linkages, were used as hosts for incorporation of the well-known coordination complex of trivalent europium (Eu3+) ions described by the formula [Eu(TTA)(3)(H2O)(2)] (where TTA stands for thenoyltrifluoroacetone). By comparing with Eu3+-doped di-ureasil without complex form the new materials prepared here enhanced the quantum efficiency for photoemission of Eu3+ ions. The enhancement can be explained by the coordination ability of the organic counterpart of the host structure which is strong enough to displace water molecules in [Eu(TTA)(3)(H2O)(2)] from the rare earth neighbourhood after the incorporation process. High intensity of Eu3+ emission was observed with a low non-radiative decay rate under ultraviolet excitation. The quantum efficiency calculated from the decay of D-5(0) emission was 74%, which in the same range of values previously obtained for the most efficient Eu3+ coordination compounds reported in literature. Luminescence, X-ray absorption and infrared absorption results considered together leads to a picture where the first coordination shell of Eu3+ is composed of the 6 oxygen atoms of the 3 beta-diketonate ligands and 2 ether-like oxygen atoms of the host. (C) 2003 Elsevier B.V. B.V. All rights reserved.

DFT study of the reaction between VO2+ and C2H6

The molecular mechanisms of the reaction VO2+ ((1)A(1)/(3)A'') + C2H6 ((1)A(g)) to yield V(OH)(2)(+) ((1)Sigma(+)/(3)Sigma(-)) + C2H4 ((1)A(g)) and/or VO+ ((1)Delta/(3)Sigma) + H2O ((1)A(1)) + C2H4 (Ag-1) have been investigated with density functional theory (DFT) at the B3LYP/6-311G(2d,p) level. Calculations including geometry optimization, vibrational analysis, and Gibbs free energy for the stationary points on the reactive potential energy surfaces at both the singlet (s) and first excited triplet (t) electronic states have been carried out. The most thermodynamically and kinetically favorable pathway is the formation of t-V(OH)(2)(+) + C2H4 along a four-step molecular mechanism (insertion, two consecutive hydrogen transfers, and elimination). A crossing point between s and t electronic states has been characterized. A comparison with previous works on VO2+ + C2H4 (Gracia et al. J. Phys. Chem. A 2003, 107, 3107-3120) and VO2+ + C3H8 (Engeser et al. Organometallics 2003, 22, 3933-3943) reactions allows us a rationalization of the different reactivity patterns. The catalytic role of water molecules in the tautomerization process between hydrated oxide cation, VO(H2O)(+,) and dihydroxide cation, V(OH)(2)(+), is achieved by a water-assisted mechanism.

Synthesis, crystal structure, spectroscopic and electrochemical characterization of the dinuclear complex {tetra-mu-[(+/-)-2-(p-methoxyphenoxy)-propionato-O,O']bis(aqua)dicopper(II)}

Structural, electrochemical and spectroscopic data of a new dinuclear copper(II) complex with (+/-)-2-(p- methoxyphenoxy) propionic acid are reported. The complex {tetra-mu-[(+/-)-2-(p-methoxyphenoxy)propionato-O,O']-bis( aqua) dicopper(II)} crystallizes in the monoclinic system, space group P2(1)/n with a = 14.149(1) angstrom, b = 7.495(1) angstrom, c = 19.827(1) angstrom, beta = 90.62(1) and Z = 4. X-ray diffraction data show that the two copper(II) ions are held together through four carboxylate bridges, coordinated as equatorial ligands in square pyramidal geometry. The coordination sphere around each copper ion is completed by two water molecules as axial ligands. Thermogravimetric data are consistent with such results. The ligand has an L' type shape due to the angle formed by the beta-carbon of the propionic chain and the linked p-methoxyphenoxy group. This conformation contributes to the occurrence of a peculiar structure of the complex. The complex retains its dinuclear nature when dissolved in acetonitrile, but it decomposes into the corresponding mononuclear species if dissolved in ethanol, according to the EPR measurements. Further, cyclic voltammograms of the complex in acetonitrile show that the dinuclear species maintains the same structure, in agreement with the EPR data in this solvent. The voltammogram shows two irreversible reduction waves at E-pc = -0.73 and -1.04 V vs. Ag/AgCl assigned to the Cu(II)/ Cu(I) and Cu(I)/Cu degrees redox couples, respectively, and two successive oxidation waves at E-pa = -0.01 and +1.41 V vs. Ag/AgCl, assigned to the Cu degrees/Cu(I) and Cu( I)/Cu( II) redox couples, respectively, in addition to the oxidation waves of the carboxylate ligand.

Crystallization and X-ray diffraction data analysis of human deoxyhaemoglobin A(0) fully stripped of any anions

In this work, initial crystallographic studies of human haemoglobin (Hb) crystallized in isoionic and oxygen-free PEG solution are presented. Under these conditions, functional measurements of the O-2-linked binding of water molecules and release of protons have evidenced that Hb assumes an unforeseen new allosteric conformation. The determination of the high-resolution structure of the crystal of human deoxy-Hb fully stripped of anions may provide a structural explanation for the role of anions in the allosteric properties of Hb and, particularly, for the influence of chloride on the Bohr effect, the mechanism by which Hb oxygen affinity is regulated by pH. X-ray diffraction data were collected to 1.87 Angstrom resolution using a synchrotron-radiation source. Crystals belong to the space group P2(1)2(1)2 and preliminary analysis revealed the presence of one tetramer in the asymmetric unit. The structure is currently being refined using maximum-likelihood protocols.

New Ni(II)-sulfonamide complexes: Synthesis, structural characterization and antibacterial properties. X-ray diffraction of [Ni(sulfisoxazole)(2)(H2O)(4)] center dot 2H(2)O and [Ni(sulfapyridine)(2)]

The synthesis, structural characterization, voltammetric experiments and antibacterial activity of [Ni(sulfisoxazole)(2)(H2O)(4)] center dot 2H(2)O and [Ni(sulfapyridine)(2)] were studied and compared with similar previously reported copper complexes. [Ni(sulfisoxazole)(2)(H2O)(4)] center dot 2H(2)O crystallized in a monoclinic system, space group C2/c where the nickel ion was in a slightly distorted octahedral environment, coordinated with two sulfisoxazole molecules through the heterocyclic nitrogen and four water molecules. [Ni(sulfapyridine)(2)] crystallized in a orthorhombic crystal system, space group Pnab. The nickel ion was in a distorted octahedral environment, coordinated by two aryl amine N from two sulfonamides acting as monodentate ligands and four N atoms (two sulfonamidic N and two heterocyclic N) from two different sulfonamide molecules acting as bidentate ligands. Differential pulse voltammograms were recorded showing irreversible peaks at 1040 and 1070 mV, respectively, attributed to Ni(II)/Ni(III) process. [Ni(sulfisoxazole)(2)(H2O)(4)] center dot 2H(2)O and [Ni(sulfapyridine)(2)] presented different antibacterial behavior against Staphylococcus aureus and Escherichia coli from the similar copper complexes and they were inactive against Mycobacterium tuberculosis. (c) 2007 Elsevier B.V. All rights reserved.

Enhanced Eu3+ Emission in Aqueous Phosphotungstate Colloidal Systems: Stabilization of Polyoxometalate Nanostructures

Luminescent Eu3+-containing polyphosphate tungstate aqueous colloidal systems were prgared and studied as a function of the relative polyphosphate tungstate content. In polyphosphate-rich solutions, Eu-H- ions occupy cagelike sites composed of phosphate groups from the metaphosphate chains. In these sites, an average number of 0.5 water molecule coordinates to an Eu3+ ion and the 500 emission quantum efficiency is 0.22. Tungstatc addition leads to important modifications in neighboring Eu3+ leading to coordination sites in the aqueous medium where metal ions are completely hidden from interactions with solvent molecules. Transmission electron microscopy results clearly show \V-rich nanoparticles with sizes between 5 and 10 nm for all tungstate relative concentrations. For high tungstatc relative contents (above 30 mol %), spectroscopic results suggest the presence of Eu34- in polyoxometalate (P0M)-like sites by comparison with the well-known decatungstoeuropate [EuW10O36](9-) structure. These new aqueous colloids display surprisingly high 5llo emission quantum efficiencies of ca 80% because of the strong ligand field provided by tungstate POM ligands and the complete absence of water molecules from the Eu3+ first coordination shell.