On the Nucleophilicity of Boryllithium Compounds. A Theoretical Study

Boron compounds are widely used in synthetic chemistry. The synthesis of the compounds is relatively easy, presenting thermodynamic stability and synthetic versatility. Almost all of them show electrophilic reactivity. Recently, some boryllithium species have been reported as a base or a nucleophile in reaction with organic electrophiles in S(N)2 reactions. In the present work, the proton affinity (PA) of boryllithium compounds was calculated. These values can be useful as theoretical reference values and to provide valuable complementary information for the interpretation and discussion of the basicity of these compounds. The proton affinity was calculated using a theoretical method based on density functional theory and high-level theoretical methods through MP2 and G2MP2 levels of theory. In addition, some global and local reactivity indexes based on density functional theory (DFT) on boryllithium compounds were studied. In order to compare and discuss the chemical reactivity of these compounds, some analogues and electrophilic boron compounds were also studied. Our results showed a local and global nucleophilic reactivity of the boryllithium molecules in agreement with the experimental. reactivity. The boryllithium compounds revealed to be strong bases in comparison to other analogue compounds studied in this work.

Control of Two-Photon Absorption in Organic Compounds by Pulse Shaping: Spectral Dependence

In this work, we investigate the control of the two-photon absorption process of a series of organic compounds via spectral phase modulation of the excitation pulse. We analyzed the effect of the pulse central wavelength on the control of the two-photon absorption process for each compound. Depending on the molecules` two-photon absorption position relative to the excitation pulse wavelength, different levels of coherent control were observed. By simulating the two-photon transition probability in molecular systems, taking into account the band structure and its positions, we could explain the experimental results trends. We observed that the intrapulse coherent interference plays an important role in the nonlinear process control besides just the pulse intensity modulation.

Detection of phenolic compounds using impedance spectroscopy measurements

Langmuir-Blodgett (LB) and layer-by-layer films (LbL) of a PPV (p-phenylenevinylene) derivative, an azo compound and tetrasulfonated phthalocyanines were successfully employed as transducers in an ""electronic tongue"" system for detecting trace levels of phenolic compounds in water. The choice of the materials was based on their distinct electrical natures, which enabled the array to establish a fingerprint of very similar liquids. Impedance spectroscopy measurements were taken in the frequency range from 10 Hz to 1 MHz, with the data analysed with principal component analysis (PCA). The sensing units were obtained from five-layer LB films of (poly[(2-methoxy-5-n-hexyloxy)-p-phenylenevinylene]), OC(1)OC(18)-PPV (poly(2-methoxy,5-(n-octadecyl)-p-phenylenevinylene)), DR (HEMA-co-DR13MA (poly-(hydroxyethylmethacrylate-co-[4`-[[2-(methacryloyloxy)-ethyl]ethylamino]-2-chloro-4-nitroazobenzene]))) and five-bilayer LbL films of tetrasulfonated metallic phthalocyanines deposited onto gold interdigitated electrodes. The sensors were immersed into phenol, 2-chloro-4-methoxyphenol, 2-chlorophenol and 3-chlorophenol (isomers) solutions at 1 x 10(-9) mol L(-1), with control experiments carried out in ultra pure water. Samples could be distinguished if the principal component analysis (PCA) plots were made with capacitance values taken at 10(3) Hz, which is promising for detection of trace amounts of phenolic pollutants in natural water.

Zirconium oxide anodic films: Optical and structural properties

The photoluminescence of anodically prepared ZrO(2) films was investigated. Morphological and microstructural analyses reveal an oxide surface covered by a high distribution of blisters and the major crystallographic structure is the monoclinic phase with small quantities of tetragonal phase. The photoluminescence reveals a broad emission band in the range between 350 and 650 nm. It was proposed that the photoluminescence mechanism is originated from the emission of a recombination center related to defects (oxygen vacancies) formed during Zr anodization. (C) 2008 Elsevier B.V. All rights reserved.

Phase-transition studies of Ba(0.90)Ca(0.10)(Ti(1-x)Zr(x))O(3) ferroelectric ceramic compounds

Perovskite-structured Ba(0.90)Ca(0.10)(Ti(1-x)Zr(x))O(3) ceramics were prepared in this work and subsequently studied in terms of composition-dependent dielectric and high-resolution long-range order structural properties from 30 to 450 K. The dielectric response of these materials was measured at several frequencies in the range from 1 kHz to 1 MHz. Combining both techniques, including Rietveld refinement of the X-ray diffraction data, allowed observing that, when increasing Zr(4+) content, the materials change from conventional to diffuse and relaxor ferroelectric compounds, the transition occurring spontaneously at the x = 0.18 composition. Interestingly, this spontaneous transition turned out to be prevented for a further increase of Zr(4+). On the basis of all the dielectric and structural results processed, a phase diagram of this system is presented. (C) 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Two-photon absorption properties of a novel class of triarylamine compounds

Two-photon absorption spectra of a triarylamine compounds dissolved in toluene were measured using the well-known Z-scan technique, employing 120-fs laser pulse-width. According to the results, an extra band located at around 900 nm was observed only for triarylamine with azoaromatic units. On the other hand, a shift in the two-photon absorption band for triarylamine, with and without azoaromatic units, is observed when different electron donor/acceptors groups are changed. The fitting of the spectra, using sum-over-states model, allowed us to obtain the spectroscopic parameters of each molecule, which appears to be in reasonable agreement with molecules presenting similar structural moieties. (C) 2010 Elsevier B.V. All rights reserved.

Heterobimetallic compounds [Ru(eta(5)-Cp)(dppf)X] (X = Cl, Br, I and N(3)): synthesis, electrochemical analysis, and the crystal structure of [Ru(eta(5)-Cp)(dppf)I] [dppf=1,1`-bis(diphenylphosphino)ferrocene]

A series of new ruthenium-iron based derivatives [Ru(eta(5)-Cp)(dppf)Cl] (1), [Ru(eta(5)-Cp)(dppf)Br] (2), [Ru(eta(5)-Cp)(dppf)I] (3) and [Ru(eta(5)-Cp)(dppf)N(3)] (4) were obtained by reactions of [Ru(eta(5)-Cp)(PPh(3))(2)Cl] with 1,1`-bis(diphenylphosphino) ferrocene (dppf) and characterized by IR, NMR ((1)H, (13)C and (31)P), (57)Fe Mossbauer spectroscopy and cyclic voltammetry. Additionally, the compound (3) was structurally characterized by X-ray crystallography, and the results were as follows: orthorhombic, Pbca, a = 18.2458(10), b = 20.9192(11), c = 34.4138(19) a""<<, alpha = beta = gamma = 90A degrees, V = 13135.3(12) a""<<(3) and Z = 16.

Binuclear zinc(II) complexes with the anti-inflammatory compounds salicylaldehyde semicarbazone and salicylaldehyde-4-chlorobenzoyl hydrazone (H(2)LASSBio-1064)

Complexes [Zn(2)(HL(1))(2)(CH(3)COO)(2)] (1) and [Zn(2)(L(2))(2)] (2) were synthesized with salicylaldehyde semicarbazone (H(2)L(1)) and salicylaldehyde-4-chlorobenzoyl hydrazone (H(2)LASSBio-1064, H(2)L(2)), respectively. The crystal structure of (1) was determined. Upon recrystallization of previously prepared [Zn(2)(HL(2))(2)(Cl)(2)] (3) in 1:9 DMSO:acetone crystals of [Zn(2)(L(2))(2)(H(2)O)(2)]center dot[Zn(2)(L(2))(2)(DMSO)(4)] (3a) were obtained. The crystal structure of 3a was also determined. All crystal structures revealed the presence of phenoxo-bridged binuclear zinc(II) complexes. (C) 2011 Elsevier Ltd. All rights reserved.

Analyzing Ru(III)-dmso and Ru(III)-dms motifs in compounds used in the synthesis of the antimetastatic agents

The chemistry of Ru(III) complexes containing dmso as a ligand has become an interesting area in the cancer treatment field. Because of this, structural knowledge and chemistry of the moiety Ru(III)-dmso have become important to cancer research. The crystal structures of the compounds mer-[RuCl(3)(dms)(3)] (1) and mer-[RuCl(3)(dms)(2)(dmso)]:mer-[RuCl(3)(dms)(3)] (2) were determined by X-ray crystallography and a speciation of the presence of intramolecular hydrogen bond in these structures has been studied. Compound (1) crystallizes in the orthorhombic space group, Pna2(1); a = 16.591(8) angstrom, b = 8.724(2) angstrom. c = 10.547(3) angstrom; Z = 12 and (2) crystallizes in the space group, P2(1)/C: a = 11.9930(2) angstrom, b = 7.9390(2) angstrom, c = 15.8700(3) angstrom, beta = 93.266(1)degrees, Z = 2. From the X-ray structures solved in this work, were possible to suggest an interpretation for the broad lines observed in the EPR spectra of the Ru(III) compounds explored here. Also, the exchange interactions detected by EPR spectroscopy in solid state and in solution, confirm the presence of van der Waals interactions such as C-H center dot center dot center dot Cl in the compounds (1), (2) and (3). The use of techniques such as IR, UV-vis, (1)H NMR and EPR Spectroscopy and Cyclic Voltammetry were applied in this work to analyze the behavior of these metallocompounds. (c) 2008 Elsevier B.V. All rights reserved.

Synthesis and Characterization of Homoleptic and Heteroleptic Cobalt, Nickel, Copper, Zinc and Cadmium Compounds with the 2-(Tosylamino)-N-[2-(tosylamino)benzylidene]aniline Ligand

The electrochemical oxidation of anodic metal (cobalt, nickel, copper, zinc and cadmium) in an acetonitrile solution of the Schiff-base ligand 2-(tosylamino)-N-[2-(tosylamino)-benzylidene] aniline (H(2)L) afforded the homoleptic compounds [ML]. The addition of 1,1-diphenylphosphanylmethane (dppm), 2,2`-bipyridine (bipy) or 1,10-phenanthroline (phen) to the electrolytic phase gave the heteroleptic complexes [NiL(dppm)], [ML(bipy)] and [ML(phen)]. The crystal structures of H(2)L (1), [NiL] (2), [CuL] (3), [NiL(dppm)] (4), [CoL(phen)] (5), [CuL(bipy)] (6) and [Zn(Lphen)] (7) were determined by X-ray diffraction. The homoleptic compounds [NiL] and [CuL] are mononuclear with a distorted square planar [MN(3)O] geometry with the Schiff base acting as a dianionic (N(amide)N(amide)N(imine)O(tosyl)) tetradentate ligand. Both compounds exhibit an unusual pi-pi stacking interaction be-tween a six-membered chelate ring containing the metal and a phenylic ring of the ligand. In the heteroleptic complex [NiL(dppm)], the nickel atom is in a distorted tetrahedral [NiN(3)P] environment defined by the imine, two amide nitrogen atoms of the L(2-) dianionic tridentate ligand and one of the phosphorus atoms of the dppm molecule. In the other heteroleptic complexes, [CoL(phen)], [CuL(bipy)] and [ZnL(phen)], the metal atom is in a five-coordinate environment defined by the imine, two amide nitrogen atoms of the dianionic tridentate ligand and the two bipyridine or phenanthroline nitrogen atoms. The compounds were characterized by microanalysis, IR and UV/Vis (Co, Ni and Cu complexes) spectroscopy, FAB mass spectrometry and (1)H NMR ([NiL] and Zn and Cd complexes) and EPR spectroscopy (Cu complexes).

New insights on the Lewis acidity of diorganolead(IV) compounds: Diphenyllead(IV) complexes with N,O,S-chelating ligands

The reactions of PbPh2(OAC)(2) with alkylglyoxylate thiosemicarbazones (HRGTSC, R = Et, Bu) afforded complexes of the type [PbPh2(GTSC)] center dot H2O, [PbPh2(RGTSC)(2)] and [PbPh2Cl(BUGTSC)]. The structures of HRGTSC (R = Me, Et, Bu), [PbPh2(OAc)(RGTSC)](R = Me, Et, Bu), [PbPh2Cl(BuGTSC)] and [PbPh2(GTSC)] center dot H2O have been studied by X-ray diffraction. [PbPh2(OAc)(RGTSC)] and [PbPh2(GTSC)] center dot H2O have [PbC2NO3S] kernels and the coordination sphere of the metal is pentagonal bipyramidal. [PbPh2Cl(BuGTSC)] has a [PbC2NOSCI] kernel and the coordination geometry around lead is pentagonal bipyramidal with one vacant site. Analysis of the bond distances in [PbPh2(GTSC)] center dot H2O suggests a significant affinity between diphenyllead(IV) and carboxylate donor groups, supporting a borderline acidic character for this organometallic cation. H-1 and C-13 NMR spectra in DMSO-d(6) suggest the partial dissociation of the acetate in [PbPh2(OAc)(RGTSC)] solutions and indicate some differences in the coordination mode of the two RGTSC(-) ligands in [PbPh2(RGTSC)(2)] complexes. (C) 2007 Elsevier Ltd. All rights reserved.

The mer-[RuCl(3)(dppb)(H(2)O)] complex: A versatile tool for synthesis of Ru(II) compounds

The complex mer-[RuCl(3)(dppb)(H(2)O)] [dppb = 1,4-bis(diphenylphosphino)butane] was used as a precursor in the synthesis of the complexes tc-[RuCl(2)(CO)(2)(dppb)], ct-[RuCl(2)(CO)(2)(dppb)]. cis-[RuCl(2)(dppb)(Cl-bipy)], [RuCl(2Ac4mT)(dppb)] (2Ac4mT = N(4)-meta-tolyl-2-acetylpyridine thiosemicarbazone ion) and trans-[RuCl(2)(dppb)(mang)] (mang = mangiferin or 1,3,6,7-tetrahydroxyxanthone-C2-beta-D-glucoside) complexes. For the synthesis of Run complexes, the Ru(III) atom in mer-[RuCl(3)(dppb)(H(2)O)] may be reduced by H(2)(g), forming the intermediate [Ru(2)Cl(4)(dppb)(2)], or by a ligand (such as H2Ac4mT or mangiferin). The X-ray structures of the cis-[RuCl(2)(dppb)(Cl-bipy)], tc-[RuCl(2)(CO)(2)(dppb)] and [RuCl(2Ac4mT)(dPpb)] complexes were determined. (C) 2010 Elsevier Ltd. All rights reserved.

Synthesis and analgesic profile of conformationally constrained N-acylhydrazone analogues: Discovery of novel N-arylideneamino quinazolin-4(3H)-one compounds derived from natural safrole

In this work we reported the synthesis and evaluation of the analgesic, anti-inflammatory, and platelet anti-aggregating properties of new 3-(arylideneamino)-2-methyl-6,7-methylenedioxy-quinazolin-4 (3H)-one derivatives (3a-j), designed as conformationally constrained analogues of analgesic 1,3- benzodioxolyl-N- acylhydrazones (1) previously developed at LASSBio. Target compounds were synthesized in very good yields exploiting abundant Brazilian natural product safrole (2) as starting material. The pharmacological assays lead us to identify compounds LASSBio-1240 (3b) and LASSBio-1272 (3d) as new analgesic prototypes, presenting an antinociceptive pro. le more potent and effective than dipyrone and indomethacin used, respectively, as standards in AcOH-induced abdominal constrictions assay and in the formalin test. These results confirmed the success in the exploitation of conformation restriction strategy for identification of novel cyclic N-acylhydrazone analogues with optimized analgesic profile (C) 2009 Elsevier Ltd. All rights reserved.

Synthesis of Phthalocyanines-ALA Conjugates: Water-Soluble Compounds with Low Aggregation

Syntheses of two water-soluble phthalocyanines (Pc) containing 5-aminolevulinic acid (ALA) linked to the core structure are described. These compounds were prepared by using original functionalizations, and they present remarkable structural and photophysical features, indicating that they could be applied to photodynamic therapy (PDT).

Structure-Activity Relationship for Quaternary Ammonium Compounds Hybridized with Poly(methyl methacrylate)

Hybrid films from poly (methylmethacrylate) (PMMA) and dioctadecyldimethylammonium bromide (DODAB), cetyltrimethylammonium bromide (CTAB), or tetrapropylammonium bromide (TPAB) were characterized by determination of wettability, ellipsometry, atomic force microscopy, active compounds diffusion to water, X-ray photoelectron spectroscopy (XPS) with determination of atomic composition on the films surface, and biocidal activity against Pseudomonas aeruginosa or Staphylococcus aureus. QAC mobility in the films increased from DODAB to CTAB to TPAB. Diffusion and optimal hydrophobic hydrophilic balance imparted the highest bioactivity to CTAB. DODAB sustained immobilization at the film surface killed bacteria upon contact. TPAB ability to diffuse was useless because of its unfavorable hydrophobic hydrophilic balance for bioactivity.