Synthesis and characterization of Cu(II) complexes of tetradentate and tridentate symmetrical Schiff base ligands involving o-phenelenediamine, salicylaldehyde and diacetylmonoxime

A mononuclear complex [CuL] (1), a binuclear complex [Cu2LCl2(H2O)] (2), a trinuclear complex [Cu3L2](ClO4)(2) (3) involving o-phenylenediamine and salicylaldehyde and another binuclear complex of a tridentate ligand (H2L1) [Cu2L (2) (1) ](CH3COO)(2) (4) involving o-phenylenediamine and diacetylmonoxime have been synthesized, where H2L = N,N'-o-phenylenebis(salicylideneimine) and H2L1 = 3-(2-aminophenylimino)butan-2-one oxime. All the complexes have been characterized by elemental analyses, spectral and magnetic studies. The binuclear complex (2) was characterized structurally where the two Cu(II) centers are connected via an oxygen-bridged arrangement.

Peroxidative bromination and oxygenation of organic compounds: synthesis, X-ray crystal structure and catalytic implications of mononuclear and binuclear oxovanadium(V) complexes containing Schiffbase ligands

Treatment of of (R,R)-N,N-salicylidene cyclohexane 1,2-diamine(H(2)L(1)) in methanol with aqueous NH(4)VO(3) solution in perchloric acid medium affords the mononuclear oxovanadium(V) complex [VOL(1)(MeOH)]-ClO(4) (1) as deep blue solid while the treatment of same solution of (R,R)-N,N-salicylidene cyclohexane 1,2-diamine(H(2)L(1)) with aqueous solution of VOSO(4) leads to the formation of di-(mu-oxo) bridged vanadium(V) complex [VO(2)L(2)](2) (2) as green solid where HL(2) = (R,R)-N-salicylidene cyclohexane 1,2-diamine. The ligand HL(2) is generated in situ by the hydrolysis of one of the imine bonds of HL(1) ligand during the course of formation of complex [VO(2)L(2)](2) (2). Both the compounds have been characterized by single crystal X-ray diffraction as well as spectroscopic methods. Compounds 1 and 2 are to act as catalyst for the catalytic bromide oxidation and C-H bond oxidation in presence of hydrogen peroxide. The representative substrates 2,4-dimethoxy benzoic acid and para-hydroxy benzoic acids are brominated in presence of H(2)O(2) and KBr in acid medium using the above compounds as catalyst. The complexes are also used as catalyst for C-H bond activation of the representative hydrocarbons toluene, ethylbenzene and cyclohexane where hydrogen peroxide acts as terminal oxidant. The yield percentage and turnover number are also quite good for the above catalytic reaction. The oxidized products of hydrocarbons have been characterized by GC Analysis while the brominated products have been characterized by (1)H NMR spectroscopic studies.

BTBPs versus BTPhens: some reasons for their differences in properties concerning the partitioning of minor actinides and the advantages of BTPhens

Two members of the tetradentate N-donor ligand families 6,6′-bis(1,2,4-triazin-3-yl)-2,2′-bipyridine (BTBP) and 2,9-bis(1,2,4-triazin-3-yl)-1,10-phenanthroline (BTPhen) currently being developed for separating actinides from lanthanides have been studied. It has been confirmed that CyMe4-BTPhen 2 has faster complexation kinetics than CyMe4-BTBP 1. The values for the HOMO−LUMO gap of 2 are comparable with those of CyMe4-BTBP 1 for which the HOMO−LUMO gap was previously calculated to be 2.13 eV. The displacement of BTBP from its bis-lanthanum(III) complex by BTPhen was observed by NMR, and constitutes the only direct evidence for the greater thermodynamic stability of the complexes of BTPhen. NMR competition experiments suggest the following order of bis-complex stability: 1:2 bis-BTPhen complex ≥ heteroleptic BTBP/BTPhen 1:2 bis-complex > 1:2 bis-BTBP complex. Kinetics studies on some bis-triazine N-donor ligands using the stopped-flow technique showed a clear relationship between the rates of metal ion complexation and the degree to which the ligand is preorganized for metal binding. The BTBPs must overcome a significant (ca. 12 kcal mol−1) energy barrier to rotation about the central biaryl C−C axis in order to achieve the cis−cis conformation that is required to form a complex, whereas the cis−cis conformation is fixed in the BTPhens. Complexation thermodynamics and kinetics studies in acetonitrile show subtle differences between the thermodynamic stabilities of the complexes formed, with similar stability constants being found for both ligands. The first crystal structure of a 1:1 complex of CyMe4-BTPhen 2 with Y(NO3)3 is also reported. The metal ion is 10- coordinate being bonded to the tetradentate ligand 2 and three bidentate nitrate ions. The tetradentate ligand is nearly planar with angles between consecutive rings of 16.4(2)°, 6.4(2)°, 9.7(2)°, respectively.

Structural complexity in indium selenides prepared using bicyclic amines as structure-directing agents

The synthesis and characterization of five new indium selenides, [C9H17N2]3[In5Se8+x(Se2)1−x] (1–2), [C6H12N2]4[C6H14N2]3[In10Se15(Se2)3] (3), [C6H14N2][(C6H12N2)2NaIn5Se9] (4) and [enH2][NH4][In7Se12] (5), are described. These materials were prepared under solvothermal conditions, using 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and 1,4-diazabicyclo[2.2.2]octane (DABCO) as structure-directing agents. Compounds 1–4 represent the first examples of ribbons in indium selenides, and 4 is the first example of incorporation of an alkali metal complex. Compounds 1, 2 and 4 contain closely related [In5Se8+x(Se2)1−x]3− ribbons which differ only in their content of (Se2)2− anions. These ribbons are interspaced by organic countercations in 1 and 2, while in 4 they are linked by highly unusual [Na(DABCO)2]+ units into a three-dimensional framework. Compound 3 contains complex ribbons, with a long repeating sequence of ca. 36 Å, and 4 is a non-centrosymmetric three-dimensional framework, formed as a consequence of the decomposition of DABCO into ethylenediamine (en) and ammonia.

主在并[a] 龍財赤子愛腔蚓錢粒体編研基因衰退影蝸

The earthworm Eisenia fetida's benzo [a] pyrene (BaP) exposure experiments were carried out in artificial soil according to ISO 11268-1:1993. And then the upregulated and downregulated subtractive cDNA libraries were constructed by Clontech PCR-Select cDNA Subtration Kit. From the BaP exposure upregulated subtractive cDNA library, several cDNA segments matched mitochondrion-encoded genes were found, including cytochrome c oxidase subunit I (CO I), subunit II (CO II), subunit Ill (CO III), NADH dehydrogenase subunit 1 (NDH1), and ATP synthase subunit 6. The result indicated BaP and the subsequent oxidative stress disturbed the expression of mitochondrion-encoded genes, and this was potential biomarker for oxidative stress following xenobiotic exposure.

Caracterização do complexo de inclusão ropivacaína: β-ciclodextrina

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

Study of the interaction between hydroxymethylnitrofurazone and 2-hydroxypropyl-beta-cyclodextrin

Chagas disease is a serious health problem in Latin America. Hidroxymethylnitrofurazone (NFOH) is a nitrofurazone prodrug more active than nitrofurazone against Trypanosoma cruzi. However, NFOH presents low aqueous solubility, high photodecomposition and high toxicity. The present work is focused on the characterization of an inclusion complex of NFOH in 2-hydroxypropyl-beta-cyclodextrin (HP-beta-CD). The complexation with HP-beta-CD was investigated using reversed-phase liquid chromatography, solubility isotherms and nuclear magnetic resonance. The retention behavior was analyzed on a reversed-phase C-18 column, using acetonitrile-water (20/80, v/v) as the mobile phase, in which HP-beta-CD was incorporated as a mobile phase additive. The decrease in the retention times with increasing concentrations of HP-beta-CD enables the determination of the apparent stability constant of the complex (K = 6.2 +/- 0.3 M-1) by HPLC. The solubility isotherm was studied and the value for the apparent stability constant (K = 7.9 +/- 0.2 M-1) was calculated. The application of continuous variation method indicated the presence of a complex with 1:1 NFOH:HP-beta-CD stoichiometry. The photostability study showed that the formation of an inclusion complex had a destabilizing effect on the photodecomposition of NFOH when compared to that of the "free" molecule in solution. The mobility investigation (by NMR longitudinal relaxation time) gives information about the complexation of NFOH with HP-beta-CD. In preliminary toxicity studies, cell viability tests revealed that inclusion complexes were able to decrease the toxic effect (p < 0.01) caused by NFOH. (c) 2008 Elsevier B.V. All rights reserved.

fac-[RuCl3(no)(dppb)] (I) and mer-[RuCl3(NO)(diop)] (II) complexes: Syntheses, characterization and x-ray structures

The fac-[RuCl3(NO)(dppb)] complex I has been prepared from solution of the correspondent mer isomer in refluxing methanol (dppb = 1,4-bis(diphenylphosphino)butane). The mer-[RuCl3(NO)(diop)] (II) has been obtained from the mer-[RuCl3(diop)(H2O)] by bubbling NO for 1 h in dichloromethane (diop = 2S,3S-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane). The complexes have been characterized by microanalysis, cyclic voltammetry (CV), IR and 31P{1H} NMR spectroscopies. The crystal and molecular structures of these two compounds have been determined from X-ray studies. The mer-[RuCl3(NO)(dppb)] isomer III was characterized in solution by NMR spectra (31P{1H}, 1H{31P}, 31P-1H HETCORR, COSY 1H-1H, HMQC 1H-13C and HMBC 1H-13C). © 2002 Elsevier Science Ltd. All rights reserved.

Preparação e caracterização inicial de complexo de inclusão entre nitrofurazona e 2-hidroxipropil-β-ciclodextrina

Nitrofurazone (NF), 5-nitro-2-furaldehyde semicarbazone, a broad-spectrum antibiotic, has reported toxic effects and low solubility in water. It would be of great interest to form inclusion complexes between NF and a cyclodextrin, to develop more effective and safer antibiotic formulations. This paper focuses on the preparation of inclusion complexes of NF with 2-hydroxypropyl-β- cyclodextrin (HP-β-CD) and their initial characterization by evaluating rates of complex formation, photostability, solubility isotherms, release rate profiles, stoichiometry of the complexes and their morphology, as revealed by scanning electron microscopy. The kinetic tests of complex formation revealed that 17,3 h is enough for stabilization of the NF-cyclodextrin complex. The solubility isotherm studies showed that the isotherm changes from type A to type B, as a function of temperature. The photostability experiments showed that the insertion of the NF in the HP-β-CD cavity protects the drug from photodecomposition. The release kinetic tests showed that the profile of NF release from the complex is altered by the presence of HP-β-CD in the medium. A Job's plot indicated that the stoichiometry of the complex was 1:1 NF:HP-β-CD. The scanning electron micrographs showed changes in the crystal structure of NF in the complex. This study focused on the physicochemical properties of drug-delivery formulations that could potentially be developed into a novel type of therapy with NF.

Geometrical wave equation and the cauchy-like theorem for octonions

Riemann surfaces, cohomology and homology groups, Cartan's spinors and triality, octonionic projective geometry, are all well supported by Complex Structures [1], [2], [3], [4]. Furthermore, in Theoretical Physics, mainly in General Relativity, Supersymmetry and Particle Physics, Complex Theory Plays a Key Role [5], [6], [7], [8]. In this context it is expected that generalizations of concepts and main results from the Classical Complex Theory, like conformal and quasiconformal mappings [9], [10] in both quaternionic and octonionic algebra, may be useful for other fields of research, as for graphical computing enviromment [11]. In this Note, following recent works by the autors [12], [13], the Cauchy Theorem will be extended for Octonions in an analogous way that it has recentely been made for quaternions [14]. Finally, will be given an octonionic treatment of the wave equation, which means a wave produced by a hyper-string with initial conditions similar to the one-dimensional case.

Produção dos fragmentos de anticorpos recombinantes scFv-N e scFv-S1 e suas aplicações na detecção e diferenciação do Vírus da Bronquite Infecciosa

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Análise filogenética de Leptodeira Fitzinger, 1843 e taxonomia das espécies do clado do sul do complexo Leptodeira annulata/septentrionalis (Serpentes, Dipsadidae)

Leptodeira é um gênero Neotropical de serpentes com nove espécies, dividido em quatro grupos morfológicos: annulata com as espécies L. annulata (L. a. annulata, L. a. ashmeadi, L. a. cussiliris, L. a. pulchriceps, L. a. rhombifera), L. bakeri, L. maculata, L. frenata (L. f. frenata, L. f. malleisi, L. f. yucatanensis), L. uribei; septentrionalis com L. septentrionalis (L. s. septentrionalis, L. s. larcorum, L. s. ornata, L. s. polysticta), L. splendida (L. s. splendida, L. s. bressoni, L. s. ephippiata); nigrofasciata com apenas a espécie L. nigrofasciata; e grupo punctata representado por L. punctata. Na última revisão taxonômica do gênero, várias espécies foram consideradas como subespécies, sendo caracterizadas principalmente com base no padrão de cor. No entanto, recentes análises moleculares não corroboraram o arranjo taxonômico proposto anteriormente. As duas espécies com distribuição geográfica mais ampla e maior número de subespécies, L. annulata e L. septentrionalis, não tiveram monofila validada. Na mais recente proposta filogenética de Leptodeira, a monofilia do complexo L. annulata/septentrionalis foi obtida a partir de caracteres moleculares, sendo recuperados dois clados geograficamente distintos: um clado Norte presente no sul da América do Norte e norte da América Central (L. s. polysticta ((L. rubricata - L. a. rhombifera) ((L. a. cussiliris - L. maculata) L. a. cussiliris))); e outro clado Sul-americano presente no sul da América Central e toda América do Sul ((L. s. ornata–L. a. annulata) (L. s. ornata (L. bakeri (L. a. ashmeadi–L. a. annulata)))). Neste trabalho, apresento uma hipótese filogenética para Leptodeira e reviso taxonomicamente o clado Sul do complexo L. annulata/septentrionalis, apresentando um novo arranjo taxonômico para o grupo. Desta forma, a presente tese está organizada em: Introdução Geral, onde foram apresentadas informações sobre taxonomia e sistemática de Leptodeira, especialmente do complexo L. annulata/septentrionalis; Capítulo 1 intitulado “Análise filogenética de Leptodeira (Serpentes, Dipsadidae)”, com o objetivo de propor uma hipótese filogenética para o gênero, com base em caracteres moleculares; e o Capítulo 2 intitulado “Taxonomia das espécies do clado Sul do complexo L. annulata/septentrionalis (Serpentes, Dipsadidae)”, que teve como objetivo caracterizar morfologicamente os clados obtidos a partir da análise molecular e propor um novo arranjo taxonômico para o grupo.

Systematics of the section Virescentia of the genus Batrachospermum (Batrachospermales, Rhodophyta) in Brazil

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

The laurent series for the quaternionic case

The present work has the scope to show the Laurent Series for quaternionic functions. It will be shown that the Laurent Series for the Quaternionic Case is analogous to the textbook case of Complex Analysis [1]-[2] already well established.