Influence of ionic interactions on the photoinduced Birefringence of poly[1-[4-(3-carboxy-4 hydroxyphenylazo) benzene sulfonamido]-1 2-ethanediyl, sodium salt] films

Electrostatic interactions govern most properties of polyelectrolyte films, as in the photoinduced bire-fringence of azo-containing polymers. In this paper we report a systematic investigation of optical storage characteristics of cast and layer-by-layer (LbL) films of poly[1 -[4-(3-carboxy-4 hydroxypheny-lazo) benzene sulfonamido]-1,2-ethanediyl, sodium salt] (PAZO). Birefringence was photoinduced faster in PAZO cast films prepared at high pHs, with the characteristic writing times decreasing almost linearly with the pH in the range between 4 and 9. This was attributed to an increased free volume for the azochromophores with the enhanced electrostatic repulsion in PAZO charged to a greater extent. In contrast, in LbL films of PAZO alternated with poly(allylamine hydrochloride) (PAH), the electrostatic interactions between the oppositely charged polymers hampered photoisomerization and molecular rearrangement, thus leading to a slower writing kinetics for highly charged PAH or PAZO.

Sorption and preconcentration of metal ions on silica gel modified with 2,5-dimercapto-1,3,4-thiadiazole

Silica gel, chemically modified with 2,5-dimercapto-1,3,4-thiadiazole [=Si(CH2)(3)-NC2HNS3], abbreviated as SiB, was used to adsorb metal ions from ethanol by both batch and column techniques. Elution of Cu(II) was done with a solvent mixture of acetone and hydrochloric acid (9:1 v/v). Zn(II), Cd(II), Ni(II), Pb(II), Co(II) and Fe(III) were eluted with 0.5 mol l(-1) HC1 in ethanol solution. The modified silica was applied in the preconcentration of metal ions from commercial ethanol, normally used as engine fuel. The method is suitable for quantifying these metals at low mu g l(-1) levels.

Structure characterization of molecular complexes for non-linear optical materials. II. 1 : 1 complexes of 4-methyl-morpholine-N-oxide (1) and 3-picoline-N-oxide (2) with 2,4,6-trinitrophenol, studied by X-ray, AM1 and DFT calculations

(1) C6H2N3O7- center dot C5H12NO2+, Mr = 346.26, P2(1)/c, a = 7.2356(6), b = 10.5765(9), c = 19.593(2) angstrom, 3 beta=95.101(6)degrees, V = 1493.5(2) angstrom(3), Z = 4, R-1 = 0.0414; (2) C6H2N3O7- center dot C6H8NO+, Mr = 38.24, P2(1)/n, a = 7.8713(5), b = 6.1979(7), c = 28.697(3) angstrom, beta = 90.028(7)degrees, V = 1400.0(2) angstrom(3), Z = 4, R-1 = 0.0416. The packing units in both compounds consist of hydrogen bonded cation-anion pairs. The (hyper)polarizabilities have been calculated for the crystallographic and optimized molecules, by AM1 and at the DFT/B3LYP(6-31G**) level.

Efficacy, safety and tolerability of terbinafine for Tinea capitis in children: Brazilian multicentric study with daily oral tablets for 1, 2 and 4 weeks

Background: Tinea capitis is a common skin disease seen predominantly in children. The standard therapies for this disease are griseofulvin and ketoconazole. Nevertheless, these drugs have drawbacks in that they are only fungistatic and require treatment for at least 6 weeks. Previous studies with oral terbinafine for the treatment of Tinea capitis have shown that this agent is effective when given for 4 weeks, comparable to an 8-week regimen with griseofulvin. To date there is no data on the use of oral terbinafine in Brazilian children. Objectives: To assess the efficacy, safety and tolerability of oral terbinafine in short-term treatments (1-, 2- and 4-week treatment) of Tinea capitis in children. Patients and methods: One hundred and thirty-two children aged 1-14 years were enrolled in this study, but only 107 were considered for the final efficacy analysis. Diagnosis included clinical assessment and examination by Wood's light. Confirmation was obtained by direct microscopy and culture for fungus. Terbinafine dosage (125 or 250 mg/day) was adjusted according to patient weight. Efficacy was evaluated both by clinical and mycological assessment. Safety and tolerability variables included data on adverse reaction and clinical laboratory evaluations. Results: Mycological evaluation in the follow-up visit at week 12 showed negative direct microscopy and culture results in 48.6, 60.5 and 69.7% patients in groups 1-, 2- and 4-week, respectively (n.s.). At week 12, 84.8% patients in group 4-week achieved clinical cure with a significant difference compared to groups 1- and 2-week, 54.3 and 60.5%, respectively (P < 0.01). Adverse reactions were present in 4.8, 6.8 and 10.9% of patients in groups 1-, 2- and 4-week, respectively. Terbinafine was not associated with clinically relevant increases in liver function tests. Conclusions: Terbinafine is an effective, well tolerated and safe antifungal agent for the treatment of Tinea capitis m children. The shorter duration of treatment resulted in lower cure rates. However, it is important to note that depending on the severity of the disease, a 1-week-only treatment can also be effective in this indication.

Determination of metal ions in fuel ethanol after preconcentration on 5-amino-1,3,4-thiadiazole-2-thiol modified silica gel

This work describes the synthesis and characterization of 5-amino-1,3,4-thiadiazole-2-thiol modified silica gel (SiATT), and the results of a study of the adsorption and preconcentration (in batch, and in flow using a column technique) of Cd(II), Co(II), Cu(II), Fe(III), Ni(II), Pb(II) and Zn(II) in ethanol medium. The adsorption capacities for each metal ion were (in mmol g -1): Cd(II) = 0.11, Co(II) = 0.10, Cu(II) = 0.20, Fe(III) = 0.20, Ni(II) = 0.16, Pb(II) = 0.08 and Zn(II) = 0.12. The results obtained in the flow experiments, showed a recovery of ca. 100% of the metal ions adsorbed in a column packed with 2 g of SiATT, using 5 mL of 2.0 mol L -1 HCl solution as eluent. The sorption-desorption of the metal ions made possible the development of a preconcentration method and quantification by Flame AAS of metal ions at trace level in fuel ethanol.

Synthesis and characterization of the mer-[RuCl3(NO)(dppb)] isomer. X-ray structures of fac-[RuCl3(NO)(dppm)], cis-[RuCl2(dppm)2] and mer-[RuCl3(NO)(dppb)] [dppm=1,2-Bis(diphenylphosphino)methane and dppb=1,4-Bis(diphenylphosphino)butane]

The fac-[RuCl3(NO)(dppm)] (1) and cis-[RuCl2(dppm)2] (2) complexes were obtained with co-crystallization in the solid state from the reaction of RuCl3(NO) with the diphosphine in dichloromethane. mer-[RuCl3(NO)(dppb)] (3) was obtained from [RuCl3(dppb)(H2O)] by bubbling NO for 30 min in the same solvent. The crystal and molecular structures of these three compounds have been determined from X-ray studies. © Elsevier Science Ltd.

Preparation of a silica gel modified with 2-amino-1,3,4-thiadiazole for adsorption of metal ions and electroanalytical application

Silica gel with a specific area of 382 m2 g-1 and an average pore diameter of 60 Å was chemically modified with 2-amino-1,3,4-thiadiazole, for the purpose of selective adsorption of heavy metals ions and possible use as a chemically modified carbon paste electrode (CMCPE). The following properties of this functionalized silica gel are discussed: selective adsorption of heavy metal ions measured by batch and chromatographic column techniques, and utilization as preconcentration agent in a chemically modified carbon paste electrode (CMCPE) for determination of mercury(II). The chemical selectivity of this functional group and the selectivity of voltammetry were combined for preconcentration and determination. ©2006 Sociedade Brasileira de Química.

Adsorção dos íons cobre, cobalto e níquel na superfície organofuncionalizada 3(2-Amino-1,3,4-Tiadiazol) sílica gel, ATDSG

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Formation of 1,N-6-etheno-2 '-deoxyadenosine adducts by trans,trans-2,4-decadienal

trans,trans-2,4-Decadienal (DDE) is an important breakdown product of lipid peroxidation. This aldehyde is cytotoxic to mammalian cells and is known to be implicated in DNA damage. Therefore, attempts were made in this work to assess the reactivity of DDE with 2'-deoxyadenosine (dAdo). It was shown that DDE is able to bind to 2'-deoxyadenosine, yielding highly fluorescent products. Besides 1,N-6-etheno-2'-deoxyadenosine (epsilon dAdo), two other related adducts, 1-[3-(2-deoxy-beta-D-erythro-pentofuranosyl)3H-imidazo[2,1-i]purin-7-yl]-1,2,3-octanetriol and 1-[3-(2-deoxy-beta-D-erythro-pentofuranosyl)-3H-imidazo[2,1-i]purin-7-yl]-1,2-heptanediol, were isolated by reverse phase high-performance liquid chromatography and characterized on the basis of their UV, fluorescence, nuclear magnetic resonance, and mass spectrometry features. The reaction mechanism for the formation of the DDE-2'-deoxyadenosine adducts involves 2,4-decadienal epoxidation and subsequent addition to the N-2 amino group of 2'-deoxyadenosine, followed by cyclization at the N-1 site. Adducts differ by the length of carbon side chain and the number of hydroxyl groups. The present data indicate that DDE can be epoxidized by peroxides, and the resulting products are able to form several adducts with 2'-deoxyadenosine and/or DNA. Endogenous DNA adduct formation can contribute to the already reported high cytotoxicity of DDE to mammalian cells.

Adsorção de metais em solução aquosa pelos processos de batelada e coluna de leito fixo utilizando silsesquioxano funcionalizado com 5-amino-1,3,4-tiadiazol-2-tiol

Pós-graduação em Ciência dos Materiais - FEIS

Spectroscopic, Structural, and Conformational Properties of (Z)-4,4, 4-Trifluoro-3-(2-hydroxyethylamino)-1-(2-hydroxypheny1)-2-buten-1-one, C12H12F3NO3: A Trifluoromethyl-Substituted beta-Aminoenone

The ( Z)-4,4,4-trifluoro-3-(2-hydroxyethylamino)-1-(2-hydroxyphenyl)-2-buten-1-one (C12H12F3NO3) compound was thoroughly studied by IR, Raman, UV-visible, and C-13 and F-19 NMR spectroscopies. The solid-state molecular structure was determined by X-ray diffraction methods. It crystallizes in the P2(1)/c space group with a = 12.1420(4) angstrom, b = 7.8210(3) angstrom, c := 13.8970(5) angstrom, beta = 116.162(2)degrees, and Z = 4 molecules per unit cell. The molecule shows a nearly planar molecular skeleton, favored by intramolecular OH center dot center dot center dot 0 and NH center dot center dot center dot 0 bonds, which are arranged in the lattice as an OH center dot center dot center dot 0 bonded polymer coiled around crystallographic 2-fold screw-axes. The three postulated tautomers were evaluated using quantum chemical calculations. The lowest energy tautomer (I) calculated with density functional theory methods agrees with the observed crystal structure. The structural and conformational properties are discussed considering the effect of the intra- and intermolecular hydrogen bond interactions.

4-Organochalcogenoyl-1H-1,2,3-triazoles: synthesis and functionalization by a nickel-catalyzed Negishi cross-coupling reaction

A general method for the synthesis of triazoles containing selenium and tellurium was accomplished via a CuCAAC reaction between organic azides and a terminal triple bond, generated by in situ deprotection of the silyl group. The reaction tolerates alkyl and arylazides, with alkyl and aryl substituents directly bonded to the chalcogen atom. The products were readily functionalized by a nickel-catalyzed Negishi cross-coupling reaction, furnishing the aryl-heteroaryl products at the 4-position in good yields. (C) 2012 Elsevier Ltd. All rights reserved.

DM-1, sodium 4-[5-(4-hydroxy-3-methoxyphenyl)-3-oxo-penta-1,4-dienyl]-2-methoxy-phenolate: a curcumin analog with a synergic effect in combination with paclitaxel in breast cancer treatment

This paper describes a new method for the preparation of sodium 4-[5-(4-hydroxy-3-methoxyphenyl)-3-oxo-penta-1,4-dienyl]-2-methoxy-phenolate, DM-1, and 3-oxo-penta-1,4-dienyl-bis (2-methoxy-phenolate), DM-2. The aim of this work was to evaluate the antitumor effects of DM-1 in adjuvant chemotherapy for breast cancer treatment. Mice bearing mammary adenocarcinomas (Ehrlich ascites tumors) were treated with paclitaxel alone, DM-1 alone, and paclitaxel + DM-1. Tumor samples were used to perform cytological analysis by the Papanicolaou method and apoptosis analysis by annexin V and phosphorylated caspase 3. The paclitaxel + DM-1 group had decreased tumor areas and tumor volumes, and the frequency of metastasis was significantly reduced. This caused a decrease in cachexia, which is usually caused by the tumor. Furthermore, treatment with paclitaxel + DM-1 and DM-1 alone increased the occurrence of apoptosis up to 40% in tumor cells, which is 35% more than in the group treated with paclitaxel alone. This cell death was mainly caused through phosphorylated caspase 3 (11% increase in paclitaxel + DM-1 compared to the paclitaxel group), as confirmed by reduced malignancy criteria in the ascitic fluid. DM-1 emerges as a potential treatment for breast cancer and may act as an adjuvant in chemotherapy, enhancing antitumor drug activity with reduced side effects.

ANTI-TRYPANOSOMAL ACTIVITY OF 1,2,3,4,6-PENTA-O-GALLOYL-beta-D-GLUCOSE ISOLATED FROM Plectranthus barbatus Andrews (Lamiaceae)

MeOH extract from the leaves of Plectranthus barbatus Andrews (Lamiaceae), showed in vitro anti-trypanosomal activity. The bioassay-guided fractionation resulted in the isolation of a gallic acid derivative, identified as 1,2,3,4,6-penta-O-galloyl-beta-D-glucose (PGG), after thorough NMR and MS spectral analysis. Finally, this compound was tested against trypomastigote forms of T. cruzi and displayed an EC50 value of 67 mu M, at least 6.6-fold more effective than the standard drug benznidazole. This is the first occurrence of PGG in the Plectranthus genus and the first anti-parasitic activity described for PGG in the literature.

One-Pot, Three-Step Reaction of 5-[(Trimethylsilyl)ethynyl]pyrrolidin-2-one with Azides Catalyzed by Cu-I: Synthesis of a Novel Class of 1,4-Disubstituted 1,2,3-Triazoles

A very fast, easy and efficient synthesis is described for a novel and biologically important class of 1,4-disubstituted-4-(5-pyrrolidin-2-one)-1,2,3-triazoles by an ultrasound-assisted one-pot, three-step click reaction sequence of 5-[(trimethylsilyl)ethynyl]pyrrolidin-2-one with organic azides mediated by catalytic Cu-I salts.