NMR investigation and theoretical calculations of the effect of solvent on the conformational analysis of 4',7-di-hydroxy-8-prenylflavan

The NMR conformational study of 4',7-di-hydroxy-8-prenylflavan 1 was carried out in acetone-d6, DMSO-d6 and CDCl3 which enabled the proposition of three conformations, namely 1a, 1b and 1c, differing in the position of the prenyl group. Geometry optimizations performed using AM1 method showed that 1a (deltaHf = -86.2 kcal/mol) is as stable as 1b (deltaHf = -85.1 kcal/mol) and 1c (deltaHf = -85.4 kcal/mol). When the solvent was included, the calculations showed that the solute-solvent interactions could be explained either in the light of the electronic intermolecular delocalization or the electrostatic character between solute and solvent. Theoretical calculations (HF/6-31G*, deltaFT/BLYP/6-31G*, and deltaFT/B3LYP/6-31G*) showed that the combination of these types of interactions present in each solute-solvent system, dependent on the chemical properties of the solvent, lead to different spatial arrangements of the prenyl group, which in turn determined the conformation of 1.

Transtornos mentais como fatores de risco para o desenvolvimento de abuso/dependência de cocaína: estudo caso-controle

OBJETIVO: Avaliar o papel dos transtornos mentais e da dependência ao álcool como possíveis fatores de risco para o abuso/dependência de cocaína. MÉTODOS: Utilizou-se o desenho caso-controle e a técnica de bola-de-neve (snowball technique) para selecionar uma amostra de usuários de cocaína não tratados na comunidade (casos) e parear casos e controles por sexo, idade e amizade. A coleta de dados foi feita através da utilização do questionário CIDI (Composite International Diagnostic Interview) que gera diagnósticos de acordo com os critérios do Diagnostic and Statistical Manual of Mental Disorders-III-R. A análise dos dados foi feita através de regressão logística condicional. RESULTADOS: O estudo incluiu 208 indivíduos. Os principais resultados mostraram que história passada de dependência ao álcool era o principal fator associado a um aumento no risco de desenvolvimento de abuso de cocaína (OR=15,1; IC 95% 3,8-60,2); nenhum outro transtorno mental isolado manteve-se significativamente associado ao aumento deste risco após a análise multivariada. Aumento no risco de abuso de cocaína também foi encontrado entre os indivíduos que relataram pensamentos suicidas (OR=3,1; IC 95% 0,91-10,8), sugerindo associação entre quadros mais graves de depressão e abuso de cocaína. CONCLUSÕES: Esses achados sugerem que os programas voltados para a prevenção e tratamento do abuso de cocaína devem estar preparados para o manejo de questões relacionadas à co-morbidade do abuso de drogas com o álcool e outros distúrbios psiquiátricos.

Factores del abuso sexual en la niñez y la adolescencia en estudiantes de Morelos, México

OBJETIVO: Estimar la prevalencia y los factores asociados al abuso sexual en niñez y adolescencia. MÉTODOS: Estudio realizado en una muestra de estudiantes del estado de Morelos, México, en 2004-2005. Los participantes (n=1730) pertenecen a una cohorte de 13.293 estudiantes de 12 a 24 años. Los datos fueron colectados mediante la aplicación de un cuestionario conteniendo secciones de escalas validadas. Las variables analizadas fueron: factores sociodemográficos (sexo, zona de habitación, nivel socioeconómico); familiares (educación de los padres, adicciones de los padres, violencia entre padres); psicológicos individuales (autoestima - Inventario de Autoestima de Coopersmith, depresión, consumo de alcohol); violencia intrafamiliar (Escala de Strauss); y abuso sexual. Mediante regresión logística múltiple se evaluaron los factores asociados. Se obtuvieron Razones de Momios (RM) con intervalos de confianza al 95%. RESULTADOS: El 4.7% (n=80) de los (as) estudiantes presentaron intento de abuso y el 2.9% (n=50) fueron víctimas de abuso sexual consumado. Las mujeres tuvieron mayor prevalencia de intento (6.1%). El 3.6% de las mujeres y el 1.9% de los hombres fueron abusados sexualmente. Principal agresor en mujeres fue el novio y en hombres una persona desconocida. Edad promedio de 12.02 años en mujeres y 11.71 en hombres. Factores asociados al abuso: mayor consumo de alcohol padres (RM = 3.37; IC 95% 1.40;8.07); violencia hacia madre (RM=4.49; IC 95%1.54;13.10); ser mujer (RM = 2.47; IC 95%1.17;5.24); ser víctima de violencia intrafamiliar alta (RM=3.58; IC 95%1.32;9.67). Autoestima alta fue un factor protector (RM=0.27; IC 95% 0.09;0.75). CONCLUSIONES: En promedio el abuso sexual se presenta a los 12 años de edad en ambos sexos, siendo más frecuente en el sexo femenino. La mayoría de víctimas no lo denuncia.

Anti-leishmanial and structure-activity relationship of ring substituted 3-phenyl-1-(1,4-di-N-oxide quinoxalin-2-yl)-2-propen-1-one derivatives

A series of ring substituted 3-phenyl-1-(1,4-di-N-oxide quinoxalin-2-yl)-2-propen-1-one derivatives were synthesized and tested for in vitro leishmanicidal activity against amastigotes of Leishmania amazonensis in axenical cultures and murine infected macrophages. Structure-activity relationships demonstrated the importance of a radical methoxy at position R3', R4' and R5'. (2E)-3-(3,4,5-trimethoxy-phenyl)-1-(3,6,7-trimethyl-1,4-dioxy-quinoxalin-2-yl)-propenone was the most active. Cytotoxicity on macrophages revealed that this product was almost six times more active than toxic.

Biorremediação de solo contaminado por isobutanol, Bis-2-etil-hexilftalato e Di-isodecilftalato

Embora os ftalatos sejam um dos poluentes mais frequentemente encontrados no meio ambiente, há escassez de dados na literatura sobre biorremediação de solos tropicais contaminados por esses compostos. Por esse motivo, este estudo avaliou a biorremediação de um solo contaminado com os plastificantes DEHP (Bis-2-etilhexilftalato), DIDP (Di-isodecilftalato) e álcool isobutílico, por uma indústria no Estado de São Paulo. A biorremediação ocorreu pela utilização de microrganismos presentes no solo e pela adição de inóculo adaptado em reator em fase de lama. O reator foi monitorado durante 120 dias, sendo corrigida apenas a umidade do solo. Os resultados indicaram que a biodegradação dos ftalatos seguiu uma cinética de primeira ordem e a biorremediação ocorreu na faixa de pH entre 7,4 e 8,4 e temperaturas entre 17 e 25 ºC, com eficiência de remoção de contaminantes acima de 70 %. Após 120 dias, o teor de DEHP estava abaixo de 4 mg kg-1, limite estipulado pela legislação brasileira para solo de uso residencial.

Monoterpenos di-hidroxilados e hidróxi-nitrogenados 1,2 e 1,3 como ligantes quirais em reação de reformatsky assimétrica

This study describes the use of three (-)-alpha-pinene derivatives, one diol-1,2 [(-)-(1R, 2R, 3S, 5R)-2,6,6-trimethylbicyclo[3.1.1]heptane-2,3-diol 4] and two piridine-hydroxy derivatives [(+)-(1R,2S,3R,5S)-2,6,6-trimethyl-3-(2-pyridinylmethyl)bicyclo[3.1.1]heptan-3-ol 7 and (-)-(1R,2S,3R,5S)-2,6,6-trimethyl-3-[2-(2-pyridinyl) ethyl]bicyclo[3.1.1]heptan-3-ol 8]; one diol-1,3 [(-)-(1S,2R,5S)-2-(1-hydroxy-1-methylethyl)-5-methylcyclohexanol 5] derived from (+)-isopulegol 2 and one diol-1,3 [(+)-(1R,2R,5R)-2-(1-hydroxy-1-methylethyl)-5-methylcyclohexanol 6] derived from (+)-neo-isopulegol 3, as ligands in the asymmetric Reformatsky reaction. The best enantiomeric excess of beta-hydroxy ester obtained in the Reformatsky asymmetric reaction was 18% using ligand 6, and the chemical yield of the reactions was 65% on average.

Polarizabilidades e primeira hiperpolarizabilidades elétricas dipolares de ésteres E-4-amino-trans-1,3-butadienil-(1',2'-di-hidroxibenzeno) de boro, alumínio e gálio

Static electric dipole polarizabilities and first hyperpolarizabilites have been calculated for the title molecules and their 3' and 4'-nitro derivatives at ab-initio Hartree- Fock/6-31G(d, p) level. The influence of the pivotal p vacant 3A elements (B, Al or Ga) substitution on the electrical properties of these molecules is detailed. The axial vector components of the first hyperpolarizabilities β(0) of the push-pull 4'-nitro derivatives, -18.2×10-32 esu (B), -21.1×10-32 esu (Al) and -20.8×10-32 esu (Ga) are calculated to be as much as fourfold larger then that calculated for the p-nitroaniline, a reference organic molecule for comparison for this type of molecular property.

Caracterização da fusão peritética do cloreto de sódio di-hidratado por curvas de aquecimento

Binary mixture phase diagrams are normally obtained from thermal analysis involving freezing point curves. However, that approach is not always reliable and easy to follow to all kinds of mixtures in any proportion. In fact, even for a simple system, such as NaCl-H2O, this freezing methodology gives mixed results when one starts from a solid-solution system, due mostly to the formation of the NaCl.2H2O, which has an incongruent melting point, and the dependence of its solubility with the temperature. In this work we report a trustworthy, simple and cheap method involving heating curves to drawn the NaCl-H2O phase diagram.

Phenolic compounds from Sidastrum micranthum (A. St.-Hil.) fryxell and evaluation of acacetin and 7,4'-Di-O-methylisoscutellarein as motulator of bacterial drug resistence

From the aerial parts of Sidastrum micranthum (A. St.-Hil.) Fryxell (Malvaceae) were isolated m-methoxy-p-hydroxy-benzaldehyde, o-hydroxy-benzoic acid, acacetin, quercetin, 7,4′-Di-O-methylisoscutellarein, genkwanin and tiliroside. These compounds were identified by data analyses of spectroscopic methods. Although acacetin and 7,4′-Di-O-methylisoscutellarein did not display relevant antibacterial activity (MIC = 256 µg/mL), they modulated the activity of antibiotics, i.e. in combination with antibiotics at 64 µg/mL (¼ MIC), a two-fold reduction in the MIC was observed for norfloxacin and ethidium bromide; regarding tetracycline and erythromycin a two-fold reduction in the MIC was observed only with 7,4′-Di-O-methylisoscutellarein.

Síntese e caracterização de copolímeros de cadeia lateral derivados de acrilatos de 4,5-di-hidroisoxazol e do (-)-mentol

Five monomers 5-[4-(5-cyano-4,5-dihydroisoxazol-3-yl)phenoxy]undecyl acrylate (7a); n-alkyl 3-{4-[5-(acryloyloxyundecyl)oxyphenyl]}-4,5-dihydroisoxazole-5-carboxylate (7b,c for n-butyl and n-hexyl, respectively); 3-{4-[5-(acryloyloxyundecyl) oxyphenyl]}-4,5-dihydroisoxazole-5-carboxylic acid (7d) and (1R,2S,5R)-2-isopropyl-5-methylcyclohexyl acrylate (9) and the corresponding copolymers 10a-d,11 and homopolymers 12 from 7a and 13 from 9 were designed and synthesized. Except for acrylate 9 which is derived from (-)-menthol, all of the monomers belong to the series containing the isoxazoline ring linked to the acrylate unit by a flexible spacer chain of eleven methylene units. They presented low glass temperature and despite birefringence behavior, these copolymers showed no mesomorphic properties.