Anaerobic DNA cleavage activity in red light and photocytotoxicity of (pyridine-2-thiol)cobalt(III) complexes of phenanthroline bases

Cobalt(III) complexes [Co(pnt)(B)(2)](NO3)(2) (1-3) of pyridine-2-thiol (pnt) and phenanthroline bases (B), viz. 1,10-phenanthroline (phen in 1), dipyrido[3,2-d: 2',3'-f]quinoxaline (dpq in 2) and dipyrido[3,2-a:2',3'-c] phenazine (dppz in 3), have been prepared, characterized and their photo-induced anaerobic DNA cleavage activity studied. The crystal structure of 1a as mixed ClO4- and PF6- salt of 1 shows a (CoN5S)-N-III coordination geometry in which the pnt and phen showed N,S- and N,N-donor binding modes, respectively. The complexes exhibit Co(III)/Co(II) redox couple near -0.3 V (vs. SCE) in 20% DMF-Tris-HCl buffer having 0.1 M TBAP. The complexes show binding propensity to calf thymus DNA giving K-b values within 2.2 x 10(4)-7.3 x 10(5) M-1. Thermal melting and viscosity data suggest DNA surface and/or groove binding of the complexes. The complexes show significant anaerobic DNA cleavage activity in red light under argon atmosphere possibly involving sulfide anion radical or thiyl radical species. The DNA cleavage reaction under aerobic medium in red light is found to involve both singlet oxygen and hydroxyl radical pathways. The dppz complex 3 shows non-specific BSA and lysozyme protein cleavage activity in UV-A light of 365 nm via both hydroxyl and singlet oxygen pathways. The dppz complex 3 exhibits photocytotoxicity in HeLa cervical cancer cells giving IC50 values of 767 nM and 19.38 mu M in UV-A light of 365 nm and in the dark, respectively. A significant reduction of the dark toxicity of the dppz base (IC50 = 8.34 mu M in dark) is observed on binding to the cobalt(III) center.

The first D-pi-A octupolar cryptand molecule to exhibit bulk non-linearity

The cryptand derivative has H-bond mediated trigonal network structure that leads to octupolar bulk nonlinearity.

Structure of pregna-4,16-diene-7[alpha],14[alpha]-diol-3,20-dione

7a,14a-Dihydroxypregna-4,16-diene-3,20- dione, C21H2804, M r = 344.45, orthorhombic, P212121, a = 7.136 (1), b = 12.342 (1), c = 20.049 (3)/k, V= 1765.7 (3)/k 3, Z = 4, Dx = 1.295 g cm -3, A(Cu Kte) = 1.5418/k, /z = 6.7 cm- a, F(000) = 744, T = 293 K, R = 0.048 for 1345 observations. The A ring may be described as in a l a,2flhalf- chair conformation or a l a-sofa conformation. The B and C rings adopt normal chair conformations and the D ring has a 14a-envelope conforma tion. The molecules are held together by a hydrogen bond [0(3)...0(7)= 2.767 A].

Application of microwave heating technique for rapid synthesis of ?,?-unsaturated esters

The use of microwave heating technique for the acceleration of ortho ester Claisen rearrangement (a three step transformation) is described. Irradiation of a DMF solution of the allyl alcohol 5, triethyl orthoacetate and propionic acid (catalytic) in an Erlenmeyer flask for 10 minutes in a microwave oven generated the ester 8 in 83% yield. Analogously, ortho ester Claisen rearrangement of a variety of allyl and propargyl alcohols (9, 12-22) were achieved. The formation of the diester 10 from 2-butyne-1,4-diol (9) via the ortho ester Claisen rearrangement of two allyl alcohol moieties (involving sh steps) in 15 minutes, demonstrates the versatility of the microwave heating technique.

RAD51 as a potential biomarker and therapeutic target for pancreatic cancer

Chemotherapy is a very important therapeutic strategy for cancer treatment. The failure of conventional and molecularly targeted chemotherapeutic regimes for the treatment of pancreatic cancer highlights a desperate need for novel therapeutic interventions. Chemotherapy often fails to eliminate all tumor cells because of intrinsic or acquired drug resistance, which is the most common cause of tumor recurrence. Overexpression of RAD51 protein, a key player in DNA repair/recombination has been observed in many cancer cells and its hyperexpression is implicated in drug resistance. Recent studies suggest that RAD51 overexpression contributes to the development, progression and drug resistance of pancreatic cancer cells. Here we provide a brief overview of the available pieces of evidence in support of the role of RAD51 in pancreatic tumorigenesis and drug resistance, and hypothesize that RAD51 could serve as a potential biomarker for diagnosis of pancreatic cancer. We discuss the possible involvement of RAD51 in the drug resistance associated with epithelial to mesenchymal transition and with cancer stem cells. Finally, we speculate that targeting RAD51 in pancreatic cancer cells may be a novel approach for the treatment of pancreatic cancer. (C) 2011 Elsevier B.V. All rights reserved.

Physics-Based Band Gap Model for Relaxed and Strained 100] Silicon Nanowires

In this paper, we propose a physics-based simplified analytical model of the energy band gap and electron effective mass in a relaxed and strained rectangular 100] silicon nanowires (SiNWs). Our proposed formulation is based on the effective mass approximation for the nondegenerate two-band model and 4 x 4 Luttinger Hamiltonian for energy dispersion relation of conduction band electrons and the valence band heavy and light holes, respectively. Using this, we demonstrate the effect of the uniaxial strain applied along 100]-direction and a biaxial strain, which is assumed to be decomposed from a hydrostatic deformation along 001] followed by a uniaxial one along the 100]-direction, respectively, on both the band gap and the transport and subband electron effective masses in SiNW. Our analytical model is in good agreement with the extracted data using the extended-Huckel-method-based numerical simulations over a wide range of device dimensions and applied strain.

Averting biodiversity collapse in tropical forest protected areas

The rapid disruption of tropical forests probably imperils global biodiversity more than any other contemporary phenomenon(1-3). With deforestation advancing quickly, protected areas are increasingly becoming final refuges for threatened species and natural ecosystem processes. However, many protected areas in the tropics are themselves vulnerable to human encroachment and other environmental stresses(4-9). As pressures mount, it is vital to know whether existing reserves can sustain their biodiversity. A critical constraint in addressing this question has been that data describing a broad array of biodiversity groups have been unavailable for a sufficiently large and representative sample of reserves. Here we present a uniquely comprehensive data set on changes over the past 20 to 30 years in 31 functional groups of species and 21 potential drivers of environmental change, for 60 protected areas stratified across the world's major tropical regions. Our analysis reveals great variation in reserve `health': about half of all reserves have been effective or performed passably, but the rest are experiencing an erosion of biodiversity that is often alarmingly widespread taxonomically and functionally. Habitat disruption, hunting and forest-product exploitation were the strongest predictors of declining reserve health. Crucially, environmental changes immediately outside reserves seemed nearly as important as those inside in determining their ecological fate, with changes inside reserves strongly mirroring those occurring around them. These findings suggest that tropical protected areas are often intimately linked ecologically to their surrounding habitats, and that a failure to stem broad-scale loss and degradation of such habitats could sharply increase the likelihood of serious biodiversity declines.

A Universal Stress Protein (USP) in Mycobacteria Binds cAMP

Mycobacteria are endowed with rich and diverse machinery for the synthesis, utilization, and degradation of cAMP. The actions of cyclic nucleotides are generally mediated by binding of cAMP to conserved and well characterized cyclic nucleotide binding domains or structurally distinct cGMP-specific and -regulated cyclic nucleotide phosphodiesterase, adenylyl cyclase, and E. coli transcription factor FhlA (GAF) domain-containing proteins. Proteins with cyclic nucleotide binding and GAF domains can be identified in the genome of mycobacterial species, and some of them have been characterized. Here, we show that a significant fraction of intracellular cAMP is bound to protein in mycobacterial species, and by using affinity chromatography techniques, we identify specific universal stress proteins (USP) as abundantly expressed cAMP-binding proteins in slow growing as well as fast growing mycobacteria. We have characterized the biochemical and thermodynamic parameters for binding of cAMP, and we show that these USPs bind cAMP with a higher affinity than ATP, an established ligand for other USPs. We determined the structure of the USP MSMEG_3811 bound to cAMP, and we confirmed through structure-guided mutagenesis, the residues important for cAMP binding. This family of USPs is conserved in all mycobacteria, and we suggest that they serve as ``sinks'' for cAMP, making this second messenger available for downstream effectors as and when ATP levels are altered in the cell.

超临界煤油超声速燃烧特性实验 Experiments on Supersonic Combustion of Supercritical Kerosene

针对各种温度、压力下，马赫数2．5流场中超临界煤油的超声速燃烧性能进行了实验研究。研制并测试了一个新型二级煤油加热系统，该系统能够把0．8kg的煤油在5．5MPa压力下加热至至950K而不产生严重的结碳。超声速燃烧试验表明，在相同的来流和燃料当量比条件下，超临界煤油的燃烧效率比室温煤油提高10％～15％，与氢气泡雾化的燃烧效率相当。

QM/MM and Classical Molecular Dynamics Simulation of Histidine-Tagged Peptide Immobilization on Nickel Surface

The hybrid quantum mechanics (QM) and molecular mechanics (MM) method is employed to simulate the His-tagged peptide adsorption to ionized region of nickel surface. Based on the previous experiments, the peptide interaction with one Ni ion is considered. In the QM/MM calculation, the imidazoles on the side chain of the peptide and the metal ion with several neighboring water molecules are treated as QM part calculated by “GAMESS”, and the rest atoms are treated as MM part calculated by “TINKER”. The integrated molecular orbital/molecular mechanics (IMOMM) method is used to deal with theQMpart with the transitional metal. By using the QM/MM method, we optimize the structure of the synthetic peptide chelating with a Ni ion. Different chelate structures are considered. The geometry parameters of the QM subsystem we obtained by QM/MM calculation are consistent with the available experimental results. We also perform a classical molecular dynamics (MD) simulation with the experimental parameters for the synthetic peptide adsorption on a neutral Ni(1 0 0) surface. We find that half of the His-tags are almost parallel with the substrate, which enhance the binding strength. Peeling of the peptide from the Ni substrate is simulated in the aqueous solvent and in vacuum, respectively. The critical peeling forces in the two environments are obtained. The results show that the imidazole rings are attached to the substrate more tightly than other bases in this peptide.

Efecto de sistemas de labranza y control de malezas sobre la cenosis de las malezas, crecimiento y rendimiento del cultivo de maiz (Zea mays L.)

El presente estudio fue realizado en el Centro Experimental " La Compañía" ubicada en el municipio de Masatepe en la época de primera de 1996, durante los meses de Junio a Octubre de 1996, con el objetivo de estudiar el efecto de diferentes sistemas de labranzas y métodos de control de malezas sobre la dinámica de la cenosis de las malezas, el crecimiento y rendimiento del cultivo de maíz. El ensayo se estableció en un arreglo bifactorial de parcelas divididas en arreglo de bloques completos al azar, con cuatro repeticiones. Siendo el factor A: Labranza Convencional, Labranza Mínima, Labranza Cero y el factor B: Control Químico, Control Período Crítico y Control Limpia Periódica. Las variables evaluadas para las malezas fueron : abundancia, biomasa, diversidad, para el cultivo : crecimiento y rendimiento . Se realizó análisis descriptivo a través de figuras para las variables de las malezas y análisis de varianza ( ANDEVA) y separación de medias de rangos múltiples de DUNCAN al 5% de margen de error para las variables del cultivo . Los resultados reflejaron que la labranza convencional y el control químico tuvieron mejor influencia en cuanto a la abundancia de las malezas con respecto a las labranzas mínima y cero. La labranza cero presentó el mayor porcentaje en valor de biomasa predominando las malezas monocotiledóneas , de igual manera el control período crítico presentó el mayor valor en biomasa predominando las malezas dicotiledóneas. En el transcurso del ensayo las especies que se destacaron fueron: Ageratum conyzoides L. , Melanthera aspera ( Jacquin) L:C: y Digitaria sanguinalis L. En labranza cero y en el control químico se presentaron los mayores valores en altura de planta. Los mayores rendimientos en kg /hectárea obtuvieron en cero labranza

Evaluación de seis lineas de arroz (Oryza sativa L.), y tres variedades comerciales bajo el sistema de riego, en dos épocas de siembra, en Malacatoya

Con el objetivo de contribuir a aumentar la productividad del cultivo de arroz (Oryza sativa L), mediante la selección de genotipos con alto potencial de rendimiento de grano, que tengan un comportamiento consistente en diferentes ambientes, se evaluaron seis lineas de arroz (Oryza sativa L.) y tres variedades comerciales, bajo el sistema de riego, en dos épocas de siembra, en Malacatoya. Se establecieron dos ensayos de campo, de pruebas avanzadas de rendimiento (PAR). Los experimentos fueron establecidos en terrenos de la hacienda "Las Lajas", municipio de Malacatoya, departamento de Granada, ubicada en los 12° 04' 40" latitud norte y 86° 01 '55" longitud oeste. El primer ensayo se sembró en la época de verano, estableciéndose en Febrero y cosechándose en Junio de 1998. El segundo ensayo se sembró en la época de invierno, estableciéndose en Agosto y cosechándose en Noviembre de 1998. Se utilizó el diseño experimental de Bloques Completos al Azar para analizar los ensayos individuales y el análisis de varianza combinado para analizar la interacción de los genotipos en dos épocas de siembra. Los resultados obtenidos de ambos ensayos evidencian que la línea CT-12249-IP-IP es una línea promisoria, ya que sus componentes de rendimiento son estables tanto en verano como en invierno, destacándose por sus características tales como: aceptabilidad fenotípica y peso de 1,000 semillas, en las cuales ocupó los primeros lugares. La línea CT-12249-1P-lP, es el genotipo que tiene el mejor comportamiento productivo, destacándose por presentar un rendimiento de grano de 5,083 kg/ha en verano, y 7,222 kg/ha en invierno. Asi mismo, la época de siembra tuvo gran influencia en el comportamiento de los genotipos evaluados, ya que en la siembra de invierno los tratamientos mostraron mayor altura, mayor rendimiento de grano y adelanto en los días a flor. En la siembra de invierno, en presencia de altas precipitaciones Y humedad relativa, se determinó una mayor incidencia de enfermedades fungosas, causados por Pyricularía y Helmintosporiosis. En ambos ensayos, todas las líneas evaluadas superaron al testigo Oryzica Llanos.

Dinámica poblacional de arvenses en el cultivo de maiz (Zea mays L.) variedad NB-6 bajo los sistemas orgánico y convencional en la finca El Plantel, Tipitapa, Masaya, 2009

Las arvenses, tanto anuales como perennes, son un problema mundial en el cultivo del maíz. El crecimiento descontrolado de las malezas puede provocar grandes pérdidas de rendimiento de este cultivo. El estudio se realizó en finca experimental El Plantel de la Universidad Nacional Agraria, ubicada en el kilómetro 43 ½ carretera Tipitapa – Masaya, municipio de Masaya, de marzo a agosto 2009. Se evaluó el comportamiento de las arvenses en el cultivo de maíz, variedad NB-6, manejado bajo dos sistemas de producción: orgánico y convencional, se consideraron como dos tratamientos, establecidos en cuatro pseudorrepeticiones. El área experimental fue de 672 m2. La distancia entre pseudorrepeticiones 1 m. Las variables evaluadas fueron: diversidad, abundancia, biomasa y cobertura de arvenses y en el cultivo rendimiento en kg/ha. El predominio de las arvenses en el cultivo bajo los dos tratamientos fue similar. Se identificaron 11familias representadas por 21 especies. De éstas, 19 en el sistema orgánico y 17 en el sistema convencional. De las 21 especies, 15 pertenecen a la clase dicotiledóneas, éstas predominaron en el sistema orgánico: Cleome viscosa L. (Frijolillo de playa), Sida acuta Burn. F (Escoba lisa) y Portulaca oleracea L. (Verdolaga) de las familias Cappari daceae, Malvaceae y Portulacaceae. Las monocotiledóneas fueron Poaceae y Cyperaceae, predominando la especie: Ixophorus unicetus Presl. ( Zacate dulce). En el sistema convencional las familia Cyperaceae y Capparidaceae, en ellas predominaron las especies Cyperus rotundus L. (Coyolillo) y Cleome viscosa (L) respectivamente. La cobertura decreció en ambos sistemas a medida que el cultivo cerraba su ciclo, mostrando comportamiento similar en ambos tratamientos. La biomasa fue mayor el sistema orgánico (6,368 g/m2) con respecto a la biomasa en el sistema convencional (5,011.1 g/m2). La familia Poaceae obtuvo mayor biomasa (3205.5 g/m2) en el sistema orgánico, a diferencia del sistema convencional. (1765.4 g/m2). En el rendimiento no hubo diferencias estadísticas significativas en ambos sistemas de manejo donde (P=0.97).

Programa Fale Conosco da Câmara dos Deputados : é possível participar e interagir?

Procura conhecer o trabalho de atendimento das mensagens enviadas para o "Fale Conosco", canal de comunicação e interação com a sociedade da Câmara dos Deputados. Busca verificar, mais especificamente, como os provedores de informação, identificados nos órgãos considerados estatisticamente como os maiores receptores de mensagens, concebem o diálogo e a interação com o público externo à Casa. Examina, também, no processo dialógico gerado pela troca de mensagens, a percepção desses provedores quanto ao uso do canal como recurso facilitador de participação política. Para a consecução desse propósito, optou-se pela realização de pesquisa de cunho qualitativo por meio de entrevistas em cada órgão selecionado. São apresentadas questões de cunho teórico metodológico sobre a pesquisa qualitativa e a lógica interpretativa, e de cunho teórico sobre a Internet e os conceitos de governo eletrônico, democracia eletrônica, interação, interatividade e participação. A análise do material empírico parte de uma perspectiva hermenêutica em que se busca correlacionar concepções presentes nas entrevistas dos respondentes do Fale Conosco com algumas das perspectivas teóricas apresentadas. Espera-se com os resultados do estudo, poder contribuir para o enriquecimento dos debates que se fizerem futuramente sobre o serviço de atendimento das mensagens do Fale Conosco, principalmente, no que diz respeito aos seus aspectos valorativos.

Diário da Constituinte [gravação de vídeo] : [programa n. 034]

A Subcomissão dos Direitos Políticos, dos Direitos Coletivos e Garantias da Assembleia Nacional Constituinte (ANC) recebe Rex Nazaré Alves, Presidente da Comissão de Energia Nuclear que fala sobre as contas secretas mantidas pelo Conselho de Segurança Nacional (CSN), cujos recursos são utilizados em pesquisas. Maurílio Ferreira Lima (PMDB-CE), Presidente da Subcomissão, defende o controle das contas secretas pelo Legislativo. A Subcomissão da Nacionalidade, da Soberania e das Relações Internacionais recebe Jorge Monteiro Fernandes, representante da União Brasileira de Informática Pública, que aborda a relação de reserva de mercado de informática e a soberania nacional. Paulo Macarini (PMDB-SC) defende a reserva de mercado. A Subcomissão dos Municípios e Regiões ouve representantes da Superintendência do Desenvolvimento do Nordeste (SUDENE), da Superintendência da Zona Franca de Manaus (SUFRAMA), da Superintendência do Desenvolvimento da Amazônia (SUDAM) e da Secretaria de Articulação com Estados e Municípios (SAREM). A Subcomissão dos Estados recebe Paulo Brossard, Ministro da Justiça, que defende maior participação dos Estados nos recursos da União. Elverlindo Renklein, representante do Departamento Intersindical de Estatística e Estudos Socioeconômicos (DIEESE), defende o fim do imposto de renda (IRRF) para assalariados na Subcomissão de Tributos, Participação e Distribuição das Receitas. Simão Sessim (PFL-RJ) aprova a palestra de Elverlindo e defende a fiscalização unificada dos impostos.