Adsorption Behavior of 5-Fluorouracil on Au(111): An In Situ STM Study

The biological effects of chemical substitution of DNA bases triggered several investigations of their physicochemical properties This paper studies the adsorption behavior of a halogenated uracil, 5-fluorouracil (5FU). at the electrochemical interface of Au(111) and sulfuric acid solution. Upon modulation of the electric field across the interface, four distinct phases could be inferred by means of cyclic voltammetry (CV) At negative potentials relative to the SCE electrode, limited by the threshold of hydrogen evolution, no molecular species could be detected by scanning tunneling microscopy (STM) at the reconstructed Au(111)-(23 x root 3) surface, indicating that any physisorbed molecules are randomly distributed Incursion into more positive potentials increases the surface population but doer not form any two-dimensional (2D) physisorbed ordered structure Instead, we observed metastable structures that are only detectable. on surfaces with high defect density At sufficiently high positive potentials. limited by gold oxidation, the molecules are chemisorbed in a (3 x 2 root 3) ordered structure. with the aromatic ring perpendicular to the surface We report the densest chemisorbed monolayer for pyrimidine-derivative molecules (area per molecule 0 14 +/- 0 04 nm(2)). A comparison of the adsorption behavior of uracil derivatives has been made based on recent results of chemical substitution and solvent effects. We propose that pi-stacking is enhanced when halogens are incorporated in the uracil structure, in a similar fashion to what is observed in then crystal structure

Dependence of the product on the P-P ligand in reactions of [RuCl(3)(NO)(P-P)] complexes (P-P = aromatic diphosphines) with 2-mercaptopyridine

This study presents the syntheses and characterization of 2-mercaptopyridine (pyS(-)) complexes containing ruthenium(II) with the following general formula [Ru(pyS)(2)(P-P)], P-P = (c-dppen) = cis-1,2-bis(diphenylphosphino)ethylene) (1); (dppe)=1,2-bis(diphenylphosphino)ethane (2); (dppp)=1,3-bis(diphenylphosphino)propane (3) and (dppb) = 1,4-bis(diphenylphosphino)butane (4). The complexes were synthesized from the mer- or fac-[RuCl(3)(NO)(P-P)] precursors in the presence of triethylamine in methanol solution with dependence of the product on the P-P ligand. The reaction of pyS- with a ruthenium complex containing a bulky aromatic diphosphine dppb disclosed a major product with a dangling coordinated dppbO-P, the [Ru(pyS)(2)(NO)(eta(1)-dppbO-P)]PF(6) (5). In addition, this work also presents and discusses the spectroscopic and electrochemical behavior of 1-5. and report the X-ray structures for I and S. (C) 2009 Elsevier Ltd. All rights reserved.

Driving forces in substitution reactions of octahedral complexes: The influence of the competitive effect

The reaction of cis-[RuCl(2)(P-P)(N-N)] type complexes (P-P = 1,4-bis(diphenylphosphino)butane or (1,1`-diphenylphosphino)ferrocene; N-N = 2,2`-bipyridine or 1,10-phenantroline) with monodentate ligands (L), such as 4-methylpyridine, 4-phenylpyridine and benzonitrile forms [RuCl(L)(P-P)(N-N)](+) species Upon characterization of the isolated compounds by elemental analysis, (31)P{(1)H} NMR and X-ray crystallography it was found out that the type of the L ligand determines its position in relation to the phosphorus atom. While pyridine derivatives like 4-methylpyridine and 4-phenylpyridine coordinate trans to the phosphorus atom, the benzonitrile ligand (bzCN), a good pi acceptor, coordinates trans to the nitrogen atom. A (31)P{(1)H} NMR experiment following the reaction of the precursor cis-[RuCl(2)(dppb)(phen)] with the benzonitrile ligand shows that the final position of the entering ligand in the complex is better defined as a consequence of the competitive effect between the phosphorus atom and the cyano-group from the benzonitrile moiety and not by the trans effect. In this case, the benzonitrile group is stabilized trans to one of the nitrogen atoms of the N-N ligand. A differential pulse voltammetry experiment confirms this statement. In both experiments the [RuCl(bzCN)(dppb)(phen)]PF(6) species with the bzCN ligand positioned trans to a phosphorus atom of the dppb ligand was detected as an intermediate complex. (c) 2009 Elsevier Ltd. All rights reserved.

Gas-Phase Nucleophilic and Elimination Reactions in Simple Alkyl Nitrates

There has been increasing interest in the gas-phase reactivity of alkyl nitrates because of their well-known applications as explosives and because of then role in atmospheric and in marine processes This manuscript describes an experimental study by FT-ICR techniques of the gas-phase reactions of OH(-) and F(-) with methyl and ethyl Innate For methyl nitrate, the main reaction channel is found to be an elimination process promoted by abstraction of an a proton from the methyl group. Nucleophilic displacement of nitrate anion through an S(N)2 process at the carbon center Is also found to he an important reaction channel with methyl nitrate In ethyl nitrate, Ruination of NO(3)(-) is greatly enhanced and this is attributed to the ease of an E2-type elimination process promoted by proton abstraction at the beta position of the ethyl group. Theoretical calculations at the MP2/6-311+G(3df,2p)//MP2/6-31+G(d) level of theory ale consistent with the relative importance of the reaction channels and suggest that these reactions proceed through a double well potential The calculations also predict that nucleophilic attack by OH(-) at the nitrogen center (Sn2@N) is energetically the rueful ad pathway but experiments with (18)OH(-) showed no evidence for this channel. Single-point calculations reveal a strong preference for approach to the emboli center and may explain the lack of reactivity at the nitrogen center. Calculations were also carried out or NH(2)(-) and SH(-) to establish the reactivity pattern to provide a better understanding of environmentally relevant nitrate esters.

Improving the enantioselective bioreduction of aromatic ketones mediated by Aspergillus terreus and Rhizopus oryzae: the role of glycerol as a co-solvent

The improvement of the enzymatic performance of Aspergillus terreus and Rhizopus oryzae in enantioselective bioreductions by using glycerol as a co-solvent has been studied. In the most of the bioreductions, glycerol has demonstrated its potential for improved conversions (up to >99%) and enantioselectivities (up to >99%) when compared to reactions in aqueous or other aqueous-organic media (THF, diethyl ether, toluene, DMSO and acetonitrile). Moreover, high isolated yields of the desired chiral alcohols have been obtained on a preparative scale showing the great potential of this green solvent in biocatalysis. (C) 2009 Elsevier Ltd. All rights reserved.

Improving the Fluorescence Detectability of Polycyclic Aromatic Hydrocarbons for Evaluation of Workplace Environments of Cement Industries Processing Organic Residues

The burning of organic residues and wastes in furnaces of cement industries has been an attractive and lucrative approach to eliminate stocks of these pollutants. There is a potential risk for producing PAH in the workplace of industries burning organic wastes, so that highly sensitive analytical methods are needed for monitoring the air quality of these environments. An official method for determination of PAH is based on liquid chromatography with fluorescence detection at fixed excitation and emission wavelengths. We demonstrate that a suitable choice of these wavelengths, which are changed during the chromatographic run, significantly improves the detectability of PAH in atmosphere and particulate matter collected in cement industries.

Expedient, accurate methods for the determination of the degree of substitution of cellulose carboxylic esters: Application of UV-vis spectroscopy (dye solvatochromism) and FTIR

Two techniques, namely UV-vis- and FTIR spectroscopy, have been employed in order to calculate the degree of substitution (DS) of cellulose carboxylic esters, including acetates, CAs, butyrates, CBs, and hexanoates, CHs. Regarding UV-vis spectroscopy, we have employed a novel approach, based on measuring the dependence of lambda(max) of the intra-molecular charge-transfer bands of polarity probes adsorbed on DS of the ester films (solvatochromism). Additionally, we have revisited the use of FTIR for DS determination. Several methods have been used in order to plot Beer`s law graph, namely: Absorption of KBr pellets, pre-coated with CA: reflectance (DRIFTS) of CAs-KBr solid-solid mixtures with, or without the use of 1.4-dicyanobenzene as an internal reference; reflectance of KBr powder pre-coated with CA. The methods indicated are simple, fast, and accurate, requiring much less ester than the titration method. The probe method is independent of the experimental variables examined. (c) 2010 Published by Elsevier Ltd.

Probing the dependence of the properties of cellulose acetates and their films on the degree of biopolymer substitution: use of solvatochromic indicators and thermal analysis

Although cellulose acetates, CAs, are extensively employed there is scant information about the systematic dependence of their properties on their degree of substitution, DS; this is the subject of the present work. Nine CAs samples, DS from 0.83 to 3.0 were synthesized; their films were prepared. The following solvatochromic probes have been employed in order to determine the empirical polarity, E (T)(33); ""acidity, alpha""; ""basicity, beta"", and ""dipolarity/polarizability, pi*"" of the casted films: 2,6-dichloro-4-(2,4,6-triphenyl-pyridinium-1-yl) phenolate, WB; 4-nitroaniline; 4-nitroanisole; 4-nitro-N,N-dimethylaniline; 2,6-diphenyl-4-(2,4,6-triphenyl-pyridinium-1-yl)phenolate, RB. Additionally, two systems, ethanol plus ethyl acetate (EtOH-EtAc), and cellulose plus cellulose triacetate, CTA, were employed as models for CAs of different DS. Regarding the model systems, the following was observed: (i) For EtOH-EtAc, the dependence of all solvatochromic parameters on the ""equivalent-DS"" of the binary mixture was non-linear because of preferential solvation; (ii) The dependence of E (T)(33) on equivalent DS of the cellulose-CTA films is linear, but the slope is smaller than that of the corresponding plot for CAs. This is attributed to the more efficient hydrogen bonding in the model system, a conclusion corroborated by IR measurements. The dependence of solvatochromic parameters of CAs on their DS is described by the simple equations; a consequence of the substitution of the OH by the ester group. The thermal properties of bulk CAs samples were investigated by DSC and TGA; their dependence on DS is described by simple equations. The relevance of these data to the processing and applications of CAs is briefly discussed.

The gas-phase alcoholysis of protonated homoleptic alkoxysilanes

Tetra-alkoxysilanes are common and useful reagents in sol-gel processes and understanding their reactivity is important in the design of new materials. The mechanism of gas-phase reactions that mimic alcoholyis of Si(OMe)(4) (usually known as TMOS) under acidic conditions have been studied by Fourier transform ion cyclotron resonance techniques and density functional calculations at the B3LYP/6-311+G(d,p) level. The proton affinity of TMOS has been estimated at 836.4 kJ mol(-1) and protonation of TMOS gives rise to an ionic species that is best represented as trimethoxysilyl cations associated with a methanol molecule. Protonated TMOS undergoes rapid and sequential substitution of the methoxy groups in the gas-phase upon reaction with alcohols. The calculated energy profile of the reaction indicates that the substitution reaction through an S(N)2 type mechanism may be more favorable than frontal attack at silicon. Furthermore, the sequential substitution reactions are promoted by a mechanism that involves proton shuttle from the most favorable protonation site to the oxygen of the departing group mediated by the neutral reagent molecule.

Análise da pozolanicidade da cinza da casca da castanha do caju pelo método de difratometria de raios X

Atualmente, o aproveitamento de resíduos na construção civil tem sido estimulado, uma vez que esse setor apresenta-se como um dos maiores consumidores de materiais naturais em seus processos e produtos. As cinzas ocupam lugar de destaque entre os resíduos agroindustriais por resultarem de processos de geração de energia. Grande parte dessas cinzas possui atividade pozolânica, podendo ser utilizada como substituto parcial do cimento Portland, resultando numa economia significativa de energia e custo. Este trabalho faz parte de uma pesquisa mais ampla, a qual busca avaliar a viabilidade técnica da cinza da casca da castanha de caju (CCCC) como adição mineral em matrizes de cimento Portland, como também, propor uma metodologia de análise de cinzas agroindustriais. Aplicou-se a técnica de difratometria de raios X para avaliar a reatividade do hidróxido de cálcio pela cinza da casca da castanha de caju em pastas, empregaram-se teores de substituição entre 2,5 e 30,0% e os difratogramas das pastas foram comparados com os das pastas confeccionadas com sílica ativa, executados sobre as mesmas condições de ensaio. Os resultados apontam para a ausência de reatividade pozolânica da CCCC com o cimento Portland.

Swine deep bedding ashes as a mineral additive for cement based mortar

The sustainability of intensive swine production demands alternative destinations for the generated residues. Ashes from swine rice husk-based deep bedding were tested as a mineral addition for cement mortars. The ashes were obtained at 400 to 600ºC, ground and sieved through a 325 mesh sieve (# 0.045 mm). The characterization of the ashes included the determination of the index of pozzolanic activity with lime. The ashes were also tested as partial substitutes of Portland cement. The mortars were prepared using a cement:sand proportion of 1:1.5, and with water/cement ratio of 0.4. Three percentages of mass substitution of the cement were tested: 10, 20 and 30%. Mortar performances were assessed at 7 and 28 days determining their compressive strength. The chosen condition for calcinations at the laboratory scale was related to the maximum temperature of 600ºC since the resulting ashes contained vitreous materials and presented satisfactory values for the pozzolanic index under analysis. The pozzolanic activity indicated promising results for ashes produced at 600ºC as a replacement of up to 30% in cement masses.

Composição química, valores de energia metabolizável e aminoácidos digestíveis de subprodutos do arroz para frangos de corte

Dois experimentos foram conduzidos para determinar a composição química, os valores de energia e os coeficientes de digestibilidade dos aminoácidos, do farelo de arroz integral (FAI) e da quirera de arroz (QA). No primeiro estudo, foram utilizadas 144 aves, com 21 dias de idade, machos, linhagem Cobb, que tiveram suas excretas totalmente coletadas para determinação da energia metabolizável aparente (EMA) e energia metabolizável aparente corrigida (EMAn). O delineamento experimental foi inteiramente casualizado, com três tratamentos e seis repetições, com oito aves cada. No segundo experimento, foi utilizado o método de alimentação forçada para a determinação dos coeficientes de digestibilidade dos aminoácidos. O delineamento foi inteiramente casualizado, com dois alimentos e um jejum e seis repetições com um galo cada. Os valores de MS, PB, EE, FB, EMA e EMAn foram, respectivamente, para FAI: 88,6%; 11,8%; 15,3%; 10,2%; 2968kcal kg-1 e 2804kcal kg-1 e para QA: 93,5%; 9,1%; 0,73%; 0,45%; 3338kcal kg-1 e 3239kcal kg-1. Os valores médios encontrados dos coeficientes de digestibilidade de aminoácidos essenciais e não essenciais foram, respectivamente, de 75,9% e 73,9%, para FAI, e 77,9% e 76,5%, para QA. Embora tenham apresentado níveis inferiores de energia, FAI e a QA podem ser utilizados nas rações de aves em substituição ao milho, uma vez que tiveram níveis maiores de proteína bruta e aminoácidos digestíveis.

Respostas fisiológicas de plantas amazônicas de regiões alagadas às mudanças climáticas globais

Conforme previsões do último relatório do IPCC (Intergovernmental Panel of Climatic Change) em 2007, até meados deste século haverá um aumento na concentração de CO2 na atmosfera podendo chegar a 720 μmol mol-1. Consequentemente haverá uma elevação da temperatura de até +3 °C, o que ocorrerá em conjunto com mudanças no padrão de precipitação. O mesmo relatório sugere que isto poderá acarretar uma substituição gradual da floresta tropical por vegetação similar a uma savana na parte oriental da Amazônia, porém nada é conclusivo. Diante dessas possibilidades, pergunta-se - Como as espécies de árvores que compõem as regiões de alagamento da Amazônia irão responder às alterações climáticas por vir? Apesar dessas previsões serem pessimistas, o alagamento ainda ocorrerá por vários anos na Amazônia e é de grande importância compreender os efeitos do alagamento sobre as respostas fisiológicas das plantas num contexto das mudanças climáticas. Os principais efeitos sobre a sinalização metabólica e hormonal durante o alagamento são revisados e os possíveis efeitos que as mudanças climáticas poderão ter sobre as plantas amazônicas são discutidos. As informações existentes sugerem que sob alagamento, as plantas tendem a mobilizar reservas para suprir a demanda de carbono necessário para a manutenção do metabolismo sob o estresse da falta de oxigênio. Até certo limite, com o aumento da concentração de CO2, as plantas tendem a fazer mais fotossíntese e a produzir mais biomassa, que poderão aumentar ainda mais com um acréscimo de temperatura de até 3 °C. Alternativamente, com o alagamento, há uma diminuição geral do potencial de crescimento e é possível que quando em condições de CO2 e temperatura elevados os efeitos positivo e negativo se somem. Com isso, as respostas fisiológicas poderão ser amenizadas ou, ainda, promover maior crescimento para a maioria das espécies de regiões alagáveis até o meio do século. Porém, quando a temperatura e o CO2 atingirem valores acima dos ótimos para a maioria das plantas, estas possivelmente diminuirão a atividade fisiológica.

A novel missense mutation p.L76P in the GJB2 gene causing nonsyndromic recessive deafness in a Brazilian family

Mutations in the GJB2 gene, encoding connexin 26 (Cx26), are a major cause of nonsyndromic recessive hearing loss in many countries. We report here on a novel point mutation in GJB2, p.L76P (c.227C>T), in compound heterozygosity with a c.35delG mutation, in two Brazilian sibs, one presenting mild and the other profound nonsyndromic neurosensorial hearing impairment. Their father, who carried a wild-type allele and a p.L76P mutation, had normal hearing. The mutation leads to the substitution of leucine (L) by proline (P) at residue 76, an evolutionarily conserved position in Cx26 as well as in other connexins. This mutation is predicted to affect the first extracellular domain (EC1) or the second transmembrane domain (TM2). EC1 is important for connexon-connexon interaction and for the control of channel voltage gating. The segregation of the c.227C>T (p.L76P) mutation together with c.35delG in this family indicates a recessive mode of inheritance. The association between the p.L76P mutation and hearing impairment is further supported by its absence in a normal hearing control group of 100 individuals, 50 European-Brazilians and 50 African-Brazilians.

Sob o signo de Darwin? Sobre o mau uso de uma quimera

No ano de 2003 Francisco de Oliveria publicou um artigo intitulado "O Ornitorrinco" no qual fez considerações críticas sobre a conjectura politico-social daquele momento histórico. Tal artigo é permeado por um paralelo entre o evolucionismo darwinista e a visão do autor sobre a sociedade brasileira contemporânea. Entretanto, ao fazer tal analogia ele incorre numa série de equívocos teóricos sobre a teoria evolucionista. Tais equívocos consistem, em grande parte, numa substuição indevida entre aquilo que ficou conhecido como Darwinismo Social e a teoria neodarwinista como entendida pelos seus atuais proponentes. O presente trabalho identifica estes equívocos e os contextualiza dentro da teoria neodarwiniana. Além disso, fazemos um recorte histórico do processo de formação do pensamento evolucionista para enfatizar que a associação entre biologia e darwinismo social é mais complexa do que geralmente se assume.