Origin of the activation barrier in the process of hydrogen abstraction: the perturbation treatment

The perturbation treatment previously given is extended to explain the process of hydrogen abstraction from the various hydrogen donor molecules by the triplet nπ* state of ketones or the ground state of the alkyl or alkoxy radical. The results suggest that, as the ionization energy of the donor bonds is decreased, the reaction is accelerated and it is not influenced by the bond strength of the donor bonds. The activation barrier in such reactions arises from a weakening of the charge resonance term as the ionization energy of the donor bond increases.

A comparative study of the photochemical hydrogen-abstraction reactions of a ketone and a thione

A perturbation treatment was developed for the comparative study of the abstraction of hydrogen from methane by formaldehyde and thioformaldehyde in their nπ* and ππ* states. Both in-plane and perpendicularplane reactions are considered. Results are qualitative but reveal clearly the prominent distinguishing features of these two photochemical processes in agreement with the experimental observations.

Quantifying the effects of climate change and water abstraction on a population of barramundi (Lates calcarifer), a diadromous estuarine finfish

Many aquatic species are linked to environmental drivers such as temperature and salinity through processes such as spawning, recruitment and growth. Information is needed on how fished species may respond to altered environmental drivers under climate change so that adaptive management strategies can be developed. Barramundi (Lates calcarifer) is a highly prized species of the Indo-West Pacific, whose recruitment and growth is driven by river discharge. We developed a monthly age- and length-structured population model for barramundi. Monte Carlo Markov Chain simulations were used to explore the population's response to altered river discharges under modelled total licenced water abstraction and projected climate change, derived and downscaled from Global Climate Model A1FI. Mean values of exploitable biomass, annual catch, maximum sustainable yield and spawning stock size were significantly reduced under scenarios where river discharge was reduced; despite including uncertainty. These results suggest that the upstream use of water resources and climate change have potential to significantly reduce downstream barramundi stock sizes and harvests and may undermine the inherent resilience of estuarine-dependent fisheries. © 2012 CSIRO.

Origin of the activation barrier in the process of hydrogen abstraction: the perturbation treatment

The perturbation treatment previously given is extended to explain the process of hydrogen abstraction from the various hydrogen donor molecules by the triplet nπ* state of ketones or the ground state of the alkyl or alkoxy radical. The results suggest that, as the ionization energy of the donor bonds is decreased, the reaction is accelerated and it is not influenced by the bond strength of the donor bonds. The activation barrier in such reactions arises from a weakening of the charge resonance term as the ionization energy of the donor bond increases.

The perturbational treatment of the process of hydrogen abstraction by ketones

The change in energy during hydrogen abstraction by ketones is estimated for different electronic states as a function of the intermolecular orbital overlap employing perturbation theory. The results suggest that ketones preferentially undergo the in-plane reaction and abstract a hydrogen atom in their triplet nπ* state. For ketones where the triplet ππ* state lies below the triplet nπ* state, hydrogen abstraction can take place in the ππ* state owing to the crossing of the zero order reaction surfaces of the nπ* and ππ* states.

The Mechanism Of The Hydrogen Abstraction Process By Photo-Excited Ketones

Qualitative potential energy surfaces for hydrogen abstraction from alkanes containing primary, secondary and tertiary C-H bonds by a photo-excited ketone have been reported, The results suggest that the activation barriers for these processes decrease in the order primary > secondary > tertiary in agreement with the observed trend in the rate constants. The analysis of the electronic structure of the transition-state reveal that electron-transfer from hydrocarbon to ketone and formation of a new bond are almost synchronous in the hydrogen transfer process. The tunneling of hydrogen is not important in the normal temperature region even though the barriers are small.

Photochemical intramolecular gamma-hydrogen abstraction in a ketone and an alkene and the role of tunneling of hydrogen

Intramolecular gamma-hydrogen abstraction reactions were examined in pentane-2-one and 2-methyl-1-pentene in their lowest triplet states using the AM1 semi-empirical molecular orbital method with the complete geometry optimization in the unrestricted Hartree-Fock frame. The results reveal that the oxygen atom of the carbonyl group and the end carbon atom of the olefinic bond acquire high free valence and spin density indices in their respective lowest triplet states, leading to abstraction of hydrogen from the gamma-position relative to the carbonyl and olefinic bonds. The theoretical energy profiles fit with a polynomial and the probability of tunneling of hydrogen was estimated by the WKB (Wentzel, Kramer and Brillouin) method. The results, after thermal averaging of the rate constants, reveal that tunneling of hydrogen is significant at room temperature.

The design and synthesis of redox core-alpha amino acid composites based on thiol-disulfide exchange mechanism and a comparative study of their zinc abstraction potential from [CCXX] boxes in proteins

The design and synthesis of agents that can abstract zinc from their [CCXX] (C=cysteine; X=cysteine/histidine) boxes by thioldisulfide exchange-having as control, the redox parities of the core sulfur ligands of the reagent and the enzyme, has been illustrated, and their efficiency demonstrated by monitoring the inhibition of the transcription of calf thymus DNA by E. coli RNA polymerase, which harbors two zinc atoms in their [CCXX] boxes of which one is exchangeable. Maximum inhibition possible with removal of the exchangeable zinc was seen with redox-sulfanilamide-glutamate composite. In sharp contrast, normal chelating agents (EDTA, phenanthroline) even in a thousand fold excess showed only marginal inhibition, thus supporting an exchange mechanism for the metal removal. (C) 2002 Elsevier Science Ltd. All rights reserved.

Digestive ripening: a synthetic method par excellence for core-shell, alloy, and composite nanostructured materials

The solvated metal atom dispersion (SMAD) method has been used for the synthesis of colloids of metal nanoparticles. It is a top-down approach involving condensation of metal atoms in low temperature solvent matrices in a SMAD reactor maintained at 77 K. Warming of the matrix results in a slurry of metal atoms that interact with one another to form particles that grow in size. The organic solvent solvates the particles and acts as a weak capping agent to halt/slow down the growth process to a certain extent. This as-prepared colloid consists of metal nanoparticles that are quite polydisperse. In a process termed as digestive ripening, addition of a capping agent to the as-prepared colloid which is polydisperse renders it highly monodisperse either under ambient or thermal conditions. In this, as yet not well-understood process, smaller particles grow and the larger ones diminish in size until the system attains uniformity in size and a dynamic equilibrium is established. Using the SMAD method in combination with digestive ripening process, highly monodisperse metal, core-shell, alloy, and composite nanoparticles have been synthesized. This article is a review of our contributions together with some literature reports on this methodology to realize various nanostructured materials.

Virgin wasps develop ovaries on par with mated females, but lay fewer eggs

In the primitively eusocial wasp Ropalidia marginata, mating is not necessary for a female wasp to develop her ovaries, lay eggs, and even to become the sole egg layer of her colony despite the presence of other mated nestmates. Here, we show that virgin wasps do not differ from their mated counterparts in the extent and rapidity of their ovarian development, in the proportion of individuals that build a nest and laid eggs, and in the time taken to do so. However, a significantly larger proportion of virgin females showed resorbing oocytes, and laid fewer eggs as compared to mated individuals. Thus, virgin females have the ability to develop ovaries and lay eggs but also to refrain from necessarily laying all mature eggs produced, before mating opportunities arise. This dual ability would be adaptive in haplodiploid, tropical species with perennial nesting cycles and frequent opportunities for workers to become replacement queens or solitary nest foundresses throughout the year.

BIOCARDS AND LEVEL OF ABSTRACTION

Biocards are formal descriptions of biological phenomena and their underlying functional principles. They are used in bioinspired design to document search results and to communicate the findings for use in the further design process. The present study explored the effect of abstraction level used in biocards. This was done in two workshops conducted with design students in Denmark and India. Students were given a design assignment and instructions for how to perform the BID ideation work. Half of the students were given biocards with abstract descriptions while the other half got biocards with concrete descriptions. The novelty of found solutions was evaluated by the students by rating novelty of each solution on a scale from 1 to 5. Mean values for abstract descriptions were 0,3 higher than for concrete descriptions indicating that more innovative solutions were found when students used biocards with abstract descriptions compared to concrete descriptions. The difference in mean value is significant with a confidence level better than 1%. It seems likely that more abstract descriptions in biocards helps avoiding design fixation in biomimetic design work.

Análise de documentos encaminhados à Comissão Externa constituída para verificar a situação de saúde nos estados do Pará e Amapá e apresentação de relatório de aplicação de recursos da saúde nessas UFS

Consultoria de Orçamento e Fiscalização Financeira - Núcleo da Saúde.

Alvará com força de Ley, por que Vossa Magestade ha por bem renovar a inteira, e inviolavel observancia da Ley de doze de setembro de mil seiscentos cincoenta e tres, em quanto nella se estabeleceo, que os indios do Graõ Pará, e Maranhaõ sejão governados no temporal pelos Governadores, Ministros, e pelos seus principaes, e justiças seculares, com inhibição das administrações dos regulares, derogando todas as Leys, Regimentos, Ordens, e Disposições contrarias : para V. Magestade ver / Antonio José Galvão o fez

Coleção Marcio Moreira Alves.

A Amazonia : as provincias do Pará e Amazonas e o governo central do Brazil

O Barão de Marajó relata a situação da Amazônia (Pará e Amazonas) em relação ao governo central.