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.

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.

Groundwater abstraction and plankton in the druze pool of Azraq oasis, Jordan

The Azraq oasis lies in the Jordanian desert, about 85 km east of Amman. In this brief paper the author summarises his observations from a visit to the oasis in 1991, discusses the effects of pumping groundwater from the oasis to Amman and presents results from a plankton survey.

The Lune catchment abstraction management strategy. Consultation document September 2003

This consultation document sets out the proposed future licensing strategy for the Lune Catchment Abstraction Management Strategy (CAMS) area. Following the three month consultation period, the Environment Agency will determine the final licensing strategy and publish it in the CAMS document. The strategy will provide an indication of whether new abstraction licences are likely to be available and the conditions that should be expected on licences. Water plays a vital role in the Lune catchment, providing water for public supply, supporting recreation, such as angling and canoeing, and providing sustainable flows to preserve numerous designated sites. There is minimal abstraction throughout much of the catchment, apart from the lower reaches of the River Lune. The document is split into five sections relating to the CAMS process. Sections 1 to 4 outline the CAMS process, and Section 5 outlines the proposed licensing strategy for the Lune CAMS areas. It is important to note that this strategy deals with groundwater and surface water abstractions separately; Sections 4 and 5 are split to differentiate between the surface water and groundwater results and strategy.

The fisheries Aspects of North West Water AuthoritySchemes to Increase Water Abstraction in West Cumbria

This is the report on the Fisheries Aspects of North West Water Authority Schemes to Increase Water Abstraction in West Cumbria by the Egremont and District Anglers’ Association. Existing river pollution and water abstraction in the Ennerdale Lake-River Ehen system is shown to have caused a major deterioration in the conditions in the Ehen fishery. This is reflected by the fact that catches of salmon, sea trout and smelts on the Ehen have all fallen to roughly 6% of the 1965 level; wich is far worse than the deterioration shown in salmon catches for S. W. Cumberland as a whole. Recommendations are made, in the light of proposals by North West Water Authority to increase water abstraction in West Cumbria, to prevent further deterioration in the Ehen fishery in the short term and to improve the situation in the longer term. It contains sections on pollution, water abstraction and fisheries background, flow statistics for and discussion of high water-droughts on the River Ehen, effects of droughts on Tidal Water and a discussion of N.W.W.A. Paper entitled `Water Resources in West Cumbria’ in the light of conditions on the River Ehen.

The effect of abstraction on fish and fisheries

This is the report on the Effect of Abstraction on Fish and Fisheries presented at the 24th IFM Annual Study Course, The Changing Face of Fisheries September 1993 at Cardiff. Water is abstracted from rivers for a wide variety of uses and causing potential for conflicts between abstracters, fisheries and conservation interests, especially during natural low flows. It looks at the potential effects that flow reduction has over various stages of salmonids at various stages of their life history. The flow at the time of smolt migration has been found to be positively correlated with the number of returning adults, and flow is considered to be one of the most important environmental factors inducing salmonids to enter fresh water and ascend rivers. The importance of time series data on fish stocks and angling success together with models which ultimately relate discharge to standing stock are discussed in relation to the setting up of Minimum Acceptable Flows.