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.

Suprahelical arrangements of hydrogen bonds in peptide helices

Abstract is not available.

On measurements of formation, growth, hygroscopicity, and volatility of atmospheric ultrafine particles

Atmospheric aerosol particles affect the global climate as well as human health. In this thesis, formation of nanometer sized atmospheric aerosol particles and their subsequent growth was observed to occur all around the world. Typical formation rate of 3 nm particles at varied from 0.01 to 10 cm-3s-1. One order of magnitude higher formation rates were detected in urban environment. Highest formation rates up to 105 cm-3s-1 were detected in coastal areas and in industrial pollution plumes. Subsequent growth rates varied from 0.01 to 20 nm h-1. Smallest growth rates were observed in polar areas and the largest in the polluted urban environment. This was probably due to competition between growth by condensation and loss by coagulation. Observed growth rates were used in the calculation of a proxy condensable vapour concentration and its source rate in vastly different environments from pristine Antarctica to polluted India. Estimated concentrations varied only 2 orders of magnitude, but the source rates for the vapours varied up to 4 orders of magnitude. Highest source rates were in New Delhi and lowest were in the Antarctica. Indirect methods were applied to study the growth of freshly formed particles in the atmosphere. Also a newly developed Water Condensation Particle Counter, TSI 3785, was found to be a potential candidate to detect water solubility and thus indirectly composition of atmospheric ultra-fine particles. Based on indirect methods, the relative roles of sulphuric acid, non-volatile material and coagulation were investigated in rural Melpitz, Germany. Condensation of non-volatile material explained 20-40% and sulphuric acid the most of the remaining growth up to a point, when nucleation mode reached 10 to 20 nm in diameter. Coagulation contributed typically less than 5%. Furthermore, hygroscopicity measurements were applied to detect the contribution of water soluble and insoluble components in Athens. During more polluted days, the water soluble components contributed more to the growth. During less anthropogenic influence, non-soluble compounds explained a larger fraction of the growth. In addition, long range transport to a measurement station in Finland in a relatively polluted air mass was found to affect the hygroscopicity of the particles. This aging could have implications to cloud formation far away from the pollution sources.

Performance of RT-PCR-ELISA for the detection of peste des petits ruminants virus

A highly sensitive and specific reverse transcription polymerase chain reaction enzyme linked immunosorbent assay (RT-PCR-ELISA) was developed for the objective detection of nucleoprotein (N) gene of peste des petits ruminants (PPR) virus from field outbreaks or experimentally infected sheep. Two primers (IndF and Np4) and one probe (Sp3) available or designed for the amplification/probing of the 'N' gene of PPR virus, were chosen for labeling and use in RT-PCR-ELISA based on highest analytical sensitivity of detection of infective virus or N-gene containing recombinant plasmid, higher nucleotide homology at the primer binding sites of the 'N' gene sequences available and the ability to amplify PPR viral genome from different sources of samples. RT-PCR was performed with unlabeled IndF and Np4 digoxigenin labeled primers followed by a microplate hybridization probe reaction with biotin labeled Sp3 probe. RT-PCR-ELISA was found to be 10-fold more sensitive than the conventional RT-PCR followed by agarose gel based detection of PCR product. Based on the Mean (mean +/- 3S.D.) optical density (OD) values of 47 RT-PCR negative samples, OD values above 0.306 were considered positive in RT-PCR-ELISA. A total of 82 oculo-nasal swabs and tissue samples from suspected PPR cases were analyzed by RT-PCR and RT-PCR-ELISA, which revealed 54.87 and 58.54% positivity, respectively. From an experimentally infected sheep, both RT-PCR and RT-PCR-ELISA could detect the virus from 6 days post-infection up to 9 days in oculo-nasal swabs. On post-mortem, PPR viral genome was detected in spleen, lymph node, lung, heart and liver. The correlation co-efficient between RT-PCR-ELISA OD values and either TCID50 of virus or molecules of DNA was 0.622 and 0.657, respectively. The advantages of RT-PCR-ELISA over the conventional agarose gel based detection of RT-PCR products are discussed. (c) 2006 Elsevier B.V. All rights reserved.

Electronic structure of square planar CuO46− clusters

The results of spin-polarized MSXagr calculations show that the ground state of the CuO 4 6– cluster is essentially non-magnetic in spite of odd number of electrons in the system for short Cu–O distances (1.90 Å) as found in the highT c superconductors. This arises due to the fact that the unpaired electron resides in a molecular orbital with primarily oxygen 3s character. The stability of this molecular orbital is found to be sensitive to the cluster geometry and thus, increase in Cu–O distance (as well as other changes affecting oxygen-oxygen distance) tend to favour a magnetic state. From these calculations we have also estimated the Coulomb correlation strength within the Cu 3d to be about 5.3 eV.

Two Novel Hexadepsipeptides with Several Modified Amino Acid Residues Isolated from the Fungus

Two new cyclohexadepsipeptides have been isolated from the fungus Isaria. Fungal growth in solid media yielded hyphal strands from which peptide fractions were readily isolable by organic-solvent extraction. Two novel cyclodepsipeptides, isaridin A and isaridin B, have been isolated by reverse-phase HPLC, and characterized by ESI-MS and 1H-NMR. Single crystals of both peptides have been obtained, and their 3D structures were elucidated by X-ray diffraction. The isaridins contain several unusual amino acid residues. The sequences are cyclo(β-Gly-HyLeu-Pro-Phe-NMeVal-NMePhe) and cyclo(β-Gly-HyLeu-β-MePro-Phe-NMeVal-NMePhe), where NMeVal is N-methylvaline, NMePhe N-methylphenylalanine, and HyLeu hydroxyleucine (=2-hydroxy-4-methylpentanoic acid). The two peptides differ from one another at residue 3, isaridin A having an (S)-proline at this position, while β-methyl-(S)-proline (=(2S,3S)-2,3,4,5-tetrahydro-3-methyl-1H-pyrrole-2-carboxylic acid) is found in isaridin B. The solid-state conformations of both cyclic depsipeptides are characterized by the presence of two cis peptide bonds at HyLeu(2)-Pro(3)/HyLeu(2)-β-MePro(3) and NMeVal(5)-NMePhe(6), respectively. In isaridin A, a strong intramolecular H-bond is observed between Phe(4)CO⋅⋅⋅HNβ-Gly(1), and a similar, but weaker, interaction is observed between β-Gly(1)CO⋅⋅⋅HNPhe(4). In contrast, in isaridin B, only a single intramolecular H-bond is observed between β-Gly(1)CO⋅⋅⋅HNPhe(4

Learning Challenges in Biogas Production for Sustainability : An activity theoretical study of a network from a swine industry chain

This study is about the challenges of learning in the creation and implementation of new sustainable technologies. The system of biogas production in the Programme of Sustainable Swine Production (3S Programme) conducted by the Sadia food processing company in Santa Catarina State, Brazil, is used as a case example for exploring the challenges, possibilities and obstacles of learning in the use of biogas production as a way to increase the environmental sustainability of swine production. The aim is to contribute to the discussion about the possibilities of developing systems of biogas production for sustainability (BPfS). In the study I develop hypotheses concerning the central challenges and possibilities for developing systems of BPfS in three phases. First, I construct a model of the network of activities involved in the BP for sustainability in the case study. Next, I construct a) an idealised model of the historically evolved concepts of BPfS through an analysis of the development of forms of BP and b) a hypothesis of the current central contradictions within and between the activity systems involved in BP for sustainability in the case study. This hypothesis is further developed through two actual empirical analyses: an analysis of the actors senses in taking part in the system, and an analysis of the disturbance processes in the implementation and operation of the BP system in the 3S Programme. The historical analysis shows that BP for sustainability in the 3S Programme emerged as a feasible solution for the contradiction between environmental protection and concentration, intensification and specialisation in swine production. This contradiction created a threat to the supply of swine to the food processing company. In the food production activity, the contradiction was expressed as a contradiction between the desire of the company to become a sustainable company and the situation in the outsourced farms. For the swine producers the contradiction was expressed between the contradictory rules in which the market exerted pressure which pushed for continual increases in scale, specialisation and concentration to keep the production economically viable, while the environmental rules imposed a limit to this expansion. Although the observed disturbances in the biogas system seemed to be merely technical and localised within the farms, the analysis proposed that these disturbances were formed in and between the activity systems involved in the network of BPfS during the implementation. The disturbances observed could be explained by four contradictions: a) contradictions between the new, more expanded activity of sustainable swine production and the old activity, b) a contradiction between the concept of BP for carbon credits and BP for local use in the BPfS that was implemented, c) contradictions between the new UNFCCC1 methodology for applying for carbon credits and the small size of the farms, and d) between the technologies of biogas use and burning available in the market and the small size of the farms. The main finding of this study relates to the zone of proximal development (ZPD) of the BPfS in Sadia food production chain. The model is first developed as a general model of concepts of BPfS and further developed here to the specific case of the BPfS in the 3S Programme. The model is composed of two developmental dimensions: societal and functional integration. The dimension of societal integration refers to the level of integration with other activities outside the farm. At one extreme, biogas production is self-sufficient and highly independent and the products of BP are consumed within the farm, while at the other extreme BP is highly integrated in markets and networks of collaboration, and BP products are exchanged within the markets. The dimension of functional integration refers to the level of integration between products and production processes so that economies of scope can be achieved by combining several functions using the same utility. At one extreme, BP is specialised in only one product, which allows achieving economies of scale, while at the other extreme there is an integrated production in which several biogas products are produced in order to maximise the outcomes from the BP system. The analysis suggests that BP is moving towards a societal integration, towards the market and towards a functional integration in which several biogas products are combined. The model is a hypothesis to be further tested through interventions by collectively constructing the new proposed concept of BPfS. Another important contribution of this study refers to the concept of the learning challenge. Three central learning challenges for developing a sustainable system of BP in the 3S Programme were identified: 1) the development of cheaper and more practical technologies of burning and measuring the gas, as well as the reduction of costs of the process of certification, 2) the development of new ways of using biogas within farms, and 3) the creation of new local markets and networks for selling BP products. One general learning challenge is to find more varied and synergic ways of using BP products than solely for the production of carbon credits. Both the model of the ZPD of BPfS and the identified learning challenges could be used as learning tools to facilitate the development of biogas production systems. The proposed model of the ZPD could be used to analyse different types of agricultural activities that face a similar contradiction. The findings could be used in interventions to help actors to find their own expansive actions and developmental projects for change. Rather than proposing a standardised best concept of BPfS, the idea of these learning tools is to facilitate the analysis of local situations and to help actors to make their activities more sustainable.

Pes study of spin-state transitions in d6 transition metal complexes and oxides

Transitions from the low-to the high-spin state in Fe2+ and Co3+ compounds have been examined by X-ray and UV photoelectron spectroscopy. It has been shown that the core-level bands in XPES, in particular the metal 3s band, as well as the valence bands, are diagnosis in the study of spin-state transitions.

XPES and UVPES studies of iron oxides

X-Ray and uv photoelectron spectra of FeO, Fe2O3, and Fe3O4 have been studied along with those of a few model compounds. It has been possible to assign distinct bands due to Fe2+ and Fe3+ in the 3d, 3p, 3s, and 2p bands of Fe3O4. The spectra of Fe3O4 do not show major changes through the Verwey transition.

Total synthesis of panaxytriol and panaxydiol

The enantioselective total synthesis of the diyne containing natural products panaxytriol and (3S,10R)-panaxydiol from L-tartaric acid is reported. Key steps in the synthesis include the elaboration of a gamma-hydroxy amide derived from tartaric acid to the required alkyne and the formation of the desired diyne unit by a Cadiot-Chodkiewicz coupling. (C) 2011 Elsevier Ltd. All rights reserved.

A generalized network alignment for three-source three-destination multiple unicast networks with delays

The concept of interference alignment when extended to three-source three-destination instantaneous multiple unicast network for the case where, each source-destination pair has a min-cut of 1 and zero-interference conditions are not satisfied, is known to achieve a rate of half for every source-destination pair under certain conditions [6]. This was called network alignment. We generalize this concept of network alignment to three-source three-destination multiple unicast (3S-3D-MU) networks with delays, without making use of memory at the intermediate nodes (i.e., nodes other than the sources and destinations) and using time varying Local Encoding Kernels (LEKs). This achieves half the rate corresponding to the individual source-destination min-cut for some classes of 3S-3D-MU network with delays which do not satisfy the zero-interference conditions.

An Easy Access to Benzofurans via DBU Induced Condensation Reaction of Active 2-Hydroxy Acetophenones with Phenacyl Chlorides: A Novel Class of Antioxidant Agents

A convenient and efficient one-pot synthesis of benzofurans 3a, 3b, 3c, 3d, 3e, 3f, 3g, 3h, 3i, 3j, 3k, 3l, 3m, 3n, 3o, 3p, 3q, 3r, 3s, 3t has been described from 2-hydroxy acetophenones and phenacyl chlorides in the presence of DBU. The procedure was applicable for a variety of phenacyl chlorides and provides a variety of benzofurans with higher yields. DBU acts as a base and as well as nucleophiles. All the derivatives were subjected to in vitro antioxidant screenings against representative 2,2-diphenyl-1-picryl-hydrazyl and 2,2-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) radicals and results worth for further investigations.

Differential dynamics of the serotonin(1A) receptor in membrane bilayers of varying cholesterol content revealed by all atom molecular dynamics simulation

The serotonin(1A) receptor belongs to the superfamily of G protein-coupled receptors (GPCRs) and is a potential drug target in neuropsychiatric disorders. The receptor has been shown to require membrane cholesterol for its organization, dynamics and function. Although recent work suggests a close interaction of cholesterol with the receptor, the structural integrity of the serotonin(1A) receptor in the presence of cholesterol has not been explored. In this work, we have carried out all atom molecular dynamics simulations, totaling to 3s, to analyze the effect of cholesterol on the structure and dynamics of the serotonin(1A) receptor. Our results show that the presence of physiologically relevant concentration of membrane cholesterol alters conformational dynamics of the serotonin(1A) receptor and, on an average lowers conformational fluctuations. Our results show that, in general, transmembrane helix VII is most affected by the absence of membrane cholesterol. These results are in overall agreement with experimental data showing enhancement of GPCR stability in the presence of membrane cholesterol. Our results constitute a molecular level understanding of GPCR-cholesterol interaction, and represent an important step in our overall understanding of GPCR function in health and disease.

Jet:progress in performance and understanding

In 1990 JET operated with a number of technical improvements which led to advances in performance and permitted the carrying out of experiments specifically aimed at improving physics understanding of selected topics relevant to the "NEXT STEP". The new facilities include beryllium antenna screens, a prototype lower hybrid current drive system, and modification of the NI system to enable the injection of He-3 and He-4. Continued investigation of the hot-ion H-mode produced a value of n(D)(0)tau-E(T)(i)(0) = 9 x 10(20)m-3s keV, which is near conditions required for Q(DT) = 1, while a new peaked density profile H-mode was developed with only slightly lower performance. Progress towards steady state operation has been made by achieving ELMy H-modes under certain operating conditions, while maintaining good tau-E values. Experimental simulation of He ash transport indicates effective removal of alpha-particles from the plasma core for both L and H mode plasmas. Detailed analyses of particle and energy transport have helped establish a firmer link between particle and energy transport, and have suggested a connection between reduced energy transport and reversed shear. Numerical and analytic studies of divertor physics carried out for the pumped divertor phase of JET have helped clarify the key parameters governing impurity retention, and an intensive model validation effort has begun. Experimental simulation of alpha-particle effects with beta-fast up to 8% have shown that the slowing down processes are classical, and have given no evidence of deleterious collective effects.