Rapid, selective, and reversible Nitroxide Radical Coupling (NRC) reactions at amibient temperature

High activation of polystyrene with bromine end groups (PSTY-Br) to their incipient radicals occurred in the presence of Cu(I)Br, Me6TREN, and DMSO solvent. These radicals were then trapped by nitroxide species leading to coupling reactions between PSTY-Br and nitroxides that were ultrafast and selective in the presence of a diverse range of functional groups. The nitroxide radical coupling (NRC) reactions have the attributes of a “click” reaction with near quantitative yields of product formed, but through the reversibility of this reaction, it has the added advantage of permitting the exchange of chemical functionality on macromolecules. Conditions were chosen to facilitate the disproportionation of Cu(I)Br to the highly activating nascent Cu(0) and deactivating Cu(II)Br2 in the presence of DMSO solvent and Me6TREN ligand. NRC at room temperature gave near quantitative yields of macromolecular coupling of low molecular weight polystyrene with bromine chain-ends (PSTY-Br) and nitroxides in under 7 min even in the presence of functional groups (e.g., −≡, −OH, −COOH, −NH2, =O). Utilization of the reversibility of the NRC reaction at elevated temperatures allowed the exchange of chain-end groups with a variety of functional nitroxide derivatives. The robustness and orthogonality of this NRC reaction were further demonstrated using the Cu-catalyzed azide/alkyne “click” (CuAAC) reactions, in which yields greater than 95% were observed for coupling between PSTY-N3 and a PSTY chain first trapped with an alkyne functional TEMPO (PSTY-TEMPO-≡).

Radical nursing and the emergence of technique as healthcare technology

The integration of technology in care is core business in nursing and this role requires that we must understand and use technology informed by evidence that goes much deeper and broader than actions and behaviours. We need to delve more deeply into its complexity because there is nothing minor or insignificant about technology as a major influence in healthcare outcomes and experiences. Evidence is needed that addresses technology and nursing from perspectives that examine the effects of technology, especially related to increasing demands for efficiency, the relationship of technology to nursing and caring, and a range of philosophical questions associated with empowering people in their healthcare choices. Specifically, there is a need to confront in practice the ways technique influences care. Technique is the creation of a kind of thinking that is necessary for contemporary healthcare technology to develop and be applied in an efficient and rational manner. Technique is not an entity or specific thing, but rather a way of thinking that seeks to shape and organize nursing activity, and manage efficiently individual difference(s) in care. It emphasizes predetermined causal relationships, conformity, and sameness of product, process, and thought. In response is needed a radical vision of nursing that attempts in a real sense to ensure we meet the needs of individuals and their community. Activism and advocacy are needed, and a willingness to create a certain detachment from the imperatives that technique demands. It is argued that our responsibility as nurses is to respond in practice to the errors, advantages, difficulties, and temptations of technology for the benefit of those who most need our assistance and care.

A Radical Cyclization Route To +/-Andirolactone, A Spiro-Gamma-Butyrolactone

Synthesis of Andirolactone (Image ), starting from 4-methyl cyclohex-3-en-1-one (Image ), via the radical cyclisation of the bromoacetal (Image ), is described.

DNA bar-coding reveals source and patterns of Thaumastocoris peregrinus invasions in South Africa and South America.

Thaumastocoris peregrinus is a recently introduced invertebrate pest of non-native Eucalyptus plantations in the Southern Hemisphere. It was first reported from South Africa in 2003 and in Argentina in 2005. Since then, populations have grown explosively and it has attained an almost ubiquitous distribution over several regions in South Africa on 26 Eucalyptus species. Here we address three key questions regarding this invasion, namely whether only one species has been introduced, whether there were single or multiple introductions into South Africa and South America and what the source of the introduction might have been. To answer these questions, bar-coding using mitochondrial DNA (COI) sequence diversity was used to characterise the populations of this insect from Australia, Argentina, Brazil, South Africa and Uruguay. Analyses revealed three cryptic species in Australia, of which only T. peregrinus is represented in South Africa and South America. Thaumastocoris peregrinus populations contained eight haplotypes, with a pairwise nucleotide distance of 0.2-0.9% from seventeen locations in Australia. Three of these haplotypes are shared with populations in South America and South Africa, but the latter regions do not share haplotypes. These data, together with the current distribution of the haplotypes and the known direction of original spread in these regions, suggest that at least three distinct introductions of the insect occurred in South Africa and South America before 2005. The two most common haplotypes in Sydney, one of which was also found in Brisbane, are shared with the non-native regions. Sydney populations of T. peregrinus, which have regularly reached outbreak levels in recent years, might thus have served as source of these three distinct introductions into other regions of the Southern Hemisphere.

Julius Pick aged 93 at his grandson Gary Godshaw's Bar Mitzvah; Buffalo, New York Portraits Men

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Inhibition of H2O2 generation in rat liver mitochondria by radical quenchers and phenolic compounds

Generation of H2O2 by rat liver mitochondria with choline, glycerol 1-phosphate and proline as substrates has been shown by using high-concentration phosphate buffer. Rates obtained under these conditions were higher and more consistent as compared with the earlier reports with high-concentration mannitol/sucrose/Tris buffer. Sulphate ions could replace phosphate indicating a requirement for a high concentration of oxygen-containing anions. H2O2 generation was dependent on the presence of native mitochondria and substrate. Maximal rates with various substrates were found to be the same as with succinate. Values of Km and Vmax for H2O2 generation were considerably less than those obtained for respective dehydrogenase activities, measured by dye reduction. Scavengers of O2-. and OH. inhibited generation of H2O2. ATP, ADP, thyronine derivatives and a number of phenolic compounds also showed very potent inhibitory effects of H2O2 generation, whereas phenyl compound had no effect. Phenolic compounds did not have any effect on mitochondrial superoxide dismutase and choline dehydrogenase activities as well as on O2-. generation by the xanthine-xanthine oxidase system. Inhibition by phenolic compounds may have potential for regulation of the intracellular concentration of H2O2, that is not considered to have a "second messenger' function.

Julius Pick aged 93 at his grandson Gary Godshaw's Bar Mitzvah; Buffalo, New York Portraits Men

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Bar Mitzvah Coin

Obverse: Silver 5 Lirot coin, in the right side olive branch. Reverse: A stylized reproduction of an ancient Holy Ark which appears on a gold-vessel painted in the 13th century C.E.

Radical Enhanced Atomic Layer Deposition of Metals and Oxides

Atomic Layer Deposition (ALD) is a chemical, gas-phase thin film deposition method. It is known for its ability for accurate and precise thickness control, and uniform and conformal film growth. One area where ALD has not yet excelled is film deposition at low temperatures. Also deposition of metals, besides the noble metals, has proven to be quite challenging. To alleviate these limitations, more aggressive reactants are required. One such group of reactants are radicals, which may be formed by dissociating gases. Dissociation is most conveniently done with a plasma source. For example, dissociating molecular oxygen or hydrogen, oxygen or hydrogen radicals are generated. The use of radicals in ALD may surmount some of the above limitations: oxide film deposition at low temperatures may become feasible if oxygen radicals are used as they are highly reactive. Also, as hydrogen radicals are very effective reducing agents, they may be used to deposit metals. In this work, a plasma source was incorporated in an existing ALD reactor for radical generation, and the reactor was used to study five different Radical Enhanced ALD processes. The modifications to the existing reactor and the different possibilities during the modification process are discussed. The studied materials include two metals, copper and silver, and three oxides, aluminium oxide, titanium dioxide and tantalum oxide. The materials were characterized and their properties were compared to other variations of the same process, utilizing the same metal precursor, to understand what kind of effect the non-metal precursor has on the film properties and growth characteristics. Both metals were deposited successfully, and silver for the first time by ALD. The films had low resistivity and grew conformally in the ALD mode, demonstrating that the REALD of metals is true ALD. The oxide films had exceptionally high growth rates, and aluminium oxide grew at room temperature with low cycle times and resulted in good quality films. Both aluminium oxide and titanium dioxide were deposited on natural fibres without damaging the fibre. Tantalum oxide was also deposited successfully, with good electrical properties, but at slightly higher temperature than the other two oxides, due to the evaporation temperature required by the metal precursor. Overall, the ability of REALD to deposit metallic and oxide films with high quality at low temperatures was demonstrated.

The kinetics and reactivity of several polyatomic free radicals in reactions with NO2, O2, Cl2, and HCl

In this thesis, the kinetics of several alkyl, halogenated alkyl, and alkenyl free radical reactions with NO2, O2, Cl2, and HCl reactants were studied over a wide temperature range in time resolved conditions. Laser photolysis photoionisation mass spectrometer coupled to a flow reactor was the experimental method employed and this thesis present the first measurements performed with the experimental system constructed. During this thesis a great amount of work was devoted to the designing, building, testing, and improving the experimental apparatus. Carbon-centred free radicals were generated by the pulsed 193 or 248 nm photolysis of suitable precursors along the tubular reactor. The kinetics was studied under pseudo-first-order conditions using either He or N2 buffer gas. The temperature and pressure ranges employed were between 190 and 500 K, and 0.5 45 torr, respectively. The possible role of heterogeneous wall reactions was investigated employing reactor tubes with different sizes, i.e. to significantly vary the surface to volume ratio. In this thesis, significant new contributions to the kinetics of carbon-centred free radical reactions with nitrogen dioxide were obtained. Altogether eight substituted alkyl (CH2Cl, CHCl2, CCl3, CH2I, CH2Br, CHBr2, CHBrCl, and CHBrCH3) and two alkenyl (C2H3, C3H3) free radical reactions with NO2 were investigated as a function of temperature. The bimolecular rate coefficients of all these reactions were observed to possess negative temperature dependencies, while pressure dependencies were not noticed for any of these reactions. Halogen substitution was observed to moderately reduce the reactivity of substituted alkyl radicals in the reaction with NO2, while the resonance stabilisation of the alkenyl radical lowers its reactivity with respect to NO2 only slightly. Two reactions relevant to atmospheric chemistry, CH2Br + O2 and CH2I + O2, were also investigated. It was noticed that while CH2Br + O2 reaction shows pronounced pressure dependence, characteristic of peroxy radical formation, no such dependence was observed for the CH2I + O2 reaction. Observed primary products of the CH2I + O2 reaction were the I-atom and the IO radical. Kinetics of CH3 + HCl, CD3 + HCl, CH3 + DCl, and CD3 + DCl reactions were also studied. While all these reactions possess positive activation energies, in contrast to the other systems investigated in this thesis, the CH3 + HCl and CD3 + HCl reactions show a non-linear temperature dependency on the Arrhenius plot. The reactivity of substituted methyl radicals toward NO2 was observed to increase with decreasing electron affinity of the radical. The same trend was observed for the reactions of substituted methyl radicals with Cl2. It is proposed that interactions of frontier orbitals are responsible to these observations and Frontier Orbital Theory could be used to explain the observed reactivity trends of these highly exothermic reactions having reactant-like transition states.

Performance and physiological responses of combined t-bar and PIT tagged giant mud crabs (Scylla serrata)

Mud crabs (Scylla spp.) are intensively caught throughout South-East Asia and support a very substantial commercial, recreational fishing and aquaculture industry. Identification of individual animals is important to improve understanding and management of this species. However, tagging of crustaceans is difficult as they frequently molt and internal tags can pose a hazard to consumers. In this pilot study we tested a new method combining passive integrated transponder tags and t-bar tags externally. 45 giant mud crabs (Scylla serrata) were captured from the wild and kept in tanks for a maximum of 10 months. We inserted tags into the abdomen of 35 giant mud crabs and tested a modified method where the combined t-bar/PIT-tag was inserted into the muscle tissue of the rear leg between the dorsal carapace plate and the top of the abdominal flap. Tagged crabs with the modified method showed 85% tag retention for molting crabs. We tested the same method in the field where 852 individuals were tagged with combined t-bar/PIT-tags of which 82 were recaptured showing 100% tag retention but without any evidence of molting having occurred. The tested method of combined t-bar/PIT-tags in giant mud crabs can further improve monitoring for wild and aquaculture populations and can be deployed widely with low cost.

Performance and physiological responses of combined t-bar and PIT tagged giant mud crabs (Scylla serrata)

Mud crabs (Scylla spp.) are intensively caught throughout South-East Asia and support a very substantial commercial, recreational fishing and aquaculture industry. Identification of individual animals is important to improve understanding and management of this species. However, tagging of crustaceans is difficult as they frequently molt and internal tags can pose a hazard to consumers. In this pilot study we tested a new method combining passive integrated transponder tags and t-bar tags externally. 45 giant mud crabs (Scylla serrata) were captured from the wild and kept in tanks for a maximum of 10 months. We inserted tags into the abdomen of 35 giant mud crabs and tested a modified method where the combined t-bar/PIT-tag was inserted into the muscle tissue of the rear leg between the dorsal carapace plate and the top of the abdominal flap. Tagged crabs with the modified method showed 85% tag retention for molting crabs. We tested the same method in the field where 852 individuals were tagged with combined t-bar/PIT-tags of which 82 were recaptured showing 100% tag retention but without any evidence of molting having occurred. The tested method of combined t-bar/PIT-tags in giant mud crabs can further improve monitoring for wild and aquaculture populations and can be deployed widely with low cost.

Conversion certificate of Jacob Bar Abraham Abinu, copy made January 3, 1820

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List of offerings of Eleazer Lyons on the Bar Mitzvah of his son

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Tabulation of total marriages, births, deaths, bar mitzvahs

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