1,731 research outputs found

    Ozonolysis of a-phellandrene - Part 2 : Compositional analysis of secondary organic aerosol highlights the role of stabilized Criegee intermediates

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    The molecular composition of secondary organic aerosol (SOA) generated from the ozonolysis of α-phellandrene is investigated for the first time using high pressure liquid chromatography coupled to high-resolution Quadrupole-Orbitrap tandem mass spectrometry. In total, 21 prominent products or isomeric product groups were identified using both positive and negative ionisation modes, with potential formation mechanisms discussed. The aerosol was found to be composed primarily of polyfunctional first- and second-generation species containing one or more carbonyl, acid, alcohol and hydroperoxide functionalities, with the products significantly more complex than those proposed from basic gas-phase chemistry in the companion paper (Mackenzie-Rae et al., 2017a). Mass spectra show a large number of dimeric products are also formed. Both direct scavenging evidence using formic acid, and indirect evidence from double bond equivalency factors, suggests the dominant oligomerisation mechanism is the bimolecular reaction of stabilised Criegee intermediates (SCIs) with non-radical ozonolysis products. Saturation vapour concentration estimates suggest monomeric species cannot explain the rapid nucleation burst of fresh aerosol observed in chamber experiments, hence dimeric species are believed to be responsible for new particle formation, with detected first- and second-generation products driving further particle growth in the system. Ultimately, identification of the major constituents and formation pathways of α-phellandrene SOA leads to a greater understanding of the atmospheric processes and implications of monoterpene emissions and SCIs, especially around Eucalypt forests regions where α-phellandrene is primarily emitted

    Passive and catalytic antibodies and drug delivery

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    Antibodies are one of the most promising components of the biotechnology repertoire for the purpose of drug delivery. On the one hand, they are proven agents for cell-selective delivery of highly toxic agents in a small but expanding number of cases. This technology calls for the covalent attachment of the cytotoxin to a tumor-specific antibody by a linkage that is reversible under appropriate conditions (antibody conjugate therapy, ACT —"passive delivery”). On the other hand, the linker cleavage can be accomplished by a protein catalyst attached to the tumor-specific antibody ("catalytic delivery”). Where the catalyst is an enzyme, this approach is known as antibody-directed enzyme prodrug therapy (ADEPT). Where the transformation is brought about by a catalytic antibody, it has been termed antibody-directed abzyme prodrug therapy (ADAPT). These approaches will be illustrated with emphasis on how their demand for new biotechnology is being realized by structure-based protein engineerin

    Age structure, dispersion and diet of a population of stoats (Mustela erminea) in southern Fiordland during the decline phase of the beechmast cycle

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    The dispersion, age structure and diet of stoats (Mustela erminea) in beech forest in the Borland and Grebe Valleys, Fiordland National Park, were examined during December and January 2000/01, 20 months after a heavy seed-fall in 1999. Thirty trap stations were set along a 38-km transect through almost continuous beech forest, at least 1 km apart. Mice were very scarce (nights, C/100TN) along two standard index lines placed at either end of the transect, compared with November 1999 (>60/100TN), but mice were detected (from footprints in stoat tunnels) along an 8 km central section of the transect (stations 14-22). Live trapping with one trap per station (total 317.5 trap nights) in December 2000 caught 2 female and 23 male stoats, of which 10 (including both females) were radio collared. The minimum range lengths of the two females along the transect represented by the trap line were 2.2 and 6.0 km; those of eight radio-tracked males averaged 2.9 ± 1.7 km. Stations 14-22 tended to be visited more often, by more marked individual stoats, than the other 21 stations. Fenn trapping at the same 30 sites, but with multiple traps per station (1333.5 trap nights), in late January 2001 collected carcasses of 35 males and 28 females (including 12 of the marked live-trapped ones). Another two marked males were recovered dead. The stoat population showed no sign of chronic nutritional stress (average fat reserve index = 2.8 on a scale of 1-4 where 4 = highest fat content); and only one of 63 guts analysed was empty. Nevertheless, all 76 stoats handled were adults with 1-3 cementum annuli in their teeth, showing that reproduction had failed that season. Prey categories recorded in descending frequency of occurrence were birds, carabid beetle (ground beetle), weta, possum, rat, and mouse. The frequencies of occurrence of mice and birds in the diet of these stoats (10% and 48%, respectively) were quite different from those in stoats collected in Pig Creek, a tributary of the Borland River (87%, 5%), 12 months previously when mice were still abundant. Five of the six stoat guts containing mice were collected within 1 km of stations 14-22

    Chemical species of migrating radionuclides at commercial shallow land burial sites. Quarterly progress report, July-September 1983

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    The primary purpose of this project is to develop an understanding of chemical processes that significantly influence the migration of radionuclides at commercial low-level waste burial sites. Chemical measurements of waste trench leachate and identification of chemical changes in leachate during migration will provide a basis for geochemical waste transport models. This project will produce for the US Nuclear Regulatory Commission (NRC) information to support guidance for implementation of 10 CFR 61, particularly in the development of criteria for low level waste disposal site selection, management, permanent closure and monitoring. This project will also produce information needed by the Commonwealth of Kentucky as they finalize plans to stabilize, close and monitor the Maxey Flats site. Current research results are presented for the following tasks: (1) chemical forms inorganic and organic radionuclide species; (2) subsurface migration and infiltration studies; (3) specific radionuclide mapping at Maxey Flats and other commercial shallow land burial sites; (4) ecological monitoring at commercial shallow land burial sites; and (5) technical program coordination for low-level waste research. 17 references, 6 figures, 3 tables

    The CRI v2.2 reduced degradation scheme for isoprene

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    The reduced representation of isoprene degradation in the Common Representative Intermediates (CRI) mechanism has been systematically updated, using the Master Chemical Mechanism (MCM v3.3.1) as a reference benchmark, with the updated mechanism being released as CRI v2.2. The complete isoprene degradation mechanism in CRI v2.2 consists of 186 reactions of 56 closed shell and free radical species, this being an order of magnitude reduction in size compared with MCM v3.3.1. The chemistry initiated by reaction with OH radicals, NO3 radicals and ozone (O3) is treated. An overview of the updates is provided, within the context of reported kinetic and mechanistic information. The revisions mainly relate to the OH-initiated chemistry, which tends to dominate under atmospheric conditions, although these include updates to the chemistry of products that are also generated from the O3- and NO3-initiated oxidation. The revisions have impacts in a number of key areas, including recycling of HOx and NOx. The performance of the CRI v2.2 isoprene mechanism has been compared with those of the preceding version (CRI v2.1) and the reference MCM v3.3.1 over a range of relevant conditions, using a box model of the tropical forested boundary layer. In addition, tests are carried out to ensure that the performance of MCM v3.3.1 remains robust to more recently reported information. CRI v2.2 has also been implemented into the STOCHEM chemistry-transport model, with a customized close-variant of CRI v2.2 implemented into the EMEP MSC-W chemistry-transport model. The results of these studies are presented and used to illustrate the global-scale impacts of the mechanistic updates on HOx radical concentrations

    Critical roles of arginine in growth and biofilm development by Streptococcus gordonii

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    Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/112199/1/mmi13023.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/112199/2/mmi13023-sup-0001-si.pd

    Nanoparticulate nickel sulfides formed in low temperature aqueous solutions

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    The nature of the nickel sulfides formed in low temperature aqueous solutions is not well-understood. The material has some intrinsic interest to mineralogy, geochemistry and materials science as well as to biogeochemisty, especially as a possible catalyst involved in the origin and early evolution of life. We synthesized Ni sulfide under anoxic conditions at 25 C: (1) chemically, by the addition of 50 mL of 0.1 M NiSO4Æ7H2O to 100 mL of 0.05M Na2SÆ9H2O; (2) electrochemically, with a Ni foil and H2S gas. At pH 6 5, millerite (b-NiS) was produced electrochemically and NiS mixtures, including heazlewoodite (Ni3S2) and polydymite (Ni3S4), were obtained chemically. At pH >11, a- NiS was obtained from the chemical reaction. At pH 6–9, the product produced only two broad peaks (d = ca. 2.7 and 1.8 ) with conventional and synchrotron XRPD which could be assigned to a number of Ni sulfides. It has previously been referred to as ‘‘amorphous NiS’’ Jeong and Manthiram, 2001. Eight SAED reflections were collected which identified the material as godlevskite, orthorhombic NiS. HRTEM shows that the godlevskite particles are ca. 30 nm in diameter and plate-like. SAXS analyses show that the material is 6–8.5 nm thick. Godlevskite is structurally related to makinawite, tetragonal FeS, and is found naturally in similar parageneses-associated with the monosulfide solid solution products of high temperature nickel ores. Mackinawite is the black FeS precipitate from the reaction between Fe(II) and S(-II) in aqueous solution. It appears that, geochemically, godlevskite is the Ni analogue of mackinawite
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