Molecular characterization of polar organosulfates in secondary organic aerosol from the green leaf volatile 3-Z-hexenal

Evidence is provided That the green leaf volatiles 3-Z- hexenal serves as a precursor for biogenic secondary organic aersol through the formation of polar organosulfates (Os) with molecular weight (MW) 226. The MW 226 C-6-OSs were Chemically elucidated, along with structurally similar MW 212 C-5-OSs, whose biogenic precursor is likely related to 3-Z-hexenal but still remains unknown. The MW: 226 and 212 OSs have a substantial abundance in ambient fine aerosol from K-puszta, Hungary, which is comparable to that of the isoprene-related MW 216 OSs, known to be formed: through sulfation of C-5-epoxydiols, second-generation gas-phase photooxidation products of isoprene. Using detailed interpretation of negative-ion electrospray ionization mass spectral data, the MW 226, compounds are assigned to isomeric sulfate esters of 3,4-dihydroxyhex-5-enoic acid with the sulfate group located or C-4 position. Two MW 212 compounds present in: ambient fine aerosol are attributed to isomeric sulfate :esters of 2,3-dihydroxypent-4-enoic acid, of which two are sulfated at C-3 and one is sulfated at C-2. The formation of the MW 226 :OSs is tentatively explained through photooxidation of 3-Z-hexenal in, the gas phase, resulting in alkoxy radical, followed by a rearrangement and subsequent sulfation of the epoxy group in the particle phase

From Dual Unitarity to Generic Quantum Operator Spreading

Dual-unitary circuits are paradigmatic examples of exactly solvable yet chaotic quantum many-body systems, but solvability naturally goes along with a degree of non-generic behaviour. By investigating the effect of weakly broken dual-unitarity on the spreading of local operators we study whether, and how, small deviations from dual-unitarity recover fully generic many-body dynamics. We present a discrete path-integral formula for the out-of-time-order correlator and use it to recover a butterfly velocity smaller than the light-cone velocity, $v_B < v_{LC}$ , and a diffusively broadening operator front, two generic features of ergodic quantum spin chains absent in dual-unitary circuit dynamics. We find that the butterfly velocity and diffusion constant are determined by a small set of microscopic quantities and that the operator entanglement of the gates plays a crucial role.Comment: (6+17) pages, 5 figures Accepted versio

Further Investigation into the Formation of Alcohol during Fischer Tropsch Synthesis on Fe-based Catalysts

AbstractThe Fischer Tropsch (FT) synthesis is a complex polymerization reaction characterized by competing intermediates reaction steps. The various termination steps may result in the formation of different product classes, such as olefins, paraffins, alcohols, etc. While high synthesis gas conversion is important; a high selectivity is much desirable, which may result in.improved economics. This mechanistic study further elaborates on the elementary reaction steps for the formation of product compounds in the Fischer-Tropsch synthesis. The effect of space velocity on the products distribution, particularly on the formation of oxygen containing organic product compounds was investigated. The reactions were carried out at industrially relevant conditions on Fe-based catalyst promoted with Cu, K and alumina. The resulting catalyst precursor was characterized using TPR, XRD, BET and SEM/EDX. The alcohol/hydrocarbon ratio remains fairly constant at very high space velocity (i.e. low conversion) where secondary reactions become insignificant. This implied primary formation of alcohols in the Fischer-Tropsch synthesis

Density Functional Theory Study of the Adsorption of Oxygen and Hydrogen on 3d Transition Metal Surfaces with Varying Magnetic Ordering

We have employed density functional theory (DFT) calculations to investigate the adsorption of molecular oxygen and hydrogen on 3d transition metal&nbsp; (TM) surfaces with varying ordered magnetic structures in the bulk, namely ferromagnetic Fe(110), Co(0001), Ni(111) and diamagnetic Cu(111). The trend&nbsp; observed in the energies of adsorption was compared with the magnetic moment of the cell using the d-band centre model of chemisorption and the&nbsp;&nbsp;&nbsp; Stoner model of magnetic energy. As the gap between the d-band centre and the Fermi level of the TM decreases, more antibonding orbitals are present&nbsp; above the Fermi level and thus unoccupied, leading to stronger binding. Correspondingly, the shift in the d-band centre decreases the density of states&nbsp; (DOS) at the Fermi level giving rise to the ordered magnetic structure

Integrative comparative analysis of avian chromosome evolution by in-silico mapping of the gene ontology of homologous synteny blocks and evolutionary breakpoint regions

Avian chromosomes undergo more intra- than interchromosomal rearrangements, which either induce or are associated with genome variations among birds. Evolving from a common ancestor with a karyotype not dissimilar from modern chicken, two evolutionary elements characterize evolutionary change: homologous synteny blocks (HSBs) constitute common conserved parts at the sequence level, while evolutionary breakpoint regions (EBRs) occur between HSBs, defining the points where rearrangement occurred. Understanding the link between the structural organization and functionality of HSBs and EBRs provides insight into the mechanistic basis of chromosomal change. Previously, we identified gene ontology (GO) terms associated with both; however, here we revisit our analyses in light of newly developed bioinformatic algorithms and the chicken genome assembly galGal6. We aligned genomes available for six birds and one lizard species, identifying 630 HSBs and 19 EBRs. We demonstrate that HSBs hold vast functionality expressed by GO terms that have been largely conserved through evolution. Particularly, we found that genes within microchromosomal HSBs had specific functionalities relevant to neurons, RNA, cellular transport and embryonic development, and other associations. Our findings suggest that microchromosomes may have conserved throughout evolution due to the specificity of GO terms within their HSBs. The detected EBRs included those found in the genome of the anole lizard, meaning they were shared by all saurian descendants, with others being unique to avian lineages. Our estimate of gene richness in HSBs supported the fact that microchromosomes contain twice as many genes as macrochromosomes

Magnesium as a Methanation Suppressor for Iron- and Cobalt-Based Oxide Catalysts during the Preferential Oxidation of Carbon Monoxide

The preferential oxidation of CO (CO-PrOx) to CO2 is an effective catalytic process for purifying the H2 utilized in proton-exchange membrane fuel cells for power generation. Our current work reports on the synthesis, characterization and CO-PrOx performance evaluation of unsubstituted and magnesiumsubstituted iron- and cobalt-based oxide catalysts (i.e., Fe3O4 , Co3O4 , MgFe2O4 and MgCo2O4 ). More specifically, the ability of Mg to stabilize the MgFe2O4 and MgCo2O4 structures, as well as suppress CH4 formation during CO-PrOx was of great importance in this study. The cobalt-based oxide catalysts achieved higher CO2 yields than the iron-based oxide catalysts below 225 ◦C. The highest CO2 yield (100%) was achieved over Co3O4 between 150 and 175 ◦C, however, undesired CH4 formation was only observed over this catalyst due to the formation of bulk fcc and hcp Co0 between 200 and 250 ◦C. The presence of Mg in MgCo2O4 suppressed CH4 formation, with the catalyst only reducing to a CoO-type phase (possibly containing Mg). The iron-based oxide catalysts did not undergo bulk reduction and did not produce CH4 under reaction conditions. In conclusion, our study has demonstrated the beneficial effect of Mg in stabilizing the active iron- and cobalt-based oxide structures, and in suppressing CH4 formation during CO-PrO

Organosulfate Formation in Biogenic Secondary Organic Aerosol

Organosulfates of isoprene, α-pinene, and β-pinene have recently been identified in both laboratory-generated and ambient secondary organic aerosol (SOA). In this study, the mechanism and ubiquity of organosulfate formation in biogenic SOA is investigated by a comprehensive series of laboratory photooxidation (i.e., OH-initiated oxidation) and nighttime oxidation (i.e., NO3-initiated oxidation under dark conditions) experiments using nine monoterpenes (α-pinene, β-pinene, d-limonene, l-limonene, α-terpinene, γ-terpinene, terpinolene, Δ3-carene, and β-phellandrene) and three monoterpenes (α-pinene, d-limonene, and l-limonene), respectively. Organosulfates were characterized using liquid chromatographic techniques coupled to electrospray ionization combined with both linear ion trap and high-resolution time-of-flight mass spectrometry. Organosulfates are formed only when monoterpenes are oxidized in the presence of acidified sulfate seed aerosol, a result consistent with prior work. Archived laboratory-generated isoprene SOA and ambient filter samples collected from the southeastern U.S. were reexamined for organosulfates. By comparing the tandem mass spectrometric and accurate mass measurements collected for both the laboratory-generated and ambient aerosol, previously uncharacterized ambient organic aerosol components are found to be organosulfates of isoprene, α-pinene, β-pinene, and limonene-like monoterpenes (e.g., myrcene), demonstrating the ubiquity of organosulfate formation in ambient SOA. Several of the organosulfates of isoprene and of the monoterpenes characterized in this study are ambient tracer compounds for the occurrence of biogenic SOA formation under acidic conditions. Furthermore, the nighttime oxidation experiments conducted under highly acidic conditions reveal a viable mechanism for the formation of previously identified nitrooxy organosulfates found in ambient nighttime aerosol samples. We estimate that the organosulfate contribution to the total organic mass fraction of ambient aerosol collected from K-puszta, Hungary, a field site with a similar organosulfate composition as that found in the present study for the southeastern U.S., can be as high as 30%

Altered expression of maize PLASTOCHRON1 enhances biomass and seed yield by extending cell division duration

Maize is the highest yielding cereal crop grown worldwide for grain or silage. Here, we show that modulating the expression of the maize PLASTOCHRON1 (ZmPLA1) gene, encoding a cytochrome P450 (CYP78A1), results in increased organ growth, seedling vigour, stover biomass and seed yield. The engineered trait is robust as it improves yield in an inbred as well as in a panel of hybrids, at several locations and over multiple seasons in the field. Transcriptome studies, hormone measurements and the expression of the auxin responsive DR5(rev): mRFPer marker suggest that PLA1 may function through an increase in auxin. Detailed analysis of growth over time demonstrates that PLA1 stimulates the duration of leaf elongation by maintaining dividing cells in a proliferative, undifferentiated state for a longer period of time. The prolonged duration of growth also compensates for growth rate reduction caused by abiotic stresses