Different photochemical behavior of bis(biphenyl)ethylenes and ethenes in solution and in the solid-state: Structurally controlled Z/E-photoisomerization in the solid-state

ArticleJOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY. 184(1-2): 44-49 (2006)journal articl

Reconstruction of the biogeochemistry and ecology of photoautotrophs based on the nitrogen and carbon isotopic compositions of vanadyl porphyrins from Miocene siliceous sediments

We determined both the nitrogen and carbon isotopic compositions of various vanadyl alkylporphyrins isolated from siliceous marine sediments of the Onnagawa Formation (middle Miocene, northeastern Japan) to investigate the biogeochemistry and ecology of photoautotrophs living in the paleo-ocean. The distinctive isotopic signals support the interpretations of previous works that the origin of 17-nor-deoxophylloerythroetioporphyrin (DPEP) is chlorophylls-<i>c</i><sub>1-3</sub>, whereas 8-nor-DPEP may have originated from chlorophylls-<i>a</i><sub>2</sub> or <i>b</i><sub>2</sub> or bacteriochlorophyll-<i>a</i>. Although DPEP and cycloheptanoDPEP are presumably derived from common precursory pigments, their isotopic compositions differed in the present study, suggesting that the latter represents a specific population within the photoautotrophic community. The average δ<sup>15</sup>N value for the entire photoautotrophic community is estimated to be –2 to +1‰ from the δ<sup>15</sup>N values of DPEP (–6.9 to –3.6‰; <i>n</i>=7), considering that the empirical isotopic relationships that the tetrapyrrole nuclei of chloropigments are depleted in <sup>15</sup>N by ~4.8‰ and enriched in <sup>13</sup>C by ~1.8‰ relative to the whole cells. This finding suggests that nitrogen utilized in the primary production was supplied mainly through N<sub>2</sub>-fixation by diazotrophic cyanobacteria. Based on the δ<sup>13</sup>C values of DPEP (–17.9 to –15.6‰; <i>n</i>=7), we estimated isotopic fractionation associated with photosynthetic carbon fixation to be 8–14‰. This range suggests the importance of β-carboxylation and/or active transport of the carbon substrate, indicating in turn the substantial contribution of diazotrophic cyanobacteria to primary production. Based on the δ<sup>15</sup>N values of 17-nor-DPEP (–7.4 to –2.4‰ <i>n</i>=7), the δ<sup>15</sup>N range of chlorophylls-<i>c</i>-producing algae was estimated to be –3 to +3‰. This relative depletion in sup>15</sup>N suggests that these algae mainly utilized nitrogen regenerated from diazotrophic cyanobacteria. Given that diatoms are likely to have constituted the chlorophylls-<i>c</i>-producing algae within the biogenic-silica-rich Onnagawa Formation, cyanobacteria-hosting diatoms may have been important contributors to primary production

Hard X-ray Luminosities of Multinuclei Infrared Luminous Galaxies Showing a Radio/Far-Infrared Excess

We report the results of hard X-ray observations of four multinuclei merging infrared luminous galaxies (IRLGs). We selected these four sources for their excess of radio to far-infrared luminosity ratio compared with starburst galaxies. This excess suggests that activity associated with a supermassive black hole (SMBH) contributes strongly to the IRLGs' bolometric luminosities. Although we expect strong hard X-ray emission from the SMBH-driven activity, the radio-excess multinuclei merging IRLGs show considerably smaller hard X-ray luminosities relative to far-infrared (40$-$500 $\mu$m) and infrared (8$-$1000 $\mu$m) luminosities than active galactic nuclei (AGNs) showing a similar radio-excess. This result may demonstrate that emission in the hard X-ray region from SMBH-driven activity in the multinuclei merging IRLGs is severely suppressed compared to a typical spectral energy distribution of SMBH-driven activity in AGNs. If this is a common property of merging IRLGs, without its correction, hard X-ray observations underestimate the contribution of SMBH-driven activity to the bolometric luminosities of merging IRLGs.Comment: 25 pages of text, 4 figures, aaspp4.sty, Astrophysical Journal, in press (1999, Volume 527

Hydrostatic Compression Behavior and High-Pressure Stabilized β-Phase in γ-Based Titanium Aluminide Intermetallics

Titanium aluminides find application in modern light-weight, high-temperature turbines, such as aircraft engines, but suffer from poor plasticity during manufacturing and processing. Huge forging presses enable materials processing in the 10-GPa range, and hence, it is necessary to investigate the phase diagrams of candidate materials under these extreme conditions. Here, we report on an in situ synchrotron X-ray diffraction study in a large-volume press of a modern (α2 + γ) two-phase material, Ti-45Al-7.5Nb-0.25C, under pressures up to 9.6 GPa and temperatures up to 1686 K. At room temperature, the volume response to pressure is accommodated by the transformation γ → α2, rather than volumetric strain, expressed by the apparently high bulk moduli of both constituent phases. Crystallographic aspects, specifically lattice strain and atomic order, are discussed in detail. It is interesting to note that this transformation takes place despite an increase in atomic volume, which is due to the high ordering energy of γ. Upon heating under high pressure, both the eutectoid and γ-solvus transition temperatures are elevated, and a third, cubic β-phase is stabilized above 1350 K. Earlier research has shown that this β-phase is very ductile during plastic deformation, essential in near-conventional forging processes. Here, we were able to identify an ideal processing window for near-conventional forging, while the presence of the detrimental β-phase is not present under operating conditions. Novel processing routes can be defined from these findings. © 2016, Creative Commons

The active form of quinol-dependent Nitric Oxide reductase (qNOR) from Neisseria meningitidis is a dimer

Neisseria meningitidis is carried by nearly a billion humans, causing developmental impairment and over 100 000 deaths a year. A quinol-dependent nitric oxide reductase (qNOR) plays a critical role in the survival of the bacterium in the human host. X-ray crystallographic analyses of qNOR, including that from N. meningitidis (NmqNOR) reported here at 3.15 Å resolution, show monomeric assemblies, despite the more active dimeric sample being used for crystallization. Cryo-electron microscopic analysis of the same chromatographic fraction of NmqNOR, however, revealed a dimeric assembly at 3.06 Å resolution. It is shown that zinc (which is used in crystallization) binding near the dimer-stabilizing TMII region contributes to the disruption of the dimer. A similar destabilization is observed in the monomeric (∼85 kDa) cryo-EM structure of a mutant (Glu494Ala) qNOR from the opportunistic pathogen Alcaligenes (Achromobacter) xylosoxidans, which primarily migrates as a monomer. The monomer–dimer transition of qNORs seen in the cryo-EM and crystallographic structures has wider implications for structural studies of multimeric membrane proteins. X-ray crystallographic and cryo-EM structural analyses have been performed on the same chromatographic fraction of NmqNOR to high resolution. This represents one of the first examples in which the two approaches have been used to reveal a monomeric assembly in crystallo and a dimeric assembly in vitrified cryo-EM grids. A number of factors have been identified that may trigger the destabilization of helices that are necessary to preserve the integrity of the dimer. These include zinc binding near the entry of the putative proton-transfer channel and the preservation of the conformational integrity of the active site. The mutation near the active site results in disruption of the active site, causing an additional destabilization of helices (TMIX and TMX) that flank the proton-transfer channel helices, creating an inert monomeric enzyme

Berry phase and persistent current in disordered mesoscopic rings

A novel quantum interference effect in disordered quasi-one-dimensional rings in the inhomogeneous magnetic field is reported. We calculate the canonical disorder averaged persistent current using the diagrammatic perturbation theory. It is shown that within the adiabatic regime the average current oscillates as a function of the geometric flux which is related to the Berry phase and the period becomes half the value of the case of a single one-dimensional ring. We also discuss the magnetic dephasing effect on the averaged current.Comment: 6 pages, RevTeX, 2 figures. To appear in Phys. Rev. B Rapid Communications Vol.60 No.12 (1999

Exotic s-wave superconductivity in alkali-doped fullerides

Alkali-doped fullerides (A3C60 with A = K, Rb, Cs) show a surprising phase diagram, in which a high transition-temperature (Tc) s-wave superconducting state emerges next to a Mott insulating phase as a function of the lattice spacing. This is in contrast with the common belief that Mott physics and phonon-driven s-wave superconductivity are incompatible, raising a fundamental question on the mechanism of the high-Tc superconductivity. This article reviews recent ab initio calculations, which have succeeded in reproducing comprehensively the experimental phase diagram with high accuracy and elucidated an unusual cooperation between the electron-phonon coupling and the electron-electron interactions leading to Mott localization to realize an unconventional s-wave superconductivity in the alkali-doped fullerides. A driving force behind the exotic physics is unusual intramolecular interactions, characterized by the coexistence of a strongly repulsive Coulomb interaction and a small effectively negative exchange interaction. This is realized by a subtle energy balance between the coupling with the Jahn-Teller phonons and Hund's coupling within the C60 molecule. The unusual form of the interaction leads to a formation of pairs of up- and down-spin electrons on the molecules, which enables the s-wave pairing. The emergent superconductivity crucially relies on the presence of the Jahn-Teller phonons, but surprisingly benefits from the strong correlations because the correlations suppress the kinetic energy of the electrons and help the formation of the electron pairs, in agreement with previous model calculations. This confirms that the alkali-doped fullerides are a new type of unconventional superconductors, where the unusual synergy between the phonons and Coulomb interactions drives the high-Tc superconductivity

Persistent Currents in Quantum Chaotic Systems

The persistent current of ballistic chaotic billiards is considered with the help of the Gutzwiller trace formula. We derive the semiclassical formula of a typical persistent current $I^{typ}$ for a single billiard and an average persistent current $$ for an ensemble of billiards at finite temperature. These formulas are used to show that the persistent current for chaotic billiards is much smaller than that for integrable ones. The persistent currents in the ballistic regime therefore become an experimental tool to search for the quantum signature of classical chaotic and regular dynamics.Comment: 4 pages (RevTex), to appear in Phys. Rev. B, No.59, 12256-12259 (1999

Epidemiology of Coxiella burnetii infection in Africa: a OneHealth systematic review

Background: Q fever is a common cause of febrile illness and community-acquired pneumonia in resource-limited settings. Coxiella burnetii, the causative pathogen, is transmitted among varied host species, but the epidemiology of the organism in Africa is poorly understood. We conducted a systematic review of C. burnetii epidemiology in Africa from a “One Health” perspective to synthesize the published data and identify knowledge gaps.<p></p> Methods/Principal Findings: We searched nine databases to identify articles relevant to four key aspects of C. burnetii epidemiology in human and animal populations in Africa: infection prevalence; disease incidence; transmission risk factors; and infection control efforts. We identified 929 unique articles, 100 of which remained after full-text review. Of these, 41 articles describing 51 studies qualified for data extraction. Animal seroprevalence studies revealed infection by C. burnetii (≤13%) among cattle except for studies in Western and Middle Africa (18–55%). Small ruminant seroprevalence ranged from 11–33%. Human seroprevalence was <8% with the exception of studies among children and in Egypt (10–32%). Close contact with camels and rural residence were associated with increased seropositivity among humans. C. burnetii infection has been associated with livestock abortion. In human cohort studies, Q fever accounted for 2–9% of febrile illness hospitalizations and 1–3% of infective endocarditis cases. We found no studies of disease incidence estimates or disease control efforts.<p></p> Conclusions/Significance: C. burnetii infection is detected in humans and in a wide range of animal species across Africa, but seroprevalence varies widely by species and location. Risk factors underlying this variability are poorly understood as is the role of C. burnetii in livestock abortion. Q fever consistently accounts for a notable proportion of undifferentiated human febrile illness and infective endocarditis in cohort studies, but incidence estimates are lacking. C. burnetii presents a real yet underappreciated threat to human and animal health throughout Africa.<p></p&gt