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  • 1
    Publication Date: 2014-08-19
    Description: Zinc is an essential micronutrient for all living organisms. It is required for signalling and proper functioning of a range of proteins involved in, for example, DNA binding and enzymatic catalysis. In prokaryotes and photosynthetic eukaryotes, Zn(2+)-transporting P-type ATPases of class IB (ZntA) are crucial for cellular redistribution and detoxification of Zn(2+) and related elements. Here we present crystal structures representing the phosphoenzyme ground state (E2P) and a dephosphorylation intermediate (E2.Pi) of ZntA from Shigella sonnei, determined at 3.2 A and 2.7 A resolution, respectively. The structures reveal a similar fold to Cu(+)-ATPases, with an amphipathic helix at the membrane interface. A conserved electronegative funnel connects this region to the intramembranous high-affinity ion-binding site and may promote specific uptake of cellular Zn(2+) ions by the transporter. The E2P structure displays a wide extracellular release pathway reaching the invariant residues at the high-affinity site, including C392, C394 and D714. The pathway closes in the E2.Pi state, in which D714 interacts with the conserved residue K693, which possibly stimulates Zn(2+) release as a built-in counter ion, as has been proposed for H(+)-ATPases. Indeed, transport studies in liposomes provide experimental support for ZntA activity without counter transport. These findings suggest a mechanistic link between PIB-type Zn(2+)-ATPases and PIII-type H(+)-ATPases and at the same time show structural features of the extracellular release pathway that resemble PII-type ATPases such as the sarcoplasmic/endoplasmic reticulum Ca(2+)-ATPase (SERCA) and Na(+), K(+)-ATPase. These findings considerably increase our understanding of zinc transport in cells and represent new possibilities for biotechnology and biomedicine.〈br /〉〈br /〉〈a href="https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4259247/" target="_blank"〉〈img src="https://static.pubmed.gov/portal/portal3rc.fcgi/4089621/img/3977009" border="0"〉〈/a〉   〈a href="https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4259247/" target="_blank"〉This paper as free author manuscript - peer-reviewed and accepted for publication〈/a〉〈br /〉〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Wang, Kaituo -- Sitsel, Oleg -- Meloni, Gabriele -- Autzen, Henriette Elisabeth -- Andersson, Magnus -- Klymchuk, Tetyana -- Nielsen, Anna Marie -- Rees, Douglas C -- Nissen, Poul -- Gourdon, Pontus -- Howard Hughes Medical Institute/ -- England -- Nature. 2014 Oct 23;514(7523):518-22. doi: 10.1038/nature13618. Epub 2014 Aug 17.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉1] Centre for Membrane Pumps in Cells and Disease (PUMPkin), Danish National Research Foundation, Aarhus University, Department of Molecular Biology and Genetics, Gustav Wieds Vej 10C, DK-8000 Aarhus C, Denmark [2] Department of Biomedical Sciences, University of Copenhagen, Blegdamsvej 3B, DK-2200 Copenhagen, Denmark (K.W. and P.G.); Department of Experimental Medical Science, Lund University, Solvegatan 19, SE-221 84 Lund, Sweden (P.G.). [3]. ; 1] Centre for Membrane Pumps in Cells and Disease (PUMPkin), Danish National Research Foundation, Aarhus University, Department of Molecular Biology and Genetics, Gustav Wieds Vej 10C, DK-8000 Aarhus C, Denmark [2]. ; Centre for Membrane Pumps in Cells and Disease (PUMPkin), Danish National Research Foundation, Aarhus University, Department of Molecular Biology and Genetics, Gustav Wieds Vej 10C, DK-8000 Aarhus C, Denmark. ; Science for Life Laboratory, Department of Theoretical Physics, Swedish e-Science Research Center, KTH Royal Institute of Technology, SE-171 21 Solna, Sweden. ; Division of Chemistry and Chemical Engineering and Howard Hughes Medical Institute, California Institute of Technology, 1200 East California Boulevard, Pasadena, California 91125, USA. ; 1] Centre for Membrane Pumps in Cells and Disease (PUMPkin), Danish National Research Foundation, Aarhus University, Department of Molecular Biology and Genetics, Gustav Wieds Vej 10C, DK-8000 Aarhus C, Denmark [2] Department of Biomedical Sciences, University of Copenhagen, Blegdamsvej 3B, DK-2200 Copenhagen, Denmark (K.W. and P.G.); Department of Experimental Medical Science, Lund University, Solvegatan 19, SE-221 84 Lund, Sweden (P.G.).〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/25132545" target="_blank"〉PubMed〈/a〉
    Keywords: Adenosine Triphosphatases/*chemistry/*metabolism ; Adenosine Triphosphate/metabolism ; Binding Sites ; Cadmium/metabolism ; Calcium-Transporting ATPases/chemistry ; Conserved Sequence ; Crystallography, X-Ray ; Lead/metabolism ; Models, Molecular ; Phosphorylation ; Proteolipids/chemistry/metabolism ; Proton-Translocating ATPases/chemistry/metabolism ; Shigella/*enzymology ; Sodium-Potassium-Exchanging ATPase/chemistry ; Zinc/metabolism
    Print ISSN: 0028-0836
    Electronic ISSN: 1476-4687
    Topics: Biology , Chemistry and Pharmacology , Medicine , Natural Sciences in General , Physics
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  • 2
    Publication Date: 2016-10-29
    Description: Emission characteristics of metal halide perovskites play a key role in the current widespread investigations into their potential uses in optoelectronics and photonics. However, a fundamental understanding of the molecular origin of the unusual blueshift of the bandgap and dual emission in perovskites is still lacking. In this direction, we investigated the extraordinary photoluminescence behavior of three representatives of this important class of photonic materials, that is, CH 3 NH 3 PbI 3 , CH 3 NH 3 PbBr 3 , and CH(NH 2 ) 2 PbBr 3 , which emerged from our thorough studies of the effects of temperature on their bandgap and emission decay dynamics using time-integrated and time-resolved photoluminescence spectroscopy. The low-temperature (〈100 K) photoluminescence of CH 3 NH 3 PbI 3 and CH 3 NH 3 PbBr 3 reveals two distinct emission peaks, whereas that of CH(NH 2 ) 2 PbBr 3 shows a single emission peak. Furthermore, irrespective of perovskite composition, the bandgap exhibits an unusual blueshift by raising the temperature from 15 to 300 K. Density functional theory and classical molecular dynamics simulations allow for assigning the additional photoluminescence peak to the presence of molecularly disordered orthorhombic domains and also rationalize that the unusual blueshift of the bandgap with increasing temperature is due to the stabilization of the valence band maximum. Our findings provide new insights into the salient emission properties of perovskite materials, which define their performance in solar cells and light-emitting devices.
    Electronic ISSN: 2375-2548
    Topics: Natural Sciences in General
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  • 3
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 116 (2002), S. 6957-6960 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The equilibria involving the gaseous species SnBi, SnBi2, and SnBi3 above the condensed system Bi–Sn contained in a graphite cell have been investigated by the Knudsen effusion technique combined with mass spectrometry. Third law enthalpies for the reactions SnBin(g)=Sn(cond)+nBi(g), n=1–3, were evaluated. By combining the experimental reaction enthalpies with the appropriate thermodynamic data taken from literature, the following atomization energies, ΔaH0o, and enthalpies of formation, ΔfH298.15o, in kJ mol−1, have been derived: SnBi, 191.1±12.0 and 317.5±12.0; SnBi2, 415.2±15.0 and 303.0±15.0; SnBi3, 603.4±18.0 and 323.0±18.0. © 2002 American Institute of Physics.
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  • 4
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 113 (2000), S. 8995-8999 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: High-temperature Knudsen cell mass spectrometry has been used to study the equilibria involving the B2N molecule over the Si–BN system. Thermal functions needed in the evaluation of the mass spectrometric equilibrium data have been calculated from available experimental and theoretical molecular parameters. The enthalpy changes for the reactions 2B(g)+Si2N(g)=B2N(g)+2Si(g), and BN(s)+B(g)=B2N(g) have been measured. The following atomization enthalpy, ΔaH0o, and enthalpy of formation, ΔfH298.15o, in kJ mol−1, of 1045.5±18 and 551.3±18 for the B2N molecule have been determined from these reaction enthalpies. Atomization energies of similar molecules have been compared and discussed. © 2000 American Institute of Physics.
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  • 5
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 969-972 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Equilibria involving the isomers AlNC and AlCN above a mixture of aluminum nitride, graphite, and gold contained in a graphite Knudsen cell were investigated with a mass spectrometer. The enthalpies of formation, ΔfH0o, and of atomization, ΔaH0o, in kJ mol−1, for AlNC and AlCN, were derived as 281.3±14 and 303.8±14, and as 1228.1±15 and 1205.6±15, respectively. © 1999 American Institute of Physics.
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  • 6
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 115 (2001), S. 5470-5476 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The Knudsen cell mass spectrometric method has been employed to measure the partial pressures of the Si7 and Si8 clusters under equilibrium conditions above liquid silicon, contained in a boron nitride liner inside a graphite Knudsen cell. Gaussian 2 (G2) theory and B3LYP density functional method were employed to determine the geometry, the vibrational frequencies, and the binding energy of the Si8 cluster. From the all-gas analyzed equilibria the following atomization enthalpies, ΔaH0o(Sin), and enthalpies of formation, ΔfH298.15o(Sin), in kJ mol−1, have been obtained: Si7, 2381±36 and 743±36; Si8, 2735±65 and 837±65. Experimental literature values for the electron affinities of Sin(n=3–8) have been combined with present and previous results to obtain the bonding energies for the Sin−(n=3–8) cluster anions. The experimental atomization energies are compared with available theoretical values. © 2001 American Institute of Physics.
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  • 7
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 113 (2000), S. 1852-1856 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The Knudsen cell mass spectrometric method has been employed to measure the partial pressures of Snn (n=1–7) under equilibrium conditions above liquid tin or a tin–gold alloy, contained in a graphite Knudsen cell. From the all-gas analyzed equilibria the following atomization enthalpies ΔaH0&convolu;(Snn), and enthalpies of formation, ΔfH298.15&convolu;(Snn), in kJ mol−1, have been obtained: Sn4, 750.2±14 and 450.6±14; Sn5, 990.2±22 and 512.3±22; Sn6, 1349.7±28 and 452.8±28; Sn7, 1644.2±37 and 460.0±37. The atomization energies are compared with available theoretical values. © 2000 American Institute of Physics.
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  • 8
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 112 (2000), S. 7443-7448 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The high-temperature mass spectrometric method was employed to measure the equilibrium partial pressures of small germanium clusters above liquid germanium contained in a graphite Knudsen cell. These data were combined with new thermal functions, calculated from recent theoretical and spectroscopic molecular parameters, to evaluate the atomization enthalpies and enthalpies of formation of Ge5–Ge8. Mass spectrometric equilibrium data available in literature were also reevaluated. The following atomization enthalpies, ΔaH0o(Gen,g) and enthalpies of formation ΔfH298.15o(Gen,g), in kJ mol−1, have been obtained: Ge5, 1313±27 and 548±27, Ge6, 1649±33 and 583±33, Ge7, 2008±42 and 598±42, Ge8, 2359±60 and 618±60. The atomization energies are compared with available theoretical values. © 2000 American Institute of Physics.
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  • 9
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 115 (2001), S. 4496-4501 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Knudsen cell mass spectrometric equilibrium measurements together with theoretical computations have been employed to gain structural and thermodynamic information of the OsC and OsC2 molecules. Several levels of theory have been applied to determine the structures, molecular parameters, and physico-chemical properties of OsC(g) and OsC2(g), and their singly charged ions. Complete active space self-consistent field (CASSCF) calculations were performed on the apparent 3Σ− ground state and first 3Δ excited state of OsC. From the analyzed gaseous equilibria and the thermal functions calculated from the computed molecular parameters, the following atomization enthalpies, ΔaH0o(OsC,g) and ΔaH0o(OsC2,g), and enthalpies of formation, ΔfH298.15o(OsC,g) and ΔfH298.15o(OsC2,g), in kJ mol−1, have been obtained: OsC, 605.6±14.0 and 895.4±14.0; OsC2, 1154.6±18.0 and 1059.5±18.0. The results have been compared with those for the other platinum metal carbides and oxides. © 2001 American Institute of Physics.
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  • 10
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 113 (2000), S. 10978-10982 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The Knudsen effusion mass spectrometric method has been employed to measure the equilibrium partial pressures of the Al2N molecule over the AlN–Au–graphite system. Theoretical computations were carried out to determine the structure, molecular parameters, and thermodynamic properties of Al2N. The partial pressures have been combined with the calculated thermal functions to determine the atomization enthalpy, ΔaH0o, and enthalpy of formation, ΔfH298.15o, in kJ mol−1, of 783.2±15 and 342.7±15 for Al2N, respectively. Upper values for the dissociation energy of AlN, D0o(AlN,g)≤368±15 kJ mol−1, and for the atomization enthalpy of Al2N2, ΔaH0o(Al2N2,g)≤1402 kJ mol−1 have been obtained. These results are discussed and compared with recent theoretical literature values. © 2000 American Institute of Physics.
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