Giant spin-orbit effects on H-1 and C-13 NMR shifts for uranium(VI) complexes revisited: role of the exchange-correlation response kernel, bonding analyses, and new predictions

Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich.This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively.Previous relativistic quantum-chemical predictions of unusually large H-1 and C-13 NMR chemical shifts for ligand atoms directly bonded to a diamagnetic uranium(VI) center (P. Hrobarik, V. Hrobarikova, A. H. Greif and M. Kaupp, Angew. Chem., Int. Ed., 2012, 51, 10884) have been revisited by two- and four-component relativistic density functional methods. In particular, the effect of the exchange-correlation response kernel, which had been missing in the previously used two-component version of the Amsterdam Density Functional program, has been examined. Kernel contributions are large for cases with large spin-orbit (SO) contributions to the NMR shifts and may amount to up to similar to 30% of the total shifts, which means more than a 50 ppm difference for the metal-bonded carbon shifts in some extreme cases. Previous calculations with a PBE-40HF functional had provided overall reasonable predictions, due to cancellation of errors between the missing kernel contributions and the enhanced exact-exchange (EXX) admixture of 40%. In the presence of an exchange-correlation kernel, functionals with lower EXX admixtures give already good agreement with experiments, and the PBE0 functional provides reasonable predictive quality. Most importantly, the revised approach still predicts unprecedented giant H-1 NMR shifts between +30 ppm and more than +200 ppm for uranium(VI) hydride species. We also predict uranium-bonded C-13 NMR shifts for some synthetically known organometallic U(VI) complexes, for which no corresponding signals have been detected to date. In several cases, the experimental lack of these signals may be attributed to unexpected spectral regions in which some of the C-13 NMR shifts can appear, sometimes beyond the usual measurement area. An extremely large uranium-bonded C-13 shift above 550 ppm, near the upper end of the diamagnetic C-13 shift range, is predicted for a known pincer carbene complex. Bonding analyses allow in particular the magnitude of the SO shifts, and of their dependence on the functional, on the ligand position in the complex, and on the overall electronic structure to be better appreciated, and improved confidence ranges for predicted shifts have been obtained

The Birth of a Galaxy: Primordial Metal Enrichment and Stellar Populations

By definition, Population III stars are metal-free, and their protostellar collapse is driven by molecular hydrogen cooling in the gas-phase, leading to large characteristic masses. Population II stars with lower characteristic masses form when the star-forming gas reaches a critical metallicity of 10^{-6} - 10^{-3.5} Z_\odot. We present an adaptive mesh refinement radiation hydrodynamics simulation that follows the transition from Population III to II star formation. The maximum spatial resolution of 1 comoving parsec allows for individual molecular clouds to be well-resolved and their stellar associations to be studied in detail. We model stellar radiative feedback with adaptive ray tracing. A top-heavy initial mass function for the Population III stars is considered, resulting in a plausible distribution of pair-instability supernovae and associated metal enrichment. We find that the gas fraction recovers from 5 percent to nearly the cosmic fraction in halos with merger histories rich in halos above 10^7 solar masses. A single pair-instability supernova is sufficient to enrich the host halo to a metallicity floor of 10^{-3} Z_\odot and to transition to Population II star formation. This provides a natural explanation for the observed floor on damped Lyman alpha (DLA) systems metallicities reported in the literature, which is of this order. We find that stellar metallicities do not necessarily trace stellar ages, as mergers of halos with established stellar populations can create superpositions of t-Z evolutionary tracks. A bimodal metallicity distribution is created after a starburst occurs when the halo can cool efficiently through atomic line cooling.Comment: 11 pages, 7 figures; replaced with accepted version to ApJ; additional movies and images can be found at http://www.astro.princeton.edu/~jwise/research/GalaxyBirth.htm

Chemical Signatures of the First Galaxies: Criteria for One-Shot Enrichment

We utilize metal-poor stars in the local, ultra-faint dwarf galaxies (UFDs; L_tot < 10^5 L_sun) to empirically constrain the formation process of the first galaxies. Since UFDs have much simpler star formation histories than the halo of the Milky Way, their stellar populations should preserve the fossil record of the first supernova (SN) explosions in their long-lived, low-mass stars. Guided by recent hydrodynamical simulations of first galaxy formation, we develop a set of stellar abundance signatures that characterize the nucleosynthetic history of such an early system if it was observed in the present-day universe. Specifically, we argue that the first galaxies are the product of chemical "one-shot" events, where only one (long-lived) stellar generation forms after the first, Population III, SN explosions. Our abundance criteria thus constrain the strength of negative feedback effects inside the first galaxies. We compare the stellar content of UFDs with these one-shot criteria. Several systems (Ursa Major II, and also Coma Berenices, Bootes I, Leo IV, Segue 1) largely fulfill the requirements, indicating that their high-redshift predecessors did experience strong feedback effects that shut off star formation. We term the study of the entire stellar population of a dwarf galaxy for the purpose of inferring details about the nature and origin of the first galaxies "dwarf galaxy archaeology". This will provide clues to the connection of the first galaxies, the surviving, metal-poor dwarf galaxies, and the building blocks of the Milky Way.Comment: 9 pages (emulateapj), 2 figures, ApJ in pres

Determination of Pericardial Adipose Tissue Increases the Prognostic Accuracy of Coronary Artery Calcification for Future Cardiovascular Events

Objectives: Pericardial adipose tissue (PAT) is associated with coronary artery plaque accumulation and the incidence of coronary heart disease. We evaluated the possible incremental prognostic value of PAT for future cardiovascular events. Methods: 145 patients (94 males, age 60 10 years) with stable coronary artery disease underwent coronary artery calcification (CAC) scanning in a multislice CT scanner, and the volume of pericardial fat was measured. Mean observation time was 5.4 years. Results: 34 patients experienced a severe cardiac event. They had a significantly higher CAC score (1,708 +/- 2,269 vs. 538 +/- 1,150, p 400, 3.5 (1.9-5.4; p = 0.007) for scores > 800 and 5.9 (3.7-7.8; p = 0.005) for scores > 1,600. When additionally a PAT volume > 200 cm(3) was determined, there was a significant increase in the event rate and relative risk. We calculated a relative risk of 2.9 (1.9-4.2; p = 0.01) for scores > 400, 4.0 (2.1-5.0; p = 0.006) for scores > 800 and 7.1 (4.1-10.2; p = 0.005) for scores > 1,600. Conclusions:The additional determination of PAT increases the predictive power of CAC for future cardiovascular events. PAT might therefore be used as a further parameter for risk stratification. Copyright (C) 2012 S. Karger AG, Base

Pathways to massive black holes and compact star clusters in pre-galactic dark matter haloes with virial temperatures > 10000K

Large dynamic range numerical simulations of atomic cooling driven collapse of gas in pre-galactic DM haloes with T_vir ~ 10000 K show that the gas loses 90% and more of its angular momentum before rotational support sets in. In a fraction of these haloes where the metallicity is low and UV radiation suppresses H_2 cooling, conditions are thus very favourable for the rapid build-up of massive black holes. Depending on the progression of metal enrichment, the continued suppression of H_2 cooling by external and internal UV radiation and the ability to trap the entropy produced by the release of gravitational energy, the gas at the centre of the halo is expected to form a supermassive star, a stellar-mass black hole accreting at super-Eddington accretion rates or a compact star-cluster undergoing collisional run-away of massive stars at its centre. In all three cases a massive black hole of initially modest mass finds itself at the center of a rapid inflow of gas with inflow rates of ~ 1 M_solar\yr. The massive black hole will thus grow quickly to a mass of 10^5 to 10^6 M_solar until further inflow is halted either by consumption of gas by star formation or by the increasing energy and momentum feedback from the growing massive black hole. Conditions for the formation of massive seed black holes in this way are most favourable in haloes with T_vir ~ 15000 K and V_vir ~ 20 km\s with less massive haloes not allowing collapse of gas by atomic cooling and more massive haloes being more prone to fragmentation. This should imprint a characteristic mass on the mass spectrum of an early population of massive black hole seeds in pre-galactic haloes which will later grow into the observed population of supermassive black holes in galactic bulges.Comment: 13 pages, 8 figures. Submitted to MNRA

Tracing the Reionization-Epoch Intergalactic Medium with Metal Absorption Lines

IGM metal absorption lines observed in z>6 spectra offer the opportunity to probe early feedback processes, the nature of enriching sources, and the topology of reionization. We run high-resolution cosmological simulations including galactic outflows to study the observability and physical properties of 5 ions (C II, C IV, O I, Si II, Si IV) in absorption between z=8->5. We apply three cases for ionization conditions: Fully neutral, fully reionized, and a patchy model based on the flux from the nearest galaxy. We find that our simulations broadly fit available z~5-6 IGM metal-line data, although all observations cannot be accommodated with a single ionization condition. Variations in O I absorbers among sight lines seen by Becker et al. (2006) suggest significant neutral IGM patches down to z~6. Strong C IV absorbers at z~6 may be the result of ionization by their parent galaxy. Our outflows have typical speeds of ~200 km/s and mass loading factors of ~6. Such high mass loading is critical for enriching the IGM to the observed levels while curtailing star formation to match the observed z~6 rest-frame UV luminosity function. The volume filling factor of metals increases during this epoch, but only reaches ~1% for Z>10^(-3) Zsolar by z=5. C IV is an ideal tracer of IGM metals at z~5-6, with dropping global ionization fractions to either higher or lower redshifts. This results in a strongly increasing global Omega(C IV) from z=8->5, in contrast to its relative constancy from z=5->2. Our simulations do not support widespread early IGM enrichment from e.g. Pop III stars. High-z absorbers arise from metals on their first outward journey from galaxies, at distances less than 50 kpc. The galaxies responsible for early IGM enrichment have typical M*=10^(7.0-8.5) Msolar.Comment: Accepted to MNRAS, 34 pages, 24 figures, 1 table (Sections 5.5, 6.3.1, & 6.3.2 added as well as 5 figures and 1 table

Retinal glycoprotein enrichment by concanavalin a enabled identification of novel membrane autoantigen synaptotagmin-1 in equine recurrent uveitis.

Complete knowledge of autoantigen spectra is crucial for understanding pathomechanisms of autoimmune diseases like equine recurrent uveitis (ERU), a spontaneous model for human autoimmune uveitis. While several ERU autoantigens were identified previously, no membrane protein was found so far. As there is a great overlap between glycoproteins and membrane proteins, the aim of this study was to test whether pre-enrichment of retinal glycoproteins by ConA affinity is an effective tool to detect autoantigen candidates among membrane proteins. In 1D Western blots, the glycoprotein preparation allowed detection of IgG reactions to low abundant proteins in sera of ERU patients. Synaptotagmin-1, a Ca2+-sensing protein in synaptic vesicles, was identified as autoantigen candidate from the pre-enriched glycoprotein fraction by mass spectrometry and was validated as a highly prevalent autoantigen by enzyme-linked immunosorbent assay. Analysis of Syt1 expression in retinas of ERU cases showed a downregulation in the majority of ERU affected retinas to 24%. Results pointed to a dysregulation of retinal neurotransmitter release in ERU. Identification of synaptotagmin-1, the first cell membrane associated autoantigen in this spontaneous autoimmune disease, demonstrated that examination of tissue fractions can lead to the discovery of previously undetected novel autoantigens. Further experiments will address its role in ERU pathology