The vibrational spectrum of FeO2+ isomers

Infrared photodissociation is used to record the vibrational spectrum of FeO2+(He)2–4 which shows three bands at 1035, 980, and 506 cm−1. Quantum chemical multi-reference configuration interaction calculations (MRCISD) of structures and harmonic frequencies show that these bands are due to two different isomers, an inserted dioxo complex with Fe in the +V oxidation state and a side-on superoxo complex with Fe in the +II oxidation state. These two are separated by a substantial barrier, 53 kJ/mol, whereas the third isomer, an end-on complex between Fe+ and an O2 molecule, is easily converted into the side-on complex. For all three isomers, states of different spin multiplicity have been considered. Our best energies are computed at the MRCISD+Q level, including corrections for complete active space and basis set extension, core-valence correlation, relativistic effects, and zero-point vibrational energy. The average coupled pair functional (ACPF) yields very similar energies. Density functional theory (DFT) differs significantly from our best estimates for this system, with the TPSS functional yielding the best results. The other functionals tested are BP86, PBE, B3LYP, TPSSh, and B2PLYP. Complete active space second order perturbation theory, (CASPT2) performs better than DFT, but less good than ACPF

Is who you ask important? Concordance between survey and registry data on medication use among self- and proxy-respondents in the longitudinal study of aging Danish twins and the Danish 1905-cohort study

This work was supported by the U.S. National Institute of Health (P01AG031719, R01AG026786 and 2P01AG031719), the VELUX Foundation, and the Max Planck Society within the framework of the project “On the edge of societies: New vulnerable populations, emerging challenges for social policies and future demands for social innovation. The experience of the Baltic Sea States (2016–2021).”Background This study investigates the accuracy of the reporting of medication use by proxy- and self-respondents, and it compares the prognostic value of the number of medications from survey and registry data for predicting mortality across self- and proxy-respondents. Methods The study is based on the linkage of the Longitudinal Study of Aging Danish Twins and the Danish 1905–Cohort Study with the Danish National Prescription Registry. We investigated the concordance between survey and registry data, and the prognostic value of medication use when assessed using survey and registry data, to predict mortality for self- and proxy-respondents at intake surveys. Results Among self-respondents, the agreement was moderate (κ = 0.52–0.58) for most therapeutic groups, whereas among proxy-respondents, the agreement was low to moderate (κ = 0.36–0.60). The magnitude of the relative differences was, generally, greater among proxies than among self-respondents. Each additional increase in the total number of medications was associated with 7%–8% mortality increase among self- and 4%–6% mortality increase among proxy-respondents in both the survey and registry data. The predictive value of the total number of medications estimated from either data source was lower among proxies (c-statistic = 0.56–0.58) than among self-respondents (c-statistic = 0.74). Conclusions The concordance between survey and registry data regarding medication use and the predictive value of the number of medications for mortality were lower among proxy- than among self-respondents.Publisher PDFPeer reviewe

Enhanced molecular analyses by combination of the HOPE-technique and laser microdissection

As part of an investigation aimed at illuminating the possibilities and limits of the HOPE-fixation and paraffin-embedding technique we here describe a novel procedure which was developed in order to combine the benefits of the HOPE-technique with the capabilities of laser microdissection. The presented procedure avoids the need for amplification of template-RNA thus facilitating reliable and reproducible results. The excellent preservation of nucleic acids, proteins, and morphology in HOPE-fixed, paraffin-embedded tissues enhances the molecular applications available to date with materials acquired by laser microdissection when compared to formalin fixed, paraffin-embedded tissues, thus substantially extending the methodological panel in tissue based research

gas phase vibrational spectroscopy of V3O6-8+

We present gas phase vibrational spectra of the trinuclear vanadium oxide cations V3O6+·He1–4, V3O7+·Ar0,1, and V3O8+·Ar0,2 between 350 and 1200 cm−1. Cluster structures are assigned based on a comparison of the experimental and simulated IR spectra. The latter are derived from B3LYP/TZVP calculations on energetically low-lying isomers identified in a rigorous search of the respective configurational space, using higher level calculations when necessary. V3O7+ has a cage-like structure of C3v symmetry. Removal or addition of an O-atom results in a substantial increase in the number of energetically low-lying structural isomers. V3O8+ also exhibits the cage motif, but with an O2 unit replacing one of the vanadyl oxygen atoms. A chain isomer is found to be most stable for V3O6+. The binding of the rare gas atoms to V3O6–8+ clusters is found to be strong, up to 55 kJ/mol for Ar, and markedly isomer-dependent, resulting in two interesting effects. First, for V3O7+·Ar and V3O8+·Ar an energetic reordering of the isomers compared to the bare ion is observed, making the ring motif the most stable one. Second, different isomers bind different number of rare gas atoms. We demonstrate how both effects can be exploited to isolate and assign the contributions from multiple isomers to the vibrational spectrum. The present results exemplify the structural variability of vanadium oxide clusters, in particular, the sensitivity of their structure on small perturbations in their environment

Time-resolved and state-selective detection of single freely falling atoms

We report on the detection of single, slowly moving Rubidium atoms using laser-induced fluorescence. The atoms move at 3 m/s while they are detected with a time resolution of 60 microseconds. The detection scheme employs a near-resonant laser beam that drives a cycling atomic transition, and a highly efficient mirror setup to focus a large fraction of the fluorescence photons to a photomultiplier tube. It counts on average 20 photons per atom.Comment: 6 pages, 7 figure

Agriculture in the Face of Changing Markets, Institutions and Policies: Challenges and Strategies

Since the late 1980s, agriculture in Central and Eastern European Countries (CEECs) has been under considerable adjustment pressure due to changing political, economic and institutional environments. These changes have been linked to the transition process, as well as the ongoing integration into the European Union and the world market. Reduced subsidies, increased environmental and food quality demands, as well as structural changes in the supply, processing and food retailing sector call for major structural adjustments and the improvement of farmersâ managerial abilities. Though such changes always carry significant threats to farms, they also offer new opportunities for the farms' entrepreneurial engagement. Upcoming changes in the agricultural environment and their possible consequences for farm structures across Europe are thus still timely subjects. The objective of the IAMO Forum 2006 is to contribute to the success of agriculture in the CEECs, as well as their neighboring countries, in todayâs increasingly competitive environment. Concrete questions the conference focuses on are: What are the most suitable farm organizations, cooperative arrangements and contractual forms? How to improve efficiency and productivity? Where do market niches lie and what are the new product demands? This book contains 33 invited and selected contributions. These papers will be presented at the IAMO Forum 2006 in order to offer a platform for scientists, practitioners and policy-makers to discuss challenges and potential strategies at the farm, value chain, rural society and policy levels in order to cope with the upcoming challenges. IAMO Forum 2006, as well as this book, would not have been possible without the engagement of many people and institutions. We thank the authors of the submitted abstracts and papers, as well as the referees, for their evaluation of the abstracts from which the papers were selected. In particular, we would like to express our thanks to OLIVER JUNGKLAUS, GABRIELE MEWES, KLAUS REINSBERG and ANGELA SCHOLZ, who significantly contributed to the organization of the Forum. Furthermore, our thanks goes to SILKE SCHARF for her work on the layout and editing support of this book, and to JIM CURTISS, JAMIE BULLOCH, and DÃNALL Ã MEARÃIN for their English proof-reading. As experience from previous years documents, the course of the IAMO Forum continues to profit from the support and engagement of the IAMO administration, which we gratefully acknowledge. Last but not least, we are very grateful to the Robert Bosch Foundation, the Federal Ministry of Nutrition, Agriculture and Consumer Protection (BMELV), the German Research Foundation (DFG), the Haniel Foundation and the Leibniz Institute of Agricultural Development in Central and Eastern Europe (IAMO) for their respective financial support.Agribusiness, Community/Rural/Urban Development, Farm Management, Industrial Organization, International Development, Labor and Human Capital, Land Economics/Use, Productivity Analysis,

Stage II/III rectal cancer with intermediate response to preoperative radiochemotherapy: Do we have indications for individual risk stratification?

<p>Abstract</p> <p>Background</p> <p>Response to preoperative radiochemotherapy (RCT) in patients with locally advanced rectal cancer is very heterogeneous. Pathologic complete response (pCR) is accompanied by a favorable outcome. However, most patients show incomplete response. The aim of this investigation was to find indications for risk stratification in the group of intermediate responders to RCT.</p> <p>Methods</p> <p>From a prospective database of 496 patients with rectal adenocarcinoma, 107 patients with stage II/III cancers and intermediate response to preoperative 5-FU based RCT (ypT2/3 and TRG 2/3), treated within the German Rectal Cancer Trials were studied. Surgical treatment comprised curative (R0) total mesorectal excision (TME) in all cases. In 95 patients available for statistical analyses, residual transmural infiltration of the mesorectal compartment, nodal involvement and histolologic tumor grading were investigated for their prognostic impact on disease-free (DFS) and overall survival (OS).</p> <p>Results</p> <p>Residual tumor transgression into the mesorectal compartment (ypT3) did not influence DFS and OS rates (p = 0.619, p = 0.602, respectively). Nodal involvement after preoperative RCT (ypN1/2) turned out to be a valid prognostic factor with decreased DFS and OS (p = 0.0463, p = 0.0236, respectively). Persistent tumor infiltration of the mesorectum (ypT3) and histologic tumor grading of residual tumor cell clusters were strongly correlated with lymph node metastases after neoadjuvant treatment (p < 0.001).</p> <p>Conclusions</p> <p>Advanced transmural tumor invasion after RCT does not affect prognosis when curative (R0) resection is achievable. Residual nodal status is the most important predictor of individual outcome in intermediate responders to preoperative RCT. Furthermore, ypT stage and tumor grading turn out to be additional auxiliary factors. Future clinical trials for risk-adapted adjuvant therapy should be based on a synopsis of clinicopathologic parameters.</p

Wirkungen des SGB II auf Personen mit Migrationshintergrund: Projekt IIa1 - 04/06 ; Jahresbericht zum 31.12.2008 - Hauptband

Auf Grundlage von Geschäftsdaten, von repräsentativen telefonischen Befragungen und von qualitativen Interviews mit Betroffenen und Fallmanagern wurden die Wirkungen der "Grundsicherung für Arbeitsuchende" auf Migrant/innen untersucht. Ihr Anteil an allen ALG-II Beziehenden beträgt im bundesweiten Durchschnitt 28 Prozent. Im Vergleich zu denjenigen ohne Migrationshintergrund sind sie im Durchschnitt jünger und haben häufiger keinen, aber auch häufiger höhere (Aus-)Bildungsabschlüsse. Die häufig fehlende Anerkennung ausländischer Abschlüsse wirkt sich auf die Arbeitsmarktchancen ebenso negativ aus wie das Fehlen jeglicher Ausbildung. Migrant/innen erhalten bei den Grundsicherungsstellen im Vergleich zu Deutschen ohne Migrationshintergrund mehr Beratungsgespräche, schließen jedoch seltener Eingliederungsvereinbarungen ab und nehmen seltener an Maßnahmen teil. Einige Herkunftsgruppen werden deutlich häufiger mit Sanktionen belegt, andere Herkunftsgruppen deutlich seltener