Electronic Structure Description of a Doubly Oxidized Bimetallic Cobalt Complex with Pro-Radical Ligands

The geometric and electronic structure of a doubly oxidized bimetallic Co complex containing two redox-active salen moieties connected via a 1,2-phenylene linker has been investigated and compared to an oxidized monomeric analogue. Both complexes, CoL1 and Co2L2 are oxidized to the mono- and di-cations respectively with AgSbF6 and characterized by X-ray crystallography for the monomer, and Vis-NIR spectroscopy, electron paramagnetic (EPR) spectroscopy, SQUID magnetometry and density functional theory (DFT) calculations for both the monomer and dimer. Both complexes exhibit a water molecule coordinated in the apical position upon oxidation. [CoL1-H2O]+ displays a broad NIR band at 8500 cm-1 (8400 M-1cm-1) which is consistent with recent reports on oxidized Co salen complexes (Kochem, A. et. al., Inorg Chem., 2012, 51, 10557-10571, Kurahashi, T. et. al., Inorg. Chem., 2013, 52, 3908-3919). DFT calculations predict a triplet ground state with significant ligand and metal contributions to the singularly occupied molecular orbital (SOMO). The majority (~75%) of the total spin density is localized on the metal, highlighting both high spin Co(III) and Co(II)L• character in the electronic ground state. Further oxidation of CoL1 to the dication affords a low spin Co(III) phenoxyl radical species. The NIR features for [Co2L2-2H2O]2+ at 8600 cm-1 (17800 M-1cm-1) are doubly intense in comparison to [CoL1-H2O]+ owing to the description of [Co2L2-2H2O]2+ as two non-interacting oxidized Co salen complexes bound via the central phenylene linker. Interestingly, TD-DFT calculations predict two electronic transitions that are 353 cm-1 apart. The NIR spectrum of the analogous Ni complex, [Ni2L2]2+, exhibits two intense transitions (4890 cm-1/26500 M-1cm-1 and 4200 cm-1/21200 M-1cm-1) due to exciton coupling in the excited state. Only one broad band is observed in the NIR spectrum for [Co2L2-2H2O]2+ as a result of the contracted donor and acceptor orbitals and overall CT character

Effects and moderators of psychosocial interventions on quality of life, and emotional and social function in patients with cancer : an individual patient data meta-analysis of 21 RCTs

Objective: This individual patient data (IPD) meta‐analysis aimed to evaluate the effects of psychosocial interventions (PSI) on quality of life (QoL), emotional function (EF), and social function (SF) in patients with cancer, and to study moderator effects of demographic, clinical, personal, and intervention‐related characteristics. Methods: Relevant studies were identified via literature searches in 4 databases. We pooled IPD from 22 (n = 4217) of 61 eligible randomized controlled trials. Linear mixed‐effect model analyses were used to study intervention effects on the post‐intervention values of QoL, EF, and SF (z‐scores), adjusting for baseline values, age, and cancer type. We studied moderator effects by testing interactions with the intervention for demographic, clinical, personal, and intervention‐related characteristics, and conducted subsequent stratified analyses for significant moderator variables.Results: PSI significantly improved QoL (β = 0.14,95%CI = 0.06;0.21), EF (β = 0.13,95%CI = 0.05;0.20), and SF (β = 0.10,95%CI = 0.03;0.18). Significant differences in effects of different types of PSI were found, with largest effects of psychotherapy. The effects of coping skills training were moderated by age, treatment type, and targeted interventions. Effects of psychotherapy on EF may be moderated by cancer type, but these analyses were based on 2 randomized controlled trials with small sample sizes of some cancer types. Conclusions: PSI significantly improved QoL, EF, and SF, with small overall effects. However, the effects differed by several demographic, clinical, personal, and intervention‐related characteristics. Our study highlights the beneficial effects of coping skills training in patients treated with chemotherapy, the importance of targeted interventions, and the need of developing interventions tailored to the specific needs of elderly patients

Search for dark matter produced in association with bottom or top quarks in √s = 13 TeV pp collisions with the ATLAS detector

A search for weakly interacting massive particle dark matter produced in association with bottom or top quarks is presented. Final states containing third-generation quarks and miss- ing transverse momentum are considered. The analysis uses 36.1 fb−1 of proton–proton collision data recorded by the ATLAS experiment at √s = 13 TeV in 2015 and 2016. No significant excess of events above the estimated backgrounds is observed. The results are in- terpreted in the framework of simplified models of spin-0 dark-matter mediators. For colour- neutral spin-0 mediators produced in association with top quarks and decaying into a pair of dark-matter particles, mediator masses below 50 GeV are excluded assuming a dark-matter candidate mass of 1 GeV and unitary couplings. For scalar and pseudoscalar mediators produced in association with bottom quarks, the search sets limits on the production cross- section of 300 times the predicted rate for mediators with masses between 10 and 50 GeV and assuming a dark-matter mass of 1 GeV and unitary coupling. Constraints on colour- charged scalar simplified models are also presented. Assuming a dark-matter particle mass of 35 GeV, mediator particles with mass below 1.1 TeV are excluded for couplings yielding a dark-matter relic density consistent with measurements