Influencing the coordination mode of tbta (tbta = tris[(1-benzyl- 1H-1,2,3-triazol-4-yl)methyl]amine) in dicobalt complexes through changes in metal oxidation states

The complexes [(tbta)Co(μ-CA-2H)Co(tbta)(CH3CN)](BF4)21 and [(tbta)Co(μ-OH)2Co(tbta)](BF4)42 (tbta = tris[(1-benzyl- 1H-1,2,3-triazol-4-yl)methyl]amine and CA = chloranilic acid) were synthesized and characterized by X-ray crystallography, SQUID magnetometry and NMR spectroscopy. The reactions to form these complexes deliver 1 as a paramagnetic species containing two high spin Co(II) centers, and 2 as a diamagnetic compound with two low spin Co(III) centers. Structural analysis shows that in 1 the capped-octahedral environment around the Co(II) centers is highly distorted with rather long bonds between the metal and donor atoms. The tbta ligand binds to the Co(II) centers through the three triazole nitrogen donor atoms in a facial form, with the Co–N(amine) distance of 2.494(2) Å acting as a capping bond to the octahedron. In the crystal an unusual observation of one acetonitrile molecule statistically occupying the coordination sites at both Co(II) centers is made. 1 displays a series of intermolecular C–HCl and π–π interactions leading to extended three- dimensional structures in the solid state. These interactions lead to the formation of voids and explain why only one acetonitrile molecule can be bound to the dinuclear complexes. In contrast to 1, the cobalt centers in 2 display a more regular octahedral environment with shorter cobalt–donor atom distances, as would be expected for a low spin Co(III) situation. The tbta ligand acts as a perfect tetradentate ligand in this case with the cobalt–N(amine) distance of 2.012(3) Å falling in the range of a normal bond. Thus, we present the rare instances where the ligand tbta has been observed to bind in a perfectly tetradentate fashion in its metal complexes. The room temperature magnetic moment of 6.30 μB for 1 shows values typical of two high spin Co(II) centers, and this value decreases at temperatures lower than 30 K indicating a weak antiferromagnetic coupling and zero field splitting. Mass spectrometric analysis of 2 provided evidence for the formation of an oxo- bridged dicobalt complex in the gas phase

Influencing the coordination mode of tbta (tbta = tris[(1-benzyl- 1H-1,2,3-triazol-4-yl)methyl]amine) in dicobalt complexes through changes in metal oxidation states

The complexes [(tbta)Co(μ-CA-2H)Co(tbta)(CH3CN)](BF4)21 and [(tbta)Co(μ-OH)2Co(tbta)](BF4)42 (tbta = tris[(1-benzyl- 1H-1,2,3-triazol-4-yl)methyl]amine and CA = chloranilic acid) were synthesized and characterized by X-ray crystallography, SQUID magnetometry and NMR spectroscopy. The reactions to form these complexes deliver 1 as a paramagnetic species containing two high spin Co(II) centers, and 2 as a diamagnetic compound with two low spin Co(III) centers. Structural analysis shows that in 1 the capped-octahedral environment around the Co(II) centers is highly distorted with rather long bonds between the metal and donor atoms. The tbta ligand binds to the Co(II) centers through the three triazole nitrogen donor atoms in a facial form, with the Co–N(amine) distance of 2.494(2) Å acting as a capping bond to the octahedron. In the crystal an unusual observation of one acetonitrile molecule statistically occupying the coordination sites at both Co(II) centers is made. 1 displays a series of intermolecular C–HCl and π–π interactions leading to extended three- dimensional structures in the solid state. These interactions lead to the formation of voids and explain why only one acetonitrile molecule can be bound to the dinuclear complexes. In contrast to 1, the cobalt centers in 2 display a more regular octahedral environment with shorter cobalt–donor atom distances, as would be expected for a low spin Co(III) situation. The tbta ligand acts as a perfect tetradentate ligand in this case with the cobalt–N(amine) distance of 2.012(3) Å falling in the range of a normal bond. Thus, we present the rare instances where the ligand tbta has been observed to bind in a perfectly tetradentate fashion in its metal complexes. The room temperature magnetic moment of 6.30 μB for 1 shows values typical of two high spin Co(II) centers, and this value decreases at temperatures lower than 30 K indicating a weak antiferromagnetic coupling and zero field splitting. Mass spectrometric analysis of 2 provided evidence for the formation of an oxo- bridged dicobalt complex in the gas phase

Sensing external spins with nitrogen-vacancy diamond

A single nitrogen-vacancy (NV) center is used to sense individual, as well as small ensembles of, electron spins placed outside the diamond lattice. Applying double electron–electron resonance techniques, we were able to observe Rabi nutations of these external spins as well as the coupling strength between the external spins and the NV sensor, via modulations and accelerated decay of the NV spin echo. Echo modulation frequencies as large as 600 kHz have been observed, being equivalent to a few nanometers distance between the NV and an unpaired electron spin. Upon surface modification, the coupling disappears, suggesting the spins to be localized at surface defects. The present study is important for understanding the properties of diamond surface spins so that their effects on NV sensors can eventually be mitigated. This would enable potential applications such as the imaging and tracking of single atoms and molecules in living cells or the use of NVs on scanning probe tips to entangle remote spins for scalable room temperature quantum computers

Long-term outcomes of physical activity counseling in in-patients with major depressive disorder: results from the PACINPAT randomized controlled trial.

Major depressive disorder (MDD) is an increasingly common psychiatric illness associated with a high risk of insufficient physical activity, which in turn is associated with negative mental and physical health outcomes. Theory-based, individually tailored, in-person and remote physical activity counseling has the potential to increase physical activity levels in various populations. Given this, the present study investigated the effect of such a physical activity intervention on the physical activity behavior of in-patients with MDD. This was a multi-center, two-arm randomized controlled trial including initially insufficiently physically active adult in-patients with MDD from four study sites in Switzerland. The sample consisted of 220 participants (Mage = 41 ± 12.6 years, 52% women), 113 of whom were randomized to the intervention group and 107 to the control group. The main outcome, moderate-to-vigorous physical activity (MVPA), was assessed at three time points via hip-worn accelerometer. According to accelerometer measures, there was no significant difference in minutes spent in MVPA over a 12-month intervention period when comparing the intervention with the control group (β = -1.02, 95% CI = -10.68 to 8.64). Higher baseline physical activity significantly predicted physical activity at post and follow-up. This study showed that it is feasible to deliver an individually tailored, theory-based physical activity counseling intervention to in-patients with MDD, however yielding no significant effects on accelerometer-based MVPA levels. Further efforts are warranted to identify efficacious approaches.Trial registration: ISRCTN, ISRCTN10469580, registered on 3rd September 2018, https://www.isrctn.com/ISRCTN10469580

Short-term outcomes of physical activity counseling in in-patients with Major Depressive Disorder: Results from the PACINPAT randomized controlled trial

IntroductionA physical activity counseling intervention based on a motivation-volition model was developed and delivered to in-patients with Major Depressive Disorders with the aim of increasing lifestyle physical activity. The aim of this study is to evaluate the short-term outcomes of this intervention.MethodsA multi-center randomized controlled trial was conducted in four Swiss psychiatric clinics. Adults who were initially insufficiently physically active and were diagnosed with Major Depressive Disorder according to ICD-10 were recruited. The sample consisted of 113 participants in the intervention group (Mage = 42 years, 56% women) and 107 in the control group (Mage = 40 years, 49% women). Motivation and volition determinants of physical activity were assessed with questionnaires. Implicit attitudes were assessed with an Implicit Association Test. Physical activity was self-reported and measured with hip-worn accelerometers over 7 consecutive days starting on the day following the data collection.ResultsAccording to accelerometer measures, step count decreased on average 1,323 steps less per day (95% CI = −2,215 to −431, p < 0.01) over time in the intervention group compared to the control group. A trend was recognized indicating that moderate-to-vigorous physical activity decreased on average 8.37 min less per day (95% CI = −16.98 to 0.23, p < 0.06) over time in the intervention group compared to the control group. The initial phase of the intervention does not seem to have affected motivational and volitional determinants of and implicit attitudes toward physical activity.ConclusionPhysical activity counseling may be considered an important factor in the transition from in-patient treatment. Methods to optimize the intervention during this period could be further explored to fulfill the potential of this opportunity.Clinical trial registrationhttps://www.isrctn.com/ISRCTN10469580, identifier ISRCTN10469580

Genome-wide association meta-analysis identifies 48 risk variants and highlights the role of the stria vascularis in hearing loss

Hearing loss is one of the top contributors to years lived with disability and is a risk factor for dementia. Molecular evidence on the cellular origins of hearing loss in humans is growing. Here, we performed a genome-wide association meta-analysis of clinically diagnosed and self-reported hearing impairment on 723,266 individuals and identified 48 significant loci, 10 of which are novel. A large proportion of associations comprised missense variants, half of which lie within known familial hearing loss loci. We used single-cell RNA-sequencing data from mouse cochlea and brain and mapped common-variant genomic results to spindle, root, and basal cells from the stria vascularis, a structure in the cochlea necessary for normal hearing. Our findings indicate the importance of the stria vascularis in the mechanism of hearing impairment, providing future paths for developing targets for therapeutic intervention in hearing loss

Establishing an infrastructure for collaboration in primate cognition research

Inferring the evolutionary history of cognitive abilities requires large and diverse samples. However, such samples are often beyond the reach of individual researchers or institutions, and studies are often limited to small numbers of species. Consequently, methodological and site-specific-differences across studies can limit comparisons between species. Here we introduce the ManyPrimates project, which addresses these challenges by providing a large-scale collaborative framework for comparative studies in primate cognition. To demonstrate the viability of the project we conducted a case study of short-term memory. In this initial study, we were able to include 176 individuals from 12 primate species housed at 11 sites across Africa, Asia, North America and Europe. All subjects were tested in a delayed-response task using consistent methodology across sites. Individuals could access food rewards by remembering the position of the hidden reward after a 0, 15, or 30-second delay. Overall, individuals performed better with shorter delays, as predicted by previous studies. Phylogenetic analysis revealed a strong phylogenetic signal for short-term memory. Although, with only 12 species, the validity of this analysis is limited, our initial results demonstrate the feasibility of a large, collaborative open-science project. We present the ManyPrimates project as an exciting opportunity to address open questions in primate cognition and behaviour with large, diverse datasets

Establishing an infrastructure for collaboration in primate cognition research

Inferring the evolutionary history of cognitive abilities requires large and diverse samples. However, such samples are often beyond the reach of individual researchers or institutions, and studies are often limited to small numbers of species. Consequently, methodological and site-specific-differences across studies can limit comparisons between species. Here we introduce the ManyPrimates project, which addresses these challenges by providing a large-scale collaborative framework for comparative studies in primate cognition. To demonstrate the viability of the project we conducted a case study of short-term memory. In this initial study, we were able to include 176 individuals from 12 primate species housed at 11 sites across Africa, Asia, North America and Europe. All subjects were tested in a delayed-response task using consistent methodology across sites. Individuals could access food rewards by remembering the position of the hidden reward after a 0, 15, or 30-second delay. Overall, individuals performed better with shorter delays, as predicted by previous studies. Phylogenetic analysis revealed a strong phylogenetic signal for short-term memory. Although, with only 12 species, the validity of this analysis is limited, our initial results demonstrate the feasibility of a large, collaborative open-science project. We present the ManyPrimates project as an exciting opportunity to address open questions in primate cognition and behaviour with large, diverse datasets

Heterobimetallic Cu–dppf (dppf = 1,1′-Bis(diphenylphosphino)ferrocene) Complexes with “Click” Derived Ligands: A Combined Structural, Electrochemical, Spectroelectrochemical, and Theoretical Study

Heterodinuclear complexes of the form [(dppf)­Cu­(L)]­(BF₄) (dppf = 1,1′-bis­(diphenylphosphino)­ferrocene), where L are the chelating, substituted 4,4′-bis­(1,2,3-triazole) or 4-pyridyl­(1,2,3-triazole) ligands, were synthesized by reacting [Cu­(dppf)­(CH₃CN)₂]­(BF₄) with the corresponding “click” derived ligands. Structural characterization of representative complexes revealed a distorted-tetrahedral coordination geometry around the Cu­(I) centers, with the donor atoms being the P donors of dppf and the N donors of the substituted triazole ligands. The “local-pseudo” symmetry around the iron center in all the investigated complexes of dppf is between that of the idealized <i>D</i>_5<i>h</i> and <i>D</i>_5<i>d</i>. Furthermore, for the complex with the mixed pyridine and triazole donors, the Cu–N bond distances were found to be shorter for the triazole N donors in comparison to those for the pyridine N donors. Electrochemical studies on the complexes revealed the presence of one oxidation and one reduction step for each. These studies were combined with UV–vis–near-IR and EPR spectroelectrochemical studies to deduce the locus of the oxidation process (Cu vs Fe) and to see the influence of changing the chelating “click” derived ligand on both the oxidation and reduction processes and their spectroscopic signatures. Structure-based DFT studies were performed to get insights into the experimental spectroscopic results. The results obtained here are compared with those of the complex [(dppf)­Cu­(bpy)]­(BF₄) (bpy = 2,2′-bipyridine). A comparison is made among bpy, pyridyl-triazole, and bis-triazole ligands, and the effect of systematically replacing these ligands on the electrochemical and spectroscopic properties of the corresponding heterodinuclear complexes is investigated

Heterobimetallic Cu–dppf (dppf = 1,1′-Bis(diphenylphosphino)ferrocene) Complexes with “Click” Derived Ligands: A Combined Structural, Electrochemical, Spectroelectrochemical, and Theoretical Study

Heterodinuclear complexes of the form [(dppf)­Cu­(L)]­(BF₄) (dppf = 1,1′-bis­(diphenylphosphino)­ferrocene), where L are the chelating, substituted 4,4′-bis­(1,2,3-triazole) or 4-pyridyl­(1,2,3-triazole) ligands, were synthesized by reacting [Cu­(dppf)­(CH₃CN)₂]­(BF₄) with the corresponding “click” derived ligands. Structural characterization of representative complexes revealed a distorted-tetrahedral coordination geometry around the Cu­(I) centers, with the donor atoms being the P donors of dppf and the N donors of the substituted triazole ligands. The “local-pseudo” symmetry around the iron center in all the investigated complexes of dppf is between that of the idealized <i>D</i>_5<i>h</i> and <i>D</i>_5<i>d</i>. Furthermore, for the complex with the mixed pyridine and triazole donors, the Cu–N bond distances were found to be shorter for the triazole N donors in comparison to those for the pyridine N donors. Electrochemical studies on the complexes revealed the presence of one oxidation and one reduction step for each. These studies were combined with UV–vis–near-IR and EPR spectroelectrochemical studies to deduce the locus of the oxidation process (Cu vs Fe) and to see the influence of changing the chelating “click” derived ligand on both the oxidation and reduction processes and their spectroscopic signatures. Structure-based DFT studies were performed to get insights into the experimental spectroscopic results. The results obtained here are compared with those of the complex [(dppf)­Cu­(bpy)]­(BF₄) (bpy = 2,2′-bipyridine). A comparison is made among bpy, pyridyl-triazole, and bis-triazole ligands, and the effect of systematically replacing these ligands on the electrochemical and spectroscopic properties of the corresponding heterodinuclear complexes is investigated