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We observed the Galactic black hole X-ray binary V4641 Sgr with the high resolution transmission gratings on Chandra during the source's 2020 outburst. Over two epochs of Chandra gratings observations, we see numerous highly ionized metal lines, superimposed on a hot, disc-dominated X-ray continuum. The measured inner disc temperatures and luminosities imply an unfeasibly small inner disc radius, such that we suggest that the central engine of V4641 Sgr is obscured, and we are viewing scattered X-rays. We find that the emission lines in the Chandra spectra cannot be constrained by a single photoionized model, instead finding that two separate photoionized model components are required, one to reproduce the iron lines and a second for the other metals. We compare the observed X-ray spectra of V4641 Sgr to optical studies during previous outbursts of the source, suggesting that the lines originate in an accretion disc wind, potentially with a spherical geometry., Comment: 14 pages, 11 figures, accepted for publication in MNRAS

The radiative counterpart of the supermassive black hole at the Galactic Centre, Sagittarius A*, displays flaring emission in the X-ray band atop a steady, quiescent level. Flares are also observed in the near-infrared band. The physical process producing the flares is not fully understood and it is unclear if the flaring rate varies, although some recent works suggest it has reached unprecedented variability in recent years. Using over a decade of regular X-ray monitoring of Neil Gehrels Swift Observatory, we studied the variations in count rate of Sgr A* on time scales of years. We decomposed the X-ray emission into quiescent and flaring emission, modelled as a constant and power law process, respectively. We found that the complete, multi-year dataset cannot be described by a stationary distribution of flare fluxes, while individual years follow this model better. In three of the ten studied years, the data is consistent with a purely Poissonian quiescent distribution, while for five years only an upper limit of the flare flux distribution parameter could be determined. We find that these possible changes cannot be explained fully by the different number of observations per year. Combined, these results are instead consistent with a changing flaring rate of Sgr A*, appearing more active between 2006-2007 and 2017-2019, than between 2008-2012. Finally, we discuss this result in the context of flare models and the passing of gaseous objects, and discuss the extra statistical steps taken, for instance to deal with the background in the Swift observations., 14 pages, 10 figures, Accepted for publication in MNRAS

SMSS\,J114447.77-430859.3 ($z=0.83$) has been identified in the SkyMapper Southern Survey as the most luminous quasar in the last $\sim 9\,\rm Gyr$. In this paper, we report on the eROSITA/Spectrum-Roentgen-Gamma (SRG) observations of the source from the eROSITA All Sky Survey, along with presenting results from recent monitoring performed using Swift, XMM-Newton, and NuSTAR. The source shows a clear variability by factors of $\sim 10$ and $\sim 2.7$ over timescales of a year and of a few days, respectively. When fit with an absorbed power law plus high-energy cutoff, the X-ray spectra reveal a $\Gamma=2.2 \pm 0.2$ and $E_{\rm cut}=23^{+26}_{-5}\,\rm keV$. Assuming Comptonisation, we estimate a coronal optical depth and electron temperature of $\tau=2.5-5.3\, (5.2-8)$ and $kT=8-18\, (7.5-14)\,\rm keV$, respectively, for a slab (spherical) geometry. The broadband SED is successfully modelled by assuming either a standard accretion disc illuminated by a central X-ray source, or a thin disc with a slim disc emissivity profile. The former model results in a black hole mass estimate of the order of $10^{10}\,M_\odot$, slightly higher than prior optical estimates; meanwhile, the latter model suggests a lower mass. Both models suggest sub-Eddington accretion when assuming a spinning black hole, and a compact ($\sim 10\,r_{\rm g}$) X-ray corona. The measured intrinsic column density and the Eddington ratio strongly suggest the presence of an outflow driven by radiation pressure. This is also supported by variation of absorption by an order of magnitude over the period of $\sim 900\,\rm days$., Comment: Accepted for publication in MNRAS

N2 reduction to ammonia is catalyzed by molybdenum complexes of a bulky porphyrin, and the thermodynamics of the first PCET step are evaluated.

Background/Introduction Rural caregivers of those with chronic illnesses have higher cardiovascular disease (CVD) risk than urban caregivers. Diet is a major lifestyle factor that contributes to CVD risk. However, interventions are often not constructed with health literacy in mind. We previously found a moderation effect of health literacy on short-term (4-month) diet quality from a self-care intervention to reduce cardiovascular disease risk (RICHH) among rural caregivers. The RICHH intervention was designed to be equally effective in caregivers with marginal or adequate health literacy. Purpose To compare the impact of RICHH intervention on 12-month diet quality in rural caregivers with marginal versus adequate health literacy. Methods A total of 296 rural caregivers (54.5±13.7 years old, 76% female) of individuals with chronic illnesses participated. The newest vital sign (NVS) and Healthy Eating Index-2015 (HEI-2015) were used to determine health literacy and diet quality, respectively. The NVS was dichotomized using a cutoff score of 4. The HEI-2015 was computed based on food frequency questionnaires at baseline, 4-month, and 12-month. The RICHH intervention was delivered using video conferencing technology by nurse interventionists once a week for 12 weeks followed by bi-weekly and monthly booster sessions. A piecewise linear mixed-effect model, controlling for age, education, smoking status, and perceived stress, was used to evaluate the impact of the intervention on diet quality between the two health literacy groups. Results There was a significant difference in improvement in the HEI-2015 total scores at 4 months between control and intervention in the marginal health literacy group (beta estimate = 1.56, SE=0.74, P=0.039) but not in the adequate health literacy group (beta estimate = 0.27, SE=0.38, P=0.475). The improvement in the marginal health literacy group was sustained at 12-months (beta estimate = 8.12, SE=3.57, P=0.022). Conclusions The results of our study indicate that an intervention designed to address health literacy is effective in producing a sustained improvement in diet quality to reduce CVD risk in rural caregivers with marginal health literacy. Funding Acknowledgement Type of funding sources: Public grant(s) – National budget only. Main funding source(s): National Institutes of Health National Institute of Nursing Research

The kinetics of hydride transfer from Re(

Iodide is an essential promoter in the industrial production of acetic acid via methanol carbonylation, but it also contributes to reactor corrosion and catalyst deactivation. Here we report that iridium pincer complexes mediate the individual steps of methanol carbonylation to methyl acetate in the absence of methyl iodide or iodide salts. Iodide-free methylation is achieved under mild conditions by an aminophenylphosphinite pincer iridium(I) dinitrogen complex through net C-O oxidative addition of methyl acetate to produce an isolable methyliridium(III) acetate complex. Experimental and computational studies provide evidence for methylation via initial C-H bond activation followed by acetate migration, facilitated by amine hemilability. Subsequent CO insertion and reductive elimination in methanol solution produced methyl acetate and acetic acid. The net reaction is methanol carbonylation to acetic acid using methyl acetate as a promoter alongside conversion of an iridium dinitrogen complex to an iridium carbonyl complex. Kinetic studies of migratory insertion and reductive elimination reveal essential roles of the solvent methanol and distinct features of acetate and iodide anions that are relevant to the design of future catalysts for iodide-free carbonylation.

Terminal and bridging end-on coordination of N2 to transition metal complexes offer possibilities for distinct pathways in ammonia synthesis and N2 functionalization. Here we elucidate the fundamental factors controlling the two binding modes and determining which is favored for a given metal-ligand system, using both quantitative density functional theory (DFT) and qualitative molecular orbital (MO) analyses. The Gibbs free energy for converting two terminal MN2 complexes into a bridging MNNM complex and a free N2 molecule (2ΔGeq°) is examined through systematic variations of the metal and ligands; values of ΔGeq° range between +9.1 and -24.0 kcal/mol per M-N2 bond. We propose a model that accounts for these broad variations by assigning a fixed π-bond order (BOπ) to the triatomic terminal MNN moiety that is equal to that of the free N2 molecule, and a variable BOπ to the bridging complexes based on the character (bonding or antibonding) and occupancy of the π-MOs in the tetratomic MNNM core. When the conversion from terminal to bridging coordination and free N2 is associated with an increase in the number of π-bonds (ΔBOeqπ > 0), the bridging mode is greatly favored; this condition is satisfied when each metal provides 1, 2, or 3 electrons to the π-MOs of the MNNM core. When each metal in the bridging complex provides 4 electrons to the MNNM π-MOs, ΔBOeqπ = 0; the equilibrium in this case is approximately ergoneutral and the direction can be shifted by dispersion interactions.

NGC 5033 is an intriguing Seyfert galaxy because its subclassification may change with time, and because optical and submillimeter observations find that the massive black hole does not sit at the dynamical center of the galaxy, pointing to a past merger. We obtained a new optical spectrum of NGC 5033 using the 200″ Hale telescope at Palomar that clearly reveals a broad Hβ line (FWHM = 5400 ± 300 km s−1). This signals a clear view of the optical broad line region and requires Seyfert-1.5 designation. Some spectra obtained in the past suggest a Seyfert-1.9 classification, potentially signaling a variable or “changing-look” geometry. Our analysis of a 2019 Chandra spectrum of the massive black hole reveals very little obscuration, also suggesting a clean view of the central engine. However, the narrow Fe Kα emission line is measured to have an equivalent width of EW = 460 − 90 + 100 eV. This value is extremely high compared to typical values in unobscured active galactic nuclei . Indeed, the line is persistently strong in NGC 5033: the line equivalent width in a 2002 XMM-Newton snapshot is EW = 250 − 40 + 40 eV, similar to the EW = 290 − 100 + 100 eV equivalent width measured using ASCA in 1999. These results can likely be explained through a combination of an unusually high covering factor for reflection, and fluxes that are seen out of phase owing to light travel times. We examine the possibility that NGC 5033 may strengthen evidence for the X-ray Baldwin effect.

Dehydrogenation to give olefins offers the most broadly applicable route to the chemical transformation of alkanes. Transition-metal-based catalysts can selectively dehydrogenate alkanes using eith...

The catalytic transposition of double bonds holds promise as an ideal route to alkenes of value as fragrances, commodity chemicals, and pharmaceuticals; yet, selective access to specific isomers is a challenge, normally requiring independent development of different catalysts for different products. In this work, a single cation-responsive iridium catalyst selectively produces either of two different internal alkene isomers. In the absence of salts, a single positional isomerization of 1-butene derivatives furnishes 2-alkenes with exceptional regioselectivity and stereoselectivity. The same catalyst, in the presence of Na+, mediates two positional isomerizations to produce 3-alkenes. The synthesis of new iridium pincer-crown ether catalysts based on an aza-18-crown-6 ether proved instrumental in achieving cation-controlled selectivity. Experimental and computational studies guided the development of a mechanistic model that explains the observed selectivity for various functionalized 1-butenes, providing insight into strategies for catalyst development based on noncovalent modifications.

The catalytic hydrogenation of carbon dioxide holds immense promise for applications in sustainable fuel synthesis and hydrogen storage. Mechanistic studies that connect thermodynamic parameters with the kinetics of catalysis can provide new understanding and guide predictive design of improved catalysts. Reported here are thermochemical and kinetic analyses of a new pincer-ligated rhenium complex (tBuPOCOP)Re(CO)2 (tBuPOCOP = 2,6-bis(di-tert-butylphosphinito)phenyl) that catalyzes CO2 hydrogenation to formate with faster rates at lower temperatures. Because the catalyst follows the prototypical "outer sphere" hydrogenation mechanism, comprehensive studies of temperature and solvent effects on the H2 splitting and hydride transfer steps are expected to be relevant to many other catalysts. Strikingly large entropy associated with cleavage of H2 results in a strong temperature dependence on the concentration of [(tBuPOCOP)Re(CO)2H]- present during catalysis, which is further impacted by changing the solvent from toluene to tetrahydrofuran to acetonitrile. New methods for determining the hydricity of metal hydrides and formate at temperatures other than 298 K are developed, providing insight into how temperature can influence the favorability of hydride transfer during catalysis. These thermochemical insights guided the selection of conditions for CO2 hydrogenation to formate with high activity (up to 364 h-1 at 1 atm or 3330 h-1 at 20 atm of 1:1 H2:CO2). In cases where hydride transfer is the highest individual kinetic barrier, entropic contributions to outer sphere H2 splitting lead to a unique temperature dependence: catalytic activity increases as temperature decreases in tetrahydrofuran (200-fold increase upon cooling from 50 to 0 °C) and toluene (4-fold increase upon cooling from 100 to 50 °C). Ramifications on catalyst structure-function relationships are discussed, including comparisons between "outer sphere" mechanisms and "metal-ligand cooperation" mechanisms.

Electrocatalysts for CO2 reduction based on first-row transition metal ions have attracted attention as abundant and affordable candidates for energy conversion applications. Yet very few molecular iron electrocatalysts exhibit high selectivity for CO. Iron complexes supported by a redox-active 2,2′:6′,2″-terpyridine (tpy) ligand and a strong trans effect pyridyl-N-heterocyclic carbene ligand (1-methyl-benzimidazol-2-ylidene-3-(2-pyridine)) were synthesized and found to catalyze the selective electroreduction of CO2 to CO at very low overpotentials. Mechanistic studies using electrochemical and computational methods provided insights into the nature of catalytic intermediates that guided the development of continuous CO2 flow conditions that improved the performance, producing CO with >95% Faradaic efficiency at an overpotential of only 150 mV. The studies reveal general design principles for nonheme iron electrocatalysts, including the importance of lability and geometric isomerization, that can serve to guide future developments in the design of affordable and efficient catalysts for CO2 electroreduction.

Hemilabile ligands are found in many leading organometallic catalysts, but it can be challenging to tune the degree of hemilability in a particular catalyst. This work explores the impact of cation...

Despite advances in the development of molecular catalysts capable of reducing dinitrogen to ammonia using proton donors and chemical reductants, few molecular electrocatalysts have been discovered...

Molecular platforms capable of both photochemical H2 evolution and electrochemical catalyst regeneration hold promise for the efficient generation of solar fuels. Systems studied to date require si...

BACKGROUND AND PURPOSE: Fast and accurate quantification of globe volumes in the event of an ocular trauma can provide clinicians with valuable diagnostic information. In this work, an automated workflow using a deep learning-based convolutional neural network is proposed for prediction of globe contours and their subsequent volume quantification in CT images of the orbits. MATERIALS AND METHODS: An automated workflow using a deep learning -based convolutional neural network is proposed for prediction of globe contours in CT images of the orbits. The network, 2D Modified Residual UNET (MRes-UNET2D), was trained on axial CT images from 80 subjects with no imaging or clinical findings of globe injuries. The predicted globe contours and volume estimates were compared with manual annotations by experienced observers on 2 different test cohorts. RESULTS: On the first test cohort (n = 18), the average Dice, precision, and recall scores were 0.95, 96%, and 95%, respectively. The average 95% Hausdorff distance was only 1.5 mm, with a 5.3% error in globe volume estimates. No statistically significant differences (P = .72) were observed in the median globe volume estimates from our model and the ground truth. On the second test cohort (n = 9) in which a neuroradiologist and 2 residents independently marked the globe contours, MRes-UNET2D (Dice = 0.95) approached human interobserver variability (Dice = 0.94). We also demonstrated the utility of inter-globe volume difference as a quantitative marker for trauma in 3 subjects with known globe injuries. CONCLUSIONS: We showed that with fast prediction times, we can reliably detect and quantify globe volumes in CT images of the orbits across a variety of acquisition parameters.

Comparative kinetic studies of a series of new ruthenium complexes provide a platform for understanding how strong trans effect ligands and redox-active ligands work together to enable rapid electr...