A computationally inspired Cu(I) metal-to-ligand charge transfer (MLCT) chromophore, [Cu(sbmpep)] (sbmpep = 2,9-di(sec-butyl)-3,8-dimethyl-4,7-di(phenylethynyl)-1,10-phenanthroline), was synthesized in seven total steps, prepared from either dichloro- or dibromophenanthroline precursors. Complete synthesis, structural characterization, and electrochemistry, in addition to static and dynamic photophysical properties of [Cu(sbmpep)], are reported on all relevant time scales. UV-Vis absorption spectroscopy revealed significant increases in oscillator strength along with a concomitant bathochromic shift in the MLCT absorption bands with respect to structurally related model complexes (ε = 16 500 M cm at 491 nm). Strong red photoluminescence (Φ = 2.7%, λ = 687 nm) was observed from [Cu(sbmpep)], which featured an average excited-state lifetime of 1.4 μs in deaerated dichloromethane. Cyclic and differential pulse voltammetry revealed ∼300 mV positive shifts in the measured one-electron reversible reduction and oxidation waves in relation to a Cu(I) model complex possessing identical structural elements without the π-conjugated 4,7-substituents. The excited-state redox potential of [Cu(sbmpep)] was estimated to be -1.36 V, a notably powerful reductant for driving photoredox chemistry. The combination of conventional and ultrafast transient  absorption and luminescence spectroscopy successfully map the excited-state dynamics of [Cu(sbmpep)] from initial photoexcitation to the formation of the lowest-energy MLCT excited state and ultimately its relaxation to the ground state. This newly conceived molecule appears poised for photosensitization reactions involving energy and electron-transfer processes relevant to photochemical upconversion, photoredox catalysis, and solar fuels photochemistry.

In a stationary, general relativistic, axisymmetric, inviscid and rotational accretion flow, described within the Kerr geometric framework, transonicity has been examined by setting up the governing equations of the flow as a first‐order autonomous dynamical system. The consequent linearized analysis of the critical points of the flow leads to a comprehensive mathematical prescription for classifying these points, showing that the only possibilities are saddle points and centre‐type points for all ranges of values of the fixed flow parameters. The spin parameter of the black hole influences the multitransonic character of the flow, as well as some of its specific critical properties. The special case of a flow in the space–time of a non‐rotating black hole, characterized by the Schwarzschild metric, has also been studied for comparison and the conclusions are compatible with what has been seen for the Kerr geometric case.

Background and Objectives Posttraumatic stress symptoms (PTSD) and problem alcohol use (ALC) commonly co-occur, but the nature of this co-occurrence is unclear. Self-medication explanations have been forwarded, yet traits such as tendency toward negative emotionality and behavioral disconstraint also have been implicated. In this study we test three competing models (self-medication, trait vulnerability, combined dual pathway) of PTSD-ALC prospectively in a college sample. Method Participants (N=659; 73% female, M age=18) provided data at college matriculation (Time 1) and one year later (Time 2). Results Structural equation models showed disconstraint to meditate the path from PTSD symptoms to alcohol problems, supporting a trait vulnerability conceptualization. Findings regarding negative emotionality and self-medication were more mixed. Negative emotionality played a stronger role in cross-sectional than in prospective analyses, suggesting the importance of temporal proximity. Conclusions and Scientific Significance Self-regulation skills may be an important focus for clinicians treating PTSD symptoms and alcohol misuse disorders concurrently.

ObjectiveNeutrophil-to-lymphocyte ratio (NLR) has prognostic value in acute coronary syndromes. We investigated its utility for predicting heart failure (HF) admissions and major adverse cardiac outcomes in patients undergoing transcatheter aortic valve replacement (TAVR).MethodsData on clinical, laboratory, procedural, HF admissions, and major adverse cardiac events (MACEs) (all-cause mortality, recurrence of myocardial infarction requiring intervention, stroke) for 298 consecutive patients who underwent TAVR between 2012 and 2016 in our tertiary center were collected.ResultsAnalysis included 298 patients. The mean age was 83 ± 8 years, 51% were males, and 95% were Caucasians. The median Society of Thoracic Surgeons risk score was 9 (interquartile range: 6.3–11.8). Receiver-operating curve analysis identified a cutoff value of NLR of 4.0 for MACE after TAVR and sensitivity of 68% and specificity of 68% {area under the curve [AUC] = 0.65 [95% confidence interval (CI): 0.51–0.79], p = 0.03}. An NLR of 4.0 for HF hospitalizations after TAVR and sensitivity of 60% and specificity of 57% [AUC = 0.61 (95% CI: 0.53–0.69), p = 0.01]. NLR ≥4.0 before TAVR significantly predicted MACE after TAVR (68.4% vs. 31.6%, p = 0.02) and HF hospitalizations (58.3% vs. 41.7%, p = 0.03). NLR with TAVR risk score increased the predictive value for MACE after TAVR from AUC = 0.61 (95% CI: 0.50–0.72, p = 0.06) to AUC = 0.69 (95% CI: 0.57–0.80, p = 0.007).ConclusionNLR predicts all-cause mortality, MACE, and HF hospitalization 1 year after TAVR. NLR with TAVR risk score improved predictability for MACE. Further studies for prognostication using NLR are warranted.

Background Increased afterload and reduced left ventricular (LV) performance are sequela of mitral valve repair. However, hemodynamic left atrial and ventricular parameters that can predict outcome following mitral valve repair remain elusive. Methods One hundred and two consecutive patients undergoing MitraClip procedure from 2014 to 2017 at Banner University Medical Center were enrolled in this study. All patients underwent pre‐procedure echocardiograms and intra‐procedure invasive left atrial (LA) pressure monitoring. Clinical, laboratory, and procedural parameters were collected. The primary end‐point was the composite outcome of all‐cause mortality and repeat hospitalization within 90 days. Results The mean age was 77 ±10 years, the majority were Caucasians (93, 91.2%) and 47 (46.1%) were males. Thirty‐two patients (31.4%) had diabetes, 39 (38.2%) had renal insufficiency, and 38 (37.3%) had a history of congestive heart failure. The median society of thoracic surgeons score was 6.7% (Interquartile range [IQR]: 3.9, 10.2). Immediately post‐procedure there was a significant reduction in the LA pressure (Mean 12.0 vs. 18.6 mmHg, P < 0.001) and pulmonary artery systolic pressure (43.5 vs. 53.2 mmHg, P = 0.001) compared to baseline. LA pressure was an independent predictor of the composite outcome in an unadjusted (OR = 1.07, 95% CI: 1.00–1.13, P = 0.03) and adjusted (OR = 1.07, 95% CI: 1.00–1.14, P = 0.03) analysis respectively. Conclusion LA pressure drop is an independent predictor of outcome after the MitraClip procedure. This finding has implications for early identification of patients at risk of poor outcomes and instituting aggressive medical therapy and close follow‐up for avoiding hospitalizations for heart failure decompensation.