Excited state intramolecular proton transfer (ESIPT) has been a topic of interest due to its potential to lead to multiple emissions. Although many organic molecules showing ESIPT emission are ...already known, studies on metal complexes showing ESIPT and their related theoretical understandings are very limited. In this study, we focus on Zn(hqxc)2(DMSO)2 (Zn–hqxc: hqxc = 3-hydroxy-2-quinoxalinecarboxylate, DMSO = dimethyl sulfoxide), which shows ESIPT emission in the solid state, even though the hqxcH ligand does not show ESIPT emission. To gain insights into the role of the zinc atom and the emission mechanisms, we examined excited states of free hqxcH and the Zn–hqxc complex using time-dependent density functional theory calculations. From the results, it was shown that the zinc atom triggers a structural change of the hqxcH ligand from the lactam form (3,4-dihydro-3-oxo-2-quinoxalinecarboxylic acid) to the enol form (3-hydroxy-2-quinoxalinecarboxylic acid), where the latter form has several stable excited states. Several stable geometries were found for singlet and triplet excited states, suggesting that emissions for the Zn–hqxc complex can be both phosphorescence and fluorescence caused by the enol–enol, keto–keto, and keto–enol forms of the two hqcx ligands in the complex. We found that the photophysical properties of the Zn–hqxc complex are dominated by the ligand due to the filled d10 of Zn(II). The presented results suggest that, to design new ESIPT metal complexes, one possible approach is to combine a metal atom showing ligand centered emission and a ligand that has separate ESIPT and coordination sites.
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IJS, KILJ, NUK, PNG, UL, UM
Background: Antithrombotic therapy after left atrial appendage closure (LAAC) in patients at high risk of bleeding remains controversial. We present real-world clinical outcomes of LAAC.Methods and ...Results: Data from 74 consecutive patients who received LAAC therapy between January 2020 and June 2022 were analyzed. Patients received 1 of 3 antithrombotic therapies according to the bleeding risk category or clinical event. Regimen 1 was based on a prior study, regimen 2 comprised a lower antiplatelet drug dose without dual antiplatelet therapy, and regimen 3 was antiplatelet drug administration for as long as possible to patients with uncontrollable bleeding who were required to stop anticoagulant drugs. Overall, 73 (98.6%) procedures were successful. Of them, 16 (21.9%) patients were selected for regimen 1, 46 (63.0%) for regimen 2, and 11 (15.1%) for regimen 3. Device-related thrombosis (13% vs. 0% vs. 0%, P=0.0257) only occurred with regimen 1. There was no difference in major bleeding event rates (6% vs. 2% vs. 9%, P=0.53).Conclusions: The post-LAAC antithrombotic regimen was modified without major concerns.
A stripe pattern is an aposematic or camouflage coloration often observed among various caterpillars. However, how this ecologically important pattern is formed is largely unknown. The silkworm ...dominant mutant Zebra (Ze) has a black stripe in the anterior margin of each dorsal segment. Here, fine linkage mapping of 3,135 larvae revealed a 63-kbp region responsible for the Ze locus, which contained three candidate genes, including the Toll ligand gene spätzle3 (spz-3). Both electroporation-mediated ectopic expression and RNAi analyses showed that, among candidate genes, only processed spz-3 induced melanin pigmentation and that Toll-8 was the candidate receptor gene of spz-3. This Toll ligand/receptor set is also involved in melanization of other mutant Striped (pS
), which has broader stripes. Additional knockdown of 5 other spz family and 10 Toll-related genes caused no drastic change in the pigmentation of either mutant, suggesting that only spz-3/Toll-8 is mainly involved in the melanization process rather than pattern formation. The downstream pigmentation gene yellow was specifically upregulated in the striped region of the Ze mutant, but spz-3 showed no such region-specific expression. Toll signaling pathways are known to be involved in innate immunity, dorsoventral axis formation, and neurotrophic functions. This study provides direct evidence that a Toll signaling pathway is co-opted to control the melanization process and adaptive striped pattern formation in caterpillars.
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BFBNIB, NMLJ, NUK, PNG, SAZU, UL, UM, UPUK
Torsade de Pointes (TdP) can be triggered by a pacing spike on the T-wave, due to pacemaker undersensing. However, it is not widely known that this phenomenon can occur even during pacemaker ...implantation. An 84-year-old woman underwent pacemaker implantation for the treatment of a complete atrioventricular block with dyspnea. During the procedure, immediately following ventricular lead insertion and before torque wrench tightening, TdP was observed. Ventricular pacing was initiated by inserting the lead into the header of the generator; however, sensing remained unstable. T-waves associated with undersensed PVCs and ventricular pacing occurred simultaneously, resulting in a spike on the T-wave and TdP.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
Background
Vasospastic angina (VSA) reportedly accounts for one form of sudden cardiac arrest (SCA). Intracoronary acetylcholine (ACh) testing is useful for diagnosing VSA although invasive ...provocation testing after SCA is a clinical challenge. In addition, even if the ACh test is positive, any causal relationship between VSA and SCA is often unclear because patients with VSA may have other underlying cardiac disorders.
Methods
A total of 20 patients without overt structural heart disease who had been fully resuscitated from SCA were included. All patients underwent the ACh provocation test and scrutiny such as cardiac computed tomography or magnetic resonance imaging. Patients were followed up for all-cause death or recurrent SCA including appropriate implantable cardioverter defibrillator therapy.
Results
An ACh provocation test was performed 20 ± 17 days after cardiac arrest. Fifteen out of 20 (75.0%) patients had a positive ACh test and 2 (10.0%) had adverse events such as ventricular tachycardia and transient cardiogenic shock during the test. In patients with a positive ACh test, 6 of 15 (40.0%) patients had other overlapping cardiac disorders such as long QT syndrome, Brugada syndrome, cardiac sarcoidosis, myocarditis, or cardiomyopathy. Long-term prognosis was not different regardless of a positive ACh test or the presence of other cardiac disorders overlapping with VSA.
Conclusions
Three-quarters of the patients who had been resuscitated from SCA had a positive ACh test. Further examinations revealed other overlapping cardiac disorders in addition to VSA in 40% of patients with a positive ACh test.
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EMUNI, FIS, FZAB, GEOZS, GIS, IJS, IMTLJ, KILJ, KISLJ, MFDPS, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, SBMB, SBNM, UKNU, UL, UM, UPUK, VKSCE, ZAGLJ
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