Benzene reduction by molecular complexes remains an important synthetic challenge, requiring harsh reaction conditions involving group I metals. Reductions of benzene, to date, typically result in a loss of aromaticity, although the benzene tetra-anion, a 10π-electron system, has been calculated to be stable and aromatic. Due to the lack of sufficiently potent reductants, four-electron reduction of benzene usually requires the use of group I metals.
View Article and Find Full Text PDFObjectives: To describe myocarditis as an adverse event after coronavirus disease 2019 (COVID-19) vaccination, including a detailed description of clinical phenotypes and diagnostic test results and differences by age, sex, and degree of troponin level elevation.
Study Design: Retrospective cross-sectional study.
Setting, Participants: Cases of suspected myocarditis following the administration of a COVID-19 vaccine in Victoria during 22 February 2021 - 30 September 2022 reported to Surveillance of Adverse Events Following Vaccination In the Community (SAEFVIC), with symptom onset within 14 days of vaccination, and deemed to be confirmed myocarditis according to the Brighton Collaboration Criteria.
Reversible anion binding to lanthanide complexes in aqueous solution has emerged as an effective method for anion sensing. Through careful design of the organic ligand, luminescent lanthanide complexes capable of binding biologically relevant anions in a bidentate or monodentate manner can be realized. While single-crystal X-ray diffraction analyses and NMR spectroscopy have revealed the structural geometry of several host-guest complexes, the challenge remains in designing preorganized lanthanide receptors with enhanced anion selectivity for broader applications in diagnostics and bioimaging.
View Article and Find Full Text PDFWith freshwater resources becoming increasingly scarce, the photocatalytic seawater splitting for hydrogen production has garnered widespread attention. In this study, a novel photocatalyst consisting of a Cu core coated is introduced with N-doped C and decorated with single Co atoms (Co-NC@Cu) for solar to hydrogen production from seawater. This catalyst, without using noble metals or sacrificial agents, demonstrates superior hydrogen production effficiency of 9080 µmolgh, i.
View Article and Find Full Text PDFNonsymmetric 6π-electron ("oxidized") 6-oxoverdazyls have been synthesized for the first time. After formal incorporation of a hydrogen atom, the corresponding 7π-electron neutral verdazyl radical is generated. The 7π radical can undergo a further electrochemically reversible reduction to an 8π anion.
View Article and Find Full Text PDFA new noncyclic pentadentate N5-donor Schiff-base ligand, HL (1,1'-(3,6-di-butyl-9H-carbazole-1,8-diyl)bis(N-(2-(pyridin-2-yl)ethyl)methanimine)), prepared from 1,8-diformyl-3,6-ditertbutyl-carbazole (HU) and two equivalents of 2-(2-pyridyl)ethylamine, along with four tetrafluoroborate complexes, [ML](BF), where M = Co, Ni, Cu, and Zn, and two [CoL]·1/2[CoX] complexes where X = NCS or Cl, isolated as solvates, are reported. All six complexes were structurally characterized, revealing the cations to be isostructural, with M(II) in a trigonal bipyramidal N5-donor environment. Only the Zn(II) complex is fluorescent.
View Article and Find Full Text PDFPseudocontact shifts (PCS) generated by paramagnetic lanthanide ions deliver powerful restraints for protein structure analysis by NMR spectroscopy. We present a new lanthanide tag that generates different PCSs than that of a related tag, which differs in structure by a single oxygen atom. It is highly reactive towards cysteine and performs well in turn-on luminescence and in EPR spectroscopy.
View Article and Find Full Text PDFReservoir computing (RC) is a machine learning paradigm that excels at dynamical systems analysis. Photonic RCs, which perform implicit computation through optical interactions, have attracted increasing attention due to their potential for low latency predictions. However, most existing photonic RCs rely on a nonlinear physical cavity to implement system memory, limiting control over the memory structure and requiring long warm-up times to eliminate transients.
View Article and Find Full Text PDFBackground: Pharmacists remain an underutilized resource in the treatment of opioid use disorder (OUD). Although studies have engaged pharmacists in dispensing medications for OUD (MOUD), few studies have evaluated collaborative care models in which pharmacists are an active, integrated part of a primary care team offering OUD care.
Methods: This study seeks to implement a pharmacist integrated MOUD clinical model (called PrIMO) and evaluate its feasibility, acceptability, and impact across four diverse primary care sites.
Objectives: To determine the influence of presenting electrocardiographic (ECG) changes on prognosis in acute coronary syndrome cardiogenic shock (ACS-CS) patients undergoing percutaneous coronary angiography (PCI).
Background: The effect of initial ECG changes such as ST-elevation myocardial infarction (STEMI) versus non-STEMI among patients ACS-CS on prognosis remains unclear.
Methods: We analysed data from consecutive patients with ACS-CS enrolled in the Victorian Cardiac Outcomes registry between 2014 and 2020.
Identifying the two substrate water sites of nature's water-splitting cofactor (MnCaO cluster) provides important information toward resolving the mechanism of O-O bond formation in Photosystem II (PSII). To this end, we have performed parallel substrate water exchange experiments in the S state of native Ca-PSII and biosynthetically substituted Sr-PSII employing Time-Resolved Membrane Inlet Mass Spectrometry (TR-MIMS) and a Time-Resolved O-Electron-electron Double resonance detected NMR (TR-O-EDNMR) approach. TR-MIMS resolves the kinetics for incorporation of the oxygen-isotope label into the substrate sites after addition of HO to the medium, while the magnetic resonance technique allows, in principle, the characterization of all exchangeable oxygen ligands of the MnCaO cofactor after mixing with HO.
View Article and Find Full Text PDFBackground: The Impella (Abiomed, Danvers, MA, USA) temporary percutaneous left ventricular assist device is increasingly used as mechanical circulatory support in patients with acute myocardial infarction-cardiogenic shock (AMICS) or those undergoing high-risk protected percutaneous coronary intervention (PCI). The optimal weaning regimen remains to be defined.
Method: We implemented a structured weaning protocol in a series of 10 consecutive patients receiving Impella support for protected PCI or AMICS treated with PCI in a high volume non-cardiac surgery centre.
There is an established need to translate evidence-based practices into real-world practice. Community pharmacists and their corresponding pharmacies are well-positioned to be effective partners as researchers seek to study and implement practice-based research. Challenges exist when partnering with community pharmacies which can vary based on the study type, the nature of the community pharmacy, and stakeholder groups (i.
View Article and Find Full Text PDFBackground: Myocarditis and myopericarditis are well described adverse events of special interest (AESI) following COVID-19 vaccinations. Although reports are reassuring regarding initial clinical outcomes, information about longer term outcomes remains limited. We aimed to further this knowledge and report outcomes to 6 months post diagnosis from a single population cohort.
View Article and Find Full Text PDFReaction of the 1,2-disilylenes {( Am)Si} ( Am=[(NDip) CAr] , Dip=2,6-diisopropylphenyl, Ar=4-C H Bu (Ar') 1 a or Ph 1 b) and two abnormal N-heterocyclic silylenes, ( Am)SiOCSi{(NDip) CAr} (Ar=Ar' 3 a or Ph 3 b) with N O led to formation of unprecedented examples of uncoordinated silicon analogues of carboxylic acid anhydrides, ( Am)(O=)SiOSi(=O)( Am) (Ar=Ar' 2 a or Ph 2 b). Both compounds have been fully characterized, and the mechanism of formation of one explored using DFT calculations. Reduction of sila-acid anhydride 2 a with a dimagnesium(I) compound, [{( Nacnac)Mg} ] ( Nacnac=[(MesNCMe) CH] , Mes=mesityl), led to the one-electron reduction of the anhydride and formation of a magnesium complex of a sila-acid anhydride radical anion [( Nacnac)Mg{(OSi( Am)} O] 5.
View Article and Find Full Text PDFReaction of the dinucleating ligand 2,7-bis(6-methyl-2-pyridyl)-1,8-naphthyridine (L) with the Mn and Mn precursors MnBr(CO) and MnCl resulted in the formation of the monometallic complexes [MnBr(CO)(L)] (1) and [MnCl(L)] (3). In both cases, formation of bimetallic manganese complexes could be achieved by reduction with KC, yielding the carbonyl-bridged complex [Mn(CO)(L)] (2) and the helicate complex [Mn(L)] (4), respectively. EPR results demonstrate that 4 represents a novel, weakly antiferromagnetically coupled homovalent dimer ( = -0.
View Article and Find Full Text PDFBackground: Unfractionated heparin (UFH) is the preferred anticoagulant agent in percutaneous coronary intervention (PCI) procedures for minimising the risk of thrombotic complications. Because of the narrow therapeutic range of UFH, some society guidelines have advocated the use of the activated clotting time (ACT) test to monitor anticoagulation intensity during PCI to reduce thrombotic and bleeding complications. We aimed to assess the current practice of UFH prescription and its monitoring in Australia and New Zealand (ANZ).
View Article and Find Full Text PDFBackground: Clinical features among patients with refractory out-of-hospital cardiac arrest (OHCA) and initial shockable rhythms of ventricular fibrillation/pulseless ventricular tachycardia are not well-characterized.
Methods: We compared clinical characteristics and coronary angiographic findings between patients with refractory OHCA (incessant ventricular fibrillation/pulseless ventricular tachycardia after ≥3 direct-current shocks) and those without refractory OHCA.
Results: Between 2014 and 2018, a total of 204 patients with ventricular fibrillation/pulseless ventricular tachycardia OHCA (median age 62; males 78%) were divided into groups with (36%, 74/204) and without refractory arrest (64%, 130/204).
Defect sites present on the surface of catalysts serve a crucial role in different catalytic processes. Herein, we have investigated defect engineering within a hybrid system composed of "soft" polymer catalysts and "hard" metal nanoparticles, employing the disparity in their thermal expansions. Electron paramagnetic resonance, X-ray photoelectron spectroscopy, and mechanistic studies together reveal the formation of new abundant defects and their synergistic integrability with plasmonic enhancement within the hybrid catalyst.
View Article and Find Full Text PDFBackground: Interrelated chronic vascular diseases (chronic kidney disease (CKD), type 2 diabetes (T2D) and cardiovascular disease (CVD)) are common with high morbidity and mortality. This study aimed to assess if an electronic-technology-based quality improvement intervention in primary care could improve detection and management of people with and at risk of these diseases.
Methods: Stepped-wedge trial with practices randomised to commence intervention in one of five 16-week periods.
Aim: To describe the Heart Matters (HM) trial which aims to evaluate the effectiveness of a community heart attack education intervention in high-risk areas in Victoria, Australia. These local government areas (LGAs) have high rates of acute coronary syndrome (ACS), out-of-hospital cardiac arrest (OHCA), cardiovascular risk factors, and low rates of emergency medical service (EMS) use for ACS.
Methods: The trial follows a stepped-wedge cluster randomised design, with eight clusters (high-risk LGAs) randomly assigned to transition from control to intervention every four months.