Elucidating Polyphosphate Anion Binding to Lanthanide Complexes Using EXAFS and Pulsed EPR Spectroscopy.

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. To address this challenge, innovative and complementary methods to investigate host-anion binding geometry are becoming increasingly important. Herein, we demonstrate the combined use of Eu L3-edge extended X-ray absorption fine structure (EXAFS) and electron paramagnetic resonance (EPR) spectroscopy to elucidate the binding of nucleoside phosphates (ATP, ADP, and AMP) to a cationic lanthanide complex. We establish that ATP unequivocally binds the lanthanide center in a bidentate manner in water, while ADP adopts both bidentate and monodentate modes, and AMP binds in a monodentate manner. This interdisciplinary approach provides deeper insight into lanthanide host-guest chemistry in solution, laying the groundwork for designing emissive probes that undergo specific anion-induced structural changes and elicit desired optical responses upon binding.

Atomic Dispersed Co on NC@Cu Core-Shells for Solar Seawater Splitting.

With 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 µmolg-1h-1, i.e., 4.78% solar-to-hydrogen conversion efficiency, and exceptional long-term stability, operating over 340 h continuously. The superior performance is attributed to several key factors. First, the focus-light induced photothermal effect enhances redox reaction capabilities, while the salt-ions enabled charge polarization around catalyst surfaces extends charge carrier lifetime. Furthermore, the Co─NC@Cu exhibits excellent broad light absorption, promoting photoexcited charge production. Theoretical calculations reveal that Co─NC acts as the active site, showing low energy barriers for reduction reactions. Additionally, the formation of a strong surface electric field from the localized surface plasmon resonance (LSPR) of Cu nanoparticles further reduces energy barriers for redox reactions, improving seawater splitting activity. This work provides valuable insights into intergrating the reaction environment, broad solar absorption, LSPR, and active single atoms into a core-shell photocatalyst design for efficient and robust solar-driven seawater splitting.

Synthesis, Structure, and Redox Properties of Nonsymmetric 6-Oxoverdazyls.

Nonsymmetric 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. Both redox processes occur at more moderate potentials than the parent verdazyl, tuning the accessible potential windows of 6π, 7π, and 8π verdazyl species.

Proton-Coupled Electron Transfer between a Pendant Thiol and a Ferrous Dioxygen Adduct.

The mechanism of thiol oxidation by O2, as catalyzed by ferrous porphyrins, is investigated by trapping intermediates of the transformation at low temperatures and subsequently characterizing them using continuous wave and pulsed electron paramagnetic resonance and resonance Raman spectroscopy. A Fe(III)-O2•- species is initially formed in an iron porphyrin with a pendant thiol functional group, which undergoes proton-coupled electron transfer (PCET) (not HAT) to form an Fe(III)-OOH species. Following O-O bond homolysis, this forms a Fe(IV)═O species with concomitant oxidation of the thiol to an RSO3H group.

Complexes of a Noncyclic Carbazole-based N5-donor Schiff base: Structures, Redox, EPR and Poor Activity as Hydrogen Evolution Electrocatalysts.

A new noncyclic pentadentate N5-donor Schiff-base ligand, HL2Etpyr (1,1'-(3,6-ditert-butyl-9H-carbazole-1,8-diyl)bis(N-(2-(pyridin-2-yl)ethyl)methanimine)), prepared from 1,8-diformyl-3,6-ditertbutyl-carbazole (HUtBu) and two equivalents of 2-(2-pyridyl)ethylamine, along with four tetrafluoroborate complexes, [MIIL2Etpyr](BF4), where M = Co, Ni, Cu, and Zn, and two [CoIIL2EtPyr]·1/2[CoIIX4] 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. Cyclic voltammograms of [MIIL2Etpyr](BF4) in MeCN reveal reversible redox processes at positive potentials: 0.61 (Zn), 0.62 (Cu), 0.57 (Ni), and 0.25 V (Co), and for the cobalt complex a second quasi-reversible process occurs at 0.92 V vs Fc+/Fc. EPR data for the first oxidation product clearly demonstrate that the Zn complex undergoes a ligand centered oxidation, and support this being the case for the Ni and Cu complexes, although this is not definitively shown. After both oxidations the EPR data shows that the Co complex is best described as a low spin Co(III)-ligand radical. In the presence of 80 mM acetic acid, controlled potential electrolysis carried out on [MIIL2Etpyr](BF4) at -1.68 V in MeCN shows some electrocatalytic hydrogen evolution reaction (HER) performance in the order Ni(II) > Cu(II) > Co(II) - but the control, Ni(II) tetrafluoroborate, is more active than all three of the complexes.

Photonic next-generation reservoir computer based on distributed feedback in optical fiber.

Reservoir 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. In this work, we resolve these issues by demonstrating a photonic next-generation reservoir computer (NG-RC) using a fiber optic platform. Our photonic NG-RC eliminates the need for a cavity by generating feature vectors directly from nonlinear combinations of the input data with varying delays. Our approach uses Rayleigh backscattering to produce output feature vectors by an unconventional nonlinearity resulting from coherent, interferometric mixing followed by a quadratic readout. Performing linear optimization on these feature vectors, our photonic NG-RC demonstrates state-of-the-art performance for the observer (cross-prediction) task applied to the Rössler, Lorenz, and Kuramoto-Sivashinsky systems. In contrast to digital NG-RC implementations, we show that it is possible to scale to high-dimensional systems while maintaining low latency and low power consumption.

A lanthanide tag for a complementary set of pseudocontact shifts.

Pseudocontact 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.

Effect of COVID-19 Pandemic Lockdown on Emergency Medical Service Utilisation, and Percutaneous Coronary Intervention Volume-An Australian Perspective.

BACKGROUND: Acute coronary syndrome (ACS) admissions and percutaneous coronary intervention (PCI) volume declined during periods of COVID-19 lockdown internationally in 2020. The effect of lockdown on emergency medical service (EMS) utilisation, and PCI volume during the initial phase of the pandemic in Australia has not been well described. METHOD: We analysed data from the Victorian Cardiac Outcomes Registry (VCOR), a state-wide PCI registry, linked with the Ambulance Victoria EMS registry. PCI volume, 30-day major adverse cardiovascular and cerebrovascular events (MACCE; composite of mortality, myocardial infarction, stent thrombosis, unplanned revascularisation, and stroke), and EMS utilisation were compared over four time periods: lockdown (26 Mar 2020-12 May 2020); pre-lockdown (26 Feb 2020-25 Mar 2020); post-lockdown (13 May 2020-10 Jul 2020); and the year prior (26 Mar 2019-12 May 2019). Interrupted time series analysis was performed to assess PCI trends within and between consecutive periods. RESULTS: The EMS utilisation for ACS during lockdown was higher compared with other periods: lockdown 39.4% vs pre-lockdown 29.7%; vs post-lockdown 33.6%; vs year prior 27.1%; all p<0.01. Median daily PCI cases were similar: 31 (IQR 10, 38) during lockdown; 39 (15, 49) pre-lockdown; 39.5 (11, 44) post-lockdown; and, 42 (10, 49) the year prior; all p>0.05. Median door-to-procedure time for ACS indication during lockdown was shorter at 3 hours (1.2, 20.6) vs pre-lockdown 3.9 (1.7, 21); vs post-lockdown 3.5 (1.5, 21.26); and, the year prior 3.5 (1.5, 23.7); all p<0.05. Lockdown period was associated with lower odds for 30-day MACCE compared to pre-lockdown (odds ratio [OR] 0.55 [0.33-0.93]; p=0.026); post-lockdown (OR 0.66; [0.40-1.06]; p=0.087); and the year prior (OR 0.55 [0.33-0.93]; p=0.026). CONCLUSIONS: Contrary to international trends, EMS utilisation for ACS increased during lockdown but PCI volumes remained similar throughout the initial stages of the pandemic in Victoria, with no observed adverse effect on 30-day MACCE during lockdown. These data suggest that the public health response in Victoria was not associated with poorer quality cardiovascular care in patients receiving PCI.

Lawesson's Reagent: Providing a New Approach to the Forgotten 6-Thioverdazyl Radical.

A new method for the preparation of the underrepresented 1,5-dimethyl-6-thioverdazyl radicals has been developed employing Lawesson's reagent (LR). The synthetic route involves the direct thionation of the carbonyl group of the corresponding dialkylbishydrazone followed by cyclization to give the tetrazinanthione verdazyl precursor on a gram scale. Subsequent oxidation yields the 6-thioverdazyl radical. It was determined that thionation of substrates containing electron-withdrawing groups in the ortho- or para-positions was high yielding. In contrast, for the parent phenyl group or substrates bearing weakly electron-donating substituents, thionation efficiency was significantly reduced. This could be overcome by utilizing partial in situ cyclization, which occurs during work up, to generate the tetrazinanthione directly via a one-pot synthesis. Density functional theory suggests that the LR fragment interacts with the carbonyl prior to cycloaddition and subsequent to cycloreversion, leading to the thiocarbonyl. The electronic nature of the radical is characterized with electron paramagnetic resonance as well as the first report of 6-thioverdazyl redox properties.

Implementing a pharmacist-integrated collaborative model of medication treatment for opioid use disorder in primary care: study design and methodological considerations.

BACKGROUND: 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. The Consolidated Framework for Implementation Research is used as an organizing framework for study development and interpretation of findings. Implementation Facilitation is used to support PrIMO adoption. We assess the primary outcome, the feasibility of implementing PrIMO, using the Stages of Implementation Completion (SIC). We evaluate the acceptability and impact of the PrIMO model at the sites using mixed-methods and combine survey and interview data from providers, pharmacists, pharmacy technicians, administrators, and patients receiving MOUD at the primary care sites with patient electronic health record data. We hypothesize that it is feasible to launch delivery of the PrIMO model (reach SIC Stage 6), and that it is acceptable, will positively impact patient outcomes 1 year post model launch (e.g., increased MOUD treatment retention, medication regimen adherence, service utilization for co-morbid conditions, and decreased substance use), and will increase each site's capacity to care for patients with MOUD (e.g., increased number of patients, number of prescribers, and rate of patients per prescriber). DISCUSSION: This study will provide data on a pharmacist-integrated collaborative model of care for the treatment of OUD that may be feasible, acceptable to both site staff and patients and may favorably impact patients' access to MOUD and treatment outcomes. TRIAL REGISTRATION: The study was registered on Clinicaltrials.gov (NCT05310786) on April 5, 2022, https://www. CLINICALTRIALS: gov/study/NCT05310786?id=NCT05310786&rank=1.

Electrocardiographic patterns and clinical outcomes of acute coronary syndrome cardiogenic shock in patients undergoing percutaneous coronary intervention - A propensity score analysis.

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. Inverse probability of treatment weighting analysis (IPTW) was used to assess the effect of ECG changes on 30-day mortality. RESULTS: Of 1564 patients with ACS-CS who underwent PCI, 161 had non-STEMI and 1403 had STEMI on ECG. The mean age was 66 ± 13 years, and 74 % (1152) were males. Patients with non-STEMI compared to STEMI were older (70 ± 12 vs 65 ± 13 years), had higher rates of diabetes (34 % vs 21 %), prior coronary artery bypass graft surgery (14 % vs 3.3 %), peripheral arterial disease (10.6 % vs 4.1 %, p < 0.01), and lower baseline eGFR (53.8 [37.1, 75.4] vs 65.3 [46.3, 87.8] ml/min/1.73m2), all p ≤ 0.01. Non-STEMI patients were more likely to have a culprit left circumflex artery (29 % vs 20 %) and more often underwent multivessel percutaneous coronary intervention (30 % vs 20 %) but had lower rates of out-of-hospital cardiac arrest (21 % vs 39 %), all p ≤ 0.01. Propensity score analysis with IPTW confirmed that non-STEMI ECG was associated with lower odds for 30-day all-cause mortality (OR 0.47 [0.32, 0.69], p < 0.001), and 30-day major adverse cardiovascular and cerebrovascular events (OR 0.48 [0.33, 0.70]). CONCLUSIONS: In patients undergoing PCI, Non-STEMI as compared to STEMI on index ECG was associated with approximately half the relative risk of both 30-day mortality and 30-day MACCE and could be a useful variable to integrate in ACS-CS risk scores.

Assignment of the slowly exchanging substrate water of nature's water-splitting cofactor.

Identifying the two substrate water sites of nature's water-splitting cofactor (Mn4CaO5 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 S1 state of native Ca-PSII and biosynthetically substituted Sr-PSII employing Time-Resolved Membrane Inlet Mass Spectrometry (TR-MIMS) and a Time-Resolved 17O-Electron-electron Double resonance detected NMR (TR-17O-EDNMR) approach. TR-MIMS resolves the kinetics for incorporation of the oxygen-isotope label into the substrate sites after addition of H218O to the medium, while the magnetic resonance technique allows, in principle, the characterization of all exchangeable oxygen ligands of the Mn4CaO5 cofactor after mixing with H217O. This unique combination shows i) that the central oxygen bridge (O5) of Ca-PSII core complexes isolated from Thermosynechococcus vestitus has, within experimental conditions, the same rate of exchange as the slowly exchanging substrate water (WS) in the TR-MIMS experiments and ii) that the exchange rates of O5 and WS are both enhanced by Ca2+→Sr2+ substitution in a similar manner. In the context of previous TR-MIMS results, this shows that only O5 fulfills all criteria for being WS. This strongly restricts options for the mechanism of water oxidation.

Structured Weaning From the Impella Left Ventricular Micro-Axial Pump in Acute Myocardial Infarction With Cardiogenic Shock and Protected Percutaneous Coronary Intervention: Experience From a Non-Cardiac Surgical Centre.

BACKGROUND: 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. Weaning after revascularisation was titrated to native heart recovery using both haemodynamic and echocardiographic parameters. RESULTS: Ten patients (eight male, two female; aged 43-70 years) received Impella support for AMICS (80%) or protected PCI (20%). Cardiogenic shock was of Society for Cardiac Angiography & Interventions grade C-E of severity in 80%, and median left ventricular end-diastolic pressure was 31 mmHg. Protocol implementation allowed successful weaning in eight of 10 patients with a median support time of 29 hours (range, 4-48 hours). Explantation was associated with an increase in heart rate (81 vs 88 bpm; p=0.005), but no significant change in Cardiac Index (2.9 vs 2.9 L/min/m2), mean arterial pressure (79 vs 82 mmHg), vasopressor requirement (10% vs 10%), or serum lactate (1.0 vs 1.0). Median durations of intensive care and hospital stay were 3 and 6 days, respectively. At 30 days, the mortality rate was 20%, with median left ventricular ejection fraction of 40%. CONCLUSIONS: A structured and dynamic weaning protocol for patients with AMICS and protected PCI supported by the Impella device is feasible in a non-cardiac surgery centre. Larger studies are needed to assess generalisability of such a weaning protocol.

Engaging community pharmacies in practice-based research: Lessons from opioid-focused research.

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.e., patients, staff, leadership, physicians). This commentary seeks to describe these challenges and provide recommendations that can help mitigate and/or overcome these challenges. Recommendations are provided for team structure, communication, research tools/technology, motivational factors, workflow, and sustainability. These recommendations are based on the authors' experience in partnering with community pharmacy for opioid-related research in a variety of study types, states, and pharmacy environments.

Long term follow up and outcomes of Covid-19 vaccine associated myocarditis in Victoria, Australia: A clinical surveillance study.

BACKGROUND: 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. METHODS: Reports of myocarditis following COVID-19 vaccination were followed up by SAEFVIC (Surveillance of Adverse Events Following Vaccination in the Community), the state-wide vaccine safety service for Victoria, Australia. Confirmed myocarditis cases (Brighton Collaboration Criteria levels 1-3) were followed up via surveys at 1, 3 and 6 months post symptom onset. Responses received between 22 February 2021 and 30 September 2022 were analysed. RESULTS: 87.5 % (N = 182) of eligible participants completed at least 1 survey report. 377 reports were analysed. 76.9 % of completed reports were from male patients. The median age of patients was 21 years [IQR: 16 to 32]. 54.8 % (n = 74) of survey reports at 6 months, reported ongoing symptoms. At all follow-up time points, females were significantly more likely to have ongoing symptoms. At 6 months, 51.9 % of male respondents reported symptom resolution compared to 22.6 % of female patients (p = 0.002). Females were also more likely to continue medication and have ongoing exercise restrictions. However, males were significantly more likely to have higher initial peak troponin results and abnormal initial cardiac imaging investigations. CONCLUSIONS: There appears to be a significant proportion of patients who experience ongoing symptoms to 6 months post onset amongst patients that experience these AESI. Male patients were more likely to report earlier and more complete symptom recovery, despite significantly higher average initial peak troponin. This difference in phenotypic presentation in females compared to males warrants further investigation and there is a need for longer term follow up data.

A one-pot reduction route to bimetallic manganese 1,8-naphthyridine complexes.

Reaction of the dinucleating ligand 2,7-bis(6-methyl-2-pyridyl)-1,8-naphthyridine (MeL) with the MnI and MnII precursors MnBr(CO)5 and MnCl2 resulted in the formation of the monometallic complexes [MnBr(CO)3(MeL)] (1) and [MnCl2(MeL)] (3). In both cases, formation of bimetallic manganese complexes could be achieved by reduction with KC8, yielding the carbonyl-bridged complex [Mn2(CO)6(MeL)] (2) and the helicate complex [Mn2(MeL)2] (4), respectively. EPR results demonstrate that 4 represents a novel, weakly antiferromagnetically coupled homovalent dimer (J = -0.85 cm-1). The two formally Mn0 ions are both high spin (S = 3/2) and exhibit a zero-field splitting of ≈1 cm-1, suggesting reduction of the complex is substantially ligand centered, and may be better described as a MnII complex coupled to two open shell singlet ligands [MnII2(MeL2-)2]. X-ray crystallography, UV-Vis spectroscopy and DFT analysis support this finding.

Stabilization and One Electron Reduction of a Silicon Analogue of a Carboxylic Acid Anhydride.

Reaction of the 1,2-disilylenes {(DipAr Am)Si}2 (DipAr Am=[(NDip)2 CAr]- , Dip=2,6-diisopropylphenyl, Ar=4-C6 H4 But (Ar') 1 a or Ph 1 b) and two abnormal N-heterocyclic silylenes, (DipAr Am)SiOCSi{(NDip)2 CAr} (Ar=Ar' 3 a or Ph 3 b) with N2 O led to formation of unprecedented examples of uncoordinated silicon analogues of carboxylic acid anhydrides, (DipAr Am)(O=)SiOSi(=O)(DipAr 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, [{(Mes Nacnac)Mg}2 ] (Mes Nacnac=[(MesNCMe)2 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 [(Mes Nacnac)Mg{(OSi(DipAr' Am)}2 O] 5. A combination of EPR spectroscopic studies and DFT calculations reveal the unpaired electron to largely reside on one of the amidinate ligands of the complex.

Variability in Contemporary Heparin Prescription and Activated Clotting Time Monitoring During Percutaneous Coronary Intervention: Call for Up-To-Date Evidence-Based Guidelines.

BACKGROUND: 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). METHOD: We conducted an anonymous voluntary cross-sectional survey of interventional cardiologists (ICs) who were members of the Cardiac Society of Australia and New Zealand in 2022. The survey included 10 questions pertaining to the current practice of anticoagulation during PCI. RESULTS: Of 430 ICs surveyed, 148 responded (response rate, 34.4%). Most ICs (84.4%) prescribed 70-100 IU/kg of UFH for PCI. Over half of ICs (58.7%) routinely measured ACT during PCI, whereas only 22.2% routinely measured ACT after PCI to guide additional UFH prescription. Among ICs who prescribed additional UFH, approximately half (48%) aimed for ACT ≥250 seconds. Factors that influenced post-PCI UFH prescription included vascular access site and concomitant antiplatelet or anticoagulant therapy. CONCLUSIONS: The contemporary practice of UFH prescription during PCI and ACT monitoring in ANZ is variable and based on outdated evidence preceding current drug-eluting stents, antiplatelet therapies, and radial-first practice. Current society guideline recommendations lack clarity and agreement, reflecting the quality of the available evidence. Up-to-date clinical trials evaluating UFH prescription and ACT monitoring are needed to optimise clinical outcomes in contemporary PCI procedures.

Clinical Features and Outcomes Among Patients With Refractory Out-of-Hospital Cardiac Arrest and an Initial Shockable Rhythm.

BACKGROUND: 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). Refractory OHCA patients had longer cardiopulmonary resuscitation (23 versus 15 minutes), more frequently required ≥450 mg amiodarone (34% versus 3.8%), and had cardiogenic shock (80% versus 55%) necessitating higher adrenaline dose (4.0 versus 1.0 mg) and higher rates of mechanical ventilation (92% versus 74%; all P<0.01). Of 167 patients (82%) selected for coronary angiography, 33% (n=55) had refractory OHCA (P=0.035). Significant coronary artery disease (≥1 major vessel with >70% stenosis) was present in >70% of patients. Refractory OHCA patients frequently had acute coronary occlusion (64% versus 47%), especially left circumflex (20% versus 6.4%) and graft vessel (7.3% versus 0.9%; all P<0.05) compared with those without refractory OHCA. Refractory OHCA group had higher in-hospital mortality (45% versus 30%, P=0.036) and greater new requirement for dialysis (18% versus 6.3%, P=0.011). After adjustment, refractory OHCA was associated with over 2-fold higher odds of in-hospital mortality (odds ratio, 2.28 [95% CI, 1.06-4.89]; P=0.034). CONCLUSIONS: Refractory ventricular fibrillation/pulseless ventricular tachycardia OHCA was associated with more intensive resuscitation, higher rates of acute coronary occlusion, and poorer in-hospital outcomes, underscoring the need for future studies in this extreme-risk subgroup.

Defect engineering enhances plasmonic-hot electrons exploitation for CO2 reduction over polymeric catalysts.

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. These active defects, co-localized with plasmonic Ag nanoparticles, promote the utilization efficiency of hot electrons generated by local plasmons, thereby enhancing the CO2 photoreduction activity while maintaining the high catalytic selectivity.