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We report a facile and low temperature synthesis of Ga- and In-doped CdS nanoparticles from molecular precursors. Diethyldithiocarbamate complexes of Cd(II), Ga(III), and In(III), were synthesised and decomposed in tandem through solventless thermolysis, producing Ga- or In-doped CdS. The resultant M x Cd 1- x S 1+0.5 x (where M = Ga/In at x values of 0, 0.02, 0.04, 0.06, 0.08 and 0.1) particulate powder was analysed by powder X-ray diffraction, which showed that both Ga (through all doping levels) and In (at doping levels <8 mol%) were successfully incorporated into the hexagonal CdS lattice without any impurities. Raman spectroscopy also showed no significant change from CdS. Scanning electron microscopy and energy dispersive X-ray spectroscopy were used to investigate the morphology and elemental dispersion through the doped CdS materials, showing homogenous incorporation of dopant. The optical and luminescent properties of the doped M x Cd 1- x S 1+0.5 x materials were examined by UV-Vis absorption and photoluminescence spectroscopies respectively. All materials were found to exhibit excitonic emission, corresponding to band gap energies between 2.7 and 2.9 eV and surface defect induced emission which is more prominent for Ga than for In doping. Additionally, moderate doping slows down charge carrier recombination by increasing the lifetimes of excitonic and surface state emissions, but particularly for the latter process.

Metal-Organic Framework (MOF)-derived TiO 2 , synthesised through the calcination of MIL-125-NH 2 , is investigated for its potential as a CO 2 photoreduction catalyst. The effect of the reaction parameters: irradiance, temperature and partial pressure of water was investigated. Using a two-level design of experiments, we were able to evaluate the influence of each parameter and their potential interactions on the reaction products, specifically the production of CO and CH 4 . It was found that, for the explored range, the only statistically significant parameter is temperature, with an increase in temperature being correlated to enhanced production of both CO and CH 4 . Over the range of experimental settings explored, the MOF-derived TiO 2 displays high selectivity towards CO (98%), with only a small amount of CH 4 (2%) being produced. This is notable when compared to other state-of-the-art TiO 2 based CO 2 photoreduction catalysts, which often showcase lower selectivity. The MOF-derived TiO 2 was found to have a peak production rate of 8.9 × 10 -4 μmol cm -2 h -1 (2.6 μmol g -1 h -1 ) and 2.6 × 10 -5 μmol cm -2 h -1 (0.10 μmol g -1 h -1 ) for CO and CH 4 , respectively. A comparison is made to commercial TiO 2 , P25 (Degussa), which was shown to have a similar activity towards CO production, 3.4 × 10 -3 μmol cm -2 h -1 (5.9 μmol g -1 h -1 ), but a lower selectivity preference for CO (3 : 1 CH 4  : CO) than the MOF-derived TiO 2 material developed here. This paper showcases the potential for MIL-125-NH 2 derived TiO 2 to be further developed as a highly selective CO 2 photoreduction catalyst for CO production., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Background/purpose: Matching phasic pressure tracings between a fluid-filled catheter and high-fidelity pressure wire has received limited attention, although each part contributes half of the information to clinical decisions. We aimed to study the impact of a novel and automated method for improving the phasic calibration of a fluid-filled catheter by accounting for its oscillatory behavior., Methods/materials: Retrospective analysis of drift check tracings was performed using our algorithm that corrects for mean difference (offset), temporal delays (timing), differential sensitivity of the manifold transducer and pressure wire sensor (gain), and the oscillatory behavior of the fluid-filled catheter described by its resonant frequency and damping factor (how quickly oscillations disappear after a change in pressure)., Results: Among 2886 cases, correcting for oscillations showed a large improvement in 28 % and a medium improvement in 41 % (decrease in root mean square error >0.5 mmHg to <1 or 1-2 mmHg, respectively). 96 % of oscillators were underdamped with median damping factor 0.27 and frequency 10.6 Hz. Fractional flow reserve or baseline Pd/Pa demonstrated no clinically important bias when ignoring oscillations. However, uncorrected subcycle non-hyperemic pressure ratios (NHPR) displayed both bias and scatter., Conclusions: By automatically accounting for the oscillatory behavior of a fluid-filled catheter system, phasic matching against a high-fidelity pressure wire can be improved compared to standard equalization methods. The majority of tracings contain artifacts, mainly due to underdamped oscillations, and neglecting them leads to biased estimates of equalization parameters. No clinically important bias exists for whole-cycle metrics, in contrast to significant effects on subcycle NHPR., (Copyright © 2022 The Authors. Published by Elsevier Inc. All rights reserved.)

Background: An increase in fractional flow reserve (FFR) after percutaneous coronary intervention (PCI) is associated with improvement in angina. Coronary artery disease (CAD) patterns (focal vs diffuse) influence the FFR change after stenting and may predict angina relief., Objectives: The aim of this study was to investigate the differential improvement in patient-reported outcomes after PCI in focal and diffuse CAD as defined by the pullback pressure gradient (PPG)., Methods: This is a subanalysis of the TARGET-FFR (Trial of Angiography vs. pressure-Ratio-Guided Enhancement Techniques-Fractional Flow Reserve) randomized clinical trial. The 7-item Seattle Angina Questionnaire (SAQ-7) was administered at baseline and 3 months after PCI. The PPG index was calculated from manual pre-PCI FFR pullbacks. The median PPG value was used to define focal and diffuse CAD. Residual angina was defined as an SAQ-7 score <100., Results: A total of 103 patients were analyzed. There were no differences in the baseline characteristics between patients with focal and diffuse CAD. Focal disease had larger increases in FFR after PCI than patients with diffuse disease (0.30 ± 0.14 vs 0.19 ± 0.12; P < 0.001). Patients with focal disease who underwent PCI for focal CAD had significantly higher SAQ-7 summary scores at follow-up than those with diffuse CAD (87.1 ± 20.3 vs 75.6 ± 24.4; mean difference = 11.5 [95% CI: 2.8-20.3]; P = 0.01). After PCI, residual angina was present in 39.8% but was significantly less in those with treated focal CAD (27.5% vs 51.9%; P = 0.020)., Conclusions: Residual angina after PCI was almost twice as common in patients with a low PPG (diffuse disease), whereas patients with a high PPG (focal disease) reported greater improvement in angina and quality of life. The baseline pattern of CAD can predict the likelihood of angina relief. (Trial of Angiography vs. pressure-Ratio-Guided Enhancement Techniques-Fractional Flow Reserve [TARGET-FFR]; NCT03259815)., Competing Interests: Funding Support and Author Disclosures Dr Collet has received research grants from Biosensor, Coroventis Research, Medis Medical Imaging, Pie Medical Imaging, CathWorks, Boston Scientific, Siemens, HeartFlow, and Abbott Vascular; and has received consultancy fees from HeartFlow, OpSens, Abbott Vascular, and Philips Volcano. Dr Collison has received consultancy and speaker fees from Abbott. Dr Munhoz has received research grants provided by the Cardiopath PhD program. Dr Berry is employed by the University of Glasgow, which holds consultancy and research agreements for his work with Abbott Vascular, AstraZeneca, Auxilius Pharma, Boehringer Ingelheim, Causeway Therapeutics, Coroventis, Genentech, GlaxoSmithKline, HeartFlow, Menarini, Neovasc, Siemens Healthcare, and Valo Health; and has received research funding from the British Heart Foundation grant (RE/18/6134217) and EPSRC (EP/R511705/1, EP/S030875/1). Dr De Bruyne has received consultancy fees from Boston Scientific and Abbott Vascular; has received research grants from Coroventis Research, Pie Medical Imaging, CathWorks, Boston Scientific, Siemens, HeartFlow, and Abbott Vascular; and owns equity in Siemens, GE, Philips, HeartFlow, Edwards Life Sciences, Bayer, Sanofi, and Celyad. Dr Oldroyd is an employee of Biosensors International. All other authors have reported that they have no relationships relevant to the contents of this paper to disclose., (Copyright © 2022 The Authors. Published by Elsevier Inc. All rights reserved.)

Addition of 1,4,8,11-tetrazacyclotetradecane (cyclam) to a reaction that produces octametallic rings when simpler amines are used, produces {Cr 11 M 2 } "pretzels" (M = Zn II or Cu II ) where the cyclam coordinates to the M II ion which then sits at the centre of a twelve-metal macrocycle. Magnetic studies were fitted using the finite-temperature Lanczos method (FTLM), and the results demonstrate that exchange interactions are transferable from previous exchange-coupled Cr III rings.

Dipolar coupled multi-spin systems have the potential to be used as molecular qubits. Herein we report the synthesis of a molecular multi-qubit model system with three individually addressable, weakly interacting, spin 1 / 2 ${{ 1/2 }}$ centres of differing g-values. We use pulsed Electron Paramagnetic Resonance (EPR) techniques to characterise and separately address the individual electron spin qubits; Cu II , Cr 7 Ni ring and a nitroxide, to determine the strength of the inter-qubit dipolar interaction. Orientation selective Relaxation-Induced Dipolar Modulation Enhancement (os-RIDME) detecting across the Cu II spectrum revealed a strongly correlated Cu II -Cr 7 Ni ring relationship; detecting on the nitroxide resonance measured both the nitroxide and Cu II or nitroxide and Cr 7 Ni ring correlations, with switchability of the interaction based on differing relaxation dynamics, indicating a handle for implementing EPR-based quantum information processing (QIP) algorithms., (© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

ELDOR-detected nuclear magnetic resonance (EDNMR) spectral simulations combined with broken-symmetry density functional theory (BS-DFT) calculations are used to obtain and to assign the 55 Mn hyperfine coupling constants (hfcs) for modified forms of the water oxidizing complex in the penultimate S 3 state of the water oxidation cycle. The study shows that an open cubane form of the core Mn 4 CaO 6 cluster explains the magnetic properties of the dominant S = 3 species in all cases studied experimentally with no need to invoke a closed cubane intermediate possessing a distorted pentacoordinate Mn 4 ion as recently suggested. EDNMR simulations found that both the experimental bandwidth and multinuclear transitions may alter relative EDNMR peak intensities, potentially leading to incorrect assignment of hfcs. The implications of these findings for the water oxidation mechanism are discussed., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Background: In collaboration with its partners, the Ethiopian government has been implementing standard Emergency Obstetric and Neonatal Care Services (CEmONC) since 2010. However, limited studies documented the lessons learned from such programs on the availability of CEmONC signal functions. This study investigated the availability of CEmONC signal functions and described lessons learned from Transform Health support in Developing Regional State in Ethiopia., Method: At baseline, we conducted a cross-sectional study covering 15 public hospitals in four developing regions of Ethiopia (Somali, Afar, Beneshangul Gumz, and Gambella). Then, clinical mentorship was introduced in ten selected hospitals. This was followed by reviewing the clinical mentorship program report implemented in all regions. We used the tool adapted from an Averting Maternal Death and Disability tools to collect data through face-to-face interviews. We also reviewed maternal and neonatal records. We then descriptively analyzed the data and presented the findings using text, tables, and graphs., Result: At baseline, six out of the 15 hospitals performed all the nine CEmONC signal functions, and one-third of the signal functions were performed in all hospitals. Cesarean Section service was available in eleven hospitals, while blood transfusion was available in ten hospitals. The least performed signal functions were blood transfusion, Cesarean Section, manual removal of placenta, removal of retained product of conceptus, and parenteral anticonvulsants. After implementing the clinical mentorship program, all CEmONC signal functions were available in all hospitals selected for the mentorship program except for Abala Hospital; the number of Cesarean Sections increased by 7.25% at the last quarter of 2021compared to the third quarter of 20,219; and the number of women referred for blood transfusions and further management of obstetric complications decreased by 96.67% at the last quarter of 2021 compared to the third quarter of 20,219. However, the number of women with post-cesarean Section surgical site infection, obstetric complications, facility maternal deaths, neonatal deaths, and stillbirths have not been changed., Conclusion: The availability of CEmONC signal functions in the supported hospitals did not change the occurrence of maternal death and stillbirth. This indicates the need for investigating underlying and proximal factors that contributed to maternal death and stillbirth in the Developing Regional State of Ethiopia. In addition, there is also the need to assess the quality of the CEmONC services in the supported hospitals, institutionalize reviews, surveillance, and response mechanism for maternal and perinatal or neonatal deaths and near misses., (© 2022. The Author(s).)

Ethiopia has adopted the Integrated Community Case Management of Newborn and Child Illness (iCMNCI) strategy to expand access to neonatal and child health services. This study assessed compliance with the iCMNCI case management protocol at the primary care settings. A descriptive cross-sectional assessment was conducted in eight districts of Benishangul-Gumuz Region from April to December 2019, and 1,217 sick children aged 2 to 59 months and 43 sick young infants aged 0 to 2 months who sought clinical consultation at the 236 health posts were selected purposively. Trained supervisors reviewed the medical records of two most recent cases from each illness category to quantify the extent to which health workers correctly assessed, classified, treated, and followed up cases per the iCMNCI guidelines. A total of 32,981 children sought clinical consultation of whom 31,830 (96.5%) were aged 2 to 59 months, and 1,151 (3.5%) were young infants aged 0 to 2 months. Of the 1,217 selected children, 426 (35%) had pneumonia, 287 (23.6%) malaria, 501 (41.2%) diarrhea, and 3 (0.2%) had malnutrition. Nearly two-thirds 306 (72%) of pneumonia cases were correctly classified as having had the disease and 297 (70%) were correctly treated for pneumonia; 213 (74%) were correctly classified as having had malaria and 210 (73%) were correctly treated for malaria; and 393 (78%) were correctly classified as having had diarrhea and 297 (59%) were correctly treated for diarrhea. Generally, the current practices of child illness assessment, classification, and treatment have deviated from iCMNCI guidelines. Future interventions should support frontline health workers to comply strictly with case management protocols through training, mentorship, and supervision.

Background The objective of the GNOCCI (Glasgow Natural History Study of Covered Stent Coronary Interventions) Study was to report the incidence and outcomes of coronary artery perforations over an 18-year period at a single, high-volume percutaneous coronary intervention center. We considered both the temporal trends and long-term outcomes of covered stent deployment. Methods and Results We evaluated procedural and long-term clinical outcomes following coronary perforation in a cohort of 43,343 consecutive percutaneous coronary intervention procedures. Procedural major adverse cardiac events were defined as a composite of death, myocardial infarction, stroke, target vessel revascularization, or cardiac surgery within 24 hours. A total of 161 (0.37%) procedures were complicated by coronary perforation of which 57 (35%) were Ellis grade III. Incidence increased with time over the study period ( r =0.73; P <0.001). Perforation severity was linearly associated with procedural mortality (median 2.9-year follow-up): Ellis I (0%), Ellis II (1.7%), Ellis III/IIIB (21%), P <0.001. Procedural major adverse cardiac events occurred in 47% of patients with Ellis III/IIIB versus 13.5% of those with Ellis I/II perforations (odds ratio, 5.8; 95% CI, 2.7-12.5; P <0.001). Covered stents were associated with an increased risk of stent thrombosis at 2.9-year follow-up (Academic Research Consortium definite or probable; 9.1% versus 0.9%; risk ratio, 10.5; 95% CI, 1.1-97; P =0.04). Conclusions The incidence of coronary perforation increased between 2001 and 2019. Severe perforation was associated with higher procedural major adverse cardiac events and was an independent predictor of long-term mortality. Although covered stents are a potentially lifesaving treatment, the generation of devices used during the study period was limited by their efficacy and high risk of stent thrombosis. Registration Information Clinicaltrials.gov. Identifier: NCT03862352.

Coronary perforation is a potentially life-threatening complication of percutaneous coronary intervention (PCI). We studied incidence, outcomes and temporal trends following PCI-related coronary artery perforation (CAP)., Methods: Prospective systematic review and meta-analysis including meta-regression using MEDLINE and EMBASE to November 2020. We included 'all-comer' PCI cohorts including large PCI registries and randomised controlled trials and excluding registries or trials limited to PCI in high-risk populations such as chronic total occlusion PCI or cohorts treated only with atheroablative devices. Regression analysis and corresponding correlation coefficients were performed comparing perforation incidence, mortality rate, tamponade rate and the rate of Ellis III perforations against the midpoint (year) of data collection to determine if a significant temporal relationship was present., Results: 3997 studies were screened for inclusion. 67 studies met eligibility criteria with a total of 5 568 191 PCIs included over a 38-year period (1982-2020). The overall pooled incidence of perforation was 0.39% (95% CI 0.34% to 0.45%) and remained similar throughout the study period. Around 1 in 5 coronary perforations led to tamponade (21.1%). Ellis III perforations are increasing in frequency and account for 43% of all perforations. Perforation mortality has trended lower over the years (7.5%; 95% CI 6.7% to 8.4%). Perforation risk factors derived using meta-regression were female sex, hypertension, chronic kidney disease and previous coronary bypass grafting. Coronary perforation was most frequently caused by distal wire exit (37%) followed by balloon dilation catheters (28%). Covered stents were used to treat 25% of perforations, with emergency cardiac surgery needed in 17%., Conclusion: Coronary perforation complicates approximately 1 in 250 PCIs. Ellis III perforations are increasing in incidence although it is unclear whether this is due to reporting bias. Despite this, the overall perforation mortality rate (7.5%) has trended lower in recent years. Limitations of our findings include bias that may be introduced through analysis of multidesign studies and registries without pre-specified standardised perforation reporting CMore research into coronary perforation management including the optimal use of covered stents seems warranted., Prospero Registration Number: CRD42020207881., Competing Interests: Competing interests: None declared., (© Author(s) (or their employer(s)) 2022. Re-use permitted under CC BY-NC. No commercial re-use. See rights and permissions. Published by BMJ.)

Importance: Fractional flow reserve (FFR) after percutaneous coronary intervention (PCI) is generally considered to reflect residual disease. Yet the clinical relevance of post-PCI FFR after drug-eluting stent (DES) implantation remains unclear., Objective: To evaluate the clinical relevance of post-PCI FFR measurement after DES implantation., Data Sources: MEDLINE, Embase, and the Cochrane Central Register of Controlled Trials were searched for relevant published articles from inception to June 18, 2022., Study Selection: Published articles that reported post-PCI FFR after DES implantation and its association with clinical outcomes were included., Data Extraction and Synthesis: Patient-level data were collected from the corresponding authors of 17 cohorts using a standardized spreadsheet. Meta-estimates for primary and secondary outcomes were analyzed per patient and using mixed-effects Cox proportional hazard regression with registry identifiers included as a random effect. All processes followed the Preferred Reporting Items for Systematic Review and Meta-analysis of Individual Participant Data., Main Outcomes and Measures: The primary outcome was target vessel failure (TVF) at 2 years, a composite of cardiac death, target vessel myocardial infarction (TVMI), and target vessel revascularization (TVR). The secondary outcome was a composite of cardiac death or TVMI at 2 years., Results: Of 2268 articles identified, 29 studies met selection criteria. Of these, 28 articles from 17 cohorts provided data, including a total of 5277 patients with 5869 vessels who underwent FFR measurement after DES implantation. Mean (SD) age was 64.4 (10.1) years and 4141 patients (78.5%) were men. Median (IQR) post-PCI FFR was 0.89 (0.84-0.94) and 690 vessels (11.8%) had a post-PCI FFR of 0.80 or below. The cumulative incidence of TVF was 340 patients (7.2%), with cardiac death or TVMI occurring in 111 patients (2.4%) at 2 years. Lower post-PCI FFR significantly increased the risk of TVF (adjusted hazard ratio [HR] per 0.01 FFR decrease, 1.04; 95% CI, 1.02-1.05; P < .001). The risk of cardiac death or MI also increased inversely with post-PCI FFR (adjusted HR, 1.03; 95% CI, 1.00-1.07, P = .049). These associations were consistent regardless of age, sex, the presence of hypertension or diabetes, and clinical diagnosis., Conclusions and Relevance: Reduced FFR after DES implantation was common and associated with the risks of TVF and of cardiac death or TVMI. These results indicate the prognostic value of post-PCI physiologic assessment after DES implantation.

Polymer beads have been used as the core of magnetic particles for around twenty years. Here we report studies to attach polymetallic complexes to polymer beads for the first time, producing beads of around 115 microns diameter that are attached to 10 14 hybrid inorganic-organic [2]rotaxanes. The bead is then formally a [10 14 ] rotaxane. The number of complexes attached is counted by EPR spectroscopy after including TEMPO radicals within the thread of the hybrid [2]rotaxanes., (© 2022. The Author(s).)

Aims: A fractional flow reserve (FFR) value ≥0.90 after percutaneous coronary intervention (PCI) is associated with a reduced risk of adverse cardiovascular events. TARGET-FFR is an investigator-initiated, single-centre, randomized controlled trial to determine the feasibility and efficacy of a post-PCI FFR-guided optimization strategy vs. standard coronary angiography in achieving final post-PCI FFR values ≥0.90., Methods and Results: After angiographically guided PCI, patients were randomized 1:1 to receive a physiology-guided incremental optimization strategy (PIOS) or a blinded coronary physiology assessment (control group). The primary outcome was the proportion of patients with a final post-PCI FFR ≥0.90. Final FFR ≤0.80 was a prioritized secondary outcome. A total of 260 patients were randomized (131 to PIOS, 129 to control) and 68.1% of patients had an initial post-PCI FFR <0.90. In the PIOS group, 30.5% underwent further intervention (stent post-dilation and/or additional stenting). There was no significant difference in the primary endpoint of the proportion of patients with final post-PCI FFR ≥0.90 between groups (PIOS minus control 10%, 95% confidence interval -1.84 to 21.91, P = 0.099). The proportion of patients with a final FFR ≤0.80 was significantly reduced when compared with the angiography-guided control group (-11.2%, 95% confidence interval -21.87 to -0.35], P = 0.045)., Conclusion: Over two-thirds of patients had a physiologically suboptimal result after angiography-guided PCI. An FFR-guided optimization strategy did not significantly increase the proportion of patients with a final FFR ≥0.90, but did reduce the proportion of patients with a final FFR ≤0.80., (© The Author(s) 2021. Published by Oxford University Press on behalf of the European Society of Cardiology.)

A family of heterometallic rings [Me 4 N] 2 [Cr III 6 M II 2 F 8 (O 2 C t Bu) 16 ] is reported using tetramethylammonium hydroxide pentahydrate as the source of a template, where M = Zn, Mn, Ni, and Co. The metal cores are octagons with metal-metal edges bridged by one fluoride and two carboxylate ligands. The divalent metal ions are found ordered at positions 1 and 5 in the octagon. The tetramethylammonium cations are above and below the metal plane of the ring in the crystal structure. Magnetic studies show antiferromagnetic coupling between the paramagnetic metal ions present, leading to paramagnetic ground states in each case. 1 H NMR spectroscopy confirms that the structure of the {Cr III 6 Co II 2 } ring exists in solution, and electron paramagnetic resonance spectroscopy confirms the magnetic structure of the other three rings.

Electroactive metal-organic frameworks (MOFs) are an attractive class of materials owing to their multifunctional 3-dimensional structures, the properties of which can be modulated by changing the redox states of the components. In order to realise both fundamental and applied goals for these materials, a deeper understanding of the structure-function relationships that govern the charge transfer mechanisms is required. Chemical or electrochemical reduction of the framework [Zn(BPPFTzTz)(tdc)]·2DMF, hereafter denoted ZnFTzTz (where BPPFTzTz = 2,5-bis(3-fluoro-4-(pyridin-4-yl)phenyl)thiazolo[5,4- d ]thiazole), generates mixed-valence states with optical signatures indicative of through-space intervalence charge transfer (IVCT) between the cofacially stacked ligands. Fluorination of the TzTz ligands influences the IVCT band parameters relative to the unsubstituted parent system, as revealed through Marcus-Hush theory analysis and single crystal UV-Vis spectroscopy. Using a combined experimental, theoretical and density functional theory (DFT) analysis, important insights into the effects of structural modifications, such as ligand substitution, on the degree of electronic coupling and rate of electron transfer have been obtained.

Manganese(II) xanthate complexes of the form [Mn(S 2 COR) 2 (TMEDA)], where TMEDA = tetramethylethylenediamine and R = methyl ( 1 ), ethyl ( 2 ), n -propyl ( 3 ), n -butyl ( 4 ), n -pentyl ( 5 ), n -hexyl ( 6 ), and n -octyl ( 7 ), have been synthesized and structures elucidated using single-crystal X-ray diffraction. Complexes 1 - 7 were used as molecular precursors to synthesize manganese sulfide (MnS). Olelyamine-capped nanocrystals have been produced via hot injection, while the doctor blading followed by thermolysis yielded thick films. Free-standing polycrystalline powders of MnS are produced by direct thermolysis of precursor powders. All thermolysis techniques produced cubic MnS, as confirmed by powder X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and Raman spectroscopy. Magnetic measurements reveal that the α-MnS nanocrystals exhibit ferromagnetic behavior with a large coercive field strength ( e.g., 0.723 kOe for 6.8 nm nanocrystals)., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

Aim: Coronary angiography is indicated in many patients with known or suspected angina for the investigation of coronary artery disease (CAD). However, up to half of patients with symptoms of ischaemia have no obstructive coronary arteries (INOCA). This large subgroup includes patients with suspected microvascular angina (MVA) and/or vasospastic angina (VSA). Clinical guidelines relating to the management of patients with INOCA are limited. Uncertainty regarding the diagnosis of patients with INOCA presents a health economic challenge, both in terms of healthcare resource utilisation and of quality-of-life impact on patients., Methods: A cost-effectiveness analysis of the introduction of stratified medicine into the invasive management of INOCA, based on clinical and resource-use data obtained in the CorMicA trial, from a UK NHS perspective. The intervention included an invasive diagnostic procedure (IDP) of coronary vascular function during coronary angiography to define clinical endotypes to target with linked medical therapy. Outcomes of interest were mean total cost and QALY gain between treatment groups, and the incremental cost-effectiveness ratio. We undertook probabilistic sensitivity and scenario analyses., Results: The incremental cost per QALY gained at 12 months was £4500 (£2937, £33264). Compared with a willingness-to-pay (WTP) threshold of £20,000 per QALY, the use of the IDP test is cost-effective. At this WTP threshold there is a 96% probability of the IDP being cost-effective, based on the uncertainty described by bootstrap analysis., Conclusions: The burden of INOCA, particularly in women, is known to be significant. These findings provided new evidence to inform this unmet clinical need., Competing Interests: Declaration of competing interest A.B., B.S., R.G., H.E., A.S., M.M.L., S.H., E.Y., R.McD. have no relevant disclosures. C·B. is employed by the University of Glasgow which holds consultancy and research agreements with Abbott Vascular, AstraZeneca, Boehringer Ingelheim, Coroventis, GSK, HeartFlow, Menarini, Neovasc, and Siemens Healthcare. K.G.O. has received consultant and speaker fees from Abbott Vascular and Boston Scientific. He is employed by Biosensors. S.W. has received consultant and speaker fees from Boston Scientific. P.R. has received consultant and speaker fees from Astra Zeneca. K.R has received educational support from Abbott Vascular and speaker fees from Astra Zeneca. RMT has acted as an advisor for Novartis. MME has a proctoring agreement with Boston Scientific and Vascular Perspectives. T.F. and DC have received speakers fees from Abbott Vascular., (Copyright © 2021 The Author(s). Published by Elsevier B.V. All rights reserved.)

This work investigates tuning of the molecular structure of a series of O-alkylxanthato zinc and cadmium precursor complexes to enhance production of ZnS and CdS materials. The structures of several bis(O-alkylxanthato) cadmium(II) complexes ( 8 - 13 ) and bis(O-alkyl xanthato)zinc(II) complexes ( 18 and 19 ) are reported based on single crystal X-ray diffraction data. CdS and ZnS films were produced by the spin-coating of these metal complexes followed by their thermal decomposition to the corresponding metal sulfides. Thin films of CdS were deposited by spin-coating the bis(O-alkylxanthato) cadmium(II) precursors ( 7 - 13 ) on glass substrates, followed by annealing at 300 °C for 60 min. Thin films of ZnS were deposited by spin-coating bis(O-alkylxanthato) zinc(II) ( 14 - 20 ), followed by annealing at 200 °C for 60 min. The molecular complexes and solid state materials are characterized using a range of techniques including single-crystal X-ray diffraction, pXRD, EDS and XPS, DSC and TGA, UV-vis and PL spectroscopies, and electron microscopy. These techniques provided information on the influence of alkyl chain length on the thermal conditions required to fabricate metal sulfide films as well as film properties such as film quality, and morphology. For example, the obtained crystallite size of metal sulfide films formed is correlated to the hydrocarbon chain length of xanthate ligands in the precursor. The behavior of the complexes under thermal stress was therefore studied in detail. DTA and TGA profiles explain the relationship between hydrocarbon chain length, decomposition temperatures, and the energies required for decomposition. A higher decomposition temperature for complexes with longer hydrocarbon chains is observed compared to complexes with shorter hydrocarbon chains. Band-gap energies calculated from the optical absorption spectra alongside steady state and time-resolved photoluminescence studies are reported for CdS films.

A finite chain of thirty-one paramagnetic centers is reported, synthesized by reaction of hydrated chromium fluoride, copper carbonate and pivalic acid in the presence of 1,4,7,10-tetrazacyclododecane (cyclen). Magnetic studies show predominantly anti-ferromagnetic exchange leading to a high density of low-lying spin states and large saturation field., (© 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Gold(i) bridged dimeric and trimeric structures of a ground state spin S = 1/2 heterometallic {Cr 7 Ni} wheel have been prepared and studied by continuous wave (CW) and pulsed wave EPR spectrometry. The {Cr 7 Ni} relaxation time constants (T 1 and T m ) show rates matching well with previous observations. Four pulse Double Electron Resonance (DEER) studies suggest presence of more than one conformations. Small Angle X-ray Scattering (SAXS) in conjunction with Molecular Dynamic (MD) Simulations were performed to look at the possible conformations in solution. In line with DEER results, simulation data further indicated more flexible molecular geometry in solution than the one in solid state.

We report the development of in situ ( online ) EPR and coupled EPR/NMR methods to study redox flow batteries, which are applied here to investigate the redox-active electrolyte, 2,6-dihydroxyanthraquinone (DHAQ). The radical anion, DHAQ 3-• , formed as a reaction intermediate during the reduction of DHAQ 2- , was detected and its concentration quantified during electrochemical cycling. The fraction of the radical anions was found to be concentration-dependent, the fraction decreasing as the total concentration of DHAQ increases, which we interpret in terms of a competing dimer formation mechanism. Coupling the two techniques-EPR and NMR-enables the rate constant for the electron transfer between DHAQ 3-• and DHAQ 4- anions to be determined. We quantify the concentration changes of DHAQ during the "high-voltage" hold by NMR spectroscopy and correlate it quantitatively to the capacity fade of the battery. The decomposition products, 2,6-dihydroxyanthrone and 2,6-dihydroxyanthranol, were identified during this hold; they were shown to undergo subsequent irreversible electrochemical oxidation reaction at 0.7 V, so that they no longer participate in the subsequent electrochemistry of the battery when operated in the standard voltage window of the cell. The decomposition reaction rate was found to be concentration-dependent, with a faster rate being observed at higher concentrations. Taking advantage of the inherent flow properties of the system, this work demonstrates the possibility of multi-modal in situ ( online ) characterizations of redox flow batteries, the characterization techniques being applicable to a range of electrochemical flow systems.

Background: The index of microcirculatory resistance (IMR) of the infarct-related artery and left ventricular end-diastolic pressure (LVEDP) are acute, prognostic biomarkers in patients undergoing primary percutaneous coronary intervention. The clinical significance of IMR and LVEDP in combination is unknown., Methods: IMR and LVEDP were prospectively measured in a prespecified substudy of the T-TIME clinical trial (Trial of Low Dose Adjunctive Alteplase During Primary PCI). IMR was measured using a pressure- and temperature-sensing guidewire following percutaneous coronary intervention. Prognostically established thresholds for IMR (>32) and LVEDP (>18 mm Hg) were predefined. Contrast-enhanced cardiovascular magnetic resonance imaging (1.5 Tesla) was acquired 2 to 7 days and 3 months postmyocardial infarction. The primary end point was major adverse cardiac events, defined as cardiac death/nonfatal myocardial infarction/heart failure hospitalization at 1 year., Results: IMR and LVEDP were both measured in 131 patients (mean age 59±10.7 years, 103 [78.6%] male, 48 [36.6%] with anterior myocardial infarction). The median IMR was 29 (interquartile range, 17-55), the median LVEDP was 17 mm Hg (interquartile range, 12-21), and the correlation between them was not statistically significant ( r =0.15; P =0.087). Fifty-three patients (40%) had low IMR (≤32) and low LVEDP (≤18), 18 (14%) had low IMR and high LVEDP, 31 (24%) had high IMR and low LVEDP, while 29 (22%) had high IMR and high LVEDP. Infarct size (% LV mass), LV ejection fraction, final myocardial perfusion grade ≤1, TIMI (Thrombolysis In Myocardial Infarction) flow grade ≤2, and coronary flow reserve were associated with LVEDP/IMR group, as was hospitalization for heart failure (n=18 events; P =0.045) and major adverse cardiac events (n=21 events; P =0.051). LVEDP>18 and IMR>32 combined was associated with major adverse cardiac events, independent of age, estimated glomerular filtration rate, and infarct-related artery (odds ratio, 5.80 [95% CI, 1.60-21.22] P =0.008). The net reclassification improvement for detecting major adverse cardiac events was 50.6% (95% CI, 2.7-98.2; P =0.033) when LVEDP>18 was added to IMR>32., Conclusions: IMR and LVEDP in combination have incremental value for risk stratification following primary percutaneous coronary intervention. Registration: URL: https://www.clinicaltrials.gov. Unique identifier: NCT02257294.

Four 3d-4f hetero-polymetallic complexes [Fe 2 Ln 2 ((OCH 2 ) 3 CR) 2 (O 2 C t Bu) 6 (H 2 O) 4 ] (where Ln = La ( 1 and 2 ) and Gd ( 3 and 4 ); and R = Me ( 1 and 3 ) and Et ( 2 and 4 )) are synthesized and analyzed using elemental analysis, Fourier transform infrared spectroscopy, thermogravimetric analysis, and SQUID magnetometry. Crystal structures are obtained for both methyl derivatives and show that the complexes are isostructural and adopt a defective dicubane topology. The four heavy metals are connected with two alkoxide bridges. These four precursors are used as single-source precursors to prepare rare-earth orthoferrite pervoskites of the form LnFeO 3 . Thermal decomposition in a ceramic boat in a tube furnace gives orthorhombic LnFeO 3 powders using optimized temperatures and decomposition times: LaFeO 3 formed at 650 °C over 30 min, whereas GdFeO 3 formed at 750 °C over 18 h. These materials are structurally characterized using powder X-ray diffraction, Raman spectroscopy, scanning electron microscopy, energy-dispersive X-ray map spectroscopy, and SQUID magnetometry. EDX spectroscopy mapping reveals a homogeneous spatial distribution of elements for all four materials consistent with LnFeO 3 . Magnetic measurements on complexes 1 - 4 confirm the presence of weak antiferromagnetic coupling between the central Fe(III) ions of the clusters and negligible ferromagnetic interaction with peripheral Gd(III) ions in 3 and 4 . Zero-field-cooled and field-cooled measurements of magnetization of LaFeO 3 and GdFeO 3 in the solid-state suggest that both materials are ferromagnetic, and both materials show open magnetic hysteresis loops at 5 and 300 K, with M sat higher than previously reported for these nanomaterials. We conclude that this is a new and facile low temperature route to these important magnetic materials that is potentially universal, limited only by what metals can be programmed into the precursor complexes.

Aims: The aim of this study was to evaluate the accuracy of a continuous intracoronary (IC) adenosine infusion, administered through the novel HYPEREM™IC over-the-wire microcatheter, to measure fractional flow reserve (FFR)., Methods and Results: The HYPEREMIC trial was a randomised, non-inferiority, crossover study in which patients with intermediate coronary lesions were enrolled for sequential pressure wire studies. FFR was measured using intravenous (IV) (140-180 mcg/kg/min) versus continuous non-weight-adjusted IC (360 mcg/min) adenosine. Patients were randomised and blinded to the order in which they received the adenosine, separated by a washout period. The primary endpoint was the mean hyperaemic FFR. Forty-one patients were enrolled at three UK sites between June and November 2016. The mean (standard deviation) FFR was 0.82 (±0.09) after IC versus 0.84 (±0.09) after IV adenosine. The difference of -0.02 (95% confidence interval [CI]: -0.03 to -0.01) confirmed the non-inferiority (margin <0.05) of IC to IV adenosine. Intracoronary adenosine was associated with a shorter mean time to maximal hyperaemia (difference -44 [95% CI: -59 to -29] seconds; p<0.0001). Chest discomfort was reported in 32/41 (78.0%) patients during IV adenosine versus 12/41 (29.3%) patients during IC adenosine., Conclusions: Continuous IC adenosine was a reliable, faster and better tolerated method of achieving maximal hyperaemia compared to IV adenosine.

An amendment to this paper has been published and can be accessed via the original article.

Background: Health-related quality of life (HRQoL) is impaired in patients with stable angina but patients often present with other forms of chest pain. The aim of this study was to compare the pre-diagnostic HRQoL in patients with suspected coronary artery disease (CAD) according to angina type, gender, and presence of obstructive CAD., Methods: From the pilot study for the European DISCHARGE trial, we analysed data from 24 sites including 1263 patients (45.9% women, 61.1 ± 11.3 years) who were clinically referred for invasive coronary angiography (ICA; 617 patients) or coronary computed tomography angiography (CTA; 646 patients). Prior to the procedures, patients completed HRQoL questionnaires: the Short Form (SF)-12v2, the EuroQoL (EQ-5D-3 L) and the Hospital Anxiety and Depression Scale., Results: Fifty-five percent of ICA and 35% of CTA patients had typical angina, 23 and 33% had atypical angina, 18 and 28% had non-anginal chest discomfort and 5 and 5% had other chest discomfort, respectively. Patients with typical angina had the poorest physical functioning compared to the other angina groups (SF-12 physical component score; 41.2 ± 8.8, 43.3 ± 9.1, 46.2 ± 9.0, 46.4 ± 11.4, respectively, all age and gender-adjusted p < 0.01), and highest anxiety levels (8.3 ± 4.1, 7.5 ± 4.1, 6.5 ± 4.0, 4.7 ± 4.5, respectively, all adjusted p < 0.01). On all other measures, patients with typical or atypical angina had lower HRQoL compared to the two other groups (all adjusted p < 0.05). HRQoL did not differ between patients with and without obstructive CAD while women had worse HRQoL compared with men, irrespective of age and angina type., Conclusions: Prior to a diagnostic procedure for stable chest pain, HRQoL is associated with chest pain characteristics, but not with obstructive CAD, and is significantly lower in women., Trial Registration: Clinicaltrials.gov, NCT02400229.

Post-percutaneous coronary intervention (PCI) fractional flow reserve (FFR) ≥0.90 confers an improved cardiac prognosis. There are currently limited data available to determine how often it is possible to improve an angiographically acceptable but physiologically suboptimal result. A physiology-guided optimization strategy can achieve a clinically meaningful increase in the proportion of patients achieving a final post-PCI FFR ≥0.90 compared to standard care. Following angiographically successful PCI procedures, 260 patients will be randomized (1:1) to receive either a physiology-guided incremental optimization strategy (intervention group) or blinded post-PCI coronary physiology measurements (control group). Patients undergoing successful, standard-of-care PCI for either stable angina or non-ST-segment-elevation myocardial infarction who meet the study's inclusion and exclusion criteria will be eligible for randomization. The primary endpoint is defined as the proportion of patients with a final post-PCI FFR result ≥0.90. Secondary endpoints include change from baseline in Seattle Angina Questionnaire and EQ-5D-5L scores at 3 months and the rate of target vessel failure and its components (cardiac death, myocardial infarction, stent thrombosis, unplanned rehospitalization with target vessel revascularization) at 3 months and 1 year. 260 individual patients were successfully randomized between March 2018 and November 2019. Key baseline demographics of the study population are reported within. TARGET FFR is an investigator-initiated, prospective, single-center, randomized controlled trial of an FFR-guided PCI optimization strategy. The study has completed recruitment and is now in clinical follow-up. It is anticipated that primary results will be presented in Autumn 2020. ClinicalTrials.gov Identifier: NCT03259815. [Correction added on Apr 3 2020, after first online publication: Clinical Trials identifier added.]., (© 2020 The Authors. Clinical Cardiology published by Wiley Periodicals, Inc.)

Introduction: There is conflicting evidence regarding the benefits of percutaneous coronary intervention (PCI) in patients with grey zone fractional flow reserve ( GZ FFR artery) values (0.75-0.80). The prevalence of ischaemia is unknown. We wished to define the prevalence of ischaemia in GZ FFR artery and assess whether PCI is superior to optimal medical therapy (OMT) for angina control., Methods: We enrolled 104 patients with angina with 1:1 randomisation to PCI or OMT. The artery was interrogated with a Doppler flow/pressure wire. Patients underwent Magnetic Resonance Imaging (MRI) with follow-up at 3 and 12 months. The primary outcome was angina status at 3 months using the Seattle Angina Questionnaire (SAQ)., Results: 104 patients (age 60±9 years), 79 (76%) males and 79 (76%) Left Anterior Descending (LAD) stenoses were randomised. Coronary physiology and SAQ were similar. Of 98 patients with stress perfusion MRI data, 17 (17%) had abnormal perfusion (≥2 segments with ≥25% ischaemia or ≥1 segment with ≥50% ischaemia) in the target GZ FFR artery. Of 89 patients with invasive physiology data, 26 (28%) had coronary flow velocity reserve <2.0 in the target GZ FFR artery. After 3 months of follow-up, compared with patients treated with OMT only, patients treated by PCI and OMT had greater improvements in SAQ angina frequency (21 (28) vs 10 (23); p=0.026) and quality of life (24 (26) vs 11 (24); p=0.008) though these differences were no longer significant at 12 months., Conclusions: Non-invasive evidence of major ischaemia is uncommon in patients with GZ FFR artery. Compared with OMT alone, patients randomised to undergo PCI reported improved symptoms after 3 months but these differences were no longer significant after 12 months., Trial Registration Number: NCT02425969., Competing Interests: Competing interests: There was no industry sponsorship of this trial. CB has undertaken research, consulting and lectures for Abbott Vascular, Opsens and Coroventis based on contracts with The University of Glasgow. KGO has received speaker fees from Abbott Vascular, Boston Scientific and Biosensors. BH has received honoraria from Philips Volcano for consultancy., (© Author(s) (or their employer(s)) 2020. Re-use permitted under CC BY. Published by BMJ.)

Gaining a fundamental understanding of charge transfer mechanisms in three-dimensional Metal-Organic Frameworks (MOFs) is crucial to the development of electroactive and conductive porous materials. These materials have potential in applications in porous conductors, electrocatalysts and energy storage devices; however the structure-property relationships pertaining to charge transfer and its quantification are relatively poorly understood. Here, the cofacial Cd(ii)-based MOF [Cd(BPPTzTz)(tdc)]·2DMF (where BPPTzTz = 2,5-bis(4-(pyridin-4-yl)phenyl)thiazolo[5,4- d ]thiazole, tdc 2- = 2,5-thiophene dicarboxylate) exhibits Intervalence Charge Transfer (IVCT) within its three-dimensional structure by virtue of the close, cofacial stacking of its redox-active BPPTzTz ligands. The mixed-valence and IVCT properties are characterised using a combined electrochemical, spectroelectrochemical and computational approach. Single crystal electronic absorption spectroscopy was employed to obtain the solid-state extinction coefficient, enabling the application of Marcus-Hush theory. The electronic coupling constant, H ab , of 145 cm -1 was consistent with the localised mixed-valence properties of both this framework and analogous systems that use alternative methods to obtain the H ab parameter. This work demonstrates the first report of the successful characterisation of IVCT in a MOF material using single crystal electronic absorption spectroscopy and serves as an attractive alternative to more complex methods due to its simplicity and applicability., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Background Impaired microcirculatory reperfusion worsens prognosis following acute ST-segment-elevation myocardial infarction. In the T-TIME (A Trial of Low-Dose Adjunctive Alteplase During Primary PCI) trial, microvascular obstruction on cardiovascular magnetic resonance imaging did not differ with adjunctive, low-dose, intracoronary alteplase (10 or 20 mg) versus placebo during primary percutaneous coronary intervention. We evaluated the effects of intracoronary alteplase, during primary percutaneous coronary intervention, on the index of microcirculatory resistance, coronary flow reserve, and resistive reserve ratio. Methods and Results A prespecified physiology substudy of the T-TIME trial. From 2016 to 2017, patients with ST-segment-elevation myocardial infarction ≤6 hours from symptom onset were randomized in a double-blind study to receive alteplase 20 mg, alteplase 10 mg, or placebo infused into the culprit artery postreperfusion, but prestenting. Index of microcirculatory resistance, coronary flow reserve, and resistive reserve ratio were measured after percutaneous coronary intervention. Cardiovascular magnetic resonance was performed at 2 to 7 days and 3 months. Analyses in relation to ischemic time (<2, 2-4, and ≥4 hours) were prespecified. One hundred forty-four patients (mean age, 59±11 years; 80% male) were prospectively enrolled, representing 33% of the overall population (n=440). Overall, index of microcirculatory resistance (median, 29.5; interquartile range, 17.0-55.0), coronary flow reserve(1.4 [1.1-2.0]), and resistive reserve ratio (1.7 [1.3-2.3]) at the end of percutaneous coronary intervention did not differ between treatment groups. Interactions were observed between ischemic time and alteplase for coronary flow reserve ( P =0.013), resistive reserve ratio ( P =0.026), and microvascular obstruction ( P =0.022), but not index of microcirculatory resistance. Conclusions In ST-segment-elevation myocardial infarction with ischemic time ≤6 hours, there was overall no difference in microvascular function with alteplase versus placebo. Clinical Trial Registration URL: https://www.clinicaltrials.gov. Unique identifier: NCT02257294.

Objectives: The aim of this study was to test the hypothesis that invasive coronary function testing at time of angiography could help stratify management of angina patients without obstructive coronary artery disease., Background: Medical therapy for angina guided by invasive coronary vascular function testing holds promise, but the longer-term effects on quality of life and clinical events are unknown among patients without obstructive disease., Methods: A total of 151 patients with angina with symptoms and/or signs of ischemia and no obstructive coronary artery disease were randomized to stratified medical therapy guided by an interventional diagnostic procedure versus standard care (control group with blinded interventional diagnostic procedure results). The interventional diagnostic procedure-facilitated diagnosis (microvascular angina, vasospastic angina, both, or neither) was linked to guideline-based management. Pre-specified endpoints included 1-year patient-reported outcome measures (Seattle Angina Questionnaire, quality of life [EQ-5D]) and major adverse cardiac events (all-cause mortality, myocardial infarction, unstable angina hospitalization or revascularization, heart failure hospitalization, and cerebrovascular event) at subsequent follow-up., Results: Between November 2016 and December 2017, 151 patients with ischemia and no obstructive coronary artery disease were randomized (n = 75 to the intervention group, n = 76 to the control group). At 1 year, overall angina (Seattle Angina Questionnaire summary score) improved in the intervention group by 27% (difference 13.6 units; 95% confidence interval: 7.3 to 19.9; p < 0.001). Quality of life (EQ-5D index) improved in the intervention group relative to the control group (mean difference 0.11 units [18%]; 95% confidence interval: 0.03 to 0.19; p = 0.010). After a median follow-up duration of 19 months (interquartile range: 16 to 22 months), major adverse cardiac events were similar between the groups, occurring in 9 subjects (12%) in the intervention group and 8 (11%) in the control group (p = 0.803)., Conclusions: Stratified medical therapy in patients with ischemia and no obstructive coronary artery disease leads to marked and sustained angina improvement and better quality of life at 1 year following invasive coronary angiography. (Coronary Microvascular Angina [CorMicA]; NCT03193294)., (Copyright © 2020 The Authors. Published by Elsevier Inc. All rights reserved.)

Background: Determine the prevalence and correlates of microvascular and vasospastic angina in patients with symptoms and signs of ischemia but no obstructive coronary artery disease (INOCA)., Methods: Three hundred ninety-one patients with angina were enrolled at 2 regional centers over 12 months from November 2016 (NCT03193294). INOCA subjects (n=185; 47%) had more limiting dyspnea (New York Heart Association classification III/IV 54% versus 37%; odds ratio [OR], 2.0 [1.3-3.0]; P =0.001) and were more likely to be female (68% INOCA versus 38% in coronary artery disease; OR, 1.9 [1.5 to 2.5]; P <0.001) but with lower cardiovascular risk scores (ASSIGN score median 20% versus 24%; P =0.003). INOCA subjects had similar burden of angina (Seattle Angina Questionnaire) but reduced quality of life compared with coronary artery disease; subjects (EQ5D-5 L index 0.60 versus 0.65 units; P =0.041)., Results: An interventional diagnostic procedure with reference invasive tests including coronary flow reserve, microvascular resistance, and vasomotor responses to intracoronary acetylcholine (vasospasm provocation) was performed in 151 INOCA subjects. Overall, 78 (52%) had isolated microvascular angina, 25 (17%) had isolated vasospastic angina, 31 (20%) had both, and 17 (11%) had noncardiac chest pain. Regression analysis showed inducible ischemia on treadmill testing (OR, 7.5 [95% CI, 1.7-33.0]; P =0.008) and typical angina (OR, 2.7 [1.1-6.6]; P =0.032) were independently associated with microvascular angina. Female sex tended to associate with a diagnosis of microvascular angina although this was not significant (OR, 2.7 [0.9-7.9]; P =0.063). Vasospastic angina was associated with smoking (OR, 9.5 [2.8-32.7]; P <0.001) and age (OR, 1.1 per year, [1.0-1.2]; P =0.032]., Conclusions: Over three quarters of patients with INOCA have identifiable disorders of coronary vasomotion including microvascular and vasospastic angina. These patients have comparable angina burden but reduced quality of life compared to patients with obstructive coronary artery disease. Microvascular angina and vasospastic angina are distinct disorders that may coexist but differ in associated clinical characteristics, symptoms, and angina severity., Clinical Trial Registration: URL: https://www.clinicaltrials.gov. Unique identifier: NCT03193294.

Alkyl-xanthato gallium(iii) complexes of the form [Ga(S 2 COR) 3 ], where R = Me (1), Et (2), i Pr (3), n Pr (4), n Bu (5), s Bu (6) and i Bu (7), have been synthesized and fully characterised. The crystal structures for 1 and 3-7 have been solved and examined to elucidate if these structures are related to their decomposition. Thermogravimetric analysis was used to gain insight into the decomposition temperatures for each complex. Unlike previously explored metal xanthate complexes which break down at low temperatures (<250 °C), to form crystalline metal chalcogenides, powder X-ray diffraction measurements suggest that when R ≥ Et these complexes did not produce crystalline gallium sulfides until heated to 500 °C, where γ-Ga 2 S 3 was the sole product formed. In the case of R = Me, Chugaev elimination did not occur and amorphous Ga x S y products were formed. We conclude therefore that the low-temperature synthesis route offered by the thermal decomposition of metal xanthate precursors, which has been reported for many metal sulfide systems prior to this, may not be appropriate in the case of gallium sulfides.

We report a six coordinate Dy III single-molecule magnet (SMM) with an energy barrier of 1110 K for thermal relaxation of magnetization. The pure compound shows no retention of magnetization even at 2 K.

Catalytic chemistry that involves the activation and transformation of main group substrates is relatively undeveloped and current examples are generally mediated by expensive transition metal species. Herein, we describe the use of inexpensive and readily available tBuOK as a catalyst for P-P and P-E (E = O, S, or N) bond formation. Catalytic quantities of tBuOK in the presence of imine, azobenzene hydrogen acceptors, or a stoichiometric amount of tBuOK with hydrazobenzene, allow efficient homodehydrocoupling of phosphines under mild conditions (e.g. 25 °C and < 5 min). Further studies demonstrate that the hydrogen acceptors play an intimate mechanistic role. We also show that our tBuOK catalysed methodology is general for the heterodehydrocoupling of phosphines with alcohols, thiols and amines to generate a range of potentially useful products containing P-O, P-S, or P-N bonds.

We report an empirical correlation between the blocking temperature of large energy barrier SMMs and the relaxation time at the point where the Raman and Orbach relaxation mechanisms have the same rate; this supports the idea that the ability to retain magnetisation is controlled by the Raman relaxation process in these materials.

Background: Patients with angina symptoms and/or signs of ischemia but no obstructive coronary artery disease (INOCA) pose a diagnostic and therapeutic challenge., Objectives: The purpose of this study was to test whether an interventional diagnostic procedure (IDP) linked to stratified medicine improves health status in patients with INOCA., Methods: The authors conducted a randomized, controlled, blinded clinical trial of stratified medical therapy versus standard care in patients with angina. Patients with angina undergoing invasive coronary angiography (standard care) were recruited. Patients without obstructive CAD were immediately randomized 1:1 to the intervention group (stratified medical therapy) or the control group (standard care, IDP sham procedure). The IDP consisted of guidewire-based assessment of coronary flow reserve, index of microcirculatory resistance, fractional flow reserve, followed by vasoreactivity testing with acetylcholine. The primary endpoint was the mean difference in angina severity at 6 months (assessed by the Seattle Angina Questionnaire summary score)., Results: A total of 391 patients were enrolled between November 25, 2016, and November 12, 2017. Coronary angiography revealed obstructive disease in 206 (53.7%). One hundred fifty-one (39%) patients without angiographically obstructive CAD were randomized (n = 76 intervention group; n = 75 blinded control group). The intervention resulted in a mean improvement of 11.7 U in the Seattle Angina Questionnaire summary score at 6 months (95% confidence interval [CI]: 5.0 to 18.4; p = 0.001). In addition, the intervention led to improvements in the mean quality-of-life score (EQ-5D index 0.10 U; 95% CI: 0.01 to 0.18; p = 0.024) and visual analogue score (14.5 U; 95% CI: 7.8 to 21.3; p < 0.001). There were no differences in major adverse cardiac events at the 6-month follow-up (2.6% controls vs. 2.6% intervention; p = 1.00)., Conclusions: Coronary angiography often fails to identify patients with vasospastic and/or microvascular angina. Stratified medical therapy, including an IDP with linked medical therapy, is routinely feasible and improves angina in patients with no obstructive CAD. (CORonary MICrovascular Angina [CorMicA]; NCT03193294)., (Copyright © 2018 American College of Cardiology Foundation. Published by Elsevier Inc. All rights reserved.)

This paper describes experiments that are designed to test the influence of terminal groups incorporating carbon-halogen bonds on the current density (by hole tunneling) across self-assembled monolayer (SAM)-based junctions of the form M TS /S(CH 2 ) 9 NHCOCH n X 3- n //Ga 2 O 3 /EGaIn (where M = Ag and Au and X = CH 3 , F, Cl, Br, I). Within the limits of statistical significance, these rates of tunneling are insensitive to the nature of the terminal group at the interface between the SAM and the Ga 2 O 3 . The results are relevant to the origin of an apparent inconsistency in the literature concerning the influence of halogen atoms at the SAM//electrode interface on the tunneling current density.

Background: The majority of coronary bifurcation lesions are treated with a provisional single-stent strategy rather than an up-front 2-stent strategy. This approach is supported by multiple randomized controlled clinical trials with short- to medium-term follow-up; however, long-term follow-up data is evolving from many data sets., Methods and Results: Meta-analysis of randomized controlled trials evaluating long-term outcomes (≥1 year) according to treatment strategy for coronary bifurcation lesions. Nine randomized controlled trials with 3265 patients reported long-term clinical outcomes at mean weighted follow-up of 3.1±1.8 years. Provisional single stenting was associated with lower all-cause mortality (2.94% versus 4.23%; risk ratio: 0.69; 95% confidence interval, 0.48-1.00; P =0.049; I 2 =0). There was no difference in major adverse cardiac events (15.8% versus 15.4%; P =0.79), myocardial infarction (4.8% versus 5.5%; P =0.51), target lesion revascularization (9.3% versus 7.6%; P =0.19), or stent thrombosis (1.8% versus 1.6%; P =0.28) between the groups. Prespecified sensitivity analysis of long-term mortality at a mean of 4.7 years of follow-up showed that the provisional single-stent strategy was associated with reduced all-cause mortality (3.9% versus 6.2%; risk ratio: 0.63; 95% confidence interval, 0.42-0.97; P =0.036; I 2 =0)., Conclusions: Coronary bifurcation percutaneous coronary intervention using a provisional single-stent strategy is associated with a reduction in all-cause mortality at long-term follow-up., (© 2018 The Authors. Published on behalf of the American Heart Association, Inc., by Wiley.)

Magnetic exchange interactions within the asymmetric dimetallic compounds [hqH 2 ][Ln 2 (hq) 4 (NO 3 ) 3 ]·MeOH, (Ln = Er(III) and Yb(III), hqH = 8-hydroxyquinoline) have been directly probed with EPR spectroscopy and accurately modeled by spin Hamiltonian techniques. Exploitation of site selectivity via doping experiments in Y(III) and Lu(III) matrices yields simple EPR spectra corresponding to isolated Kramers doublets, allowing determination of the local magnetic properties of the individual sites within the dimetallic compounds. CASSCF-SO calculations and INS and far-IR measurements are all employed to further support the identification and modeling of the local electronic structure for each site. EPR spectra of the pure dimetallic compounds are highly featured and correspond to transitions within the lowest-lying exchange-coupled manifold, permitting determination of the highly anisotropic magnetic exchange between the lanthanide ions. We find a unique orientation for the exchange interaction, corresponding to a common elongated oxygen bridge for both isostructural analogs. This suggests a microscopic physical connection to the magnetic superexchange. These results are of fundamental importance for building and validating model microscopic Hamiltonians to understand the origins of magnetic interactions between lanthanides and how they may be controlled with chemistry.

Background: Remote ischaemic preconditioning (RIPC) is a cardioprotective intervention invoking intermittent periods of ischaemia in a tissue or organ remote from the heart. The mechanisms of this effect are incompletely understood. We hypothesised that RIPC might enhance coronary vasodilatation by an endothelium-dependent mechanism., Methods: We performed a prospective, randomised, sham-controlled, blinded clinical trial. Patients with stable coronary artery disease (CAD) undergoing elective invasive management were prospectively enrolled, and randomised to RIPC or sham (1:1) prior to angiography. Endothelial-dependent vasodilator function was assessed in a non-target coronary artery with intracoronary infusion of incremental acetylcholine doses (10 -6 , 10 -5 , 10 -4 mol/l). Venous blood was sampled pre- and post-RIPC or sham, and analysed for circulating markers of endothelial function. Coronary luminal diameter was assessed by quantitative coronary angiography. The primary outcome was the between-group difference in the mean percentage change in coronary luminal diameter following the maximal acetylcholine dose (Clinicaltrials.gov identifier: NCT02666235)., Results: 75 patients were enrolled. Following angiography, 60 patients (mean±SD age 57.5±8.5years; 80% male) were eligible and completed the protocol (n=30 RIPC, n=30 sham). The mean percentage change in coronary luminal diameter was -13.3±22.3% and -2.0±17.2% in the sham and RIPC groups respectively (difference 11.32%, 95%CI: 1.2- 21.4, p=0.032). This remained significant when age and sex were included as covariates (difference 11.01%, 95%CI: 1.01- 21.0, p=0.035). There were no between-group differences in endothelial-independent vasodilation, ECG parameters or circulating markers of endothelial function., Conclusions: RIPC attenuates the extent of vasoconstriction induced by intracoronary acetylcholine infusion. This endothelium-dependent mechanism may contribute to the cardioprotective effects of RIPC., (Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.)

We present an EPR instrument built for operation at Q band below 1K. Our cryogen-free Dewar integrates with a commercial electro-magnet and bridge. A description of the cryogenic and RF systems is given, along with the adaptations to the standard EPR experiment for operation at sub-Kelvin temperatures. As a first experiment, the EPR spectra of powdered Cr 12 O 9 (OH) 3 [Formula: see text] were measured. The sub-Kelvin EPR spectra agree well with predictions, and the performance of the sub-Kelvin system at 5K is compared to that of a commercial spectrometer., (Copyright © 2017 The Authors. Published by Elsevier Inc. All rights reserved.)

In situ spectroelectrochemical experiments coupled with UV/Vis/NIR, EPR, magnetism and fluorescence techniques have enabled insights into the electronic properties of the tris(p-tetrazolylphenyl)amine (H 3 TTPA) ligand and the new Mn 2+ frameworks [Mn 3 (TTPA) 2 (MeOH) 6 ] n (1) and [Mn 3 (TTPA) 2 (DMF) 6 ] n (2). Oxidation of H 3 TTPA generated the triarylamine radical which was found to be delocalised throughout the ligand backbone. Solid state Vis/NIR and EPR spectroelectrochemical experiments on the frameworks were used to probe the optical properties of the accessible redox states and their relative stabilities, as well as the charge transfer interactions which were generated upon infiltration of electron acceptor guests. These studies provide a basis for the application of electroactive frameworks in functional electronic and optical devices, where knowledge of the properties of the distinct redox states and their interconversion is essential.