Unveiling KuQuinone Redox Species: An Electrochemical and Computational Cross Study.

The study of the electrochemical properties of variegated quinones is a fascinating topic in chemistry. In fact, redox reactions occurring with quinoid scaffolds are essential for most of their applications in biological systems, in photoelectrochemical devices, and in many other fields. In this paper, a detailed investigation of KuQuinones' redox behavior is presented. The distinctiveness of such molecules is the presence in the structure of two condensed naphthoquinone units, which implies the possibility to undergo multiple one-electron reduction processes. Solvent, supporting electrolyte, and hydrogen bond donor species effects have been elucidated. Changing the experimental parameters provoked significant shift of the redox potential for each reduction process. In particular, additions of 2,2,2-trifluoroethanol as a hydrogen bond donor in solution as well as Lewis acid coordination were crucial to obtain important shifts of the redox potentials toward more favorable values. UV-vis-NIR spectroelectrochemical experiments and DFT calculations are also presented to clarify the nature of the reduced species in solution.

The importance of ventilatory thresholds to define aerobic exercise intensity in cardiac patients and healthy subjects.

BACKGROUND: Although structured exercise training is strongly recommended in cardiac patients, uncertainties exist about the methods for determining exercise intensity (EI) and their correspondence with effective EI obtained by ventilatory thresholds. We aimed to determine the first (VT1 ) and second ventilatory thresholds (VT2 ) in cardiac patients, sedentary subjects, and athletes comparing VT1 and VT2 with EI defined by recommendations. METHODS: We prospectively enrolled 350 subjects (mean age: 50.7±12.9 years; 167 cardiac patients, 150 healthy sedentary subjects, and 33 competitive endurance athletes). Each subject underwent ECG, echocardiography, and cardiopulmonary exercise testing. The percentages of peak VO2 , peak heart rate (HR), and HR reserve were obtained at VT1 and VT2 and compared with the EI definition proposed by the recommendations. RESULTS: VO2 at VT1 corresponded to high rather than moderate EI in 67.1% and 79.6% of cardiac patients, applying the definition of moderate exercise by the previous recommendations and the 2020 guidelines, respectively. Most cardiac patients had VO2  values at VT2 corresponding to very-high rather than high EI (59.9% and 50.3%, by previous recommendations and 2020 guidelines, respectively). A better correspondence between ventilatory thresholds and recommended EI domains was observed in healthy subjects and athletes (90% and 93.9%, respectively). CONCLUSIONS: EI definition based on percentages of peak HR and peak VO2  may misclassify the effective EI, and the discrepancy between the individually determined and the recommended EI is particularly relevant in cardiac patients. A ventilatory threshold-based rather than a range-based approach is advisable to define an appropriate level of EI.

Bicuspid aortic valve and sports: From the echocardiographic evaluation to the eligibility for sports competition.

Bicuspid aortic valve (BAV) is the most common congenital heart defect in adults. Although a BAV may remain without clinical consequences for a lifetime, it can deteriorate in aortic valve stenosis and regurgitation and aortic dilatation. Unfortunately, the impact of regular training on patients with BAV and its natural course is not fully understood, although preliminary evidence suggests that the progression of valvular disease occurs primarily in an independent manner from sports practice. The current review aims to report how to perform a comprehensive echocardiographic examination in athletes with BAV and analyze the current literature on the influence of sports practice and how it impacts the aortic valve in athletes with BAV. The article also summarizes the current recommendations on sports eligibility and disqualification for competitive athletes with BAV.

The role of type 2 diabetes mellitus on hypertensive-related aortic stiffness.

BACKGROUND: Hypertension is strongly related to arterial stiffness in a cause-effect fashion. Diabetes mellitus is also thought to determine vascular damage, mostly by means of advanced glycosylation end-products (AGEs). Aim of our study was to study the role of type 2 diabetes mellitus (T2DM) as regard ascending aortic elastic properties in hypertensive patients. METHODS: We prospectively enrolled outpatients with hypertension (n = 99) and type 2 diabetes mellitus plus hypertension (n = 42) without cardiovascular events. They underwent a transthoracic echocardiography to measure aortic diameters, aortic elastic properties (ie, compliance, distensibility, stiffness index, Peterson's elastic modulus, pulse wave velocity, M-mode strain), tissue Doppler imaging (TDI) to calculate diastolic (E' and A') and systolic (S') velocities, and tissue strain. Multivariable analysis was run to assess the association between T2DM and these variables after correcting for possible confounders (age, sex, body mass index [BMI], dyslipidemia). RESULTS: The two groups did not differ as regards age, sex, BMI, and blood pressure. However, T2DM patients were more likely to be dyslipidemic (43% vs 71%, P = .003). Aortic diameters were similar in the two groups, but the aortic elastic properties significantly more impaired in T2DM group. At multivariable analysis, stiffness index, Peterson's elastic modulus, the TDI waves, and the tissue strain remained associated with the co-presence of T2DM and hypertension. CONCLUSION: Our data suggest that people suffering from both T2DM and hypertension have more impaired aortic elastic properties than those hypertensive alone. Considering the prognostic role of aortic stiffness, these patients may benefit from a closer follow-up.

Blood pressure control in older patients with carotid artery stenosis.

Stroke is the second largest cause of European cardiovascular and total mortality, largely due to atherosclerotic carotid artery narrowing or thromboembolism consequent to internal carotid artery stenosis. Current therapeutic indications suggest lifestyle interventions (smoking cessation, healthy diet and physical activity), adequate control of LDL-cholesterol and glycemic balance. It is nonetheless established that the most important factors in preventing stroke are antiplatelet therapy and blood pressure regulation. In fact, many physiological parameters, including age, drugs' effects and especially systemic blood pressure, can be involved in maintaining cerebral blood flow through compensation for impairment of flow within carotid arteries. Many studies demonstrate the benefits of blood pressure lowering in terms of prevention of stroke, but there are conflicting data about a specific pressure target to achieve, with some evidence in favor of "the lower the better" idea, while other identifying a too low systolic blood pressure as a cause of cerebral ischemia worsening, especially in symptomatic patients. In summary, the available data suggest the need of a tailored blood pressure treatment without inflexible targets, according to the assessment of the cardiovascular risk of each patient, the benefits of an intensive antihypertensive therapy and the comorbidities-related response to the treatment.

Echocardiographic evaluation of diastolic dysfunction in young and healthy patients with psoriasis: A case-control study.

Psoriasis is a systemic inflammatory disease with a great prevalence in general population. The inappropriate activation of the cellular immune system has been hypothesized to be an independent cardiovascular risk factor, given the higher incidence of cardiovascular disorders in psoriatic patients. Echocardiographic abnormalities have been demonstrated too: the aim of our study was to evaluate the presence of preclinical cardiac dysfunction in a cohort of psoriatic patients without cardiovascular risk factors. We enrolled 52 patients with the diagnosis of chronic plaque psoriasis, compared with a control group not affected by any relevant systemic diseases and inflammatory disorders. In all patients and control group, echocardiographic conventional and tissue Doppler (TDI) studies were conducted. The analysis of echocardiographic parameters revealed normal dimension, mass and systolic function of the left ventricle. Left ventricular diastolic dysfunction was found in 36.5% patients in the psoriasis group versus 0% in control group, and significant reduction of the E/A ratio was found also for the right ventricle. A significant increase of mitral regurgitation has been found in psoriatic patients (p=0.005). The early recognition of cardiovascular pre-clinic disease in psoriatic patients may guide a strict follow up and an early treatment, potentially improving cardiovascular prognosis.

KuQuinones: a ten years tale of the new pentacyclic quinoid compound.

Quinones are widespread in nature, as they participate, mainly as redox mediators, in several biochemical processes. Up to now, various synthetic quinones have been recommended in the literature as leading molecules in energy, biomedical and catalytic fields. In this brief review, we retraced our research activity in the last ten years, mainly dedicated to the study of a new class of peculiar pentacyclic conjugated quinoid compounds, synthesized in our group. In particular, their application as sensitive materials in photoelectrochemical devices and in biosensors, as photocatalysts in selective oxidation reactions, and their anticancer activity is here reviewed.

A Stoichiometric Solvent-Free Protocol for Acetylation Reactions.

Considering the remarkable relevance of acetylated derivatives of phenols, alcohols, and aryl and alkyl thiols in different areas of biology, as well as in synthetic organic chemistry, a sustainable solvent-free approach to perform acetylation reactions is proposed here. Acetylation reactions are classically performed using excess of acetic anhydride (Ac2O) in solvent-free conditions or by eventually working with stoichiometric amounts of Ac2O in organic solvents; both methods require the addition of basic or acid catalysts to promote the esterification. Therefore, they usually lead to the generation of high amounts of wastes, which sensibly raise the E-factor of the process. With the aim to develop a more sustainable system, a solvent-free, stoichiometric acetylation protocol is, thus, proposed. The naturally occurring phenol, thymol, can be converted to the corresponding-biologically active-ester with good yields, in the presence of 1% of VOSO4. Interestingly, the process can be efficiently adopted to synthesize other thymyl esters, as well as to perform acetylation of alcohols and aryl and alkyl thiols. Remarkably, a further improvement has been achieved replacing Ac2O with its greener alternative, isopropenyl acetate (IPA).

Diagnostic and prognostic value of low QRS voltages in cardiomyopathies: old but gold.

The interpretation of 12-lead resting electrocardiogram (ECG) in patients with a definitive diagnosis or with the suspicion of a cardiomyopathy represents a cornerstone for the diagnostic work up and management of patients. Although low electrocardiographic QRS voltages (LQRSV) detected by 12-lead resting ECG have historically been acknowledged by physicians, in view of recent evidence on the demonstration of myocardial scar by cardiac magnetic resonance and its relevance as a cause of sudden cardiac death even in young individuals, a new interest has been raised about the utility of LQRSV in the clinical practice. Beyond their diagnostic value, LQRSV have also demonstrated a prognostic role in different cardiomyopathies. The present review summarizes the diagnostic and prognostic value of LQRSV in cardiomyopathies, reporting the new evidence, primarily based on advanced imaging studies, supporting the clinical utility of this parameter.

The acute effects of an ultramarathon on biventricular function and ventricular arrhythmias in master athletes.

AIMS: Endurance sports practice has significantly increased over the last decades, with a growing proportion of participants older than 40 years. Although the benefits of moderate regular exercise are well known, concerns exist regarding the potential negative effects induced by extreme endurance sport. The aim of this study was to analyse the acute effects of an ultramarathon race on the electrocardiogram (ECG), biventricular function, and ventricular arrhythmias in a population of master athletes. METHODS AND RESULTS: Master athletes participating in an ultramarathon (50 km, 600 m of elevation gain) with no history of heart disease were recruited. A single-lead ECG was recorded continuously from the day before to the end of the race. Echocardiography and 12-lead resting ECG were performed before and at the end of the race. The study sample consisted of 68 healthy non-professional master athletes. Compared with baseline, R-wave amplitude in V1 and QTc duration were higher after the race (P < 0.001). Exercise-induced isolated premature ventricular beats were observed in 7% of athletes; none showed non-sustained ventricular tachycardia before or during the race. Left ventricular ejection fraction, global longitudinal strain (GLS), and twisting did not significantly differ before and after the race. After the race, no significant differences were found in right ventricular inflow and outflow tract dimensions, fractional area change, s', and free wall GLS. CONCLUSION: In master endurance athletes running an ultra-marathon, exercise-induced ventricular dysfunction, or relevant ventricular arrhythmias was not detected. These results did not confirm the hypothesis of a detrimental acute effect of strenuous exercise on the heart.

Causes of sudden cardiac death in young athletes and non-athletes: systematic review and meta-analysis: Sudden cardiac death in the young.

INTRODUCTION: The etiology of sudden cardiac death (SCD) in young people continues to attract much attention. This meta-analysis aimed to identify the most frequent causes of SCD in individuals aged ≤35 years, the differences between athletes and non-athletes and geographic areas. METHODS: Studies published between 01/01/1990 and 01/31/2020 and evaluating post-mortem the aetiology of SCD in young individuals (≤35 years) were included. Individuals were divided into athletes and non-athletes. Studies that did not report separate data between athletes and non-athletes were excluded. RESULTS: Thirty-four studies met the inclusion criteria, and a total population of 5,060 victims of SCD were analyzed (2,890 athletes, 2,170 non-athletes). Comparing the causes of SCD between athletes and non-athletes, non-ischemic left ventricular scar (NILVS) (5.1% vs. 1.1%, p=0.01) was more frequent in the former, while coronary artery disease (CAD) (19.6% vs. 9.1%, p=0.009), arrhythmogenic cardiomyopathy (ACM) (11.5% vs. 4.7%, p=0.03) and channelopathies (8.4% vs. 1.9%, p=0.02) were more frequent in the latter. In studies published in the last decade, hypertrophic cardiomyopathy (HCM) (p=0.002), dilated cardiomyopathy (p=0.047), and anomalous origin of coronary arteries (AOCA) (p=0.009) were more frequently the causes of SCD in athletes while aortic dissection (0.022) was the cause in non-athletes. HCM (p=0.01) and AOCA (p=0.004) were more frequently the causes of SCD in the US while ACM (p=0.001), structurally normal heart (p=0.02), and channelopathies (p=0.02) were more frequent in Europe. CONCLUSIONS: Among the causes of SCD, NILVS was the more frequent cause in athletes, while CAD, ACM and channelopathies were more frequent causes in non-athletes. The causes of SCD differ between the US and Europe.

Transcatheter Mitral Valve Repair in Cardiogenic Shock and Mitral Regurgitation: A Patient-Level, Multicenter Analysis.

OBJECTIVES: The aim of this study was to evaluate the outcome of transcatheter mitral valve repair (TMVr) in patients with cardiogenic shock and significant mitral regurgitation (MR). BACKGROUND: Patients in cardiogenic shock with severe MR have a poor prognosis in the setting of conventional medical therapy. Because of its favorable safety profile, TMVr is being increasingly used as an acute therapy in this population, though its efficacy remains unknown. METHODS: A multicenter, collaborative, patient-level analysis was conducted. Patients with cardiogenic shock and moderate to severe (3+) or severe (4+) MR who were not surgical candidates were treated with TMVr. The primary outcome was in-hospital mortality. Secondary outcomes included 90-day mortality, heart failure (HF) hospitalization, and the combined event rate of 90-day mortality and HF hospitalization following dichotomization by TMVr device success. RESULTS: Between January 2011 and February 2019, 141 patients across 14 institutions met the inclusion criteria. In-hospital mortality occurred in 22 patients (15.6%), at 90 days in 38 patients (29.5%), and at one year in 55 patients (42.6%). Median length of hospital stay following TMVr was 10 days (interquartile range: 6 to 20 days). HF hospitalization occurred in 26 patients (18.4%) at a median of 73 days (interquartile range: 26 to 546 days). When stratified by TMVr procedural results, successful TMVr reduced rates of in-hospital mortality (hazard ratio [HR]: 0.36; 95% confidence interval [CI]: 0.13 to 0.98; p = 0.04), 90-day mortality (HR: 0.36; 95% CI: 0.16 to 0.78; p = 0.01), and the composite of 90-day mortality and HF hospitalization (HR: 0.41; 95% CI: 0.19 to 0.90; p = 0.03). CONCLUSIONS: TMVr may improve short- and intermediate-term mortality in high-risk patients with cardiogenic shock and moderate to severe MR. Randomized studies are needed to definitively establish MR as a therapeutic target in patients with cardiogenic shock.

Evaluation of systo-diastolic cardiac function and arterial stiffness in subjects with new diagnosis of coeliac disease without cardiovascular risk factors.

In literature, there are conflicting opinions on the development of cardiovascular disease risk in patients with coeliac disease (CD). The aim of the research was to identify in young subjects without cardiovascular risk factor and newly diagnosed CD, alterations in different instrumental parameters that are associated with an augmented cardiovascular risk. Twenty-one consecutive young adults with a new diagnosis of CD and without cardiovascular risk factors were prospectively enrolled and underwent transthoracic echocardiography to analyse ascending aorta elastic properties [including tissue Doppler imaging strain (TDI-ε)] and left ventricular 2D strains (global longitudinal, radial and circumferential), and applanation tonometry by SphygmoCor. Cases were compared with 21 age- and sex-matched healthy controls. Mean age of the cases was 38 ± 9 years and 15 of them (71%) were female. Brachial and central blood pressure was higher in the CD group. Elastic properties of the ascending aorta were all impaired in the CD group: TDI-ε was altered in 57% of cases (0% of controls, p < 0.001). Concentric remodelling and grade I diastolic dysfunction were present in 38% and 24% of cases, respectively (0% of controls, p < 0.001). Global longitudinal strain was normal in all subjects, while radial and circumferential strain were altered in 67% and 35%, respectively (0% of controls, p < 0.001). In young subjects without cardiovascular risk factor, a newly diagnosed CD is associated with altered aortic elastic properties, left ventricular concentric remodelling and diastolic dysfunction and altered radial and circumferential strain.

Photoanodes for water oxidation with visible light based on a pentacyclic quinoid organic dye enabling proton-coupled electron transfer.

A pentacyclic quinoid dye, KuQ(O)3OH, combining (i) extended visible absorption up to 600 nm, (ii) excited state reduction potential >2 V vs. NHE, and (iii) a photoinduced proton-coupled electron transfer mechanism, has been used for the fabrication of dye-sensitized SnO2 photoanodes integrating a ruthenium polyoxometalate water oxidation catalyst. The resulting photoelectrode SnO2|KuQ(O)3OH|Ru4POM displays a light harvesting efficiency up to 90% in the range 500-600 nm, an onset potential as low as 0.2 V vs. NHE at pH 5.8, photoinduced oxygen evolution with a faradaic efficiency of 70 ± 15% and an absorbed-photon-to-current efficiency up to 0.12 ± 0.01%.

Focus on echocardiographic right ventricular strain analysis in cystic fibrosis adults without cardiovascular risk factors: a case-control study.

Strain echocardiography is able to detect subclinical ventricular systolic and diastolic dysfunction. Prolonged survival to cystic fibrosis favors heart and vessel involvement. The purpose of the present study was to compare clinically stable adult patients affected by cystic fibrosis without overt pulmonary hypertension with controls to evaluate right ventricular (RV) systolic and diastolic function by means of strain and tissue Doppler imaging (TDI), respectively. 22 adults affected by cystic fibrosis and 24 healthy volunteers matched for age and sex were enrolled. None had known cardiovascular risk factors or overt pulmonary hypertension. All people underwent blood pressure measurement and transthoracic echocardiography. Cystic fibrosis patients showed higher sPAP [median 25 (IQR 21-30) vs 22 (22-22) mmHg; p = 0.02] and more frequent RV diastolic dysfunction (p < 0.001). Among cases, some RV systolic parameters were significantly altered than controls, such as TAPSE [20 (18-24) vs. 23 (21-28) mm; p = 0.001], FAC [34 (26-44) vs. 49 (48-50)%; p < 0.001], midwall tissue strain [- 25.0 (- 31.3 to - 22.8) vs. - 30.5 (- 31.8 to - 29.3)%; p = 0.03], apical tissue strain [- 22 (- 29.3 to - 19.0) vs. - 30.5 (- 32.8 to - 28.3)%; p = 0.001] and 2D strain [- 22.0 (- 25.1 to - 19.0) vs. - 29.5 (- 31.8 to - 27.3)%; p < 0.001]. Finally, 2D strain correlated with spirometric FEV1 (ρ = - 0.463, p = 0.03) and nearly with FEF25-75% (ρ = - 0.393, p = 0.07). Our study confirmed a RV subclinical systo-diastolic dysfunction in clinically stable patients affected by cystic fibrosis without overt pulmonary hypertension nor cardiovascular risk factors. This may be due to systemic inflammation and temporary recurrent pulmonary hypertension. We retain that RV 2D strain and TDI echocardiography could become an important tool in the follow-up of these patients.

Electrocardiographic Changes Induced by Endurance Training and Pubertal Development in Male Children.

Training-induced electrocardiographic changes are common in adult athletes. However, a few data are available on electrocardiogram (ECG) in preadolescent athletes and little is known about the potential changes induced by training on 12-lead electrocardiogram (ECG) at rest. Twelve-lead ECGs at rest and complete echocardiographic examinations were performed in 94 children (57 endurance athletes, 37 sedentary controls; mean age 10.8 ± 0.2 and 10.2 ± 0.2 years, respectively) at baseline and after 5 months of growth and training in athletes and of natural growth in controls. At baseline, athletes had lower heart rate at rest compared with controls (p = 0.046) and a further decrease was observed after training (p <0.0001). An incomplete right bundle branch block was found in 19% of athletes and 15% of controls (p = 0.69) with no changes after training. Although none of the athletes showed negative T waves from V1 to V3, 6% of controls at baseline had T-wave inversion V1 to V3 with a decrease to 3% after 5 months (p = 0.16). The early repolarization pattern did not differ between athletes and controls and was correlated with Tanner's scale score in the overall population both at first and second evaluation (R = 0.30, R = 0.27, p = 0.005, p = 0.012, respectively). No correlations were found between ECG and echocardiographic data. In conclusion, 12-lead ECG at rest is not substantially affected by training in children, despite a physiological increase in cavity size. Thus, in preadolescent athletes, 12-lead ECG at rest does not reflect exercise-induced morphologic remodeling and seems to be influenced more by sexual maturation than by training.

Training-induced right ventricular remodelling in pre-adolescent endurance athletes: The athlete's heart in children.

AIMS: Little is known about the adaptation of the right ventricle (RV) to endurance exercise in children. The aim of this study was to assess the effects of 5months of intensive training on RV morphology and function in preadolescent endurance athletes. METHODS: Ninety-four children were evaluated in this study. Fifty-seven male competitive swimmers (aged 10.8±0.2years) were evaluated before (baseline) and after 5months of the training (peak-training), and compared to 37 age- and sex-matched non-athlete children evaluated at baseline and after 5months of natural growth. All subjects were asymptomatic, with negative family history for cardiomyopathies. RESULTS: At baseline no differences were found between athletes and controls for indexed RV outflow tract (RVOT) (18.5±2.7 vs. 16.8±5.0mm/m2, p=0.18) and RV basal end-diastolic diameter (EDD) (24.9±4.1 vs. 23.6±3.0mm/m2, p=0.15). After 5months, indexed RVOT and RV basal EDD significantly increased in athletes (20.2±2.9mm/m2 and 25.4±3.3mm/m2, p<0.0001 vs. baseline) while no differences were observed in controls (p=0.84 and p=0.25). Despite the increase in RV size, RV function remained normal in athletes, with no changes in RV fractional area change (p=0.97), s' value (p=0.22), and RV longitudinal strain (p=0.28). CONCLUSIONS: Endurance training influences the growing heart of male preadolescent athletes with an addictive increase in RV dimensions, with a preserved RV function. Therefore, in children engaged in endurance sports the increase in RV size associated with normal RV function represents a physiological expression of the athlete's heart and should not be misinterpreted as an expression of incipient RV cardiomyopathy.