Replacement of Volatile Acetic Acid by Solid SiO2@COOH Silica (Nano)Beads for (Ep)Oxidation Using Mn and Fe Complexes Containing BPMEN Ligand.

Mn and Fe BPMEN complexes showed excellent reactivity in catalytic oxidation with an excess of co-reagent (CH3COOH). In the straight line of a cleaner catalytic system, volatile acetic acid was replaced by SiO2 (nano)particles with two different sizes to which pending carboxylic functions were added (SiO2@COOH). The SiO2@COOH beads were obtained by the functionalization of SiO2 with pending nitrile functions (SiO2@CN) followed by CN hydrolysis. All complexes and silica beads were characterized by NMR, infrared, DLS, TEM, X-ray diffraction. The replacement of CH3COOH by SiO2@COOH (100 times less on molar ratio) has been evaluated for (ep)oxidation on several substrates (cyclooctene, cyclohexene, cyclohexanol) and discussed in terms of activity and green metrics.

Organic Solvent-Free Olefins and Alcohols (ep)oxidation Using Recoverable Catalysts Based on [PM12O40]3- (M = Mo or W) Ionically Grafted on Amino Functionalized Silica Nanobeads.

Catalyzed organic solvent-free (ep)oxidation were achieved using H3PM12O40 (M = Mo or W) complexes ionically grafted on APTES-functionalized nano-silica beads obtained from straightforward method (APTES = aminopropyltriethoxysilane). Those catalysts have been extensively analyzed through morphological studies (Dynamic Light Scattering (DLS), TEM) and several spectroscopic qualitative (IR, multinuclear solid-state NMR) and quantitative (1H and 31P solution NMR) methods. Interesting catalytic results were obtained for the epoxidation of cyclooctene, cyclohexene, limonene and oxidation of cyclohexanol with a lower [POM]/olefin ratio. The catalysts were found to be recyclable and reused during three runs with similar catalytic performances.

Physical activity for patients with heart failure: Position paper from the heart failure (GICC) and cardiac rehabilitation (GERS-P) Working Groups of the French Society of Cardiology.

Physical activity is important in heart failure to improve functional capacity, quality of life and prognosis, and is a class IA recommendation in the European Society of Cardiology guidelines (Ponikowski et al., 2016). The benefits of exercise training are widely recognized. Cardiac rehabilitation centres offer tailored exercise training to patients with heart failure, as part of specialized multidisciplinary care, alongside pharmacological treatment optimization and patient education. After cardiac rehabilitation, maintenance of regular physical activity long term is essential, as the benefits of exercise training vanish within a few weeks. Unfortunately, only 10% of patients benefit from a cardiac rehabilitation programme after hospitalization for acute heart failure, and the majority of patients do not pursue long-term physical activity. In this paper, two Working Groups of the French Society of Cardiology (the heart failure group [Groupe Insuffisance Cardiaque et Cardiomyopathies; GICC] and the cardiac rehabilitation group [Groupe Exercice Réadaptation Sport et Prévention; GERS-P]) discuss the obstacles to broader access to cardiac rehabilitation centres, and propose ways to improve the diffusion of cardiac rehabilitation programmes and encourage long-term adherence to physical activity.

Identification of Second Shell Coordination in Transition Metal Species Using Theoretical XANES: Example of Ti-O-(C, Si, Ge) Complexes.

X-ray absorption near-edge structure (XANES) is a common technique for elucidating oxidation state and first shell coordination geometry in transition metal complexes, among many other materials. However, the structural information obtained from XANES is often limited to the first coordination sphere. In this study, we show how XANES can be used to differentiate between C, Si, and Ge in the second coordination shell of Ti-O-(C, Si, Ge) molecular complexes based on differences in their Ti K-edge XANES spectra. Experimental spectra were compared with theoretical spectra calculated using density functional theory structural optimization and ab initio XANES calculations. The unique features for second shell C, Si, and Ge present in the Ti K pre-edge XANES are attributed to the interaction between the Ti center and the O-X (X = C, Si, or Ge) antibonding orbitals.

Synthesis and characterization of tantalum silsesquioxane complexes.

Tantalum polyhedral oligosilsesquioxane (POSS) complexes have been synthesised and characterized. X-ray structures of these complexes revealed that the coordination number of the tantalum center greatly affects the cube-like silsesquioxane framework.

Photocatalyzed sulfide oxygenation with water as the unique oxygen atom source.

In our research program aiming to develop new ruthenium-based polypyridine catalysts for oxidation we were interested in combining a photosensitizer and a catalytic fragment within the same complex to achieve catalytic light-driven oxidation. To respond to the lack of such conjugates, we report here a new catalytic system capable of using light to activate water molecules in order to perform selective sulfide oxygenation into sulfoxide via an oxygen atom transfer from H(2)O to the substrate with a TON of up to 197 ± 6. On the basis of electrochemical and photophysical studies, a proton-coupled electron-transfer process yielding to an oxidant Ru(IV)-oxo species was proposed. In particular, the synergistic effect between both partners in the dyad yielding a more efficient catalyst compared to the bimolecular system is highlighted.

A dyad as photocatalyst for light-driven sulfide oxygenation with water as the unique oxygen atom source.

With the objective to convert light energy into chemical oxidation energy, a ruthenium-based dyad constituted of the assembly of a photosensitizer and a catalytic fragment was synthesized. Upon irradiation with blue LEDs, and in the presence of an electron acceptor, the complex is able to catalyze selective sulfide oxygenation involving an oxygen atom transfer from water to the substrate. Electrochemical and photophysical studies highlighted a proton-coupled electron transfer (PCET) to access to a high valent oxidant Ru(IV) oxo species.

Synthesis, electrochemical and photophysical properties of heterodinuclear Ru-Mn and Ru-Zn complexes bearing ambident Schiff base ligand.

While ruthenium tris(diimine) complexes have been extensively studied, this is not the case with ruthenium bis(diimine)X(2) complexes where X represents a pyridinyl-based ligand. The synthesis of a new complex ([2][PF(6)](2)) bearing two ambident Schiff base ligands (HL) constituted by the assembly of phenol and pyridinyl moieties is reported. Thanks to the heteroditopic property of HL, compound [2](2+) was used as an original metalloligand for the coordination of a redox-active (Mn(III)) and redox-inactive (Zn(II)) second metal cation affording three heterodinuclear complexes, namely, [(bpy)(2)Ru(2)Mn(acac)][PF(6)](2) ([3][PF(6)](2); acac = acetylacetonate), [(bpy)(2)Ru(2)Mn(OAc)][PF(6)](2) ([4][PF(6)](2), OAc = acetate), and [(bpy)(2)Ru(2)Zn][PF(6)](2) ([5][PF(6)](2)). The influence of the second metal with regard to the photophysical and electrochemical properties of the ruthenium bis(diimine)X(2) subunit was then investigated. In the case of Ru(II)-Mn(III) heterodinuclear complexes, a partial quenching of the luminescence was observed as a consequence of an efficient electron transfer process from the ruthenium to the manganese. EPR and spectrophotometric analyses of the oxidized species resulting from the one-electron oxidation of compounds [3](2+) and [4](2+) showed the formation of a Mn(IV) species for [3](2+) and an organic free radical for [4](2+).

Sustained positive impact of a coronary rehabilitation programme on adherence to dietary recommendations.

BACKGROUND: Nutrition has a major influence after coronary events but long-term adherence to dietary advice is poorly evaluated. AIM: To evaluate if a cardiovascular rehabilitation programme including dietary counselling has a positive impact on adherence to dietary recommendations. METHODS: Two groups of coronary patients were compared in an observational non-randomized study. Group I included 32 patients at the acute phase of a coronary syndrome and group II included 104 patients between six months and three years after completing a cardiovascular rehabilitation programme. The evaluation was performed with (1) a validated 14-item food frequency questionnaire (FFQ), which gives scores for the consumption of saturated fatty acids (SFA), monounsaturated fatty acids (MUFA), Omega-6 and Omega-3 polyunsaturated fatty acids (PUFA), fruits and vegetables, and a global cardiovascular protective dietary score; and (2) biological markers. RESULTS: SFA score was higher in group I vs II (7.4+/-2.8 vs 4.4+/-2.1, p<0.001) whereas Omega-3 PUFA (2.2+/-2.0 vs 4.7+/-2.1, p<0.001), fruit and vegetables score (3.3+/-1.4 vs 4.3+/-1.7, p=0.001) and global dietary score (-1.1+/-4.5 to 7.0+/-4.9, p<0.001) were higher in group II. The Omega-6:Omega-3 PUFA ratio was higher in group I (14.2+/-12.7 vs 6.3+/-5.4, p<0.001). Biological markers showed higher plasma contents of Omega-3 PUFA (4.05+/-1.70% vs 2.80+/-1.07%, p<0.001), folate (19.7+/-12.2 nmol/L vs 13.0+/-5.0 nmol/L, p<0.001) and vitamin C (7.60+/-3.99 mg/L vs 4.18+/-3.46 mg/L, p<0.001), and a higher erythrocyte membrane Omega-3 PUFA content (6.60+/-2.19% vs 5.38+/-2.17%, p=0.016) in group II vs I. CONCLUSION: Using a short FFQ, this study showed sustained improvement in dietary habits in patients with coronary heart disease who receive nutritional education during a cardiovascular rehabilitation programme.

Relative validity and reproducibility of a 14-item semi-quantitative food frequency questionnaire for cardiovascular prevention.

BACKGROUND: Dietary habits play a major role in cardiovascular disease risk but few simple nutrition assessment tools are available for clinical practice. We developed a 14-item food frequency questionnaire to evaluate dietary patterns in relation with coronary risk in a French population. DESIGN AND METHODS: This food frequency questionnaire gave different scores of intake: saturated fatty acids (six questions), mono-unsaturated fatty acids, Omega-3 and Omega-6/Omega-3 polyunsaturated fatty acids (five questions), and fruits and vegetables (three questions). Validity was assessed against a 7-day dietary history (n = 49 subjects) and against biomarkers (n = 181). The food frequency questionnaire was also administered twice with an interval of 15 days to evaluate its reproducibility (n = 20). RESULTS: Validity against dietary history was assessed with Spearman correlation coefficients which ranged from 0.47 (fruits and vegetables) to 0.63 (polyunsaturated fatty acids/saturated fatty acids) (all P < 0.05), with a mean value of 0.54. On average, 39% of the subjects were classified in the same quartile with the food frequency questionnaire and the dietary history and 84% in the same or adjacent quartile. Biomarker-based validity using Spearman correlation coefficients varied from 0.21 (saturated fatty acids) to 0.53 (Omega-3 polyunsaturated fatty acids) (all P < 0.05), with a mean value of 0.35. On average, 37% of the participants were classified in the same quartile with the food frequency questionnaire and the corresponding biomarkers and 73% in the same or adjacent quartile. Reproducibility assessed by the intraclass correlation coefficient ranged from 0.71 (mono-unsaturated fatty acids) to 0.93 (global score), with a mean value of 0.81. CONCLUSION: We validated a short food frequency questionnaire for dietary pattern assessment in coronary prevention.

Validation of a two-axis accelerometer for monitoring patient activity during blood pressure or ECG holter monitoring.

OBJECTIVES: The aim of the study was to evaluate the efficiency of a position/activity monitoring system based on a dual-axis accelerometer strapped to the subject's thigh and a position sensor located within a monitor placed on the subject's belt. METHODS: Twenty-six subjects wearing two monitors (one accelerometer on each thigh) were submitted to various activities and positions under the control of an observer. An analysis of each tracing was performed both manually by a technician and automatically by dedicated software before being compared with the information gathered during the study. RESULTS: The accelerometer allowed accurate discrimination between the standing versus the sitting and lying positions. The sitting and lying positions were correctly detected by the built-in position sensor provided the unit was firmly attached. Walking was adequately detected by the accelerometer. The activity score was well correlated with treadmill speed. Changes in position and activity were detected with a mean error of less than 3 s. CONCLUSIONS: The combination of an accelerometer placed on the subject's thigh and a position sensor located at the subject's waist appeared to be a suitable system for position/activity monitoring during ambulatory ECG and blood pressure monitoring.

Combined effects of enalapril and spironolactone in hamsters with dilated cardiomyopathy.

Chronic angiotensin I-converting enzyme inhibition can be associated with aldosterone escape. We investigated the effects of enalapril, spironolactone, and their combination on hemodynamics and cardiac remodeling in cardiomyopathic hamsters to determine whether these drugs could exert additive effects. Cardiomyopathic hamsters, Bio TO-2 dilated strain, were orally treated with enalapril (20 mg. kg. day ) and/or spironolactone (20 mg. kg. day ) according to a 2 x 2 factorial design from 120 days of age. Animals were investigated at 180 (10 animals per group) and 240 (16 animals per group) days of age. Compared with corresponding untreated groups, enalapril significantly decreased mean blood pressure (-18%); enalapril and spironolactone significantly increased cardiac output (+28%, +11%) and femoral blood flow (+10%, +12%) and significantly decreased systemic (-38%, -17%) and femoral (-26%, -13%) vascular resistances. Enalapril and spironolactone significantly decreased left ventricle cavity area (-21%, -26%) and left (-34%, -47%) and right (-37%, -48%) ventricle collagen density. Spironolactone significantly increased left ventricle wall thickness (+4%). There were significant enalapril x spironolactone interactions for most variables (compared with control group, +52%, +36%, +45% for cardiac output; +26%, +28%, +26% for femoral blood flow; -50%, -30%, -45% for systemic vascular resistance; -33%, -20%, -35% for femoral vascular resistance; -27%, -31%, -40% for left ventricle cavity area; and -46%, -58%, -60% for left and -39%, -50%, -66% for right ventricle collagen density in enalapril, spironolactone, and enalapril + spironolactone groups, respectively). In cardiomyopathic hamsters, enalapril and spironolactone in combination did not improve hemodynamics more than enalapril alone but induced stronger effects than each drug alone on cardiac remodeling.

Combined effects of metoprolol and spironolactone in dilated cardiomyopathic hamsters.

The use of beta-blockers reduces angiotensin II levels, but could not adequately suppress aldosterone production. Thus, the combination of a beta-blocker with an aldosterone receptor antagonist could exert additive effects. The effects of metoprolol and spironolactone and their combination on hemodynamics and cardiac remodeling in cardiomyopathic hamsters (CMH) were investigated. The Bio TO-2 dilated strain of CMH was treated orally with metoprolol (10 mg/kg/day), spironolactone (20 mg/kg/day), or both according to a 2 x 2 factorial design (24 animals per group) from 120 days of age and during 120 days. As compared to corresponding untreated groups, metoprolol significantly decreased mean blood pressure (-7%), and metoprolol and spironolactone significantly increased cardiac output (18% and 19%, respectively), mesenteric blood flow (11% and 14%), and femoral blood flow (13% and 17%), and significantly decreased systemic (-24% and -15%), mesenteric (-14% and -13%) and femoral (-19% and -10%) vascular resistances. Metoprolol significantly increased renal blood flow (22%) and significantly decreased renal vascular resistance (-23%). Metoprolol and spironolactone significantly decreased the cavity area of the left ventricle (-21% and -32%, respectively) and the collagen density of the left (-36% and -39%) and right (-38% and -43%) ventricles. Although the combination did not induce stronger effects than each drug alone on the systemic and most regional hemodynamic variables, it did have a stronger effect on the cardiac remodeling (compared to control group: -24%, -34%, and -46% for the left ventricle cavity area, -33%, -35%, and -62% for collagen density in the left ventricle, and -52%, -57%, and -59% for collagen density in the right ventricle, respectively, in the metoprolol, spironolactone, and metoprolol + spironolactone groups). In CMH, metoprolol and spironolactone combined did not improve hemodynamics more than each drug alone, but did exert additive effects on cardiac remodeling.

Systemic and regional hemodynamic and cardiac remodeling effects of candesartan in dilated cardiomyopathic hamsters with advanced congestive heart failure.

The effects of the selective angiotensin II type 1 receptor antagonist candesartan on cardiac, systemic, and regional hemodynamics and on cardiac, pulmonary, and hepatic histomorphometry were investigated in cardiomyopathic hamsters (CMHs), Bio TO-2 dilated strain, with advanced congestive heart failure (CHF). Two groups were treated orally with candesartan cilexetil at 22 or 50 mg/kg/d from 190 days of age and compared with a control group (38 animals/group). Investigations were performed at 225, 255, and 285 days of age. Left ventricle (LV) and systemic blood pressures and cardiac output and mesenteric and femoral blood flows were measured in anesthetized animals. LV cavity area, LV and right ventricle (RV) wall thickness and collagen density, and pulmonary and hepatic congestion were assessed. Compared with the control group, candesartan did not modify cardiac hemodynamics but significantly and dose-dependently decreased systemic vascular resistances (on average: -23 and -32% after 22 and 50 mg/kg, respectively) and increased stroke volume (+32 and +42%) and cardiac output (+27 and +34%). Candesartan did not modify mesenteric vascular resistances and blood flow but significantly and dose-dependently decreased femoral vascular resistances (-19 and -33%) and increased femoral blood flow (+33 and +43%). Candesartan significantly decreased LV cavity area (-14 and -8%) and LV (-15 and -31%) and RV (-16 and -24%) collagen density but did not modify LV and RV wall thickness. Candesartan decreased pulmonary congestion at 255 and 285 days of age but did not modify hepatic congestion. In CMHs with advanced CHF, candesartan cilexetil improves systemic and femoral hemodynamics, partly reverses cardiac remodeling, and decreases pulmonary congestion.

Early anti-remodeling effect of labetalol in the congestive heart failure model induced by aortic constriction in the guinea pig.

We investigated the effects of the beta1-beta2-alpha1-blocker, labetalol, in the congestive heart failure (CHF) model induced by aortic constriction in the guinea pig. One hundred days after aortic constriction, 52 animals were given either placebo, labetalol 2 mg/kg/d, or labetalol 20 mg/kg/d for 60 days. Eighteen sham-operated animals were used as controls. Investigations were performed at the end of the treatment period. Compared with sham-operated animals, banded animals receiving placebo showed signs of overt CHF with cardiac, systemic and regional (mesenteric and femoral) hemodynamic dysfunction, and pulmonary and hepatic congestion. An increase in whole heart, atria, and left and right ventricle weights associated with left ventricular cavity enlargement and left and right ventricular wall thickening indicated a remodeling process. Compared with placebo, labetalol did not significantly modify cardiac, systemic, or regional hemodynamic variables but significantly decreased pulmonary and hepatic congestion. Labetalol significantly reduced left ventricular cavity area (-10 and -20% after 2 and 20 mg/kg, respectively) and left ventricular (-4 and -16%) and right ventricular (-4 and -19%) wall thickness. In conclusion, labetalol induced partial regression of cardiac remodeling before hemodynamic improvement. This early anti-remodeling effect could play a role in the favorable effects observed with beta1-beta2-alpha1-blockers in humans.