Risk profiles and one-year outcomes of patients with newly diagnosed atrial fibrillation in India: Insights from the GARFIELD-AF Registry.

BACKGROUND: The Global Anticoagulant Registry in the FIELD-Atrial Fibrillation (GARFIELD-AF) is an ongoing prospective noninterventional registry, which is providing important information on the baseline characteristics, treatment patterns, and 1-year outcomes in patients with newly diagnosed non-valvular atrial fibrillation (NVAF). This report describes data from Indian patients recruited in this registry. METHODS AND RESULTS: A total of 52,014 patients with newly diagnosed AF were enrolled globally; of these, 1388 patients were recruited from 26 sites within India (2012-2016). In India, the mean age was 65.8 years at diagnosis of NVAF. Hypertension was the most prevalent risk factor for AF, present in 68.5% of patients from India and in 76.3% of patients globally (P < 0.001). Diabetes and coronary artery disease (CAD) were prevalent in 36.2% and 28.1% of patients as compared with global prevalence of 22.2% and 21.6%, respectively (P < 0.001 for both). Antiplatelet therapy was the most common antithrombotic treatment in India. With increasing stroke risk, however, patients were more likely to receive oral anticoagulant therapy [mainly vitamin K antagonist (VKA)], but average international normalized ratio (INR) was lower among Indian patients [median INR value 1.6 (interquartile range {IQR}: 1.3-2.3) versus 2.3 (IQR 1.8-2.8) (P < 0.001)]. Compared with other countries, patients from India had markedly higher rates of all-cause mortality [7.68 per 100 person-years (95% confidence interval 6.32-9.35) vs 4.34 (4.16-4.53), P < 0.0001], while rates of stroke/systemic embolism and major bleeding were lower after 1 year of follow-up. CONCLUSION: Compared to previously published registries from India, the GARFIELD-AF registry describes clinical profiles and outcomes in Indian patients with AF of a different etiology. The registry data show that compared to the rest of the world, Indian AF patients are younger in age and have more diabetes and CAD. Patients with a higher stroke risk are more likely to receive anticoagulation therapy with VKA but are underdosed compared with the global average in the GARFIELD-AF. CLINICAL TRIAL REGISTRATION-URL: http://www.clinicaltrials.gov. Unique identifier: NCT01090362

The reaction energies of ethylene, CO, and N 2 with proton, hydrogen atom, and hydride ion

It is shown by quantum chemical simulation (MP2/aug-cc-pVTZ) that the energy of addition of H +, H ̇, and H - decreases in the order ethylene, CO, and N 2. The energies of additions of CF 4, dimethyl ether, and BF 3 to the ions and radicals formed were calculated. Unlike the CH 3CH 2 - ion, the HCO - ion can add exothermically not one, but two BF 3 molecules. © 2011 Springer-Verlag

Mechanism of oxygen transfer from the vanadium(V) complexes with ligands O2 2- and O3 2-

The oxygen transfer from the vanadium(V) complexes containing peroxo, oxo, and ozonide ligands to electron-donating substrates (ethylene and vinyl methyl ether) was studied in the framework of the DFT with the M06 hybrid functional. The O atom of the ozonide fragment in the O3VO(η-O2)- complex is transferred to the electron-donating substrates with lower energy expenses than the O atom of the peroxo group of the isomeric triperoxo complex, in spite of the fact that the presence of the peroxo group in the ozonide complexes stabilizes it favoring the formation of the V-Oc bond according to the data of topological analysis of the electron density in terms of the theory of atoms in molecules (AIM). The calculation results are in agreement with the experimental kinetic data indicating somewhat lower reactivity of triperoxovanadate compared to the isomeric oxygenyl complexes. © 2014 Springer Science+Business Media New York

Mechanism of oxygen transfer from the vanadium(V) complexes with ligands O2 2- and O3 2-

The oxygen transfer from the vanadium(V) complexes containing peroxo, oxo, and ozonide ligands to electron-donating substrates (ethylene and vinyl methyl ether) was studied in the framework of the DFT with the M06 hybrid functional. The O atom of the ozonide fragment in the O3VO(η-O2)- complex is transferred to the electron-donating substrates with lower energy expenses than the O atom of the peroxo group of the isomeric triperoxo complex, in spite of the fact that the presence of the peroxo group in the ozonide complexes stabilizes it favoring the formation of the V-Oc bond according to the data of topological analysis of the electron density in terms of the theory of atoms in molecules (AIM). The calculation results are in agreement with the experimental kinetic data indicating somewhat lower reactivity of triperoxovanadate compared to the isomeric oxygenyl complexes. © 2014 Springer Science+Business Media New York

The reaction energies of ethylene, CO, and N 2 with proton, hydrogen atom, and hydride ion

It is shown by quantum chemical simulation (MP2/aug-cc-pVTZ) that the energy of addition of H +, H ̇, and H - decreases in the order ethylene, CO, and N 2. The energies of additions of CF 4, dimethyl ether, and BF 3 to the ions and radicals formed were calculated. Unlike the CH 3CH 2 - ion, the HCO - ion can add exothermically not one, but two BF 3 molecules. © 2011 Springer-Verlag

Special features of ethylene epoxidation by peroxyacetic acid

The B3LYP/6-31G(d, p) method of density functional theory was used to study the influence of carboxylic acid and water molecules on parallel ethylene oxidation reactions (epoxidation and hydroxylation) by peroxyacetic acid with the formation of various products. It was shown that carboxylic acid in the nondissociated form always present in the reaction mixture for several reasons had a catalytic action on this reaction and therefore contributed to an increase in its selectivity. We also found that the water molecule and its dimer facilitated epoxide formation. The suggestion was made that, if the reaction was performed in an aqueous medium, where the acid dissociated, the situation could radically change, and the hydroxylation reaction with the formation of glycol and/or its ester of the corresponding carboxylic acid would become predominant. © 2010 Pleiades Publishing, Ltd

A quantum-chemical study of the oxidation of ethylene by peroxyacetic acid derivatives

Density functional theory (B3LYP/6-31G(d, p)) and the Möller-Plesset perturbation theory (MP2/6-31G(d, p)) were used to study the electronic and geometric structure and relative stability of possible peroxyacetic acid and its trifluorinated derivative tautomers (including conformers), R-C(=O)(-OOH), R = CH3, CF3. Four types of stable tautomers of both compounds were found, and the energy characteristics of transitions between them were determined. The results of quantum-chemical modeling were used to study some special features of the oxidation of ethylene with the participation of all the tautomeric forms of both peroxy acids. For the acyclic form (ground state) of both peroxy acids and its conformers, two reactions are possible, namely, epoxidation with the formation of ethylene oxide (plus acid) and hydroxylation with the formation of ethanediol acetate ester and/or its isomer acetaldehyde semiacetal. At the same time, the oxidation of ethylene with the participation of all the other tautomeric forms (dioxirane and tautomers of the type of carbonyl and water oxides) only results in ethylene epoxidation. © Pleiades Publishing, Ltd., 2010

A quantum-chemical study of the oxidation of ethylene by peroxyacetic acid derivatives

Density functional theory (B3LYP/6-31G(d, p)) and the Möller-Plesset perturbation theory (MP2/6-31G(d, p)) were used to study the electronic and geometric structure and relative stability of possible peroxyacetic acid and its trifluorinated derivative tautomers (including conformers), R-C(=O)(-OOH), R = CH3, CF3. Four types of stable tautomers of both compounds were found, and the energy characteristics of transitions between them were determined. The results of quantum-chemical modeling were used to study some special features of the oxidation of ethylene with the participation of all the tautomeric forms of both peroxy acids. For the acyclic form (ground state) of both peroxy acids and its conformers, two reactions are possible, namely, epoxidation with the formation of ethylene oxide (plus acid) and hydroxylation with the formation of ethanediol acetate ester and/or its isomer acetaldehyde semiacetal. At the same time, the oxidation of ethylene with the participation of all the other tautomeric forms (dioxirane and tautomers of the type of carbonyl and water oxides) only results in ethylene epoxidation. © Pleiades Publishing, Ltd., 2010

Special features of ethylene epoxidation by peroxyacetic acid

The B3LYP/6-31G(d, p) method of density functional theory was used to study the influence of carboxylic acid and water molecules on parallel ethylene oxidation reactions (epoxidation and hydroxylation) by peroxyacetic acid with the formation of various products. It was shown that carboxylic acid in the nondissociated form always present in the reaction mixture for several reasons had a catalytic action on this reaction and therefore contributed to an increase in its selectivity. We also found that the water molecule and its dimer facilitated epoxide formation. The suggestion was made that, if the reaction was performed in an aqueous medium, where the acid dissociated, the situation could radically change, and the hydroxylation reaction with the formation of glycol and/or its ester of the corresponding carboxylic acid would become predominant. © 2010 Pleiades Publishing, Ltd

Tautomerism of peroxyacetic acid derivatives: A quantum chemical study

The electronic and molecular structures and the relative stabilities of organic peracids X=C(R)-COOH and their cyclic tautomers, dioxiranes HX-C(R)-C-O-O, with R = Me, CF3; X = O, NH, were studied using the ab initio Hartree-Fock method and the density functional theory (B3LYP version) as well as at the MP2-MP4 Møller- Plesset levels of perturbation theory. Geometry optimization was performed by the UHF and B3LYP methods with the 6-31G** basis set and at the MP2/cc-pvtz level of theory. The acyclic form of the peracid is more stable than the cyclic dioxirane form irrespective of the nature of the substituent. The energy difference between these tautomers increases as the CF3 and NH groups are replaced by Me and O, respectively. Parameters of the activation barrier to tautomeric conversion increase in parallel with enhancement of the electron-accepting properties of both substituents. The transition state of tautomeric interconversion, which is topologically similar to the acyclic structure of the carbonyl oxide derivative R(HX)C=O+-O-, was found and characterized taking peroxyacetic acid as an example. The characteristic features of the transition state are an intramolecular "multicenter" H-bond and the charge distribution that is inconsistent with the canonical structure mentioned above. An appropriate reaction coordinate for the transformation of the quasi-tetrahedral dioxirane structure into a planar peroxyacetic acid structure is provided by the dihedral angle. Deprotonated anionic systems are characterized by much smaller differences between the relative stabilities of the open and closed forms of isomers and by much lower activation barriers to isomeric conversions. © 2005 Springer Science+Business Media, Inc