Theoretical study of the OH-initiated atmospheric oxidation mechanism of perfluoro methyl vinyl ether, CF_3OCF=CF_2

Product formation in the reaction of perfluorinated methyl vinyl ether, CF_3OCF=CF_2, with OH radicals is studied theoretically using the M06-2X/aug-cc-pVTZ and CCSD(T) levels of theory. The stable end-products in an oxidative atmosphere are predicted to be perfluorinated methyl formate, CF_3OCFO, and fluorinated glycolaldehyde, CFOCF_2OH, both with CF_2O as coproduct. The prediction of glycolaldehyde as a product contrasts with experimental data, which found perfluoro glyoxal, CFOCFO, instead. The most likely explanation for this apparent disagreement is conversion of CFOCF_2OH to CFOCFO, e.g. by multiple catalytic agents present in the reaction mixture, wall reactions, and/or photolysis. The formation routes for the glyoxal product proposed in earlier work appear unlikely, and are not supported by theoretical or related experimental work

Temperature-(208-318 K) and pressure-(18-696Torr) dependent rate coefficients for the reaction between OH and HNO3

Abstract. Rate coefficients (k5) for the title reaction were ob- tained using pulsed laser photolytic generation of OH cou- pled to its detection by laser-induced fluorescence (PLP– LIF). More than 80 determinations of k5 were carried out in nitrogen or air bath gas at various temperatures and pres- sures. The accuracy of the rate coefficients obtained was en- hanced by in situ measurement of the concentrations of both HNO3 reactant and NO2 impurity. The rate coefficients show both temperature and pressure dependence with a rapid in- crease in k5 at low temperatures. The pressure dependence was weak at room temperature but increased significantly at low temperatures. The entire data set was combined with se- lected literature values of k5 and parameterised using a com- bination of pressure-dependent and -independent terms to give an expression that covers the relevant pressure and tem- perature range for the atmosphere. A global model, using the new parameterisation for k 5 rather than those presently ac- cepted, indicated small but significant latitude- and altitude- dependent changes in the HNO 3 / NO x ratio of between − 6 and + 6 %. Effective HNO 3 absorption cross sections (184.95 and 213.86 nm, units of cm 2 molecule − 1 ) were ob- tained as part of this work: σ 213 . 86 = 4.52 + 0 . 23 − 0 . 12 × 10 − 19 and σ 184 . 95 = 1.61 + 0 . 08 − 0 . 04 × 10 − 17

Rationale, design and methodology of APPROACH-IS II: International study of patient-reported outcomes and frailty phenotyping in adults with congenital heart disease.

In recent years, patient-reported outcomes (PROs) have received increasing prominence in cardiovascular research and clinical care. An understanding of the variability and global experience of PROs in adults with congenital heart disease (CHD), however, is still lacking. Moreover, information on epidemiological characteristics and the frailty phenotype of older adults with CHD is minimal. The APPROACH-IS II study was established to address these knowledge gaps. This paper presents the design and methodology of APPROACH-IS II. APPROACH-IS II is a cross-sectional global multicentric study that includes Part 1 (assessing PROs) and Part 2 (investigating the frailty phenotype of older adults). With 53 participating centers, located in 32 countries across six continents, the aim is to enroll 8000 patients with CHD. In Part 1, self-report surveys are used to collect data on PROs (e.g., quality of life, perceived health, depressive symptoms, autonomy support), and explanatory variables (e.g., social support, stigma, illness identity, empowerment). In Part 2, the cognitive functioning and frailty phenotype of older adults are measured using validated assessments. APPROACH-IS II will generate a rich dataset representing the international experience of individuals in adult CHD care. The results of this project will provide a global view of PROs and the frailty phenotype of adults with CHD and will thereby address important knowledge gaps. Undoubtedly, the project will contribute to the overarching aim of improving optimal living and care provision for adults with CHD

Rivaroxaban Compared with Standard Anticoagulants for the Treatment of Acute Venous Thromboembolism in Children: a Randomised, Controlled, Phase 3 Trial

Background: Treatment of venous thromboembolism in children is based on data obtained in adults with little direct documentation of its efficacy and safety in children. The aim of our study was to compare the efficacy and safety of rivaroxaban versus standard anticoagulants in children with venous thromboembolism. Methods: In a multicentre, parallel-group, open-label, randomised study, children (aged 0–17 years) attending 107 paediatric hospitals in 28 countries with documented acute venous thromboembolism who had started heparinisation were assigned (2:1) to bodyweight-adjusted rivaroxaban (tablets or suspension) in a 20-mg equivalent dose or standard anticoagulants (heparin or switched to vitamin K antagonist). Randomisation was stratified by age and venous thromboembolism site. The main treatment period was 3 months (1 month in children <2 years of age with catheter-related venous thromboembolism). The primary efficacy outcome, symptomatic recurrent venous thromboembolism (assessed by intention-to-treat), and the principal safety outcome, major or clinically relevant non-major bleeding (assessed in participants who received ≥1 dose), were centrally assessed by investigators who were unaware of treatment assignment. Repeat imaging was obtained at the end of the main treatment period and compared with baseline imaging tests. This trial is registered with ClinicalTrials.gov, number NCT02234843 and has been completed. Findings: From Nov 14, 2014, to Sept 28, 2018, 500 (96%) of the 520 children screened for eligibility were enrolled. After a median follow-up of 91 days (IQR 87–95) in children who had a study treatment period of 3 months (n=463) and 31 days (IQR 29–35) in children who had a study treatment period of 1 month (n=37), symptomatic recurrent venous thromboembolism occurred in four (1%) of 335 children receiving rivaroxaban and five (3%) of 165 receiving standard anticoagulants (hazard ratio [HR] 0·40, 95% CI 0·11–1·41). Repeat imaging showed an improved effect of rivaroxaban on thrombotic burden as compared with standard anticoagulants (p=0·012). Major or clinically relevant non-major bleeding in participants who received ≥1 dose occurred in ten (3%) of 329 children (all non-major) receiving rivaroxaban and in three (2%) of 162 children (two major and one non-major) receiving standard anticoagulants (HR 1·58, 95% CI 0·51–6·27). Absolute and relative efficacy and safety estimates of rivaroxaban versus standard anticoagulation estimates were similar to those in rivaroxaban studies in adults. There were no treatment-related deaths. Interpretation: In children with acute venous thromboembolism, treatment with rivaroxaban resulted in a similarly low recurrence risk and reduced thrombotic burden without increased bleeding, as compared with standard anticoagulants. Funding: Bayer AG and Janssen Research & Development. © 2020 Elsevier Ltd

Kinetics and mechanism of the reaction of perfluoro propyl vinyl ether (PPVE, C₃F₇OCH=CH₂) with OH: assessment of its fate in the atmosphere

Absolute rate coefficients for the reaction between OH radicals and perfluoro propyl vinyl ether (PPVE) were obtained using the technique of pulsed laser photolysis with the detection of OH radicals by laser induced fluorescence. Rate coefficients were measured over a range of temperatures (212-298 K) and at either 50 or 200 Torr bath-gas (N-2 or N-2/O-2). The temperature dependence of the rate coefficient is given by k(1)(212-298 K) = (4.88 +/- 0.49) x 10(-13) exp[(564 +/- 10)/T] cm(3) molecule(-1) s(-1) with a value at room temperature of (3.4 +/- 0.3) x 10(-12) cm(3) molecule(-1) s(-1). No pressure dependence was observed, indicating that the reaction is at the high pressure limit under atmospheric conditions. The accuracy of the rate coefficient obtained was enhanced by on-line optical absorption measurements of PPVE at 184.95 nm using a value of sigma(184.95) nm = (5.64 +/- 0.28) x 10(-18) cm(2) molecule(-1) determined in this work. An atmospheric lifetime of a few days for PPVE was calculated. Extensive quantum chemical calculations as a complement to the experimental work are presented in order to determine its probable tropospheric degradation mechanism

Theoretical study of the OH-initiated atmospheric oxidation mechanism of perfluoro methyl vinyl ether, CF₃OCF=CF₂

Product formation in the reaction of perfluorinated methyE vinyE ether, CF3OCF=CF2, with OH radicals is studied theoretically using the M06-2X/aug-cc-pVTZ and CCSD(T) Eevek of theory. The stable end-products in an oxidative atmosphere are predicted to be perfluorinated methyE formate, CF3OCFO, and fluorinated glycolaldehyde, CFOCF2OH, both with CF2O as coproduct. The prediction of glycolaldehyde as a product contrasts with experimental data, which found perfluoro glyoxal, CFOCFO, instead. The most likely explanation for this apparent disagreement is conversion of CFOCF2OH to CFOCFO, e.g. by multiple catalytic agents present in the reaction mixture, wall reactions, and/or photolysis. The formation routes for the glyoxal product proposed in eater work appear unlikely, and are not supported by theoretical or related experimental work

Absolute and relative-rate measurement of the rate coefficient for reaction of perfluoro ethyl vinyl ether (C₂F₅OCF=CF₂) with OH

The rate coefficient (k1) for the reaction of OH radicals with perfluoro ethyl vinyl ether (PEVE, C2F5OCF[double bond, length as m-dash]CF2) has been measured as a function of temperature (T = 207–300 K) using the technique of pulsed laser photolysis with detection of OH by laser-induced fluorescence (PLP-LIF) at pressures of 50 or 100 Torr N2 bath gas. In addition, the rate coefficient was measured at 298 K and in one atmosphere of air by the relative-rate technique with loss of PEVE and reference reactant monitored in situ by IR absorption spectroscopy. The rate coefficient has a negative temperature dependence which can be parameterized as: k1(T) = 6.0 × 10−13 exp[(480 ± 38/T)] cm3 molecule−1 s−1 and a room temperature value of k1 (298 K) = (3.0 ± 0.3) × 10−12 cm3 molecule−1 s−1. Highly accurate rate coefficients from the PLP-LIF experiments were achieved by optical on-line measurements of PEVE and by performing the measurements at two different apparatuses. The large rate coefficient and the temperature dependence indicate that the reaction proceeds via OH addition to the C[double bond, length as m-dash]C double bond, the high pressure limit already being reached at 50 Torr N2. Based on the rate coefficient and average OH levels, the atmospheric lifetime of PEVE was estimated to be a few days

Kinetics of the OH + NO₂ reaction: rate coefficients (217-333 K, 16-1200 mbar) and fall-off parameters for N₂ and O₂ bath gases

The radical terminating, termolecular reaction between OH and NO2 exerts great influence on the NOy∕NOx ratio and O3 formation in the atmosphere. Evaluation panels (IUPAC and NASA) recommend rate coefficients for this reaction that disagree by as much as a factor of 1.6 at low temperature and pressure. In this work, the title reaction was studied by pulsed laser photolysis and laser-induced fluorescence over the pressure range 16–1200 mbar and temperature range 217–333 K in N2 bath gas, with experiments at 295 K (67–333 mbar) for O2. In situ measurement of NO2 using two optical absorption set-ups enabled generation of highly precise, accurate rate coefficients in the fall-off pressure range, appropriate for atmospheric conditions. We found, in agreement with previous work, that O2 bath gas has a lower collision efficiency than N2 with a relative collision efficiency to N2 of 0.74. Using the Troe-type formulation for termolecular reactions we present a new set of parameters with k0(N2) = 2.6×10−30  cm6 molecule−2 s−1, k0(O2) = 2.0×10−30 cm6 molecule−2 s−1, m=3.6, k∞=6.3×10−11 cm3 molecule−1 s−1, and Fc=0.39 and compare our results to previous studies in N2 and O2 bath gases