The highly reactive dihalogens play a significant role in the oxidative chemistry of the troposphere. One of the main reservoirs of these halogens is hypohalous acids, HOX, which produce dihalogens in the presence of halides (Y-), where X, Y = Cl, Br, I. These reactions occur in and on aerosol particles and seawater surfaces and have been studied experimentally and by field observations. However, the mechanisms of these atmospheric reactions are still unknown. Here, we establish the atomistic mechanism of HOCl + Cl- → Cl2 + OH- at the surface of the water slab by performing ab initio molecular dynamics (AIMD) simulations. Main findings are (1) This reaction proceeds by halogen-bonded complexes of (HOCl)···(Cl-)aq surrounded with the neighboring water molecules. (2) The halogen bonded (HOCl)···(Cl-)aq complexes undergo charge transfer from Cl- to OH- to form transient Cl2 at neutral pH. (3) The addition of a proton to one proximal water greatly facilitates the Cl2 formation, which explains the enhanced rate at low pH.

Background

Physicians are not always comfortable deferring treatment of a stenosis in the left anterior descending (LAD) artery because of the perception that there is a high risk of major adverse cardiac events (MACE). The authors describe, using the DEFINE-FLAIR (Functional Lesion Assessment of Intermediate Stenosis to Guide Revascularisation) trial, MACE rates when LAD lesions are deferred, guided by physiological assessment using fractional flow reserve (FFR) or the instantaneous wave-free ratio (iFR).

Objectives

The purpose of this study was to establish the safety of deferring treatment in the LAD using FFR or iFR within the DEFINE-FLAIR trial.

Methods

MACE rates at 1 year were compared between groups (iFR and FFR) in patients whose physiological assessment led to LAD lesions being deferred. MACE was defined as a composite of cardiovascular death, myocardial infarction (MI), and unplanned revascularization at 1 year. Patients, and staff performing follow-up, were blinded to whether the decision was made with FFR or iFR. Outcomes were adjusted for age and sex.

Results

A total of 872 patients had lesions deferred in the LAD (421 guided by FFR, 451 guided by iFR). The event rate with iFR was significantly lower than with FFR (2.44% vs. 5.26%; adjusted HR: 0.46; 95% confidence interval [CI]: 0.22 to 0.95; p = 0.04). This was driven by significantly lower unplanned revascularization with iFR and numerically lower MI (unplanned revascularization: 2.22% iFR vs. 4.99% FFR; adjusted HR: 0.44; 95% CI: 0.21 to 0.93; p = 0.03; MI: 0.44% iFR vs. 2.14% FFR; adjusted HR: 0.23; 95% CI: 0.05 to 1.07; p = 0.06).

Conclusions

iFR-guided deferral appears to be safe for patients with LAD lesions. Patients in whom iFR-guided deferral was performed had statistically significantly lower event rates than those with FFR-guided deferral.