Guanine radical cations are formed upon oxidation of DNA. Deoxyguanosine (dG) is used as a model, and the gas-phase infrared (IR) spectroscopic signature and gas-phase unimolecular and bimolecular ...chemistry of its radical cation, dG˙(+), A, which is formed via direct electrospray ionisation (ESI/MS) of a methanolic solution of Cu(NO3)2 and dG, are examined. Quantum chemistry calculations have been carried out on 28 isomers and comparisons between their calculated IR spectra and the experimentally-measured spectra suggest that A exists as the ground-state keto tautomer. Collision-induced dissociation (CID) of A proceeds via cleavage of the glycosidic bond, while its ion–molecule reactions with amine bases occur via a number of pathways including hydrogen-atom abstraction, proton transfer and adduct formation. A hidden channel, involving isomerisation of the radical cation via adduct formation, is revealed through the use of two stages of CID, with the final stage of CID showing the loss of CH2O as a major fragmentation pathway from the reformed radical cation, dG˙(+). Quantum chemistry calculations on the unimolecular and bimolecular reactivity are also consistent with A being present as a ground-state keto tautomer.
Background: Whether unidirectional conduction block (UB) can be observed after creation of a radiofrequency (RF) line is still debated. Previous studies reported a prevalence of 9 to 33% of UB, but ...the assessment was performed using a point-by-point recording across the line. Ultra-high-density (UHD) system may bring some new insights on the exact prevalence of UB. Purpose: A prospective study was conducted to assess the prevalence of UB and bidirectional block (BB) using UHD system after RF line creation. Methods: Patients referred for atrial RF ablation procedure were included in this multicenter prospective study. UHD maps were performed by pacing both sides of the created line. Results: A total of 80 maps were created in 40 patients (67 ± 12 years, 70% male) by pacing (mean cycle length 600 ± 57 ms) from both sides of the cavotricuspid isthmus line. After a 47 ± 17 min waiting time after the last RF application, UHD maps (mean number of 4842 ± 5010 electrograms, acquired during 6 ± 5 min) showed that BB was unambiguously confirmed on all of them. UB was not observed in any map. After a mean follow-up of 12 ± 4 months, 6 (14%) patients experienced an arrhythmia recurrence. Conclusion: After creation of an RF line, no case of UB was observed using UHD mapping, suggesting that the presence of a conduction block along a RF line is always associated with a block in the opposite direction.
Photo-chemistry provides a non-intuitive but very powerful way to probe kinetically limited, sometimes thermodynamically non-favored reactions and, thus, access highly specific products. However, ...reactivity in the excited state is difficult to characterize directly, due to short lifetimes and challenges in controlling the reaction medium. Among photo-activatable reagents, rhodamine dyes find widespread uses due to a number of favorable properties including their high absorption coefficient. Their readily adaptable synthesis allows development of tailor-made dyes for specific applications. Remarkably, few studies have directly probed the chemical reactivity of their triplet excited state. Here we present a new conceptual approach to examine the specific chemistry of the triplet excited state. We have developed a pump (488 nm) - probe (600 nm) strategy to examine the gas-phase lifetime and reactivity of the triplet cation of Rhodamine 6G (
Rh6G
) in an ion trap mass spectrometer. The confounding effects of solvent, aggregation and formation of other reactive intermediates is thus avoided allowing fundamental reactivity to be explored. In the presence, in the ion trap, of helium seeded with 1% of nitric oxide (˙NO) (∼ 60 ion/˙NO collisions per second), the triplet lifetime is shortened from 1.9 s to 0.7 s. Simultaneously, the reaction products Rh6G-H˙
and Rh6G-H + NO
are observed. Reaction of
Rh6G
with ˙NO
yields Rh6G-H˙
, Rh6G-H + NO
and Rh6G-2H
. None of these products are observed for the singlet,
Rh6G
. DFT calculations suggest a stepwise mechanism only allowed from
Rh6G
, in which H atom abstraction by ˙NO
(
= 1 or 2) yields Rh6G-H˙
which, then, reacts with another ˙NO
molecule. This illustrates the power of light to initiate specific chemical reactions, and the relevance of gas-phase ion-molecule reaction approaches to understand stepwise reaction mechanism from specific excited states.
In repaired tetralogy of Fallot (TOF), little is known about characteristics of patients with rapid ventricular tachycardia (VT). Also, whether patients with a first episode of nonrapid VT may ...subsequently develop rapid VT or ventricular fibrillation (VF) has not been addressed.
The objectives of this study were to compare patients with rapid VT/VF with those with nonrapid VT and to assess the evolution of VT cycle lengths (VTCLs) overtime.
Data were analyzed from a nationwide registry including all patients with TOF and implantable cardioverter-defibrillator (ICD) since 2000. Patients with ≥1 VT episode with VTCL ≤250 ms (240 beats/min) formed the rapid VT/VF group.
Of 144 patients (mean age 42.0 ± 12.7 years; 104 72% men), 61 (42%) had at least 1 VT/VF episode, including 28 patients with rapid VT/VF (46%), during a median follow-up of 6.3 years (interquartile range 2.2-10.3 years). Compared with patients in the nonrapid VT group, those in the rapid VT/VF group were significantly younger at ICD implantation (35.2 ± 12.6 years vs 41.5 ± 11.2 years; P = .04), had more frequently a history of cardiac arrest (8 29% vs 2 6%; P = .02), less frequently a history of atrial arrhythmia (11 42% vs 22 69%; P = .004), and higher right ventricular ejection fraction (43.3% ± 10.3% vs 36.6% ± 11.2%; P = .04). The median VTCL of VT/VF episodes was 325 ms (interquartile range 235-429 ms). None of the patients with a first documented nonrapid VT episode had rapid VT/VF during follow-up.
Patients with TOF and rapid VT/VF had distinct clinical characteristics. The relatively low variation of VTCL over time suggests a room for catheter ablation without a backup ICD in selected patients with well-tolerated VT.
The previously unknown congenital absence of inferior vena cava, an otherwise benign condition, may create difficulties for catheter ablation of arrhythmias. We describe a case of a typical‐like ...atrial flutter, in which magnetic navigation was important for conserving the femoral approach. Electroanatomic mapping with image integration helped define the critical isthmus between the ostia of the suprahepatic veins and the tricuspid valve. (PACE 2012; 35:e312–e315)
Abstract
Aims
There has been an increasing focus on integrated, multidisciplinary, and holistic care in the treatment of atrial fibrillation (AF). The ‘Atrial Fibrillation Better Care’ (ABC) pathway ...has been proposed to streamline integrated care in AF. We evaluated the impact on outcomes of an ABC adherent management in a contemporary real-life European-wide AF cohort.
Methods and results
Patients enrolled in the ESC-EHRA EURObservational Research Programme in AF General Long-Term Registry with baseline data to evaluate ABC criteria and available follow-up data were considered for this analysis. Among the original 11 096 AF patients enrolled, 6646 (59.9%) were included in this analysis, of which 1996 (30.0%) managed as ABC adherent. Patients adherent to ABC care had lower CHA2DS2-VASc and HAS-BLED scores (mean ± SD, 2.68 ± 1.57 vs. 3.07 ± 1.90 and 1.26 ± 0.93 vs. 1.58 ± 1.12, respectively; P < 0.001). At 1-year follow-up, patients managed adherent to ABC pathway compared to non-adherent ones had a lower rate of any thromboembolic event (TE)/acute coronary syndrome (ACS)/cardiovascular (CV) death (3.8% vs. 7.6%), CV death (1.9% vs. 4.8%), and all-cause death (3.0% vs. 6.4%) (all P < 0.0001). On Cox multivariable regression analysis, ABC adherent care showed an association with a lower risk of any TE/ACS/CV death hazard ratio (HR): 0.59, 95% confidence interval (CI): 0.44–0.79, CV death (HR: 0.52, 95% CI: 0.35–0.78), and all-cause death (HR: 0.57, 95% CI: 0.43–0.78).
Conclusion
In a large contemporary cohort of European AF patients, a clinical management adherent to ABC pathway for integrated care is associated with a significant lower risk for cardiovascular events, CV death, and all-cause death.
Graphical Abstract
Women with congenital heart disease at high risk for sudden cardiac death have been poorly studied thus far.
The aim of this study was to assess sex-related differences in patients with tetralogy of ...Fallot (TOF) and implantable cardioverter-defibrillators (ICDs).
Data were analyzed from the DAI-T4F (French National Registry of Patients With Tetralogy of Fallot and Implantable Cardioverter Defibrillator) cohort study, which has prospectively enrolled all patients with TOF with ICDs in France since 2010. Clinical events were centrally adjudicated by a blinded committee.
A total of 165 patients (mean age 42.2 ± 13.3 years) were enrolled from 40 centers, including 49 women (29.7%). Among the 9,692 patients with TOF recorded in the national database, the proportion of women with ICDs was estimated to be 1.1% (95% CI: 0.8%-1.5%) vs 2.2% (95% CI: 1.8%-2.6%) in men (P < 0.001). The clinical profiles of patients at implantation, including the number of risk factors for ventricular arrhythmias, were similar between women and men. During a median follow-up period of 6.8 years (IQR: 2.5-11.4 years), 78 patients (47.3%) received at least 1 appropriate ICD therapy, without significant difference in annual incidences between women (12.1%) and men (9.9%) (HR: 1.22; 95% CI: 0.76-1.97; P = 0.40). The risk for overall ICD-related complications was similar in women and men (HR: 1.33; 95% CI: 0.81-2.19; P = 0.30), with 24 women (49.0%) experiencing at least 1 complication.
Our findings suggest that women with TOF at high risk for sudden cardiac death have similar benefit/risk balance from ICD therapy compared with men. Whether ICD therapy is equally offered to at-risk women vs men warrants further evaluation in TOF as well as in other congenital heart disease populations. (French National Registry of Patients With Tetralogy of Fallot and Implantable Cardioverter Defibrillator DAI-T4F; NCT03837574)
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