Herein, we conceptualized a transient mediator approach that has the capability of para-selective C-H functionalization of monosubstituted aromatics. This approach is enabled by in situ generation of a versatile sulfonium salt via highly electrophilic phenoxathiine or thianthrene dication intermediate which can be readily generated from its sulfoxide with trifluoromethanesulfonic anhydride. Preliminary mechanistic study implied that the remarkable para selectivity might be related to the incredible electrophilicity of thianthrene dication intermediate. The versatility of this approach was demonstrated via para-borylation of various monosubstituted simple aromatics combining the sulfonium salt formation with further photocatalyzed transformation. 4 Scheme 4. Transformation of Aryl Boron Conditions: a) CH=CHCO2Et, Pd(OAc)2 (10 mol %), Na2CO3 (2.0 equiv), DMF, 50 o C, O2, 3 h; b) PhBr (1.0 equiv), Pd(dppf)Cl2 (5 mol %), K3PO4 (3.0 equiv), H2O (5.0 equiv), THF, 70 o C, 3 h; c) KI (1.5 equiv), CuI (10 mol %), 1,10-phenanthroline (20 mol %), MeOH/H2O (4:1), 80 o C, 20 h; d) MeOH, Cu(OAc)2 (1.0 equiv), DMAP (2.0 equiv), 4 Å MS, rt, air, 24 h; e) morpholine (2.0 equiv), Cu(OAc)2 (1.0 equiv), Et3N (2.0 equiv), 4 Å MS, CH3CN, 80 o C, air, 24 h. In summary, para-borylation of monosubstituted benzenes has been demonstrated using phenoxathiine or thianthrene as the transient mediator. Preliminary mechanistic study indicated that the key to the remarkable para-selectivity might be the use of highly electrophilic phenoxathiine or thianthrene dication species. Detailed mechanistic study and the application of this transient mediator approach for site-selective functionalization are ongoing projects in our laboratory. Experimental procedures, complete characterization data, copies of

The success rate of catheter ablation in atrial fibrillation (AF) is known to be lower in females than in males. However, while the exact mechanism for this phenomenon remains to be elucidated, tissue fibrosis may play an important role in this regard. It has been shown that fibrosis promotes AF and its recurrence, thereby substantially reducing the efficacy of catheter ablation in AF patients. Thus, we hypothesized that fibrosis may contribute to gender differences in the outcomes of AF catheter ablation.Here we systematically assessed pulmonary vein sleeves obtained from 166 patients with and without long-standing persistent-AF (LSP-AF) in order to identify gender-specific mechanistic differences in fibrosis remodeling of AF patients.Histological analysis revealed that the female LSP-AF group, rather than its male counterpart, had a higher degree of fibrosis when compared to the NON-AF group. Further analysis using microarray, immunohistochemistry and Western Blot displayed that gender differences in fibrosis remodeling of LSP-AF were mainly due to the inherent differential expression of fibrosis-related genes (n=32) and proteins (n=6). Especially, those related to the TGFβ/Smad3 pathway appeared to be up-regulated in the female LSP-AF group thus promoting an aggravation of fibrosis remodeling. In summary, our data suggest that the aggravation of fibrosis remodeling in women may be an important reason for the low success rate of AF catheter ablation when compared to men. Therefore, inhibiting the TGFβ/Smad3 pathway-mediated fibrosis could represent an interesting target for future therapeutic concepts to improve the success rate of AF catheter ablation in women.

Addition of the CSM to an MVR procedure can decrease the risk of stroke or death and high sinus rhythm at 1 year without increasing the operative risk. CSM is a safe and effective approach to treating AF associated with RMVD.

BackgroundWe retrospectively reported our 26-year experience with operative repair of total anomalous pulmonary venous connection (TAPVC) with biventricular physiology.MethodsBetween December 1982 and December 2008, 122 TAPVC patients with biventricular heart underwent surgical repair in our department. Moderate or deep hypothermia was induced at the time of cardiopulmonary bypass (CPB). Follow-up was conducted for 5 postoperative years. Surgical outcomes of early and intermediate deaths after TAPVC repair were retrospectively analyzed.ResultsSix deaths occurred operatively; and three deaths, during follow-up. The 5-year survival rates after TAPVC repair was 92.6 %, without gradient across the anastomosis. The survival rate of the patients who were younger was 78.8 %, significantly lower than those older than 1 year. It was also lower in those who were less than 6 kg in weight. Three patients died during follow-up. Three patients died of ventricular arrhythmia, right heart failure, and pneumonia, respectively, during follow-up. If the left atrium pressure was higher than 15 mm Hg, the snare of the vertical vein was loosened after CPB ceased in the patients with supracardiac connection. It decreased from 21 ± 5 to 13 ± 3 mm Hg. The vertical vein was ligated in 57 cases and left open in 20 cases. A patient with an intact vertical vein had a large shunt and was cured by intervention afterward. Supraventricular arrhythmia occurred in 19 patients with the supercardiac type repaired through a biatrial incision. One patient died of ventricular arrhythmia, and none of the remaining patients had arrhythmias.ConclusionSurgical treatment of TAPVC carried a low operative risk and had satisfactory immediate and intermediate results. Age younger than 1 year and weight less than 6 kg were risk factors. It was a good choice to leave the vertical vein open in the patients with a left atrial pressure higher than 15 mm Hg.

Pulsatile pulmonary blood flow plays an important role in regulating shear-stress-mediated release of endothelium-derived nitric oxide and endothelin-1, and it reduces pulmonary vascular resistance by passive capillary recruitment. The aim of this study was to demonstrate changes in pulmonary capillary structure and endothelial function induced by the chronic nonpulsatile flow of the Fontan circulation. A canine model with nonpulsatile flow in the right lung was established, and sacrificed 3 months later. Compared to the left lung, wall thickness of the pulmonary arterioles was thinner, endothelin-1 expression was weaker, endothelial nitric oxide synthase activity was stronger, and there was a good correlation between the histomorphometric and immunohistochemical findings. These data indicate that long-term nonpulsatile flow can lead to endothelial dysfunction, which may be involved in distention and vascular structure remodeling due to the increase in pulmonary vascular resistance; but it also can lead to increased patency of the arteriovenous shunt, which might be at least partly involved in pulmonary arteriovenous fistula development and exercise limitation after the Fontan operation.

No abstract

Decreased preoperative RV diastolic function and lack of suitable target bypass vessels are independent risk factors for early death following CABG in patients with severely impaired left ventricular function. Therefore, assessment of preoperative RV diastolic function will be helpful in predicting early death after CABG in these patients. Additionally, Et/Et' ≥ 10 is significantly associated with early death after CABG.

Long-term survival after surgical correction of CA is good. Routine closure of a cleft in the mitral valve is very important for successful surgery.