A shape changing tandem Rh(CNC) catalyst: Preparation of bicyclo[4.2.0]octa- 1,5,7-trienes from terminal aryl alkynes

The preparation of a range of tetraaryl-substituted bicyclo[4.2.0]octa-1,5,7-trienes using a one-pot procedure starting from terminal aryl alkynes and catalysed by a rhodium(i) complex is reported. This synthesis proceeds by a reaction sequence involving head-to-tail homocoupling of the terminal alkyne and zipper annulation of the resulting gem-enyne. The rhodium catalyst employed is notable for the incorporation of a flexible NHC-based pincer ligand, which is suggested to interconvert between mer- and fac-coordination modes to fulfil the orthogonal mechanistic demands of the two transformations. Evidence for this interesting auto-tandem action of the catalyst is provided by reactions of the precatalyst with model substrates, corroborating proposed intermediates in both component cycles, and norbornadiene, which reversibly captures the change in pincer ligand coordination mode, along with a DFT-based computational analysis

Liver Graft Revascularization by Donor Portal Vein Arterialization Following “No Touch” Donor Hepatectomy

Unsatisfactory immediate function of the transplanted liver together with technical complications contribute to a persisting early mortality for hepatic transplantation in the 20% range. We report our initial clinical experience with methods, one not previously used clinically, that resulted in uniformly well-functioning liver grafts in 11 patients and contributed to a satisfactory success rate for the procedure. Donors were heart-beating. During the donor operation all manipulations of the liver were avoided until after cold preservation, achieved by external cooling at the same time as circulatory interruption, donor exsanguination and perfusion of the liver with cold oxygenated fluid of “extracellular̵ type. The organs were then gently dissected. At transplantation the livers were revascularized with arterial blood shunted from the recipient iliac artery to the graft portal vein after completion of the suprahepatic IVC anastomosis. The infrahepatic IVCs and hepatic arteries were then joined, the iliac artery shunts discontinued and the portal veins joined. Total ischaemic intervals for the allografts were 3½–8 (average 5). Anhepatic intervals were 1–2¼ (average 2). The arterio-portal shunts were operating for 18–85 (mean 46) min. Blood loss and haemodynamic, acid-base and electrolyte abnormalities at revascularization were minimal. All grafts secreted bile immediately and all parameters reflected continuing improvement of liver function thereafter. Nine patients (82%) are alive between 4 and 18 (mean 11) months after transplantation. We conclude that these methods offer effective avoidance of serious organ damage during donor hepatectomy and preservation, reduced allograft ischaemic interval and reduced recipient anhepatic time. They result in avoidance of blood loss at the time of revascularization, together with minimal haemodynamic, acid-base or biochemical changes. In addition, they allow the surgeon to perform and test all anastomoses without time constraints, provide the capability to deal with unexpected complications, and assure good early graft function

On the sign of the real part of the Riemann zeta-function

We consider the distribution of $\arg\zeta(\sigma+it)$ on fixed lines $\sigma > \frac12$, and in particular the density $$d(\sigma) = \lim_{T \rightarrow +\infty} \frac{1}{2T} |\{t \in [-T,+T]: |\arg\zeta(\sigma+it)| > \pi/2\}|\,,$$ and the closely related density $$d_{-}(\sigma) = \lim_{T \rightarrow +\infty} \frac{1}{2T} |\{t \in [-T,+T]: \Re\zeta(\sigma+it) < 0\}|\,.$$ Using classical results of Bohr and Jessen, we obtain an explicit expression for the characteristic function $\psi_\sigma(x)$ associated with $\arg\zeta(\sigma+it)$. We give explicit expressions for $d(\sigma)$ and $d_{-}(\sigma)$ in terms of $\psi_\sigma(x)$. Finally, we give a practical algorithm for evaluating these expressions to obtain accurate numerical values of $d(\sigma)$ and $d_{-}(\sigma)$.Comment: 22 pages, 3 tables. To appear in Proceedings of the International Number Theory Conference in Memory of Alf van der Poorten (Newcastle, Australia, 2011

A comparison of the effect of high- and low-dose fentanyl on the incidence of postoperative cognitive dysfunction after coronary artery bypass surgery in the elderly

BACKGROUND: Postoperative cognitive dysfunction (POCD) after coronary artery bypass graft surgery is a common complication for which, despite many clinical investigations, no definitive etiology has been found. The current use of both high- and low-dose fentanyl as anesthetic techniques allowed us to investigate the effect of fentanyl on the incidence of POCD. METHODS: Three hundred fifty patients scheduled to undergo elective coronary artery bypass graft surgery were randomized to receive either high-dose fentanyl (50 microg/kg) or low-dose fentanyl (10 mug/kg) as the basis of the anesthetic. All patients underwent neuropsychological testing before surgery and at 1 week, 3 months, and 12 months after surgery. RESULTS: One hundred sixty-eight patients in the low-dose group and 158 patients in the high-dose group were included in the final analysis. Neuropsychological testing was performed on 88%, 93%, and 92% of patients at 1 week, 3 months, and 12 months, respectively. There was no difference between group mean scores at any of the three testing times. Analysis of individual patients by the 20% rule did not detect any differences between groups. The one SD rule, which has fewer false-positive results, detected significantly more patients with POCD in the low-dose group than in the high-dose group at 1 week (23.6% vs. 13.7%; P = 0.03) but not at the other testing times. Patients with POCD spent an average of 1.2 days longer in the hospital than those without POCD (P = 0.021). CONCLUSIONS: High-dose fentanyl is not associated with a difference in the incidence of POCD at 3 or 12 months after surgery. Low-dose fentanyl leads to shorter postoperative ventilation times and may be associated with a greater incidence of POCD 1 week after surgery. Early POCD is associated with an increased duration of stay in the hospital