63-22.64 kcal/mol. A combined experimental and theoretical vibrational analysis indicates the existence
of intramolecular H-bonding between pyrrole N-H as proton donor and N atom of cyanide as proton acceptor. To investigate the strength and nature of H-bonding, topological and energetic parameters at bond critical points (BCP) have been analyzed by ‘Quantum theory of Atoms in molecules’ (QTAIM). Global see more electrophilicity index (omega = 4.58 eV) shows that title molecule (3) is a strong electrophile. The maximum values of local electrophilic reactivity descriptors (P-k(+), f(k)(+), omega P-k(+),NPk+) at vinyl carbons (C6/C22) of (3) indicate that they are more prone to nucleophilic attack. (C) 2013 Elsevier B.V. All rights reserved.”
“The quaternary isoquinoline alkaloid, sanguinarine (SG) plays an important role in both traditional and modern medicine, exhibiting a wide range of biological activities. Under physiological conditions, there is an equilibrium between the MDV3100 clinical trial quaternary cation (SG(+)) and a pseudobase (SGOH) forms of SG. In the gastrointestinal tract, SG is converted to dihydrosanguinarine (DHSG). All forms
exhibit bright fluorescence. However, their spectra overlap, which limited the use of powerful techniques based on fluorescence spectroscopy/microscopy. Our experiments using a combination of steady-state and time-resolved techniques enabled the separation of individual components. The results revealed that (a) the equilibrium constant between SG(+) and SGOH is pK (a) = 8.06, while fluorescence of DHSG exhibited no changes in the pH range 5-12, (b) the SGOH has excitation/emission spectra with maxima at 327/418 nm and excited-state lifetime 3.2 ns, the spectra of the SG(+) have maxima at 475/590 nm and excited-state lifetime 2.4 ns. The DHSG spectra have maxima at 327/446 nm and 2-exponential decay with components 4.2 and 2.0 ns, (c) NADH is able to convert SG to DHSG, while there is no apparent interaction between ICG-001 NADH and DHSG. These techniques are applicable for monitoring
the SG to DHSG conversion in hepatocytes.”
“The superior vena cava syndrome encompasses a constellation of symptoms and signs resulting from obstruction of the superior vena cava. We report a successful surgical management after failed endovascular stenting for superior vena cava syndrome, caused by a post-radiation fibrosis after conventional radiotherapy for breast cancer. We emphasize the rarity of this uncommon surgical procedure and the bailout procedure for failed angioplasty and intravascular stenting. Key points of superior vena cava syndrome and its management are discussed.”
“Most models of spoken production predict that shorter utterances should be initiated faster than longer ones. However, whether word-length effects in single word production exist is at present controversial. A series of experiments did not find evidence for such an effect.