Regio- and 1,2- cis-stereoselective chemical glycosylation of unprotected glycosyl acceptors has been in great demand for the efficient synthesis of natural glycosides. However, simultaneously regulating these selectivities has been a longstanding problem in synthetic organic chemistry. In nature, glycosyl transferases catalyze regioselective 1,2- cis-glycosylations via the Si mechanism, yet no useful chemical glycosylations based on this mechanism have been developed. In this paper, we report a highly regio- and 1,2- cis-stereoselective Si-type glycosylation of 1,2-anhydro donors and unprotected sugar acceptors using p-nitrophenylboronic acid (10e) as a catalyst in the presence of water under mild conditions. Highly controlled regio- and 1,2- cis-stereoselectivities were achieved via the combination of boron-mediated carbohydrate recognition and the Si-type mechanism. Mechanistic studies using the KIEs and DFT calculations were consistent with a highly dissociative concerted Si mechanism. This glycosylation method was applied successfully to the direct glycosylation of unprotected natural glycosides and the efficient synthesis of a complex oligosaccharide with minimal protecting groups.
The detailed composition of cellular lipid of more than 23 species of yeast has been determined quantitatively by thinchrography on quartz rods, a method previously used for estimating cellular lipids of seven species of yeast. That data was fortified by neutral and phospholipid quantitations on 30 species of yeast cells. Most of the test organisms contained 7-15% total lipid and 3-6% total phospholipid per dry cell weight, except for the extremely high accumulation of triglycerides in two species of Lipomyces. Qualitatively, 30 species of yeast cells contained similar neutral lipid constituents (triglyceride, sterol ester, free fatty acid, and free sterol) and polar lipid components (phosphatidyl choline, phosphatidyl ehtanolamine, phosphatidyl serine, phosphatidyl inositol, cardiolipin, and ceramide monohexoside) without minor constituents. Based on the quantitative composition of neutral lipids, the 30 species of yeast were divided into two groups , the triglyceride predominant group and the sterol derivative group. These groupings were fairly well overlapped from the standpoint of the distribution characteristics of fatty acid. The relative polar lipid compositions also grossly resembled each other. Only one exception of polar lipid composition in yeast cells was found in Rhodotorula rubra species which contained phosphatidyl ethanolamine as the most abundant phospholipid. Fatty acid distribution patterns in yeast cells consistently coincided with other reports concerning fatty acid composition of yeast cells. Correlation of lipid composition and classification of yeasts are suggested and discussed.
Oxidative stress has been implicated in the pathogenesis of heart failure. Reactive oxygen species (ROS) are produced in the failing myocardium, and ROS cause hypertrophy, apoptosis/cell death and intracellular Ca2+ overload in cardiac myocytes. ROS also cause damage to lipid cell membranes in the process of lipid peroxidation. In this process, several aldehydes, including 4-hydroxy-2-nonenal (HNE), are generated and the amount of HNE is increased in the human failing myocardium. HNE exacerbates the formation of ROS, especially H2O2 and ·OH, in cardiomyocytes and subsequently ROS cause intracellular Ca2+ overload. Treatment with beta-blockers such as metoprolol, carvedilol and bisoprolol reduces the levels of oxidative stress, together with amelioration of heart failure. This reduction could be caused by several possible mechanisms. First, the beta-blocking effect is important, because catecholamines such as isoproterenol and norepinephrine induce oxidative stress in the myocardium. Second, anti-ischemic effects and negative chronotropic effects are also important. Furthermore, direct antioxidative effects of carvedilol contribute to the reduction of oxidative stress. Carvedilol inhibited HNE-induced intracellular Ca2+ overload. Beta-blocker therapy is a useful antioxidative therapy in patients with heart failure.
Regioselective and 1,2-cis-α-stereoselective glycosylations using 1α,2α-anhydro glycosyl donors and diol glycosyl acceptors in the presence of a glycosyl-acceptor-derived boronic ester catalyst. The reactions proceed smoothly to give the corresponding 1,2-cis-α-glycosides with high stereo- and regioselectivities in high yields without any further additives under mild reaction conditions. In addition, the present glycosylation method was successfully applied to the synthesis of an isoflavone glycoside.
Spontaneous AF and VF are closely linked clinically and electrophysiologically in BrS patients. Patients with spontaneous AF have more severe clinical backgrounds in BrS. SCN5A mutation is associated with electrical abnormality but not disease severity.
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