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1.
Unexpected benzimidazole ring formation from a quinoneimide species in the presence of ammonium acetate as supporting electrolyte used in the coupling of electrochemistry with mass spectrometry 下载免费PDF全文
2.
Ulrik Gran 《Tetrahedron》2003,59(24):4303-4308
A new macrocyclic NADH model 1 has been designed and synthesised. The new model consists of the same subunits as previously reported models. However, the present model is designed as such that the pyridine nitrogen of the nicotinamide units are not incorporated in the macrocyclic framework. Thus, properties such as solubility can easily be varied by alkylation with an appropriate agent. The macrocyclic framework was prepared in 7 steps. Methylation of the pyridine nitrogens followed by reduction gave the desired model. This model compound was found to reduce methyl benzoylformate stereoselectively in good yield with 48% enantiomeric excess. 相似文献
3.
Jurva U Wikström HV Bruins AP 《Rapid communications in mass spectrometry : RCM》2002,16(20):1934-1940
Oxygen radicals are generated in vivo by various processes, often as toxic intermediates in different metabolic transformations, and have been shown to play an important role for a large number of diseases. In this article we introduce an electrochemical flow-through system that allows generation of hydroxyl radicals for reaction with xenobiotics and subsequent detection of the oxidation products on-line with high-performance liquid chromatography/tandem mass spectrometry (HPLC/MS/MS). The system is based on the Fenton reaction and is predominantly aimed at the generation of hydroxyl radicals; however, by minor variations to the system, a broad range of other radicals can be produced. Optimization of the system was performed with the radical scavenger 5,5-dimethyl-1-pyrroline-N-oxide (DMPO). Under the same physical conditions, one injection through the electrochemical cell gave a higher yield of the oxidation product N-hydroxy-5,5-dimethylpyrrolidin-2-one than what was attained after 60 min with a chemical Fenton system catalyzed by ascorbic acid. Since the iron is added as Fe(3+), the initial mixture is 'inactive' until it reaches the electrochemical cell. This makes it very suitable for on-line analysis of the generated compounds, since the whole reaction mixture, including substrate, can be kept in a vial in an autosampler. The system described provides a useful tool for investigation of new radical scavengers and antioxidants. Since the hydroxyl radical adds readily to unsaturated pi-systems, the technique is also suitable for on-line generation and characterization of potential drug metabolites resulting from hydroxylation of double bonds and aromatic systems. 相似文献
4.
De Jonghe S Lamote I Venkataraman K Boldin SA Hillaert U Rozenski J Hendrix C Busson R De Keukeleire D Van Calenbergh S Futerman AH Herdewijn P 《The Journal of organic chemistry》2002,67(3):988-996
The synthesis of a new series of D-erythro-homoceramide analogues is described. Several synthetic approaches were investigated. Homoceramides can be successfully synthesized from L-homoserine as chiral building block and a protected Weinreb-amide as a key intermediate. The synthesis of short-chain analogues with a heptyl side chain, as well as with a phenyl residue in the sphingoid part (instead of the naturally occurring tridecyl side chain), was effected. The homoceramides 15-17 and 24 were investigated for their potential to reverse the inhibitory effect of fumonisin B(1) on axonal growth. Unfortunately, none of the tested compounds showed any biological activity due to their lack of metabolism to glucosylhomoceramide. 相似文献
5.
[structures: see text] A versatile (S)-3-(hydroxymethyl)butane-1,2,4-triol building block has been synthesized starting from D-isoascorbic acid, a common food preservative. The key transformation in this approach was the introduction of branching through a high yield and fully regioselective epoxide opening. This flexible synthon has been elaborated to a new class of (dihydro-)N-homo(phyto)ceramides. 相似文献
6.
From the basic light microscope through high-end imaging systems such as multiphoton confocal microscopy and electron microscopes, microscopy has been and will continue to be an essential tool in developing an understanding of cardiovascular development, function, and disease. In this review we briefly touch on a number of studies that illustrate the importance of these forms of microscopy in studying cardiovascular biology. We also briefly review a number of imaging modalities such as computed tomography (CT), magnetic resonance imaging (MRI), ultrasound, and positron emission tomography (PET) that, although they do not fall under the realm of microscopy, are imaging modalities that greatly complement microscopy. Finally we examine the role of proper imaging system calibration and the potential importance of calibration in understanding biological tissues, such as the cardiovascular system, that continually undergo deformation in response to strain. 相似文献
7.
8.
Aza-Michael reactions between primary amines and methyl propenoate have been investigated under environmentally-friendly solventless heterogeneous catalysis in order to obtain the mono- or the bis-adduct. The reaction conditions can be altered so as to maximise the yields of the required product with high selectivity. 相似文献
9.
Ugo Bussy Illa Tea Véronique Ferchaud-Roucher Michel Krempf Virginie Silvestre Nicolas Galland Denis Jacquemin Moa Andresen-Bergström Ulrik Jurva Mohammed Boujtita 《Analytica chimica acta》2013
The coupling between an electrochemical cell (EC) and a mass spectrometer (MS) is a useful screening tool (EC-MS) to study the oxidative transformation pathways of various electroactive species. For that purpose, we showed that the EC-MS method, carried out in the presence and absence of isotope 18O labeled water leads not only to a fast identification of oxidation products but also leads to a fast elucidation of the mechanism pathway reaction. We examined herein the case of the electrochemical hydrolysis of activated aromatic ether. Acebutolol (β-blockers) was selected herein as model of activated aromatic ether, and its electrochemical oxidation was examined in both the presence and absence of isotope 18O labeled water. To elucidate electrochemical hydrolysis pathway reaction: O-dealkylation or O-dealkoxylation, our approach was used to prove its applicability. The electrochemical oxidation mechanism was then elucidated showing an O-dealkoxylation reaction. In addition, density functional theory (DFT) calculations fully support the experimental conclusions. 相似文献
10.
Prof. Pil Seok Chae Andrew C. Kruse Dr. Kamil Gotfryd Rohini R. Rana Kyung Ho Cho Prof. Søren G. F. Rasmussen Hyoung Eun Bae Richa Chandra Prof. Ulrik Gether Prof. Lan Guan Prof. Brian K. Kobilka Prof. Claus J. Loland Dr. Bernadette Byrne Prof. Samuel H. Gellman 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(46):15645-15651
Integral membrane proteins play central roles in controlling the flow of information and molecules across membranes. Our understanding of membrane protein structures and functions, however, is seriously limited, mainly due to difficulties in handling and analysing these proteins in aqueous solution. The use of a detergent or other amphipathic agents is required to overcome the intrinsic incompatibility between the large lipophilic surfaces displayed by the membrane proteins in their native forms and the polar solvent molecules. Here, we introduce new tripod amphiphiles displaying favourable behaviours toward several membrane protein systems, leading to an enhanced protein solubilisation and stabilisation compared to both conventional detergents and previously described tripod amphiphiles. 相似文献