A variety of beta- or alpha-C-glycosides may be readily accessed in an entirely stereoselective fashion from esters derived from the reaction of carboxylic acids and 3-hydroxy glycals, by way of a tandem reaction sequence of Tebbe methylenation and Claisen rearrangement. Though of wide scope, for example allowing the synthesis of 1-6 linked C-disaccharides, the methodology does not currently allow the synthesis of C-glycosyl alpha-amino acids. 相似文献
The cytochrome c oxidase enzyme from the Rhodobacter sphaeroides bacteria exists as a complex of four peptide subunits, two hemes, and a variety of lipids and metal ions held together by non-covalent forces. While the native enzyme functions as an associated unit, this complex usually dissociates during MALDI- TOF analysis. Through the use of matrix additives such as sucrose, the complete complex and partial complexes can be stabilized in the MALDI-TOF experiment. The dissociation of the complex allows for the detection of the components of the enzyme. The direct detection of associated lipids from an aqueous solution of the intact enzyme may eliminate the need for enzyme disruption and lipid extraction. The partial dissociation of multisubunit enzymes in such experiments may allow for the determination of subunit-subunit and subunit-lipid interactions 相似文献
This review provides a broad overview of the literature related to the importance of ligands in homogeneous catalysis. In particular, it describes the types of nitrogen donor ligands that have typically been used for homogeneous catalysis. We surveyed the important transition metal homogenous catalysts explicitly from 2011 up to early 2014 and summarize their comparative catalytic activities. Generally, the main factors observed are the ligand structure, electron donor property and steric bulk which can affect the catalytic activity. Electron count and inductive effect can also influence the efficiency of homogeneous catalyst. 相似文献
Despite first evidence for the cytochrome P450-mediated enantioselective biosynthesis and activity of cis-epoxyeicosatrienoic acids (EETs), as yet little is known about the stereospecifity of EET generation and physiology, because
the existing chiral methods are time consuming, labor intensive, and not sensitive enough. We present a method for highly
sensitive, direct, and simultaneous chiral analysis of all eight EET enantiomers consisting of (i) solid-phase extraction, (ii) reversed-phase high-performance
liquid chromatographic purification followed by (iii) consecutive regio- and enantiomeric separation of the four underivatized EET regioisomers within one chromatographic run employing capillary tandem column chiral-phase liquid chromatography with (iv) reliable dual online photodiode
array and gentle electrospray ionization tandem mass spectrometric identification and quantitation of the eluting optical
antipodes. This one-step, simple, expeditious, and highly sensitive measurement allows profiling of all eight EET enantiomers
at once, thus avoiding substance loss and enabling high sample throughput. Limits of quantification in the low picogram range
were achieved by the use of capillary columns with typical high quantitative sensitivity instead of conventional columns with
low chromatographic signal intensity employed by previous methods. Application to tissue homogenates demonstrated the suitability
of this approach for routine and reliable “enantioprofiling” of free endogenous EETs, i.e., EETs not esterified into cellular membrane phospholipids, typically occurring at very low concentrations.
The technique can readily be employed for preparative purification of enantiomers in the microgram range using large-inner-diameter
columns.
Figure Direct and simultaneous enantioprofiling of the four free endogenous epoxyeicosatrienoic acids (EETs) from a complex biological matrix, like the cardiopulmonary system, within one
chromatographic run by highly sensitive, one-step capillary tandem column chiral-phase liquid chromatography with dual online photodiode array and tandem mass spectrometric
detection (CapTC-CP-LC-PDAD-ESI-MS2) enables accurate, systematic, and routine correlation between the absolute configuration of EETs and their physiological
actions
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
A theoretical study of the molecular circular dichroism (CD) of the antitumor antibiotic natural product streptonigrin is described, aiming at the secure assignment of its absolute configuration by comparison of the CD spectra predicted for M and P, with the experimental one. The stereostructure of streptonigrin was previously investigated by two other groups, yet leading to two different attributions. Although streptonigrin possesses two biaryl axes, only the ‘southern’ one is configurationally stable and thus responsible for the chiroptical properties, since the ‘northern’ AB-ring system of the molecule is kept in plane with ring C by hydrogen bonding. All computational methods applied within this work to simulate the CD spectrum—semiempirical approaches and time-dependent density functional theory (TDDFT)—consistently attribute the M-configuration to streptonigrin. 相似文献
The main aim of this work is to develop and validate a spectrophotometric method for the determination of nicorandil in commercial tablets. The method is based on the reduction of the nitroxy ethyl group of nicorandil into carbonyl compound and nitrite ion by NH4Cl and Zn dust. The nitrite ion thus formed reacts with potassium iodide and starch in dilute HCl medium to form a blue product, which absorbs maximally at 550 nm. Beer's law is obeyed in the concentration range 0.4‐4.0 μg mL?1 with molar absorptivity of 7.92 × 104L mol?1 cm?1. The detection limit is 0.017 μg mL?1. The reaction conditions are optimized and validated as per the International Conference on Harmonisation guidelines (USA). The proposed method has been applied successfully for the determination of nicorandil in commercial tablets. The results of analyses are compared statistically with those of the author's spectrophotometric method, which confirmed that there is no significant difference between the methods compared. 相似文献
Coumarins are the phytochemicals, which belong to the family of benzopyrone, that display interesting pharmacological properties. Several natural, synthetic and semisynthetic coumarin derivatives have been discovered in decades for their applicability as lead structures as drugs. Coumarin based conjugates have been described as potential AChE, BuChE, MAO and β-amyloid inhibitors. Therefore, the objective of this review is to focus on the construction of these pharmacologically important coumarin analogues with anti-Alzheimer’s activities, highlight their docking studies and structure–activity relationships based on their substitution pattern with respect to the selected positions on the chromen ring by emphasising on the research reports conducted in between year 1968 to 2017.
Spectroscopic studies of Methyl violet in protic (water, methanol, ethanol, isopropanol and n-butanol) and aprotic solvents (acetone, DMF) were carried out. UV-Visible absorption spectra of Methyl violet in protic solvents showed a hypsochromic shift, as the solvent polarity was changed from less polar to more polar, while a bathochromic shift was observed for aprotic solvents. Transition energy of Methyl violet in different solvents was correlated with solvatochromic parameters to study solute–solvents interactions. The Kamlet–Taft, Catalan and unified scale models were applied to investigate interactions between Methyl violet and solvents. The best agreement is found for the Catalan model. 相似文献
A marine‐derived fungus of the genus Stachylidium was isolated from the sponge Callyspongia cf. C. flammea. Chemical investigation of the bioactive fungal extract led to the isolation of the novel phthalimidine derivatives marilines A1 ( 1 a ), A2 ( 1 b ), B ( 2 ), and C ( 3 ). The absolute configurations of the enantiomeric compounds 1 a and 1 b were assigned by a combination of experimental circular dichroism (CD) investigations and quantum chemical CD calculations. The skeleton of marilines is most unusual, and its biosynthesis is suggested to require uncommon biochemical reactions in fungal secondary metabolism. Both enantiomers, marilines A1 ( 1 a ) and A2 ( 1 b ), inhibited human leukocyte elastase (HLE) with an IC50 value of 0.86 μM . 相似文献