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11.
T. L. Clemens L. J. Fraher J. L. H. O'Riordan C. J. Little A. Dale 《Chromatographia》1980,13(3):141-144
Summary A simple, reproducible method for the biological synthesis of tritiated 24,25-dihydroxycholecalciferol, 25,26-dihydroxycholecalciferol and 1,25-dihydroxycholecalciferol is described. Kidney homogenates from both vitamin D deficient and replete chicks were usedin vitro to generate these dihydroxylated metabolites using 25 (23,24-3H) hydroxycholecalciferol as the substrate. Tritiated products were purified by Sephadex LH 20 chromatography followed by high-performance liquid chromatography; the identity of each metabolite was established by chromatography with authentic crystalline preparations.Presented at the Symposium organised by the Chromatography Discussion Group, held at Hatfield Lodge on 29 November 1979. 相似文献
12.
Edwards HG Seaward MR Attwood SJ Little SJ de Oliveira LF Tretiach M 《The Analyst》2003,128(10):1218-1221
The FT-Raman spectra of five epilithic lichen taxa growing on dolomite and magnesium-rich carbonate rocks have been analysed and interpreted for the key molecular marker bands associated with calcium oxalate monohydrate (whewellite), calcium oxalate dihydrate (weddelite) and magnesium oxalate dihydrate. From the results, it can be concluded that the biomineral product of lichen biodeterioration involves the calcareous part of the substratum only; no trace of magnesium oxalate has been found in the Raman spectra. Two of the species, Lecanora sulfurea and Aspicilia calcarea, produce calcium oxalate monohydrate exclusively, but Dirina massiliensis f. sorediata, D. massiliensis f. massiliensis and Tephromela atra produce significant quantities of the dihydrate. An explanation is advanced for the exclusive accumulation of calcium oxalate into the lichen thallus despite the significant presence of magnesium ions. 相似文献
13.
A convergent synthetic route to the 1,2-aziridinopyrrolo(1,2-a)indole 34 has been developed. Key features of this route include the deuterium kinetic isotope effect to block undesired indole lithiation during tin-lithium exchange from 27a to 30a, the intramolecular Michael addition to generate the enolate 31a, and conversion into 34 by trapping with phenylselenenyl chloride. Reductive cleavage of the N-trityl group in 34 allows access to tetracyclic aziridinomitosenes containing the aziridine N-H subunit. Reduction of the C(9) ester in 34 with LAH gives the primary alcohol 35 with the correct C(9), C(9a), C(10) oxidation state corresponding to the aziridinomitosenes, and deprotection of 34 affords 37. 相似文献
14.
C Little 《Acta chemica Scandinavica. Series B: Organic chemistry and biochemistry》1977,31(4):267-272
The hydrolysis by phospholipase C from B. cereus of several lecithins of different fatty acyl chain length was examined. The enzyme showed significant activity towards mono-molecularly dispersed short chain lecithins and the reaction obeyed normal Michaelis-Menten kinetics. Rate vs. substrate concentration curves obtained with dihexanoyl-, diheptanoyl- and dioctanoyllecithins showed marked discontinuities in the region of the known critical micelle concentrations for these substrates and distinctly higher rates were obtained just above these levels. Using these three lecithins at levels below their respective critical micelle concentrations, rate increases were noted if the reactions were allowed to proceed to a sufficiently great extent. The presence of deoxycholate in the reaction system had little or no effect on the rate of enzyme-catalysed hydrolysis of lecithins of fatty acyl chain length less than or equal to Cbeta, but for fatty acyl chain lengths greater than C10, significant rate increases occurred. The pH profile for the enzyme activity was also examined. 相似文献
15.
Bayliss MK Little D Mallett DN Plumb RS 《Rapid communications in mass spectrometry : RCM》2000,14(21):2039-2045
Recent years have seen increasing usage of large particle size stationary phases and ultra-high flow rate liquid chromatography/mass spectrometry (LC/MS) for rapid determination of pharmaceuticals in plasma without prior sample preparation. This lack of sample preparation prior to analysis, together with the extremely high throughput of the chromatography, makes the technique extremely attractive to the bioanalyst. Further, the introduction of multiple sprayer interfaces to mass spectrometers provides the potential for even higher throughput. In this paper, we present parallel ultra-high flow rate liquid chromatography using four columns in parallel and a four-way multiple sprayer interface to the mass spectrometer. We have applied this on both the narrow-bore and capillary scale. This technique enables the quantification of drugs from four plasma samples simultaneously, at nanogram per millilitre concentrations, from small aliquots of plasma without sample preparation and with throughputs of up to 120 samples per hour. 相似文献
16.
17.
Treatment of 11a with methyllithium affords the destannylated product 12 together with a small amount of tetracyclic product derived from intramolecular Michael addition. The same procedure from the deuterated analogue 11b gives the tetracyclic 18 as the major product, the result of a substantial kinetic deuterium isotope effect that favors formation of 16 and 17 by suppressing indole ring lithiation to the undesired 15. When the product mixture is quenched with phenylselenenyl chloride, 17 is converted into the aziridinomitosene 19 in 80% yield. Conversion into the aziridinomitosene alcohol 21 and the deprotected aziridine 20 is also demonstrated. 相似文献
18.
Marc A. Little Jonathan J. Loughrey Amedeo Santoro Malcolm A. Halcrow Michaele J. Hardie 《Tetrahedron letters》2014
The synthesis of four 3,4-di(alkylsulfanyl)benzyl alcohol derivatives is described, in five steps from methyl 3,4-di(hydroxy)benzoate via a Newman–Kwart rearrangement. Incubation of these derivatives in formic acid affords 2,3,7,8,12,13-hexakis(alkylsulfanyl)-10,15-dihydro-5H-tribenzo[a,d,g]cyclononene products, which are hexa-sulfanyl analogues of the well-known supramolecular cavitand host, cyclotriveratrylene (CTV). The yield of this cyclization depends strongly on the alkylsulfanyl substituents present, in the order SMe > SEt ≈ SiPr ? SBn. A crystal structure determination of one of the cyclotrimers shows a mode of self-association that is commonly exhibited by CTV itself. 相似文献
19.
C. J. Little O. Stahel K. Hales 《International journal of environmental analytical chemistry》2013,93(1-2):11-23
Abstract Our objective in using column switching is primarily to achieve the desired separation in the minimum analysis time. Complimentary to this aim is the need for sample and column cleanup followed by column re-equilibration. Finally, all operations should be capable of automation. Fundamental to column switching methodology is the concept of Zone cutting, where part of the chromatogram is transferred to another column. This forms the basis of sample cleanup and is a very versatile and powerful method. Multiple zone cutting is also possible to further increase the scope of cleanup or to minimise analysis time. Zone cutting is also complimentary to the techniques of trace enrichment and recycling. Examples will be given involving the use of these techniques in the analysis of complex matrices such as urine, plant extracts, wine and serum. The latter will be used to propose a novel approach to the quantitative analysis of anti-convulsants in serum using hexobarbital as internal standard. 相似文献
20.