Steroids sulphates

Gaskell SJ, Brownsey BG, Brooks PW, Green BN. 1983. Fast atom bombardment mass spectrometry of steroid sulphates qualitative and quantitative analyses. Biomed Mass Spectrom 10 215-219. 

Murry S, RendeU NB, Taylor GW. 1996. Microbore high-performance liquid chromatography-electrospray ionization mass spectrometry of steroid sulphates. J Chromatogr... 

Watson D, Taylor GW, Murry S. 1985. Thermospray liquid chromatography negative ion mass spectrometry of steroid sulphates conjugates. Biomed Mass Spectrom 12 ... 

Sjovall, J. and Sjovall, K. (1970) Steroid sulphates in plasma from pregnant women with pruritus and elevated plasma bile acid levels. Annals of Clinical Research, 2 (4), 321-337. 

The pentaol disulphate 243, the tetraol disulphate 248 and the A -steroidal sulphates 245 and 247 have moderate cytotoxic activity (39). In the frame of a project devoted to the evaluation of the anti-HIV activity of sulphated sterols by the National Cancer Institute, Frederik, MD, US A, a selection of sulphated polyhydroxysteroids from ophiuroids (243,244,248,254,258,251,264) has been tested and found to inhibit the cytopathic effects of HIV-1 infections (130). 

A variant form shows a far wider range of stored products, including glycosaminoglycans and cholesteryl sulphate. In this there is deficit of aryl sulphatases A, B and C. Thus, this is a disease that is a mucopolysaccharidosis of the Maroteaux-Lamy type, superimposed upon classical metachromatic leukodystrophy, with a lack of aryl sulphatase C leading to a further accumulation of a steroidal sulphate. 

However, the utilization of Qg SPE prior to shotgun negative-ESI-MS, or online Qg LC-ESI-MS, allows the facile analysis of steroid sulphates [38]. Shown in Figure 2.6 is a negative-ion ESI-MS of the steroid fraction from infant plasma (Figure 2.7). 

Figure 2.6 Shotgun steroidomic analysis of infant plasma. Steroids were isolated from infant plasma by SPE on a Qg cartridge. Direct negative-ion ESI-MS analysis was performed on an LTQ Orbitrap XL (Thermo Fisher). Peaks which correspond to steroid sulphates are indicated. Steroid structures (see Figure 2.7) are postulated but have not been confirmed. (A) Androstane. (p) Pregnane, location of double bonds indicated by a superscript.

Figure 2.7 Structures postulated for the steroid sulphates. Annotated and abbreviations as described in Figure 2.6.

Even when adopting a targeted approach, the coverage of lipids in a specific class can still be restricted by the dominance of a few very abundant lipids. This may be the case for steroid analysis where cholesterol is often the most abundant steroid by two orders of magnitude. This problem can be minimized by subdivision of the steroid class according to hydropho-bicity where cholesterol and more hydrophobic steroids represent one class, and oxysterols (oxidized forms of cholesterol and its precursors) and less hydrophobic metabolites represent a second class [45]. This is an approach we adopted for the analysis of steroid sulphates and bile acid/ alcohol conjugates by shotgun steroidomics, and in our LC-ESl-MS/MS work on oxysterols and cholestenoic acids in brain [46,47], plasma [48], and cerebrospinal fluid (CSF) [49]. 

The purification and properties of LCAT, together with a discussion of its mechanism of reaction are given by Marcel (1982). A number of disease states involve LCAT activity. Familial LCAT deficiency has been described (Glomset and Norum, 1973) and patients with this rare complaint have been thoroughly investigated. Many of the abnormalities seem in such patients have been found in those with cholestasis also. A discussion of cholesterol ester metabolism in relation to other liver diseases and dyslipoproteinaemia has been reported (Marcel, 1982). Similarly, the metabolism of cholesterol esters in relation to arteries and arterial disease has been fully discussed (Kritchevsky and Kothari, 1978). Mammalian steroid sulphates have been reviewed by Farooqui (1981). 

DNS steroid sulphates and glucurono-sides [490], sugar phosphates and nucleotides [162]... 

Alkyl-, aryl- and steroid sulphate esters can likewise be separated on sihca gel G. Wusteman and co-workers [91] have used the following solvents for chromatography ... 

Sulphate conjugates, once called ethereal sulphates because of their extraction characteristics, are of two major types aryl or alkyl sulphates (which are esters of phenols or alcohols) and steroid sulphates. The sulphate moiety is transferred from the cofactor adenosine-3 -phosphate-S -phosphosulphate (PAPS) to an acceptor by enzymes known as sulphotransferases or sulphokinases. The enzymes which catalyse the formation of PAPS as well as the sulphokinases are in the soluble fraction of liver ... 

Gaskell, S. J., B. G. Brownsey, P. W. Brooks, and B. N. Green Fast Atom Bombardment Mass Spectrometry of Steroid Sulphates Qualitative and Quantitative Analyses. Biomed. Mass Spectrometry 10, 215 (1983). 

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