Sitosterols

First obtained from Physosligma venenosum (Calabar bean) and is readily isolated from many plant sources where it often co-occurs with sitosterol. It has served as a starting substance for the synthesis of steroid hormones. 

Sitosterols SI units Sivola process Six-pack holders Six-row barley Size distribution Size enlargement... 

In milk fat, cholesterol is associated with Hpoproteins in the milk fat globule. It is also a component of animal membranes and controls rigidity and permeabihty of the membranes. Cholesterol has interesting surface properties and can occur in Hquid crystalline forms. Plants contain sterols such as P-sitosterol [83-46-5] (4b) or stigmasterol [83-48-7] (4c). Their functions in plant metaboHsm are not yet well understood. Analysis of sterols has proven useful for detection of adulteration of edible fats (9). 

Several other naturally occurring antioxidants have been identified in oils. Sesamol [533-31-3] (6) occurs as sesamoline [526-07-8], a glycoside, in sesame seed oil. FemUc acid [1135-24-6] (7) is found esterified to cycloartenol [469-38-5] in rice bran oil and to 3-sitosterol in com oil. Although it does not occur in oils, rosemary extract has also been found to contain powerful phenoHc antioxidants (12). 

Bacterial removal of sterol side chains is carried out by a stepwise P-oxidation, whereas the degradation of the perhydrocyclopentanophenanthrene nucleus is prevented by metaboHc inhibitors (54), chemical modification of the nucleus (55), or the use of bacterial mutants (11,56). P-Sitosterol [83-46-5] (10), a plant sterol, has been used as a raw material for the preparation of 4-androstene-3,17-dione [63-05-8] (13) and related compounds using selected mutants of the P-sitosterol-degrading bacteria (57) (Fig. 2). 

Oil CAS Registry Campesteiot Number [474-62-4] Stigmasterol [83-48-7] p-Sitosterol [83-46-5] A -Avenasterol A -Stigmasterol [83-45-4]... 

Processing Raw Materials. Along with the aforementioned chemical methods of processing steroid raw materials, microbial transformations have been and are used in a number of commercial degradation processes. The microbial degradation of the C17 side chain of the two most common sterols, cholesterol (2) and P-sitosterol (41), is a principal commercial method for the preparation of starting materials in Japan and the... 

The rate of side-chain cleavage of sterols is limited by the low solubiUty of substrates and products and thek low transport rates to and from cells. Cyclodextrins have been used to increase the solubiUties of these compounds and to assist in thek cellular transport. Cyclodextrins increase the rate and selectivity of side-chain cleavage of both cholesterol and P-sitosterol with no effect on cell growth. Optimal conditions have resulted in enhancement of molar yields of androsta-l,4-diene-3,17-dione (92) from 35—40% to >80% in the presence of cyclodextrins (120,145,146,155). 

Com endosperm oil—A reddish brown Hquid composed chiefly of glycerides, fatty acids, sitosterols, and carotenoid pigments obtained by isopropyl alcohol and hexane extraction from the gluten fraction of yellow com grain. 

Alkylphenols, ammonia, asbestos, chlorinated paraffins, 4-chloroaniline, cyanide, detergents, di- -butyl phthalate, polyaromatic hydrocarbons (PAHs e.g. anthracene, benzopyrene, methylcholanthrene, /i-naphthoflavone), nitrate, nitrite, petroleum oil, phenol, pentachlorophenol, 4-nitrophenol, dinitro-o-cresol, polychlorinated biphenyls (PCBs especially coplanar), polychlorinated dioxins, polybrominated naphthalenes, /i-sitosterol, sulfide, thiourea, urea, acid water, coal dust... 

If a molecule contains several asymmetric C atoms, then the diastereomers show diastereotopic shifts. Clionasterol (28a) and sitosterol (28b) for example, are two steroids that differ only in the absolute configuration at one carbon atom, C-24 Differing shifts of C nuclei close to this asymmetric C atom in 28a and b identify the two diastereomers including the absolute configuration of C-24 in both. The absolute configurations of carboxylic acids in pyrrolizidine ester alkaloids are also reflected in diastereotopic H and C shifts which is used in solving problem 54. 

The practical development of plant sterol drugs as cholesterol-lowering agents will depend both on structural features of the sterols themselves and on the form of the administered agent. For example, the unsaturated sterol sitosterol is poorly absorbed in the human intestine, whereas sitostanol, the saturated analog, is almost totally unabsorbable. In addition, there is evidence that plant sterols administered in a soluble, micellar form (see page 261 for a description of micelles) are more effective in blocking cholesterol absorption than plant sterols administered in a solid, crystalline form. 

Assume that you have a culture of a Mycobacterium sp which is able to use cholesterol or -sitosterol as its sole source of carbon and energy. 

The strains described in Table 9.4 are all of commerdal value since they produce compounds which are either pharmacologically active or can be converted to pharmacologically important compounds. For example, the production of 1,4-androstadiene-3,17-dione from (5-sitosterol provides material which can be readily converted to estrone, while 4-androstene-3,l 7-dione can be converted to testosterone. 

A. Molecular Ion Because of low volatility, most steriods are derivatized before analysis by GC/MS. Molecular ions are usually observed for steriods sufficiently volatile to be analyzed underivatized by GC/MS (see Figure 31.1) Some important steroids in urine include estrone, estradiol, estriol, pregnanediol, and 17-ketosteroids. which can be analyzed by GC/MS as the TMS or the MO-TMS derivatives. The plant steroids, such as camposterol, ergosterol. stigmasterol, cholestanol, and sitosterol, are generally analyzed as the TMS derivatives. 

Other organic raw materials P-Sitosterol Lanolin, wool wax, cotton seed, wheat germ oil... 

Applezweig, N. Steroid Drugs, Vol. 1, 66 (New York, Toronto, London 1962). from sitosterol ... 

Triasional (Intermuti) F Sitosterol Delalande (Delalande) wfm USA Cytellin (Lilly) wfm... 

Lipids, e.g. sitosterol, geraniol, dolichol, squalene, cholesterol 200 C, 15 min Induced fluorescence detection limits <1 pg cholesterol. [3]... 

Fig. 1. Relative composition of root microsomal membranes from 24 land races, varieties and breeding lines of rice which differ in their salt resistance. Campesterol, Stigmasterol and Sitosterol as % of total sterols 16 0, 18 1, 18 2 and 18 3 fatty acids as % of total fatty acids Na transport on a relative scale from (1) lowest to (9) highest. Data of D.R. Lachno, T.J. Flowers A.R. Yeo (unpublished).

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