Steroids definition

A definitive method for stmctural deterrnination is x-ray crystallography. Extensive x-ray crystal stmcture deterrninations have been done on a wide variety of steroids and these have been collected and Hsted (270). In addition, other analytical methods for steroid quantification or stmcture determination include, mass spectrometry (271), polarography, fluorimetry, radioimmunoassay (264), and various chromatographic techniques (272). 

Protonation of the a-carbanion (50), which is formed both in the reduction of enones and ketol acetates, probably first affords the neutral enol and is followed by its ketonization. Zimmerman has discussed the stereochemistry of the ketonization of enols and has shown that in eertain cases steric factors may lead to kinetically controlled formation of the thermodynamically less stable ketone isomer. Steroidal unsaturated ketones and ketol acetates that could form epimeric products at the a-carbon atom appear to yield the thermodynamically stable isomers. In most of the cases reported, however, equilibration might have occurred during isolation of the products so that definitive conclusions are not possible. 

Lipids are naturally occurring organic molecules that have limited solubility in water and can be isolated from organisms by extraction with nonpolar organic solvents. Fats, oils, waxes, many vitamins and hormones, and most nonprotein cell-meznbrane components are examples. Note that this definition differs from the sort used for carbohydrates and proteins in that lipids are defined by a physical property (solubility) rather than by structure. Of the many kinds of lipids, we ll be concerned in this chapter only with a few triacvlglycerols, eicosanoids, terpenoids, and steroids. 

There is no room within the definition for nitric oxide, the prostaglandins and steroids mainly because they are not released in a controlled manner by neuronal activity and only the last are preformed. Thus if they are to be classified as NTs then the definition must be simplified so that a NT becomes ... 

Much of the early work with certified reference materials was linked to the derivation of reference methods and there was a period in which primary or definitive (i.e. very accurate but usually very complex) and secondary (or usable) methods were reported e.g. steroid hormones (Siekmann 1979), creatinine (Siekmann 1985), urea (Welch et al. 1984) and nickel (Brown et al. 1981). Although there are some application areas, such as checking the concentrations of preparations listed in a pharmacopoeia, where a prescribed, defined method has to be used, in practice such work is limited. However, this approach to chemical analysis is no longer widely used and will not be further discussed. The emphasis now is placed on using RMs to demonstrate that a method in use meets analytical criteria or targets deemed to be appropriate for the application and to develop figures of merit (Delves 1984). 

SlEKMANN L (1979) Determination of steroid hormones by the use of isotope dilution mass spectrometry a definitive method in clinical chemistry. J Steroid Biochem 11 117-123. 

The alkyl ketone candidates With definition of the finasteride manufacturing process came a new challenge. The most efficient synthesis of the second generation candidate would make use of the penultimate in the finasteride process 33 as starting material (Scheme 3.25). With a pilot plant campaign to make 3 scheduled, realizing this objective became a priority. None of the methods reported in the literature for ester to ketone conversion had been applied to a hindered steroidal C17 ester. 

Another example of a nudibranch, which probably modifies dietary metabolites to obtain more effective allomones, is seen in Aldisa cooperi (= A. sanguinea cooperi) [155]. It elaborates two fish antifeedant bile acids (104,105) that are absent in its prey, the sponge Anthoarcuata graceae, where the main steroid is 4-cholesten-3-one (106). Biosynthetic experiments starting from both labelled mevalonic acid and labelled 4-eholesten-3-one would definitely clarify, whether, the two allomones (104-105) are biosynthetized de novo by the mollusc, or if they are derived from a food source. 

Although most insects are flexible about their steroid sources, senita flies definitely are not They lack a set of enzymes indispensable for utilizing most steroids, cholesterol included. The enzymes they do have can handle only a few rare natural steroids, and only with these unusual compounds as starting points can they produce their own essential steroids. The single Sonoran source of these rare steroids seems to be senita cactus, and thus senita flies must incorporate the cactus into their diets or perish. As the only Sonoran fruit flies resistant to senita toxins, senita flies experience no competition from their relatives for the one plant that keeps them alive. 

The term lipid includes all compounds that release fatty acids on digestion, so that this definition is more extensive than that of fat. Compounds which are insoluble in water, soluble in organic solvents but not derived from fatty acids have been termed non-saponifiable lipids. They include steroids, terpenes and ubiquinone. 

Ultraviolet light causes a chemical change in dihydrocholesterol to produce cholecalciferol, a precursor of vitamin D. The latter conforms better to the definition of a steroid hormone than a vitamin. Indeed, the classification of vitamin D as a vitamin is an historical accident. The precursor is released from the skin and is further modified in the liver and kidney to form dihydroxycholecalciferol, which is the active form of the hormone (see Chapter 15 for the reactions). It increases calcium absorption from the... 

Steroids all contain a tetracyclic ring system comprised of three six-membered rings and one five-membered ring fused together. Cholesterol is the best known of the steroids. It is an essential structural component of animal cells, though the presence of excess cholesterol in the blood is definitely associated with the incidence of heart disease and heart attacks. 

Definitive rules for steroids Pure Appl Chem. (1972) 31, 285-322. 

In addition, it will be our intention to present a deeper insight into the biosynthesis of steroid hormones, which will allow definition of new targets and approaches for the treatment of endocrine-responsive cancer. Enzymes involved in mechanisms of steroid hormone biosynthesis might be novel targets for endocrine therapy. Moreover, further therapeutic indications for modulators of steroid hormone receptors will be discussed. In summary, many promising new opportunities for endocrine therapy of breast and prostate cancer are now arising. 

The intravenous curve is, by definition, a representation of 100% bioavailability as the drug was put in its entirety into the vein. The oral curve has an area under it approximately 75% the size of the intravenous curve, and this suggests that 25% of the oral dose failed to get into the circulation. The oral bioavailability of the drug is the proportion getting into the vascular compartment, and can be measured if there is an intravenous dose curve available for the same subject at the same dose. In this example, F (the fraction bioavailable) is 0.75. It might be as high as 1.0 (100%) for some steroids, or as low as 0.1 (10%) or even less for poorly absorbed aminoglycosides. 

Although these definitions are vague, it appears that partial synthesis is restricted to those modifications which do not change the basic chemical structure, whereas ex-chiral-pool synthesis generally leads to a new type of compound. For instance, the introduction of new substituents into a steroid nucleus is partial synthesis , whereas the conversion of D-glucose into the pheromone e.vo-brevicomin is ex-chiral-pool synthesis . 

Steroids that possess angular methyl groups at both the 10 and 13 positions but which are devoid of acetyl side chains at the 17 position are usually classed as derivatives of the hypothetical hydrocarbon, androstane. The endogenous male sex hormones, such as, for example, testosterone, can all be classified as androstanes as will be noted below, the biological activity of compounds in this stmctural class goes beyond that narrow definition. 

Not only a zinc-copper couple, but also a zinc-lead couple forms a gem-dimetal species from diiodomethane, according to the 1975 Nysted patent5. He also insisted that treatment of dibromethane with a zinc-lead couple in THF at 80 °C forms a characteristic gem-dizinc species 1 (equation 3). However, there was no further evidence concerning the structure except H NMR data, which was not enough for the complete structural determination. The obtained compound was definitely a gem-dizinc species, but the written structure 1 was not fully characterized. The white solid 1 is obtained as a dispersion in THF, and does not dissolve in DMF and DMI (l,3-dimethyl-2-imidazolidinone). This THF dispersion is commercially available from Aldrich Co. as Nysted reagent. Nysted also showed that this dizinc compound is effective for the methylenation of a-hydroxy ketone moiety in steroid derivatives5. 

I consider hormonal steroid profiles to be those analyses that encompass a panel of steroids that can diagnose different endocrine abnormalities. A panel of multiple steroids used to diagnose a single condition, for example 21-hydroxylase deficiency, would not be a steroid profile under this definition. 

Infants with salt-losing crisis and adrenal insufficiency in infancy may have adrenal hypoplasia congenita. This can be of two types recessive, for which the cause has not been defined and which affects mostly the fetal zone, and X-linked, which is caused by mutations in the DAX-1 gene, which (with steroidogenic factor-1) controls definitive zone development and steroidogenesis [71]. GC-MS analysis of patients with the disorder show variant patterns from absence of neonatal A5 steroids, appropriate for the recessive form [81], to extremely low cortisol production and transient 11/Lhy-droxylase deficiency, as evidenced through increased THS excretion (Malunowicz, personal communication). 

Shackleton CH (1976) Congenital adrenal hyperplasia caused by defect in steroid 21-hydroxylase. Establishment of definitive urinary steroid excretion pattern during first weeks of life. Clin Chim Acta 67 287-298... 

The IUPAC Definitive Rules for Nomenclature of Steroids15 contain proposals for naming steroid alkaloids and steroids containing fused... 

IUPAC Nomenclature of Organic Chemistry and IUPAC-IUB Biochemical Nomenclature, Definitive Rules for Nomenclature of Steroids, J. PureAppl. Chem. 31, 283(1972). 

---