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Biomedical subjects

T W Goodwin

Publications and source records attributed to T W Goodwin.

At least 19 recordsLinked to original sources

Mechanism of dealkylation of clionasterol in the insect Tenebrio molitor.

1. 25-3H- and 26-14C-labelled (24S)-24-ethylcholest-5-en-3beta-ol (clionasterol) were synthesized from (24S)-24-ethylcholesta-5,25-dien-3beta-ol. 2. These labelled substrates were mixed and administered, together with the hypocholesterolemic agent, triparanol citrate, to Tenebrio molitor larvae. 3. The 3H label from the clionasterol substrate was retained in both the desmosterol and the cholesterol isolated from the larvae. 4. Location of this 3H label in the desmosterol showed that dealkylation of the clionasterol involved 3H migration from C-25 to C-24. A possible mechanism for dealkylation is presented.

Animals

Stereochemistry of olefinic bond formation in defensive steroids of Acilius sulcatus (Dytiscidae).

The defensive secretion of Acilius sulcatus contains a number of pregnane derivates: cortexone, 20alpha-hydroxy-4-pregnen-3-one, together with the unusual delta4,6 dienes, 6,7-dehydrocortexone, 20alpha-hydroxy-4,6-pregnadien-3-one and 4,6-pregnadien-3,20-dione. The synthesis of all these steroids except cortexone is described. Complete separation of the steroids of Acilius can be achieved by high-performance liquid chromatography on the reversed-phase column system. During biosynthesis of the Acilius steroids from cholesterol, introduction of the delta4 and delta6 bonds involves elimination of the 4beta and 7beta hydrogens, respectively. Possible mechanisms of formation of the delta4,6 steroids are discussed.

Animals

Carotenoid biosynthesis in Rhodomicrobium vannielii. Experiments with nicotine and 2-(4-chlorophenylthio)triethylammonium chloride (CPTA).

Nicotine and 2-(4-chlorophenylthio)triethylammonium chloride (CPTA) each inhibit production of the normal carotenoids of Rhodomicrobium vannielii (Rhodospirillaceae), especially rhodopin, beta-carotene and spirillixanthin, and cause the accumulation of lycopene. The inhibition of hydration of the C-1,2 double bond as well as cyclization is in agreement with proposals that these two reactions involve similar mechanisms. After removal of nicotine, cells reincubated in buffer solution or in the presence of diphenylamine convert accumulated lycopene into rhodopin. Under other conditions rhodopis is synthesized, on removal of nicotine, not from accumulated lycopene but from early precursors. The pathway of rhodopin and spirilloxanthin biosynthesis in Rm. vannielii is discussed briefly, and the possible involvement of enzyme aggregates in carotenoid biosynthesis is considered.

Carotenoids

The carotenoids of Flavobacterium strain R1560.

The main carotenoid of Flavobacterium strain R1560 has been identified as (3R,3'R)-zeaxanthin. Also present were small amounts of 15-cis-phytoene, phytofluene, "zeta-carotene" (7,8,7',8'-tetrahydro-psi, psi-carotene plus 7,8,11,12-tetrahydro-psi, psi-carotene), neurosporene, lycopene, beta-zeacarotene, gamma-carotene, beta-carotene, beta-cryptoxanthin, rubixanthin, 3-hydroxy-beta-zeacarotene and several apo-carotenals. Zeaxanthin production was inhibited by nicotine (10 mM), and lycopene and rubixanthin accumulated. The biosynthesis of zeaxanthin is discussed in terms of pathways and also of "half-molecule" reaction sequences. The presence of zeaxanthin may be a characteristic of a group of Flavobacterium species, and may thus be useful in the taxonomic classification of these organisms.

Carotenoids

Separation of C27, C28 and C29 sterols by reversed-phase high-performance liquid chromatography on small particles.

The application of reversed-phase high-performance liquid chromatography to the analytical- and preparative-scale separation of sterols has been evaluated. The capacity factors, k', for a number of compounds chromatographed on a muBondapak C18 (LESS THAN 10 MUM) COLUMN ARE PRESENTED. C27, C28 and C29 sterols and also sterols differing in degree of unsaturation could be readily separated as their acetates in this system. The present reversed-phase chromatographic method is apparently not as selective as silver nitrate-silica gel thin-layer chromatography for the position of unsaturation in the sterol molecule.

Chromatography, Liquid

Some properties and a suggested reclassification of mevaldate reductase.

Mevaldate reductase was purified 70-fold from rat liver. The partly purified enzyme had a molecular weight of 27000-30000, reduced certain aromatic aldehydes and was inhibited by barbiturates. These properties are similar to those of other animal tissue aldehyde reductases (EC 1.1.1.2) and it is suggested that mevaldate reductase be reclassified as one of this group.

Alcohol Oxidoreductases

Alternative pathways of zeaxanthin biosynthesis in a Flavobacterium species.

In Flavobacterium R1519, nicotine blocks zeaxanthin biosynthesis by specifically inhibiting the cyclization reaction. Lycopene (at high nicotine concentrations, e.g. 7.5mm) and rubixanthin (at low nicotine concentration, e.g. 1mm) replace zeaxanthin as the main carotenoid. On removal of the nicotine lycopene is converted into beta-carotene under anaerobic conditions and into zeaxanthin in the presence of O(2). The conversion in vivo of beta-carotene into zeaxanthin was also demonstrated. Cyclization (an anaerobic process) thus precedes hydroxylation (O(2)-requiring) in the biosynthesis of zeaxanthin. The conversion in vivo of rubixanthin into beta-cryptoxanthin and into zeaxanthin was demonstrated, thus indicating the operation of alternative pathways of zeaxanthin biosynthesis. Several alternative biosynthetic pathways are considered and the results are also discussed in terms of reaction sequences of carotenoid ;half-molecules'.

Carotenoids

Biosynthesis of spheroidene and hydroxyspheroidene in Rhodopseudomonas species: experiments with nicotine as inhibitor.

Neurosporene replaces spheroidene and hydroxyspheroidene as the main carotenoid in Rhodopseudomonas spheroides and Rhodopseudomonas gelatinosa grown in the presence of nicotine. On removal of the nicotine, spheroidene and hydroxyspheroidene are formed at the expense of the accumulated neurosporene. This shows that nicotine inhibits introduction of the C-1 tertiary hydroxyl groups, and supports the postulated pathway neurosporene-->spheroidene-->hydroxyspheroidene.

Aerobiosis