Gadusol, C8H12O6, has been isolated from roes of the cod (Gadus morhua L.), i.e., ovaries that contain ripe eggs just before spawning. The concentration is about 4 g/kg dry wt. It has been identified as 1,4,5-trihydroxy-5-hydroxymethyl-2-methoxycyclo-hex-1-en-3-one and this structure was confirmed by synthesis of the anhydro tetra-acetate derivative from methyl 3,5-diacetoxy-4-methoxybenzoate. Concentrations of gadusol in the roes of other marine teleost fish examined are of the same order as in cod roes. Gadusol has some properties similar to ascorbic acid and both compounds, after oxidation, react with 2,4-dinitrophenylhydrazine in the commonly-used assay procedure for ascorbic acid. Specific assays showed that the concentrations of gadusol in the roes of marine fish are severalfold greater than those of ascorbic acid. Gadusol is structurally related to the mycosporines previously reported from a number of different organisms.
DETERMINATION OF VITAMIN A2 ALDEHYDE 561 found for different preparations of antimony trichloride, the characteristics of a particular preparation should be determined with pure vitamin A2 aldehyde for accurate work, but for determinationsof thealdehydeinnatural materials, the mean value of 4200 can be used. The variations in A... (739-743 mru, mean 741 m,u) are not significant since, with the broad maximum of the absorption curve, values of extinction over this range would be essentially the same, within the experimental error of the test. SUMMARY 1. Crystalline vitamin A2 aldehyde with m.p. 66-680 has been prepared from vitamin A1 aldehyde. 2. With purified antimony trichloride, 14 % (w/w) in chloroform containing 2 % (v/v) acetic anhydride, the wavelength of maximum absorption of the green-blue colour produced with vitamin A2 aldehyde increased with concentration of the aldehyde and decreased with time. 3. In the absence of acetic anhydride, the wavelength of maximum absorption of the colour product was steady at 741 m,i, the colour developed remained at full intensity for about 15 sec., the maximum extinction varied linearly with concentration of aldehyde and E1:,,, (741 mi/) was 4200 (range 4000-4400). 4. Some observations on antimony pentachloride and glycerol dichlorohydrin (1:3-dichloropropan-2-ol) as colorimnetric reagents for vitamin As aldehyde are presented. * Grant-aided by the Development Fund.
SUMMARYCod (Gadus morhua L.) from the Arcto-Norwegian stock that spawns off northern Norway were caught at various times during their gonadal maturation cycle over a period of 16 months. The ovaries were removed and either fixed for histological work or deep-frozen for the determination of vitamin A compounds.The ovaries were inactive from June to September. Maturation began in late September-October and fully ripe eggs were present in February-March, the range of sizes being 500-650 /x. After spawning there was a period of resorption and regeneration, until May, followed by the quiescent summer period.dry matter rose from about 16 to 29%; the total amount of vitamin A aldehyde, vitamin A esters and alcohol, carotenoids and lipids in the ovaries also increased, though the concentrations of the carotenoids and vitamin A esters + alcohol on a dry-matter basis fell. Vitamin A aldehyde was only found in maturing ovaries and in February, just before spawning, the weight ratio of aldehyde to esters + alcohol was about 10 to 1. The other substances were present in resting ovaries. The appearance of aldehyde in the ovaries occurred when there was histological evidence for the onset of vitellogenesis.
Cod (Gadus morhua L.) from the Arcto-Norwegian stock that spawns off northern Norway were caught at various times during the course of their gonadal maturation cycle, and plasma samples were collected for the determination of vitamin A compounds and lipids.The main changes found concerned vitamin A aldehyde, which increased from a resting level of2μg/100 ml. plasma for adult females caught in September to 10 μ/100 ml. in ripe females caught in January-March approaching their spawning grounds; by contrast little change was observed in the males. In the fish of both sexes caught in September, just prior to the onset of maturation, dehydroretinal formed about 38 % of the total aldehyde, but in the plasma of ripe females the proportion was only 16 %. In both sexes there was a fairly steady decline in the levels of vitamin A esters and alcohol in the plasma during the winter. Similarly, the concentration of plasma lipids fell during the winter in the male cod, but in the adult females, during the period of ovarian maturation, the concentration of lipids increased and was maintained at about 0·5 g/100 ml. higher than in the males; in spent fish the concentration of lipids fell to the same low levels in both sexes.It was considered that the changes in vitamin A aldehyde, and also of blood lipid, in the females were directly linked with sexual maturation, these compounds being transported to the developing eggs in the ovary. On the other hand, the general decline of vitamin A esters and alcohol in both sexes, and of lipids in the males, was probably due to the obligatory winter starvation which occurs in this stock.
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