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Studies on Oxidative Chemiluminescent Reactions with Substances of Definite Composition

light, esculin, lophin, blood and pyrogallol

STUDIES ON OXIDATIVE CHEMILUMINESCENT REACTIONS WITH SUBSTANCES OF DEFINITE COMPOSITION.

Since the researches of Radziszewski in 1877 (u) and 1880 (35) on lophin and various oils, alcohols, and aldehydes, we have come to rec ognize an ever-increasing number of substances which will luminesce under appropriate conditions at temperatures approaching those com patible with life. Lophin (triphenylglyoxaline) gives an especially good light with alcoholic potash at 60° C., as do many essential oils. Trautz (36) has added other substances to the list of chemiluminescent reac tions. R. Dubois (37) discovered the luminescence of esculin, a glu coside obtained from horse-chestnut bark and chemically a combination of glucose and esculetin.

These substances all require fairly strong alkali, although I have a sample of bergamot oil which gives a beautiful light when mixed with n/10 NaOH at 20° C. and a faint light at 5° C. At 20° C. a faint light appears with n/80 NaOH. On warming, the light is brighter.

n/80 NaOH is, however, incompatible with life.

Lophin and esculin will not luminesce except with alcoholic NaOH or KOH.

McDermott (38) has described the production of light if to urine is added some 99 per cent KCN or potassium formate or formaldehyde and then a strong alkaline solution of The substance in urine responsible for this effect is unknown. He describes light-production upon adding strong alkaline to the cleavage products of Witte's peptone or glue made with alkali in absence of oxygen and to which a little commercial formaldehyde is added. (Note that the light is connected in these cases with substances found in organisms.) Ville and Derrien (39) made an interesting step forward when they showed that lophin would luminesce with blood and and Du bois (1o) has recently discovered that esculin also will give light with blood and H202. The blood contains an oxygen carrier, hemoglobin, which accelerates the oxidation of the lophin and esculin. I can confirm

the statement of Dubois and of Ville and Derrien, and find, also, con trary to Dubois, that esculin will give light with and 11202. It is best to keep the temperature about 60° C. I found also that esculin would give light with FeC13-1-H202, but not with or or alone, nor with plant extracts rich in oxidases (turnip, potato, and horseradish root), either with or without and that blood extract still retains its power to produce light with lophin after boiling. This is not surprising, as blood will also oxidize guaiac after boiling and upon addition of Ozonized turpentine can take the place of in oxidation of esculin.

Trautz (3a) has shown that if we mix 35 c.c. of a 50 per cent solution, 35 c.c. of 10 per cent pyrogallol, and 35 c.c. of 35 per cent formaldehyde, and to this mixture add 50 c.c. of 30 per cent a glow occurs, accompanied by much foaming. I can confirm this result, and find in addition that when the glow has died, if we add some a reddish glow again appears. The tube becomes perceptibly warm.

It is not necessary to use such strong reagents to obtain light from oxidation of pyrogallol, however, for a very weak solution of pyrogallol will give a bright light if oxidized under the proper conditions. The oxidation of a mixture of pyrogallol + by the vegetable oxidases occurs with the production of light. The reaction is highly interesting and remarkable for the following reasons: Perceptible light is pro duced with the concentration of pyrogallol m/32,000—i. e., 1 part in 254,000 parts of solution; a faint light is produced at 0° C. and a bright light at 10° C.; KCN inhibits the reaction in m/2,000 concentration; boiling destroys the oxidase, and the power of producing light just as boiling destroys the light-producing power of organisms.