224 Papers from the Department of Marine Biology. 



STUDIES ON OXIDATIVE CHEMILUMINESCENT REACTIONS WITH 

 SUBSTANCES OF DEFINITE COMPOSITION. 



HISTORICAL. 



Since the researches of Radziszewski in 1877 (34) 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 esculetm. 



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 c ? 



light at 5 C. At 20 C. a faint light appears with H ' x - 

 n/80 NaOH. On warming, the light is brighter. 

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



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 H 2 O 2 . The 

 substance in urine responsible for this effect is unknown. He describes 

 light-production upon adding strong alkaline H 2 2 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 H 2 2 , and Du- 

 bois (10) has recently discovered that esculin also will give light with 

 blood and H 2 O 2 . 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 KMn0 4 and H 2 2 . 

 It is best to keep the temperature about 60 C. I found also that esculin 

 would give light with FeCl 3 +H 2 2 , but not with FeCl 3 , or KMn0 4 or 

 H 2 O 2 alone, nor with plant extracts rich in oxidases (turnip, potato, 

 and horseradish root), either with or without H 2 2 , 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 H 2 O 2 . Ozonized turpentine can take the place 

 of H 2 O 2 in oxidation of esculin. 



