304 CHEMISTRY OF THE PROTEIDS CHAP. 



formed synthetically seems to have been a copper compound, 

 and, therefore, the copper albuminates are discussed in the first 

 instance. 



7c. Copper Albuminates 



The copper compounds of albumin were first made by Orfila 1 

 because of their toxological importance. To him and to Christison 

 belongs the credit of having clearly recognised that copper unites with 

 albumin only in the form of its oxide, and not in the form of a salt. 

 This view was also held by Rose, 2 the discoverer of the biuret-reaction. 

 Mitscherlich's 3 statements to the opposite effect were disproved by 

 Mulder 4 and Lieberkiihn. 5 Other early workers were Lassaigne, 6 

 Bielicki, 7 Neebe, 8 Ritthausen, 9 Ritthausen and Pott, 10 and Morner. 11 The 

 recent investigations date from Harnack, 12 who preferred, by means of 

 copper salts, 'ash-free ' albumin, after Wiirtz, in 1844, had failed in pre- 

 paring ash-free compounds by means of lead salts. Harnack's investi- 

 gation called forth papers by Griibler, 13 Chittenden, and Whitehouse, 14 



1 Orfila, Toxic. Gen. I 535. See also Christison, Uber d. Gifte, Weimar, 1831, pp. 

 480 and 482. 



2 F. Rose, Poggendor/'s Annalen, 28. 132 (1833), Inaug. Dissert., Rostock (1833). 



3 C. G. Mitscherlich, Arch. f. Anat. u. Physiol. 4. 91 (1837). 



4 Mulder, Versuch einer allgem. physiol. Chem. Braunschweig, 1851. 



5 N. Lieberkiihn, Poggendor/'s Annalen, 86. 117 and 298 (1852). 



6 Lassaigne, Journ. de chem. medic. (2nd series), vol. 6 (according to Harnack). 



7 R. Bielicki, Qucedam de metallorum albuminatibus, eorumque e/ectu ad organismum 

 animalium, Dissertation, Dorpat, 1853. 



8 C. W. Neebe, Versuche u. d. Wirk. d. essigsduren Kupferoxyds und einiger anderen 

 organischsduren Kupferoxyde, Dissertation, Marburg, 1857. 



9 H. Ritthausen, Die Eiweisskorper der Getreidearten, etc. Bonn, 1871. 



10 H. Ritthausen and R. Pott, Journ. f. prakt. Chem. 7. 361 (1873). 



11 K. A. H. Morner. ' Alkali-albuminates in combination with alkaline earths and 

 copper, ' Upscda Ldkare forenings forhandl. 13. 24 (1877). See Maly's Berichte, 7. 6 

 (1877). 



12 E. Harnack, (a) 'The Copper Compounds of Albumin,' Zeitschr. f. physiol. Chem. 

 5. 198 (1881) ; (b) 'Method of Preparation and Properties of Ash-free Albumin,' Ber. 

 d. deutsch. chem. Ges. 22. 30, 46 (1889) ; (c) 'Sulphur Content of Ash-free Albumin,' 

 Ber. de deutsch. chem. Ges. 23. 40 (1890) ; (d) 'Studies of so-called Ash-free Albumin,' 

 Ber. de deutsch. chem. Ges. 23. 3745 (1890) (here is given a detailed account of how to 

 prepare 'ash-free' albumin); (e) 'Further Studies of Ash-free Albumin, 'Ber. de deutsch. 

 chem. Ges. 25. 204 (1892); (/) 'Discussion on Crystallised and Ash-free Albumins,' 

 Zeitschr. f. physiol. Chem. 19. 299 (1894); (g) 'The Sulphur of Ash-free Albumins 

 as compared with that of Halogen Albuminates,' Ber. d. deutsch. chem. Ges. 31. 1938 

 (1898). 



13 G. Griibler, Journ. f. prakt. Chem. 23. 97 (1881). 



14 R. H. Chittenden and H. H. Whitehouse, 'On the Metallic Combinations of 

 Albumin and Myosin, ' Studies from the Laborat. of Physiol. Chemist. , Yale Univers. , 

 New Haven, 2. 95 (1887). 



