It is the purpose of this paper to describe the behavior of sulfur in wool under conditions which are very different from those ordinarily used in studies on sulfur lability and to point out a probable mechanism by which sulfur is split from wool during alkali treatment. The data indicate tha t the primary process in the alkali cleavage of the disulfide linkage consist s in a hydrolytic rupture of the disulfide group with the formation of a sulfh ydryl compound and a sulfenic acid. The sulfenic acid is ext remely reactive a nd u nstable in alkaline solution and immediately loses hydrogen sulfide and forms a n a ld eh yde. The results of the investigation indica t e that the existence of labile sulfur in prot eins is not an indication that the bulk of the sulfur is present in more than one form.
In 1903 Hilger1 hydrolyzed flaxseed mucilage and found in the hydrolytic products the sugars ¿-glucose, ¿-galactose, Z-xylose and Z-arabinose, together with an acid by-product. In 1913 Neville2 3verified the work of Hilger on this mucilage. Abderhalden8 states that this mucilage yields in addition to sugars, an acid complex which contains pentoses and hexoses.The investigation reported in this paper deals with the aldobionic acid formed during the partial hydrolysis of flaxseed mucilage. This acid is composed of one molecule of ¿-galacturonic acid joined through its aldehyde group to a molecule of Z-rhamnose. While the position of the oxide ring in the galacturonic acid and of the glucosidic union on the Z-rhamnose have not been established, the following structure is suggested. H Experimental PartPreparation of the Calcium Salt of the Aldobionic Acid.-Flaxseed mucilage was prepared according to the directions of Neville.2•4 One kilogram of the air-dry mucilage was dissolved in 6 liters of 4% sulfuric acid and heated in a boiling water-bath for twenty hours. The solution was cooled, neutralized by excess calcium carbonate, heated in a boiling water-bath to complete the neutralization and filtered from the insoluble material. The filtrate was concentrated in vacuo to a volume of 1.5 liters, decolorized by norit and the salts precipitated in a large dish by addition of 3 volumes of 95% ethanol. After standing overnight with fresh 95% ethanol the salts were triturated with a pestle until granular, filtered, washed with alcohol and ether and dried on a porous plate. The yield was 340 g.Purification and Analysis of the Calcium Salts.-The crude calcium salts were purified by the method of Levene.5 For this purpose 340 g. of salts was dissolved in
w-Heptaldehyde Me-n-Hex Me-«-Am ketones EtOAc Moles used 8.0 9.4 6.2 8.3 ( )-Methylnonanol-( ) 2,3 3,3 4,4 5,5 Intermediate products Yield, % 66 77 76 79 B. p. (10 mm.), °C. 90-95 87-88 86-87 83-86 «20 d 1.435 1.436 1.434 1.434 ^J (
Schon in der ersten chemischen Untersuchung an Tuberkelbazülen konnte Hammerschlag 1 ) keine Sterine entdecken, und dieser Befund ist von einer ganzen Reihe späterer Untersucher bestätigt worden. Vor etwa 20 Jahren berichtete Tamura 2 ) über die Abwesenheit von Sterinen in Mycobacterium lacticola sowie in Tuberkel-und Diphtheriebazillen. Gor i s 3 ) analysierte eine größere Menge von Tuberkelbazillen und fand ebenfalls keine Sterine. Anderson und seine Mitarbeiter 4 ) konnten auch in großen Mengen von menschlichen Tuberkelbazillen keinerlei Substanzen entdecken, die die Farbreaktionen von Sterinen gaben. Chargaff 5 ) fand keine Sterine in "B.C.G.", anderen säurefesten Bakterien und Diphtheriebazillen. In einer speziellen Sterinuntersuchung vermißte auch v. Behring 8 ) irgendwelche Sterine in B. coli und Diphtheriebazillen.Die Mitteilungen, die vor kurzem von Hecht 7 ) in dieser Zeitschrift erschienen, widersprechen all diesen Beobachtungen. Hecht behauptet, daß Tuberkelbazillen, andere säurefeste Bazillen und auch B. coli Sterine enthalten. Sie wurden durch Digitoninf ällung und Farbreaktionen nachgewiesen, aber es wurden keinerlei quantitative Daten gegeben. In Anbetracht dieser Mitteilungen fanden wir es wünschenswert, schon jetzt einige Resultate des letzten Jahres mitzuteilen, die im Gegensatz zu denen von Hecht völlig negativ waren.Wir hatten Gelegenheit, den Ätherextrakt von fünf verschiedenen Tuberkelbazillenstämmen zu untersuchen; vier davon waren kürzlich von menschlichen Fällen isoliert; und der andere war frisch von dem alten humanen Stamm H 37 gezüchtet. Die
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