N,N'-bis-L-amino acid-L-cystine-peptide containing amino acid pr

Drug – bio-affecting and body treating compositions – Designated organic active ingredient containing – Peptide containing doai

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530330, 530331, A61K 3702, C07K 508, C07K 510

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049686968

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BRIEF SUMMARY
The sulfur containing amino acid cysteine and its stable dimeric disulfide product cystine, which is formed therefrom readily upon oxidation, do not belong to the classic essential amino acids, but nevertheless cystine is considered an indispensible component in amino acid preparations provided for the nutrition of babies, for chronical uremia, hepatic cirrhosis and of the injured. The reason for the essentiality in said cases is a non-sufficient or completely missing synthesis of cystine from the respective sulfur-containing amino acids methionine and cystine serving as intermediates in the body.
Since in many cases newborn or premature infants as well as patients showing the above syndromes have to be fed intravenously, it is essential to incorporate cystine in adequate amounts into the respective nutritious solutions. However, this is prevented by the very poor solubility of free cystine in water, which is only 0:1 g/l H.sub.2 O.
A soluble derivative has been provided by the acetylation of cystine, the product being used in small amounts in amino acid preparations. However, this cysteine compound, too, is readily oxidized to the disulfide product in aqueous solution. On the other hand, in contrast to free cystine, this N,N'-bis-acetylcystine has a relatively high solubility in water and therefore stays in solution, which is the reason why it has been tried to use this diacetyated cystine in infusion preparations. However, new studies show unambiguously that acetylated amino acids have a poor utilization in man only and can be used to a small extent only for the synthesis of endogenous protein. Diglycylcystine is known as a soluble cystine compound for a long time and has been used as a substrate for peptidase studies, as the cleavage of this peptide can be readily measured due to the precipitation of insoluble cystine, cf. J. Biol. Chemistry, vol. 128, 241-243 (1939). In spite of an existing need, this cystine peptide has not been used for nutritional purposes in practice so far.
It is further known to transform poorly soluble amino acids as tyrosin and also cystine into very readily water soluble peptides by condensation with the dibasic amino acid lysine. For example, the European Patent specification 87 751 describes the preparation and use of N.sup.2 -L-cystinyl-N.sup.6 -L-cystinyl-L-lysine, which is a tripeptide readily soluble in water in spite of its two cystinyl groups, the two cystinyl residues being attached to the two amino groups of the lysine by one of their respective carboxyl groups.
Experiments to provide a simple and inexpensive but also well metabolizable and water soluble cystine peptide by synthesis of a tripeptide from two moles of alanine and one mole of cystine, in which in an analoguous way to the known lysine derivatives the amino groups of the alanine molecules are bound to the carboxyl groups of the cystine have shown indeed that this L-cystinyl-bis-L-alanine having the two carboxyl groups of the cystine each bound to the amino group of an alanine, is well soluble in water, however, is unstable upon heat sterilization (121.degree. C.) and results in the formation of other derivatives already after 8 minutes, this leading to a reduction or loss of the bio-availability of the cystine.
Surprisingly, it has now been found that in contrast to this tripeptide N,N'-bis-L-alanyl-L-cystine-peptide as well as, in general, the N,N'-bis-L-amino acid-L-cystine-peptides of the general formula ##STR1## wherein R represents a L-amino acid residue, are not only well soluble in water, but also remain stable upon heat sterilization in aqueous solutions, i.e. are not modified thereby, and in spite of this stability can be readily cleaved and utilized in the body, which renders them well suited as highly bio-available cystine compounds in amino acid and oligopeptide preparations for oral and parenteral nutrition.
Since the composition with respect to the amino acids is identical in the two types of peptides, e.g. in L-cystinyl-bis-alanine and bis-L-alanyl-L-cystine of the invention, the reason for

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"Chemistry of Aliphatic Disulfides. XII. Synthesis of Unsymmetrical Open-in Cystine Derivatives.sup.1-3 ", Richard G. Hiskey et al., Journal of Organic Chemistry, vol. 32 (Jan. 1967), pp. 97-102.
"Amino Acids and Peptides. Part XL. Protection Removable by Electrolytic Reduction: the Use of S-4-Picolyl-L-Cysteine and 0-4-Picolyl-L-Tyrosine in Synthesis", Anthony Gosden et al., Chemical Abstracts, vol. 86, No. 107036u (1977), p. 555.
"A Refinement of the Crystal Structure of N,N'-Diglycyl-L-Cystine Dihydrate", William C. Stallings, Jr., et al., Chemical Abtracts, vol. 85, No. 71026d (1976), p. 564.
"Chromatographic Properties of Peptides of Cystine and Glycine and Some Related Derivatives", Marvin D. Armstrong, Chemical Abstracts, vol. 91, No. 170996a (1979), p. 304.

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