Highly reactive esters of carboxy polysaccharides and carboxy po

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

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514 23, 514 26, 514 54, 514178, 514181, 514453, 536 3, 536 187, 536 551, 536 53, 536115, 536119, C07H 1300, A61K 31215

Patent

active

058562990

DESCRIPTION:

BRIEF SUMMARY
BACKGROUND OF THE INVENTION

1. Field of the Invention
The present invention relates to active esters of carboxy polysaccharides and semisynthetic derivatives of such carboxy polysaccharides, wherein all or a part of the carboxy functions of the polysaccharides are esterified with alcohols of the aromatic, heterocyclic aromatic, or N-hydroxylamine series and, in the case of active partial esters, the remaining carboxy functions are salified with quaternary ammonium salts or metals. The present invention also relates to a method for the synthesis of said active esters starting with carboxy polysaccharides and their semisynthetic derivatives.
The present invention also relates to the use of such active esters as intermediates in the synthesis of modified carboxy polysaccharides and modified semisynthetic derivatives of carboxy polysaccharides, the modified polysaccharides and modified semisynthetic derivatives thereof per se, and the use of such modified polysaccharides and semisynthetic derivatives thereof to produce health care and surgical articles for use in the pharmaceutical and biomedical fields.


DESCRIPTION OF RELATED ART

There are reports in the literature of methods for for the synthesis and appliation of active esters for amino acids which comprise stable intermediates for use in the synthesis of peptides (see Fields, C. B. and Noble, R. L. (1990) Int. J. Peptide Protein Res. 35:613-214; Atherton, E. and Sheppard, R. C. (1989) in Solid Phase Peptide Synthesis, A Practical Approach, IRL Press, Oxford; M. Bodansky (1984) in Principles of Peptide Synthesis, Springer-Verlag, Berlin, Heidelberg). Said esters result in greater reactivity of the carboxy group in nucleophilic substitution reactions as the strongly electron-attracting group bound to the carbonyl carbon can be easily substituted with a nucleophile (sulfide, amine, alcoholic hydroxyl) to produce thioesters, amides, and esters under suitable reaction conditions, i.e., solvents, temperature, catalysts, etc. Esters with aromatic, substituted aromatic, aromatic heterocyclic, and substituted aromatic heterocyclic alcohols, and N-hydroxylamines, belong to this class of active esters.
International patent application WO-A-92/20349 discloses water insoluble biocompatible compositions. The compositions of WO-A-92//20349 are made by mixing in a "one-pot" reaction a polyanionic polysaccharide, an activating agent, a modifying agent and a nucleophile. The reactions of WO-A-92/20349 are done in a single reaction vessel; and because of the reaction conditions used, it is not possible to isolate any intermediates.


SUMMARY OF THE INVENTION

The present invention provides a novel method for producing esters, amides, and thioesters of carboxy polysaccharides via the formation of active ester intermediates, and subsequent nucleophilic substitution at the carboxyl functions of the polysaccharides.
Apart from being used as intermediate products which are stable and easily stored, due to subsequent nucleophile substitution reactions, the active esters of carboxy polysaccharides and their semisynthetic derivatives can be used as reaction intermediates for the preparation of diagnostic kits as surfaces for the activation of proteins.
The production method is mainly based upon plasma-coating applied between the polymeric surface of the support, e.g., polystyrene, and the activated polysaccharide with the formation of stable bonds.
According to the intended diagnostic use, the activated polysaccharide-based surface is treated with a polypeptide or protein that binds to the polysaccharide by a nucleophilic substitution reaction. The treated material can therefore be used (a) to identify biochemical targets, such as antibodies or other polypeptides compatible with the molecules bound to the hyaluronic acid by spectrophotometry or immunological methods (ELISA), and (b) to coat laboratory equipment and dishes for the cultivation and regeneration of cells and tissues.
For example, the typical hydrophilic characteristics of hyaluronic acid, in association with suitabl

REFERENCES:
patent: 5122598 (1992-06-01), Della Valle et al.
patent: 5202431 (1993-04-01), Della Valle et al.
patent: 5332809 (1994-07-01), Della Valle et al.
patent: 5336668 (1994-08-01), Della Valle et al.
patent: 5676964 (1997-10-01), Della Valle et al.

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