Inhibitor resistant serine proteases

Drug – bio-affecting and body treating compositions – Enzyme or coenzyme containing – Hydrolases

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435217, 4352523, 4353201, 435325, 435358, 435365, 435367, 435369, 435357, 435352, 435356, 536 232, A61K 3848, C12N 968, C12N 1555, C12N 1563

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056458339

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BRIEF SUMMARY
The present invention relates to serine proteases of the chymotrypsin superfamily which have been modified so that they exhibit resistance to serine protease inhibitors. The invention also relates to the precursors of such compounds, their preparation, to nucleic acid coding for them and to their pharmaceutical use.
Serine proteases are endopeptidases which use serine as the nucleophile in peptide bond cleavage. There are two known superfamilies of serine proteases and these are the chymotrypsin superfamily and the Streptomyces subtilisin superfamily (Barrett, A. J., in: Proteinase Inhibitors, Ed. Barrett, A. J. et al., Elsevier, Amsterdam, pp 3-22 (1986) and James, M. N. G., in: Proteolysis and Physiological Regulation, Ed. Ribbons, D. W. et al, Academic Press, New York, pp 125-142 (1976)).
The present invention is particularly concerned with serine proteases of the chymotrypsin superfamily which includes such compounds as plasmin, tissue plasminogen activator (t-PA), urokinase-type plasminogen activator (u-PA), trypsin, chymotrypsin, granzyme, elastase, acrosin, tonin, myeloblastin, prostate-specific antigen (PSA), gamma-renin, tryptase, snake venom serine proteases, adipsin, protein C, cathepsin G, complement components C1R, C1S and C2, complement factors B, D and I, chymase, hepsin, medullasin and proteins of the blood coagulation cascade including kallikrein, thrombin, and Factors VIIa, IXa, Xa, XIa and XIIa. Members of the chymotrypsin superfamily have amino acid and structural homology of the catalytic domains, although a comparison of the sequences of the catalytic domains reveals the presence of insertions or deletions of amino acids. However, these insertions and deletions map to the surface of the folded molecule and thus do not affect the basic structure although it is likely that they contribute to the specificity of interactions of the molecule with substrates and inhibitors (Strassburger, W. et al, FEBS Lett., 157, 219-223 (1983)).
Serine protease inhibitors are also well known and are divided into the following families: the bovine pancreatic trypsin inhibitor (BPTI) family, the Kazal family, the alpha-2-macroglobulin (A2M) family, the Streptomyces subtilisin inhibitor (SSI) family, the serpin family, the Kunitz family, the four-disulphide core family, the potato inhibitor family and the Bowman-Birk family.
Serine protease inhibitors inhibit their cognate serine proteases and form stable 1:1 complexes with these proteases. Structural data are available for several protease-inhibitor complexes including trypsin-BPTI, chymotrypsin-ovomucoid inhibitor and chymotrypsin-potato inhibitor (Read, R. J. et al., in: Proteinase inhibitors, Ed. Barrett, A. J. et al., Elsevier, Amsterdam, pp 301-336 (1986)). A structural feature which is common to all the serine protease inhibitors is a loop extending from the surface of the molecule which contains the recognition sequence for the active site of the cognate serine protease and, in fact, there is remarkable similarity in the specific interactions between different inhibitors and their cognate serine proteases, despite the diverse sequences of the inhibitors.
The serine proteases of the chymotrypsin superfamily play an important role in human and animal physiology. Some of the most important serine protease inhibitors are those which are involved in blood coagulation and fibrinolysis. In the process of blood coagulation, a cascade of enzyme activities is involved in generating a fibrin network which forms the framework of a clot or thrombus. Degradation of the fibrin network (fibrinolysis) involves the protease inhibitor plasmin. Plasmin is formed in the body from its inactive precursor plasminogen by cleavage of the peptide bond between arginine 561 and valine 562 of plasminogen. This reaction is catalysed by t-PA or by u-PA.
If the balance between the clotting and fibrinolytic systems becomes locally disturbed, intravascular clots may form at inappropriate locations leading to conditions such as coronary thrombosis and myocardial infarction, deed vein t

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