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(12) United States Patent (10) Patent No.: US 7,045,140 B2 Motterlini Et Al

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(12) United States Patent (10) Patent No.: US 7,045,140 B2 Motterlini Et Al USOO7045140B2 (12) United States Patent (10) Patent No.: US 7,045,140 B2 Motterlini et al. (45) Date of Patent: May 16, 2006 (54) THERAPEUTIC DELIVERY OF CARBON FOREIGN PATENT DOCUMENTS MONOXDE HU 211 084 B 4f1990 WO WO 91/O1128 2, 1991 (75) Inventors: Roberto Angelo Motterlini, Middlesex WO WO 91/O1301 2, 1991 (GB); Brian Ernest Mann, Sheffield WO WO 94,22482 10, 1994 (GB) WO WO95/05814 3, 1995 WO WO 98.29115 7, 1998 WO WO 98.48848 11, 1998 (73) Assignee: Hemocorm Limited, London (GB) WO WOOO,56743 9, 2000 WO WO O2/O78684 10, 2002 (*) Notice: Subject to any disclaimer, the term of this WO WO O2/O80923 10, 2002 patent is extended or adjusted under 35 WO WO O3,OOO114 1, 2003 WO WO O3,0666067 8, 2003 U.S.C. 154(b) by 384 days. WO WO O3,O72O24 9, 2003 WO WO O3,O88923 10, 2003 (21) Appl. No.: 10/143,824 WO WO O3,O88981 10, 2003 WO WO O3,O94932 11/2003 (22) Filed: May 14, 2002 OTHER PUBLICATIONS Furchgott, et al. Blood Vessels 1991:28:52-61 (65) Prior Publication Data "Endothelium-Dependent and -Independent Vasodilation US 2003/0064114 A1 Apr. 3, 2003 Involving Cyclic GMP: Relaxation Induced by Nitric Oxide, Carbon Monoxide and Light'. (30) Foreign Application Priority Data Wang et al, Biochemistry, vol. 18, No. 22, 1979, 4960-4977 May 15, 2001 (GB) ................................. O111872.8 “A Correlation of the Visible and Soret Spectra of Dioxygen and Carbon Monoxide-Heme Complexes and Five-Coordi (51) Int. Cl. nate Heme Complexes with the Spectra of Oxy-, Carboxy A6F 2/02 (2006.01) and Deoxyhemoglobins'. A6F I3/02 (2006.01) A6 IK 9/48 (2006.01) (Continued) A6 IK 9/20 (2006.01) Primary Examiner Carlos A. Azpuru (74) Attorney, Agent, or Firm Nixon & Vanderhye P.C. (52) U.S. Cl. ...................... 424/423; 424/434; 424/435: (57) ABSTRACT 424/436: 424/451; 424/464 (58) Field of Classification Search ................ 424/423, 424/434, 435, 436, 451, 464 Metal carbonyls are used to deliver CO having biological See application file for complete search history. activity, for example vasodilatation and inhibition of trans plant rejection. The metal of the carbonyl is typically of (56) References Cited groups 7 to 10, e.g. Fe and Ru. The carbonyl preferably has one or more ligands other than CO. Such as amino acids, to U.S. PATENT DOCUMENTS modulate the CO release property and solubility. 5,882,674. A * 3/1999 Herrmann et al. .......... 424/448 2002fO155166 A1 10, 2002 Choi et al. 31 Claims, 17 Drawing Sheets iron pentacarbonyl Dimanganese decacarbonyl Fe(CO) Mn(CO)4 US 7,045,140 B2 Page 2 OTHER PUBLICATIONS Yan et al., Pharmazie, 2000, 55(4), 307-313 “Cytotoxicity of Schubert, Nov., 1933 Carbon Monoxide on Iron and Cobalt rhenium (I) alkoxo and hydroxo carbonyl complexes in Cysteine Complexes, vol. 55, 4563-4570 “The Action of murin and human tumor cells'. Becker et al, Medical Sciences (1979), vol. 15, No. 2, Carbon Monoxide on Iron and Cobalt Complexes of 147-150, “Age related changes in antibody dependent cell Cysteine'. mediated cytotoxicity in mouse spleen'. Carroll et al, Can. J. Chem. vol. 52, 1974, 1914-1922 Nagai et al., Biochemistry, 1991, vol. 30, No. 26, 6495 “Ligand Abstraction in the Reaction of Aryldiazonium Ions 6503, “Unusual CO Bonding Geometry in Abnormal Sub with some Iron Complexes Containing Coordinated units of Hemoglobin M Boston and Hemoglobin M Cysteine, Maleonitriledithiol, or Triarylphosphine'. Saskatoon'. Sjöstrand, Scan. J. Clin. Lab Invest., 1949, 1:201-214 Tomita et al., Inorganic and Nuclear Chemistry Letters 1968, "Endogenous Formation of Carbon Monoxide In Man Under vol. 4, 715-718 “Structure and Reaction of Bis(L- Normal and Pathological Conditions”. cysteinato)Dicarbonyliron(II)”. Coburn et al., J. of Clinical Investigation, vol. 42, No. 7, Ferrier et al., J. of Molecular Structure 344, 1995, 189-193 1963, 1172-1178 “Endogenous Carbon Monoxide Produc “FTIR spectrometric study of geometrical isomers of tion in Man'. dicarbonyl ferrobiscysteinate Influence of the counter cat Tenhunen et al., J. of Biological Chemistry, vol. 244, No. 23, ion'. 6388-6394 (1969) “Microsomal Heme Oxygenase”. Szakács-Schmidt et al. Inorganica Chimica Acta, 198-200, Maines, Dept. of Biophysics, University of Rochester, 1992, 401-405 “Iron (II) thiolates as reversible-carbon mon FASEB J 2:2557-2568 (1988) “Heme oxygenase: function, oxide carriers’. multiplicity, regulatory mechanisms, and clinical applica Takács et al. Inorganic Chimica Acta, 166, 1989, 39-46 tions'. “Synthesis and Molecular Structure of Carbonyl Derivatives Morita et al., Proc. Natl. Acad. Sci. USA, Cell Biology, 1995, of Iron(II) Thiolates Containing Nitrogen-donor Ligands’. vol. 92, 1475-1479, “Smooth muscle cell-derived carbon Tomita et al. Inorg. Nucl. Chem. Letters vol. 4, 715-718, monoxide is a regulator of vascular cGMP'. 1968, “Structure and Reaction of Bis(L- Sammut et al. British J. of Pharmacology, 1998, 125, 1437 cysteinato)Dicarbonyliron(II)”. 1444 “Carbon monoxide is a major contributor to the Huang et al., J. Am. Chem. Soc., 1991, 113, 9141-91.44 regulation of vascular tone in aortas expressing high levels “Photolysis of the Histidine-Heme-CO Complex”. of haeme oxygenase-1'. Silver et al., Inorganica Chimica Acta, 91, 1984, 279-283 Maines, Annu. Rev., Pharmacol. Toxocol, 1997, 517-554, “Mossbauer Studies on Protoprophyrin IX Iron(II) Solutions “The Heme Oxygenase System: A Regulator of Second Containing Sulphur Ligands and their Carbonyl Adducts. Messenger Gases”. Models for the Active Site of Cytochromes P-450”. Soares et al, Nature Medicine, vol. 4, No. 9, 1998, 1073 Diamantis et al. Inorg. Chem., 1981, 20, 1141-1150 Prepa 1077, “Expression of heme oxygenase-1 can determine ration and Structure of Ethylenediaminetetraacetate Com cardiac Xenograft Survival'. plexes of Ruthenium(II) with Dinitrogen, Carbon Monox Willis et al, Nature Medicine, vol. 2, No. 1, 1996, 87-90 ide, and other JC-Acceptor Ligands. “Heme oxygenase: A novel target for the modulation of the Urban et al., J. of Organometallic Chemistry 517, 1996, inflammatory response'. 191-200 Metal complexes of biologically important ligands, Motterlini et al. Regulation of Pressor Responses by HO-1- LXXXVII C.-Amino carboxylate complexes of pal Derived CO, 1998, 568-577 “Heme Oxygenase-1-Derived ladium(II), iridium(III) and ruthenium(II) from chloro Carbon Monoxide Contributes to the Suppression of Acute bridged ortho-metallated metal compounds and Hypertensive Responses In Vivo”. (OC) Ru(Cl)(L-Cl). Otterbein et al, Am. J. Physiol., 1999, 688-694 Carbon Motterlini et al. Carbon Monoxide-Releasing Molecules: monoxide provides protection against hyperoxic lung injury. Characterization Of Biomedical And Vascular Activities, Otterbein et al., J. Clin. Invest., 103: 1047-1054, 1999, Circulation Research. 2002, vol. 90, No. 2, 1-8. "Exogenous administration of heme oxygenase-1 by gene Motterlini, R. et al., “Characterization of vasoactive effects transfer provides protection against hyperoxia-induced lung elicited by carbon monoxide-releasing molecules.”: Journal injury”. of Vascular Research, Abstracts, 8" International Sympo Herrick et al., Inorg. Chem. 1984, 23, 4550-4553 “Flash sium on Mechanisms of Vasodilation; May 31—Jun. 3, Photolytic Investigation of Photoinduced Carbon Monoxide 2001; 055. Dissociation from Dinuclear Manganese Carbonyl Com Durante W.; "Heme Oxygenase-1 in Growth Control and its pounds’. Clinical Application to Vascular Disease'; J. Cell. Physiol.: Alessio et al, Inorg. Chem., 1995, 34, 4722-4734 “Carbonyl 2003; 195; 373-82. Derivatives of Chloride-Dimethyl Sulfoxide-Ruthenium (II) Gordeuk, V. P. et al: “Carbonyl Iron Therapy for Iron Complexes: Synthesis, Structural Characterization, and Deficiency Anemia: Blood; 1986; 67(3); 745-752. Reactivity of RU(CO)(DMSO). CI Complexes (x=1-3). Huebers, H. A. et al.: “Absorption of carbonyl iron’: J. Lab. Sato et al. The J. of Immunology, 2001, 4185-4195, “Carbon Clin. Med., 1986; 108: 473-8. Monoxide Generated by Heme Oxygenase-1 Suppresses the Sacks, P. V. et al.: “Comparative bioavailability of elemental Rejection of Mouse-to-Rat Cardiac Transplants”. iron powders for repair of iron deficiency anemia in rats. Pneumatikakis et al. Inorganica Chimica Acta, 151, 1988, Studies of efficacy and toxicity of carbonyl iron': The 243-248 “Interactions of Bis-ul-chloro chlorotricarbonylruthenium(II) and poly-L-dichloro American Journal of Clinical Nutrition, 1978; 31:566-73. dicarbonylruthenium (II) with Nucleotides'. * cited by examiner U.S. Patent May 16, 2006 Sheet 3 of 17 US 7,045,140 B2 1.00 Ru(CO)(C) O,75 O 5 O 0.25 0.00 500 S2O 540 560 580 6OO A (nm) Fig. 2(e) 100 75 t 3.S. E 50 25 O ------ 0 100 200 300 Ru(CO)Cl. (nmoles) U.S. Patent May 16, 2006 Sheet 4 of 17 US 7,045,140 B2 CO C Cl, o-ocY YoYYco2. C CO Tricarbonyldichloro ruthenium(I) dimer Ru(CO)(C), OSMe2 SOMe. SOMe2 C. w -C C. -C C.f't -OSMe. oc1 NYoo ocY NNco ocy N CO CO SOMe. C Fig. 3 U.S. Patent May 16, 2006 Sheet 5 of 17 US 7,045,140 B2 120 100 3 h O3 h + 21 h SSS 24 h ?Ø. O 2 0.5222222222222 O 8 10 222222222ZZZZZZZZ % DMSO Fig. 40a) 120 100 3 h O3 h 4, 21 h {ØZZZZZZ* SNS 24 h. (222ZZZZZZ* *(322222222 O 2222222222222222 O O4. O.11?. 0.17 O 21 0.42 Fig. 4(b) 120 |(55&=Å «N ~ ~ [[]ÈS 3&8ºg –E q???????????????????????????????????????? —E? HÄNSSN· –H INNS» O §NNNNNNN 0.08:S 0.21 0 &----¬33 0.42L.),~~~ ? 0.84 RuCi (mM) Fig. 4(c) U.S. Patent May 16, 2006 Sheet 6 of 17 US 7,045,140 B2 CO-RM(-) 2 vehicle (--) O 1 C O C 9 O time (min) Fig.
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