(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (10) International Publication Number (43) International Publication Date , , · , . , . _ 24 March 2011 (24.03.2011) 2011/034931 A2 (51) International Patent Classification: (81) Designated States (unless otherwise indicated, for every C09D 5/16 (2006.01) C07K 7/00 (2006.01) kind of national protection available): AE, AG, AL, AM, C09D 7/12 (2006.01) A01N 63/00 (2006.01) AO, AT, AU, AZ, BA, BB, BG, BH, BR, BW, BY, BZ, C09D 5/14 (2006.01) CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, (21) International Application Number: HN, HR, HU, ID, IL, IN, IS, JP, KE, KG, KM, KN, KP, PCT/US20 10/048946 KR, KZ, LA, LC, LK, LR, LS, LT, LU, LY, MA, MD, (22) International Filing Date: ME, MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, 15 September 2010 (15.09.2010) NO, NZ, OM, PE, PG, PH, PL, PT, RO, RS, RU, SC, SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN, TR, (25) Filing Language: English TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW. (26) Publication Language: English (84) Designated States (unless otherwise indicated, for every (30) Priority Data: kind of regional protection available): ARIPO (BW, GH, 61/242,485 15 September 2009 (15.09.2009) US GM, KE, LR, LS, MW, MZ, NA, SD, SL, SZ, TZ, UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, MD, RU, TJ, (71) Applicant (for all designated States except US): REAC¬ TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, DK, TIVE SURFACE, LTD. [US/US]; 300 West Ave., Suite EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU, 13 13, Austin, Texas 78701 (US). LV, MC, MK, MT, NL, NO, PL, PT, RO, SE, SI, SK, SM, TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, (72) Inventors; and GW, ML, MR, NE, SN, TD, TG). (75) Inventors/ Applicants (for US only): WALES, Melinda [US/US]; 723 Shady Lane, Bryan, Texas 77802 (US). Published: McDANIEL, C , Steven [US/US]; 300 West Ave., Suite — without international search report and to be republished 13 13, Austin, Texas 78701 (US). upon receipt of that report (Rule 48.2(g)) (74) Agent: MCDANIEL, C , Steven; c/o Daffer McDaniel, — with sequence listing part of description (Rule 5.2(a)) LLP, P.O. Box 684908, Austin, Texas 78768-4908 (US). < o - (54) Title: ANTI-FOULING PAINTS AND COATINGS (57) Abstract: Disclosed herein are a materials such as a coating, an elastomer, an adhesive, a sealant, a textile finish, a wax, and a filler for such a material, wherein the material includes an proteinaceous molecule such as a peptide and/an enzyme that confer a metal binding, an anti-fouling and/or an antibiotic property to the material. In particular, disclosed herein are marine coatings such ¾ as a marine paint that comprise an anti-fouling peptide sequence that reversibly binds a metal cation that is toxic to a fouling or- ganism. Also disclosed herein are methods of reducing fouling on a surface by treating the surface with a metal binding peptide. ANTI-FOULING PAINTS AND COATINGS A. BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention generally relates to anti-fouling compositions (e.g., coatings, paints, elastomers, adhesives) comprising a metal binding, an anti-fouling, and/or an anti-biological proteinaceous molecule (e.g., a peptide, a polypeptide, a protein, an enzyme) and methods employing such compositions to deter or prevent fouling or another biological infestation on a susceptible surface. 2. Description of the Related Art [0002] The su rface of a material may be su bject to addition of a surface treatment such as a coating, an adhesive, a sealant, a textile finish, and/or a wax, with a surface treatment typically used, fo example, to protect, decorate, attach, and/or seal a surface and/or the underlying material. An exa mpl of a surface that may be treated with a surface treatment includes a marine surface, such as surface frequently or continuously in contact with water. An example of such a marine surface may include the bottom of a ship. [0003] A biomolecule comprises a molecule often produced and isolated from an organism, such a proteinaceous molecule. Examples of a proteinaceous molecule include a peptide, a polypeptide, a protein, or an enzyme. A proteinaceous molecule such as a peptide may possess a binding function to another atom or molecule, including a metal, a biomolecule such as a lipid, or another proteinaceous sequence. An example of an enzyme comprises a lipolytic enzyme (e.g., a lipase) that catalyzes a reaction on a lipid su bstrate, such as a vegeta ble oil, a phospholipid, a sterol, and other hydrophobic molecule; or an enzyme that detoxifies an organophosphorus compound ("organophosphate compound," "OP compound") include an organophosphorus hydrolase ("OPH"), an organophosphorus acid anhydrolase ("OPAA"), and a DFPase. B. BRIEF SUMMARY OF THE INVENTION [0004] The embodiments of the invention provides a marine coating composition comprising, a marine coating and a proteinaceous molecule, wherein the proteinaceous molecule comprises a metal binding sequence binding a metal ligand in a sufficient amount to inhibit the accu mulation of biofouling on an ina nimate surface coated with the marine coating composition; wherein the metal binding sequence comprises at least one mem ber of the group consisting of SEQ ID Nos. 204-243 and 250-302 and functionally equivalent su bstituted metal binding amino acid sequences thereof. In some embodiments, the proteinaceous molecule is a peptide between 3 and 30 amino acids in length. In other embodiments, about 5% to about 100% of the amino acids of the metal binding sequence are electron donor amino acids. In further embodiments, at least 25% of the electron donor amino acids are one or more amino acids selected from the group consisting of a histidine, a lysine, and an arginine. In other aspects, the proteinaceous molecule is cysteine-free. In some aspects, each amino acid of the proteinaceous molecule is independently selected from the group consisting of the D-stereoisomer and L-stereoisomer forms of the amino acids. In further aspects, the marine coating possesses an enha nced metal binding activity. In additional aspects, the metal binding activity is reversible. [0005] In some embodiments, the marine coating comprises an immobilization agent, and wherein the proteinaceous molecule is immobilized to the immobilation agent. In other embodiments, the immobilization of the proteinaceous molecule by the immobilization agent is reversible so that the proteinaceous molecule may be released from the immobilization agent, and wherein upon release of the proteinaceous molecule the immobilization agent may immobilize another like or different proteinaceous molecule. In additional embodiments, the marine coating comprises at least one anti- biological agent selected from the group consisting of a peptidic agent of SEQ ID Nos 1-203, a peptidic agent having functionally equivalent amino acid su bstituted sequences having no more than a +/- 2 difference in hyd ropathic value of the Kyte-Doolittle scale relative thereto SEQ ID Nos. 1-203, a preservative, an anti-fouling agent, an anti-microbial agent, a phosphoric triester hydrolase, a phytochelatin, a lysozyme, a lysostaphin, a libiase, a lysyl endopeptidase, a mutanolysin, a cellulase, a chitinase, an a-agarase, an β-agarase, a /V-acetylmuramoyl-L-alanine amidase, a lytic transglycosylase, a glucan endo-l,3 -D-glucosidase, an endo-l,3(4 )- -glucanase, a β-lytic metalloendopeptidase, a 3- deoxy-2-octulosonidase, a peptide-N4-(N-acetyl - -glucosaminyl)asparagine amidase, a mannosyl- glycoprotein endo- -N-acetylglucosaminidase, a L-carrageenase, a κ-carrageenase, a λ-carrageenase, an a-neoagaro-oligosaccharide hydrolase, an endolysin, an autolysin, a mannoprotein protease, a glucanase, a mannose, a zymolase, a lyticase, a lipolytic enzyme, and a cell-based particulate material. In further embodiments, the accumulation of biofouling on the ina nimate surface is inhibited by a reduced adherence to the marine coating, an enhanced ease of washing to remove the biofouling, or a com bination thereof. In certain aspects the biofouling accumulation that is inhibited comprises the accumulation of at least one fouling organism select from the group consisting of a soft fouling microorganism, a hard fouling organism, a small brush/grass type organism, and a spineless organism. In other facets, the coating is a paint or a clear coating. In specific facets, the marine coating comprises a multicoat system. In particular facets, the marine coating is a multipack coating. [0006] Also provided is a composition comprising, at least one material selected from the group consisting of: a coating, an elastomer, an adhesive, a sealant, a textile finish, a wax, a thermoplastic, and a thermoset; wherein the coating is at least one coating selected from the group consisting of an architectural coating, a pipeline coating, an automotive coating, a can coating, a chemical agent resistant coating, a camouflage coating, a traffic marker coating, an aircraft coating, and a nuclear power plant coating; wherein the material comprises a proteinaceous molecule, wherein the proteinaceous molecule comprises a metal binding sequence binding a metal ligand in a sufficient amount t o inhibit the biological infestation of the material, wherein the metal binding sequence comprises at least one mem ber of the group consisting of SEQ ID Nos. 204-243 and 250-302 and functionally equivalent su bstituted metal binding amino acid sequences thereof. In some embodiments, the material comprises at least one anti-biological agent selected from the group consisting of a peptidic agent of SEQ ID Nos 1- 203, a peptidic agent having functionally equivalent amino acid su bstituted sequences having no more than a +/- 2 difference in hydropathic value of the Kyte-Doolittle scale relative thereto SEQ ID Nos.