WO2007016223A2 - Filter materials with biocidal phytochemical agents - Google Patents

Abstract

This invention relates to filter membranes or coatings incorporating environmentally benign biocidal phytochemical compositions that can prevent or reduce fouling caused by microbial biofÊlms, bacteria, algae, fungi, or other unwanted fouling organisms. The invention particularly provides a phytochemical composition encompassing grapefruit seed extract, pomegranate extract, capsaicin and menthol. The phytochemical compositions may directly inhibit the growth of an invasive organism or inhibit the establishment of a biofilm substrate. Additional phytochemicals may also be used. The phytochemical compositions may be incorporated directly into the filter material, microencapsulated or be applied within a coating layer on an underlying porous filtration substrate.

Description

TITLE OF THE INVENTION

FILTER MATERIALS WITH BIOCIDAL PHYTOCHEMICAL AGENTS

INCORPORATION BY REFERENCE

This application claims priority to U.S. Provisional Patent Application No. 60/703,327 filed July 28, 2005.

The foregoing applications, and all documents cited therein or during their prosecution ("appln cited documents") and all documents cited or referenced in the appln cited documents, and all documents cited or referenced herein ("herein cited documents"), and all documents cited or referenced in herein cited documents, together with any manufacturer's instructions, descriptions, product specifications, and product sheets for any products mentioned herein or in any document incorporated by reference herein, are hereby incorporated herein by reference, and may be employed in the practice of the invention. FIELD OF THE INVENTION

This invention relates to filter membranes, filter materials, glassy polymers, composites, polymer granules, fiber glass and charcoal incorporating biocidal phytochemical agents. BACKGROUND OF THE INVENTION

Filters in general are systems for separating materials contained in liquids or air as liquids or air passes through the filtration system. Filter membrane types such as Reverse Osmosis, Gas Separation, Air Purification, Pervaporation, Microfiltration, Ultramicrofiltration, Nitrogen Filtration, Granular or Charcoal Filtration capture and hold materials that often contain pathogens or fouling organisms that can subsequently replicate on the filter membrane or filter material. In particular, the formation of microbial biofilms, by themselves, may block filter pores as well as providing a suitable substrate for the establishment of other life forms that can render the filtration system inoperable. Ultimately, the filtration systems may become less effective due to flow blockage, thereby increasing costs and decreasing overall efficiency.

Phytochemicals are known that have broad activity, preventing or inhibiting the growth of a wide spectrum of microbes, as well as exhibiting efficacy against a range of potential organisms that may affect filter membranes and filter materials, such as algae, fungi, mold, mildew, bacteria and aquatic organisms such as bryozoans and barnacles. For example, biocidal phytochemicals have been incorporated into polymer films useful for wrapping and protecting foodstuffs during storage as described in U.S. Patent Serial Number 5,906,825, incorporated herein by reference. Capsicum, albeit at high pungency levels, has been added to marine paints to prevent the fouling of ships bottoms, as described in U.S. Patent Serial Number 5,397,385.

A need exists, however, for safe, environmentally benign methods to prevent, reduce or delay the onset the fouling of filter membranes and filter materials. Citation or identification of any document in this application is not an admission that such document is available as prior art to the present invention. SUMMARY OF THE INVENTION

There are several types of filter membrane such as reverse osmosis, gas separation, pervaporation, microfiltration, ultramicrofiltration, nitrogen filtration, air filtration, water filtration and the like. These and other types of filter membranes such as fibrous filters and block or cylinder filters frequently foul due to the build up of the materials that contain such microbes as; algae, mold, mildew, bacteria, bryozoans and in some cases larger organisms such as barnacles and mussels. There are non-membrane filtration systems in granular form whereby the incorporation of phytochemicals in the processing of the granules or coated with phytochemicals would also serve as a system to control or reduce fouling.

The present invention encompasses filter membranes, or coatings suitable for application to a filter surface, that incorporate biocidal phytochemical compositions comprising environmentally benign phytochemicals that can prevent or reduce fouling caused by microbial biofilms, bacteria, algae, fungi, crustatation or other invertebrate larvae, or other unwanted fouling organisms. The present invention particularly provides for the use of biocidal phytochemical compositions, which may comprise a grapefruit seed extract, a pomegranate extract, a capsicum product and a menthol, which have been demonstrated to control surface colonization and proliferation of a wide variety of organisms. The effects of the phytochemical compositions according to the invention may be direct by inhibiting the growth of an invasive organism, or indirect by inhibiting the establishment of a biofilm substrate, thereby preventing colonization. It is contemplated that additional phytochemicals may also be used and incorporated into the material of the filter membrane or filter materials during the preparation and/or processing stage of the filter membranes and filter materials. It is further contemplated that the active biocidal phytochemicals may be incorporated into or applied as a coating layer on an underlying porous filtration substrate.

It is noted that in this disclosure and particularly in the claims and/or paragraphs, terms such as "comprises", "comprised", "comprising" and the like can have the meaning attributed to it in U.S. Patent law; e.g., they can mean "includes", "included", "including", and the like; and that terms such as "consisting essentially of and "consists essentially of have the meaning ascribed to them in U.S. Patent law, e.g., they allow for elements not explicitly recited, but exclude elements that are found in the prior art or that affect a basic or novel characteristic of the invention. These and other embodiments are disclosed or are obvious from and encompassed by, the following Detailed Description. DETAILED DESCRIPTION OF THE INVENTION

The present invention provides filter membranes or coatings suitable for application to the surfaces of filters and which incorporate biocidal phytochemical compositions comprising environmentally benign phytochemicals that can prevent or reduce fouling caused by microbial biofilms, bacteria, algae, fungi, crustatation and other invertebrate larvae or other unwanted fouling organisms. The present invention particularly provides for the use of a biocidal phytochemical composition encompassing, but not limited to, a grapefruit seed extract, a pomegranate extract, a capsicum preparation and a menthol that has been demonstrated to control surface colonization and proliferation of a wide variety of organisms. The effect of the phytochemical compositions according to the invention may be direct by inhibiting the growth of an invasive organism, or indirectly by inhibiting the establishment of a biofilm substrate, thereby preventing colonization. It is contemplated that additional phytochemicals may also be used and incorporated into the material of the filter membrane or filter materials during the preparation and/or processing stage of the filter membranes and filter materials. It is further contemplated that the active biocidal phytochemicals may be incorporated into or applied as a coating layer on an underlying porous filtration substrate.

The terms "filter polymer" or "porous polymer" as used herein refer to an organic or inorganic polymer that may be processed to provide a porous filter membrane suitable for the entrapment of particles from a gaseous or liquid fluid.

The term "filter" as used herein may refer to a sheet or membrane of any thickness produced from a filter polymer and which has pores of a predetermined size range to entrap particles of a desired size from a gaseous or liquid fluid. It is contemplated that the filters according to the present invention may be flexible membranes, rigid or semi-rigid sheets or fashioned into a block or any other form that provides a desired filtration of a liquid applied to one surface of the membrane or sheet and which passes through the filter thereby leaving particulate material or undesired substance(s) on the first surface contacted by the liquid. Alternatively, but not considered limiting, the porous polymer filter may be a cylinder having a hollow lumen. A liquid to be filtered may pass from the exterior of the cylinder into the lumen, whereupon the filtered particles are concentrated on the external surface of the cylinder. Alternatively a liquid to be filtered may pass from the lumen of the cylinder, through the porous material to the exterior of the cylinder, whereupon the filtered particles are concentrated on the surface of the lumen.

A filter as contemplated by the present invention may also be a fibrous net or mesh such as an air conditioner or automobile air filter or a filter bed such as used for the purification of water, wherein the filter bed may comprise a bed or layer of granulated or spherical polymer beads or balls.

Filters and Porous Polymer Filter Polymers.

Porous filtration materials which are useful for the incorporating of biocidal phytochemical compositions according to the invention encompass membranes such as, but not limited to, reverse osmosis membranes comprised of cellulose-based materials (for example, nitrocellulose, cellophane, cellulose acetate, interfacial composite membranes and cellulose triacetate polymer hollow-fine-fiber membranes), noncellulose polymer membranes (including, but not limited to polyamide membranes, aliphatic polyamides and aromatic polyamides. Exemplary aromatic polyamides for use in the invention mab supplied under the trade names TORAY™ (Monsanto) and PERMASEP™ (DuPont)) and interfacial composite membranes. Other suitable membranes suitable for use in the filters of the invention are made of acetate polymers and may be blended with small amounts of triacetate polymer or other cellulose esters such as acetate butyrate. .These blends are currently used to form acetate membranes.

Composite membranes are high-flux and high rejection and can be made by interfacial polymerization. This method has become the new industry standard. Interfacial composite membranes have significantly higher salt rejections and fluxes than cellulose acetate membranes. Another interfacial composite membrane is an all aromatic structure based on the reaction of phenylenediamine and trimesoyl chloride.

Other composite membranes materials may be produced by condensation of furfuryl alcohol and sulfuric acid. These membranes are not made by the interfacial composite process; rather a polysulfone microporuous support membrane is contacted first with an aqueous solution of furfuryl alcohol and then with sulfuric acid.

Interfacial polymerization reverse osmosis membranes include, but are not limited to, polyethylenimine cross linked with toluene 2,4 disocyanate (NSIOO™), epichlorohydrinethylenediamine adduct cross linked with isophthalyl or toluene 2,4- disocyanate EP AMINE™ , piperazine cross linked with trimesoyl chloride (PA300/RC- 100™) and m-phenylenediamine cross linked with trimesoyl chloride (FT-3O/SW-3O™).

Ultrafiltration membranes are typically, but not only, made from polyacylonitrile, polyvinychloride-polyacrylonitrile copolymers, polysulfone, polyether sulfone, poly(vinylidene fluoride), aromatic polyamides, and cellulose acetate.

Poly(vinylpyrrolidone) or poly(vinyl methyl ether) may optionally be added to the membrane.

Other types of membranes for which the polymer compositions according to the invention are suitable include ultrafiltation modules, microfiltration membranes and modules, and air separation membranes, such as; hdrogen sparation membranes, oxygen/nitrogen sparation membranes. Ultrafiltration membranes, primarily used in water purification, include spiral wound, capillary modules, tubular modules and plate and frame systems. Microfiltration membranes in the form of plate and frame cartridges, pleated cartridges (most largely used) are used for the biological testing of water. Mechanical properties and chemical stability of these filters include the use of polyacrylonitrile- polyvinyl, chloride copolymers, poly(vinylidene fluoride), polysulfone, cellulose triacetate and various nylons. Hydrogen separation membranes have a major application of hydrogen-selective membranes in the recovery of hydrogen from waste gases produced in various refinery operations where unwanted fouling exists. Oxygen/nitrogen separator systems and other air separation systems typically use membranes made of the following polymers; poly(l- tremethylsilyl-1-propyne) (PTMSP), silicone rubber, poly(4-methyl-l-pentene) (TPX), poly(phenylene oxide) (PPO), ethyl cellulose, SFDA-DAF (polymide), polysulfone, polyaramide and tetrabrome bis polycarbonate. Glassy polymers are also used.

Pervaporation membranes are used for dehydration of organics, VOC/water separation and organic/organic separation. Pervaporation membrane materials consist of microporous polyacrylonitrile coated with a 5 to 20 μm layer of cross linked polyvinyl alcohol). It is also possible to use polylectrolyte membranes, silicone rubber and other rubbers such as ethylene-propylene terapolymers. Polyamide-polyether block copolymers, cellulose acetate and polyurethane-polyamide block copolymers may also be suitable. The filters may, for example, be, but not limited to, a membrame wherein the polymer base material is inherently porous or may have pores formed chemically, mechanically, by radiation poration and the like. Filters could also be fibrous as a mesh , a net, or regularly spaced fibers. Biocidal Phytochemicals

The following is a list, as examples, of phytochemicals that are contemplated as useful as antifouling agents or antimicrobial agents for filter membrane and filter materials during the processing stage of the membrane or materials or the coating of filter membranes and filter materials. It is considered within the scope of the invention for the biocidal phytochemical composition to be an isolated compound or a mixture extracted from a botanical source or synthesized so as to chemically similar to the active ingrediants of a biocidal botanical extract.

The term 'phytochemicals' is herein defined to include complete, naturally occurring phytochemical molecular constructions, derivatives thereof, functional moieties thereof, and functionally identical manufactured molecular constructions as may be obtained based upon the naturally occurring compositions herein described.

The term "phytochemical" as used herein refers to a compound or combination of compounds that may be isolated from botanical sources, or synthesized or obtained from a non-botanical source (providing the synthesized or obtained compound or mixture of compounds has substantially the same composition as the preparartion isolated from the original botanical source and includes the active biocidal agents). Exemplary phytochemical compounds or mixtures include, but are not limited to: Helichrysum italicum (flavonoids); Corydalis pallida fprotoberberine alkloids); Shiraia bambusicola (perylenequinones); Fraxinum omus (hydroxycoumarins); Podocarpus nagi (totarol and nortiterpene dilactones); Heterotheca inuloides (sesquiterpenoids); Pelargonium spp. (essential oils); Piper sarmentosum (phenylpropanoids); Allium spp. (extract); Juniperus procera (diterpenes); Achillea conferta (flavonoids, flavones, sesquiterpenoid lactones); Magnolia virginiana (lignans, neolignans); Eucalyptus euglobal (euglobal); Armillaria mellea (armillaric acid); Dracena mannii (spirostanol saponin); Piper aduncum (chromenes, prenylated benzoic acid); Rhamnaceae spp. (cyclopeptide alkaloids); Buddleja globosa (Verbascoside); Cephalocereus senilis (phytoalexin aurone); Salvia albocaerulea (diterpene); Gomphrena martiana and Gomphrena boliviana (extracts); Paepalanthus spp. (vioxanthin); Helichrysum stoechas and Helichrysum crispum (extracts); Achillea ptarmica (trans-pinocarveyl hydroperoxides); Dehaasia incrassata (alkaloids); Asteraceae spp. (extracts); Arctotis auriculate (extracts); Eriocephalus africanus (extracts): Felicia erigeroides (extracts); Hemerocallis fulva (phytosterols, fatty acid esters); Psoralea juncea (plicatin B); Pluchea symphytifolia (caffeic acid esters); Tovomitopsis psychotrifolia (Vitamin E derivative); Celosia argentea (triterpenoid saponins and flavonoids); Azadirachta indica (tetranortriterpenoid, mahmoodin, protolimonoids, naheedin); Moraceae spp. (coumarins); Hypericum erectum (phloroglucinol derivatives); Podospora appendiculate (Appenolides A, B, & C, furanones); Artemisia princeps var. orientalis, Artemisia capillaris, Artemisia mexicana and Artemisia scoparia (extract); Paddy malt (mash extract); Kigelia pinnata (extract); Acalypha wilkesiana (extract); seaweeds, seagrass and lemongrass (essential oils); Borrieria latifolia, Borreria setidens, Hedyotis diffusa), Hedyotis nudicaulis, Morinda elliptica, Morinda umbellata, Sida rhombifolia, and Vitex ovata (extracts); Tabebuia impetiginosa, Achyrocline spp., Larrea divaricata, Rosa borboniana, Punica granatum, Psidium guineense, Lithrea ternifolia (extracts); Lepechinia caulescens, Lepidium virginicum and Tanacetum parthenium (extracts); Talaromyces flavus (extracts); Daucus carota (extract); Flabellia petiolata, Caulerpa prolifera, Halimeda tuna, Corallina elongata, Lithophyllum lichenoides, Phyllophora crispa, Cystoseira spp., Halopteris spp., Codium spp., Valonia utricularis, Posidonia oceanica, Zostera noltii and Cymodocea nodosa (extracts); Centauraea orientalis, Diospyros khaki, Sida hermaphrodita, Forsythia intermedia, Scutellaria polydon, Eugenia malaccensis and Eugenia jambolana (extracts); Fritillaria L. spp. (ebeinone, steroidal alkaloids); Kigelia pinnata, Peperomia pellucida, Populus nigra, Populus balsamifera and Populus deltoides (extracts); Melaleuca alternifolia (essential oil); Elfvingia applanata (naringenin); Ficus sycomorus, grapefruit seed, Garlic, Allicin, Peat, Strophanthus hispidus, Secamone afzeli, Mitracarpus scabeή, Entada abyssinjca, Terminalia spinosa, Harrisonia abyssinica, Ximinea caffra, Azadirachta indica, Spilanthes mauritiana, Terminalia spinosa (extracts); Cyanobacteria (ambigols A and B, tjipanazole); coffee (extract); Sporochnus pedunculatus, Dalbergia melanozylon, Celastrus scandens, Juglans nigra, Kalmia latifolia, Pelargonium xhortorum, Rhus glabra and Lindera benzoin (extracts); Striga densiflora, Striga orobanchioides, Striga lutea, Pistacia lentiscus L., Mitracarpus villosus, Bixa orellana, Bridelia ferruginea, Alpinia katsumadai, Alpinia officinarum, Artemisia capillaris, Casia obtusifolia, Dendrobium moniliforme, Epimedium grandiflorum, Glycyrrhiza glabra, Lithosperum erythrorhizon, Magnolia obovata, Morus bonbycis, Natopterygii incisium, Polygonum multiflorum, Prunus mume, Rheum palmatum, Ricinus communis, Sophora flavescens, Swertia japonica, black pepper, rosemary, red pepper, Isopyrum thalictroides, Calotropis procera, Chrysanthemum spp., Holarrhena antidysenterica, Lunularia crusiata, Dumertiera hirsuta, Exormotheca tuberifera, and liverwort (extracts); Filipendula ulmaria, Salix glauca, Usnea filipendula, Cllcadina arbuscula (salicylic compounds); Tanacetum parthenium, Thymus capitatus, and Elfingia applanata (extracts); Fraxinus ornus (hydroxycoumarins, esculin, esculetin, fraxin, and fraxetin); Zizyphus nummularia, LONGO VITAL, Pelargonium spp., Scaevola sericea, Psychotria hawaiiensis, Pipturus albidis, Aleurites moluccana, Solanum niger, Piper methysticum, Barringtonia asiatica, Adansonia digitata, Harungana madagascariensis, Jacaranda mimosaefolia, Erythroxylum catauba, Bidens pilosa, Lemna minor, Potamogeton spp., Nasturtium officinale, Apium nodiflorum, Agaricus subrutilescens, Amanita virosa, Amanita pantherina, Lycoperdon perlatum, Psidium guajava, Averrhoa carambola, musa sapientum, Carica papaya, Passiflora edulis, Lansium domesticum and Baccaurea motleyana (extracts); horse radish, celandine grass, bur marigold, marigold root and yarrow grass (extracts); Abuta grandifola, Cyperus articulatus, Gnaphalium spicatum, Pothomorphe peltata, Ficus sycomorus, Ficus Benjamina, Ficus bengalensis, Ficus religiosa, Alchornea cordifolia, Bridelia feruginea, Eucalyptus citriodora, Hymenocardia acida, Maprounea africana, Monachora arbuscula, Tedania ignis, Arenosclera spp., Amphimedon viridis, Polymastia janeirensis, Aplysina fulva, Pseudaxinella lunaecharta, Nelumbium speciosum and Mycale arenosa (extracts); cloves (eugenol acetate and iso-eugenol); Chrysthanemum boreale fsesquiterpenoid lactones); Eucalyptus globulus, Punica granatum, Anacardium occidentale (cashew shell nut oil), Bocconia arborea, Syzygium brazzavillense, Syzygium guineense, Carthamus tinctorius), Ginkgo biloba, Mosla chinensis, Salvia officinalis, and Cinnamomum cassia (extracts); Cryptolepis sanguinolenta (alkaloids, cryptolepine); Chelidonium majus (alkaloids, berberine, coptisine); Vitex agnus-castus ^extract); Cladonia substellata (usnic acid); Ellagic acid, Fuligo septica, Tubifera microsperma (extract); Mundulea monantha, Tephrosia linearis (flavonoids); Lpomoea fistulosa (extract); Pimenta dioica (essential oils); Ratibida latipalearis, Teloxys graveolens, Dodonaea viscosa, Hypericum calycinum, Hyptis albida, Hyptis pectinata, Hyptis suaveolens and Hyptis verticillata (extracts); Asteriscus graveolones (bisabolone hydroperoxides); Derris scandens, Alnus rubra, Araliaceae family (extracts); Vinca rosea, Australian tea tree oil, peppermint oil, sage oil, thymol, eugenol and Thuja orientalis (extracts); Anacardium occidentale (phenolic lipids); Oidiodendron tenuissimum (extract); Acacia nilotica and Acacia farnesiana (polyphenol, tannin); Teminalia alata and Mallotus phillipinensis (extracts); Piectranthus grandidentatus (abientane diterpenoids); Pumica granatum and Datura metel (extracts); tea, Agave lecheguilla, Chamaesyce hirta, Baccharis glutinosa and Larrea tridentata (extracts); Camelia sinensis and Euphorbia hirta (theaflavin, polyphenon 60); Tabernaemontana pandacaqui, Yucca shidigera, Hemistepa lyrata, Yougia japonica, Prunella vulgaris, Lamium amplexicaule, Juniperus chinensis, heris dentata, Gnaphalium affine, Chelidonium majus, Spirea prunifolia, Erythronium japonicum, Taxus wallichiana, Ganoderma lucidum Drava nemorosa, Youngia capillaris, Equisetum arvense, Australiam Lavender, Black Seed, Catuaba casca, Cineole, Damiana, Dicranum scoparium, Eucalptus oil, Ginger, and Grape seed (extracts); Neem seed, bark, and leaf extract; Neem oil; New Zealand Manuka extract; Nicotiana tabacum extract; olive leaf extract; a-pinene and b-pinene extracts; Rhubarb root extract; Syringa vulgaris extract; Tea tree oil (Terpinen-4-ol, a-terpinene, y-terpinene, a- terpineol, Terpinolene); Thyme (extract) and Vitamin E (extract), or a combination of one or more of the phytochemicals. Microorganisms Inhibited by Phytochemicals

Microorganisms which may be inhibited by biocidal phytochemicals useful in the present invention include, but are not limited to:

Fungi: Aspergillus fiavus, A. fumigalus, A. niger, Blastomyces dermatitidis, Candida spp., Coccidioides immitis, Ciyptococcus neoformans, Fusarium culmorum, Geotrichum spp., Histoplasma capsulatum, Malassezia furfur, Microsporum spp., Mucor racemosus, Nocardia spp., Paracoccidioides brasiliensis, Penicillium spp., Rhizopus higricans, Saccharomyces cerevisiae, Sporothrix schneckii, Torulopsis spp., Trichophyton spp.

Bacteria: Aerobacter aerongenes, Aeromonas hydrophila, Bacillus cereus, Bacillus subtilis, Bordetella pertussis, Borrelia burgdorferi, Campylobacter fetus, C. jejuni, Corynebacterium diphtheriae, C. bovis, Desulfovibrio desulfurica, Escherichia coli 0157:H7, Enteropathogenic E. coli, Enterotoxin-producing E. coli, Helicobacter pylori, Klebsiella pneumoniae, Legionella pneumophila, Leptospira interrogans, Mycobacterium tuberculosis, M. bovis, Neisseria gonorrhoeae, N. meningitidis, Proteus mirabilis, P. vulgaris, Pseudomonas aeruginosa, Rhodococcus equi, Salmonella choleraesuis, S. enteridis, S. typhimurlum, S. typhosa, Shigella sonnei, S. dysenteriae, Staphylococcus aureus, S. epidermidis, Streptococcus anginosus, S. mutans, Vibrio cholerae, Yersinia pestis, Y. pseudotuberculosis, Actinomycetes, Stretomyces reubrireticuli, Streptoverticillium reticulum, Thermoactinomyces vulgaris.

Viruses: Adenoviruses, Coronaviruses, Cytomegalovirus, Enteroviruses, Epstein-Barr virus, Herpes simplex virus, Hepatitis viruses, Human Immunodeficiency virus, Human Parvoviruses, Influenza viruses, Morbillivirus, Mumps virus, Norwalk viruses, Papillomaviruses, Paramyxovirus, Poxvirus, Rabies virus, Reoviruses, Rotaviruses, Rubella virus, Respiratory Synctial virus, Rhinoviruses, Varicella zoster virus. Parasites: Ancyclostoma braziliense, Anisakis, Babesia microti, Balantidum coli, Blastocystis hominis, Chilomastix mesnili, Cryptosporidium parvum, Cyclospora, Dientamoeba fragilis, Diphyllobothrium latum, Echinococcus granulosus, Entamoeba coli, E. histolytica, Enterocytozoon, Fasciola hepatica, Giardia lamblia, Iodamoeba butschlii, Isospora belli, Leishmania brasiliensis, L. donovani, L. tropica, Paragonimus westermani, Plasmodium vivax, Pnemocystis carinii, Sarcocytis hominis, Strongyloides stercoralis, Taenia solium, Toxoplasma gondii, Trichomonas vaginalis, Trichinella spiralis, Trypanosoma cruzi.

It is further intended that the compositions of the present invention will be effective against water born or air born organisms capable of attaching to and colonizing on the surfaces and in the matrix of filter membranes and filter materials, including parazoans, coelenterates such as polychaete and oligochaete worms, molluscs, arthropods including crustaceans such as, but not limited to, acorn and goose barnacles and to be effective in inhibiting the attachment and or development of the adult or larval forms of the targeted organisms. The compositions of the present invention can also be effective against marine and freshwater plants including algae and higher plants that can foul filter membranes and filter materials. Exemplary phytochemicals useful in the present invention and which exhibit activity against multiple organisms are illustrated in Table 1 below. Each phytochemical is classified as to general activity (anti-bacterial; anti-viral; anti-fungal; anti-crustacean; larvicidal; insecticidal; molluscicidal; or anti-nematodal) and specific examples of organisms against which the phytochemical is active are provided. However, it is to be recognized by one of ordinary skill in the art that the phytochemicals included in the table are provided for illustrative purposes only and are not meant to an exhaustive listing and with the recognition that certain phytochemicals may be active against more than one class of organism:

Table 1

*strong activity for phytochemical

One aspect of the present invention provides compositions of filters, filter membranes and filter materials either treated, coated or incorporated into the membrane matrix during production using an additive in the form of at least one phytochemical for protection against organism growth and fouling. A preferred additive according to the invention is a biocidal phytochemical composition comprising a grapefruit seed extract, a pomegranate extract, a capsicum preparation and a menthol, which may be supplemented by additives or additional phytochemicals to preferentially target a contaminating species. In general terms, the present invention is directed to filter membranes and filter materials containing phytochemicals and methods of making and using the same. Phytochemicals especially useful in the present invention include, but are not limited to, grapefruit seed extract and fractions thereof, capsicum, capsaicin, pomegranate extract of rind, pulp & seed and fractions thereof, pure menthol (or other lactones) or menthol combined with other active agents. Cashew nut shell (liquid) extract, marigold root extract, clove oil, garlic (deodorized), tobacco dust extract, capsicum (other alkaloids), capsaicin (synthetic), tannic acid, neem oil, sage oil, thyme oil, and other phytochemicals exhibiting biocidal activity to be used in any combination of phytochemicals and methods of making and using the same. The phytochemicals may be fractioned and encapsulated. Grapefruit Seed Extract and fractions thereof is an effective phytochemical biocide with activity against bacteria, fungi, and some parasites and is available commercially as P-50 from Chemie Research, Castleberry, Florida. Partheniol, a compound taken from the guayule plant, is a filter preservative against certain organisms. The rate of migration or the release of the phytochemical composition contained within the filter membranes and materials, may be further modified by including in the compositions a release agent such as Vitamin E, a chemical releaser such as citric acid, or an anti-oxidant such as Vitamin E. The chemical releaser may be the same as the phytochemical agent. Vitamin E further possesses antimicrobial properties, and thus may itself function as a biocidal phytochemical, which may work in conjunction with or separately from filter membrane and filter material binders.

Phytochemicals suitable for use in the compositions of the present invention and which are known to function as anti-oxidants, as well as to possess antimicrobial properties include, but are not limited to, Panax ginseng; Panax quinquefolius; Bixa orellana; Humulus lupulus; Spinacia oleracea; Arctium lappa; Cichorium intybus; Cynara scolymus; Helianthus annuus; Inula helenium; Armor acia rusticana; Momordica charantia; Vaccinium corymbosum; Vaccinium myrtillus; Avena sativa; Oryza sativa; Lavandula latifolia; Marrubium vulgare; Melissa officinalis; Mentha pulegium; Mentha spicata; Nepeta cataria; Ocimum basilicum; Origanum onites; Perillafi'utescens; Prunella vulgaris; Rosmarinus officinalis; Salvia officinalis; Salvia sclarea; Satureja hortensis; Thymus vulgaris; Laurus nobilis; Arachis hypogaea; Glycine max; Glycyrrhiza glabra;

Glycyrrhiza uralensis; Lens culinaris; Phaseolus coccineus; Phaseolus lunatus; Phaseolus vulgaris; Phaseolus vulgaris; Pisum sativum; Psophocarpus tetragonolobus; Pueraria lobata; Tamarindus indica; Tamarindus indica;* Vicia faba; Vigna angularis; Vigna mungo; Vigna radiata; Allium ampeloprasum; Allium cepa; Allium sativum; Asparagus officinalis; Linum usitatissimum; Moms alba; Eucalyptus globulus; Pimenta dioica;

Syzygium aromaticum; Olea europaea; Oenothera biennis; Sesamum indicum; Plantago asiatica; Fagopyrum esculentum; Prunus cerasus; Prunus spinosa; Rosa canina; Rubus fruticosus; Rubus idaeus; Coffea arabica; Citrus aurantium; Citrus paradisi; Ribes nigrum; Ribes rubrum; Capsicum frutescens; Solanum tuberosum; Solanum tuberosum;* Theobroma cacao; Camellia sinensis; Coriandrum sativum; Cuminum cyminum; Daucus carota; Trachyspermum ammi; Vitis vinifera; Curcuma longa; Zingiber officinale. Other antioxidants that are useful in the present invention include, but are not limited to, lysine, butylatedhydroxytoulene (BHT), butylatedhydroxyanisole (BHA), grape seed extract, pine bark extract (Proanthocyanidins), β-carotene, bilberry extract, ascorbic acid, Ginkgo biloba extract, green tea extract, tumeric, zinc picolinate, zinc oxide, iron oxide, calcium carbonate and selenium. Selected antioxidant(s) may be used alone or in combination when combined with the phytochemical(s) in the coating formulas of the present invention.

The amounts of the biocidal agents added to the composition are also dependent upon the particular application. Factors to consider are the conditions under which the composition is to be used, the microorganisms to be inhibited, the duration of the use, the desired pH of the phytochemicals used, which may have to be chemically buffered, whether emulsufϊers are used, whether the filter membrane to be protected is used in reverse osmosis, refinery seperation, air seperation, gas separation, pervaporation, microfiltration, ultramicrofiltration or nitrogen filtration. Different active concentrations of the antimicrobial agents may be desired, depending on the type of filter used. For example, capsicum can be added in an amount from about 1 ppm to about 2,000,000 ppm, depending upon the desired application.

It should be understood that the present invention is broadly drafted, in one embodiment, towards incorporating phytochemicals as biocidal agents into filter membranes and filter materials. The present invention may also take the form and shape of other filtration materials such as, polymer granules, polymer glass granules, sand or charcoal granules incorporating phytochemicals in the processing stage to become part of the matrix where possible or the phytochemicals may be coated on these granules (or beaded) materials. These granules (or beaded) materials may be placed in cylinders made of different materials such as metal, plastic, glass, or composite materials. The cylinders may be of any size (diameter and length) depending on the specific need for filtration and serve as a container to house the granules. Water or air passing over the granules containing phytochemicals would thereby be filtered.

It should be understood that the present invention is broadly drafted, in one embodiment, towards incorporating phytochemicals as biocidal agents into filter membranes and filter materials. The present invention may also take the form and shape of other filtration materials such as fiber glass used in heating and air conditioning filters.

In yet another embodiment, aerosol spray devices with automatic timers containing phytochemicals reservoirs may be attached to the perimeter framework (duct system) of heating and air conditioning filter systems. Phytochemicals as disinfectant agents or antifouling agents would be sprayed over the surface of the filters at timed intervals to control unwanted airborne pathogens such as legionaries disease. The aerosol spray devices could be battery operated or connected to the electrical system with back up battery power. In the event of a high alert status the aerosol spray device could be automatically activated to salvo the contents of the phytochemical reservoir. The phytochemical aerosol spray may contain, dispersing agents, surfactants, solving agents, adhesives and emulsifying agents. In several embodiments of the present invention, cashew nut shell (liquid) extract, marigold root extract, clove oil, garlic (deodorized), tobacco dust extract, capsicum (other alkaloids), Capsaicin (synthetic), grapefruit seed extract or fractions thereof, pomegranate extract or fractions thereof, tannic acid, menthol (and other lactones), guayule plant extract (partheniol), Neem oil, Zostera noltil (eel grass) (natual or synthetic), sage, bayleaf, oregano, pansy coral synthetic extract and camphor oil may be used as biocidal agents. The present invention, however, encompasses the use of many other biocidal phytochemical agents. These phytochemical may be encapsulated if necessary to disguise odor and to last longer or for other purposes. These phytochemicals may be fractioned.

Of the various embodiments of the invention, a phytochemical is capsicum/synthetic capsaicin in combination with other phytochemicals is used as a preservative agent and antifouling agent in filter membranes and materials (coatings). Capsicum is a food or food seasoning commonly known as "hot pepper." The active heat ingredient in capsicum is capsaicin which is a mixture of two unsaturated and three saturated homologs. This mixture is also referred to as capsaicinoids, and includes dihydrocapsaicin and nordihydrocapsaicin. The pungency of capsaicin (capsiacinoids) is measured in Scoville heat units and typically range from 60,000 to 1,500,000 heat units. The compositions of the present invention comprise capsicum having Scoville heat units derived from natural capsicum or synthetic capsaicin from 50,000 to 1,500,00 Scoville heat units. The pungency (the heat ingredients) of the capsicum may be removed, either partially or totally, for use as a preservative additive or antifouling agent in filter membranes and filter materials, even though the heat unit index is below 50,000 Scoville heat units.

Chemical ingredients in capsicum do have antimicrobial activity, including such as; 1,8-cineole, acetic acid, alpha-terpineol, benzaldehyde, beta-ionone, caffeic acid, caryophyllene, chlorogenenic acid, cinnamic acid, delta-3-carene, ferulic-acid, limonene, myrcene, p-coumaric-acid, pulegone, querectin, rutin, scopoletin, terpinen-4-ol and thujone.

Also useful in the present invention as a preservative additive in filter membranes and materials (coatings) is the phytochemical tannic acid. Tannins are classified into two broad groups: the hydrolysable and the condensed or non-hydrolysable tannins. The hydrolysable tannins are usually compounds containing a central core of glucose or other polyhydric alcohol esterified with gallic acid (gallotannins) or hexahydroxydiphenic acid (ellagitannins). The condensed ones are mostly flavolans or wood s of flavan-3-ols (catechins) and/or flavan 3:4-idols (leucoanthocyanidins). They are more resistant to breakdown. Frequently, tannins isolated from a plant bear the characteristics of both groups. Tannins may occur in almost any part of a plant-root, stem, trunk bark, leaves and fruit.

The compositions of the invention further comprise a menthol such as, but not limited to, mentholpropylreneglycolcarbonate. A particularly useful synthetic menthol preparation for inclusion in the compositions of the present invention is FRESCALIN (Symrise GmbH & Co, Holzminden, Germany) and comprising at least 50% by weight of isopulegol, between 25% and 49.99% by weight of 5-methyl-2-(l-methylethyl)- cyclohexanol and between 25% and 49.99% by weight of mentholpropylreneglycolcarbonate. This synthetic menthol preparation is especially effective in combination with capsicum at inhibiting fouling growth on surfaces. Pomegranate extract and certain prepared fractions is especially effective in combination with Grapefruit Seed Extract at inhibiting fouling growth when incorporated in or coated on filter membranes and filter polymers and materials.

The biocidal phytochemical compositions of the invention comprise a grapefruit seed extract having a concentration of between about 10% to about 40% v/v, a pomegranate extract having a concentration of between about 10% to about 40% v/v, a capsicum preparation having a concentration of between about 5% to about 20% w/w and a menthol having a concentration of between about 5% to about 20% w/w.

The biocidal phytochemical composition may comprises a grapefruit seed extract having a concentration of about 30% v/v, a pomegranate extract having a concentration of about 30% v/v, a capsicum preparation having a concentration of about 5% w/w and a menthol having a concentration of about 5% w/w in a glycerin based solution before addition to the polymer base that forms a filter although it is contemplated that other concentrations may be used if added to the polymer base inan effective amount to inhibit the colonization of the filter.

The compositions of the present invention may further include a chemical releaser, which is used to facilitate the controlled release of the phytochemical from the filter membrane matrix. The chemical releaser facilitates the release of the phytochemical composition from the filter membrane or filter material. The releaser may be, for example, citric acid, a phytochemical that also exhibits antibacterial activity. Zinc oxide, iron oxide or citric acid extract can be added to the filter membrane or filter material alone or in combination with other phytochemicals, with or without anti-oxidants like Vitamin E. The release agents used in the phytochemicals and the release agents used in the and filter membranes and filter materials can have a synergistic effect, depending on the desired release containing phytochemicals to prevent unwanted growth of organisms and pests in or on filter membranes and filter materials.

The amounts of the biocidal agents added to the composition are also dependent upon the particular application. Factors to consider are the conditions under which the composition is to be used, the microorganisms to be inhibited, the duration of the use, whether the object to be protected is a submerged, and the active concentration of the antimicrobial agents that is desired. For example, capsicum can be added in an amount from about 1 ppm to about 2,000,000 ppm, depending upon the desired application.

The amounts (by volume) and combinations (number) of the phytochemical agents added to the filter membranes and filter materials may be adjusted according to the particular application, relevant factors including the conditions under which the phytochemical composition and related additives used in the filter membranes and filter materials is to be used, thickness or composition of the membranes or materials, whether or not it is a copolymer membrane, granule, the rate of release of the phytochemical, the types of organisms and pests that need controlling may vary, the duration of the use of the phytochemicals in the treatment and coating or incorporation into filter membranes and filter materials , and the active concentration of the phytochemical desired. In some cases there may be a need for additional substances such as wetting or emulsifying agents, pH buffering agents, adjuvants, gelling or viscosity enhancing additives, preservatives, colors, and the like, depending upon the use. The present invention also provides biocidal phytochemicals formulated for application in filter membranes, glassy polymers, composites, granules, beads and charcoal incorporating biocidal phytochemical agents.

When making any of the compositions of the present invention, the phytochemicals, antioxidants, and chemical releasers or chemical enhancers may be added either together or sequentially to the filter membranes and filter materials. The mixture is then mixed until the phytochemicals are evenly dispersed and incorporated within the filter membrane and filter materials during the processing stage of the membrane or materials. The applications of the finished product may be in any form of filter products for private or commercial use.

One aspect of the invention, therefore, is a composition comprising a polymer and at least one biocidal phytochemical, wherein the poymer is a porous filtration membrane or a coating to a porous filtration membrane. The phytochemical may be in a homogenous mix with the polymer, embedded therein as granules or microbeads but in any case is able to diffuse from the interior of the filter to the surface thereof where it may contact and inhibit contaminating bioforms. The phytochemicals may be held to the polymers by electrostatic bonding or by covalent chemical bonds (thereby not diffusing but providing a stable biocidal surface). Inclusion of the phytochemical(s) will not impair the mechanical properties of a filter formed from the composition to the extent that the filtration properties are significantly reduced. One example of such a composition is a nylon filter wherein the nylon is impreganted with menthol and a pomegranite seed extract or the purified effective agents therefrom. It is contemplated that the additives according to the present invention may be admixed with the polymer filter bases during the manufacture of the polymeric material before, during or after the formation of the porosity of the material that acts as the filtration mechanism. The compositon additives may be mixed with the polymers to form homogenious mixes with a uniform distribution of the additive(s) throughout the filter material. Alternatively the additives may be microencapsulated by materials that allow for the controlled release of the additives, thereby prolonging the efficacy of the biocidal activity. Methods to microencapsulate compounds are wll known in the art, the composition of the microcapsules depending on the composition of the additives and the particular filter polymer base selected. In various embodimenst of the invention is a biocidal composition as described in the preceding paragraph, wherein the composition is layered on a supporting filter. In this case, the biocidal layer comprises a porous sheet bonded to an underlying porous polymer to form a sheet-like filter which may be in the form of a sheet or rolled as a tube or capillary. Alternatively, the bonded layers are not porous but are extruded or spun as fibers wherein an outer biocidal layer encloses an inniier polymeric fiber.

The filter membranes and filter materials of the present invention, biocidal phytochemicals of the present invention may be added in any combination for filter membrane or filter materials for preservation or fouling agent at levels of at least 0.001% to about 60% by volume or by weight, at least 0.5% to about 60% by weight or by volume, at least 2.5% to about 60% by weight or by volume, at least 10% to about 60% by weight or by volume, at least 20% to about 60% by weight or by volume, at least 30% to about 60% by weight or by volume, at least 1% to about 40% by weight or by volume, at least 1% to about 30% by weight or by volume, or at least 1% to about 20% by weight or by volume. It is contemplated that the filter materials may include any of the phytochemicals as listed above or any combination thereof that inhibit the bioforms encountered by a particular use of the filters. For example, but not limited thereto, a filter contacting a marine environment must inhibit the growth of such as barnacles marine algae and the like. A filter or filtration unit for filtering biofluids may require antibacterial agents to prevent the formation of bacterial biofilms or cell growth that may clog the pores of the filter.

A particularly advantageous additive to the filter polymers of the invention comprises a grapefruit seed extract, a pomegranate extract, a capsicum preparation and a menthol. Other biocidal phytochemicals, such as tea tree oil, neem oil, clove oil, alga extracts and the like, may be added to this base composition. The phytochemical capsicum, having a degree of pungency of between 50,000 to

1,500,000 Scoville heat units, may be combined with one or more biocidal phytochemicals and added to a filter membranes and filter materials solution during processing or added as a coating to control organisms such as, bacteria, mold, mildew, fungi, and fouling organisms such algae, bryozoans and barnacles. Capsicum may be combined with other phytochemicals and added to filter membranes and filter materials during the processing stage of the filter membrane or filter materials or added as a coating wherein the capsicum is substantially free of the heat causing ingredient capsaicin.

The phytochemical grapefruit seed extract may be added to filter membranes and filter materials solutions during the processing stage of the membrane or materials or added as a coating to control organisms such as, bacteria, mold, mildew, fungi, algae, bryozoans and larger organisms such as barnacles or tubeworms.

The phytochemical grapefruit seed extract may be processed into a concentrated state and the glyercine substantially reduced or removed from the extract before being added to filter membranes and filter materials during the processing stage of the membrane or materials or added as a coating. In another embodiment, the phytochemical may be selected from extracts of cloves, garlic and/or clove oil.

The filter membranes and filter materials during the processing stage of the membrane or materials or added as coating comprises a base solution, grapefruit seed extract or fractions thereof, pomegranate extract or fractions thereof, a pure menthol or menthol derivative such as FRESCALIN™ and capsicum.

The phytochemical may include grapefruit seed extract, which exhibits antibacterial, anti-parasitic, and anti-fungal activity. One example of a grapefruit seed extract suitable for incorporation into the compositions of the present invention is available commercially as P-50 from Chemie Research, Castleberry, Florida. The grapefruit seed extract can be added to filter membranes and filter materials solutions during the processing stage of the membrane or materials or added as coating alone or in combination with other phytochemicals, such as pomegranate extract or fractions thereof.

The phytochemical may include pomegranate extact or fractions thereof alone, or in combination with Grapefruit Seed Extract. The extract of pomegranate rind, seed and pulp has shown to have algaecide properties. Pomegranate extract in combination with

Grapefruit Seed Extract has shown to have a synergist antimicrobial effect.

The compositions of the invention further comprise an extract of pomegranate,

Punica granatum, L.(punicaceae) using in whole or in part as fractions the following active chemicals found in pomegranate 1,2,3,4,6-penta-o-galloyl-β-glucose; 1,2,4,6-tetra-o- galloyl-b-D-glucose; ascorbic acid; Asiatic acid; b-sitosterol; betulinic acid; boric acid; calcium oxalate; casuarinin; chlorogenic acid; citric acid; corilagin; delphinidin-3- glucoside; elaidic acid; ellagic acid; ellagitannin; estradiol; estrone; friedelin; gallic acid; granatin-A, granatins; isopelletierine; linoleic acid; malic acid; malvidin; malvadin-pentose- glycoside; maslinic acid; neo-chloro genie acid; nicin; palmitic acid; pantothenic acid; pelletirene; phosphatidyl-choline; polyphenols; protocatechuic acid; punicafolin; punicalagin; punicalin; riboflavin; stearic acid; strictin; tannin; thiamin; ursolic acid. Pomegranate extract and certain prepared fractions are especially effective in combination with Grapefruit Seed Extract at inhibiting aquatic organism growth.

The phytochemical camphor may be used in combination with other phytochemicals as an antimicrobial agent added to filter membranes and filter materials solutions during the processing stage of the membrane or materials or added as coating. Camphor is a crystalline ketone derived from the wood of the camphor tree Cinnamomum camphora.

The phytochemical additive to filter membranes and filter materials solutions during the processing stage of the membrane or materials or added as coating may be lemon grass oil which is a natural by-product of lemon grass and is extracted by steam and other nontoxic extraction methods. Lemon grass oil exhibits anti-fungal and anti-bacterial activity and may be added to filter membranes and materials in combination with other phytochemicals. Antioxidants, such as Vitamin E, or releasers, such as citric acid may also be added with the phytochemical composition to filter membranes and filter materials solutions during the processing stage of the membrane or materials or added as coating. The filter membranes and filter materials solutions during the processing stage of the membrane or materials or added as coating may also include Tea Tree oil as an antimicrobial agent. Tea Tree oil is a natural by-product of the tea tree, {Melaleuca species) extracted through natural non-toxic processes such as steam. Tea Tree oil exhibits antifungal and anti-bacterial activity. Tea Tree oil may be added to filter membranes and filter materials solutions and coatings in combination with other phytochemicals.

The phytochemical component may be selected from cashew nut shell oil, tobacco dust, tannic acid (tannins), menthol or derivatives thereof, camphor oil, Guayule plant extract (Partheniol), thyme, clove and/or clove oil, Zostera noltil (eel grass), synthetic pansy coral extact and garlic. The phytochemical combination according to the present invention also includes a capsicum preparation having between 50,000 and 1,500,000 Scoville units, and menthol or a derivative thereof. In another embodiment the phytochemical combination comprises capsicum having between 50,000 and 1,500,000 Scoville units, tannic acid, clove oil, garlic and menthol. In yet another embodiment the phytochemical combination comprises a capsicum preparation having between 50,000 to 1,500,000 Scoville heat units), tannic acid, garlic, cashew shell oil, tobacco dust, marigold root extract and clove oil. The phytochemicals may be encapsulated.

The phytochemical combination may comprise capsicum having between 50,000 to 1,500,000 Scoville heat units and clove oil and optionally garlic. In another embodiment the phytochemical combination comprises capsicum having between 50,000 to 1,500,000 Scoville heat units, clove oil, garlic and cashew nut shell oil, with or without vitamin E. In one embodiment the phytochemical combination comprises capsicum having between 50,000 to 1,500,000 Scoville heat units), tannic acid, menthol and tobacco dust. In still another embodiment the phytochemical combination comprises capsicum having between 50,000 to 1,500,000 Scoville heat units), tannic acid, camphor, pomegranate, menthol, guayule plant extract and marigold root extract. These phytochemical may also be encapsulated if necessary to disguise odor and to last longer.

The filter membranes and filter materials during the processing stage of the membrane or materials or added as coating of the present invention, biocidal phytochemicals of the present invention may be added in any combination to the filter membranes and filter materials solutions and coatings, at levels from about 0.1% to about 60% by volume.

The filter membranes and filter materials of the present invention, phytochemicals of the present invention may be added in any combination to levels from about 0.001% to about 40% by volume.

The filter membranes and filter materials of the present invention, phytochemicals of the present invention may be added in filter membranes and filter materials and at levels from about 10% to about 60% by volume. One aspect of the invention, therefore, is a biocidal polymer composition for inhibiting the colonization of a surface of a filter by organisms and comprising a polymer base suitable for forming a filter, and a biocidal phytochemical composition comprising a grapefruit seed extract, a pomegranate extract, a capsicum preparation and a menthol, wherein the amount of the biocidal phytochemical composition is sufficient to inhibit the colonization of a surface of a filter by organisms.

The embodiments of this aspect of the invention the biocidal phytochemical composition may further comprise at least one additional biocidal phytochemical agents, wherein the biocidal phytochemical agent is an anti-bacterial; an anti-viral; an anti-fungal; an anti-crustacean; a larvicidal; an insecticidal; a molluscicidal or an anti-nematodal biocidal phytochemical, wherein the anti-bacterial biocidal phytochemical is isolated from Annona muricata (Annonaceae), A.squamosa, Panax ginseng (Araliaceae), Capparis spinosa (Capparidaceae), Calendula officinalis {Compositae), Cynara scolymus (Compositae), Cucurbita pepo (Cucurbitaceae), Cymbopogon citratus (Gramineae), Mentha spicata (Labiatae), Ocimum basilicum (Labiatae), Rosmarinus officinalis (Labiatae), Glycyrrhiza glabra (Leguminosae), Allium sativum (Liliaceae), Aloe vera {Liliaceae), Citrus reticulata (Rutaceae), Oenothera biennis (Onagraceae), Plantago major (Plantaginaceae), Punica granatum (Punicaceae), Ribes nigrum (Saxifragaceae), Camellia sinensis (Theaceae), Curcuma longa {Zingiber aceae), Zingiber officinale (Zingiberaceae) or an alga, the anti-fungal biocidal phytochemical is isolated from Annona muricata (Annonaceae), Panax ginseng (Araliaceae), Capparis spinosa (Capparidaceae), Calendula officinalis (Compositae), Cucurbita pepo (Cucurbitaceae), Cymbopogon citratus (Granimeae), Mentha spicata (Labiatae), Ocimum basilicum (Labiatae), Rosmarinus officinalis (Labiatae), Glycyrrhiza glabra (Leguminoseae), Allium sativum (Liliaceae), Aloe vera (Liliaceae), Sesamum indicum (Pedaliaceae), Punica granatum {Punicaceae), Citrus aurantium {Rutaceae), Citrus reticulata {Rutaceae), Ribes nigrum {Saxifragaceae), Camellia sinensis {Theaceae), Curcuma longa {Zingiberaceae) or Zingiber officinale {Zingiberaceae) or an alga, the anti-crustacean biocidal phytochemical is isolated from Annona muricata (Annonaceae) or Zingiber officinale {Zingiberaceae), the larvicidal biocidal phytochemical is isolated from Annona squamosa, Mammea americana {Guttiferae), Ocimum Basilicum (Labiateae), Allium sativum {Liliaceae) or Curcuma longa {Zingiberaceae), the insecticidal biocidal phytochemical is isolated from Annona muricata (Annonaceae), Annona reticulata {Annonaceae), Annona squamosa (Annonaceae), Cucurbita pepo (Cucurbitaceae), Mammea americana {Guttiferae), Mentha spicata (Labiatae), Ocimum basilicum (Labiateae), Rosmarinus officinalis (Labiatae), Citrus reticulata {Rutaceae or Curcuma longa {Zingiberaceae), the molluscicidal biocidal phytochemical is isolated from Annona squamosa (Annonaceae), Ocimum Basilicum (Labiateae) or Camellia sinensis {Theaceae) and the anti-nematodal biocidal phytochemical is isolated from Glycyrrhiza glabra (Leguminoseae) or Phaseolus vulgaris {Leguminosae), or any combination thereof.

In one embodiment of the invention, the biocidal phytochemical preparation may further comprise a phytochemical selected from lemon grass oil, a camphor, a camphor oil, zosteric acid, Zostera noltil, partheniol, myrtle oil, garlic extract, tea tree oil, citric acid, thyme, eel grass extract or derivatives thereof, tannin, neem oil or derivatives, or any combination thereof.

In the embodiments of the invention, the polymer base is selected from a cellulose- based material, a noncellulose polymer, an acetate polymer, an organic polymer, a composite comprising an organic and an inorganic polymers a polyelectrolyte material, a silicone rubber, a synthetic or a natural latex rubber, wherein the polymer base may be selected from a nitrocellulose, a cellophane, or a cellulose acetate, a polyamide, an aliphatic polyamide and aromatic polyamides, a high-flux and high rejection composite manufactured by interfacial polymerization, polyacylonitrile, polyvinychloride-polyacrylonitrile copolymers, polysulfone, polyether sulfone, poly(vinylidene fluoride), aromatic polyamides, polyacrylonitrile-polyvinyl chloride copolymers, poly(vinylidene fluoride), cellulose triacetate, a nylon, poly(l-tremethylsilyl-l-propyne) (PTMSP), silicone rubber, poly(4-methyl-l-pentene) (TPX), ρoly(ρhenylene oxide) (PPO), ethyl cellulose, SFDA- DAF (polymide), polyaramide and tetrabrome bis polycarbonate, poryamide-polyether copolymers, or a polyurethane-polyamide block copolymer. In the various embodiments of the invention, the capsicum preparation may be selected from a capsicum preparation having between about 4% capsicum and about 90% capsicum and has a concentration in the polymer base of between about 0.01% to about 60% weight to weight, or wherein the capsicum preparation is about 4% capsicum and has a concentration in the polymer base of between about 0.01% to about 60% v/v or weight to weight, is about 14% capsicum and has a concentration in the polymer base of between about 0.01% to about 60% v/v or weight to weight, or is about 90% capsicum and has a concentration in the polymer base of between about 0.01% to about 60% v/v or weight to weight.

In one embodiment of the invention, the capsicum preparation is substantially free of capsaicin.

In the embodiments of the invention, the biocidal phytochemical may be a mixture comprising grapefruit seed extract and menthol (liquid, crystals or powder) in a weight-to- weight ratio range of from about 1 :1 to about 2:1, the final concentration of the phytochemical mixture in the composition being between about 0.01% to about 60% v/v or weight to weight of a polymer base or between about 0.01% to about 25% v/v or weight to weight of a polymer base, or wherein the menthol and the menthol derivative each has a concentration in the polymer base of between about 0.01% and about 60% v/v or weight to weight of a polymer base or between about 0.01% and about 15% v/v or weight to weight of a polymer base. The embodiments of the invention further encompass comprising a biocidal polymer composition comprising a grapefruit seed extract having a concentration of between about 10% to about 40% v/v, a pomegranate extract having a concentration of between about 10% to about 40% v/v, a capsicum preparation having a concentration of between about 5% to about 20% w/w and a menthol having a concentration of between about 5% to about 20% w/w.

In one embodiment of the invention, the biocidal phytochemical composition comprises a grapefruit seed extract having a concentration of about 30% v/v, a pomegranate extract having a concentration of about 30% v/v, a capsicum preparation having a concentration of about 5% w/w and a menthol having a concentration of about 5% w/w in a glycerin based solution.

In the embodiments of the invention, the biocidal phytochemical composition may be homogeneously admixed with the polymer base, heterogeneously admixed with the polymer base, dispersed on the surface of a polymer base, or microencapsulated.

In this aspect of the invention, the biocidal phytochemical composition may further comprise a chemical releaser that facilitates a controlled release of a biocidal phytochemical from the polymer, and optionally one or more additives selected from the group consisting of a wetting or emulsifying agent, a pH buffering agent, a gelling or viscosity enhancing agent, a preservative and a coloring agent.

In another embodiment of the invention, the chemical releaser is citric acid, zinc oxide, iron oxide, or vitamin E.

Another aspect of the invention is a filter comprising the polymer composition according to the above paragraphs In the embodiments of this aspect of the invention, the filter may be a membrane filter, a composite membrane, an ultrafiltation membrane, a microfiltration membrane, a fibrous filter, a pelleted filter bed, a cylindrical filter, a gas separation membrane or a pervaporation membrane.

The present invention is not limited to the specific compositions or methods described herein and that any composition having a formula or method steps equivalent to those described falls within the scope of the present invention. Preparation routes of the composition and method steps for treating filter membranes and filter materials are merely exemplary so as to enable one of ordinary skill in the art to make the composition and use it according to the described process and its equivalents. It will also be understood that although the form of the invention shown and described herein constitutes embodiments of the invention, it is not intended to illustrate all possible forms of the invention. The words used are words of description rather than of limitation. Various changes and variations may be made to the present invention without departing from the spirit and scope of the invention. * * *

Having thus described in detail preferred embodiments of the present invention, it is to be understood that the invention defined by the above paragraphs is not to be limited to particular details set forth in the above description as many apparent variations thereof are possible without departing from the spirit or scope of the present invention.

Claims

WHAT IS CLAIMED IS:

1. A biocidal polymer composition for inhibiting the colonization of a surface of a filter by organisms, the polymer composition comprising: a polymer base suitable for forming a filter; and a biocidal phytochemical composition comprising a grapefruit seed extract, a pomegranate extract, a capsicum preparation and a menthol, wherein the amount of the biocidal phytochemical composition is sufficient to inhibit the colonization of a surface of a filter by organisms.

2. The biocidal composition of Claim 1 further comprising at least one additional biocidal phytochemical agent, wherein the biocidal phytochemical agent is an antibacterial; an anti-viral; an anti-fungal; an anti-crustacean; a larvicidal; an insecticidal; a molluscicidal or an anti-nematodal biocidal phytochemical.

3. The biocidal polymer composition of Claim 2, wherein the biocidal phytochemical composition comprises a grapefruit seed extract having a concentration of between about 10% to about 40% v/v, a pomegranate extract having a concentration of between about 10% to about 40% v/v, a capsicum preparation having a concentration of between about 5% to about 20% w/w and a menthol having a concentration of between about 5% to about 20% w/w.

4. The biocidal polymer composition of Claim 3, wherein the biocidal phytochemical composition comprises a grapefruit seed extract having a concentration of about 30% v/v, a pomegranate extract having a concentration of about 30% v/v, a capsicum preparation having a concentration of about 5% w/w and a menthol having a concentration of about 5% w/w in a glycerin based solution.

5. The biocidal polymer composition of Claim 2, wherein the anti-bacterial biocidal phytochemical is isolated from Annona muricata (Annonaceae), A.squamosa, Panax ginseng (Araliaceae), Capparis spinosa (Capparidaceae), Calendula officinalis (Compositae), Cynara scolymus (Compositae), Cucurbita pepo (Cucurbitaceae), Cymbopogon citratus (Gramineae), Mentha spicata (Labiatae), Ocimum basilicum (Labiatae), Rosmarinus officinalis {Labiatae), Glycyrrhiza glabra (Leguminosae), Allium sativum (Liliaceae), Aloe vera (Liliaceae), Citrus reticulata {Rutaceae), Oenothera biennis (Onagraceae), Plantago major (Plantaginaceae), Punica granatum (Punicaceae), Ribes nigrum (Saxifragaceae), Camellia sinensis {Theaceae), Curcuma longa {Zingiberaceae), Zingiber officinale (Zingiberaceae) or an alga, the anti-fungal biocidal phytochemical is isolated from Annona muricata (Annonaceae), Panax ginseng {Araliaceae), Capparis spinosa (Capparidaceae), Calendula officinalis (Compositae), Cucurbita pepo (Cucurbitaceae), Cymbopogon citratus (Granimeae), Mentha spicata (Labiatae), Ocimum basilicum (Labiatae), Rosmarinus officinalis (Labiatae), Glycyrrhiza glabra (Leguminoseae), Allium sativum (Liliaceae), Aloe vera (Liliaceae), Sesamum indicum (Pedaliaceae), Punica granatum (Punicaceae), Citrus aurantium (Rutaceae), Citrus reticulata (Rutaceae), Ribes nigrum {Saxifragaceae), Camellia sinensis (Theaceae), Curcuma longa (Zingiberaceae) or Zingiber officinale (Zingiberaceae) or an alga, the anti- crustacean biocidal phytochemical is isolated from Annona muricata (Annonaceae) or Zingiber officinale {Zingiberaceae), the larvicidal biocidal phytochemical is isolated from Annona squamosa, Mammea americana {Guttiferae), Ocimum Basilicum (Labiateae), Allium sativum {Liliaceae) or Curcuma longa {Zingiberaceae), the insecticidal biocidal phytochemical is isolated from Annona muricata (Annonaceae), Annona reticulata {Annonaceae), Annona squamosa (Annonaceae), Cucurbita pepo (Cucurbitaceae), Mammea americana {Guttiferae), Mentha spicata (Labiatae), Ocimum basilicum (Labiateae), Rosmarinus officinalis (Labiatae), Citrus reticulata {Rutaceae) or Curcuma longa {Zingiberaceae), the molluscicidal biocidal phytochemical is isolated from Annona squamosa (Annonaceae), Ocimum Basilicum (Labiateae) or Camellia sinensis {Theaceae) and the anti-nematodal biocidal phytochemical is isolated from Glycyrrhiza glabra (Leguminoseae) or Phaseolus vulgaris {Leguminosae), or any combination thereof, and wherein the biocidal phytochemical preparation may further comprise a phytochemical selected from lemon grass oil, a camphor, a camphor oil, zosteric acid, Zostera noltil, partheniol, myrtle oil, tea tree oil, citric acid, thyme, eel grass extract or derivatives thereof, a garlic extract, tannin, neem oil or derivatives, or any combination thereof.

6. The biocidal polymer composition according to claim 1, wherein the polymer base is selected from a cellulose-based material, a noncellulose polymer, an acetate polymer, an organic polymer, a composite comprising an organic and an inorganic polymers a polyelectrolyte material, a silicone rubber, a synthetic or a natural latex rubber.

7. The biocidal polymer composition according to claim 6, wherein the polymer base is further selected from a nitrocellulose, a cellophane, or a cellulose acetate, a polyamide, an aliphatic polyamide and aromatic polyamides, a high-flux and high rejection composite manufactured by interfacial polymerization, polyacylonitrile, polyvinychloride-polyacrylonitrile copolymers, polysulfone, polyether sulfone, ρoly(vinylidene fluoride), aromatic polyamides, polyacrylonitrile-polyvinyl chloride copolymers, poly(vinylidene fluoride), cellulose triacetate, a nylon, poly(l- tremethylsilyl-1-ρropyne) (PTMSP), silicone rubber, poly(4-methyl-l-pentene) (TPX), poly(phenylene oxide) (PPO), ethyl cellulose, SFDA-DAF (polymide), polyaramide and tetrabrome bis polycarbonate, polyamide-polyether copolymers, or a polyurethane-polyamide block copolymer.

8. The biocidal polymer composition according to claim 1, wherein the capsicum preparation is selected from a capsicum preparation having between about 4% capsicum and about 90% capsicum and has a concentration in the polymer base of between about 0.01% to about 60% weight to weight, or wherein the capsicum preparation is about 4% capsicum and has a concentration in the polymer base of between about 0.01% to about 60% v/v or weight to weight, is about 14% capsicum and has a concentration in the polymer base of between about 0.01% to about 60% v/v or weight to weight, or is about 90% capsicum and has a concentration in the polymer base of between about 0.01% to about 60% v/v or weight to weight.

9. The biocidal polymer composition according to claim 1, wherein the capsicum preparation is substantially free of capsaicin.

10. The biocidal polymer composition according to claim 1, wherein the biocidal phytochemical composition is a mixture comprising grapefruit seed extract and menthol (liquid, crystals or powder) in a weight-to-weight ratio range of from about 1 :1 to about 2:1, the final concentration of the phytochemical mixture in the composition being between about 0.01% to about 60% v/v or weight to weight of a polymer base or between about 0.01% to about 25% v/v or weight to weight of a polymer base, or wherein the menthol and the menthol derivative each has a concentration in the polymer base of between about 0.01% and about 60% v/v or weight to weight of a polymer base or between about 0.01% and about 15% v/v or weight to weight of a polymer base.

11. The biocidal polymer composition of Claim 1, wherein the biocidal phytochemical composition is homogeneously admixed with the polymer base, heterogeneously admixed with the polymer base, dispersed on the surface of a polymer base, or microencapsulated.

12. The biocidal polymer composition of Claim 1, wherein the biocidal phytochemical composition further comprises a chemical releaser that facilitates a controlled release of a biocidal phytochemical from the polymer base, and optionally one or more additives selected from the group consisting of a wetting or emulsifying agent, a pH buffering agent, a gelling or viscosity enhancing agent, a preservative and a coloring agent.

13. The biocidal polymer composition of Claim 12 wherein the chemical releaser is citric acid, zinc oxide, iron oxide, or vitamin E.

14. A filter comprising the polymer composition of claim 1.

15. The filter according to claim 13, wherein the filter is a membrane filter, a composite membrane, an ultrafiltation membrane, a microfiltration membrane, a fibrous filter, a pelleted filter bed, a cylindrical filter, a gas separation membrane or a pervaporation membrane.