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WO1993000815A1 - Compositions polymeres - Google Patents

Compositions polymeres Download PDF

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Publication number
WO1993000815A1
WO1993000815A1 PCT/GB1992/001191 GB9201191W WO9300815A1 WO 1993000815 A1 WO1993000815 A1 WO 1993000815A1 GB 9201191 W GB9201191 W GB 9201191W WO 9300815 A1 WO9300815 A1 WO 9300815A1
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WO
WIPO (PCT)
Prior art keywords
photosensitiser
polymer
article
composition
visible light
Prior art date
Application number
PCT/GB1992/001191
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English (en)
Inventor
Raymond Bonnett
Dennis Graham Buckley
Aslam Buda Bachu Galia
Brian Saville
Original Assignee
Courtaulds Plc
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Filing date
Publication date
Application filed by Courtaulds Plc filed Critical Courtaulds Plc
Publication of WO1993000815A1 publication Critical patent/WO1993000815A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A01N25/10—Macromolecular compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0058—Biocides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B47/00—Porphines; Azaporphines
    • C09B47/04—Phthalocyanines abbreviation: Pc
    • C09B47/045—Special non-pigmentary uses, e.g. catalyst, photosensitisers of phthalocyanine dyes or pigments
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/02—Dyestuff salts, e.g. salts of acid dyes with basic dyes
    • C09B69/06—Dyestuff salts, e.g. salts of acid dyes with basic dyes of cationic dyes with organic acids or with inorganic complex acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • C09B69/108—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing a phthalocyanine dye
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/001—Treatment with visible light, infrared or ultraviolet, X-rays
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
    • D06P1/642—Compounds containing nitrogen
    • D06P1/6426—Heterocyclic compounds

Definitions

  • This invention relates to polymers, polymer compositions and articles which incorporate photosensitisers, to their manufacture, to their use in applications where light-induced sterility is desired over a period of time, to methods of sterilising a surface, and to cytotoxic agents.
  • Known methods of sterilisation include treatment with cytotoxic substances, for example in solution or as a gas, heat treatment, for example autoclaving, and exposure to high energy radiation, for example ultraviolet light or gamma rays.
  • cytotoxic substances for example in solution or as a gas
  • heat treatment for example autoclaving
  • high energy radiation for example ultraviolet light or gamma rays.
  • the sterility induced by such methods of treatment is not permanent, and repeated treatments may be needed to restore sterility during and after use.
  • materials which were autosterile that is to say materials which had at least some inherent bactericidal and sterilising ability. It is an object of the present invention to provide such materials and articles made from them.
  • Oxygen is a triplet molecule in its ground state.
  • Singlet oxygen is much more reactive than triplet oxygen and can react with biomolecules such as unsaturated lipids, cholesterol and the indole moiety of tryptophan in proteins.
  • Compounds which absorb electromagnetic radiation, for example visible light, to generate an excited singlet state, which decays by the process known as intersystem crossing to yield a triplet state. Such compounds may be called photosensitisers. Some such triplet state molecules can then react with triplet oxygen, for example oxygen of the air, to generate singlet oxygen. This reaction may proceed with re-formation of the singlet state photosensitiser molecule, in which case the overall process is catalytic.
  • Japanese Published Unexamined Patent Publication 63- 296875 describes the preparation of membranes for preserving the freshness of food.
  • a composition which comprises a metallic phthalocyanine polycarboxylic acid and a binder resin is spray-dried onto a base film, for example polyester film.
  • 2665-2669 describe the addition polymerisation of 5-(4- acryloyloxyphenyl)-10,15, 20-triphenylporphyrin.
  • a polymer composition is characterised in that it comprises (1) a polymer and (2) a photosensitiser which is capable of catalysing the formation of singlet oxygen from triplet oxygen under the influence of visible light and in that it exhibits bactericidal activity when the composition comprising the photosensitiser is exposed to visible light.
  • Such compositions have autosterile character, being toxic to microorganisms when exposed to light in the absence of any other external stimulus, and are photocytotoxic.
  • the compositions of the invention exhibit photobactericidal activity on exposure to visible light, photobactericidal activity being bactericidal activity induced by exposure to electromagnetic radiation.
  • bactericidal activity includes bacteriostatic activity wherein bacterial growth is inhibited.
  • an article is characterised in that at least the surface of the article comprises a polymer composition which includes a photosensitiser capable of catalysing the formation of singlet oxygen from triplet oxygen under the influence of visible light and in that the surface exhibits photobactericidal activity when the composition comprising the photosensitiser is exposed to visible light.
  • the surface may be a coated or formed surface.
  • a method for sterilising a surface is characterised in that the surface contains or consists of a polymer composition which includes a photosensitiser capable of catalysing the formation of singlet oxygen from triplet oxygen under the influence of visible light and in that the surface is exposed to visible light.
  • the surface preferably consists of a polymer composition which includes the photosensitiser.
  • the surface may be a coated or formed surface.
  • the salts of the meso-tetra(N-R-4-pyridinium)porphyrin tetracation wherein R represents a 1-hexyl or 1-octyl group are claimed as novel compounds.
  • the photosensitisers used in the invention are preferably stable molecules which resist attack by singlet oxygen. Such photosensitisers provide a catalytic and long- lived effect.
  • Preferred examples of such molecules are provided by the porphyrins and the phthalocyanines.
  • a wide range of synthetic and naturally-occurring porphyrins and of synthetic phthalocyanines has been prepared and is available, as described for example in Comprehensive Heterocyclic Chemistry, ed. A.R. Katritsky and CW. Rees, Pergamon Press (1984), Volume 4, page 377.
  • Other examples are provided by hydroporphyrins, naphthalocyanines, and photosensitiser dyes, for example xanthene dyes such as Rose Bengal, and azine dyes such as Methylene Blue.
  • Porphyrins and phthalocyanines may be used in the invention in the etallated or unmetallated form.
  • Preferred metallated compounds contain a metal ion which does not have a partially filled d-shell, for example aluminium and zinc.
  • Metallated compounds containing a metal ion which has a partially filled d-shell, for example transition metals such as copper and iron, are generally not suitable for use in the invention. When such metallated compounds are exposed to light they are believed to form a triplet state which is very short-lived and therefore is not active in catalysing the formation of singlet oxygen.
  • Such metallated compounds have been used as colorants, for example in the form of pigments, for which purpose stability and inertness to light are desirable properties.
  • One preferred class of photosensitiser for use in the invention consists of the salts of the meso-tetra(N-alkyl-4- pyridinium)porphyrin tetracation.
  • the nature of the counteranion is in general not critical and may suitably be chosen for ease of synthesis and handling or for compatibility with a polymer.
  • An example of a counteranion is tosylate (4-methylbenzenesulphonate) .
  • the alkyl group is preferably a C ⁇ to C alkyl group, for example methyl, ethyl, butyl or octyl, more preferably a C ⁇ to C4 alkyl group, most preferably a 1-butyl group.
  • the alkyl group may be branched or unbranched.
  • the alkyl groups may be the same or different.
  • Other substituents may be used in place of one or more of the alkyl groups, for example aryl, aralkyl and substituted alkyl and aryl groups.
  • Polymer compositions containing meso-tetra(N-R- -pyridinium)porphyrin tetratosylate wherein R represents a 1-decyl or 1-dodecyl group were surprisingly found not to be useful in the invention, and articles made of these compositions did not exhibit photobactericidal behaviour. These compositions and articles were therefore not according to the invention.
  • the photosensitisers used in the invention preferably absorb and are activated by visible light (wavelength 400- 750 nm) at every-day intensities. They are therefore coloured compounds.
  • Use of such photosensitisers has the advantage that daylight or normal artificial light can be used to induce bactericidal activity and consequent sterilisation. It has the further advantage that high-energy radiation such as ultraviolet light or gamma rays is not required to induce sterilisation. Such high-energy radiation may have harmful biological effects and may alter the properties of the material to be sterilised.
  • the proportion of photosensitiser in a polymer composition or article according to the invention may be varied over a wide range, depending on the activity of the photosensitiser and on the desired level of photobactericidal and sterilising activity. It may be as low as 0.1 or 0.01% by weight or even lower, so providing mildly photobactericidal compositions and articles.
  • Use of a low level of photosensitiser has the advantage that the degree of coloration of the composition or article due to the presence of the photosensitiser is low. Higher proportions of up to 1 or 10% by weight or more provide more strongly photobactericidal compositions. Proportions in the range 0.1 to 1% by weight may be preferred.
  • polymers can be used in the invention.
  • the polymer is preferably chosen to resist attack by singlet oxygen.
  • the invention is not limited by the class of polymer.
  • suitable polymers include, but are not limited to, regenerated cellulose, for example viscose rayon; cellulose esters, for example cellulose acetate; and addition polymers, for example polyolefins and olefinic polymers.
  • Porphyrins, phthalocyanines and other photosensitisers having a variety of different chemical functionalities and characteristics are known, and suitable functionalities and characteristics can be selected for reactivity with or compatibility towards a particular polymer.
  • Polymer compositions which include a photosensitiser may be prepared in a variety of ways.
  • a polymer is dyed using a solution of the photosensitiser in a suitable solvent.
  • the polymer may for example be in the form of a fibre or film.
  • the polymer may be a natural polymer, for example cotton, or an artificial polymer, for example viscose rayon.
  • the photosensitiser is included in a polymer melt or dope which is then formed by casting, moulding or extrusion to produce a solid article.
  • the photosensitiser may be dissolved or dispersed in the melt or dope. Such methods of casting, moulding and extrusion are well known in the field of polymer manufacture.
  • the photosensitiser is a chemical entity bonded to a polymer, so being a photosensitive polymer.
  • Such polymers may be made by the inclusion of one or more suitable photosensitive monomers containing a photosensitiser group in a polymerisation reaction, for example an addition polymerisation, so as to incorporate the photosensitiser in the polymer.
  • Such polymers may alternatively be made by reacting a photosensitiser or precursor thereof with a polymer, so grafting photosensitiser molecules onto a polymer, for example in the form of dependent groups.
  • the polymer composition of the invention may be a coating composition.
  • Photobactericidal articles according to the invention can be manufactured in a variety of physical forms.
  • a polymer composition which includes a photosensitiser can be utilised in the form of coatings, films, fibres or pellets, optionally incorporated into more complex articles.
  • fibres may be converted into woven, knitted or non-woven textile articles. It is a feature of the photobactericidal articles of the invention that they provide a photobactericidal surface.
  • the photobactericidal articles of the invention may take the form of textile articles, for example cleaning cloths, wipes, surgeons' gowns, bedlinen, wound dressings and bandages. They may alternatively take the form of self- supporting films, for example for use in food packaging or wound dressings. Wound dressings may be sterilised by exposure to light before application and then covered up, once they have been placed over a wound, to restrict or eliminate exposure to light in order to stop the formation of singlet oxygen, which may be harmful and consequently undesirable in a wound environment.
  • the compositions and articles of the invention are useful in medical and clinical auxiliaries for domestic and hospital use, for example tubing, bags and mats used in dialysis procedures, for example kidney dialysis.
  • the articles may take the form of polymer laminates with a photobactericidal surface for use in hygienic applications, in which one or more layers of the laminate contains or consists of a polymer composition which includes a photosensitiser. Preferably at least one surface layer of the laminate contains or consists of a polymer composition which includes a photosensitiser.
  • the articles may take the form of a substrate having a photobactericidal coated or painted surface. The substrate can for example be wood, metal, glass or plastic, but is not limited thereto.
  • a particular aspect of the invention is to provide a surface on an architectural or underwater article which inhibits the growth and adhesion of organisms such as algae and bacteria when exposed to light.
  • the articles may take the form of polymer beads. Such beads are of use in water treatment plants in which a bed or column of such beads exposed to sunlight is used to inhibit the growth of and to kill organisms such as bacteria and algae.
  • the method for sterilising a surface according to the invention has a number of advantages over known methods of sterilising surfaces.
  • the rate of production of the sterilising batericide believed to be singlet oxygen, can be controlled by varying the intensity of irradiation by visible light, either generally or in selected areas. This control is in addition to that provided by the activity and concentration of the photosensitiser. It is an advantage of the invention that no special equipment or treatment is required to induce bactericidal activity. It is a further advantage of the invention that the bactericidal effect continues during exposure to light and diminishes only little with the passage of time. It is an advantage of the invention that repeated treatments with a sterilising agent are not required.
  • Figure I shows the structure of meso-tetra(N-methyl-4- pyridinium)porphyrin tetratosylate
  • Figure II shows the structure of tetra-t-butylphthalo- cyanine
  • Figure III shows the structure of protoporphyrin dimethyl ester.
  • Ethanol (2.36 g, 50 mmol) was mixed with tosyl chloride (5.01 g, 26 mmol) and cooled to 0°C in an ice-salt bath. Pyridine (4.89 g) was added dropwise to the mixture over 2 hours. The solution was then acidified with dilute HC1 (50 ml) and extracted with ether (3 x 50 ml). The ether extract was dried (K-CO,), filtered and evaporated to yield ethyl tosylate (3.51g, 66%) as a white solid (m.pt. 32- 33°C).
  • Butan-1-ol (3.70 g, 50 mmol) was reacted with tosyl chloride (10.50 g, 50 mmol) and pyridine (8.51 g) in the manner described for ethyl tosylate.
  • the product was distilled (162°C/0.5 mm Hg) to yield butyl tosylate (10.61 g, 86%).
  • Dodecan-1-ol (8.07 g, 40 mmol), pyridine (20.05 g) and tosyl chloride (6.01 g, 30 mmol) were reacted as described for octyl tosylate.
  • Dodecyl tosylate (7.89 g, 76%) was obtained in the form of a white solid (m.pt. 27-28°C) .
  • TPP meso-tetra(4-pyridyl)porphyrin
  • TMPyP meso-tetra(N-methyl-4-pyridinium)porphyri tetratosylate
  • TMPyP (1 g, 1.6 mmol) and methyl tosylate (2 g, 11 mmol) in DMF (60 ml) was heated under reflux for 6 hours and cooled gradually to 0°C. The product was collected by filtration, washed with water (100 ml), and dried in a desiccator to yield TMPyP (1.96 g, 90%).
  • the structure of TMPyP is shown in Figure I.
  • TEtPyP 60 mg, 26%) in the form of a fine purple powder.
  • TEtPyP were very soluble in water, TBuPyP was soluble, and TOcPyP and TDoPyP were slightly soluble.
  • a regenerated viscose film 25 micron thick was refluxed in 10 M TMPyP in solution in methanol or water.
  • the film was dyed to a yellow-brown colour, and showed absorption maxima at 520, 556, 606 and 641 n , the absorbance at 520 nm being 0.20.
  • Sterile agar plates were prepared and a sample of sterile undyed or dyed film 3 cm square placed in contact with the top surface of the agar on each plate.
  • a standard amount (20 ⁇ l ) of a bacterial culture was placed on top of the film, and the plates incubated either in the dark or illuminated by a 100 watt electric lamp. Plates inoculated with Escherichia coli were incubated at 37°C for 48 hours, and those with Bacillus subtilis and Micrococcus luteus at 27°C for 24 hours. Bacterial growth was observed on all squares of film incubated in the dark and on the undyed square of film incubated in the light. No growth of E. coli or B. subtilis and slight growth of M. luteus was observed on dyed squares of film incubated in the light.
  • TMPyP (50.3 mg) was dissolved in 6:5 methanol/water (110 ml) at 40°C to give a 1.39 mM solution.
  • the concentration of porphyrin in the dyed films was measured by visible spectroscopy at the 519 nm absorption band, and the films were found to contain the following amounts of porphyrin (in mg) :
  • 1 represents no bacterial growth; 2 fewer than five colonies; 3 patchy bacterial growth; 4 medium growth; and 5 maximum bacterial growth, corresponding to the control.
  • TEtPyP and TBuPyP were photocytotoxic in that they exhibited bactericidal behaviour in the light but not in the dark.
  • the films impregnated with TOcPyP were surprisingly both cytotoxic and photocytotoxic in that they exhibited autosterile behaviour in both the dark and the light.
  • Protoporphyrin dimethyl ester (PDME, 10 parts) and meth methacrylate (17 parts) were polymerised in solution in dimethy formamide, using the thermal degradation o azobisisobutyronitrile (AIBN, 5.4 parts) to initiate th reaction. A light brown polymer (23 parts) was recovered. Film were prepared by spreading a solution of the polymer i chloroform on glass plates and allowing the solvent t evaporate. These films showed absorption maxima at 503, 536 570, 624 and 661 nm. The structure of protoporphyrin dimethy ester is shown in Figure III.
  • Example 5 was repeated, except that the weight ratio o methyl methacrylate to PDME was 50:1. A dark brown polymer wa obtained.
  • Example 5 was repeated, except that the weight ratio of methyl methacrylate to PDME was 400:1. A light brown polymer was obtained.
  • Example 5 was repeated, except that divinylbenzene and PDME in a weight ratio of 100:1 were used. A dark brown polymer was obtained.
  • Example 5 was repeated, except that styrene and PDME in a weight ratio of 50:1 were used. A light brown polymer wa obtained.
  • Tetra-5,10,15,20-(4-hydroxyphenyl)porphyrin was treated with excess acrylic anhydride and potassium carbonate in solution in dimethyl formamide to prepare the tetraacrylate.
  • MHTTP 5-(4-Hydroxyphenyl)-10,15,20-triphenylporphyrin
  • Regenerated cellulose film was dyed with a 2xlO "4 M solution of TMPyP in water for 30 minutes at 50°C.
  • the dyed film was irradiated by a xenon arc lamp for times up to 50 hours and its visible spectrum recorded. 50 hours' exposure corresponds to 20 days' continuous sunlight.
  • the colour of the film changed gradually during irradiation from pinkish brown to greenish brown.
  • the visible spectrum showed the gradual disappearance of the absorption peak at 641 nm and the gradual appearance of an absorption peak at 663 nm.
  • Electron spin resonance studies were carried out on undyed and dyed film. There was no evidence of unpaired electrons in the undyed film. The results on the dyed film showed evidence for the presence of a free radical species whose concentratio increased during irradiation by the xenon arc lamp.
  • Regenerated cellulose film was dyed for various times usin a solution of TMPyP (10 mg) in water (150 ml) (4.9xlO "5 M) a 43°C.
  • the absorbance of the samples of film at 519 nm was measured and used to estimate the concentration of TMPyP in th film. The results were as follows:
  • Regenerated cellulose film was dyed with meso-tetra(4- trimethylammoniophenyl)porphyrin available from Aldrich Chemical Company Limited and tested for cytotoxic activity in the manner of Example 3. No bacterial growth was observed on plates incubated in the light (rating 1). Bacterial growth was observed on plates incubated in the dark (rating 5) .
  • Decyl tosylate (1.0 g, 3.2 mmol), TPyP (25 mg, 0.04 mmol) and DMF (3 ml) were heated at 140°C for 20 hours. The solution was allowed to cool to room temperature and stored overnight at -5°. The solid product was collected by lengthy filtration, washed with acetone, and recrystallised from methanol/acetone to yield TDePyP (27.8 mg, 37%) as a dark brown powder.
  • Regenerated cellulose film was dyed with either THePyP or TDePyP and tested for cytotoxic activity in the manner of Example 3. No bacterial growth was observed on squares of film inoculated with THePyP incubated in either the light or the dark. Bacterial growth was observed on squares of film inoculated with TDePyP incubated in either the light or the dark.
  • Example 3 was repeated, except that TBuPyP, THePyP and TOcPyP were tested. After conclusion of the incubation in light, the agar plate carrying the films was incubated in the dark for a further 72 hours. No bacterial growth was observed on any of the dyed films. This demonstrated that at least the combination of film dyed with TBuPyP and light exhibited bactericidal behaviour.

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Abstract

Compositions à base d'un polymère et d'un photosensibilisateur capables de catalyser la formation d'un oxygène singulet à partir d'un oxygène triplet, sous l'influence de la lumière visible, et possédant des propriétés photobactéricides, ainsi que des caractéristiques autostériles à l'exposition à la lumière visible. Procédé de stérilisation d'une surface consistant en l'exposition de ladite surface contenant ledit photosensibilisateur à la lumière visible. La composition peut contenir entre 0,1 et 1 % en poids du photosensibilisateur. Le photosensibilisateur peut être, par exemple, une porphyrine ou une phtalocyanine, de préférence sous forme non métallée. Les sels du tétracation de la méso-tétra(N-octyl-4-pyridinium)porphyrine possèdent des propriétés cytotoxiques et photocytotoxiques.
PCT/GB1992/001191 1991-07-02 1992-07-01 Compositions polymeres WO1993000815A1 (fr)

Applications Claiming Priority (2)

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GB9114290.1 1991-07-02
GB919114290A GB9114290D0 (en) 1991-07-02 1991-07-02 Polymer compositions

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Cited By (34)

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FR2723694A1 (fr) * 1994-08-19 1996-02-23 Oreal Utilisation de sels de derives cationiques de porphine comme agents photosensibilisants de bacteries de type gram-negatif
WO1996024385A1 (fr) * 1995-02-09 1996-08-15 Unilever Plc Articles, compositions et procedes de nettoyage de surfaces a l'aide de catalyseurs deposes sur celles-ci
WO1997029636A1 (fr) * 1996-02-19 1997-08-21 Schaffer, Moshe Composition photosensible
DE19606081A1 (de) * 1996-02-19 1997-08-21 Schaffer Moshe Dr Med Verfahren zum Entkeimen von Wasser
DE19606082A1 (de) * 1996-02-19 1997-08-21 Schaffer Moshe Dr Med Neues Schädlingsbekämpfungsmittel
WO1998033503A1 (fr) * 1997-02-05 1998-08-06 Board Of Regents, The University Of Texas System Composes de porphyrine utilises comme inhibiteurs de telomerase
EP0891977A1 (fr) * 1997-07-16 1999-01-20 DLR Deutsches Zentrum für Luft- und Raumfahrt e.V. Dérivés de la 5-(4-hydroxyphényl)-porphyrine comme photosensibilisateurs
DE19730469A1 (de) * 1997-07-16 1999-01-21 Deutsch Zentr Luft & Raumfahrt Metallierte oder unmetallierte Porphyrinderivate
DE19855881A1 (de) * 1998-12-03 2000-06-08 Fraunhofer Ges Forschung Verfahren zur Aktivierung von Wasser und Verwendung derartig aktivierten Wassers
US6248733B1 (en) 1998-01-09 2001-06-19 3M Innovative Properties Company Method for limiting the growth of microorganisms using metal-containing compounds
WO2002002153A1 (fr) * 2000-06-29 2002-01-10 University Of North Carolina At Chapel Hill Inactivation d'agents pathogenes par des porphyrines
WO2001047932A3 (fr) * 1999-12-23 2002-03-14 Moshe Schaffer Action microbicide de porphyrines a l'obscurite
US6420455B1 (en) 1999-06-18 2002-07-16 3M Innovative Properties Company Antimicrobial composition containing photosensitizers articles, and methods of use
US6432396B1 (en) 2000-07-06 2002-08-13 3M Innovative Properties Company Limiting the presence of microorganisms using polymer-bound metal-containing compositions
EP1204431A4 (fr) * 1999-06-30 2003-01-08 Ceramoptec Gmbh Dispositifs medicaux resistants aux bacteries
WO2003015833A1 (fr) * 2001-08-16 2003-02-27 Ceramoptec Industries, Inc. Procede et substance permettant d'obtenir des surfaces presentant des proprietes antimicrobiennes
WO2003026646A1 (fr) * 2001-09-26 2003-04-03 Frontier Scientific, Inc Agents antimicrobiens photodynamiques a base de porphyrine
US6692694B1 (en) * 1998-11-09 2004-02-17 Clean Earth Technologies, Llc Method and apparatus for photosensitized ultraviolet decontamination of surfaces and aerosol clouds
EP1308481A3 (fr) * 1992-08-14 2004-04-28 The Trustees Of The University Of Pennsylvania Couplage croisé induit par un métal de porphyrines à cycle metallisé
WO2007088392A1 (fr) * 2006-02-03 2007-08-09 The Queen's University Of Belfast Matériau et utilisations de ce dernier
WO2008015445A2 (fr) 2006-08-04 2008-02-07 Ucl Business Plc Dispositifs informatiques et accessoires
WO2010014728A1 (fr) * 2008-07-29 2010-02-04 Frontier Scientific Inc. Utilisation de dérivés de tétrakis (n-alkylpyridinium) porphyrine pour détruire des microbes ou empêcher leur croissance
US7820143B2 (en) * 2002-06-27 2010-10-26 Health Research, Inc. Water soluble tetrapyrollic photosensitizers for photodynamic therapy
WO2011045029A1 (fr) * 2009-10-14 2011-04-21 Humboldt-Universität Zu Berlin Composite comprenant au moins un type de perfluoroalkyl-perfluoro-phtalocyanine
ITRM20100524A1 (it) * 2010-10-08 2012-04-09 Ct Nat De Rech Scient Ifique Et Tech Composizione comprendente un larvicida fotoattivabile
US8580192B2 (en) * 2006-10-31 2013-11-12 Ethicon, Inc. Sterilization of polymeric materials
US8580309B2 (en) 2006-08-04 2013-11-12 Ucl Business Plc Antimicrobial mixtures
US8859760B2 (en) 2008-07-29 2014-10-14 Frontier Scientific, Inc. Compositions for killing or preventing the growth of microbes
EP3308646A1 (fr) * 2016-10-14 2018-04-18 Commissariat à l'Énergie Atomique et aux Énergies Alternatives Biocide photoactivable et/ou matériaux bactéricides et procédé de fabrication de ces matériaux
WO2021001445A1 (fr) 2019-07-01 2021-01-07 Chemical Intelligence Limited Colorants antimicrobiens pour vêtements de soins de santé
WO2021007638A1 (fr) 2019-07-16 2021-01-21 Universidade De São Paulo - Usp Procédé d'obtention de surfaces polymères fonctionnalisées avec photosensibilisateurs, matériau polymère fonctionnalisé et son utilisation
US20210269604A1 (en) * 2016-05-10 2021-09-02 North Carolina State University Photodynamic compositions, methods of making, and uses thereof
EP3933102A1 (fr) * 2020-06-29 2022-01-05 Ortner Cleanroom Engineering GmbH Nappe textile, vêtement, son procédé de fabrication, fonctionnalisation d'une nappe textile et l'utilisation d'un photosensibilisateur fixé à la surface d'une nappe textile
US12049095B2 (en) 2019-07-01 2024-07-30 Bmg (British Medical Group) Limited Antimicrobial medical glove printing method

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EP1308481A3 (fr) * 1992-08-14 2004-04-28 The Trustees Of The University Of Pennsylvania Couplage croisé induit par un métal de porphyrines à cycle metallisé
WO1996005862A1 (fr) * 1994-08-19 1996-02-29 L'oreal Utilisation de sels de derives cationiques de porphine comme agents photosensibilisants de bacteries de type gram-negatif
FR2723694A1 (fr) * 1994-08-19 1996-02-23 Oreal Utilisation de sels de derives cationiques de porphine comme agents photosensibilisants de bacteries de type gram-negatif
WO1996024385A1 (fr) * 1995-02-09 1996-08-15 Unilever Plc Articles, compositions et procedes de nettoyage de surfaces a l'aide de catalyseurs deposes sur celles-ci
WO1997029636A1 (fr) * 1996-02-19 1997-08-21 Schaffer, Moshe Composition photosensible
DE19606081A1 (de) * 1996-02-19 1997-08-21 Schaffer Moshe Dr Med Verfahren zum Entkeimen von Wasser
DE19606082A1 (de) * 1996-02-19 1997-08-21 Schaffer Moshe Dr Med Neues Schädlingsbekämpfungsmittel
US6454951B1 (en) 1996-02-19 2002-09-24 Giulio Jori Photosensitive composition
DE19606082C2 (de) * 1996-02-19 1999-04-08 Schaffer Moshe Dr Med Neues Schädlingsbekämpfungsmittel
US6087493A (en) * 1997-02-05 2000-07-11 Regents Of The University Of Texas System Porphyrin compounds as telomerase inhibitors
WO1998033503A1 (fr) * 1997-02-05 1998-08-06 Board Of Regents, The University Of Texas System Composes de porphyrine utilises comme inhibiteurs de telomerase
DE19730469A1 (de) * 1997-07-16 1999-01-21 Deutsch Zentr Luft & Raumfahrt Metallierte oder unmetallierte Porphyrinderivate
US6107480A (en) * 1997-07-16 2000-08-22 Dlr, Deutsche Zentrum Fur Luft Und Raumfahrt E.V. Metallated or unmetallated porphyrin derivatives having amphiphilic properties
EP0891977A1 (fr) * 1997-07-16 1999-01-20 DLR Deutsches Zentrum für Luft- und Raumfahrt e.V. Dérivés de la 5-(4-hydroxyphényl)-porphyrine comme photosensibilisateurs
US6248733B1 (en) 1998-01-09 2001-06-19 3M Innovative Properties Company Method for limiting the growth of microorganisms using metal-containing compounds
US6692694B1 (en) * 1998-11-09 2004-02-17 Clean Earth Technologies, Llc Method and apparatus for photosensitized ultraviolet decontamination of surfaces and aerosol clouds
DE19855881A1 (de) * 1998-12-03 2000-06-08 Fraunhofer Ges Forschung Verfahren zur Aktivierung von Wasser und Verwendung derartig aktivierten Wassers
US6420455B1 (en) 1999-06-18 2002-07-16 3M Innovative Properties Company Antimicrobial composition containing photosensitizers articles, and methods of use
EP1204431A4 (fr) * 1999-06-30 2003-01-08 Ceramoptec Gmbh Dispositifs medicaux resistants aux bacteries
WO2001047932A3 (fr) * 1999-12-23 2002-03-14 Moshe Schaffer Action microbicide de porphyrines a l'obscurite
WO2002002153A1 (fr) * 2000-06-29 2002-01-10 University Of North Carolina At Chapel Hill Inactivation d'agents pathogenes par des porphyrines
US6432396B1 (en) 2000-07-06 2002-08-13 3M Innovative Properties Company Limiting the presence of microorganisms using polymer-bound metal-containing compositions
US6573258B2 (en) * 2000-09-27 2003-06-03 Frontier Scientific, Inc. Photodynamic porphyrin antimicrobial agents
WO2003015833A1 (fr) * 2001-08-16 2003-02-27 Ceramoptec Industries, Inc. Procede et substance permettant d'obtenir des surfaces presentant des proprietes antimicrobiennes
EP1420832A4 (fr) * 2001-08-16 2004-11-24 Ceramoptec Gmbh Procede et substance permettant d'obtenir des surfaces presentant des proprietes antimicrobiennes
US6951630B2 (en) * 2001-08-16 2005-10-04 Ceramoptec Industries, Inc. Method and substance for obtaining surfaces with antimicrobial properties
KR100907762B1 (ko) * 2001-08-16 2009-07-15 세람옵텍 인더스트리스, 인크. 항균 특성을 가지는 표면을 얻기 위한 방법 및 성분
WO2003026646A1 (fr) * 2001-09-26 2003-04-03 Frontier Scientific, Inc Agents antimicrobiens photodynamiques a base de porphyrine
JP2005505574A (ja) * 2001-09-26 2005-02-24 フロンティア サイエンティフィック インコーポレイテッド 光力学的ポルフィリン抗菌剤
JP4698948B2 (ja) * 2001-09-26 2011-06-08 フロンティア サイエンティフィック インコーポレイテッド 光力学的ポルフィリン抗菌剤
US7820143B2 (en) * 2002-06-27 2010-10-26 Health Research, Inc. Water soluble tetrapyrollic photosensitizers for photodynamic therapy
WO2007088392A1 (fr) * 2006-02-03 2007-08-09 The Queen's University Of Belfast Matériau et utilisations de ce dernier
AU2007210947B2 (en) * 2006-02-03 2012-12-13 The Queen's University Of Belfast Material and uses thereof
US8450359B2 (en) 2006-02-03 2013-05-28 The Queen's University Of Belfast Polymer-supported photosensitizers for the generation of singlet oxygen
JP2009525108A (ja) * 2006-02-03 2009-07-09 ザ クイーンズ ユニバーシティ オブ ベルファスト 材料とその利用
WO2008015445A2 (fr) 2006-08-04 2008-02-07 Ucl Business Plc Dispositifs informatiques et accessoires
WO2008015445A3 (fr) * 2006-08-04 2008-08-14 Ucl Business Plc Dispositifs informatiques et accessoires
US8580309B2 (en) 2006-08-04 2013-11-12 Ucl Business Plc Antimicrobial mixtures
US8585965B2 (en) 2006-10-31 2013-11-19 Ethicon, Inc. Sterilization of polymeric materials
US8580192B2 (en) * 2006-10-31 2013-11-12 Ethicon, Inc. Sterilization of polymeric materials
CN102245027A (zh) * 2008-07-29 2011-11-16 尖端科学公司 四(n-烷基吡啶)-卟啉衍生物用于杀死微生物或防止微生物生长的用途
US8859760B2 (en) 2008-07-29 2014-10-14 Frontier Scientific, Inc. Compositions for killing or preventing the growth of microbes
US8633311B2 (en) 2008-07-29 2014-01-21 Frontier Scientific, Inc. Topical application of porphyrins for killing or preventing the growth of bacteria or fungi on a mammal
WO2010014728A1 (fr) * 2008-07-29 2010-02-04 Frontier Scientific Inc. Utilisation de dérivés de tétrakis (n-alkylpyridinium) porphyrine pour détruire des microbes ou empêcher leur croissance
WO2011045029A1 (fr) * 2009-10-14 2011-04-21 Humboldt-Universität Zu Berlin Composite comprenant au moins un type de perfluoroalkyl-perfluoro-phtalocyanine
ITRM20100524A1 (it) * 2010-10-08 2012-04-09 Ct Nat De Rech Scient Ifique Et Tech Composizione comprendente un larvicida fotoattivabile
US20130296370A1 (en) * 2010-10-08 2013-11-07 Universita Degli Studi Di Padova Composition comprising a photoactivatable larvicide
WO2012046214A3 (fr) * 2010-10-08 2012-06-21 Universita´ Degli Studi Di Camerino Composition comprenant un larvicide photoactivable
WO2012046214A2 (fr) 2010-10-08 2012-04-12 Universita´ Degli Studi Di Camerino Composition comprenant un larvicide photoactivable
US20210269604A1 (en) * 2016-05-10 2021-09-02 North Carolina State University Photodynamic compositions, methods of making, and uses thereof
US11884784B2 (en) * 2016-05-10 2024-01-30 North Carolina State University Photodynamic compositions, methods of making, and uses thereof
EP3308646A1 (fr) * 2016-10-14 2018-04-18 Commissariat à l'Énergie Atomique et aux Énergies Alternatives Biocide photoactivable et/ou matériaux bactéricides et procédé de fabrication de ces matériaux
WO2018069508A1 (fr) * 2016-10-14 2018-04-19 Commissariat À L'Énergie Atomique Et Aux Énergies Alternatives (Cea) Matériaux biocides et/ou bactéricides photoactivables et procédé de fabrication de tels matériaux
WO2021001445A1 (fr) 2019-07-01 2021-01-07 Chemical Intelligence Limited Colorants antimicrobiens pour vêtements de soins de santé
US12049095B2 (en) 2019-07-01 2024-07-30 Bmg (British Medical Group) Limited Antimicrobial medical glove printing method
WO2021007638A1 (fr) 2019-07-16 2021-01-21 Universidade De São Paulo - Usp Procédé d'obtention de surfaces polymères fonctionnalisées avec photosensibilisateurs, matériau polymère fonctionnalisé et son utilisation
EP3933102A1 (fr) * 2020-06-29 2022-01-05 Ortner Cleanroom Engineering GmbH Nappe textile, vêtement, son procédé de fabrication, fonctionnalisation d'une nappe textile et l'utilisation d'un photosensibilisateur fixé à la surface d'une nappe textile
WO2022002489A1 (fr) * 2020-06-29 2022-01-06 Ortner Cleanroom Engineering Gmbh Surface textile, vêtement, procédé de fabrication et de fonctionnalisation d'une surface textile et utilisations d'un photosensibilisateur lié à une structure textile

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