Patent Application
20240052560
Chemical and biological agents (CWA), microbial pathogens, deliberately harmful or accidental radiation exposure, and other related threats to health can present with direct damage to skin surfaces, conjunctival surfaces, hair, and mucosa when transmitted through the air or by direct and indirect touch and surface contact, which may include exposure via damaged surface tissues and injections or any process that breaches the skin. In addition to direct and indirect biological surface skin, conjunctival, hair, and mucosal toxicity, these agents, substances, and pathogens may be absorbed through these same surfaces and induce systemic toxic effects, leading to major morbidity and mortality. Various threats may include, but are not exclusively organophosphates, nerve agents, sulphur and nitrogen mustards, chlorine compounds, opioids, ricin, all manner of pathogenic viruses, bacteria, parasites, fungi, prions, spores, ammonia compounds, poisonous gases, cyanide compounds, acids, bases, and other many types and classes of toxins, venoms, and poisons, and various forms of radiation. Some of these agents are intrinsically or by design colorless, odorless, dispersible in air or on surfaces, with no known antidotes or effective treatments or therapies. Clearly, there is a need for prevention of biological surface contact and other countermeasures for the plethora of CWA and other pathogens, and deleterious substances, natural or artificially created, and harmful radiation exposures, which is the subject of the present disclosure.
The present disclosure describes methods and physical substances, which are based on known and contemplated photoactive substances herein referred to as photosensitizers. It should be noted that said photosensitizers are also potentially active in dark or very low light levels, below light levels usually associated with known photodynamic actions. Photosensitizers included in the present disclosure include known and contemplated photosensitizers including but not limited to all types of methylene blue derivatives and methylene blue itself, chlorophyll derivatives, tetrapyrrole structures, porphyrins, chlorins, bacteriochlorins, phthalocyanines, texaphyrins, prodrugs such as aminolevulinic acids, phenothiaziniums, squaraine, boron compounds, various transition metal complexes, hypericin, riboflavin, curcumin, titanium dioxide, psoralens, tetracyclines, indocyanine green, flavins such as riboflavin, erythrosine, and the like. The invention also includes known or contemplated nanocompositions of photosensitizers and photosensitizers linked to a variety of other substances, or utilized in combination with other substances which may improve the photodynamic decontaminating effect. Light sources enabling photoactivation include can include, but are not limited to lasers, laser diodes, light emitting diodes, and other semiconductor light sources such as those using quantum dot technology. Fluorescent, incandescent lighting, ambient outdoor light, light from combustion of materials causing flame, are also included in the present disclosure. In general, at least one photosensitizer including methylene blue (MB), riboflavin (RF) its derivatives and the like, and optionally a skin penetrant enhancer such as low molecular weight hyaluronic acid are part of the present invention disclosure. Other skin penetrants may optionally include a variety of oils, dextrins, dimethylsulphoxide, cholates, surfactants, saponins, bile salts, ethers, liposomal formulations, azones, urea, pyrrolidones, alcohols, polysorbates, and other solvents known and used commercially as skin penetrants.
Photosensitizer concentration range: 0.001 micromolar to 1.0 molar, with preferred ranges of 10 micromolar to 1000 micromolar.
Hyaluronic acid concentration range: 0.001 micromolar to 1000 micromolar, though ranges above or below are part of the present disclosure.
Hyaluronic acid molecular weight: For skin penetration, low molecular weight 20-300 kDa are preferred, and to impede or prevent skin penetration, high molecular weight 1000-1400 kDa are preferred, though ranges above and below these putative parameters are part of the present disclosure.
In one embodiment MB and/or RF are topically applied to the biological surface which includes skin, conjunctiva, hair, and mucosa which when photoactivated produce singlet oxygen and other reactive oxygen species (ROS). Singlet oxygen and other ROS are known to inactivate and degrade CW agents, toxins, and various pathogens. Other beneficial inactivation reactions may occur when light exposure is limited or nonexistent, when photosensitizers are used at high concentrations, or in combination with reducing or oxidizing agents. Non-limiting examples include inactivation of SARS CoV-2 virus which causes COVID-19 by methylene blue at a concentration of 10 micrograms/ml, and a redox reaction of methylene blue and ascorbate producing antimicrobial hydrogen peroxide. In another embodiment, MB which may induce a blue surface stain due to its activity as a biological and textile dye, when applied to a biological surface is decolorized to leucomethylene blue using a reducing agent, such as ascorbate or vitamin C, if decolorization is desired. In yet another embodiment, methylene blue and/or riboflavin or other photosensitizers are applied as needed in an aqueous solution to hair, using a comb for example, in order to decontaminate CWA or other pathogens, toxins, and poisons contacting hair and the hair bearing surfaces.
In another embodiment, at least one photosensitizer is incorporated into a liquid formulation known in the commercialized “liquid bandage” field, whereby the liquid formulation is contained in an air tight, opaque spray or roll—on applicator type bottle, where upon application to a cutaneous wound exposed to air polymerizes into a hardened but flexible coating protecting the disinfecting the wound surface. Liquid bandage formulations may be comprised of various known biocompatible polymers dissolved in a biocompatible water or alcohol-based solvent. Upon contact with air, a protective thin film is rapidly formed which protects the cutaneous wound/injury when the excipient/carrier evaporates. Polymers used may non—exclusively include various substances and compounds such as polyvinylpyrrolidone, ethyl cellulose, pyroxylin/nitrocellulose or poly methylacrylate-isobutene-monoisopropylmaleate and acrylate or siloxane polymers.
In some embodiments, at least one photosensitizer such as methylene blue which was originally developed as a textile dye is sprayed, dipped, sublimated, spin coated, printed, or otherwise incorporated into fabrics and textiles using commonly known dyeing and dye application methods. Another embodiment adds at least one photosensitizer as needed or on demand as a spray formulation which may also optionally be applied during a laundering or drying process, to the fabric or textile to be treated, in order to replenish the photosensitizer which could be photobleached, or reduced in quantity by abrasion of the protective fabric. Methylene blue as a non-limiting example can be incorporated as a powder in the amount from 0.1 to 20 grams or more as a dissolvable in aqueous solution laundry pod, added to a washing cycle when laundering the protective fabric. Methylene blue and/or other photosensitizers could also be incorporated into a dryer sheet such as those used to add scent to drying clothes, by spraying the sheet with methylene blue and/or other photosensitizers and added during the protective fabric drying cycle.
In another embodiment, at least one photosensitizer such as methylene blue, riboflavin, rose bengal, and/or indocyanine green, as non-limiting photosensitizer examples can be added to a wetting agent or solvent such as methanol or super critical carbon dioxide as known substances that can be utilized to adhere at least one photosensitizer in concentrations ranging from 0.1% to 2.0% to a hydrophobic surface, such as may be found on water repellant coated fabrics or textiles, or that may be innately water repellant, such as a hydrophobic polymer such as polypropylene.
In yet another embodiment, the color of the photosensitizer(s) embedded or deposited on or within a fabric or textile or film is adjusted by combining photosensitizers of various types, such as methylene blue and riboflavin to create a greenish color, or methylene blue, riboflavin, and rose bengal to create a greenish brown range of color, as non-limiting examples.
In another embodiment, known phase change substances such as but limited to polyethylene glycol which are microencapsulated for containment purposes, are incorporated into the protective fabric, as is known in commercially available textiles in order to heat or cool the fabric as needed. In another embodiment the protective fabric incorporating the cooling or heating phase change substances are located proximate to the so called “pulse points”, where major blood vessels including arteries are close to the skin surface. Pulse points can non-exclusively include the wrists, elbows, knees, feet, neck, groin, axilla, and the like.
Phase change materials are also comprised of various salts or organic compounds that can absorb heat till a melting point or phase change temperature is reached, at which point more heat is absorbed without the phase change materials changing in temperature.
In some embodiments, known phase change materials are incorporated into a face shield which is part of the protective suit. In some embodiments phase change materials may non-exclusively include waxes such as eicosane, octadecane, nonadecane, heptadecane, and hexadecane, which are known to be microencapsulated for incorporation into textiles and fabrics. Other phase change substances include paraffin wax, carboxylic acids, Glauber's salt which is sodium sulfate decahydrate, and calcium chloride hexahydrate. Such fabrics include knits, woven, or nonwoven materials, which can incorporate phase change substances in microcapsules, which may be comprised of polymers during manufacture of the fabric. Known fabric and textile manufacturing techniques that incorporate phase change materials include wet-spinning, matrix coating using coating substances such as polyurethanes, acrylics, and the like, various knifing techniques, padding techniques, dip and transfer coating, gravure processing, and foam dispersion using polyurethanes, as examples of application and incorporation methods and techniques known in the textile and fabric manufacturing industry.
In another embodiment, methylene blue and low molecular weight hyaluronic acid or other known skin penetrants are combined and applied topically to skin, to reduce skin blood flow. The known effect of methylene blue as a vasoconstrictor is used in this case to reduce skin blood flow which in turn reduces systemic exposure of CWA, toxins, poisons, dangerous gases and the like by restricting access of any skin penetrating deleterious, dangerous substances and agents to the blood stream. In another embodiment riboflavin and/or other photosensitizers are applied topically to skin, with or without a skin penetrant such as, but not limited to hyaluronic acid, and with light exposure, can induce cross-linking of collagen in the skin, which provides an added barrier function, augmenting the natural squamous cell barrier layer, in addition to generation of toxin inactivating and antimicrobial singlet oxygen and other reactive oxygen species. In yet another embodiment topical riboflavin and/or methylene blue or other photosensitizer application without a skin penetration enhancer leaves a thin film superficial to the skin surface which inactivates and kills microbes or detoxifies poisons contaminating the skin surface. In another embodiment a cross-linkable biocompatible substance such as hyaluronic acid and/or collagen is incorporated into the photosensitizer containing thin film, which when exposed to light produces a protective crosslinked layer or coating superficial to the skin. In yet another embodiment riboflavin is applied to the conjunctival surfaces of the eyes, and exposed to light which superficially crosslinks collagen in the cornea, helping to provide a barrier to toxins and poisons on the eye surface layers. For example, riboflavin briefly exposed to ultraviolet light is known to crosslink collagen, and is used clinically for this purpose to treat an abnormal eye condition known as keratoconus. Ultraviolet light can be delivered from a light emitting diode light source or ambient sunlight. In addition, a blue light source which activates riboflavin to induce crosslinking can be used if desired.
In one or more embodiments, where riboflavin is utilized, and a blue light source is used as a photoactivating energy source, the energy can range from 1 millijoule to 100 joules per cm, though ranges outside of these parameters are included in the present disclosure. In embodiments where riboflavin is used on biological surfaces, including skin and eyes, the formulation may optionally include aqueous 20% dextran with 0.146% riboflavin, which is approved by the US Food and Drug Administration for use in the eye to treat keratoconus. Ranges above and below the approved parameters are included in the present disclosure.
In another embodiment, in air generation of protective immunogens and immunologically beneficial antigens from the skin surface that are inhaled and/or swallowed, or contact the eyes with potential transfer via the nasolacrimal ducts to the nasal cavity can be protective by generating an innate and acquired immune response at the biological surface, which also includes the mucosal surfaces of the body.
In another embodiment, concentrations of at least one photosensitizer above 500 micromolar incorporated and embedded into, or sprayed, dipped, swabbed, or brushed onto the protective suit fabric to enable both known type I and type II photodynamic reactions to occur simultaneously, with the type II reactions generating singlet oxygen, and the type I reactions leading to electron transfer reactions generating various reactive oxygen species and other reactants by way of known chemistries. In yet another embodiment, other chemicals such as ascorbate, urea, DNA, RNA, and a variety of known reactants participate in the generation of other reduction/oxidation reactions in concert with at least one photosensitizer, generating hydrogen peroxide and other reactants, all of which are known to inactivate toxins, poisons, viruses, and kill a variety of pathogens.
In another embodiment, at least one photosensitizer such as methylene blue is formulated in an aqueous solution with ascorbates such that when illuminated, singlet oxygen is generated, via type 11 reactions, and when light levels are low, or when dark conditions prevail, hydrogen peroxide or other reactive species are generated via different reaction pathways, such as type 1, known in the photodynamic field. Of course, other beneficial and tissue and fabric/material protective chemical reactions by photosensitizers interacting with poisons, toxins, harmful gases, pathogens and the like are not precluded.
In one embodiment, at least one photosensitizer such as methylene blue when exposed to ionizing radiation generates reactive species which are quenched by adjacent photosensitizing molecules, protecting normal tissues from radiation injury.
In another embodiment, rapid donning of a protective suit is enabled by use of thin shape memory nitinol struts with similar flexibility to medical guidewires, which are reversibly inserted through fabric tunnels on the surface of the protective suit, keeping open, any portion of the protective suit such as the sleeves, thorax and abdominal part of the body suit, leggings, gloves, socks, neck area, and hood for rapid donning in case of emergent and imminent pathogen, toxin, poison, and dangerous gas exposure. The struts are thin, with diameters ranging from 0.01 inch to 0.10 inch. In one embodiment the nitinol struts are in a collapsed configuration, or folded flat but deployed in the rounded shape, into the fabric, enabling the protective suits to be folded in a flat shape or form. When the need arises to rapidly don the protective suit in an emergency, the struts can deploy virtually instantly into a rounded or ovoid shape, which enables rapid donning of the protective suit due to reduced friction, less impediment due to folded fabric during the donning process. Shape memory polymers or conventional polymers such as, but not exclusively nylon, in the form of bands such as those used as cable tie fasteners used for bundling, can also be used in the same fashion as an alternative to the nitinol struts. The polymeric bands may optionally incorporate a trigger release mechanism, as can be found on commercially available ties, allowing for tightening and loosening, such as may be required for emergency use as a tourniquet in the event of distal limb bleeding. The polymeric struts may be nonexclusively comprised of flexible nylon, hold an open loop configuration due to the thickness of the material as is the case for commercially available cable tie fasteners, and range in width from 1.0 mm to 1.0 cm, and with a thickness ranging from 1.0 to 5.0 mm, though ranges below or above these parameters are included in this disclosure.
In another embodiment, tabs or loops on suit that enable no-touch removal in case of significant contamination/radiation exposure, by enabling removal using a rod or hook, thus obviating the need for direct close contact and direct manual handling during doffing. In some embodiments the tabs or loops are of such a length that a gap of 1-2 inches in height are created by sewing or using an epoxy to fasten the tabs or loops to the protective fabric suit. In some embodiments the tabs or loops are located externally at the vertex of the head/hood segment of the protective suit, at the shoulders and/or wrists and/or volar hand surface and/or the dorsum of the feet segments, as non-limiting examples.
In another embodiment, the protective fabric is breathable, comprised of woven natural or synthetic fibers, in a manner creating loops of fibers outwardly and/or inwardly facing, which increases the protective surface area of the fabric, and the ability to capture or trap pathogens, toxins, and poisons. The loops can range in height 0.1 millimeter to 1.0 millimeter and occur at intervals of 0.001 millimeters to 1.0 millimeters.
In one embodiment, an optically clear polymeric, impact resistant face shield is hermetically sealed to the protective fabric suit, using known hermetic techniques such as compression sealing and/or epoxy sealing methods, to prevent exposure of the wearer/user of the protective suit to pathogens, toxins, and/or poisons by inadvertent leakage through a seam. In another embodiment, a sacrificial removable thin film, optically clear and incorporating countermeasures such as dilute formulations of at least one photosensitizer, is used to protect the face shield and the sacrificial thin film, which is positioned on the outward facing side of the face shield. Techniques and methods for embedding at least one photosensitizer into a polymer is known in the art, and an aqueous spray on formulation is included as part of the present disclosure.
In another embodiment, the head, neck, face, hands, and all other body surfaces can be protected by incorporating non-imaging lenses which admit ambient light to the inner fabric surface proximate to the skin of the user, where at least one photosensitizer coated or embedded into the fabric is localized. This feature permits effective protective photoactivation to occur on the undersurface of the fabric which otherwise may attenuate ambient external light falling upon the fabric surface when the fabric is worn by the user.
In another embodiment, a clean sticky but removable photoactive polymeric film such as polyethylene or polyurethane incorporating methylene blue and or other photosensitizers can be placed over high touch suit areas prior to doffing as well, to reduce potential touch contamination during doffing. Many types of adhesives are known in the medical adhesive art, and a non-stick removable backing such as are used on bandages prevents unwanted adhesion till use.
In one embodiment, a protective fabric incorporating at least one photosensitizer is fashioned into tubular shapes including for example (non-exclusively) sleeves, gaiters, chaps, aprons, gowns, caps, hats, shoe covers, gloves, and the like which can be used to cover wounds and infected skin surfaces, insulating the environment, and other proximate living organisms from the infective pathogens, such as various bacteria, fungi, viruses known to spread from superficial lesions. For example, monkeypox skin lesions which may present as rashes, pustules, and blisters are known to be infectious to others when contact occurs, whereas the protective fabric manufactured in a tubular or related shape, or cut to size and applied as a cover over the lesions can serve as a protective actively disinfecting barrier. Known biocompatible adhesives around the edges of the fabric, or tapes can be used to secure the protective fabric to the skin/body surface.
In another embodiment, a protective fabric can be re-treated with at least one photosensitizer by spraying an aqueous solution onto the fabric surface, or by soaking the fabric in a water tight container or bag filled with at least one photosensitizer solution, or by laundering the protective fabric in a washing machine containing a dissolving laundry pod containing at least one photosensitizer formulation, or photosensitizer in a powder or granule form.
In another embodiment, straps surrounding the protective fabric suit limbs, pelvic area, torso, which when tightened down by pulling against an incorporated friction lock can serve to isolate that segment from the rest of the protective suit in the event that the fabric comprising the suit is torn or otherwise breached. This embodiment may also serve as an emergency tourniquet in the event of significant uncontrolled bleeding or oozing from a distal injury, such as may occur to a limb. In one embodiment, the straps are manufactured from a polymer with a known lubricious surface, which may be comprised of Teflon, silicone, polytetrafluoroethylene, or related substances, which reduces friction as straps are tightened or loosened. The removable straps are held in place by sewn or flexible epoxy formulations used to attach fabric tunnels, located on the external surface of the protective suit, through which the polymeric straps readily slide, in a loosening or tightening manner.
In another embodiment, methylene blue and/or riboflavin are provided in a small opaque polymeric spray bottle with a collagen formulation, for use as a spray on sealant, to seal tears, gashes, rips, worn areas or leaks in the protective suit fabric. The spray crosslinks in light to provide an adherent physical barrier and chemical countermeasure in the event of breaching of the protective fabric. In this embodiment the spray may also serve to provide hemostasis in the event of a bleeding injury, as hemostasis is known in photodynamic therapy to induce vascular stasis.
In yet another embodiment, urine and fecal passage, containment, and removal is allowed by incorporating a pouch or pocket which contains an absorbent material liner, comprised of known materials such as those used in baby diapers, which is reversibly attached on the inner groin region of the protective suit, anteriorly for urine capture and containment, and posteriorly for stool capture and containment, by an adhesive or Velcro type of attachment. The pocket or pouch is comprised of an impermeable polymer such as is found comprising the outer surfaces of baby diapers, and also incorporates an adhesive strip on the superior surface of the pouch which can be pressed closed after evacuation of urine or stool.
In yet another embodiment, the antimicrobial action of light and at least one photosensitizer on biological surfaces creates antimicrobial breakdown products which may be immunogenic, mimicking the natural, stereotypic immune response to infections. In this embodiment, a type of immunization and/or variolation effect occurs at the biological surface, which stimulates antibody and cellular immune responses, capable of activating both the innate and acquired arms of the immune system against a range of pathogens. In this manner, singlet oxygen and other reactive oxygen species generated by photodynamic action not only inactivate and decontaminate pathogens, toxins, poisons, and other deleterious dangerous substances but also serve to stimulate protective beneficial immune responses against said substances. In another embodiment the breakdown of pathogens or toxins or poisons by the action of light and at least one photosensitizer producing singlet oxygen and/or other reactive species occurs on a protective fabric suit which is proximate to a biological surface, generates immunogens which are inhaled, ingested, or contacted to skin, which lead to a beneficial protective immune response.
In another embodiment, methylene blue and/or other photosensitizers are combined with a reducing agent such as ascorbate, generating reactive species such as hydrogen peroxide, in the case of methylene blue and ascorbate, which further serves to decontaminate, disinfect, or otherwise render safer a biological surface or protective fabric. In yet another embodiment the ascorbate is provided in a slow release formulation such as is known in the art, which leads to a combination of effects such as simultaneous generation of hydrogen peroxide and singlet oxygen in lighted conditions, or hydrogen peroxide generation which can occur in dark non-lighted conditions. Light conditions can range from darkness to 50,000 lux, to full sunlight conditions.
In another embodiment, a two compartment or chamber spray bottle, such as is commercially available, is utilized, with one compartment or chamber containing at least one photosensitizer such as methylene blue, and the other compartment or chamber containing another reactant such as ascorbate. The spray from both compartments may be delivered simultaneously or sequentially in order, photosensitizer first, then the second reactant, or in reverse order, in an embodiment with two pump head triggers, each being fed from a different compartment or chamber by separate dip tubes (U.S. Pat. No. 9,931,656). In one embodiment a series of laboratory tests are performed against toxins, poisons, and pathogens in order to ascertain an optimal spray sequence of at least one photosensitizer and at least one reactant such as, but not limited to ascorbate, which generates an adequate amount and composition of reactive oxygen species such as but not limited to singlet oxygen and hydrogen peroxide, in quantities that provide optimal protection without damaging or degrading material substrates that they are applied to. Optimal spray pattern, droplet/mist size, and droplet/mist deposition speed are determined experimentally as well. Other reactants may optionally include citric acid, and/or acetic acid, and/or acidic fruit juices such as those derived from lemons, oranges, and the like. The various optional reactants, and/or the photosensitizers can be supplied as a powders, granules, pellets, capsules, tablets, and the like, either pre-loaded into the spray container, or supplied separately as part of a kit. In addition to a spray bottle, the combined solutions can be applied to fabrics and/or hard or soft surfaces, filter type materials, protective garments, headwear, face covers and masks, footwear, gloves, bandages, and the like, from sponges, sponge sticks, roll-on type of applicator devices, wipes, and the like, and/or sprayed into the air as an aerosol.
In yet another embodiment, protection against ionizing radiation is provided by the interaction of at least one photosensitizer, which are capable of absorbing ionizing radiation from radioactive sources, generating reactive species which are secondarily quenched. These types of quenching reactions provide protection of normal tissues by neutralizing reactive species generated by ionizing radiation, which would otherwise react with and damage normal cells and tissues.
Quenching agents include one or more of antioxidants and substances such as ascorbate, beta-carotene, lycopene, astaxanthin, alpha-tocopherol, polyphenols, vitamin A, Vitamin E, beta-carotene, glutathione, selenium, magnesium, coenzyme Q10, flavonoids, resveratrol, phenols, polyphenols, phytoestrogens, lycopene, lutein, zeaxanthin, astaxanthin, furfuryl alcohol, and the like, preferably generally recognized as safe substances and normally ingested substances, at concentrations ranging from 0.001 to 1000 micromolar utilized as quenching agents. In some embodiments, at least one photosensitizer such as methylene blue and/or riboflavin are applied topically to the skin, eyes, ingested, and/or inhaled in combination with at least one quenching agent, in combination or sequentially. The action of the photosensitizers are to absorb the radiation, producing singlet oxygen and/or other reactive oxygen or non-oxygen species which are rapidly quenched or scavenged, protecting normal cells and tissues.
In one embodiment, one or more quenching agents is co-mingled with at least photosensitizer and applied as a coating to the protective suit fabric, or to the skin, the eye surface, and/or the mucous membranes. The coating can be applied as a spray, or swabbed on in the event of a potential radiation exposure accident or deliberate attack.
In another embodiment, at least one photosensitizer taken internally into the body through ingestion, topical application, and/or injection serves as a radiation protectant by absorbing radiation from the radioactive sources followed by quenching of the reactive products. In one embodiment, photosensitizers known to be safe to ingest or inject intravenously or intramuscularly, or parenterally, are administered prior to expected radiation exposure, or after radiation exposure, with simultaneous quenching of the reactive species generated by the interaction of the ionizing radiation (alpha, beta, gamma, X-rays) with at least one photosensitizer. In another embodiment, at least one photosensitizer is applied as an outward facing layer or coating to a protective fabric or surface, or to the skin, with an undercoating of a quenching agent deep to the photosensitizer coating/layer, which serves to quench the radiation absorbing and activated photosensitizer layer generated reactive species, protecting the tissue layers underneath.
In one embodiment, dimethyl sulfoxide 0.1 to 60.0% range is combined with at least one photosensitizer such as methylene blue and riboflavin, as non-limiting examples, and a quenching agent and administered topically as a spray, a roll—on formulation, or in a patch leading to systemic absorption, due to the well known skin penetration properties of dimethyl sulfoxide, for the purposes of normal tissue protection from radiation injury or poisoning. In another embodiment dimethyl sulfoxide ranges below 0.1% or above 60.0% are used as a skin penetrant in combination with at least one photosensitizer and quenching agent.
In some embodiments, the slow release vehicles/substances used to deliver quenching substances over an extended duration include chitosan, hydrogels, waxes, cellulosic formulations, and a large number of various known polymers (Huang 2017, Adepu 2021). It is understood that a wide variety of slow release vehicles/substances have been developed and are included in the present disclosure. Slow release vehicles/substances are known, and include cellulosic formulations with methoxyl or hydroxypropyl side chains, waxes, acrylics, chitin substances, matrices incorporating lipids, minerals, and the like, polyvinyl alcohols, polyvinyl acetates, polysaccharides such as alginate, methacrylates, natural gums, polyethylene oxides, cellulose ethers, hypromellose, povidone, propylene glycol ethers, and other non-limiting substances developed for sustained drug release.
In some embodiments, protection of the skin and internal anatomic structures in the path of ionizing radiation, administered for therapeutic purposes or by accident are protected by methylene blue as a mono-agent, and/or at least one other photosensitizer, combined with at least one quenching agent, all of which are administered topically, and/or injected, in an immediate or sustained release formulation is used to protect normal tissues from ionizing radiation damage.
In some embodiments, methylene blue is administered topically to skin and/or mucous membranes, or injected internally, or applied to wounds for pain control.
In another embodiment the ionizing radiation protective photosensitizer/quencher formulation is applied rapidly to the outer surface of protective suit fabric using a spray bottle, and/or a sponge stick, and/or a roller, with the photosensitizer/quencher formulation contained in the handle, which is flowed and/or sprayed and/or swabbed onto the outer surface of the protective suit fabric. In yet another embodiment, the photosensitizer formulation is applied as one layer, followed by application of the quencher in a second layer, sequentially, with the photosensitizer deep or superficial to the quencher layer, with reapplication as needed depending on the degree and duration of the ionizing radiation threat.
In another embodiment, imbibing of liquids easily and safely is achieved by incorporating a protected water bladder within the interior or on the exterior surface of the protective garment or suit, which optionally contains a riboflavin and/or methylene blue or other safe, ingestible photosensitizer formulation which serves to decontaminate the water if accidental contamination occurs, and that provides a protective effect in the gastrointestinal tract and oropharyngeal tissue due to the dark reactions of, for example methylene blue, which can potentially treat organophosphate poisoning.
In another embodiment, an aqueous methylene blue formulation with low molecular weight hyaluronic acid is applied to hair bearing skin using a sponge stick with a hollow handle containing the formulation. In yet another embodiment a formulation containing riboflavin and high molecular weight hyaluronic acid is applied to skin using a sponge stick with a hollow handle. In another embodiment a riboflavin formulation incorporating hydroxypropyl methylcellulose is applied to the conjunctiva using an eye dropper bottle.
Other eye protective formulations contain one or more of:
In one embodiment, the protective suit or garment is or a one-piece design, which includes a hood for head and neck protection, and built-in gloves and socks, with a front zipper oriented vertically, as can be found in some wetsuit designs, with an overlapping strip of protective fabric which covers the zipper and is closed over the zipper with an adhesive, pre-applied to the undersurface of the flap, and protected prior to use by a nonstick peel-away backing as is used in conventional bandages. In another embodiment, the protective suit or garment is a two piece design, whereby one piece protects the lower extremities and waist, and the other piece protects the torso, head, and neck. In yet another embodiment, the protective suit or garment is a three piece design, with one piece protects the lower extremities and waist, the second piece protects the torso, and the third piece acts as a cowl that protects the head and neck. In these embodiments, an adhesive with a nonstick peel-away backing, located on the internal surface next to the skin, of a width of 0.5-2 inches, and circumferential in design, is used to create a seal to the openings of the suit/garment pieces, after donning prior to use. Wherever a reversibly sealed seam exists within the protective suit fabric, a flap incorporating at least one photosensitizer, of 1-2 inches in width, with an adhesive with a nonstick peel-away backing is optionally incorporated as an added barrier when adhered to the fabric, and covering the seam.
In another embodiment, methylene blue and/or riboflavin and/or other photosensitizers are added during the protective suit laundering and/or drying process. In this manner, the photosensitizer concentration on the protective suit is enhanced or renewed in the event of photobleaching, abrasion, or other processes which may degrade the protective performance of the suit. In one embodiment between 1-20 grams, of at least one photosensitizer in powder or granule form is contained in a dissolvable laundry pod whose coating is comprised of known dissolving substances such as polyvinyl alcohol. In this embodiment the laundry pod is added during the wash cycle when laundering the protective suit fabric, which renews the protective photosensitizer coating on the surface and within the substance of the protective suit fabric. In yet another embodiment at least one photosensitizer is incorporated into one or more dryer sheets and/or on the surface of one or more dryer balls in a range of 1-5 grams of dry photosensitizer which when added during the drying cycle, serves to renew the photosensitizer coating on the surface and within the substance of the protective suit fabric.
In another embodiment, the photosensitizer formulation incorporates a high concentration of at least one photosensitizer, above 500 micromolar, which also optionally contains indocyanine green (10 to 1000 micromolar concentration range), which can absorb light in the near infrared range, such that the suit still provides protection if incident visible light absorption by the suit is reduced by surface coating of dust, grime, mud, blood, or other substances. The incorporation of indocyanine green into the protective suit enables photoactivating light transmission producing singlet oxygen in the near infrared range, around 800 nm, which is known to penetrate opaque substances such as soil and sand (Woolley 1978, Baranoski 2019). The indocyanine green can also visibly fluoresce, enabling visual identification of an individual wearing the protective suit using a near infrared light source directed at the individual, in order to avoid friendly fire types of incidents, or for localization of the wearer of the protective fabric suit as may be needed for various purposes such as search and rescue types of operations.
In another embodiment, a removable protective fabric sleeve, containing or incorporating at least one photosensitizer, optionally held in an open position by a nitinol or polymeric ring at one end, is reversibly attached to the protective suit material externally, such as using a Velcro type of attachment, or contained within a pocket. At one end of the sleeve, which is held in an open position by the nitinol or polymeric ring incorporated into the end of the sleeve, the inner 0.5 mm to 2.5 cm of the sleeve is coated with known medical grade adhesive(s) such as silicones, acrylics, polyurethanes, cyanoacrylates, polyethylene glycols, and/or vinyl resins, with a non-stick backing strip protecting the adhesive till use, as is used in ordinary bandages. In one embodiment, this end of the sleeve is reversibly attached to the protective suit fabric such that the mouth of this open end encompasses an area or region of the protective suit which requires manual access, such as may be the case with a wound or injury, where the protective suit fabric may need to be cut open for access, or previously breached. The other end of the sleeve may incorporate an elastic band or a polymeric reversible tie, which can be tightened around an inserted upper limb, for example around the wrist or forearm, thus enabling continued isolation and protection of the exposed skin area deep to the cut or breached protective suit fabric. In this embodiment, manual access is enabled to control bleeding or perform other medical procedures while maintaining isolation of the treatment area from the environment, which may be contaminated.
In another embodiment, gloves which are hermetically sealed to the upper limb distal sleeves of the protective suit are comprised of any individual or combination of known high performance polyethylene, glass fibers, high molecular weight polyethylene, nylon, nitrile, neoprene, Kevlar or other similar materials, also known to be heat resistant, which can be used to create cut proof and puncture resistant or proof glove material. In another embodiment the glove material incorporates at least one photosensitizer, and is permeable to air, or impermeable to liquid. The glove material ranges in thickness from 1.0-3.0 mm, though ranges below or above this are part of the present disclosure.
In another embodiment, polymers incorporating at least one decontaminating and/or antimicrobial photosensitizer such as methylene blue and riboflavin, and biodegradable/compostable polymers synthesized from corn, potato, tapioca starches, cellulose, soy protein, polylactic acid, and the like are utilized to manufacture eating utensils, plates, bowls, cups, and food storage containers that are antimicrobial. Though polyethylene/polyolefins can be used in this embodiment, with photodynamic dyes incorporated during processing, biodegradable/compostable polymers for utensils, tableware, and food/liquid consumables storage containers, such as polylactide are preferred, and are produced by injection molding, heat forming, extrusion, and similar known production methods, with photodynamic dyes such as methylene blue and/or riboflavin incorporated in aqueous or powder form at one or more steps during the processing. Concentrations of at least one photosensitizer can range from 10 micromolar to 1000 micromolar, or up to 1% (w/v). In some embodiments a plasticizer such as water, glycerin, urea, polyethylene glycol, citric acid, or sorbitol is also used as part of the manufacturing process.
In another embodiment, a number of commercially available water repellent finishes for fabrics based on silicones, waxes, and the like are combined with at least one photosensitizer such as, but not exclusively methylene blue and/or riboflavin, with the option to incorporate known dispersing agents or known carriers that aid in incorporation of at least one photosensitizer into the water repellent substance, which is applied to the surface of the fabric or textile as a spray, or as a liquid during the manufacturing or the textile or fabric.
In yet another embodiment, a multilayer fabric is created from a polypropylene and/or other polymers or natural fibers known to utilized for viral, pathogen, or particle trapping and filtration. Polymers can also include polyester, polyethylene, polyacrylonitrile, polycarbonate, polystyrene, polyvinyl chloride, polyamide, nylon, polylactic acid and the like. Natural fibers can also include cotton, wool, silk, other cellulosic materials, and the like. In some embodiments these filter materials are embedded with at least one photosensitizer such as methylene blue and/or riboflavin during manufacture, using known dip and nip techniques, knifing techniques, sublimation techniques, dispersal agents, methanol, supercritical carbon dioxide, jet spraying, dye printing, and other established dyeing techniques. In one embodiment, an outer layer is comprised of a cotton or other cellulosic material that is between 0.1 millimeter to 5 millimeters thick, incorporating at least one photosensitizer, and an inner layer of polypropylene which is optionally meltblown, optionally incorporating at least one photosensitizer, with a thickness between 0.1 millimeter to 5 millimeters. A variety of known adhesives and/or thermal and/or mechanical techniques can be used to adhere the layers together, or the fabric layers can be separate and not bonded. Needle punching, hot calendar rolls, gravure bonding, adhesive resins, epoxies, urethane adhesives, cyanoacrylates, and other known fabric glues can be used to bond fabrics together. In some embodiments, the fabric is used to construct bandages, protective clothing, garments, hats, caps, hoods, sleeves, chaps, gaiters, face coverings, shoe covers, socks, gloves, aprons, and the like. In other embodiments, drapes, sheets, pillow cases, towels, wipes, and other high touch and cleaning fabrics are created. In bilayer or multilayer fabric compositions at least the outer facing layer incorporates at least one photosensitizer, and/or metals with known antimicrobial properties such as silver, or copper, or zinc, or titanium dioxide particles. In one embodiment, the outer photoactive layer disinfects and kills pathogens while the inner layer also serves to trap pathogens, acting as a form of source control. In other embodiments, the fabric layers are air permeable, breathable, or fluid repellent or fluid resistant or water proof.
In one embodiment, a protective fabric consists of at least one layer of porous fabric incorporating at least one photosensitizer and/or other substances capable of neutralizing pathogens, toxins, poisons, radioactive particles, and the like that are in the ambient environment surrounding the user of the protective fabric. For example, the fabric may be fashioned into a pouch or pocket or compartment incorporated into the protective suit, uniform, clothing worn by the user. Preferentially, but not exclusively, the pouch or pocket is incorporated or attached to the torso of the protective suit, uniform, or clothing, contiguous with at least one tube or duct or channel which transfers air which has passed through at least one layer of protective fabric used to create the pouch or pocket. The air transfer component is impermeable to ambient air, and can be comprised of a flexible polymer or plastic, which further incorporates at least one photosensitizer and/or other substances in the interior lumen of the at least one tube, duct, or channel, capable of neutralizing pathogens, toxins, poisons, radioactive particles, and the like that are in the ambient environment.
As the user inspires air from the ambient potentially contaminated, toxic, or poisonous environment, the air passes through at least one protective layer, and then through at least one tube, duct, or channel which directs the decontaminated or threat neutralized air towards the face of the user, where it is inhaled. Exhaled air can pass through a one way valve incorporated into the construct in front of the user's face, which may be a face cover, mask, face shield, and the like. The one-way valve permits treated decontaminate or threat neutralized air to be exhaled, while preventing the user from inhaling untreated air directly from the ambient environment. The pouch, pocket or compartment may be comprised of two porous, breathable surfaces, or one non-porous surface which is inward facing and one porous breathable outward facing surface which admits air. In all cases, all air contacting surfaces are coated with and incorporate at least one photosensitizer and/or other substances capable of neutralizing pathogens, toxins, poisons, radioactive particles, and the like that are in the ambient environment.
In another embodiment, at least one photosensitizer in a solution or in a dry form is dispersed into the air or environment in an area suspected of, or actually contaminated by a pathogen or radioactive substance. Dispersal can be accomplished using a sprayer type of device (manually or battery powered), or a smoke generator type of device incorporating a propellant, or an explosive type of device for extremely rapid and widespread photosensitizer dispersal. A safe, non-toxic, photosensitizer such as, but not limited to riboflavin can be used, as an example, which absorbs radiation or interacts with a pathogen in the air, or on a surface, or on equipment, which can react with light generating reactive oxygen species and/or singlet oxygen, which inactivates or kills the pathogen, or when interacting with a radioactive substance in the air, on a surface, or on equipment, is quenched, reducing or elimination the radioactive threat.
In another embodiment, the environmentally dispersed photosensitizer is initially in an aqueous formulation, a lipid or oil based formulation, or in a powder form, prior to being dispersed. The dispersed droplet or aerosol size, speed of deployment, volume of deposition, droplet or aerosol fall rate, and airborne concentration and surface contact concentration is experimentally determined and optimized for various environmental conditions, such as still air, wind, rain/fog, variable humidity, and the like, in a laboratory setting, using known equipment and techniques known in the art, such as particle counters and particle size measuring equipment. Aerosol or droplet size can range from 1 nanometer to 1.5 millimeters and in concentration, from 1 part per million to 900,000 part per million.
In another embodiment, a system of multiple neutralizing modalities and are tested and deployed, comprising air disinfection and decontamination, remote to persons or animals or plants and objects or equipment to be protected, an air disinfection and decontamination device(s) used in close proximity to persons, animals, equipment and the like, wearing of fabric that acts as personal protective equipment, and protection of the airway and orifices.
For neutralization and decontamination of air proximate to persons and/or animals, or to decontaminate air the contacts surfaces, objects, and/or equipment, one or more fan devices which incorporate a photoactivating light source, and internally disposed photosensitizer activated by said light, are utilized to inactivate pathogens in the air, or absorb and quench radioactive particles by way of the known quenching mechanisms of singlet oxygen and other reactive oxygen species generated by the interaction of ionizing radiation and photosensitizers.
In one embodiment, a fan device is comprised of an axial type of fan within a tube, located at the distal end or proximal end or middle section of the tube. The interior of the tube incorporates a layer of at least one photosensitizer, with a thickness ranging from 1.0 micron to several millimeters thick or more, and a concentration ranging from 0.1 micromolar to 1.5 molar or greater. In another embodiment the fan blades are coated with at least one photosensitizer, and a light source preferentially, but not exclusively battery powered is incorporated which photoactivates the interior photosensitizer coating. As air passes through the fan device, pathogens and radioactive particles are inactivated by way of singlet oxygen and reactive oxygen species followed by quenching. In one embodiment the fan device housing is optically clear, which augments the photoactivation process using ambient light. In another embodiment, a non-toxic quenching agent is expelled into the air after the photosensitizer is dispersed into the air, augmenting the naturally occurring quenching processes in air. In another embodiment the quenching agent expelled into the air and environment after photosensitizer dispersal is comprised of a water vapor droplet or aerosol formulation.
In another embodiment, a visible to the naked eye aerosolized dye marker is included in the formulation dispersed in the air, in order to monitor the location and movement of the aerosol/droplet cloud after dispersal.
In yet another embodiment, a protective breathable face cover is worn by a person or animal to be protected that incorporates an outer layer of at least one photosensitizer formulated into a dry powder that is applied upon detection of an airborne pathogen or contaminant, or that is manufactured into the fabric. The photosensitizer formulation is such that an amount of photosensitizer is released into the air anterior to the face cover with exhalation by the user of the face cover or mask, which provides an additional decontaminated protective space in front of the user prior to inhalation. The quantity of photosensitizer released into the air is adjusted and optimized in a series of experiments such that an amount of sensitizer is released that is effective over a period of time due to retention of another amount of sensitizer on the face cover surface. Inhalation of the photosensitizer on the surface of the face cover or mask is precluded by the use of known filter materials deep to the photosensitizer layer.
In one embodiment, one or more photosensitizers which reflect different wavebands of visible light are combined in varied concentrations in solution or in a relatively dehydrated state to create a palette of colors as desired for purposes of camouflage, attractiveness, high visibility for safety purposes, to convey feelings or messages by way of various designs and patterns. For example, methylene blue as a fabric dye imparts a blue to purple color on a white cotton or artificial polymeric or blended fabric, with the shade ranging from light to dark, depending on the concentration. Riboflavin which can be supplied as a yellow powder combined with methylene blue powder, in a fluidic solution will create various shades of green, as a fabric dye. Combining rose bengal and/or erythrosine which have a pinkish hue with methylene blue and riboflavin can create a dark, mottled green or brown colored fabric dye as a further non-limiting example.
In one embodiment, the photosensitizer concentrations range from 0.001 micromolar to 2000 micromolar, or from 000.1% weight/volume to 2.0% weight/volume. In another embodiment the color of the photosensitizer combination in ambient light is adjusted using a color matching chart or an app, such as can be done for matching paint colors. In another embodiment all types of known disperse dyes of various colors and hues are also combined with photosensitizers to create various colors. In another embodiment known dispersal agents are used in combination with photosensitizers to enhance color fastness.
In a variety of embodiments photosensitizers as a single or in combination used as a fabric dye can inactivate microbes and volatile organic compounds to reduce or obviate infection risks and for purposes of odor control.
Though many photosensitizers such as methylene blue were synthesized as a fabric dye, the present invention optionally includes the use of known or contemplated disperse dyes and compounds, such as soda ash (as a nonexclusive example), as a color fixative, and to enhance color fastness if desired, or as needed.
In another embodiment, ultraviolet (UV) light absorption for sunburn skin protection is enabled, non-limiting examples of which include methylene blue which is associated with an absorption waveband in the UV as is riboflavin and most other known photosensitizers.
Bright colors are known to attract insects such as mosquitoes and the present invention unexpectedly acts as a mosquito repellent in another embodiment, despite the display of bright fabric colors, due to generation of singlet oxygen and reactive oxygen species well known to be generated by photosensitizer light absorption.
Thermal energy absorption may be enabled by using indocyanine green as a heat dissipation element— cooling when irradiated by external heat source in ambient light, and cooling of skin when skin is emitting near infrared radiation (NIR)/infrared radiation (IR) radiation.
Methylene blue as well as other known water soluble photosensitizers are hygroscopic and may improve wicking of sweat which also reduces physiologic heat load and heat perception.
In another embodiment, a fabric, cloth, hard or soft surface, natural or synthetic fiber, cutaneous surface, mucous membranes and the like incorporates an activated carbon or activated charcoal formulation, applied during manufacture, or on biological surfaces as a spray or wipe, or as a swallowed liquid.
Activated carbon with specific surface area ranging from about 2000-2500 m2/gm and micropore volume of 1.6 ml/gm or more, or less, are part of an fabric and/or spray formulation embodiment for surface, fabric, equipment, and air and environmental decontamination. As an air decontamination procedure, an activated carbon powder or granule formulation can be sprayed or dispersed into the air, followed by filtration and/or capture by known filter materials, incorporated in fans or related air circulation devices, in personal protective equipment (PPE) and masks, and the like.
Applied using a dip, spray on, wipe, sponge, or other related application methods, fabrics, garments, PPE, equipment, hard and soft surfaces, and the like can be imbued with activated carbon with or without at least one photosensitizer formulation in combination, with the activated carbon admixed with the photosensitizer, or applied separately in any sequence.
In another embodiment, in combination with at least one photosensitizer, admixed with the activated carbon or activated charcoal formulation, or disposed as a separate layer superficial or deep to the activated carbon or activated charcoal formulation, used on fabrics, garments, PPE, equipment, hard and soft surfaces, and the like.
In addition to activated carbon substances, other known and contemplated absorbents would include silica gel formulations, and active alumina, as non-exclusive examples, in combination with at least one photosensitizer, for hard and soft surfaces, equipment, devices, PPE of all types, and in air, for decontamination purposes. In yet another embodiment, toxins, pathogens, poisons, malodorous compounds, and other noxious chemicals, biochemicals, and the like are captured and trapped not only by activated carbon, silica gel, active alumina and related compounds applied to fan blades, filter material, hollow tubes, pipes conducting air to be purified and disinfected.
In one or more embodiments, a thin flexible medical grade optically clear silicone elastomer consisting of known polymers and crosslinkers is molded or cut into pieces and glued or bonded into a configuration that fits comfortably around the nose and mouth, as a one piece naso-oral construct, held in place with ear loops or straps, or using known medical grade adhesives such as those used for removable wound dressings and bandages, enabling many hours of comfortable wear. In one embodiment, the outer rim of the one piece construct follows and adheres to the cartilaginous portion of nose, continuing inferiorly following and adhering to the nasolabial fold or adjacent tissue, continuing and adhering to the lateral commissure or adjacent lateral tissue, and continuing and adhering just inferior and below the lower lip, creating a comfortable reliable seal that can last for hours to days, around the nose and mouth. In another embodiment the upper portion of the construct is glued or otherwise bonded to the lower rim of a pair of glasses, goggles, or similar eyewear. One or more flexible polymeric medical grade tubing, of which many grades are commercially available used for intravenous injections and air delivery, which is optionally corrugated and/or contains multiple intraluminal baffles incorporating at least one photosensitizer and optionally at least one light source, and optionally at least one polymeric focusing lens directing light into the construct and/or tubing, is joined or bonded to the naso-oral construct. Tubing parameters such as length, diameter, shape, configuration, internal surface shape, transparency, photosensitizer concentration, disposition, and the like are optimized for expected environmental conditions, air quality and the like, using known laboratory techniques which can assay microbial, pathogen, toxin, poison, and radiation contamination. An optional air filter of which many types are commercially available is optionally incorporated at either or both ends of the tube, or located internally along a portion or the entire length of the tube.
In another embodiment, body heat generated by normal cellular metabolic processes and muscle contraction is captured by clothing, garments, body worn coverings and the like and transferred to ambient air proximate to the anterior aspect of the torso, neck, and other body parts. In relatively still indoor air, the captured and transferred heat to the air anterior to the body rises towards the mouth and nose, as well as the eyes and face. In this embodiment, the clothing, garments, body worn coverings and the like incorporate at least one photosensitizer, and utilize at least one light source that induces photoactivation processes that decontaminate the air which flows proximate to the user's mouth and nose where decontaminated air is inhaled and exhaled, and at the same time, the air curtain also protects the eye surfaces from pathogens and toxins.
In another embodiment, objects and surfaces proximate to the user can also incorporate at least one photosensitizer which can decontaminated air proximate to the user's face as well. In this embodiment, at least one photosensitizer can be applied as a spray to objects and surfaces proximate to the user, or incorporated into transparent thin films, optionally comprised of known polymers, applied reversibly or permanently to objects and surfaces proximate to the user, preferably but not exclusively located anterior to the user, for the purpose of decontaminating inhaled and exhaled air, and protecting the eyes and face of the user.
In another embodiment, head or neck worn jewelry, glasses, and other types of eyewear, can also incorporate at least one photosensitizer and provide added air proximate to the user's face that is decontaminated.
In another embodiment, hats, caps, visors, helmets, head worn gear and the like, which may or may provide a brim anterior to the user's forehead are cooled, causing air superior to the user's face to sink, where it can protect the user's eyes, and be inhaled and exhaled.
In one or more embodiments, cooling methods, techniques, and devices may optionally be incorporated into the decontamination tube device. In another embodiment, the disinfecting device is rectangular or share, or oblate in cross section.
In another embodiment, high molecular weight polyethene fibers and yarns with high strength, cut resistance, and excellent heat transfer capabilities are used with incorporation of at least one photosensitizer, and/or activated carbon and/or antioxidants such as but not limited to ascorbate to create a fabric with high absorptive capacity for toxins, pathogens, poisons, neutralization of ionizing radiation and other threats to health.
In another embodiment, essential or aromatic oils containing photoactive substances such as but not exclusively bergamot, citrus oils, limonene, or their known photoactive components and the like are diffused or aerosolized into the air and photoactivated by at least one light source.
In another embodiment, the essential or aromatic oils are applied or deposited on any hard or soft surface, whereupon diffusion into the air can occur, and when photoactivated by at least one light source, generating photoactivation products such as singlet oxygen and/or other reactive oxygen species on surfaces, and in the ambient air.
In one embodiment, the essential or aromatic oils are applied to fabric used to fashion clothing, garments, scarves, neckwear, hats, face protectors, helmets, and any flexible or rigid fabrics, generating singlet oxygen and/or other reactive oxygen species, which inactivates and kills pathogens, toxins, poisons and the like. In another embodiment, all types of hats and visors incorporating a brim anterior to the user's forehead incorporates at least one photosensitizer and/or photoactive essential oil with an optional fan or blower as part of the headwear, neckwear, clothing, garments, and the like which aids in shunting decontaminated, treated air towards the user's face, where inhalation of decontaminated air can occur. In another embodiment, high molecular weight polyethylene known to conduct heat from the body surface to the environment, incorporating at least one photosensitizer, generates a heat driven rising air current towards the user's face with or without the added use of headwear with a brim incorporating a phase change material which cools proximate air, generating a volume of sinking air anterior to the user's face. In this way, decontaminated air is passively directed towards the user's face for inhalation. In another embodiment, the hard or soft surfaces, and/or clothing, garments, headwear, neckwear, and the like also incorporate activated carbon with or without at least one photosensitizer, for absorption of toxins, poisons pathogens, and the like.
In another embodiment, a skin adherent polymeric thin film incorporating at least one photosensitizer which is optionally of the volatile type can be applied to the facial area around the mouth and nose, creating a zone of decontaminated air for inhalation when photoactivated.
In another embodiment, a volatile oil is admixed with at least one photosensitizer and applied or incorporated into soft and/or hard surfaces, thin films, clothing, eyewear, glasses, goggles, garments, head wear, scarves, neckwear, helmets, hats, visors, and the like. When photoactivated by at least one light source, air in proximity is decontaminated for inhalation. In another embodiment, an air disinfection device is comprised of a rigid or flexible polymeric tube, which is created with baffles, and/or corrugations, which enable greater surface area for incorporation of at least one photosensitizer, and with optional incorporation of least one light source which serves to photoactivate the photosensitizer within the air disinfection device. In another embodiment, one end of the tubular air disinfection device incorporates an active or cooling feature, and the other opposite end of the tubular air disinfection device contains a heating feature which is active or passive.
For one or more embodiments, exemplary cooling features may include: Passive cooling that may be accomplished using a phase change substance such as, but not exclusively a paraffin, polyethylene glycol, and the like. Another exemplary embodiment of a cooling method/technique can employ evaporative cooling using a liquid such as a water reservoir at one end of the air disinfection tube with or without a fan which with a fan, can provide for an active cooling mechanism as the fluid which may be water evaporates.
One or more exemplary embodiments of heating features may include known, commercially available air activated products incorporating cellulose, iron, activated carbon, vermiculate, and salt, as a non-exclusive example, which induces an exothermic reaction. In another embodiment, cool air is drawn into the inlet of the air disinfection device which is decontaminated in the interior of the tube and ejected or flowed out of the other end of tube from active or passive heating of the decontaminated air, creating a zone of decontaminated air which disperses into the environment.
In another embodiment, a warming technique/mechanism consisting of known, commercially available crystallization based reusable warmers, which may be comprised of a sealed container or pocket of chemicals in the form of a supersaturated sodium acetate solution incorporating a metallic chip. Upon flexing or bending the metallic chip, a reaction occurs at the metallic surface and the solution crystallizes, releasing heat. Reuse is enabled by applied heat for example using hot water which dissolves the crystals again.
In another embodiment, a portion of the tubular air disinfection device is comprised of a transparent or optically clear polymer, which may be rigid or flexible, or a combination of both, which admits ambient photoactivating light to the interior of the tubular air disinfection device, which may incorporate at least one photosensitizer along a length of the tube, in the lumen and/or extraluminally. In another embodiment, a flexible elongate air disinfecting polymeric tube is incorporated into clothing, garments, face covers, masks, eyewear, scarves, headwear, helmets, and the like, and may optionally incorporate at least one light source, or be positioned externally to the environment such that ambient light is admitted to at least one portion or the entire length of the tube. In another embodiment, the variable such as tube length, shape, dimensions, configuration, internal photosensitizer concentration, disposition, optional cooling and/or heating mechanism are optimized for various expected environmental conditions using known laboratory techniques such as antimicrobial testing, air flow testing and the like.
In another embodiment, the Venturi effect/Bernoulli principle may be exploited in design of a constriction at the heated or warmer end of the decontamination tube to direct an air stream in a desired manner, such as towards the user's face where inhalation occurs. Additionally, in another embodiment, any or all of the above embodiments may be combined.
In one or more fabric embodiments, clothing or garments, headwear, helmets, hats, gowns, shirts, pants, scarves, and the like, incorporate at least one photosensitizer, and optionally at least one light focusing lens, which directs ambient light or light from a discrete light source such as a light emitting diode array, directly onto at least one optically transparent tube with is incorporated into the fabric of the garments, headwear, gowns, shirts, pants, and the like. The optically transparent tube, or multiple spaced apart tubes, may be located under or external to the fabric, or in both locations, and may be comprised of an optically clear polymer, which optionally acts as an optical fiber as is known in the art, capturing, and transmitting light along the length of the tube which may incorporate at least one photosensitizer. One end of the tube, which is defined as the distal end of the tube in the present disclosure, terminates proximate to the nose/mouth area, and/or eye area, by optionally wrapping around the ear, or optionally by extending from the neck area towards the corners of the mouth and/or pointing towards the nares or nostrils of the nose. The fabric is optionally comprised of a breathable film or material, woven or nonwoven, incorporating at least one photosensitizer, with the polymeric tubes arranged to entrain/capture ambient air that has passed through the fabric layer, and decontaminated and treated by the photosensitizer/light photodynamic action, generating singlet oxygen and other reactive oxygen species, with air directed passively into the tubing by using body heat or a chemical warmer system proximate to the distal end of each tube and/or actively, using a small portable, rechargeable fan or blower incorporated into the proximal or middle segments of the tubing, of which there may be multiple. The chemical warming system may optionally be comprised of sodium acetate which is in a supersaturated aqueous solution that can be reused, or a single use system as is well known in the art of manufacturing and using chemical hand warmers, such as those comprised of iron powder, water, salt, activated charcoal, and vermiculite. In one embodiment contaminated air that is decontaminated by passage through fabric and tubing incorporating at least one photosensitizer, is warmed at the distal end of at least one tube, whose distal end is proximate to the nose/mouth area, and/or eye area, where inhalation of decontaminated treated air occurs as air rises in a plume proximate to the face.
In an embodiment, a polymeric tube(s) are perforated along the length of the tube(s) which enable passage of decontaminated, treated air which has passed through the fabric from the outer fabric surface to the inner fabric surface, for inhalation and exposure to the eye surfaces. In this embodiment, warmed air rises within each tube, driven by body heat or by at least one chemical warming system and is fed into eye protective glasses, goggles and the like.
In another embodiment, the distal portion of air tube(s) are incorporated into the torso garment or shirt or jacket neck or cowl. In another embodiment, at least one tube is able to elongate by way of a telescoping mechanism and design.
In yet another embodiment, contaminated air warmed and decontaminated by the body clothed or covered by fabric incorporating at least one photosensitizer, rises passively due to the typical ambient temperature difference, proximate to the face of the wearer, for inhalation and facial protection.
In another embodiment, the fabric incorporating at least one photosensitizer is produced/manufactured/created by dipping or spraying the fabric in a formulation containing at least one photosensitizer, the formulation containing a liquid component that solubilizes at least one photosensitizer, which may further optionally contain binding agents or dispersing agents, other dyes, known in the fabric dyeing art. Pressure from 1 to 10 bar or greater is optionally applied using rollers, and/or steam pressure, and heat from room temperature to up to 140 degrees C. is optionally applied by way of a temperature controlled container or vat, or oven as can be performed in an adjustable manner by commercially available fabric dyeing machines and devices and equipment. Fabric speeds as it passes through the dyeing equipment can reach up to 300 meters/minute.
In antimicrobial and decontamination natural and/or synthetic fabric and textile embodiments, methylene blue, riboflavin, at least one other photosensitizer, excipients that improve or enhance photosensitizer function, other types of known fabric dyes and coloring agents, binders, and other substances used to help with dye incorporation into fabric, disperse dyes, antimicrobial agents such as metals including silver, copper and the like, antibiotics of all classes used to combat infections and the like, are combined individually or in any combination with known and commercially available “wash-in” or spray applied water repellents including brands such as Nikwax, Gear Aid Wash-in, Revivex, 303 Fabric Guard, Nanoman water repellent, various silicone formulations, fluorocarbon/fluoropolymer/fluorochemical/formulations, wax formulations, and the like. In any case, the water repellent substances are combined with other agents/substances listed above with antimicrobial and decontaminating properties for incorporation into textiles and fabrics.
For example, in one or more embodiments, a formulation of commercially available Nikwax combined with 0.001 to 1% methylene blue in aqueous or powder form can be sprayed, wiped, sponged, or otherwise applied using any of the known fabric dyeing techniques onto fabrics or textiles, and/or added to a washing machine or liquid agitator container for adding or renewing water repellency to fabrics and textiles, along with incorporation of antimicrobial and decontaminating substances.
In another embodiment, a fabric, which may be woven or non-woven, breathable, or non-breathable, is fashioned from fibers, yarns, threads, and the like, dyed with at least one photosensitizer, is subsequently sprayed with a water repellent formulation also incorporating at least one photosensitizer, essentially locking in the photosensitizer already in the fabric substance. A feature of this embodiment renders the fabric more resistant to photosensitizer leaching from the fabric layer during washing of the fabric and reduces fiber loss from the fabric itself from washing or abrasion of the fabric. The added photosensitizer in the outermost water repellent layer which is washed-in or sprayed, or applied with a wipe or sponge, or a squeegee, to the dyed fabric also reduces the impact of photobleaching due to the added concentration and volume of photosensitizer in the fabric/water repellent construct. In another embodiment, the construction of the fabric in its entirety is manufactured using 3-d printing processes known in the art.
In another embodiment, the fabric is manufactured with a pattern of small optically clear polymeric discs, 0.1-10 millimeters in diameter, which may act as a lens, or optical diffuser, spaced apart, spaced intermittently, at 3 to 50 millimeter intervals, in a grid pattern, which serve to admit and disperse light to the underside of the fabric when worn proximate to the skin, scalp, body surface, or body orifices. Transmitted light in this embodiment can photoactivate at least one photosensitizer previously applied to the skin surface, body surface, scalp, or body orifices, hair, lips, face, eyes, and the like, or to the underside of the fabric incorporating at least one photosensitizer.
In another embodiment, dark or very low light level photoactivation of at least one photosensitizer is enabled by various combinations of the known classes of photosensitizers, in different or various concentrations, with or without excipients and substances that improve or enhance photosensitizer function.
For example, in one or more embodiments, 0.001 to 1% methylene blue in powder or aqueous formulation is optionally combined with any other photosensitizers in similar concentrations, with or without reducing agents such as ascorbic acid, with or without oxidizing agents and the like.
In another embodiment, layers of dyed or otherwise treated antimicrobial and decontaminating fabrics, polymeric filters natural or synthetic, supporting layers of materials, providing some degree of rigidity or reducing multilayer fabric deformation are bonded together using known dental adhesives and dental curing agents, epoxies, and resins, known dermal bonding agents and adhesives, such as commercially available Mastisol, Dermabond, other benzoin derivatives, cyanoacrylates, some of which rely on light illumination as a curing mechanism. In another embodiment, the known bonding agents, dental adhesives and dental curing agents, epoxies, and resins, some of which rely on light illumination as a curing mechanism, are combined with at least one photosensitizer, dyeing agents, or other excipients and substances listed above. The bonding pattern can encompass the entire fabric or other layer surfaces, or be applied in a spot pattern.
In another embodiment, drapes, fabrics, films and the like, with embedded photosensitizer(s) can be used as a liner or cover, enabling non-contact decontamination and prevention of contamination by a non-adherent fabric or film, by singlet oxygen and other reactive oxygen species diffusing into air proximate to the object to be protected by the drapes, fabrics, films. In another embodiment, synthetic polymers or natural fibers and the like incorporating at least one photosensitizer are fashioned into gloves with the option of applying water repellent containing at least one photosensitizer to the material before or after shaping or creating the glove construct.
A riboflavin/high molecular weight hyaluronic acid formulation is rapidly applied to the skin surface using a sponge swab or roller or brush, wherein the handle contains at least one photosensitizer. A sponge swab or a roller with a hollow handle is also used to apply at least one photosensitizer to the external surface of protective fabric of the suit.
Laboratory testing is utilized to determine and optimize at least one photosensitizer concentration and formulation which is incorporated in a protective fabric or film, or sprayed or applied by swabbing or brushing on the protective fabric, which is maximally protective against a range of pathogens, toxins, poisons, and radiation particles. Laboratory testing may use various types of known analytic methods, techniques, equipment, such as, but not exclusively, Raman spectroscopy, mass spectrometry, chromatography, and the like to characterize the uptake of at least one photosensitizer into and onto the protective fabric, followed by inactivation testing using known toxins and poisons or surrogates, and pathogen killing using known pathogens or surrogates, in vitro and in vivo, and optional chemical testing for reactive species. Known photobleaching, abrasion testing, laundering and drying, as non-exclusive tests are also performed in order to characterize protective capabilities during simulated use, and in field and actual use, which helps to optimize photosensitizer application and incorporation parameters, as well as optimize inclusion of other protective substances into and onto the fabric.
Utilizing known laboratory testing techniques, at least one photosensitizer and at least one quenching agent are tested on skin surfaces, and on internal organs to determine the optimum formulations for normal tissue protection against ionizing radiation.
A dirty bomb explosion or accidental radiation release event occurs in a combat zone or in an urban setting. Upon detection of the event, countermeasures are deployed consisting of launching of multiple photosensitizer containing canisters, which after launching to a pre-determined height and distance, rapidly release the photoactive droplets into the air. The radioactive particles emit radiation as they decay, activating the photosensitizer molecules which in turn generates singlet oxygen and other reactive oxygen species, which are rapidly quenched, in essence neutralizing the radioactive emission.
A quencher such as water vapor can also be deployed, followed by repeated deployments of photosensitizer droplets/aerosols in order to continue the decontamination process as needed. In addition, all surfaces, equipment, objects and the like can be sprayed repeatedly with the photosensitizer solution with optional repeated quenching using water solutions as an example, to achieve decontamination.
Additional decontamination can be accomplished by using a fan or filter incorporating a light source which employs a photosensitizer that decontaminates air proximate to persons. A decontamination photosensitizer can be applied to fabric, clothing, materials, worn or used by persons as well. Breathable nets or screens or nonbreathable films incorporating photosensitizers can be deployed surrounding persons and equipment that require protections as well. A non-toxic formulation of riboflavin and high molecular weight hyaluronic acid can be used on the skin for decontamination purposes in addition.
In a series of laboratory-based experiments and studies, a variety of photosensitizers and quenching agents are tested in varying concentrations and dispersed into the air, and sprayed or otherwise applied to surfaces and equipment, in order to ascertain optimal speed, volume, timing, and droplet/aerosol diameter, in relationship to air movement and humidity. Neutralization of surrogate pathogens and contaminants released into the air can used in air chamber experiments, in vivo and in vitro to determine optimal formulations and release and dispersal modes and equipment used for environmental dispersal.
In another embodiment, at least one photosensitizer or photosensitizer combination such as methylene blue, riboflavin, and the like are sprayed as an aqueous solution or as a powder to an activated charcoal/carbon powder or coating, in order to combine the effect of pathogen/toxin/volatile organic compounds (VOC)/malodorous substances and the like, capture by activated charcoal/carbon with the photoactivation decontaminating/neutralizing effect of at least one photosensitizer. The activated charcoal/carbon is prepared by known methods including heating, oxidation, using known chemical activators, and the like, with pore sizes ranging from 1 nanometer to 5000 nanometers, and a surface area of 200 to 8000 meters squared per gram, prepared using known methods as a powder, as granules, in pellet form, from wood, coal, peat, olive pits, peach pits, corn cobs, bamboo, rice hulls, soybean hulls, leaves of various sorts, nutshells, and the like. The combination of activated charcoal/carbon and at least one photosensitizer is tested in the laboratory and in field testing environments to optimize the ratio of activated charcoal/carbon concentration and particle size to photosensitizer concentration, in terms of speed and completeness of decontamination and photosensitizer photobleaching rates, and pathogen or toxin capture or VOC absorption by the activated charcoal formulation.
In one embodiment, the combination of at least one photosensitizer and the activated charcoal/carbon formulation is applied as a spray, using a wipe, a sponge, or a roller, and the like, to a fabric, filter material for air or liquids, a suit, a surface, a face cover, a helmet, equipment, and any surface in need of a protective feature. In another embodiment the non-toxic photosensitizer, such as but not limited to riboflavin/activated charcoal/carbon formulation is applied to the skin surface, a mucous membrane surface, or ingested. In another embodiment, the activated charcoal/carbon and photosensitizer formulation are embedded in fibers using known methods. In all cases, the photosensitizer can optionally be activated by a light source in order to kill, inactivated, or decontaminate pathogens and toxins, VOC and the like, that are absorbed by the activated charcoal/carbon formulation, by photoactivation, or activation using ultrasound, microwave, ionizing radiation, or by direct chemical interaction.
In one experiment, a nylon/cotton blend material with a weight of 5.87 oz per square yard was dyed with 1% methylene blue in an aqueous solution, at a sublimation temperature of 121 degrees C. temperature, yielding a pickup of 70%. Tested fabric samples incorporated a range of 0.02-0.06 gm of methylene blue per square yard.
In another experiment, a 1% methylene blue solution was brought to a boil, at 100 degrees C., removed from heat and the nylon/cotton fabric soaked for 60 min. Methylene blue was incorporated into the fabric in a range of 0.01-0.07 gm of methylene blue per square yard.
In more experiments, nylon/cotton fabric was sublimated at 205 degrees C.) for 40 seconds, and in yet another experiment, a jet dye cycle involving agitation at 140 degrees C. and a pressure of 2 bar for 60 min yielded a similar range, of 0.01-0.07 gm of methylene blue per square yard.
This application is a Utility Patent application based on previously filed U.S. Provisional Patent Application No. 63/397,321, filed on Aug. 11, 2022, and U.S. Provisional Patent Application No. 63/398,796, filed on Aug. 17, 2022, and U.S. Provisional Patent Application No. 63/441,139, filed on Jan. 25, 2023, and U.S. Provisional Patent Application No. 63/463,437, filed on May 2, 2023, and U.S. Provisional Patent Application No. 63/523,596, filed on Jun. 27, 2023, and U.S. Provisional Patent Application No. 63/525,312, filed on Jul. 6, 2023, the benefit of the filing dates of which is hereby claimed under 35 U.S.C. § 119(e) and the contents of these provisional applications is herein incorporated by reference in their entirety.
| Number | Date | Country | |
|---|---|---|---|
| 63397321 | Aug 2022 | US | |
| 63398796 | Aug 2022 | US | |
| 63441139 | Jan 2023 | US | |
| 63463437 | May 2023 | US | |
| 63523596 | Jun 2023 | US | |
| 63525312 | Jul 2023 | US |
