Synthetic, multifaceted halogenated, functionalized fullerenes engineered for microbicidal effects employing controlled contact for safe therapeutic and environmental utility

Abstract

The present invention relates to a bioactive or real-time and pathogen killing material comprised of a carbon nanostructure (preferably a fullerene but including other functionalized carbon-based nanostructures) that possess potent broad-spectrum antimicrobial properties. The present invention relates to the utilization of functionalized carbon nanostructures as a bioactive antimicrobial substance that is incorporated into a material, including a textile, fabric, solution, salve, or cream. The preferred embodiment of the present invention is fullerene derivatives that are chemically functionalized on the cage with a halogen element. The present invention pertains to a material that is suitable for barrier garments, accessory garments (shoe covers, masks, facial visors, etc.), textiles (bed sheets, blankets, towels, personal clothing, gowns, surgical drapes, curtains, drapes, pads, etc.), filtration matrices (for use in hemodialysis, hemofiltration, etc.), or aerosolized solutions, sprays, liquids, salves, or creams. The present invention further relates to a production method thereof.

Claims

1. A textile comprising (i) a hydrophilic fabric; and (ii) a carbon nanomaterial antimicrobial agent impregnated therein, wherein the carbon nanomaterial antimicrobial agent consists of a spherical halofullerene having the structure C.sub.2n whereby n=12, 13, 14, 15, . . . , 360 with halogen side chains attached to the carbon cage, wherein the carbon nanomaterial precludes proliferation of, inhibits growth of, or destroys a microorganism in biological, non-biological, or physiological fluids.

2. The textile according to claim 1, wherein the textile causes pathogen destruction is ex vivo.

3. The textile according to claim 1, further comprising a coating selected from the group consisting of polymers or copolymers of: acrylic acid (PAA), polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), polyethylene oxide (PEO), methacrylic acid (PMA), itaconic acid (PIA), propylene oxide and ethylene oxide [P(EO/PO)], maleic acid (PLA), 3-butene-1,2,3-tricarboxylic acid (PBA), and combinations thereof.

4. The textile according to claim 1, wherein the hydrophilic fabric is selected from the group consisting of cotton, wool, linen, silk, nylon, and blends thereof.

5. The textile according to claim 1, wherein the spherical halofullerene is a C.sub.60 halofullerene.

6. The textile according to claim 5, wherein the spherical halofullerene has the formula C.sub.60X.sub.6, C.sub.60X.sub.8, or C.sub.60X.sub.24, wherein X is a halogen selected from iodine, bromine, chlorine, and fluorine.

7. The textile according to claim 1, which is in the form of a garment.

8. The textile according to claim 7, wherein the garment is selected from the group consisting of gowns, shirts, gloves, masks, shoe covers, and clothing.

9. The textile according to claim 1, wherein the textile is selected from the group consisting of sheets, table covers, linens, pads, drapes, towels, dressings, and bedding material.

Description

BRIEF DESCRIPTION OF SEVERAL VIEWS OF THE DRAWING

(1) FIG. 1A is a side cross sectional view of a typical hydrophobic article and FIG. 1B is a cross sectional view of ultra-hydrophilic coated article according to an embodiment of this invention, wherein a thin hydrophilic coating is applied to the article.

(2) FIG. 2 represents a cross sectional view of a hydrophilic coating and illustrates the phenomenon of capillary action acting upon microscopic voids in a hydrophilic surface, wherein a liquid droplet would be drawn into and contained.

(3) FIG. 3A and FIG. 3B represent a cross sectional view of functionalized halofullerenes application to the hydrophilic coating surface. FIG. 3A illustrates the relaxed void at an increased temperature when halofullerenes would be applied. FIG. 3B illustrates the undeformed void after cooling to ambient temperature and entrapping the halofullerenes within.

(4) FIG. 4A, FIG. 4B, and FIG. 4C are molecular representations of an exemplary fullerene derivative (FD) of 60 carbons functionalized with 4, 8, or 24 halogens (X).

(5) FIG. 5 is a flow-chart detailing the process of imbuing fabric material with hydrophilic coating and halofullerenes.

(6) FIG. 6 illustrates a plan view of proposed quality control measures in a personal protection garment embodiment of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

(7) For the purpose of invention, the term pathogen describes microorganisms including, but not limited to, bacteria, protozoa, viruses, molds, yeasts, fungi and the like. The term antimicrobial is intended to convey the propensity to inhibit, prevent, or destroy a pathogen, as well as preclude proliferation and growth of a microorganism.

(8) From an infectious disease outlook, pathogens are transmitted through contagion and require a host organism to survive and proliferate. Similarly, pathogens are unable to survive numerous antimicrobial processes. Most pathogens are highly aqueous in nature and airborne pathogens can remain active and viable outside of the host, however the organisms are not shielded or protected in the gas form and are especially vulnerable. These lightweight particles can linger or diffuse in the air for different periods of time, largely dictated by temperature and humidity. These characteristics of a pathogen enable airborne transfer, however their vulnerability outside of the hosts represents an opportunistic method for elimination with a bioactive and functional antimicrobial article.

(9) Briefly, the proposed invention is to impregnate an article with halofullerenes or use the particles in a controlled and inescapable manner, therapeutically. The antimicrobial potency of the fullerene and linked halogen molecule(s) coupled with the regenerative nature of the fullerene renders the article an inexhaustible pathogen killing magnet upon contact. Secondarily, the article is coated with an ultra-hydrophilic polymer that synthetically creates molecular space that attracts and adsorbs water or moisture (moisture rich microbe). Microscopic hydrophilic voids are shaped to attract and retain water (until evaporation). The hydrophilic polymer coated article would draw pathogenic materials towards the article and into the surface voids, which are imbued with an abundance of spatially trapped FD. Once a pathogen contacts the garment it is immediately pulled into the cavities that are loaded with antimicrobial FDs. Within these voids the aqueous pathogenic material would surface contact a concentration of FDs that stimulate pathogen death in rapid succession. In this embodiment, the pathogen is subjected to three lethal forces at the atomic level: inescapable hydrophilic energy, electron exchange and caustic halogen.

(10) The proposed article material may be comprised of hydrophilic fabrics such as cotton, wool, linen, silk, nylon blends, and blends thereof and sometimes liquids. The article is further subject to an ultra-hydrophilic polymer coating that is polymeric and has elastomeric characteristics reactive to specific temperature gradations. The ultra-hydrophilic polymer coating is comprised of polymers or copolymers of: acrylic acid (PAA), polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), polyethylene oxide (PEO), methacrylic acid (PMA), itaconic acid (PIA), propylene oxide and ethylene oxide [P(EO/PO)], maleic acid (PLA) and 3-butene-1,2,3-tricarboxylic acid (PBA), or combinations thereof. An additional aspect of the proposed invention is to make the article rugged and enduring in a demanding environment without losing the antimicrobial properties. This includes routine washing and drying without harm to the hydrophilic properties of the article or dissociation of the FDs from the article. Thus article design must ensure that the FDs do not fall out of the voids or are not destroyed by laundering. As such, the initial coating of the article would be performed at a relatively high temperature (65.5 C.) such that the initial dried state of the hydrophilic coating is slightly larger than at cooler temperatures (i.e: room temperature). Thus, the hydrophilic void diameter is slightly smaller than the original normo-thermic at the coating step. Additionally, the hydrophilic voids are filled with FDs. After inclusion of FDs, the article is gradually cooled to a low temperature (0 C.), thereby shrinking the polymer, yet increasing the void volume. Upon air drying of the material, using a dehumidifying process, the temperature can be slowly raised to ordinary room temperatures without material deformation. The polymers expand and void space decreases and consequently the FDs are trapped inside of the void. The halogen sidechains of the fullerene cage act in a cross-hatching feature better trapping the bonded FDs inside of the article cavities.

(11) The entire process renders the garment polymeric and resistance to soiling and capable of routine and easy washing without loss or escape of impregnated FDs. The primary hydrophilic nature of the article remains the predominate feature, even though microscopically the fibers are coated with a polymer resistant to staining or soiling.

(12) In one embodiment, the present invention provides a method of manufacturing a protective antimicrobial article, that is a garment for wear routine wear. Examples of this embodiment include PPE, apparel, and accessory garments, including, but are not limited to gowns, shirts, gloves, masks, shoe covers, and other types of clothing material. Alternatively, in another embodiment, the antimicrobial coating composition is usable in a wide variety of textiles. Such textiles include, but are not limited to, sheets, table covers, linens, pads, drapes, towels, dressings, bedding material and other upholstered structures common to healthcare, household, travel, and hotel settings.

(13) Contemporary PPE and textiles are hydrophobic and do not absorb moisture, as such the material functions as a moisture repellent. The nature of hydrophobic articles provides barrier protection but imparts little direct benefit for the control of pathogen elimination or transmissibility. As shown in FIG. 1A, the contact angle (8) of a liquid droplet (1) on a surface (2) is shown, this relationship is directly associated to the physical properties of the material. Whereby, a hydrophobic surface (2) has contact angle (8) with water that is greater than 90 (3). Upon contact with a droplet (1), hydrophobic articles function to repel the droplet (and pathogenic material contained inside the aqueous suspension) such that the liquid is not adsorbed into the material (2). These hydrophobic interactions illustrate a possible mechanism for transference of viable pathogenic material by allowing continued transference throughout the environment.

(14) As shown in FIG. 1B, the conventional definition for a hydrophilic surface (4) is described as the surface-water contact angle (8) being less than 90 (5). In this proposed patent a hydrophilic article is coated with an elastomeric ultra-hydrophilic polymer (4) that enhances the adsorption of aqueous material (1) into the article. This affinity with water functions to reduce the likelihood of transference of pathogen from the article to another surface.

(15) Intermolecular forces mediate the interaction between molecules. Such forces are observable at the macroscopic level and associated with the bulk properties of material. When liquid contacts a surface, the strength of the adhesive and cohesive forces imparted on the liquid via the surface will define the shape of the liquid. As shown in FIG. 2, if adhesive forces are dominant, the liquid (1) will be pulled into the ultra-hydrophilic surface (4), whereas when cohesive forces prevail, adhesion is resisted, and the shape of the liquid is retained on the surface (as seen FIG. 1A).

(16) Capillary action is defined as one substance's ability to draw a liquid inward. The upward and downward movement of liquid on a substrate is directly related to intermolecular forces, surface tension and contact angle, which is observable in nature. Shorebirds capture water between their upper and lower mandibles; however due to the geometry of their long beak and the opposing gravitational force, suction does not transport the droplets inward (towards the mouth). Still, by repeatably opening and closing their beak, the shorebird transfers the droplets inward toward their mouth. While surface tension plays a role in the process, the physical mechanisms responsible for the droplet transport are characterized by the spontaneous movement of a droplet on a shorebird's beak associated with hydrophilic surfaces of the beak and the contact angle of the interaction; a phenomenon coined a capillary ratchet.

(17) As shown in FIG. 2, the application of hydrophilic coatings across a material creates irregularities, cavities, void spaces, and patterns across the surface (6). This geometric manipulation (or hydrophilic functionalization) of the article's surface will influence the behavior and properties of the material, altering the material's structure, surface area and energy, and enhancing capillary motion. On a hydrophilic surface the contact angle (8) is less than 90-degrees (5) and results in wetting. As the droplet is drawn inward (7, indicated by the arrow in FIG. 2.) the v-shaped cavities (6), created by the hydrophilic coating (4) function as a capillary tube. In the proposed invention, the entire article surface is coated with an ultra-hydrophilic polymer (4), creating a ubiquitous pattern of cavities (6) dispersed throughout the material that facilitates inward movement of aqueous droplets (7).

(18) As shown in FIG. 3A, the application of an elastomeric hydrophilic polymer (4) at an elevated temperature (between 55.0 C.-75.0 C.) will result in spontaneous formation of cavities (6) across the article. As shown in FIG. 3A, at higher temperatures, the formed cavities (6) are relaxed, possessing a larger size or diameter compared to ambient temperatures. While temperatures are elevated and the voids regions are stretched, each cavity (6) can be imbued with a plurality of materials with antimicrobial functionalities. In the present invention, these regions are filled with an abundance of antimicrobial FD (8).

(19) Fullerenes are capable of functionalization via numerous chemical reactions. In the present invention a halogen FD, or halofullerenes, represents a fullerene of C.sub.2n, whereby n=10, 12, 13, 14, 15, . . . , 360, that contains multiple side-chains halogens attached to the carbon cage. As shown in FIG. 4A-C, a C.sub.60 fullerene is functionalized with a halogen molecule. Three typical functionalization patterns for a C.sub.60 halofullerene include: C.sub.60X.sub.6 (FIG. 4A), C.sub.60X.sub.8 (FIG. 4B), and C.sub.60X.sub.24 (FIG. 4C); whereby X=a halogen molecule (i.e.: iodine, bromine, chlorine and fluorine). The halofullerene has molecular affinity towards and attraction of pathogenic species and functionalization with highly antimicrobial halogens that caustically kill a microbe instantaneously, without losing any energy, virulence or the ability to maintain a continuous antimicrobial capability.

(20) The use of halogenated fullerenes in the proposed invention is preferable because of the antimicrobial nature of the fullerene and halogen, as well as the incompressible properties of the fullerene. As related to this invention, the FD will occupy the void space in the coated material. At elevated temperatures the article is relaxed by the heat, creating a larger cavity region that can accept greater volumes of FD than a similar material at cool or ambient temperatures. The FD is loaded into the relaxed voids at increased temperatures and after cooling these recesses constrict, trapping the FD into the material.

(21) As shown in FIG. 3B, after FD (8) application the article is gradually cooled, between 0.0 C.-5.0 C., to contract the relaxed cavities (9), affixing the FD contents. The FD (8) are held in space inside the cavities (6) due to shrinkage of the cavity from slowly decreasing the ambient temperature. The FD is permanently held inside the cavity after surrounding temperatures are dropped and the material is returned to an inactive memory state. The undeformed natural material shape contracts around the FD and the projecting halogenated side chains interweave or entangle with each other, locking the FD into the void. Notably, while material constricts at cooler temperatures, the fullerenes themselves are not compressible and do not change shape or structural confirmation. The incompressible nature and large negative space of the fullerene (empty inner cage), allows for the region to accept external aqueous material via capillary action, as the packed fullerenes do not occupy space, topographically.

(22) Upon contact with the article in this invention, microscopic void spaces or cavities (6) created by the hydrophilic coating draw the aqueous material containing pathogens inward via capillary action, the movement of water (7) is indicated by the arrow in FIG. 2. Upon capillary uptake, as shown in FIG. 3, the pathogenic material is localized to void regions (6) that are densely packed with the halogen FD (FIGS. 4A, 4B and 4C), establishing a caustic microenvironment that exerts a broad-spectrum antimicrobial effect on the adsorbs pathogenic material.

(23) The method for preparing a composition comprising of an antimicrobial FD (halofullerene) is shown in FIG. 5 and includes: coating a hydrophilic fabric material with an elastomeric ultra-hydrophilic polymer at an elevated temperature (between 55.0 C.-75.0 C.); filling the relaxed cavities or void spaces of the heated elastomeric ultra-hydrophilic polymer coated article with FDs; cooling the article (between to 0.0 C.-5.0 C.); and gradually air drying and dehumidifying the coated and imbued FD containing article to room temperature.

(24) A quality control technique (easy and visible) must be incorporated to verify that the fullerenes did not disassociate from the material. As such, one or multiple regions of the article (9) may be filled with magnetic endohedral fullerenes of similar size as a quality control mechanism (10), as shown in FIG. 6. The magnetic endohedral fullerene would be comprised of a ferrimagnetic material (i.e.: iron) inside of the cage or functionalized on the outer shell of the fullerene. These coated regions would enable direct end-user determination of antimicrobial FD coating by applying a small magnetic wafer or disc (11) to the region that would be held on the surface to indicate the presence of the magnetic nanomaterials in the article. The absence of magnetism in the region would convey that the FD impregnated cavities of the material were no longer filled. Additionally several magnetic endohedral fullerene doped spots can be decorated throughout the fabric.

(25) In another embodiment, the FD coated material can be formed into an article as described above and introduced into a canister or cartridge as a bioactive, antimicrobial filter membrane. The surface of the filter article is modified with halogen functionalized FD in a process described above. Briefly, blood would flow into the antimicrobial cartridge using traditional hemodialysis methods. The blood is passed through sidewalls radially into a funnel composed of the FD modified article, before exiting through an outlet at the top of the cartridge or cannister. The antimicrobial capacity of the cartridge is linked to the high surface area of the filter membrane and FD that would be presented to the circulating blood. Specifically, free-floating pathogens would contact the caustic halogen functionalized on the cage of the fullerene resulting in pathogen destruction, mechanistically as described above. The hemofiltration cartridge, canister, column or funnel would interact with and kill circulating pathogenic material and pathogenic material associated with or bound to cellular material. The bioactive halogen FD filter would confer antimicrobial activity to pathogens in the blood, however the configuration does not function to remove, filter or separate destroyed pathogenic material. Similarly, the FDs would be retained or affixed to the membrane and not dispersed into the incoming blood or subsequently distributed systemically to the host.

(26) In another embodiment, a saline based fluid comprised of halogen functionalized FD is used as a lavage or irrigation fluid that would exert an antimicrobial effect on pathogenic material contained in the region. The desired region of irrigation would be rinsed with the FD containing solution and then followed by a saline rinse to ensure that all particles were evacuated from the region. In a similar embodiment, a FD containing nasal spray, sinus rinse, or mouthwash could be administered by the user as an antimicrobial solution. In yet a similar embodiment, a FD salve could be applied to the external tissue regions of the mouth, nose, or other regions of the body as a bioactive barrier or used for wound healing applications. Alternatively, a FD-based mist, solution, salve, cream, or carrier would be suitable for application onto or into any region that would not result in systemic distribution of the nanomaterial in the user. Examples include a lung saline rinse rich in FD (rinse and remove), sinus cavity rinse (rinse and remove), synovial joint space rinse (rinse and remove). Encompassing the pleura, the lungs, the pericardium, the heart, the peritoneum, and the digestive organs (for treatment of bacterium like Clostridioides difficile). Other closed organs treatable with irrigation include the uterus, bladder and urethra. Additional applications include the eye orbital space when infections are untreatable due to the lack of circulation and lastly, as a mouth and throat gargle and rinse