WO2013176755A1

WO2013176755A1 - Environmental textile with hygiene sensor

Info

Publication number: WO2013176755A1
Application number: PCT/US2013/031579
Authority: WO
Inventors: Mitchell C. Sanders; Jennifer M. Havard; Martin A. JENSEN
Original assignee: Eci Biotech, Inc.
Priority date: 2012-05-22
Filing date: 2013-03-14
Publication date: 2013-11-28
Also published as: EP2852703A1; AU2013266849A1

Abstract

The invention provides, inter alia, environmental textiles (such as sponges and wipes), with an associated labile color indicator (e.g. a releasable or modifiable dye), which, with use, indicates a loss of hygiene and/or useful life. The invention also provides methods of making and using these textiles.

Description

ENVIRONMENTAL TEXTILE WITH HYGIENE SENSOR

RELATED APPLICATION

This application claims the benefit of U.S. Provisional Application No. 61/650,432, filed on May 22, 2012. The entire teachings of the above application are incorporated herein by reference.

BACKGROUND OF THE INVENTION

Sponges and wipes are often used to clean surfaces for food preparation and cleaning of surfaces in the home and in professional care (most notably health care and food service industries). The problem with sponges and wipes and any textile surface cleaning cloth that is reused is that they are often not properly disinfected before and after use. Without proper cleaning of the textile material after use, the bacterial bio-burden can be quite significant. In as little as eight hours without proper cleaning, a sponge or wipe can contain greater that one million bacteria per square centimeter.

For good hygienic practices, it is recommended that wipes only be used for 24 hours and sponges should only be used for up to a week with proper cleaning before and after each use. The difficulty in maintaining better cleanliness and hygiene is to throw out these materials properly when they have reached the end of their usefulness rather than to spread bacteria and viruses over surfaces that are presumed clean. Accordingly, a need exists for environmental textiles (e.g., sponges and wipes) that can be readily monitored for good hygienic practices.

SUMMARY OF THE INVENTION

The invention provides environmental textiles that can be readily monitored for good hygienic practices. We have developed an innovative hygiene sensor that changes color over time in the presence of, e.g. , common dish detergents and indicates when the wipe, sponge or other textile material should be thrown away. The present invention provides, inter alia, detergent sensitive reactive groups and linking molecules such as BSOCOES, Diels- Alder containing compounds, and ion exchange functional groups to release dyes from the surface of textiles when the material is no longer considered hygienic and/or has been used beyond its useful life. In certain embodiments, the dye used in the textile can be sensitive to the bacterial bioburden, whereby the dye or pattern of dye decolorizes in the presence of bacteria. Thus, the hygiene sensor measures not only the useful life, but also the amount or level of bacteria in a biofilm on the surface at a certain threshold which is not hygienic.

Accordingly, in a first aspect, the invention provides an environmental textile comprising a visually detectable labile color indicator, where the labile color indicator is labile under conditions of use, and where the release of the labile color indicator indicates that the product is no longer hygienic.

In some embodiments, the labile color indicator is a food grade dye that is generally regarded as safe (GRAS) by the United States Food and Drug

Administration (U.S. F.D.A.). See, e.g., Sections 201 (s) and 409 of the Federal Food, Drug, and Cosmetic Act and 21 CFR 170.3 and 21 CFR 170.30.

In certain embodiments, the labile color indicator is covalently attached to the surface of the textile.

In some embodiments, the labile color indicator is non-covalently attached to the surface of the textile.

In certain embodiments, the lability of the labile color indicator is sensitive to time, temperature, level of detergent or bacterial bioburden, resulting in the release of the labile color indicator from the surface.

In some embodiments, the labile color indicator is released by an ionic interaction between a detergent and a cationic or anionic charged environmental textile.

In certain embodiments, the environmental textile comprises a functional group selected from a trimethylammonium, triethylaminoethyl, diethylaminoethy anchored group or other ion exchange charged group. In some embodiments, the labile color indicator is releasable by base hydrolysis with a detergent sensitive linker such as BSOCOES or a Diels- Alder containing compound.

In certain embodiments, the labile color indicator is associated with the textile via a silane linker, such as a silanol. In some particular embodiments, the silane linker is N-(2-aminoethyl)-3-aminosilanetriol.

In some embodiments, the labile color indicator is maleimide-functionalized.

In some embodiments, the labile color indicator is an azo dye or azo-linked dye cleavable by a bacterial extract. In certain embodiments, the textile further comprises an antibiotic agent select from an anti-viral agent, a fungicide, an antibacterial agent, or a combination thereof.

In some embodiments, the textile further comprises non-labile colorant, fragrance, lotion, cream, detergent, or a combination thereof. In certain embodiments, the labile color indicator comprises El 02, El 10,

El 33, or a combination thereof.

In some embodiments, about 40, 50, 60, 70, 80, 90, 91, 92, 93, 94, 95, 96, 97, 98, or 99% (e.g., at least about 70-90%), or more of the labile color indicator is releaseable following 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, or 30 wash cycles (e.g., about 7-13).

In some embodiments, about 40, 50, 60, 70, 80, 90, 91, 92, 93, 94, 95, 96, 97, 98, or 99% (e.g. at least about 70-90%) or more of the labile color indicator is releaseable following incubation of the textile with about 10⁴ to about 10⁷, or greater, cfu/mL of Pseudomonas aeruginosa, Escherichia coli, Staphylococcus aureus, Proteus mirabiiis, iEnterococcus faecalis, or combinations thereof, for 24 hours at 25°C or 37°C.

In another aspect, the invention provides methods of producing an environmental textile with an integral hygiene sensor. The methods entail associating a labile color indicator with the surface of a environmental textile. In more particular embodiments, the environmental textile is the textile of any one of the preceding aspects and embodiments. In more particular embodiments, the textile is functionalized by incubating the textile with a silanol-containing solution having a pH within about 3 to about 5, comprising about 0.1% to about 40% silanol in a solution about 90% to about 100% alcohol, balance aqueous solution, condensing the silane chemistry, and contacting the functionalized textile with a suitably functionalized labile color indicator.

In some embodiments, the labile color indicator is maleimide-functionalized.

In certain embodiments, the methods provided by the invention further include the step of removing any excess silanol-containing solution before condensing the silane chemistry.

In another aspect, the invention provides methods of cleaning a surface. These methods entail contacting the surface with an environmental textile according to any aspect or embodiment provided by the invention. In certain embodiments, the environmental textile is at least partially hydrated. In more particular embodiments, the environmental textile is at least partially hydrated with a detergent-containing solution.

In yet another aspect of the invention, are provided methods of using an environmental textile. The methods entail using any aspect or embodiment of the environmental textiles provided by the invention, and monitoring the visually detectable labile color indicator and, in time, disposing of the textile after the expiry of its useful life, as indicated by the visually detectable labile color indicator.

BRIEF DESCRIPTION OF THE DRAWINGS

The foregoing will be apparent from the following more particular description of example embodiments of the invention, as illustrated in the accompanying drawings in which like reference characters refer to the same parts throughout the different views. The drawings are not necessarily to scale, emphasis instead being placed upon illustrating embodiments of the present invention. The patent or application file contains at least one drawing executed in color. Copies of this patent or patent application publication with color drawings will be provided by the Office upon request and payment of the necessary fee.

FIGs. 1A-1B illustrate base sensitive dye release of Bis[2- (succinimidooxycarbonyloxy)ethyl]sulfone (BSOCOES), a base sensitive cross linker that was used to couple free amino groups to the surface. A three-step reaction was used, with all reactions performed in 10 mM sodium bicarbonate, pH 8.0: first was labeling BSOCOES with amino acids cysteine and glutamine, second the base sensitive linker BSOCOES labeled cysteine was attached to the dye using a custom maleimide derivative of erioglaucine, and third the heterobifunctional crosslinker PMPI, which reacts with hydroxyl groups on the surface of the textile and the primary amine of the glutamine, was used. The chemical structure of the erioglaucine malimide is provided in FIG. IB. The maleimide version of blue dye # 1 was conjugated to cysteine using a dye-to-cysteine molar ratio of 1 : 1 in phosphate buffer pH 7.2, for 3 hours at room temperature. The labeled cysteine was then removed from the unincorporated dye by washing the surface of the textile. The custom synthesis of this dye is challenging because it is difficult to prevent the maleimide group from forming multiple bonds to the sulfonate groups.

FIG. 2 shows another example of detergent sensitive release of a dye using a Diels-Alder containing compound. The incubation with dish soap has a mildly basic pH that, in combination with temperature, will cause the opening of the cyclic ring and the release of the blue dye molecule.

FIG. 3 illustrates wash-dependent release of dye molecules from a hygiene sensor. TMA is trimethylammonium anchored group. Other anionic or cationic compounds such as dimethylethanol ammonium (DMEA), sulfopropyl (SH) or carboxy (COOH) anchored groups can also be used. The weaker binding capacity of the functional group results in a shorter wash cycle required to release the dye from the textile.

FIGs. 4A-4B show photographs of hygiene sensor prototypes on sponges and wipes. On the left side (4 A) is a prototype for a wipe hygiene sensor that changes color in approximately 24 hours. On the right side (4B) is a sponge that has dye bound to the surface with a quaternary ammonium compound that releases the dye after approximately 5-7 days which is equivalent to 10 full loads of dishes washed with the sponge.

FIGs. 5A-5H show a time series of hygiene sensor decolorization: after repeated washes with soapy water used to simulate washing dishes. The sponge was washed for approximately 1 hour each time, resulting in the complete dissolution of the color from the surface.

FIGs. 6A-6B are graphical representations of embodiments provided by the invention.

FIG. 7 is a structure of an exemplary azo dye, yellow #6. The azo bond can be seen near the center of the molecule. Azoreductases catalyze the breakdown of nitrogen-nitrogen double bonds (also referred to as azo bonds). When the azo bond is broken the dye is no longer colored. Dyes are classified as azo dyes when they have at least one azo bond.

FIG. 8 shows experimental results of incubating two azo dyes with five common bacteria (P. aeruginosa, E. coli, S. aureus, P. mirabilis and E. faecalis) resulting in decolorization of the dyes. Also shown is Control (PBS + dye).

FIGs. 9A-9B show experimental results of a color change in a mixture of Yellow #5 (75%) and Blue #1 (25%), decolorized by S, aureus at 0 hours (9 A) and 24 hours (9B) at 37 °C.

FIG. 10 shows experimental results of additional color change reactions with S. aureus.

FIG. 11 shows different cationic ion exchange membranes useful in the present invention. Color change was observed after -48 hrs at 37°C in bacteria with 10⁷ CFU /ml initial bioburden.

FIGs. 12A-12B show azo dyes in a hydrogel matrix.

FIGs. 13A-13B show conjugation of a textile with N-(2-aminoethyl)-3- aminosilanetriol using a rapid condensation reaction. The reaction was driven to completion in under 1 minute using a concentrated solution of silane (20% (13 A) or 10%) (13B)) sprayed onto the surface for 30 seconds and dried with a heat gun at 350°F-500°F for 10-30 seconds prior to binding blue dye. FIGs. 14A-14C demonstrate Infrared (IR) Condensation of Silane Chemistry. The silane chemistry (N-(2-aminoethyl)-3-aminosilanetriol) can be coupled to textiles using a medium to high intensity IR light source. The samples shown were treated with a 6400 Watt (or greater) light source running at 84 linear feet per minute. After drying, the textile retained the eriogluacine (blue dye #1)

demonstrating that that the chemistry is covalently attached to the surface (14 A). Instead of labeling the entire surface, the dye can be printed in a line or any pattern (14B). Unlabeled textile wipes do not retain the blue dye after washing briefly (1-10 seconds) with water (14C). DETAILED DESCRIPTION OF THE INVENTION

A description of example embodiments of the invention follows.

The invention provides environmental textiles (such as sponges and wipes) with associated hygiene sensors comprising labile color indicators, e.g., in some embodiments, via labile (detergent sensitive) linkers.

"Environmental textile" refers to traditional woven fabrics as well as and non- woven fabrics and preparations, including sponges (both natural and synthetic) or paper towels suitable for surface cleaning. The fabric can include natural fibers, such as those comprising cotton, linen, wool, silk, cellulose, sea sponge or paper; or synthetic fibers, comprising polyester, nylon, rayon, polyurethane, spandex, and the like; as well as blends of natural and synthetic fibers. In particular embodiments, the environmental textile is a sponge or wipe. In particular embodiments, natural sponges comprise sea sponge, silk, wool, or cellulose; synthetic sponges may comprise non woven fibers, e.g., polyurethane. In certain embodiments, the environmental textile contains free hydroxyl groups, e.g. , on the surface of the textile.

"Labile color indicator" is a visually detectable compound, such as a dye, associated with an environmental textile of the invention, which is at least partially modified, e.g., partially released from the environmental textile under conditions of use, such as time, temperature, level of detergent and/or microbial bioburden, such as bacterial bioburden, resulting in a change or loss of color, thereby indicating use and loss of hygiene. The labile color indicator may be associated with the surface of the environmental textile directly (by either covalent or non-covalent interactions), or, optionally, may be associated with the surface of the environmental textile through one or more linker molecules. The one or more linker molecules associate the labile color indicator with the surface of the environmental textile by covalent or non-covalent interactions or a combination thereof (e.g., by covalent association with the environmental textile and non-covalent association with the labile color indicator, or vice versa). Of course, the labile color indicator need not only be associated with the surface of the environmental textile. In certain embodiments, it is also impregnated throughout the entire thickness of the environmental textile. The labile color indicator may be applied to substantially the entire surface of the environmental textile, or about e.g., 1, 2, 3, 4, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 95, 96, 97, 98, 99, or 100% of the surface of the environmental textile. In some embodiments, the labile color indicator is not associated with the surface, but is visually detectable, e.g., where the nature of the textile permits visual detection of a color loss or change below the surface.

In some embodiments, the labile color indicator is a small area indicator, such as a circle, square, line or other geometric feature, as well as other images including one or more spots, designs (e.g. graphical design or otherwise fanciful figures and/or patterns, such as smiley faces, et cetera). In other embodiments, the labile color indicator remains partially associated with the environmental textile, but is partially released, e.g., part of the labile color indicator is cleaved or otherwise released under conditions of use, thereby showing a loss or change in color.

Suitable linking molecules include covalent linkers such as BSOCOES or a Diels-Alder containing compound, or non-covalent ionic interactions between a dye and an anchored ion-exchange molecule (either anionic or cationic) in the textile, such as trimethylammonium (TMA), dimethylethanol ammonium (DMEA), sulfopropyl (SP), or carboxy (COOH) anchored groups. A "Diels-Alder containing compound" is a molecule capable of undergoing an intramolecular retro Diels-Alder reaction. In certain embodiments, textiles are coupled with silane reactive chemistry (R-(CH₂)n-Si-X₃) using, for example, the free hydroxyl groups on or within the textiles (e.g. on the textile surface), where X is a hydrolyzable group, such as alkoxy, acyloxy, halogen, or amine, and where n is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or more, and in particular embodiments where n is 1. The reactive silane linkers can have a plethora of functional R-groups that mimic BSOCOES, Diels- Alder cyclic rings, and ion exchange functional groups (such as trimethylammonium (TMA), dimethylethanol ammonium (DMEA), diethylaminoethyl (DEAE), Quaternary aminoethyl ammonium (QAE), sulfopropyl (SP), or carboxy (COOH) anchored groups) that are detergent sensitive.

The silanol chemical reaction on the textile can be broken down into 5 steps: hydrolysis, condensation, hydrogen bonding, bond formation, and dye binding as described by B. Arkeles, "Tailoring Surfaces with Silanes" (CHEMTECH, 7, 766, 1977), which is incorporated by reference in its entirety. Using conventional means, this process takes from several hours to overnight. By the advantageous methods provided by the invention, the complete chemical reaction can be done in less than 10 minutes (e.g. less than 9, 8, 7, 6, 5, 4, 3, 2, or 1 minutes, e.g. about 60, 50, 40, 30, 20, 10 seconds, or less) allowing for high speed printing of textiles.

In the present invention, the silane compound hydrolysis occurs prior to printing on the wipe, in some embodiments, of a 95% ethanol/ 5% water solution at pH in a range of about 3 to about 5. By conventional methods, condensation and hydrogen bonding normally takes approximately 2 hours to overnight to perform. In the methods provided by the invention, this time has been reduced, in some embodiments, to about 30 seconds using a concentration of silane chemistry of less than about 40% (e.g. , about 40, 35, 30, 25, 20, 15, 10, 9, 8, 7, 6 or 5 % (W/V), or less), e.g., from about 1% to about 40%, e.g., from about 1% to about 20%, e.g., about 10% to about 20% a solution of, e.g., about 90% to about 100% (V/V) alcohol, e.g., about 95%o to about 100%>, e.g., ethanol, in some embodiments, not methanol, e.g., about 80%, 85%, 90, 95, 96, 97, 98, 99 or 100% (V/V) alcohol (such as ethanol), e.g., about 90-100% ethanol, e.g., about 95-100%) ethanol, where the balance of the solution is an aqueous solution, such as deionized water, e.g., about 20, 15, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1%> (V/V) aqueous solution. In other embodiments, buffers, salts, and other solutes may be present in the aqueous solution. In certain embodiments, the pH of the solution is in the range of about 3 to about 5.

Bond formation occurs when the sample is dried and the water molecules are rapidly removed. In some embodiments, the sample can be dried with a high intensity heat source (e.g. a heat gun, infrared light source or using microwave-radio frequency drying technology). Prior to drying, the excess liquid should be removed using an suitable means including, but not limited to, forced air (air knife, e.g., at about 40, 50, 60, 70, 80, 90, 100 PSI, or more), a vacuum conveyor dryer, or a squeegee roller system in a production line can be used to reduce the dry time to 10 seconds (compared to about 1-2 hours by conventional means, such as incubating in a oven at e.g., about 300°F. Once the water is removed, the bond formed is stabilized and the textile will bind dye. The dye can be dipped, printed or sprayed on the surface in a defined pattern or shape.

Exemplary dyes include food grade dyes (both artificial and natural), such as E150, E160b, E140, E120, E162, E100, E160a, E160c, E160d, E133, E132, E143, E129, E127, E102, El 10, Elderberry juice, pandan, and butterfly pea; as well as azo- dyes (or azo-linked dyes) that are hydrolysable by microbial enzymes, such as bacterial enzymes, e.g., oxido reductases. Exemplary azo dyes useful in the present invention are described in, e.g. , Wang et ah, African J. Biotechnology 10(75): 17186- 91 (2011) and Supaka et al, Chem. Eng. J. 99: 169-76 (2004), which are

incorporated by reference in their entirety. In particular embodiments, the dye is yellow 5 (E102), yellow 6 (El 10), blue 1 (E133), or a combination thereof, e.g. E102+E133, E110+E133, et cetera. Dyes may be suitably functionalized so as to bind {e.g. covalently or non-covalently) the particular textile being used, depending on, for example, the functionalization of the textile {e.g. silane reactive chemistry, TMA (trimethylammonium), or any other strong or weak cation or anion exchange group described above, BSOCOES, et cetera). For example, in some embodiments the dye is a maleimide derivative, such as a maleimide derivative of erioglaucine (E133).

In some embodiments, the textile comprises an agent, such as an antibiotic agent selected from an anti-viral agent, a fungicide, an antibacterial agent, or a combination thereof. In some embodiments, the textile comprises non-labile dye, fragrance, lotion, cream, detergent, or a combination thereof.

Also encompassed in the invention are methods of producing an

environmental textile with an integral hygiene sensor, including methods comprising associating a labile color indicator with an environmental textile, e.g., with the surface of an environmental textile.

The invention also includes methods of using the environmental textiles and sensors described herein. In some embodiments, the method comprises cleaning a surface, comprising contacting the surface with an environmental textile described herein. In some embodiments, the environmental textile is at least partially hydrated, e.g., with a detergent-containing solution.

In certain embodiments, the labile color indicator is releasable in a certain number of wash cycles, or bacteria counts as described herein. "Wash cycle" refers to treatment in a 1% solution of a household liquid dish detergent (such as

DAWN®) while shaking at about 30, 60, 90, 120, 130, 160, 180 rmp, for one hour at 25, 30, 37, 40, 50, 60, 70, 80, 90°C, or more.

EXEMPLIFICATION

The innovation provides, inter alia, sponges and wipes that change color when the material is no longer hygienic. The color change indicates the textile has been washed for an extended period time that is beyond the useful life of the product.

We have shown that dye molecules such blue dye #1 (erioglaucine) can be released from the surface of a textile material through, e.g., the interaction of the detergent that is used in common dish soaps that contain high concentrations of sodium chloride, quaternary amines, and detergents. In FIG. 1, we demonstrated that this dye release can be achieved with a molecule such as Bis [2- (succinimidooxycarbonyloxy)ethyl]sulfone (BSOCOES) that is sensitive to base hydrolysis. Most dish soap detergents are mildly basic and in combination with hot water will slowly release the dye from the surface. Another group that has been shown to be sensitive to temperature and base hydrolysis is a Diels- Alder functional group. Diels-Alder cyclic ring structure can be irreversibly converted to a diene and a substituted alkene, commonly referred to as a dienophile (as shown FIG. 2). Incubating a sponge or wipe that has dye attached to the surface with a Diels-Alder sensitive group will result in the loss of blue color from the surface after repeated wash cycles.

In yet another embodiment, the food grade dye is non-covalently attached to the surface through a strong ionic interaction between the dye and an anchored ion exchange molecule (FIG. 3). Ion exchange groups can be incorporated into the textiles either during the cross linking polymerization process of the textile or alternatively free hydroxyl (OH) on the textile can be cross linked with p- maleimidophenyl isocyanate (PMPI) to modify the surface with cationic or anionic moieties such as trimethyl ammonium groups, dimethylethanol ammonium

(DMEA), diethylaminoethyl (DEAE), sulfopropyl (SP) and/or carboxyl (COOH) anchored groups.

In some embodiments, spacers such as polyethylene glycol (PEG) or N-e- Fmoce-aminocaproic acid (AHx) groups can be included to remove the ion exchange charge away from the surface material preventing any steric inhibition of dye binding.

In FIG. 4, prototypes for the sponge and the wipe sensor are provided. For wipes, a chemistry that was more sensitive to the detergents (diethylaminoethyl groups) was used so that the dissolution time could be within 24 hours. In contrast, the sponge hygiene sensor used more robust chemistry (quaternary aminoethyl- Sephadex (QAE), QAE, BSOCOES, or Diels-Alder containing compounds) that kept the dye bound to the surface for up to ten compete wash cycles (FIG. 5).

Additional exemplification of the present invention is provided in FIGs. 6- 14. FIG. 6 is a representation of the decolorization of azo dyes incubated with bacteria. In FIG. 6, the top panel (6A) shows the decolorization of an azo dye in the presence of bacteria. In the bottom panel of FIG. 6 (6B), blue dye number 1 is mixed with a yellow azo dye that looks green to the eye and would decolorize from green to blue in the presence of bacteria because the yellow dye decolorizes, while the non-azo blue dye is insensitive to bacteria. FIG 7 depicts the chemical structure of yellow dye #6 with the labile azo bond visible in the center of the molecule. In FIG. 8, yellow dyes #5 and 6 were treated with bacteria for overnight at room temperature 25°C and 37°C. After overnight incubation with common bacterial pathogens, each dye decolorizes. In FIG. 9, a yellow azo dye is mixed with blue dye number 1 and incubated with bacteria as depicted in FIG. 6. Upon incubation with bacteria the azo dye decolorizes turning the sensor from green "good" to blue "bad". In FIGs. 10 and 11, respectively, it is demonstrated that increased bacteria concentration accelerates the azo dye decolorization process regardless of whether the dye is in solution (FIG. 10) or coupled to the surface using ion exchange group attached to a textile (FIG. 11). In FIG. 12, the azo dyes are shown coupled to a hydrogel material, a hyaluronic acid gel. Other hydrogels such as gelatin, agarose, or caragenin are also suitable consonant with the present invention. In FIGS. 13 and 14, the rapid chemical process of coupling the silane chemistry to a textile is demonstrated. Normally it takes several hours to perform this chemistry but using the conditions provided by the invention and aggressive drying/curing procedures this period was substantially shortened.

It should be understood that for all numerical bounds describing some parameter in this application, such as "about," "at least," "less than," and "more than," the description also necessarily encompasses any range bounded by the recited values. Accordingly, for example, the description at least 1, 2, 3, 4, or 5 also describes, inter alia, the ranges 1-2, 1-3, 1-4, 1-5, 2-3, 2-4, 2-5, 3-4, 3-5, and 4-5, et cetera.

For all patents, applications, and other references cited herein, such as non- patent literature and reference sequence information, it should be understood that it is incorporated by reference in its entirety for all purposes as well as for the proposition that is recited. Where any conflict exits between a document incorporated by reference and the present application, this application will control.

Headings used in this application are for convenience only and do not affect the interpretation of this application. Preferred features of each of the aspects provided by the invention are applicable to all of the other aspects of the invention mutatis mutandis and, without limitation, are exemplified by the dependent claims and also encompass

combinations and permutations of individual features (e.g. elements, including numerical ranges and exemplary embodiments) of particular embodiments and aspects of the invention including the working examples. For example, particular experimental parameters exemplified in the working examples can be adapted for use in the claimed invention piecemeal without departing from the invention. For example, for material that are disclosed, while specific reference of each various individual and collective combinations and permutation of these compounds may not be explicitly disclosed, each is specifically contemplated and described herein, as are methods of making and using such compounds. Thus, if a class of elements

A, B, and C are disclosed as well as a class of elements D, E, and F and an example of a combination of elements, A-D is disclosed, then even if each is not individually recited, each is individually and collectively contemplated. Thus, is this example, each of the combinations A-E, A-F, B-D, B-E, B-F, C-D, C-E, and C-F are specifically contemplated and should be considered disclosed from disclosure of A,

B, and C; D, E, and F; and the example combination A-D. Likewise, any subset or combination of these is also specifically contemplated and disclosed. Thus, for example, the sub-group of A-E, B-F, and C-E are specifically contemplated and should be considered disclosed from disclosure of A, B, and C; D, E, and F; and the example combination A-D. This concept applies to all aspects of this application including, elements of a composition of matter, and steps of method of making or using the compositions. The forgoing aspects of the invention, as recognized by the person having ordinary skill in the art following the teachings of the specification, can be claimed in any combination or permutation to the extent that they are novel and non-obvious over the prior art. Thus, to the extent an element is described in one or more references known to the person having ordinary skill in the art, they may be excluded from the claimed invention by, inter alia, a negative proviso or disclaimer of the feature or combination of features. While this invention has been particularly shown and described with references to example embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the invention encompassed by the appended claims.

Claims

CLAIMS What is claimed is:

1. An environmental textile comprising a visually detectable labile color

indicator, wherein the labile color indicator is labile under conditions of use, and wherein the release of the labile color indicator indicates that the product is no longer hygienic.

2. The environmental textile of claim 1 wherein the labile color indicator is a food grade dye that is generally regarded as safe (GRAS) by the United States Food and Drug Administration (U.S. F.D.A.).

3. The environmental textile of Claim 1 or 2, wherein the labile color indicator is covalently attached to the surface of the textile.

4. The environmental textile of any of the preceding claims, wherein the labile color indicator is non-covalently attached to the surface of the textile.

5. The environmental textile of any of the preceding claims, wherein the lability of the labile color indicator is sensitive to time, temperature, level of detergent or bacterial bioburden, resulting in the release of the labile color indicator from the surface.

6. The environmental textile of any of the preceding claims, wherein the labile color indicator is released by an ionic interaction between a detergent and a cationic or anionic charged environmental textile.

7. The environmental textile of any of the preceding claims, wherein the

environmental textile comprises a functional group selected from a trimethylammonium, triethylaminoethyl, diethylaminoethy anchored group or other ion exchange charged group.

8. The environmental textile of any of the preceding claims, wherein the labile color indicator is releasable by base hydrolysis with a detergent sensitive linker such as BSOCOES or a Diels-Alder containing compound.

9. The environmental textile of any of the preceding claims, wherein the labile color indicator is associated with the textile via a silane linker, such as a silanol.

10. The environmental textile of any of the preceding claims, wherein the silane linker is N-(2-aminoethyl)-3-aminosilanetriol.

11. The environmental textile of any of the preceding claims, wherein the labile color indicator is maleimide-functionalized.

12. The environmental textile of any of the preceding claims, wherein the labile color indicator is an azo dye or azo-linked dye cleavable by a bacterial extract.

13. The environmental textile of any of the preceding claims, wherein the textile further comprises an antibiotic agent select from an anti-viral agent, a fungicide, an antibacterial agent, or a combination thereof.

14. The environmental textile of any of the preceding claims, wherein the textile further comprises non-labile colorant, fragrance, lotion, cream, detergent, or a combination thereof.

15. The environmental textile of any of the preceding claims, wherein the labile color indicator comprises E102, E110, E133, or a combination thereof.

16. The environmental textile of any one of the preceding claims, wherein about 40, 50, 60, 70, 80, 90, 91, 92, 93, 94, 95, 96, 97, 98, or 99%, or more of the labile color indicator is releasable following 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, or 30 wash cycles.

17. The environmental textile of any one of the preceding claims, wherein about 40, 50, 60, 70, 80, 90, 91, 92, 93, 94, 95, 96, 97, 98, or 99% or more of the labile color indicator is releaseable following incubation of the textile with about 10⁴ to about 10⁷, or greater, cfu/rnL of Pseudomonas aeruginosa, Escherichia coli, Staphylococcus aureus, Proteus mirabilis, Enterococcus faecalis, or combinations thereof, for 24 hours at 25°C or 37°C. A method of producing an environmental textile with an integral hygiene sensor, comprising associating a labile color indicator with the surface of a environmental textile.

The method of Claim 18, wherein the environmental textile is the textile of any one of Claims 1-17.

The method of Claim 18 or 19, wherein the textile is functionalized by the steps of: incubating the textile with a silanol-containing solution comprising about 0.1% to about 40% (W/V) silanol and the solution is about 90% to about 100% (V/V) alcohol, the balance of the solution being an aqueous solution, condensing the silane chemistry, and contacting the functionalized textile with a suitably functionalized labile color indicator.

The method of Claim 20, wherein the labile color indicator is maleimide- functionalized.

The method of Claim 20, further comprising removing any excess silanol- containing aqueous solution before condensing the silane chemistry.

A method of cleaning a surface, comprising contacting the surface with an environmental textile according to any one of Claims 1-17 or produced by the method of any one of Claims 18-22.

The method of Claim 23, wherein the environmental textile is at least partially hydrated.

The method of Claim 24, wherein the environmental textile is at least partially hydrated with a detergent-containing solution.

A method of using the environmental textile of any one of Claim 1-17, or made by the method of any one of Claims 18-22, or uses of Claims 23-25, further comprising monitoring the visually detectable labile color indicator and disposing of the textile after the expiry of the useful life of the textile, as indicated by the visually detectable labile color indicator.