Articles, methods for functionalizing articles and articles obtained therefrom, methods for binding peptides and use of articles for binding peptides - Patents.com

Abstract

The present invention relates to an article having a polymer, wherein a first ionic group is attached to the surface of the polymer or the article via a distance piece. The present invention further relates to a method for functionalizing an article, and the article obtained therefrom. Finally, the present invention relates to a method for binding substances, and to the use of the article for binding substances.

Description

[Technical Field]

[0001] The present invention relates to an article, a method for functionalizing an article, and the article obtained therefrom. Furthermore, the present invention relates to a method for binding (and thereby removing) substances, and to the use of the article for binding substances. [Background technology]

[0002] To remove unwanted or harmful substances such as allergens, peptides, proteins or bacteria from the air in living spaces, for example, functionalized, in particular ionically functionalized, surfaces, for example of upholstered furniture, curtains or bed linen, are a promising approach. In this regard, it may be advantageous, in particular, for the fibers, yarns or foams used for this purpose to themselves be ionically functionalized or provided with functional groups. These in most cases consist of polymers or at least have polymers on their surface.

[0003] Cationization is known to improve dye binding, advantageously with acid dyes, during dyeing of fibers and textiles, especially those made from cellulose fibers (and other polymers in the form of blended fabrics). Furthermore, cationization of textile surfaces, so-called "dye catchers," to preferentially enhance dye staining during the washing process, is described, for example, in EP 1 775 372 A1 and DE 10 2005 049 015 A1. WO 2015 / 091740 describes the application of hydrophilic silanes to textiles, preferably polyester (PET), to make it difficult for bacteria and the resulting biofilms to adhere, thus representing the opposite approach. EP 3 192 923 A1 describes bed textiles and chemical application methods, such as applying anionic functional polysiloxanes to bed textiles. These are limited to specific amide-functional aminopolydiorganosiloxanes. The aim of this application is to non-permanently bind mite excreta allergens to textile surfaces. Various forms of antimicrobial application of textiles are described in WO 2015 / 028852, EP 3061864 and WO 2021 / 180930.

[0004] However, none of the solutions proposed so far in the prior art allow the ionization of the polymer surface to be intentionally and as needed adjusted.

[0005] Therefore, there is a need to intentionally and optionally adjustably provide ionic functional groups on polymer surfaces in order to bind unwanted or harmful substances such as allergens, peptides, proteins, bacteria, etc., and thereby render them harmless or remove them from the environment. Summary of the Invention

[0006] The inventors of the present invention have found that by means of a distance piece between the ionic functional group and the polymer surface, the length and amount (charge density) of which can be intentionally varied and adjusted, it is possible to achieve intentional and, if necessary, adjustable ionization of the polymer surface.

[0007] Accordingly, the present invention relates to an article having a polymer (at least on the surface of the article) and a first ionic group bound (immobilized) to the polymer or the surface of the article via a distance piece (spacer).

[0008] The present invention further provides a method for functionalizing an article, the method comprising the steps of: preparing an article having a polymer (at least on the surface of the article) with binding sites (reactive groups) on the surface; applying a functionalizing agent comprising a first ionic group and a distance piece to the surface of the polymer or article; and binding the functionalizing agent to the binding sites such that the first ionic group binds to the surface of the polymer or article via the distance piece.

[0009] Additionally, the present invention relates to articles obtainable by the methods described herein.

[0010] Additionally, the present invention relates to a method for binding (and thereby removing) (unwanted / harmful) substances having second ionizable groups on their surface, the method comprising contacting the substance with an article as described herein, wherein the second ionizable groups are oppositely charged to the first ionizable groups (and thus the substance is physically bound (by ionic interactions) to the first ionizable groups).

[0011] Furthermore, the present invention relates to the use of an article as described herein to bind (and thereby remove) (undesirable / harmful) articles having second ionic groups on their surface, the second ionic groups being oppositely charged to the first ionic groups (so that the substance is physically bound (by ionic interactions) to the first ionic groups).

[0012] Further objects and advantages of embodiments of the present invention will become apparent from the following detailed description and accompanying drawings. [Brief explanation of the drawings]

[0013] [Figure 1] 1 illustrates the functionalization of fabrics made from cellulosic fibers with a cationic functionalizing agent, according to an exemplary embodiment. [Figure 2] According to further exemplary embodiments, reactive epoxides or chlorohydrins suitable for cationic functionalization of fabrics from cellulose fibers with cationic distance pieces are specifically illustrated. [Figure 3] Further illustrative examples demonstrate the functionalization of fabrics made from cellulosic fibers with cationic functionalizing agents. DETAILED DESCRIPTION OF THE INVENTION

[0014] Further details of the invention and further embodiments thereof are described below, however, the invention is not limited to the following details, which are merely illustrative of the teachings of the present invention.

[0015] It should be noted that features described in connection with one exemplary embodiment may be combined with any other exemplary embodiment, in particular features described in connection with an exemplary embodiment of an article according to the invention may be combined with any other exemplary embodiment of an article according to the invention, and with an exemplary embodiment of a method according to the invention, and with each exemplary embodiment of a use according to the invention, unless expressly stated otherwise.

[0016] For example, when a term followed by an indefinite or definite article such as "ein," "eine," "eines," "der," "die," or "das" is expressed in the singular, this also includes the plural, and vice versa, unless the context clearly dictates otherwise. As used herein, the words "have" or "include" can mean not only "contain" or "include," but also "consist of" and "consist essentially of."

[0017] In a first aspect, the present invention relates to an article. The article is not particularly limited, as long as it has a polymer at least on the surface thereof. The article may consist essentially of a polymer. Of course, the article may contain two or more polymers or may be a composite material made of a polymer and a non-polymeric substance. In the context of the present application, "polymer" is understood to mean in particular a structure having more than 10 monomer units (repeating units).

[0018] According to exemplary embodiments, the article is a fiber, a filament, a thread (yarn), a roving, a film and / or a foam. In the context of the present application, "roving" is understood to mean in particular a bundle, a strand or a multifilament yarn from parallel-arranged filaments (continuous fibers) that is primarily used for the production of fiber-reinforced plastics or fiber-reinforced plastics.

[0019] According to exemplary embodiments, the article is a textile sheet material (woven, nonwoven, knitted, laminated fiber bundle), a membrane, a filter, a cloth, a mask (e.g. mouth-nose covering, medical mask, FFP2 mask), a mattress cover, a bedspread, a bed linen, a cushion, a blanket, upholstered furniture, a seat cover (e.g. car, train or airplane seat cover), a carpet, a curtain and / or a dressing (e.g. wound covering, bandage or adhesive plaster). The term "textile sheet material" is understood in the context of the present application to mean in particular a two- or three-dimensional textile product which may be woven or nonwoven.

[0020] According to an exemplary embodiment, the polymer is selected from the group consisting of cellulose, polyamides (both synthetic and natural), polyesters, polyketones, chitosan, polyurethanes, polyvinyl halides, epoxides, polyolefins, in particular polyethylene or polypropylene, polyethylene terephthalate, polystyrene, polyvinyl alcohol, ethylene-vinyl alcohol copolymer (EVOH) and polyacrylonitrile (PAN). These polymers have been found to be particularly suitable for the attachment of ionic groups. Combinations of polymers or copolymers can also be used. Hereinafter, whenever the term polymer is mentioned, it should be understood that copolymers are also always meant.

[0021] According to an exemplary embodiment, the polymer is present on or at least at the surface of the article.

[0022] According to an exemplary embodiment, the surface of the article or polymer has binding sites (reactive groups, functional groups) to which first ionic groups are attached (at least in part) via distance pieces.

[0023] The term "distance piece," sometimes referred to as "spacer," is understood in this application to mean a plurality of atoms or a chain of atoms disposed between the first ionizable group and the surface (binding site) of the article or polymer. The distance piece allows the first ionizable group to be disposed at a certain distance from the surface of the article, which can be intentionally set by the length of the distance piece. Furthermore, the amount / number of the distance pieces can be intentionally set to the amount / number of the first ionizable groups, and thus the charge density or charge spacing of the article.

[0024] According to exemplary embodiments, the distance pieces are covalently bonded to the surface (binding sites) of the polymer or article. This allows the distance pieces, including the first ionic groups, to bind particularly strongly and persistently to the article, thereby enabling stable and persistent functionalization of the article. Alternatively, but if desired, the distance pieces may be bonded to the surface (binding sites) of the polymer or article via van der Waals forces and / or hydrogen bonds. This can be particularly advantageous when less strong or merely temporary functionalization of the article is desired, or when the article, particularly its polymer, would be inhibited or damaged by covalent bonds (especially when they are formed by chemical reactions).

[0025] According to exemplary embodiments, the distance pieces are attached to the surface of the polymer or article by at least one of an amide bond, an ether bond, an ester bond, and a urethane bond, which allows for the functionalization of a wide variety of polymers in a variety of ways.

[0026] According to an exemplary embodiment, the distance piece comprises a group (advantageously having a valence of 2 or 2) selected from the group consisting of a straight-chain or branched, saturated or unsaturated, substituted or unsubstituted alkylene group; a straight-chain or branched, saturated or unsaturated, substituted or unsubstituted heteroalkylene group; a saturated or unsaturated, substituted or unsubstituted cycloalkylene group; a saturated or unsaturated, substituted or unsubstituted heterocycloalkylene group; a substituted or unsubstituted arylene group; a substituted or unsubstituted heteroarylene group; or a silicon-containing divalent group.

[0027] The terms "straight-chain," "branched-chain," "saturated," "unsaturated," and "unsubstituted," as used herein, correspond to their established meanings known to those skilled in the art. The term "substituted," as used herein, means that one or more, particularly 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, hydrogen atoms of the respective group are replaced by a substituent. Examples of suitable substituents include halogen atoms, such as -F, -CI, -Br, -I; -OH, hydroxyalkyl groups (ethers), -SH, thioalkyl groups (thioethers), =O, ester groups, amide groups, nitrile groups, and nitro groups. When two or more substituents are present, they may be the same or different and may be linked together to form a ring. The terms "heteroalkylene group," "heterocycloalkylene group," and "heteroarylene group" refer respectively to alkylene groups, cycloalkylene groups, and arylene groups in which one or more, particularly 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, carbon atoms have been replaced by a heteroatom, such as O, N, or S, particularly O and / or N. When a group contains more than one heteroatom, the heteroatoms may be the same or different.

[0028] Suitable examples of alkylene groups include C1 to C20 alkylene groups, particularly C2 to C10 alkylene groups, particularly C3 to C8 alkylene groups, and especially C4 to C6 alkylene groups.

[0029] Suitable examples of cycloalkylene groups include C3 to C20 cycloalkylene groups, particularly C4 to C15 cycloalkylene groups, particularly C5 to C10 cycloalkylene groups, and especially C6 to C8 cycloalkylene groups.

[0030] Suitable examples of arylene groups include C6 to C20 arylene groups, particularly C6 to C16 arylene groups, especially C6 to C14 arylene groups, and especially C6 to C10 arylene groups. In particular, the arylene group may be a phenylene group.

[0031] A "divalent silicon-containing group" may in particular comprise a group containing one or more silicon (Si) atoms and optionally further one or more, for example, C-, O-, N-, P- and / or H atoms. Suitable examples thereof include -[Si-dialkyl] (or -[alkyl-Si-alkyl]), -[alkyl-Si-alkoxy]- and -[Si-dialkoxy] (or -[alkoxy-Si-alkoxy]).

[0032] According to an exemplary embodiment, the first ionic group is a cationic (partially positively charged) group. This allows for the binding of partially negatively charged substances, as is common in peptides and proteins. It has been reported in the literature that 85% of protein structures have excess acidic amino acids, i.e., are partially negatively charged. For example, DerP1, an important allergen from house dust mite excretion, has excess acidic amino acids, which allows it to be bound by a cationic functionalized surface.

[0033] Suitable examples of cationic groups include (primary, secondary, tertiary) amino groups, particularly primary amino groups, (quaternary) ammonium groups, guanidino groups, imidazole groups, triazole groups, tetrazole groups, creatine groups, (primary, secondary, tertiary) phosphine groups (phosphane groups), and (quaternary) phosphonium groups. Different cationic groups can also be combined as the first ionic group, for example, a permanently charged cationic group such as an ammonium group can be combined with a pH-dependently charged cationic group such as a primary amino group.

[0034] According to another exemplary embodiment, the first ionic group is an anionic ((partially) negatively charged) group, which allows for the opening up of different, particularly complementary, fields of application to cationic groups, so that particularly great versatility can be achieved thereby.

[0035] Suitable examples of anionic groups include carboxyl groups, sulfonate groups, sulfate groups, phosphonate groups, and phosphate groups. Again, various anionic groups can be combined as the first ionic group.

[0036] According to an exemplary embodiment, the ionic group is a permanently charged group. In particular, it may be advantageous that when the ionic group comes into contact with, for example, water, the charge state does not depend on the pH value. This allows a constant binding capacity to be achieved regardless of the environmental conditions. A suitable example of a permanently charged (cationic) group is a (quaternary) ammonium group.

[0037] According to another exemplary embodiment, the ionic group is a pH-dependent (temporarily) charged group, and this charge state depends on the pH value when the ionic group comes into contact with, for example, water. This allows the charge state and therefore the charge density of the article to be adjusted as needed. A suitable example of a pH-dependent charged (cationic) group is a primary amino group.

[0038] According to an exemplary embodiment, the ionic group has a (average, median) distance from the surface of the polymer or article of 0.3 to 5 nm, particularly 0.5 to 4 nm, particularly 0.8 to 2.5 nm, and particularly 1 to 2 nm. To this end, the distance pieces advantageously have a (average, median) molecular length of 0.3 to 5 nm, particularly 0.5 to 4 nm, particularly 0.8 to 2.5 nm, and particularly 1 to 2 nm. The distance between the ionic group and the surface of the polymer or article can be intentionally adjusted by selecting the distance pieces, thereby taking into account, for example, the folding of the peptide structure. The (average, median) distance between the ionic group and the surface of the polymer or article and the (average, average) molecular length of the distance pieces can be calculated, in particular, based on the (known) bond lengths of the bonds between atoms in the distance piece molecules. The (average, median) distance between the ionic group and the surface of the polymer or article, and the (average, median) molecular length of the distance piece can be determined, for example, using an electron microscope, such as a transmission electron microscope (TEM) or a high-resolution scanning electron microscope (REM).

[0039] Suitable examples of distance pieces and their corresponding lengths are shown in the table below: [Table 1]

[0040] The length of the distance pieces can be extended as needed. For this purpose, general preparative chemistry methods based on polymer-like synthesis methods are suitable. Such methods include chain extension, for example, by addition and / or condensation reactions, using native or capped bis-2-oxazolines, bis-acyl-lactams, bifunctional silanes and siloxanes, diepoxides, and alkylene oxides.

[0041] According to an exemplary embodiment, the distance pieces have a (average, median) distance of 1 to 100 nm, particularly 2 to 50 nm, and particularly 5 to 25 nm from adjacent distance pieces, particularly from the nearest adjacent distance pieces. The distance between adjacent distance pieces, and thus the charge density, can be intentionally adjusted by selecting the distance pieces (e.g., their steric extension) or the amount of distance pieces per unit surface, which is particularly important for binding large protein units, and other steric effects can also be taken into consideration. The (average, median) distance between a distance piece and an adjacent distance piece can be measured, for example, using an electron microscope, such as a transmission electron microscope (TEM) or a high-resolution scanning electron microscope (SEM).

[0042] According to an exemplary embodiment, the surface has binding sites (reactive groups, functional groups), and distance pieces are bound to 0.5 to 20%, particularly 1 to 10%, and particularly 2 to 5% of the binding sites. In this case, the remaining binding sites may be substantially unbound (free), and in particular may be substantially free of distance pieces and / or ionic groups. This allows the binding capacity of the functionalized surface to be tailored as needed, making it particularly suitable for binding large, sterically demanding molecules.

[0043] According to exemplary embodiments, a substance having second ionizable groups on its surface can be or may be bound (through ionic interactions, i.e., physically) to the first ionizable groups. For this purpose, the second ionizable groups are desirably oppositely charged to the first ionizable groups. Therefore, when the first ionizable groups are cationic groups, the second ionizable groups are desirably anionic groups or (partially) negatively charged groups. Therefore, when the first ionizable groups are anionic groups, the second ionizable groups are desirably cationic groups or (partially) positively charged groups.

[0044] According to exemplary embodiments, the substance is substantially permanently or irreversibly bound to the first ionic group, which is particularly advantageous when the substance is a nuisance or harmful substance that should be bound as persistently as possible and thus removed from the environment.

[0045] According to another embodiment, the substance is reversibly (latently) bound to the first ionic group, which is particularly advantageous when it is desired to bind the substance to the article only temporarily.

[0046] For example, the substance may be a pharmaceutical and / or cosmetic active substance that is to be released again from the article. Thus, the article according to the invention, for example a dressing (e.g., a wound covering, bandage or adhesive bandage), can be provided with pharmaceutical active ingredients, such as peptide pharmaceuticals, anti-inflammatory pharmaceuticals and / or antibiotic pharmaceuticals, which can be released in a delayed manner over an extended period of time, if desired. Such delayed release can also be adjusted as desired by deliberate functionalization according to the invention.

[0047] According to exemplary embodiments, pharmaceutical agents may be reversibly (latently) or persistently (permanently) bound to the first ionic group. Exemplary pharmaceutical agents include anionic fungicides and bactericides, such as piroctone, octopirox, ciclopirox, pyrithione, and perillic acid. This may be of particular interest for filters and topical medical applications.

[0048] According to exemplary embodiments, the substance is selected from the group consisting of peptides, proteins, microorganisms such as bacteria, viruses, yeasts and fungi, metabolites such as allergens, toxins, enzymes, microorganisms such as mites, peptide surface structures such as spores, pollen, skin particles and mites eggs, etc. These are primarily disturbing or harmful substances, usually intended to be permanently bound to the article.

[0049] In a further aspect, the present invention relates to a method for the functionalization of an article, as a result of which in particular an article according to the first aspect as explained above can be obtained, which method can therefore also be called a method for producing a (functionalized) article.

[0050] The article to be functionalized may be, for example, a fiber, a filament, a yarn, a roving, a film and / or a foam, or a textile sheet material (woven, nonwoven, knitted, laminated fiber bundle), a membrane, a filter, a cloth, a mask (e.g. mouth-nose covering, medical mask, FFP2 mask), a mattress cover, a bedspread, bed linen, a cushion, a blanket, upholstered furniture, a seat cover (e.g. car, train or airplane seat cover), a carpet, a curtain and / or a dressing (e.g. wound covering, bandage or adhesive plaster).

[0051] In the first step, an article is prepared that has a polymer (at least on the surface of the article) with binding sites (reactive groups) on the surface.

[0052] According to an exemplary embodiment, the polymer present on the surface of the article already has bonding sites or reactive groups. Suitable examples of such polymers include cellulose, polyvinyl alcohol, ethylene-vinyl alcohol copolymer (EVOH) (each having a hydroxyl group (-OH)), polyamide (having an amide group (-CONH-)), polyester (having an ester group (-COO-)), polyketone (having a ketone group (-CO-)), chitosan (having an amino group (-NH2)), polyurethane (having a urethane group (-NH-COO-)), polyvinyl halides (having a halogen, for example, chlorine (-Cl)), epoxides (having, for example, -CH(OH)-CH2-NH-), and polyacrylonitrile (having a nitrile group (-CN)). In these cases, no special surface treatment is required to create bonding sites on the surface, although it may still be performed, for example, to strengthen or optimize the bonding sites or for other reasons.

[0053] According to another embodiment, the polymer present on the surface of the article does not itself have any (suitable) reactive binding sites or has only a few or only a few reactive binding sites, examples of such polymers include polyolefins, in particular polyethylene or polypropylene, polyethylene terephthalate and polystyrene.

[0054] Thus, according to an exemplary embodiment, preparing an article having surface binding sites includes surface treatment to form binding sites on the surface of the article or polymer.

[0055] According to an exemplary embodiment, the surface treatment is selected from the group consisting of plasma treatment, oxidation treatment and flame treatment (flaming), in particular plasma treatment using a reactive gas or gas mixture (e.g., containing ammonia or hydrazine) among others, which allows the formation of extensive bonding sites on the polymer surface.

[0056] According to exemplary embodiments, the binding sites, sometimes also called reactive groups, are groups from the group consisting of hydroxyl groups (-OH), carboxyl groups (-COOH), amide groups (-CONH-), ester groups (-COO-), carbonyl groups (-CO-), in particular ketone or aldehyde groups, amino groups (-NH2), urethane groups (-NH-COO-), halogens, in particular chlorine (-Cl) or bromine (-Br), and epoxide groups (oxirane groups). A combination of different binding sites is also possible, especially when it is intended to apply different functionalizing agents, which can result in different binding possibilities, for example, for one or more substances to be removed.

[0057] In a further step, a functionalizing agent comprising a first ionic group and a distance piece is applied to the surface of the polymer or article. Multiple different functionalizing agents can be applied. For example, a (first) functionalizing agent comprising a distance piece can be applied first, followed by a (second) functionalizing agent comprising a first ionic group. In this case, the first functionalizing agent can be bound to a binding site on the surface of the article before applying the second functionalizing agent, and the second functionalizing agent also binds to the first functionalizing agent (particularly its appropriate functional group).

[0058] The application of the functionalizing agent is advantageously carried out by dissolving or dispersing it in a solvent, but is not particularly limited and can be carried out by any suitable method known to those skilled in the art. For example, the functionalizing agent can be applied by spraying it onto the surface of a polymer or an article, or the article can be immersed in the functionalizing agent. In particular, a padding process (a process using a pad) can also be used to functionalize a textile article. The pad typically includes a system of two or more rollers and a trough (also called a chassis) for containing the liquid formulation of the functionalizing agent. In the padding process, a wide textile article is typically immersed in the liquid formulation, and then a roller is used to remove the excess absorbed liquid formulation uniformly across the entire width of the product. However, the functionalizing agent can also be applied to the surface of a polymer or an article by vapor deposition, without being dissolved or dispersed in a solvent.

[0059] The functionalizing agent has a first ionic group and a distance piece (spacer), which may in particular be the first ionic group or distance piece described in detail above in relation to the first embodiment.

[0060] According to an exemplary embodiment, the functionalizing agent further comprises a functional group capable of interacting, in particular reacting, with a binding site on the surface of the polymer or article, thereby achieving a (strong) bond between the functionalizing agent and the surface of the polymer or article. In particular, advantageously, the functional group of the functionalizing agent is capable of reacting with a binding site on the surface of the polymer to form a covalent bond.

[0061] According to exemplary embodiments, the functional groups are selected from the group consisting of hydroxyl groups (-OH), carboxyl groups (-COOH), amide groups (-CONH-), ester groups (-COO-), carbonyl groups (-CO-), in particular ketone or aldehyde groups, amino groups (-NH2), urethane groups (-NH-COO-), halogens, in particular chlorine (-Cl) or bromine (-Br), and epoxide (oxirane) groups. The functional groups of the functionalizing agent are selected taking into account, in particular, the type of binding site on the surface of the polymer. For example, if the binding site contains a hydroxyl or amino group, the functional group of the functionalizing agent can in particular contain a carboxyl group, and vice versa.

[0062] According to an exemplary embodiment, the functionalizing agent is selected from the group consisting of betaine, choline, taurine, caprolactam, laurolactam, alkoxysilane, lysine, arginine, ornithine, histidine, creatinine and succinylcholine betaine, which have been found to be particularly suitable for achieving the functionalization according to the invention of polymer surfaces, in particular for functionalizing polymer surfaces, for example made of cellulose, with cationic groups.

[0063] According to exemplary embodiments, the functionalizing agent is an oligomer and / or copolymer, in particular a terpolymer. "Oligomer" is understood in the context of the present application to mean in particular a structure having up to 10 monomer units, for example 2 to 8 monomer units. "Copolymer" is understood in the context of the present application to mean an oligomer or polymer having at least two different monomer units. "Terpolymer" is understood in the context of the present application to mean an oligomer or polymer having (exactly) three different monomer units.

[0064] According to an exemplary embodiment, the functionalizing agent is a terpolymer comprising a first monomer, a second monomer, and a third monomer, wherein the first monomer comprises a first ionic group, the second monomer comprises a distance piece, and the third monomer comprises a functional group that can interact, particularly react, with binding sites on the surface of the polymer or article.

[0065] According to an exemplary embodiment, the first monomer is a cationic monomer, the second monomer is a neutral (uncharged) monomer, and the third monomer is an anionic monomer. In the case of a particularly easy-to-prepare terpolymer, the first monomer may be a cationic vinyl monomer (e.g., acrylic acid-2-(dimethylamino)ethyl ester), the second monomer may be a neutral vinyl monomer (e.g., methyl methacrylate), and the third monomer may be a carboxyl group-containing vinyl monomer (e.g., acrylic acid). The third monomer may, for example, bind to a polymer binding site, particularly a hydroxyl group, such as a primary hydroxyl group of cellulose, while the first monomer may provide the first ionic group as a cationic group. The length of the distance piece can also be adjusted by the number of second (neutral) monomers. A further advantage of such terpolymers is that they are either easily soluble or easily emulsifiable in water. Further suitable examples of the second monomer include acrylates, methacrylates, maleic esters, and styrenes. A further suitable example of a first monomer is diallyldimethylammonium chloride, which can provide a permanently positively charged first ionic group.

[0066] According to an exemplary embodiment, a substoichiometric amount of functionalizing agent is applied to the binding sites. It may be particularly advantageous for the (molar) ratio of functionalizing agent to binding sites to be in the range of 1:200 to 1:5, particularly 1:100 to 1:10, and particularly 1:50 to 1:20. This allows the degree of functionalization or charge density of the polymer surface to be adjusted in a particularly simple manner, for example, so that only 0.5% to 20%, particularly 1% to 10%, particularly 2% to 5% of the binding sites are bound to distance pieces, while the remaining binding sites are substantially unbound (free).

[0067] In a further step, the functionalizing agent is attached to the binding site such that the first ionizable group is attached to the surface of the polymer or article via the distance piece, i.e., the functionalizing agent is attached to the binding site such that the first ionizable group is spaced from the binding site.

[0068] According to an exemplary embodiment, the step of attaching the functionalizing agent to the binding site comprises a chemical reaction that forms a covalent bond (between the functionalizing agent, particularly its functional group, and the binding site).

[0069] According to an exemplary embodiment, the step of attaching the functionalizing agent to the binding sites comprises heating to a temperature in the range of 50-220°C, in particular 100-200°C, in particular 150-190°C, in particular 160-180°C, for a period of 5 seconds to 5 minutes, in particular 10 seconds to 2 minutes, in particular 15 seconds to 60 seconds.

[0070] In a further aspect, the present invention relates to an article obtainable or obtained by a functionalization method as described above.

[0071] In a further aspect, the invention relates to a method for binding (and thereby removing) (unwanted / harmful) substances.

[0072] The substances may in particular be peptides, proteins, peptide surface structures of microorganisms such as bacteria, viruses, yeasts and fungi, metabolites such as allergens, toxins, enzymes, etc., microorganisms such as mites, e.g. spores, pollen, skin particles and mite eggs.

[0073] The method includes contacting a substance with a (functionalized) article as described above, which has first ionizable groups, and the substance has second ionizable groups on its surface that are oppositely charged to the first ionizable groups, thereby allowing the substance to become bound (through ionic interactions, i.e., physically) to the first ionizable groups.

[0074] According to an exemplary embodiment, the substance is reversibly bound to the first ionizable group, which is particularly advantageous when it is desired to bind the substance to the article only temporarily.

[0075] According to another exemplary embodiment, the article is permanently, i.e., irreversibly, bound to the first ionic group, which is particularly advantageous when the article is a harmful or hazardous article that should be bound as permanently as possible and removed from the environment.

[0076] In yet another aspect, the present invention relates to binding (and thereby removing) (undesirable / harmful) articles that have second ionic groups on their surface, as described above, with the second ionic groups having an opposite charge to the first ionic groups (and thus the article is physically bound (by ionic interactions) to the first ionic groups).

[0077] According to an exemplary embodiment, the substance is reversibly bound to the first ionizable group.

[0078] According to another exemplary embodiment, the article is permanently, ie, irreversibly, bonded to the first ionic group.

[0079] The substances may in particular be peptides, proteins, peptide surface structures of microorganisms such as bacteria, viruses, yeasts and fungi, metabolites such as allergens, toxins, enzymes, etc., microorganisms such as mites, e.g. spores, pollen, skin particles and mite eggs.

[0080] The present invention is further illustrated by the following examples, which are intended merely to clarify the teachings of the present invention and are not intended to limit the scope of the invention. [Example]

[0081] Application to organic fibers and textiles is based on impregnation with an aqueous bath and application liquid containing dissolved or dispersed binding agents, possibly accompanied by additional finishing aids. This process is industrially established under the term "padding." In this case, the substrate is passed through the bath (liquid) until it is completely immersed, after which the excess liquid is reduced to a predetermined amount by means of several roller pairs. This is usually immediately followed by a drying / fixing step, followed by the final geometric transformation (stretching, ironing, etc.). This method can be further improved by various exhaustion, spray, or foam application processes. The basic steps are maintained: impregnation - removal of excess - heat fixing and drying - finishing treatment.

[0082] Application to smooth (film) surfaces is equivalent: spray - heat-bond - remove unbonded excess (wash) - dry.

[0083] Comparative Example 1 From the teachings of EP 3192923, it can be concluded that the mite excreta allergen (DerP1) is positively charged and therefore binds to anionic (-) surfaces via electrostatic interactions. In contrast, the allergen-binding effect of textiles is attributed to "amide-functional aminopolydiorganosiloxane compounds," i.e., compounds with a moderate cationic charge. Accordingly, the textile must be loaded with a high amount (30-200 g per liter of liquor = 3-20%). This represents a large stoichiometric excess compared to the (estimated) reactive OH groups of the pulp textile. Nevertheless, the allergen is only fully fixed at a maximum of 75%. The fixation rate can only be increased by adding additional additives.

[0084] Example 1 55% TENCEL (cellulose fiber produced by the Lyocell process of Lenzing AG) and 45% cotton, with a basis weight of 150 g / m 2 (150g / m 2 = 1 m of glucose 2 The blended fabric (approximately 1 mole of cellulose / glucose per 100g) absorbed 42% of the liquor during padding and subsequent roller squeezing. The liquor contained 1.2% active ingredient (aqueous formulation adjusted to pH 10 with NaOH). 2-[2-(2-chloroethyl)sulfonyl]ethoxyethanamine HCl Cl-CH2-CH2-SO2-CH2-CH2-O-CH2-NH2·HCI (C6H 15 Cl2NO3S)MG:252.15 CAS:98231-71-1 Spacer length: Cell-O- to -NH2: 1400pm = 1.4nm

[0085] The concentrations correspond to: 100g of textile + 42g of liquid equivalent to (0.5g of active ingredient) 150g fiber + 63g liquid equivalent to (0.75g active ingredient) Or every 30th primary OH group of cellulose is substituted.

[0086] Afterwards, the pressed textile was dried at 180-200°C for 10-15 seconds (IR radiator with ventilation).

[0087] DerP1-uptake was quantified to be greater than 99% by ELISA test (enzyme-linked immunosorbent assay).

[0088] Example 2 This example demonstrates that even a small spacer extension and slight increase in basicity significantly increases absorption capacity compared to anionic peptides.

[0089] TENCEL C (LENZING AG) is a lyocell fiber with a core material from cellulose and an integral layer (outer) of chitosan.

[0090] In contrast to cellulose, chitosan has amino groups (-CH2NH2) instead of primary hydroxy groups (-CH2OH), and is therefore clearly cationic active, which manifests itself in charge-exchange-based antibacterial, antiviral, and / or fungicidal effects.

[0091] Textiles made from TENCEL C are preferably used for sportswear, hosiery wool, etc. Further functionalization according to the invention significantly increases the binding properties.

[0092] 80g / m2 made from TENCEL C (50%) and VISKOSE-MODAL (50%) 2 The padding is made of a fabric having

[0093] Liquid: 6% of a 50% technical cyanamide solution (SKW-Cyanamide L500), adjusted to pH 9.5 with acetic acid and maintained at this pH during padding. Temperature: 70-85°C. Pressed to a liquid content of 35% by weight and dried at 150°C.

[0094] The formation of guanyl groups 13 This was confirmed by C NMR or FT-IR. Elemental analysis showed that the nitrogen content of the fabric increased from 0.41% (corresponding to a chitosan content of about 9.5% in the TENCEL C fraction) to 0.52%, with every fifth: -CH2NH2 groups from chitosan -CH2-NH-C(=NH)-NH2 It can be inferred that:

[0095] At the same time, this substitution increases the spacer length by approximately 300 pm, thus increasing its mobility. Similarly, it increases the basicity and thus the electrical (+) potential for the anchoring of anion-active proteins. This manifests itself in the increased immobilization of envelope proteins from Pseudomonas aeruginosa and Escherichia coli.

[0096] Example 3 Anionically modified cellulose fibers The base is a 43% solution of 3-(1-carboxyethyl)-thio-N-hydroxymethyl-propionic acid amide (Na salt): (Na)HOOC-CH(CH3)-S-CH2-CH2-CO-NH-CH2OH Spacer length: 1400pm = 1.4nm which is obtained according to Example 4 of EP 0 189 373.

[0097] The cellulose fiber woven or nonwoven fabric is padded with about 10-20% aqueous solution adjusted to pH 3 with hydrochloric acid according to stoichiometric requirements, and condensed at a temperature of ≥ 130°C (preferably 180-200°C) to the primary hydroxyl groups of the glucose units of the polymer chain.

[0098] In this way, the degree of substitution can be adjusted according to the present invention (e.g., every OH group, every second, third, fourth, fifth, ... every tenth). Anionically modified cellulose can be used to ionically bind cationic antibacterial agents, such as gentamicin, erythromycin, gramicidin, kanamycin, neomycin, streptomycin, tetracycline, tyrothricin, paromomycin, quinolones, floxacin, penicillin, cephalosporins, and macrolides. Furthermore, fungicides, acaricides, etc. are also used. Applications include dressings, wound care, and skin care, as well as filters and masks for operating rooms.

[0099] Examples 4 to 10 Fabrics made from cellulose fibers, anionized (statistically) at every tenth primary hydroxyl group according to Example 3, are subsequently cationized in a padding step by neutralizing the carboxyl groups with an excess of polycationized polymers, in particular those with their free amino / imino groups.

[0100] The following were tested: Example 4: Polyethyleneimine (Luprasol, BASF) MW approximately 25,000 Example 5: Polylysine (CAS25104-18-1) MW>4700 Example 6: Polyarginine (CAS26982-20-7) MW>5000 Example 7: Polyvinylimidazole (CAS25232-42-2) MW>10000 Example 8: Copolymer of DADMAC and diarylamine (10:1) Example 9: Condensation product of dicyandiamide / formaldehyde / ammonium chloride (1:3:1 (molar ratio)) Example 10: Copolymer of vinylpyrrolidone and vinylimidazole (LUV / QUANT FC550, BASF)

[0101] If the drying / fixing temperature after the second padding step is below 80-100°C, the expected salts are formed. These salts are therefore not wash-resistant, but are highly active against anionic peptide structures (viruses, bacteria, mites), making them particularly suitable for dressings or filters. Increasing the drying step to above 150°C, preferably 180°C, leads to intramolecular condensation to form amides, which are wash-resistant (and therefore suitable for textile processing). This is the case for Examples 4, 5, 6, 8, and 9, since the amines have a free NH group (but not for Examples 7 and 10!).

[0102] FIG. 1 illustrates the functionalization of a fabric made from cellulose fibers with a cationic functionalizing agent according to Example 4 (polyethyleneimine (PEI)).

[0103] The amino groups present after drying and fixing in Examples 4 and 5 can be converted to guanidyl residues in a further reaction step using cyanamide, similar to Example 2. This increases the ion density and therefore the basicity (see Figure 1, Step 4: Increase in ion density).

[0104] Furthermore, it should be noted that the amide formation from -COOH (spacer) and -NH2 (catalyst polymer) is easier than the condensation of COOH with -NH- as in Examples 7 and 10, where drying times >180°C, preferably 200°C / 2 min, are required.

[0105] Furthermore, it should be noted that parallel chains of cellulose are formed, i.e., in steps 2 and 3, and they are kept spaced apart by spacers. It can be assumed that during the normal helical formation of cellulose, these parallel structures also wind together, and the (yet unbound) cationic centers intended for absorption remain evenly spaced.

[0106] Examples 11 to 13 (Preliminary Considerations) Particularly suitable cationic functionalizing agents are the so-called "Quabs™", which covalently bond to cellulose as reactive epoxides or as chlorohydrins in a strongly alkaline environment, as shown in FIG. 2.

[0107] This modification of cellulose fibers is known from the prior art and is widely used for dye fixation in dyeing processes with acid dyes (-SO3H groups). Its use as a cationic center for adsorption on anionic protein surfaces is new. This has already been successful for R = C1 to C6. R => C6, especially C8 to C 20 , particularly preferably C 12 ~C 18 In addition to absorbing (immobilizing) bacteria, it also has a significant antibacterial effect, causing the lysis of envelope proteins and ultimately killing microorganisms.

[0108] Examples 11 to 13 In the padding process, cellulose fibers or nonwoven fabrics are reacted with a 0.1-5.0% QUAB™ solution (depending on the desired degree of functionalization and appropriate liquor uptake) at a pH of 8.5-11.5 and at >50°C, preferably >80°C. After squeezing, the fibers are washed at a neutral pH (measured in the wash water) at a temperature of 20-35°C and dried. Due to the rapid chemical reaction in the liquor, subsequent high-temperature fixing is not required.

[0109] FIG. 3 shows a fabric made from the corresponding cellulose fibers functionalized with QUAB™.

[0110] Example 11 QUAB™ 188 X) R=CH3(methyl)- Example 12 QUAB™ 342 X) R=CH 12 (Lauryl)- Example 13 QUAB™ 426 X) R=CH 18 (Stearyl)- x)Supplier:QUAB-Chemicals

[0111] result Protein binding (ELISA test) using DER p1 as an example [Table 2]

[0112] Tests according to DIN EN ISO 20743 and DIN EN 14119 make it possible to determine the immobilization of bacteria, such as Pseudomonas aeruginosa, or fungi, such as Aspergillus niger.

[0113] Although the present invention has been described with reference to specific embodiments and examples, it is to be understood that the present invention is not limited thereto and that various modifications can be made thereto without departing from the scope of the present invention.

Claims

1. An article having a polymer, wherein a first ionizable group is bound to a surface of the polymer via a distance piece, the first ionizable group being at a distance in the range of 0.3 to 5 nm from the surface of the polymer, such that a peptide or protein having a second ionizable group oppositely charged to the first ionizable group can be physically bound to the first ionizable group.

2. The article of claim 1 , wherein the first ionic group is a cationic group.

3. 3. The article of claim 2, wherein the cationic groups are selected from the group consisting of amino groups, ammonium groups, guanidino groups, imidazole groups, triazole groups, tetrazole groups, creatine groups, phosphine groups, and phosphonium groups.

4. The article of claim 1 , wherein the first ionic group is an anionic group.

5. 5. The article of claim 4, wherein the anionic groups are selected from the group consisting of carboxyl groups, sulfonic acid groups, sulfate groups, phosphonic acid groups, and phosphate groups.

6. The article of claim 1 , wherein the ionic groups are permanently charged groups.

7. The article of claim 1 , wherein the ionic groups are pH-dependent charged groups.

8. The article of claim 1 , wherein the distance piece is covalently bonded to the surface of the polymer.

9. The article of claim 8 , wherein the distance piece is attached to the surface of the polymer by at least one of an amide bond, an ether bond, an ester bond, and a urethane bond.

10. 2. The article of claim 1, wherein the distance piece comprises a group selected from the group consisting of a straight-chain or branched, saturated or unsaturated, substituted or unsubstituted alkylene group; a straight-chain or branched, saturated or unsaturated, substituted or unsubstituted heteroalkylene group; a saturated or unsaturated, substituted or unsubstituted cycloalkylene group; a saturated or unsaturated, substituted or unsubstituted heterocycloalkylene group; a substituted or unsubstituted arylene group; a substituted or unsubstituted heteroarylene group; or a divalent group containing silicon.

11. 2. The article of claim 1, wherein the distance pieces have a distance of 1 to 100 nm, in particular 2 to 50 nm, from adjacent distance pieces.

12. 2. The article of claim 1, wherein the surface has bonding sites, and the distance pieces are bonded to 1 to 10% of the bonding sites.

13. 2. The article of claim 1, wherein the polymer is selected from the group consisting of cellulose, polyamide, polyester, polyketone, chitosan, polyurethane, polyvinyl halides, epoxides, polyolefins, in particular polyethylene or polypropylene, polyethylene terephthalate, polystyrene, polyvinyl alcohol, ethylene-vinyl alcohol copolymers and polyacrylonitrile.

14. 10. The article of claim 1, wherein the article is selected from the group consisting of fibers, filaments, yarns, rovings, films, and foams.

15. 10. The article of claim 1, wherein the article is selected from the group consisting of textile sheeting, membranes, filters, cloths, masks, mattress covers, bedspreads, bed linens, cushions, blankets, upholstered furniture, seat covers, carpets, curtains, and dressings.

16. The article of claim 1 , wherein the peptide or protein is reversibly bound to the first ionizable group.

17. The article of claim 1 , wherein the peptide or protein is a pharmaceutical and / or cosmetic active ingredient.

18. 18. The article of claim 17, wherein the peptide or protein is a peptide drug, an anti-inflammatory drug and / or an antibiotic drug.

19. 1. A method for functionalizing an article, comprising: The functionalization method comprises the following steps: providing an article having a polymer with bonding sites on its surface; applying a functionalizing agent comprising a first ionic group and a distance piece to a surface of the polymer; attaching the functionalizing agent to the binding site such that the first ionizable group is attached to the surface of the polymer through the distance piece. Including, wherein the first ionizable group is at a distance in the range of 0.3 to 5 nm from the surface of the polymer, so that a peptide or protein having a second ionizable group oppositely charged to the first ionizable group can be physically bound to the first ionizable group.

20. 20. The method of claim 19, wherein the step of providing an article with bonding sites on a surface comprises a surface treatment.

21. 21. The method of claim 20, wherein the surface treatment is selected from the group consisting of a plasma treatment, an oxidation treatment, and a flame treatment.

22. 20. The method of claim 19, wherein the binding site is selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, an ester group, a carbonyl group, in particular a ketone or aldehyde group, an amino group, a urethane group, a halogen, in particular a chlorine or bromine group, an epoxide group and a nitrile group.

23. 20. The method of claim 19, wherein the functionalizing agent further comprises a functional group that can interact, particularly react, with the binding sites on the surface of the polymer.

24. 24. The method of claim 23, wherein the functional groups are selected from the group consisting of hydroxyl groups, carboxyl groups, amide groups, ester groups, carbonyl groups, in particular ketone or aldehyde groups, amino groups, urethane groups, halogens, in particular chlorine or bromine, and epoxide groups.

25. 20. The method of claim 19, wherein the functionalizing agent is selected from the group consisting of betaine, choline, taurine, caprolactam, laurolactam, alkoxysilane, lysine, arginine, ornithine, histidine, creatinine, and succinylcholine betaine.

26. 20. The method of claim 19, wherein the functionalizing agent is an oligomer and / or copolymer, in particular a terpolymer.

27. 27. The method of claim 26, wherein the functionalizing agent is a terpolymer comprising a first monomer, a second monomer, and a third monomer, wherein the first monomer comprises the first ionic group, the second monomer comprises a distance piece, and the third monomer comprises a functional group that can interact, particularly react, with the binding sites on the surface of the polymer.

28. 28. The method of claim 27, wherein the first monomer is a cationic monomer, the second monomer is a neutral monomer, and the third monomer is an anionic monomer.

29. 20. The method of claim 19, wherein a substoichiometric amount of functionalizing agent is applied to the binding site.

30. 20. The method of claim 19, wherein the step of attaching the functionalizing agent to the binding site comprises a chemical reaction that forms a covalent bond.

31. 31. The method of claim 30, wherein the step of binding the functionalizing agent to the binding sites comprises heating at a temperature in the range of 50°C to 220°C for a period of 5 seconds to 5 minutes.

32. The method of any one of claims 19 to 31, wherein the article is selected from the group consisting of fibers, filaments, yarns, rovings, films, and foams.

33. 32. The method of any one of claims 19 to 31, wherein the article is selected from the group consisting of textile sheet materials, membranes, filters, cloths, masks, mattress covers, bedspreads, bed linen, cushions, blankets, upholstered furniture, seat covers, carpets, curtains and dressings.

34. 1. A method for attaching a peptide or protein having a second ionizable group to a surface, the method comprising:

20. A method comprising contacting the peptide or protein with the article of any one of claims 1 to 18, wherein the second ionizable group is oppositely charged to the first ionizable group.

35. 35. The method of claim 34, wherein the peptide or the protein is reversibly bound to the first ionizable group.

36. 19. Use of an article according to any one of claims 1 to 18 for binding a peptide or protein having second ionizable groups on its surface, said second ionizable groups being oppositely charged to said first ionizable groups.

37. 37. The use of claim 36, wherein the peptide or the protein is reversibly bound to the first ionizable group.

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