EP4329932A1

EP4329932A1 - Functionalized cellulose decontamination agent

Info

Publication number: EP4329932A1
Application number: EP22726012.2A
Authority: EP
Inventors: Vanja Kokol; Vera VIVOD; Branko NERAL; Ales Mihelic
Original assignee: Univerza v Mariboru
Current assignee: Univerza v Mariboru
Priority date: 2021-04-29
Filing date: 2022-04-26
Publication date: 2024-03-06
Also published as: WO2022229230A1

Abstract

[1] The present invention is based on both the contaminant-capturing and anti-microbial effect of functionalized nanocellulose that was subjected to amination and quaternization reactions. These features are highly complementary and are the basis for a decontamination agent comprising functionalized cellulose as an active agent. In a second aspect, a use of functionalized cellulose for the removal of chemical, particle-based and biological contaminants from a medium is provided. Furthermore, the invention pertains to a method for treatment of laundry in a laundry-appliance that is operating in an automated cycle comprising different phases, wherein in one of the phases the decontamination agent of the invention is used in.

Description

FUNCTIONALIZED CELLULOSE DECONTAMINATION AGENT

FIELD OF THE INVENTION

[1] The present invention is based on the both the contaminant-capturing and anti-microbial effect of functionalized nanocellulose that was subjected to amination and quaternization reactions. These features are highly complementary and are the basis for a decontamination agent comprising functionalized cellulose as an active agent. In a second aspect, a use of functionalized cellulose for the removal of chemical, particle-based and biological contaminants from a medium is provided. Furthermore, the invention pertains to a method for the treatment of laundry in a laundry treating appliance that is operating to an automated cycle of operation comprising different phases, and in one of which the aforementioned decontamination agent is used in.

DESCRIPTION

[2] Pollution is the largest environmental cause of disease and premature death in the world today. Diseases caused by pollution were responsible for an estimated 9 million premature deaths in 2015—16% of all deaths worldwide— three times more deaths than from AIDS, tuberculosis, and malaria combined and 15 times more than from all wars and other forms of violence. In the most severely affected countries, pollution-related disease is responsible for more than one death in four. Principal diseases linked to water pollution are acute and chronic gastrointestinal diseases, most importantly diarrhoeal diseases (70% of deaths attributed to water pollution), typhoid fever (8%), paratyphoid fever (20%), and lower respiratory tract infections (2%). These diseases affect more than 1 billion people, predominantly in low-income and middle income countries. (Landrigan et al, The Lancet Commissions, 2018, 391, 10119, DOI : 10.1016/S0140- 6736(17)32345-0)

[3] To combat this issue, the last years have shown a growing trend in politics for environmental protection. For example, increasingly stringent EU directives such as Directive 2012/ 27/EU, Directive (EU) 2016/2284 and Directive (EU) 2018/2002 on reducing pollution and energy consumption are set. These developments have also transferred into our laundry washing habits at home. Manufactures advertise eco-friendly washing machines that feature energy saving programs and need only reduced amounts of water.

[4] On the consumer-side, people wash their clothes at low temperatures and avoid washing only half-filled machines, which gives rise to two problems: 1.) The individual pieces of clothing washed in a single batch are restricted by colour and colour-intensity. During washing, dye molecules can be detached from fabrics and deposit on other clothes. This “bleeding” leads to cross-contamination, and complicates the planning of eco-friendly washing. 2.) When treating laundry at low temperatures in the range of 20 - 40 °C, microorganisms can significantly survive the laundry treatment process and can cross-contaminate the whole laundry batch. This is unhygienic and can lead to the formation of bad odours.

[5] Cellulose is a polysaccharide that consists of b(i- 4) linked D-glucose units. Depending on their size and crystallinity, several distinct types cellulose are distinguished: Among nanocellulose variants, these are cellulose nanocrystals (CNC), cellulose nanofibrils (CNF) and microfibrillated cellulose (MFC). These cellulose types can be produced from bacteria or various plant-based sources such as wood, cotton, hemp, flax, sugar beet and potato tuber fibre. Cellulose is easily produced in large quantities and highly biocompatible. In form of nanocellulose, the material features great surface areas that can interact with their surrounding medium. Further, this large surface allows to fixate chemical functionalizations to a solid backbone. The combination of these properties make nanocellulose an interesting material for washing and water-decontamination applications.

[6] One of the common ways to functionalize cellulose is by introduction of cationic functional groups, which can be realized by amination or quaternization. In a typical amination process, individual glucose units of the cellulose polymer are first oxidized to display aldehyde groups. These are then functionalized in further reaction steps to exhibit amino group-bearing molecules. In case of quaternization, the individual hydroxyl-groups at the glucose constituents of the cellulose polymer are replaced by quaternary ammonium derivatives. Overall, both reactions result in a polymer, that exhibits cationic functionalities and thus is called cationized cellulose.

[7] A prominent example that is making use of the high-surface area of nanocellulose is given by heavy-metal capturing: In CN1054Q8733A. this is demonstrated on polyethyleneimine- functionalized and cross-linked nanocellulose. This functionalized cellulose can complex soluble metal-ions by their amino-containing Lewis-basic groups. CN107138135A uses the metal capturing properties of ethylenediamine- and thiocarbamide-functionalized crystalline nanocellulose to “imprint” the cellulose with metal-ions. The material can further be used to capture ions such as mercury, lead and copper.

[8] The anti-microbial effects of cellulose that is cationized by quaternization are well-known and thought to be the result of the interactions between their quaternary ammonium groups and bacterial cytoplasmic membranes. Cationic cellulose can therefore be used to inhibit bacterial growth and kill bacteria. An example for this is shown in CN1078408Q5A. were the anti-microbial effect of cationically modified nanocellulose is disclosed. In this application, cationized plant extracted cellulose nanoparticles are obtained in a three-step procedure that is based on low- temperature esterification, grafting of 2,3-epopropyltrimethylammonium-chloride via an addition reaction, and a final polymerization step. CN 100608 4 A discloses anti-microbial nanofibrillated cellulose. They obtain their product by quaternizing cellulose bulk material (a cellulose slurry) with a mixture of different ammonium-chlorides and which is subsequently broken down into functionalized cellulose with a desired shape. CN10Q678Q72A discloses the use of 2,3-dialdehyde-6-carboxy-nanocellulose in the field of antimicrobial textiles. This functionalized cellulose was obtained by conducting first an oxidation reaction on plant based cellulose that was performed in a 2,2,6,6,-tetramethylpiperidine oxide/NaBr/NaCIO oxidiation system. This reaction resulted in a carboxyl-group with anti-microbial effect at the C6 position in the individual glucose-units. Subsequently, the material was pulverized and further modified by oxidation with periodate, resulting in additional aldehyde groups at the carbon positions C2 and

C3.

[9] The commercial use of cationized cellulose nanoparticles as cleaning composition is shown in EP227284QA1 and EP3272848A1. In these applications, a mixture of a dispersing agent and cationically modified (via quaternization) cellulose particles that are gained from wood pulp and bacterial origin is shown. Both applications aim at using the aforementioned cellulose- materials to capture dye-molecules released by laundry. The use of aminated-cellulose as a washing agent is given by Liquiang et al. In their publication, they provide cellulose that is produced by subsequently conducting periodate-oxidation and ethylene diamine functionalization. In particular, they used this modification technique on cellulose nanocrystals, which resulted in a material capable of binding anionic dyes in acidic conditions via chemisorption (Liquiang et al., Cellulose, 2015, 22, 4, DOI: 10.1007/S10570-015-0649-4).

[10] Patent application WO 01/66600 discloses microfibrillar functionalized with amine or a quarternary amine for adsorption of detrimental substances in water, wherein the functionalized cellulose exhibits a degree of substitution of hydroxy groups in glucose units of 17%. Similarly, patent application WO 2016/181034 discloses a process for removing ions from waste water, wherein plant-derived cationic nanofibrillar cellulose having a degree of substation of maximally 27% was used. Chaker Achraf et al (doi: 10.1016/J.CARBPOL.2015.06.003) disclose a quarternized nanofibrillar cellulose with degree of substitution of around 6%.

[11] In laundry treatment, the nuisances of dye-capturing and bacterial cross-contamination can be solved by the use of differently specialized laundry washing agents. However, the compatibility of such agents is hardly predictable by experts, less so by the average consumer. This is all the more important for general water decontamination, where many of the currently used agents are based on chlorine or ozone and are potentially dangerous to the untrained individual. Furthermore, such as in the case of chlorine agents, they may require machinery or chemicals to be to removed from the decontaminated water, which defeats the purpose of decontamination.

[12] Therefore, there is a need for simple all purpose decontamination agents that are easily removable, once they have fulfilled their purpose. Furthermore, there is a need for new washing agents, that simultaneously provide anti-microbial and dye-capturing properties.

[13] The problem of the current invention is to overcome the various drawbacks indicated above for the prior art and to provide an improved decontamination and laundry treatment agent.

DESCRIPTION

BRIEF DESCRIPTION OF THE INVENTION

[14] The current invention solves the above problem by providing a cellulose-based decontamination agent that is characterized by a simultaneous anti-microbial effect and contaminant-removal function. It pertains to a decontaminant agent (cationized cellulose) that allows for the removal of chemical, particle-based and biological contaminants from a medium. Furthermore it can be used in laundry treatment, where it allows for the removal of dyes and colours present in the washing waters during the laundering of textiles, thus preventing "white" articles from being dyed from dye re-deposition. As a consequence, "coloured" and "white" garments may be washed at the same time in a washing machine in the presence of the product of the invention. At the same time, the invention eliminates microbiological species from the washing liquid and prevents their re-deposition among the washing articles as well as cross contamination.

[15] Generally, and by way of brief description, the main aspects of the present invention can be described as follows:

[16] In a first aspect, the invention pertains to a decontamination agent, comprising functionalized cellulose as an active agent.

[17] In a second aspect, the invention pertains to a method for the treatment of laundry in a laundry treating appliance that is operating to an automated cycle of operation, comprising (sequentially):

(i) A soaking phase,

(ii) Optionally, a prewashing phase,

(iii)A washing phase, and, wherein the decontamination agent of the previous aspect of the invention is used in at least one of the phases (i)-(iii).

[18] In a third aspect, the invention pertains to a use of functionalized cellulose for the removal of chemical, particle-based and biological contaminants from a medium.

[19] The technical problem is solved with the invention as defined in the independent claims, wherein preferred embodiments of the invention are defined in dependent claims. DETAILED DESCRIPTION OF THE INVENTION

[20] In the following, the elements of the invention will be described. These elements are listed with specific embodiments, however, it should be understood that they may be combined in any manner and in any number to create additional embodiments. The variously described examples and preferred embodiments should not be construed to limit the present invention to only the explicitly described embodiments. This description should be understood to support and encompass embodiments which combine two or more of the explicitly described embodiments or which combine the one or more of the explicitly described embodiments with any number of the disclosed and/or preferred elements. Furthermore, any permutations and combinations of all described elements in this application should be considered disclosed by the description of the present application unless the context indicates otherwise.

[21] In a first aspect, the invention pertains to a decontamination agent, comprising functionalized cellulose as an active agent. In the context of the invention, the term “cellulose” refers to a biopolymer having one or multiple polysaccharide chains, that is composed of b(i- 4) linked D-glucose units. In the context of the invention, the term “functionalized cellulose” refers to a polysaccharide that comprises cellulose with chemically modified b(i- 4) linked D-glucose units. In the context of the invention, a “chemical modification” refers to the alteration of the chemical nature of the modified cellulose either by allowing reactive groups in the cellulose to react with a modifying agent, for example by binding of molecules or atoms via covalent and/ or coordinative covalent bonds or by non-covalent interactions such as to hydrogen bonding and/ or dipole-dipole, van der Waals and/or electrostatic interactions.

[22] The term „agent“ in context of the invention shall be interpreted in its broadest sense and include both (i) a pure or essentially pure preparation of the functionalized cellulose of the invention, and (ii), which is particular preferred, a composition comprising the functional cellulose of the invention together with other compounds, such as a non-functionalized cellulose, or a differently functionalized cellulose, or other non-cellulose active agents useful for the intended purpose of the agent of the invention, as well as additives, carriers and/or excipients, and any combinations of the foregoing.

[23] In preferred embodiments of the invention, the decontamination agent is an aqueous suspension, dispersion and/or gel, or film, membrane or powder. In the context of the invention, the decontamination agent can be provided as solid films and/or powders that are redispersible in water to provide a colloidal suspension. These forms are preferred for transportation and packaging of the invention. Such powders and/or films maybe produced by drying at least one suspension of the components of the decontamination agent on a surface or in a mold, either at room temperature or at elevated temperatures. This drying can be done under air, nitrogen, vacuum or with a comparable method. Such a powder and/ or film may also be produced by spray- drying or freeze-drying at least one suspension of the components of the decontamination agent on a surface or in a mold. The decontamination agent can also be provided in form of a suspension and/or gel. In such a suspension, the decontamination agent comprises at least one solid phase, that is suspended in at least one liquid phase. The at least one liquid phase comprise soluble components of the decontamination agent, water and/or any other suitable solvents such as ethanol and/or isopropanol. Such a suspension can also be produced by sonicating at least one gel, dried powder and/ or film of components of the decontamination agent under exposure of the liquid phase and/or a solvent. In case of sufficient cross-linking of components of the suspension, the suspension can also be called a “gel”.

[24] In preferred embodiments of the invention, the decontamination agent is a coating, part of a composite material, membrane and/ or non-woven mat. In preferred embodiments of the invention, the decontamination agent is provided in form of a composite material, for example a composite textile. Such a composite material comprises the decontamination agent and at least one other material. The other material preferably is a carrier material such as a man-made synthetic polymer that comprises at least one of high density polyethylene, low density polyethylen, polypropylene, polyvinylchloride, polyamides, ethylene vinyl acetate copolymer, polyimides, and/or organic polymers such as viscose, and/or any other organic-based materials such as cellulose, wool, silk, flax or hemp. In preferred embodiments of the invention, the decontamination agent is a carrier material for active agents with different function, for example zeolites. In preferred embodiments of the invention, the carrier material is a inorganic fiber such as glass fibers, microglass, carbon fibers, hydrated magnesium sulfat fibers, potassium titanate fibers, ceramic fibers, calcium silicate fibers and/or rockwool.

[25] In preferred embodiments of the invention, the decontamination agent may be provided in form of a membrane and/ or non-woven mat or as a component thereof. Such a body that features dominantly a 2 dimensional spatial extension can be fixated or self-standing. In preferred embodiments of the invention, the membrane and/ or mat is in form of a three dimensional shape. In preferred embodiments of the invention, this is realized by at least two membranes and/or mats that are connected to form 3-dimensional shapes. A membrane in the context of the invention, is a material that is woven from individual fibers. Such fibers can be generated with common techniques such as electrospinning, wet spinning, dry spinning, melt spinning such as extrusion spinning and direct spinning, gel spinning and/or drawing. A mat in the context of the invention is a material that comprises fibers that are connected by chemical and/or physical interactions, or entangled mechanically. In preferred embodiments of the invention, in addition to the aforementioned technqiues for fiber generation, the mat can be generated with techniques such as melt-blowing or spinlaying.

[26] The contamination agent may also be provided in form of a coating. Such a coating can be situated on the internal and/or external surface of a carrier material. External surface in the context of the invention is the interface of a material with its surrounding medium, for example the surface of a sphere or a cube. Internal surface in the context of the invention is the interface of a material an its penetrating medium, for example the surface in pores. In the context of the invention, the cellulose may assume any shape of the carrier material that it may be coated on. Such a carrier material can for example be a sponge, a grid or a cylinder. A coating in the context of the invention can be applied by any methods that are state of the art. Preferably, such methods comprise simple drying of emulsions containing the decontamination agent on a target surface under ambient air or vacuum, vacuum filtration, spin coating, dip coating, slot-die coating, spray painting, powder coating techniques, air knife coating, and/ or roll coating techniques such as roll- to-roll coating or roll-coating on a flat target surface. The target surface bind the decontamination agent by chemical and physical means. These comprise binding of the decontamination agent via covalent and/ or coordinative covalent bonds or by non-covalent interactions such as to hydrogen bonding and/or dipole-dipole, van der Waals and/or electrostatic interactions and/or by steric interaction. [27] In preferred embodiments of the invention, the decontamination agent is an anti microbial and dye-capturing agent. The most preferred embodiment of the invention is that the decontamination agent is a laundry treatment additive.

[28] In preferred embodiments of the invention, the functionalized cellulose comprises at least one covalently modified glucose unit. A “covalently modified glucose” unit maybe modified using any modification technique that is common to the field. These modification techniques include preferably but are not limited to hydrolysis, oxidation, esterification (acylation), amidation, imination, carbamation, etherification (carboxymethylation) and/or nuclephilic substitution. Functional groups that are introduced by these techniques can also act as precursors for subsequent modification steps. [29] In preferred embodiments of the invention, the functionalized cellulose exhibits functional groups that replace at least a part of hydroxy groups in glucose units. In the context of the invention, a “functional group” is a substituent or chemical moiety that is associated with the cellulose polysaccharide chain. A functional group features distinct biological, chemical and/or physical properties and/or effects. These distinct biological, chemical and/or physical properties and/or effects include preferably, although not necessarily being limited to, chemical reactivity, capturing of colloids, molecules and/or atoms, anti-microbial effects, colour changes and/or the emission of light.

[30] In preferred embodiments of the invention, the functionalized cellulose can first be generated and then shaped or applied to another material. In preferred embodiments of the invention, the functionalized cellulose can be generated and shaped or applied to another material simultaneously. In preferred embodiments of the invention, the cellulose can be first shaped or applied to another material, and then functionalized.

[31] In a preferred embodiment of the invention, the glucose unit is modified to exhibit at least one aldehyde group at its positions C2 and/or C3. In this preferred embodiment, the aldehyde group can be introduced by exposing the cellulose or functionalized cellulose to oxidizing reaction conditions and agents. Any oxidation method or agent that is suitable and results in the desired functional group can be used. To achieve an aldehyde-functionalization at the ring positions C2 and C3, such suitable oxidation agents comprise preferably periodates chosen from sodium iodate, potassium iodate and/or periodic acid.

[32] In preferred embodiments of the invention, the glucose unit is further modified by substituting the at least one aldehyde group at its C2 and C3 positions. In another preferred embodiment of the invention, the covalently modified glucose unit is modified by substituting at least one hydroxyl group at its ring positions C2, C3 or C6. A “substitution” in the context of the invention refers to the presence of a functional group that is, directly or via other bridging atoms, covalently bound to a carbon atom in a covalently modified glucose unit of a functionalized cellulose, wherein this functional group differs from the functional group that was bound to this carbon atom before the chemical modification was performed. A substitution can be conducted to both modified or non-modified glucose units. The entirety of the atoms that is substituting the at least one hydroxyl group at the ring positions C2, C3 or C6 respectively is referred to as a substituent.

[33] In preferred embodiment of the invention, the functionalized cellulose further is cationized, for example with quarternization. In the context of the invention, cationized cellulose refers a functionalized cellulose that comprises positively charged functional groups, when suspended in water at pH = 7. In case that the functionalized cellulose also exhibits negatively charged functional groups such as carboxylic, sulphate and phosphate groups, these positively charged functional groups are in a majority compared to the negatively charged groups. In preferred embodiments of the invention, these positively charged functional groups are attached to the cellulose structure by techniques such as quaternization and amination. However, the methods to obtain such cationized cellulose are not limited to these two techniques. Other possible methods include the capturing of positively charged metal ions either via complexation (for example by Lewis-basic functional groups in the framework) or by association of cations to negatively charged functional groups in the framework. [34] In preferred embodiments of the invention, the functionalized cellulose is quaternized cellulose. In the context of the invention, quaternized cellulose is a type of functionalized cellulose that is obtained by a quaternization reaction. According to the invention, a quaternization reaction comprises a covalent binding of a quaternary molecule to a carbon atom in a modified or non-modified glucose unit by a bridging oxygen atom and thus results in a substitution of the functional group that would normally be at this position. In a preferred method of such an quaternization reaction cellulose is dispersed in aqueous basic conditions and stirred at elevated temperatures. The exposure of cellulose to these basic conditions results in deprotonated cellulose, that allows for a binding of quaternary compounds such as glycidyltrimethylammonium chloride to the cellulose, and thereby, generates quaternized cellulose. Hence, quaternization results in a “substitution” as in the context of the invention. Quaternary molecules in the context of the invention comprise a positively charged central atom that is covalently linked to four aryl or alkyl substituents. In solid form, these cations can be associated with any possible anion to form a quaternary compound. Such a quaternary molecules can be chosen from ammonium- (R₄N⁺), phosphonium- (i^P⁺l, arsonium- (R₄As⁺), stibonium- (R₄Sb⁺) or bismuthonium- (R₄Bi⁺) molecules.

[35] In a preferred embodiment of the invention, the quaternized cellulose comprises at least one covalently bound quaternary ammonium molecule. In the context of the invention, a quaternary ammonium-molecule constitutes the cation of a quaternary compound described with the formula [R₄N⁺X ], wherein R, refers to ammonium molecules selected from up to four different aryl or alkyl residual chains, X- refers to a counter-ion that can be any suitable counter ion such as a halide or sulfate. In a particularly preferred embodiment of the invention the quaternary ammonium molecule is a glycidyltrimethylammonium chloride.

[36] In preferred embodiments of the invention, the modification according to one of the disclosed methods does not result in substitution of substantially all hydroxyl groups of the initial cellulose. In preferred forms of this embodiment, the functionalized cellulose is exhibiting a degree of substitution of at least 33%, preferably 40%, most preferably 50% of its hydroxyl groups. Depending on the reaction conditions used to obtain the functionalized cellulose of the present invention, the functionalized cellulose features different degrees of hydroxyl substitution. The degree of hydroxyl substitution (%) in the functionalized cellulose is given by the following relationship:

Equation 1 100 wherein the n(hy dr oxy l groups _bef_{0re modi}fi_cation) is the amount of hydroxyl groups in functionalized or non-functionalized cellulose, before the hydroxyl groups are substituted and n iydroxyl groups_af_{ter modi}f_ication) is the residual amount of hydroxyl groups in the functionalized cellulose after modification. This ratio can easily be determined with methods commonly found in many general laboratories such as nuclear magnetic resonance (NMR)-spectroscopy, X-ray photon spectroscopy (XPS) and Fourier-transform infrared (FTIR)- spectroscopy.

[37] In preferred embodiments of the invention, the functionalized cellulose is aminated cellulose. Amination in the context of the invention, refers to covalently binding molecules, that are bearing amino functional groups so that the resulting functionalized cellulose comprises amino-groups. Such a cellulose is referred to as “aminated cellulose”. Amination in the context of the invention is conducted in “amination reactions”. Preferred methods for such an amination reaction are given in the examples. Amination is conducted in a two-step process: First, (selected) hydroxyl groups of cellulose are oxidized with a suitable agent such as sodium periodate, potassium periodate or periodic acid. The resulting functionalized cellulose therefore comprises at least one aldehyde group. Second: The functionalized cellulose is then reacted in a Schiff-base reaction with an amine. The obtained material thus exhibits free amino groups and is referred to as “aminated cellulose”.

[38] In preferred embodiments of the invention, wherein the functionalized cellulose is modified with a type of functional group chosen from a list comprising primary, secondary and tertiary amino groups and quaternary ammonium groups. In the context of the invention, the at least one modified glucose unit of the functionalized cellulose comprises substitutions, in which hydroxyl or aldehyde groups may be substituted with amino groups. Depending on their degree of substitution, these amino groups are categorized as primary, secondary and tertiary amino groups or quaternary ammonium groups. Primary amino groups can be described with the formula (G-NH₂), secondary amino groups can be described with the formula (G-NHR¹), tertiary amino groups can be described with the formula (G-NR’R²) and quaternary ammonium groups can be described with the formula (G-NRT^R³*), wherein G is the (modified) glucose unit of the functionalized cellulose and R¹, R², and R³ are residual organic groups and wherein between the (modified) glucose and the N of the amino and/ or ammonium group may be one or more bridging atoms. Such amino groups may be introduced by binding of primary, secondary, and/ or tertiary amine molecules and/ or quaternary ammonium groups (that comprise corresponding residual organic groups) to the polysaccharide chain of a cellulose polymer with the methods described herein or with methods that are commonly used in saccharide chemistry. [39] In preferred embodiments of the invention, the aminated cellulose comprises at least one covalently bound amine molecule. Aminated cellulose also refers to functionalized cellulose, whose modified glucose units are modified with molecules that comprise at least one amino functional group and at least one other functional group by which they are bound to the modified glucose chains. These other functional groups, such as hydroxyl groups, aldehyde groups and/or carboxylic acids can react with hydroxyl and/or aldehyde groups of modified and/or unmodified glucose units. In preferred forms of this embodiment the amine molecule is bound via the at least one aldehyde group. In such a case, the amine molecule that comprises at least one amino group, covalently binds to an aldehyde functional group that is part of a modified glucose unit in the functionalized cellulose.

[40] In other preferred embodiments, the amine molecule is a diamine molecule. In the context of the invention, a diamine molecule is any molecule, that exhibits two amino groups and refers to the formula H₂N-R-NH₂. R in the context of such a diamine can be a linear or branched or cyclic aliphatic chain or a xylylenediamine or an aromatic ring system. Linear aliphatic amines can be chosen from a list comprising diaminomethane, 1,2-diaminoethane, propane-i, 3-diamine, butane-i, 4-diamine, pentane-i, 5-diamine and hexane-i, 6-diamine. Branched aliphatic amines can be chosen from a list comprising 1,2-diaminopropane, diphenylethylenediamine and 1,2- diaminocyclohexane. Cyclic aliphatic amines can be chosen from a list comprising 1,4- diazacycloheptane, 1,5 diazacyclooctane, 1,4 diazacyclohexane. Amines with aromatic ring can be chosen from a list comprising o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,5-diaminotoluene, dimethyl-4-phenylenediamine, A V-di-2-butyl-i,4-phenylenediamine, 4,4’-diaminobiphenyl and/or 1,8-diaminonaphthalene.

[41] In preferred embodiments of the invention, the amine molecule is bound by at least one of its amino groups. In these preferred embodiments, if the amine molecule is a diamine molecule, the diamine can bind to the polysaccharide chain of functionalized cellulose by one of its amino groups and then still feature another free amino group. This free amino functionality is capable of interacting with its environment. For example, it can excerpt dye-capturing or anti-microbial effects, or can bear charges that may stabilize the functionalized nanocellulose when in suspension. Furthermore, under suitable reaction conditions, the free amino group can bind to functional groups of the same or other cellulose chains and crosslink these chains. In a most preferred form of these embodiments, the amine molecule is a linear primary diamine (H₂N-R- NH₂) with R being a C to C₆ alkyl, preferably C₃ to C₆ alkyl, most preferably C₆ alkyl (hexane 1,6 diamine).

[42] In preferred embodiments of the invention, the modification according to one of the disclosed methods does not result in substitution of substantially all hydroxyl groups of the initial cellulose. In preferred forms of this embodiment the functionalized cellulose exhibits a degree of substitution of at least 50% of its aldehyde groups. Depending on the reaction conditions used to obtain the functionalized cellulose of the present invention, the functionalized cellulose is characterized by different degrees of aldehyde substitution. The degree of aldehyde substitution (%) in the context of the present invention is defined by the following relationship:

Equation 2 wherein the n(aldehyde groups_bef_0re amination) is the initial amount of aldehyde groups in aldehyde-functionalized cellulose before the completion of an amination reaction, and n(aldehyde groups_af_ter amination ) is the residual amount of aldehyde groups in amine- functionalized cellulose after the completion of this amination-reaction. This ratio can easily be stoichiometrically determined with methods commonly found in many general laboratories such as NMR-spectroscopy, XPS-spectroscopy, and FTIR-spectroscopy, and stoichiometrically using other relevant spectrophotometric methods.

[43] The decontamination agent, comprising aminated cellulose as an active agent, wherein individual glucose units of the cellulose exhibiting three hydroxy groups are first oxidized to display aldehyde groups, and then said aldehyde groups are substituted with amino groups, and wherein the aminated cellulose exhibits a degree of substitution of 50% of its aldehyde groups or at least 33% of its original hydroxy groups, and wherein said cellulose is selected from microfibrillated cellulose, cellulose nanocrystals, cellulose nanofibrils and combinations thereof, exhibits a surprising effect of improved pigment and dye removal as well as superior antimicrobial activity. Namely, during washing laundry dyes are released from the textile fibers in very first minutes after being in contact with the water, when the washing detergent is not yet delivered or dissolved. The decontamination agent significantly improves the shortcomings of existing products as it efficiently and quickly catches dyes and pigments extracted and/or released from textile fibers in the first minutes of washing after contact with water, even at very low temperatures, i.e. at 20 °C. Furthermore, the effect of such decontamination agent is inhibition of the transfer of potentially present microbial substances duirng laundry, or in some cases even acts bacteriocidly. In addition, the decontamination agent has been surprisingly found to catch or filter microplastic particles and bacteria, which is a significant improvement of currently known similar agents.

[44] In preferred embodiments of the invention, the functionalized cellulose comprises at least two different substituents each selected from an amino group-containing substituent or a quaternary ammonium group-containing substituent. The amino group-containing substituent in the context of the invention may be any of the aforementioned covalently bound amine- molecules. An ammonium group-containing substituent in the context of the invention may be any of the aforementioned ammonium-molecules.

[45] In preferred embodiments of the invention, the functionalized cellulose comprises at least two different types of functional groups, selected from amino group, aldehyde group, hydroxyl group, and quaternized ammonium group. In the context of the invention, functionalized cellulose can be obtained with different modification methods. Generally, such methods are used to obtain functionalized cellulose, wherein the initial hydroxyl groups in the modified glucose units of the cellulose are substituted. In preferred embodiments of the invention, the functionalized cellulose comprises more than one functional group at the same time. In preferred embodiments of the invention, the modification according to one of the disclosed methods does not result in substitution of substantially all hydroxyl groups of the initial cellulose, and thus results in a functionalized cellulose with both the initial aldehyde/hydroxyl groups and newly introduced functional groups such as amino or ammonium groups. In other preferred embodiments of the invention, the functional cellulose may be subjected to multiple successive or simultaneous functionalization reactions. Therefore, the resulting functionalized cellulose may comprise at least one type of amino group, at least one type of quaternary ammonium group, (residual) aldehyde groups, (residual) hydroxyl groups and/or any other functional group that is covalently bound or associated by other chemical modifications in the context of the present invention. For example, the decontamination agent may comprise the functionalized cellulose in any of the following combinations: aminated and native cellulose; aminated and quarternized cellulose; aminated and oxidized cellulose; native, aminated and oxidized cellulose; quarternized and oxidized cellulose; oxidized, aminated and quarternized cellulose; or oxidized, native, aminated and quarternized cellulose; or any other suitable combination.

[46] In preferred embodiments of the invention, the decontamination agent comprises at least two different types of functionalized cellulose. In preferred embodiments of the invention, the decontamination agent comprises at least three types of functionalized cellulose. In these preferred embodiments, the decontamination agent according to the invention may comprise multiple types functionalized cellulose. These functional cellulose types can be chosen from any type of functionalized cellulose that are disclosed in the present invention. This comprises functionalized cellulose types that were functionalized separately from each other and subsequently mixed in the decontamination agent. This also comprises different functionalized cellulose types such as at least one type of functionalized cellulose nanocrystals, functionalized cellulose nanofibers and/ or functionalized microfib rillated cellulose that were functionalized with the same or different types of functional groups. In the case of different types of functional celluloses that are exhibiting the same types of functional groups, this embodiment also comprises functional cellulose types that were functionalized simultaneously in the same reaction vessel. This embodiment also comprises functional cellulose types that only differ by their respective amount of substituted hydroxyl or aldehyde groups. In certain embodiments of the invention, the aqueous suspension, dispersion and/or gel and/or film and or powder comprises at least o.i-o.2wt% quaternized cellulose.

[47] In preferred embodiments of the invention, the decontamination agent further comprises at least one additional component selected from the group of surfactants, builders, anti redeposition agents, corrosion inhibitors, processing aids, colorants, fragrances, bleaching agents, enzymes, suds control agents, opacifiers and/or fabric softeners. In these embodiments, the decontamination agent comprises at least one type of functional cellulose as described in any other embodiment of the invention. Additionally, the decontamination agent may comprise other components that are commonly used in laundry treatment compositions. These comprise a) surfactants for penetrating and wetting fabric, loosening soils, and emulsifying soils to keep them suspended in the wash solution; b) builders for enhancing the action of surfactants by, for example, softening the water, helping to disperse soils and prevent their redeposition out of solution, and assisting in dissolving oil-based soils; c) alkalis to raise the pH of wash water; d) anti-redeposition agents to prevent dislodged soils from being redeposited; e) enzymes to effect stain removal and provide color and fabric care; f) active bleaches to improve fabric whiteness and brightness; g) additional antimicrobial agents to hygienically clean fabrics; h) fabric softeners to impart softness, reduce static electricity and reduce crinkling; i) fragrances to neutralize odor in both the detergent chemicals and the soils in the laundry wash; j) optical brighteners to enhance the light reflected from washed fabric to make the fabric look whiter and brighter; k) preservatives to prevent detergent spoilage during storage; i) solubizers to help maintain the pouring characteristics of liquid detergent; m) processing aids to maintain the physical characteristics of laundry detergents during process, storage and use; n) foam regulators (suds control agents) to inhibit the formation of suds during washing; 0) corrosion inhibitors to inhibit corrosion of metallic parts in the laundry treating appliance; and p) opacifiers to provide a rich, zeamy opaque appearance to liquids.

[48] In preferred embodiments, the functionalized cellulose is functionalized microfibrillated cellulose and/ or functionalized cellulose nanocrystals and/ or functionalized cellulose nanofibrils. In the context of the invention, three types of functionalized nanocellulose are distinguished, based on the cellulose type that they are originating from. “Functionalized cellulose nanofibrils” result from functionalizing cellulose nanofibrils, also known as CNF, cellulose nanofibers and nanofibrillated cellulose. Cellulose nanofibrils are a cellulose type that features long and thin specimen. This type of nanocellulose features a diameter of below 150 nm, and a length of at least 8oo nm. “Functionalized cellulose nanocrystals” result from functionalizing cellulose nanocrystals. Cellulose nanocrystals are commonly also known as nanocrystalline cellulose, cellulose (nano) whiskers, CNC, or rod-like cellulose microcrystals. They exhibit a similar diameter than cellulose nanofibrils, however feature a much shorter length that is below 8oo nm. “Functionalized microfibrillated cellulose” results from functionalizing microfibrillated cellulose. Microfibrillated cellulose, also known as MFC, is a material that is not composed of individual particles or fibers but is composed of an interconnected network for cellulose nanofibrils. The nanofibrils in such a network exhibit a diameter of less than 200 nm, and a length of several micrometers. Crystalline nanocellulose may be produced by different hydrolysis conditions and cellulose precursors by using strong acids or any other suitable method. Microfibrillated cellulose may be generated by delamination from wood pulp cellulose by using mechanical pressure in combination with chemical/enzymatic treatment methods or any other suitable method.

[49] In preferred embodiments of the invention, the functionalized cellulose nanofibrils exhibit a diameter of 5 to 150 nm, preferably 10 to 150 nm, more preferably 20 to too nm, or most preferably 50 to 80 nm. In another preferred embodiment, the functionalized cellulose nanofibrils exhibit a length of 0.8 to 6 pm, preferably 0.8 to 4 pm, or more preferably 0.8 to 2 pm. In another preferred embodiment of the invention, the functionalized cellulose nanocrystals exhibit a diameter of 10 to 80 nm, preferably 20 to 60 nm or more preferably 30 to 50 nm. In preferred version of this embodiment, the functionalized cellulose nanocrystals exhibit a length of too to 400 nm, preferably too to 300 nm, more preferably too to 200 nm. In other preferred embodiments the functionalized microfibrillated cellulose exhibits a diameter of 10 to 200 nm, preferably 20 to 200 nm, more preferably 20 to 150 nm, or most preferably 20 to too nm and length of 2 to 10 pm. In the context of the invention, these sizes refer to the physical extensions of the cellulose particles or fibres as determined by scanning electron microscopy. They include both the average values and a standard deviation of ± to. Due to the of the non-spherical morphology of the cellulose structures, the term “length” refers to the physical extension of the particles along their longer direction. The term “diameter” refers to the extension of the particles perpendicular to this direction.

[50] In preferred embodiments of the invention, the functionalized cellulose is semi crystalline. In the context of the invention, crystallinity refers to the feature that the functionalized cellulose, when examined in an X-ray diffractometer or by electron microscopy, results in diffraction patterns that show significant reflections. The atoms in a crystalline material are repeating in a periodic manner along the spatial dimensions of the particle. The functionalized cellulose in this invention can feature different amounts of crystallinity, which is defined by the percentage of the volume of a particle that is crystalline, when compared to the volume of the particle that is both crystalline and not crystalline (“amorphous”). In context of the invention, particles of functionalized cellulose may have any degree of crystallinity. Although some preferred embodiments of the invention refer to particles as “crystalline nanocellulose”, this does not imply the actual degree of crystallinity of these particles. Semi-crystalline in the context of the invention refers to particles that feature a degree of crystalline in the range of 10-80%. The degree of crystallinity of the functionalized cellulose referred to in the invention does not affect its usage as a decontamination agent.

[51] In preferred embodiments of the invention, the decontamination agent comprises functionalized cellulose as an active agent, wherein the functionalized cellulose is quaternized- and/or aminated cellulose selected from microfibrillated cellulose, cellulose nanocrystals, cellulose nanofibrils, and combinations thereof, and wherein the functionalized cellulose exhibits a degree of substitution of at least 33% of its hydroxyl groups.

[52] In another aspect, the invention refers to a method for the treatment of laundry in a laundry treating appliance that is operating to an automated cycle of operation, comprising (sequentially): (i) A soaking phase,

(ii) Optionally, a prewashing phase, and

(iii)A washing phase, wherein the decontamination agent of the first aspect is used in at least one of the phases (i)-(iii).

[53] In the context of the present invention, a “soaking phase” refers to an incubation period during laundry washing, in which the laundry is first contacted with water. The vessel, in which the soaking is conducted, comprises the laundry and water in this vessel is referred to as “soaking water”. During this soaking phase, the laundry appliance does not excerpt physical forces on the laundry. In preferred forms of this embodiment, the soaking water may be heated. In preferred embodiments, the decontamination agent is added to the incubation mixture, thus the vessel of the laundry treatment appliance, in which the soaking is conducted, comprises laundry, soaking water and the decontamination agent that is described in this invention. Optionally, other decontamination agents and laundry detergents can be added during this soaking phase. This soaking phase can range between 1 to 35 min, preferably 1 to 25 min, most preferably 1 to 15 min. Optionally, at the end of the soaking phase, the soaking water can be drained and replaced with new water in subsequent laundry treatment phases. In certain embodiments of the invention, the wastewater of the soaking phase is filtrated or non-filtrated and reused or discarded. In the context of the present invention, the optional “prewashing phase” refers to a period of time, in which the laundry is submerged or partially submerged in water, and is subjected to treatment by the laundry treating appliance. This treatment may comprise heating periods and/or excerption of physical force on the laundry. During this prewashing phase, the laundry is subjected to the decontamination agent and, optionally, a laundry detergent. Optionally, at the end of the prewashing phase, the water is drained and replaced with new water in subsequent laundry treatment phases. In the context of the present invention, a “washing” phase refers to a phase, in which the laundry is submerged or partially submerged in water, and is subjected to treatment by the laundry treating appliance. During this washing phase, the laundry is subjected to a laundry detergent, and optionally the decontamination agent. The water during this washing phase is referred to as “washing water”. At the end of the washing phase, the washing water is drained. In preferred embodiments, depending on the laundry treating appliance, multiple washing phases can sequentially be conducted that are each started with first replacing or partially replacing the drained water previous washing phase. A further aspect of the invention is also a method for decontamination or treatment of wastewater created during laundry washing. According to this embodiment the treatment of wastewaters of a laundry treating appliance is intended occurs at the outlet from the drum of the washing machine, wherein the functionalized cellulose according to the invention is provided in any suitable form, preferably as a filter or a cartridge comprising the invention, so as to clean the water prior to its release into the environment. This treated cleaned water can be reused for cleaning, laundry washing or any other use.

[54] In preferred embodiments of the invention, the decontamination agent is contacted with the laundry water for 1 to 240 min, preferably 1 to 120 min, most preferably 1 to 35 min. Overall, the phases of the automated cycle of operation of the laundry treating appliance do cumulatively not exceed treatment times of more than 4 hours. These treatment times depend on the type of laundry treating appliance and the amount and length of the individual phases. Shorter treatment times of any length are also preferred embodiments.

[55] In other embodiments of the invention, the laundry treating appliance comprises a rotatable treating chamber in which the laundry is received for treatment. In the context of the present invention, this ratable treatment chamber is also referred to as “drum” or “washing drum”.

[56] In preferred forms of this embodiment, the rotatable treating chamber is rotating or spinning at the speed of o to 2000 rpm.

[57] In preferred embodiments of the invention, the laundry is treated at water temperatures of 15 to 95°C, preferably 20 to 80 °C, more preferably 30 to 70 °C, most preferably at 20 to 40 °C.

[58] In another aspect, the invention pertains to a use of functionalized cellulose for the removal of chemical, particle-based and biological contaminants from a medium.

[59] Removal in the context of the invention refers to the ability of an agent to change the concentration of the contaminants in a medium. The removal of biological contaminants is based on the anti-microbial effect of the functionalized cellulose of the invention, which refers to its ability of capturing or destroying microorganisms such as bacteria and viruses. In preferred embodiments of the invention, the removal of chemical and particle-based contaminants is referred to as dye and pigments, nano- and micro-plastics capturing. This does not indicate any mechanism by which the removal of chemical and particle-based contaminants occurs. Possible mechanisms comprise altering the color of a dye via chemical reaction, or by chemically and/or physical binding the dye molecules, pigments and/or particles to the surface of the dye binding agent. In preferred embodiments of the invention, this can be determined by the decrease in the optical absorption of the dye and pigment-solutions after incubation. Such a decrease can easily be determined from aliquots of the incubation solution with any spectrometer measuring at UV/Vis wavelengths.

[60] In preferred embodiments of the invention, the chemical contaminants are atoms and/or molecules. In preferred embodiments of the invention, the chemical and particle-based contaminants are ionic, hydrophobic, organic and/or inorganic contaminants. Ionic contaminants in the context of the invention comprise anionic and cationic contaminants in atomic, molecular and/or particle-based form. In preferred embodiments of the invention, the cationic contaminants comprise cationic molecules such as cationic dyes, surfactants such as benzalkonium chloride and pharmaceuticals such as tetracycline hydrochloride. In other preferred embodiments of the invention, the cationic contaminants are heavy metal ions such as lead, copper, nickel, chromium, bismuth, mercury, cadmium, palladium, zinc, thallium, silver or non-heavy metal ions such as calcium and magnesium. These metals comprise particles of single metals, alloys of metals, metal-containing compounds and/or metal ions that exist in the form of free cations or in form of metal-complexes. The metal-containing compounds may be, for example, a metal-containing organic compound or a metal-containing inorganic compound. In preferred embodiments of the invention, the anionic molecules of the contaminants comprise charged molecules such as nitrates, phosphates, fluoride, sulfate ions and humic acids. In preferred embodiments of the invention, the contaminants are radioactive isotopes or compounds that comprise radioactive isotopes of iodine, radon, radium, cesium, sulfur, chromium, cobalt, technetium, uranium and/or phosphorous. In some preferred embodiments of the invention, the hydrophobic contaminants comprise oil spills or dissolved drugs such as docetaxel. In preferred embodiments of the invention, the ionic or hydrophobic molecules of the contaminant are pesticides that are preferably selected from a group consisting of organophosphorus, carbamates, organochlorines, chlorophenols and pyrethroids. In preferred embodiments of the invention, the contaminants are dye-molecules. Preferably, the dye molecules comprise reactive dyes, disperse dyes, direct dyes, solvent dyes and pigment dyes. In preferred embodiments of the invention, the particle-based contaminants are nanoparticles and/or microparticles. In certain preferred embodiments of the invention, the particle-based contaminants are inorganic or organic particles. In preferred embodiments of the invention, the inorganic particle-based contaminants are metal oxides such as Ti0₂, ZnO or iron oxides or pigment dyes. In other preferred embodiments of the invention, the inorganic particle-based contaminants are zero-valent metals such as iron or silver. In further preferred embodiments of the invention, the organic particle-based contaminants are plastic particles, carbon particles and/or disperse dyes. [61] In preferred embodiments of the invention, the biological contaminants are microorganisms. In preferred embodiments of the invention, the microorganisms comprise Burkholderia pseudomallei, Cryptosporidium parvum, Giardia lamblia, Salmonella, Norovirus, Enterococcus faecium (Ef) or Staphylococcus aureus (Sa).

[62] Anti-microbial effect in the context of the present invention, refers to the ability of capturing or destroying microorganisms such as bacteria upon exposure to the active agent (functionalized cellulose). In the present invention, the strength of the anti-microbial effect was determined by a reduction factor R that is defined by the following definition:

Equation 3 wherein N₀ is the mass of the microorganisms before exposure to the agent and N is the mass of the microorganisms after exposure to the agent. In this definition, a larger factor R is equivalent to a stronger anti-microbial effect of the agent.

[63] In the context of the invention, “applied concentration” refers to the actual concentration, in which the agent is used. This is different from the concentration, in which the agent is sold.

[64] In preferred embodiments of the invention, the medium is a liquid phase, preferably washing water and/or waste water. Liquid phase in the context of the invention comprises aqueous solutions and/or organic solvents. Aqueous solutions in the context of the invention comprise industrial or domestic waste water, washing water, ground water, rain, rivers, the ocean and/or any kind of drinking water. In other preferred embodiments, the medium is a gaseous phase such as air and exhaust fumes. In most preferred embodiments of the invention, the medium is industrial or domestic wastewater such as in laundry treatment. [65] In preferred embodiments of this aspect, the decontamination agent is used in laundry treatment. In preferred embodiments of the invention, removal of chemical, particles and biological contaminants from a medium is laundry treatment. The decontamination agent can be added to the drum via the container or directly in the drum, or at the outlet from the drum, i.e. before water would be reused (returns back to the drum) or be discharged from the washing machine.

[66] In other preferred embodiments of this aspect, the functionalized cellulose is the functionalized cellulose recited in any one of the previous embodiments and aspects of the invention. As previously disclosed, the decontamination agent according to the invention can be transported and sold in form of an aqueous suspension, gel, film and/or powder. Any of the previously disclosed methods or other common methods for generating such a decontamination agent can be used. This also comprises mixing different types of functionalized cellulose of the invention and the mixing of other components to the functionalized cellulose that are chosen from a list of surfactants, builders, anti-redeposition agents, corrosion inhibitors, processing aids, colorants, fragrances, bleaching agents, enzymes, suds control agents, opacifiers and/or fabric softeners.

[67] In preferred embodiments of the invention, the decontamination agent is recycled. In preferred embodiments, recycling comprises the removal of contaminations that are bound to the functionalized cellulose. This can be conducted, for example, by exposing the decontamination agent to a solution and subsequently changing the pH of the solution to a level at which electrostatically and/or coordinatively bound contamimants are detached. In preferred embodiments of the invention, recycling comprises the repeated use of the decontaminating agent. For example this can be realized by recovering a sheet of functionalized cellulose after laundry treatment and using it again in a later laundry treatment process.

[68] In preferred embodiments of this aspect, the functionalized cellulose is used in a concentration from 0.01 g/L to 0.5 g/L, preferably from 0.01 g/L to 0.2 g/L, most preferably from 0.01 g/L to 0.1 g/L in soaking water or washing water.

[69] In other preferred embodiment of this aspect, wherein the functionalized cellulose is used in a concentration from 0.1 g/L to 1 g/L, preferably from 0.1 g/L to 0.5 g/L, most preferably from 0.1 g/L to 0.2 g/L in soaking water or washing water.

[70] The terms “of the [present] invention”, “in accordance with the invention”, “according to the invention” and the like, as used herein are intended to refer to all aspects and embodiments of the invention described and/ or claimed herein.

[71] As used herein, the term “comprising” is to be construed as encompassing both “including” and “consisting of’, both meanings being specifically intended, and hence individually disclosed embodiments in accordance with the present invention. Where used herein, “and/or” is to be taken as specific disclosure of each of the two specified features or components with or without the other. For example, “A and/or B” is to be taken as specific disclosure of each of (i) A, (ii) B and (iii) A and B, just as if each is set out individually herein. In the context of the present invention, the terms “about” and “approximately” denote an interval of accuracy that the person skilled in the art will understand to still ensure the technical effect of the feature in question. The term typically indicates deviation from the indicated numerical value by ±20%, ±15%, ±10%, and for example ±5%. As will be appreciated by the person of ordinary skill, the specific such deviation for a numerical value for a given technical effect will depend on the nature of the technical effect. For example, a natural or biological technical effect may generally have a larger such deviation than one for a man-made or engineering technical effect. As will be appreciated by the person of ordinary skill, the specific such deviation for a numerical value for a given technical effect will depend on the nature of the technical effect. For example, a natural or biological technical effect may generally have a larger such deviation than one for a man-made or engineering technical effect. Where an indefinite or definite article is used when referring to a singular noun, e.g. "a", "an" or "the", this includes a plural of that noun unless something else is specifically stated.

[72] It is to be understood that application of the teachings of the present invention to a specific problem or environment, and the inclusion of variations of the present invention or additional features thereto (such as further aspects and embodiments), will be within the capabilities of one having ordinary skill in the art in light of the teachings contained herein.

[73] Unless context dictates otherwise, the descriptions and definitions of the features set out above are not limited to any particular aspect or embodiment of the invention and apply equally to all aspects and embodiments which are described.

[74] All references, patents, and publications cited herein are hereby incorporated by reference in their entirety.

BRIEF DESCRIPTION OF THE FIGURES

[75] The figures show:

[76] Figure 1: (A) The degree of aldehyde functionalization for various functionalized CNF samples. The functionalized CNF samples are obtained by using different concentrations (1.3- 1.9 g) of sodium periodate per weight (in g) of CNF. On the left axis, the degree of aldehyde functionalization (mmol/g CNF) vs the reaction time in h is given. The corresponding weight-loss (%) is shown on the right axis vs. reaction time in h. (B) Particle size data on the various of various CNF samples is provided in form of the Z-size (nm) as determined by dynamic light scattering and corresponding zeta potential values (mV) are shown.

[77] Figure 2: (A) Samples of aldehyde-functionalized cellulose (o.5wt%, CNFox) with different amounts of aldehyde groups (o.57 mmol/g, i.i2 mmol/g) were treated with hexamethylenediamine (HMDA) in different weight ratios related to their content of aldehyde groups ( aldehyde groups /HMDA = 1:1, 1:3, 1:6) for 6 hours, followed by reaction with 2.9 g/1 of NaBH₄ for 3 hours at 30°C or 50°C. The absolute amount of aldehyde groups prior and after the respective modification reactions is shown. (B) Dye removal kinetics and capacity of the resulting products are shown.

[78] Figure 3: Depicted are the washing programs that are used the experiments using a domestic washing machine. For both the respective washing baths A and B, a SensoCare W8665K GORENJE d.d was used. The abbreviations GP, IZi, IZ2 and OZ are abbreviations of the respective washing programs. GP = household washing, IZi = rinsing 1, IZ2 = rinsing 2, OZ = spinning.

[79] Figure 4: (A) Potentiometric titration of HMDA-functionalized cellulose (aCNF, CNF- ox-HMDA) with total charge values vs. the corresponding pH values, and discoloration kinetics of bath A containing a dye concentration of 0.1 g/L. These room temperature experiments were performed with a cellulose concentration of 1 g/L. Dye concentrations are monitored at the wavelengths of 598 nm (B) and 474 nm (C).

[80] Figure 5: (A) Reduction of dye concentration in bath A after 30 min and 24 h of incubation at room temperature without shaking. Bath images after 90 min and 24 h of incubation: aCNF-dispersion (left), aCNF-powder (middle), DP-sheet (right). (B) Reduction of dye concentration in bath A after 30 min and 24 h of incubation at room temperature without shaking. Bath images after 90 min and 24 h of incubation: aCNF-dispersion (left), aCNF-powder (middle), DP-sheet (right).

[81] Figure 6: Dye removal kinetics in baths A (without detergent) or B (addition of IEC 60456 standard detergent) using water-dispersed aCNF (0.1 g/L) and a reference DP sheet (10 g/L, called “1:100”) and different dye concentrations (0.05, 0.1 and 0.5 g/L).

[82] Figure 7: (A) Stability measurements of 3wt% aCNF dispersions (aggregation and sedimentation) in case of storage at room temperature for extended periods of time (4 weeks, 12 weeks). The samples show from left to right: aCNF, aCNF + o.iwt% qCNF, aCNF + o.2wt% qCNF). (B) Discoloration kinetics of bath A containing 0.1 g/L dye monitored at two wavelengths (598 nm and 474 nm). The experiments were performed at room temperature with a aCNF concentration of = 0.2 g/L and various time intervals.

[83] Figure 8: Cells of S. Aureus (at 1000 x magnification) in the presence of aCNC (A). The log reduction factor of selected bacteria in dependence on the concentration of aCNC are shown for a suspension (B) without and (C) in the presence of o.i g/L of a Bezaktiv Black V-CMR reactive dye.

[84] Figure 9: (A) Normalized dye removal (according to Equation 5) in washing water of a domenstic washing machine according to bath A conditions in depencence of time (from left to right: o, 5, 10, 15, 20, 25, 30, 35 min). Each measurement point is determined from aliquots taken in accordance with Figure 3A. (B) Corresponding dye concentrations (g/L) in washing bath A in dependence of washing time. Data is shown for a reference, a DP sheet reference in the drum, aCNF positioned at the outlet of the drum and aCNF, which was added to the washing-drum. (C) Fotographs of the corresponding aliquots.

[85] Figure 10: (A) Normalized dye removal (according to Equation 5) in washing water of a domenstic washing machine in dependence of time (from left to right: o, 5, 10, 15, 20, 25, 30, 35 min). The experiment startet out without detergent, after 15 min however, laundry detergent according to bath B conditions was added. Data is shown for a reference, a DP sheet-containing drum, and aCNF, which was added to the drum. (A) Fotographs of the corresponding aliquots.

[86] Figure 12: Zeta-size analysis of (0.01 wt%) native (CNF/CNC), oxidized (CNF/CNC-ox), and HMDA-functionalized CNF/CNCs (CNF/CNC-ox-HMDA) in milli-Q water before and after 24h/48h of storage.

[87] Figure 13: SEM images of (0.01 wt%) native (CNF/CNC), oxidized (CNF/CNC-ox) and HMDA-functionalized (CNF/CNF-ox-HMDA) samples dispersed in miliQ.

[88] Figure 14: Multiple filtration of S. aureus with aCNF and qCNF decontamination agents, wherein the qCNF shows significantly inferior bacterial filtration properties.

[89] Figure 15: Reduction of Bacteriophage phi6 after being placed upon the visous (VIS) membrane surface containing aCNF and qCNF decontamination agents.

[90] Figure 16: Biodegradation properties in soil by analysing weight loss, wherein CNF-ox and CNC-ox are fully biodegradable, while CNF-ox-HMDA and CNC-ox-HMDA are not.

[91] Figure 17: Influence of CNF-ox-HMDA on the aggregation of synthetic microfibers in laundry wastewater and b) aggregates removal by sequential filtration of such a water using membranes of different porosity (180, too and 10 pm), compared to the control (without CNF) or that containing qCNF. EXAMPLES

[92] Certain aspects and embodiments of the invention will now be illustrated by way of example and with reference to the description, figures and tables set out herein. Such examples of the methods, uses and other aspects of the present invention are representative only, and should not be taken to limit the scope of the present invention to only such representative examples.

[93] The examples show:

[94] Materials and Methods

[95] Commercial colour-catcher sheet: In certain experiments, a commercial colour- catcher sheet (“DP-sheet”) is used as a reference. This sheet is a product of Delta Pronatura (DP) Dr. Krauss & Dr. Beckmann KG (Germany).

[96] Cationized-nanocellulose: Dispersions of differently cationized (aminated and quaternized) cellulose nanofibrils (CNF), cellulose nanocrystals (CNC) and microfibrillated cellulose (MFC) are used in the experiments disclosed. The CNF with chain-like structures feature diameters in the range of 10-70 nm and a length of a few micrometers (1-3 pm). They were supplied by the University of Maine (USA). The MFC was a commercial product of Exilva from Borregard, Norway and features a greater branching and interweaving of multi-micrometer long fibrils. The CNC with up to 50 nm in diameter and up to a few 100 nm in length was a product of the University of Maine (USA).

[97] Aminati on-Reaction - Overview: The functionalization of cellulose (CNC, MFC and CNF) with hexamethylenediamine (HMDA) was performed by the following two-step procedure: (i) By sodium periodate oxidation, glucose units in the cellulose were oxidized to exhibit aldehyde functional groups at the ring positions C2 and C3 (“CNFox”, “CNCox” and “MFCox”). (ii) Further reaction with HMDA through a Schiff-base reaction was conducted to obtain functionalized cellulose in which the previous aldehyde groups are replaced by amino-bound HMDA (CNF-ald- HMDA (“aCNF”), CNC-ald-HMDA (“aCNC”), and MFC-ald-HMDA (“aMFC”)).

[98] A detailed description for this method is given in case of aCNF: An aqueous dispersion of CNF (iwt%, 100 mL) and sodium periodate (either 1.9 g NaI0₄ /g CNF or 1.3 g NaI0₄ /g CNF or 1.6 g NaI0₄ /g CNF (Figure 1); stoichiometrically, for a 100% oxidation degree, 1.32 g / g CNF would be necessary) were mixed and stirred for 48 h (or 2, 4, 6, 8, 24 h, Figure 1) in the absence of light at room temperature (or 50 °C, Figure 1). The residual sodium periodate was then removed by adding ethylene glycol (10 mL). The product was thoroughly washed several times (in case of CNFox and MFCox) with deionized water or dialyzed (in case of CNCox) against deionized water for up to 3 days using a dialysis membrane with a molecular weight cut-off of 12,000-14,000. The maximum dialdehyde content of the CNFox sample was determined to be 1.32 mmol/g (Figure 1). This CNFox suspension (200 mL; 0.5 wt%) was ultrasonicated for 5 min, then, HMDA in the ratio aldehyde groups /HMD A = 1:6 (or 1:1 and 1:3, Figure 2A),was added. The mixture was stirred continuously for 6 h at 30 °C (or 50 °C). Subsequently, an in situ reduction of the resulting imine intermediate was conducted at room temperature (or 30 °C vs 50 °C, Figure 1) employing 2.9 g/1 of NaBH₄. After stirring for 3 h, the product was thoroughly washed several times (in case of aCNF and aMFC) with deionized water or dialyzed (in case of aCNC) using a dialysis membrane with a molecular weight cut-off of 12.000-14.000 against deionized water until a neutral pH was reached. Overall, this resulted in a total amine functionalization of i.i9 mmol/g. HMDA-functionalized cellulose nanocrystals (aCNC) and microfib rillated cellulose (aMFC) have been produced analogously.

[99] In ah following experiments, unless otherwise specified, aCNF, aCNC and aCMF refers the HMDA functionalized cellulose, that was prepared by the following procedure: oxidation with 1.9 g/g of sodium periodate for 48I1 at RT, and functionalization with HMDA at 30 °C for 6 hours using aldehyde groups /HMD A = 1:6 ratio, followed by reaction with 2.9 g/1 of NaBH₄ for 3 hours at 30 °C.

[100] Quatemization-Reaction: A quaternization modification was performed on CNFs according to the patent WO/2016/075370 using glycidyltrimethylammonium chloride.

[101] A detailed description for this method is given in case of qCNF: An aqueous dispersion of CNF (3 wt%, 100 mL) was activated by adding NaOH (15.6 g) and stirred at 6o°C for 30 minutes. An aqueous glycidyltrimethylammonium chloride solution (180 mL, 79% aqueous solution) was added and the reaction was further stirred for 120 minutes at the same temperature. After 120 minutes, the reaction was cooled down and washed with deionized water until ra neutral pH was reached. The mass readily formed a hydrogel, resulting in a substitution degree (SD) of about 0.23 as determined by conductometric titration. This product is called “qCNF”.

[102] White fabrics selected: To monitor the influence of the dye-capturing properties of the functionalized cellulose materials, two types of white fabrics were used:

Standardized (ISO 2267/DIN 53919, WFK liA, Testgewebe GmbH) 100% plain weaved cotton fabric of 170 g/cm² weight, 270/270 pick/dm, 295/295 dtex.

Standardized (ISO 2267/DIN 53919, WFK 60A, Testgewebe GmbH) 100% plain weaved wool fabric of 125 g/cm² weight, 210/180 pick/dm, and 300/300 dtex.

[103] Dyes and colours selected: The different reactive dyes that are shown in the experiments below represent colourants with a high “bleeding” effect (up to 70%). These dyes include three mono-chromatic Bezaktiv Yellow V-5GL, Bezaktiv Red V-GG, and Bezaktiv Blue V-R, and tri-chromatic Bezaktiv Black V-CMR. In addition, direct dyes ( Tubantin Yellow 4GL, Tubantin Purple 4B, Tubantin Blue FF2GL 200 and Tubantin Black VSF 600 ) and disperse dyes ( Bemacron Red SE-RDL), as well as pigment dyes ( Bezaprint Colormatch 210 Red) were used. [104] Laundry washing baths used: Two washing baths, “bath A” and “bath B”, were used to simulate different washing conditions. Both laundering baths met the characteristics of the following standard: SIST EN 60456:2010 (Clothes washing machines for household use - Methods for measuring the performance). These parameters include: Conductivity of < 10 pS/cm, total water hardness of 14 ± 1.12 °dH, and a pH of 7.3-7.7.

[105] Washing bath B was prepared from bath A by adding the IEC 60456 standard detergent A * ( WFK , Germany), composed of 77% of basic washing powder (containing: 8.8% of anionic surfactant sodium alkyl benzene sulfonate, 4.7% of the non-ionic surfactant ethoxylated fatty alcohol C12/14 / 7 EO, 3.2% of anionic surfactant sodium soap (tallow soap), 3.9% of foam inhibitor concentrate, 12% silicon on a inorganic carrier, 28.3% of zeolite 4 A, 11.6% of sodium carbonate, 2.4% of sodium salt of a copolymer from acrylic and maleic acid, 3.0% of sodium silicate (Si0₂Na₂0), 1.2% of carboxymethylcelluse, 2.8% of phosphonate (DEQUEST 2066 with 25% active acid), 0.2% of optical stilbene type whitener, 6.5% of sodium sulfate (Glauber's salt), 0.4% of protease (Savinase 8.0), 20% of the bleaching agent sodium perborate tetrahydrate with active oxygen of 10 - 10.4%, and 3% of the bleach activator tetraacetylethylenediamine with an active content of 90 - 94%, to reach a pH of 9.8.

[106] Labomat-based dye-absorption studies: The experiments for both washing baths (A and B) were performed in a Labomat BFA8 apparatus (Werner Mathis AG, Switzerland) using a rotational speed of 40 rpm and the washing cycle presented in Table 1. In these experiments, the influence of DP-sheet pieces as well as dispersions of aCNF or qCNF in a dry weight of 0.1 g/L were examined.

[107] Table 1: Washing program used in civet’s LABOMAT study.

[108] Washing conditions and cycle used (experiments performed in a household washing machine): In these experiments (compare to Figure 3), the domestic washing machine SensoCare W8665K GORENJE d.d. was used that is operating with the following parameters:

• washing program: BOM NORMAL 200C using 3.500 g ballast (PES),

• standard cotton fabric (100%, DIN 53919 / ISO 2267:1986): size 10x20 cm, 1 piece/cycle · with/without addition of standard cotton with 5 impurities (SIST EN 60456):

3 pieces/cycle • with/without addition of textile bioindicators and the colonies Enterococcus faecium (Ef (EXB-L-880)) and Staphylococcus aureus (Sa (EXB-V54))

• addition of Bezaktiv Black V-CMR (1.5 g/L) without (reference) or with addition of 2 DP sheets or equivalent weight of aCNF (approx. 2.9 g)

• An overall concentration of the respective decontamination agents of 0.1 g/L

[109] Survival assay of selected microorganisms upon exposure to aminated-CNC (aCNC) without/with addition of 0.1 g/L Bezaktiv Black V-CMRi Strains of Enterococcus faecium ( EXB-L-880 ) and Staphylococcus aureus ( EXB-V54 ) were resuscitated on TSB media. The grown cultures were inoculated into TSB liquid medium after 48 hours and incubated for a further 24 hours. After incubation, the suspension was diluted to an optical density OD620 = 0.3. The liveliness of bacteria was tested in test tubes using different concentrations of aCNC without or with addition of 0.1 g/L Bezaktiv Black V-CMR. The suspension tubes were incubated at 37 °C on a shaker for 24 hours. After incubation, dilution types were prepared for each tube and too pL of suspension was applied to TSA plates. The media were re-incubated at 37 °C for 24 hours. After the incubation, the bacterial growth was checked. In the case of observed growth, colonies were counted and the number of living cells (N = CFU / mL), reduction factor (Log (N₀/N)) and percentage reduction (%) were calculated.

[110] Washing bath dye removal measurements: The dye concentration in both washing solutions A and B, before and after the washing experiments, was determined by optical absorption evaluated at the wavelengths of maximal adsorptions for each dye (i.e. Bezaktiv Yellow V-5GL at 406 nm; Bezaktiv Red V-GG at 504 nm; Bezaktiv Blue V-R at 594 nm; Bezaktiv Black V-CMR at 398 nm, 474 nm and 598 nm; Tubantin Yellow 4GL cone at 384 nm; Tubantin Purple 4B cone at 498 nm; Tubantin Blue FF2GL 200 at 576 nm; Tubantin Black VSF 600 at 482 nm; Bemacron Red SE-RDL at 464 nm; Bezaprint Colormatch 210 Red at 558 nm;). The data was generated using a plate-reader equipped with a Tecan UV-Vis spectrophotometer (USA). Dye removal (%) was calculated using the following equation:

(Cb - Ca)

Equation 4 Dye removal (%) = x 100 Cb

[111] where Cb and Ca (mg/L) are dye concentrations before and after the laundering in washing baths.

[112] Alternatively, dye removal is also presented as normalized values of maximal absorptions in both washing solutions based on a difference in bath absorbances, using the following equation: ( Abs_n - Abs₀ )

Equation 5 Norm Abs₀

[113] Where Abs₀ and Abs_n are absorbance values at the beginning and for aliquots taken at different washing times.

[114] Fabric whiteness, colour strength and colour change measurements: The

Reflectance (%R) of the fabrics before and after different treatments in both washing baths A and B was measured within a spectral range of 400-700 nm wavelengths using the Spectra ash SF 600

Plus ( Datacolor Inc, Switzerland ) spectrophotometer equipped with an Ulbricht sphere and measuring geometry of d/8⁰ under the standard illuminant D65 ( LAV/Spec . Inch).

[115] The CIE whiteness index ( W) of the samples was quantified in accordance with the AATCC test method 153 (1985). The whiteness index (W) is given by:

Equation 6 W = Y + 800 (x_n - x) + 1700(y_n - y) where Y shows the lightness value, and x, y, and x„, y„ are the chromaticity coordinates of the samples and the illuminant, respectively.

[116] The samples were examined for their colour strength (K/S) and CIE L*a*b* colour characteristics' values (i.e. lightness L* red/green axis a* yellow/blue axis b*, chroma C* and hue h*) by using Datamaster Datacolor Software (CH) according to CIE. The CIE L*a*b* colour differences between unwashed and differently washed fabrics were calculated from the coordinate differences in all three directions of the colour space, i.e. L*, a *, b*, C* and hue h*, by the following equation:

Equation 7

[117] where dE* is the total colour difference, L is the brightness difference (L_sampie-Lref), da * is the difference at the red/green axis, and dh* is the difference at the yellow/blue axis. All the results were the average values of ten readings.

[118] Experimental Data

[119] Example 1: Studies on the Dye-removal kinetics

[120] Determination of functionalized cellulose surface charge: A first comparative analysis by titration experiments was performed to assess the surface charge of the functionalized cellulose types (aCNC, aCNF and aMFC). This was conducted in a two-phase titration (i.e. from acidic to alkaline medium and back, “Forth” and “Back”, functionalized cellulose cone. = o.i g/mL). The data presented in Figure 4A, shows differences in the samples’ charge- and pK_a-values. These differences were observed during back and forth titration of an individual sample, as well as when comparing the different types of functionalized cellulose. This is resulting from different degrees of modification (amination + oxidation) as well as from the chemistry of the bound HMDA molecules. In general, the overall charge measured for the different functional cellulose types is decreasing with increasing size and/or branching of the cellulose fibrils or with a reduction of their active surface area. For the measured charge values, a dependency on the respective pH values could be observed. In the case of aCNC (with the largest surface area), a charge of 6.62 mmol/g was measured at pH =3. For the aCNF sample a charge of 5.99 mmol/g and for aMFC, a charge of 4.35 mmol/g was determined respectively. aCNC and aCNF feature similar pK_A values (5.6-7 and 5.99 respectively, both titration curves have a fairly similar course: the inverse titration curve from low to high pH values results in a lower overall charge titration from high to low pH values. This means that no presence of additional reactive groups could be detected. In contrast, in the case of MFC (pK_A =6.8-7), the return curve is higher than the original curve (and more charge is detected), indicating that, after the first titration, some HMDA may be released from the functionalized cellulose surface. Alternatively, its detectability might have increased, due to an opening of a more networked fibrillar structure).

[121] Comparative dye-removal experiments: Dye removal kinetic studies in “bath A”- conditions were performed on the different water-dispersed aminated cellulose types (aCNC, aCNF and aMFC). The following set of experiments is based on a study using laboratory equipment and was based on batch-adsorption equilibrium experiments. In these experiments, the removal of the dye tri-chromatic Bezaktiv Black V-CMR was examined. The initial dye concentration was set at 0.1 g/L and the functionalized cellulose was used in a concentration of 0.1 g/L. The course of the dye discoloration was recorded at two wavelengths (Figure 4B: 598 nm and Figure 4C: 474 nm) - and shows a comparable discoloration rate for all three cellulose types in the water bath A. However, kinetically the best effect was observed for aCNF, where discoloration was observed after 5 min, followed by aMFC and aCNC.

[122] Batch dye adsorption studies: The adsorption capacity and kinetics of aCNF suspensions, as well as DP sheets for tri-chromatic Bezaktiv Black V-CMR reactive dye were analysed using a batch equilibrium method in reaction times for up to 140 min (see Figure 6). To examine their different adsorption properties, cellulose or DP substrates (0.1 g/L respectively) were each immersed in the baths solutions A and B. To optimally measure the change in dye- concentrations, the experiments were performed at dye-concentrations of 0.1, 0.5 and 1.0 g/L. To simulate an entire washing cycle, the colorized bath solutions were stirred for up to 140 min at a speed of too rpm at room temperature using a horizontal shaker ( Heidolph Promax 1020, Germany ). The dye-concentrations, before and after exposure to the decontamination agent, were determined by measuring the samples’ optical absorption at two or three wavelengths corresponding to the three absorption maximums of the dye (398 nm, 474 nm and 598 nm). These experiments where conducted using a plate-reader equipped with an ultraviolet-visible (UV-Vis) spectrophotometer ( Tecan , USA). [123] Further testing the dye capturing performance of aCNF under different conditions: Dye removal studies were conducted, that were comparing the discoloration performance of aCNF to a DP sheet when used in bath A or bath B conditions. In these experiments, the functionalized cellulose types were added in a powder-form (freeze-dried) or in form of a dispersion. In bath A-conditions, the aCNF and DP sheet was examined both in a concentration of 0.1 g/L and 0.2 g/L. In bath B-conditions, the study was conducted at higher concentrations of 1.0 g/L. In these dye removal studies (dye-conc. = 0.1 g/L), the usage of re suspended aCNF powder resulted in almost complete clearance after 24 h of incubation. (Figure 5a). On the other hand, a aCNF suspension that was never dried, exhibited faster dye removal kinetics and a higher efficiency compared to both the resuspended aCNF-powder and the DP sheet, which was the least effective (aCNF and DP sheet cone. = 0.1 g/L). At a higher aCNF concentration of 0.2 g/L, full clearance was examined after 30 min of incubation.

[124] Table 2: Reduction of dye concentration (%) in bath A after 30 min and 24 h of incubation at room temperature without shaking.

[125] In bath B-conditions (Figure 5b), the dye-removal was examined at a higher aCNF concentration of 1.0 g/L. In these conditions, the examined aCNF-dispersion was kinetically and quantitatively the most effective in removing the dye. This resulted in a minimal residual dye-concentration after 15 min incubation. The dye removal in presence of aCNF powder was slower, more evenly and similar to the reference DP sheet. The reference DP sheet performed overall the worst out of the three samples regarding adsorption speed and removal capacity. [126] Table 3: Reduction of dye concentration (%) in bath B after 30 min and 24 h of incubation at room temperature without shaking. [127] Testing the performance of aCNF and qCNF mixtures: Water-suspended aCNF shows a tendency to aggregate and settle over time, because of the presence of hydrophobic ethylene chains in HMDA that cause water separation and excretion. This may affect the sampling and dye adsorption efficiency, especially at low spinning speeds, and results in a more pronounced sedimentation if aCNF is suspended at low concentrations (<0.3 g/L). Using a highly viscous and homogenously dispersed suspension of low concentrated (o.i-o.2wt%) qCNF, which also acts as an additional dye adsorber, has been shown to be highly effective in dispersing aCNF (3wt%) (Figure 7A). In these experiments, aCNF (0.1 wt%) /qCNF (0.0067 wt%) mixtures feature the same dye removal kinetics and efficacy as a corresponding pure dispersion of aCNF, but do not aggregate and/or sediment (Figure 7B).

[128] Example 2: Dye capturing studies performed in a Labomat apparatus

[129] In these experiments, the colour change of a piece of textile that was washed in dye solutions according to the bath A and bath B conditions, was examined. As a negative reference, a textile washed in bath A or bath B conditions without any dye addition and without any CNF material or DP sheet was examined. As a positive reference, a textile washed in bath A or bath B with dye addition and without any CNF material or DP sheet was examined. The textile that is being washed in bath A or bath B with dye addition and with CNF material (and optionally a DP sheet) is expected to show a lower dE* than the positive reference, for a sufficient dye capturing performance.

[130] In all of the studies in this example, a theoretical standard concentration of a dye-capture agent was defined to be 0.1 g/L (=100%). In the following tables, if a table entry refers to aCNF 80%, this therefore refers to a aCNF concentration of 0.08 g/L.

[131] As shown in Tables 4 - 9, parameters that influence the dye-capturing performance comprise aCNF concentration, the type of dye and the washing conditions (bath A or bath B conditions). Dye capturing generally performed better for aCNF than for corresponding DP sheets, and is more effective in bath A than in bath B.

The following data shows the dye-capturing performance of aCNF used in the conditions of bath A (therefore without washing powder) when incubated along with a WFK 11A cotton fabric and different dyes. As seen in the data of Table 4, in all cases but one aCNF performed considerably better than an equal amount of DP sheet in removing various dyes from the washing solutions. According to the data of Table 5, the dE* values of cotton, when it is exposed to various dye- solutions, are generally lower in case of the aCNF containing samples when compared to the DP sheet containing samples. In these experiments aCNF performed consistently better in dye capturing than a corresponding amount of DP sheet. Table 4: The table depicts the removal (%) of different dyes (0.1 g/L) from solution according to the condition “bath A”. In these solutions, a WFK 11A cotton fabric was incubated with the dyes, either with/without the addition of different concentrations of DP sheet and aCNF.

[132] Table 5: The table shows the averages of whiteness (W) and colour differences (dE*) of a WFK 11A cotton fabric, when washed with various dyes (0.1 g/L) in the condition “bath A” with/without the addition of DP sheet and aCNF in different concentrations.

[133] The data shown in Table 6 and Table 7 was generated in a study on the dye-capturing performance of aCNF when used simultaneously with washing powder (bath B-conditions). As shown in Table 6 aCNF featured an increased dye-removal-performance in all examined wavelengths, when compared to DP sheet. Table 7 gives the optical absorption data from experiments in which FK 11 A cotton fabric was incubated in a solution that both contained dye and either DP or aCNF in different concentrations. Here, experiments, WFK 11 A cotton fabric that was incubated with aCNF, showed the least increase in colour (dE*).

[134] Table 6: Removal (%) of Bezaktiv Black V-CMR (0.1 g/L) when washing WFK 11A cotton fabric with/without the addition of DP sheet and aCNF in different concentrations. Table 7: The averages of whiteness ( W) and colour differences ( dE *) for WFK 11A cotton fabric, washed with o.i g/L of Bezaktiv Black V-CMR with/without the addition of DP sheet or aCNF.

[135] Table 8 and Table 9 show analogue dye-capturing performance of aCNF in bath A-conditions, wherein WFK 60A 100% plain weaved wool was incubated in a dye-solution along with the different decontamination agents without additional washing powder.

[136] Table 8: Removal (%) of different dyes (0.1 g/L) from bath A in which WFK 60A wool fabric was incubated with/without the addition of DP sheet or aCNF in different concentrations.

[137] Table 9: The averages of whiteness (W) and colour differences ( dE *) for WFK 60A wool fabric that was washed in a dye-solution (0.1 g/L) with/without the addition of DP sheet or aCNF in different concentrations.

[138] According to the data in Table 8, aCNF shows improved dye-capturing performance compared to DP sheet for all but one case ( Blue-VR , 95.51% for DP, 94.86% for aCNF, 95.82% without addition of a decontamination agent). In the corresponding data of Table 9 the colour increase of wool when incubated with the respective dye solutions and with/without DP, and aCNF (see dE* values) is shown.

[139] Example 4: Anti-microbial effect of aCNC in laboratory conditions:

[140] The survival rate of Enterococcus faecium (EXB-L-880) and Staphylococcus aureus (EXB-V54) after 24 hours of aCNC exposure, with/without presence of 0.1 g/L Bezaktiv Black V- CMR was examined. The corresponding data is shown in (Figure 8). Compared to the control, aCNC affected the viability of the test microorganisms above a concentration of o.iwt%. In this case of dye-presence, the agent affected the viability of the test microorganisms above a concentration of 0.05 wt%. The anti-microbial effect is visualized in Figure 8A, in which free bacteria are visible along with bacteria that are glued to the surface of the aCNC particles. The minimum inhibitory concentration (MIC) of aCNC, at which no growth was observed with the naked eye after overnight incubation and at which a reduction factor 6 or more was achieved (mortality = 99.9999%), was 0.2 wt%. This was independent of the presence of a dye. This is also the concentration that is required to reach the microbiological standard for an effective antibacterial, bacteriostatic and even bactericidal washing. The minimum bactericidal concentration (MBC) of aCNC, at which 100% mortality of test microorganisms in suspension was achieved, was 1.6 wt% (without dye) or 0.8 wt% (with dye). [141] Example 5: Anti-microbial effect of functionalized cellulose in a domestic washing machine.

[142] Anti-microbial effect of aCNC: In these experiments, a small amount of aCNC (dry weight of 0.24 g compared to the previous dry weight of 2.9 g for aCNF) was added to a 30 L drum with laundry and a washing program was run at 30 °C. The amount of bacteria prior and after washing was examined. Compared to a reference, the reduction of microorganisms during laundry treatment had almost quadrupled (Table 10) in case of aCNC addition.

[143] Table 10: Microorganism removal using aCNC: Results of microorganism removal with aCNC fabric in bath A conditions, and the presence of Enterococcus faecium (Ef) or Staphylococcus aureus (Sa) bacteria.

[144] Dye and microorganism removal/disinfectant effect using aCNF: The results of a microorganism removal study with aCNF are shown in Table 11. Here, 11A cotton fabric is washed at 20 °C in the presence of Enterococcus faecium (Ef) or Staphylococcus aureus (Sa) bacteria under Bath A conditions. The effect of aCNF or a reference DP sheet addition on the viability of the micro-organisms is shown. For both bacteria types, the addition of aCNF (2.9 g/30 L) resulted in an anti-microbial effect that is higher than for the reference cloth alone and similar to a comparable DP sheet reference.

[145] Table 11: Results of microorganism removal with aCNF during the washing of cotton fabric in different washing conditions, and the presence of Enterococcus faecium (Ef) or Staphylococcus aureus (Sa) bacteria.

[146] Example 6: Dye capturing and impurity removal effect of aCNF using a domestic washing machine

[147] Dye-capturing experiments: The dye removal kinetics of aCNF (2.9 g/ 30 L) compared to an equal solid weight of DP sheet is shown. This study was performed in a laundry containing domestic washing machine, in which 11A cotton fabric was incubated in bath A, and the washing was performed according to the washing procedure and conditions illustrated in Figure 3A, where 1.5 g/L of Bezaktiv Black V-CMR reactive dye was added immediately after starting the washing program. Additionally, different feed methods, for the supply of aCNF during the washing process are demonstrated. The kinetics of the dye-removal are shown in Figure 9 and Table 12.

[148] Table 12: 11A cotton fabric was washed with 1.5 g/L of tri-chromatic Bezaktiv Black V- CMR reactive dye with/without the addition of DP sheet or aCNF in the drum or at the outlet. Average colour differences dE* as well as the amount of adsorbed dye on the fabric or the dye- removal agent are shown.

[149] Both the colour differences dE* and the amount of dye-absorbed on the fabric shown in Table 12 are the lowest for the samples with aCNF. This shows the improved performance of aCNF compared to the reference DP sheets. Figure 9A shows the normalized differences in absorption wavelengths of aliquots taken from the washing solutions according to Equation 5. In the aliquot taken at 5 minutes, an initial increase in the normalized absorption differences of the respective samples can be monitored due to the addition of the dye. For the aCNF containing samples, the increase of normalized absorbance was the lowest, as aCNF was adsorbing the highest amount of the dye added in this first period of time. Then, with increasing time and aliquot number, a decrease of normalized absorption differences can be monitored for all samples, caused by the continuing dye adsorption in all sarnies. Figure 9B depicts the same data, however the absorbance values are transformed into the respective dye-concentrations in the drums. Figure 9C demonstrates the decreasing dye-concentration in the aliquots with the help of fotographs. Regardless of the feed method, aCNF most effectively removes dye from the washing bath. It prevents its adsorption/re-deposition on the cotton fabric and performs better than any of the reference samples. The dye-capturing effect occurs within the first 15 minutes of the washing, when aCNF is present in the washing drum, or when the washing bath with the dye is passing a filter bag with an equal amount of dryed aCNF that is placed at the outlet of the washing bath.

[150] Dye and impurities removal experiments: Here, the kinetics of a combinatory dye and impurities removal study on aCNF as compared to a DP sheet reference are shown. The experiments where performed in a domestic washing machine in the presence of 1.5 g/L tri chromatic Bezaktiv Black V-CMR reactive dye, and additional addition 3 pieces of 11A cotton fabric that each feature the impurities shown in Table 13. First, laundry washing is performed under bath A conditions. After 15 min washing powder was added (bath B conditions), and the bath samples were taken and analysed according to the scheme in Figure 3B . The results of the study are depicted in Figure 10 and Table 13. A washing effect was calculated according to the standard SIST EN 60456:2010. This washing effect is the ratio of the sum of reflectance values for each soil type when washed according to the conditions of Table 13 and the corresponding values of a reference washing machine. The Impurities Removed ( IR_{dE *}) were also calculated from the examined CIE L*a* b* colour characteristics ' values, according to Equation 7, and based on the following Equation 8:

Equation 8 100 (%) where dE*_wash-unsou is a colour difference dE*_D65/ o between washed soil sample and unwashed unsoiled fabric, and dE*_soii-msoais a colour difference dE _D65/ _o between the unwashed soil sample and the unwashed unsoiled fabric.

Table 13: 11A cotton fabric is contaminated with various respective impurities and washed with the addition (i.e. in the presence) 1.5 g/L tri-chromatic Bezaktiv Black V-CMR dye with or without a reference DP sheet or aCNF in the drum.

[151] In Table 13, the amount of dye that is adsorbed by the cotton, when it is washed with aCNF, is decreased compared to the amount of dye adsorbed by the cotton when washed alone or with the reference DP sheet. Furthermore, both the amount of impurities removed and the washing effect are comparable between all three samples. The study shows, that aCNF effectively removes dye from the washing bath without interfering with the laundry washing process and prevents its adsorption/re-deposition on the cotton fabric without reducing the overall washing efficiency by the washing machine. Figure 10A shows the normalized differences in absorption wavelengths of aliquots taken from the washing solutions according to Equation 5. Initally, a large increase in the normalized absorption differences can be monitored, due to the addition of dye. aCNF shows the least increase in the initial absorption difference, as it adsorbs most of the dye initially. With the addition of laundry detergent after 15 minutes, again the absorption differences increase, presumably due to different optical properties of the laundry containing solutions. With increasing time, the normalized absorption differences decrease again, due to the ongoing dye-adsorption by the dye-catcher materials and laundry in the drum. Figure 10B demonstrates the decreasing dye-concentration and the changes of the optical properties of the washing solutions visually fotographs of the corresponding aliquots.

[152] Example 7: Properties of CNF, CNF-ox, CNF-ox-HMDA and CNC, CNC-ox and CN C-ox-HMD A

[153] The titration curve (not shown) of native CNF shows one small bend at pH 4.4, given the small quantity (0.12 mmol/g) of negative charge that may be related to the presence of rare anionic (preferably sulfonate) surface groups, formed during the preparation of CNF or resulting from the presence of lignin residues. These groups were reduced to 0.096 mmol/g after the oxidation (CNF-ox, figure 4), also giving another peak at pH -9.1, which might be related to the aforementioned phenomenon, while they could not be detected anymore after attachment of HMDA (CNF-ox-HMDA, figure 4), yielding a positive charge of around 5.64 mmol/g at pH ~8.i. The titration curve of pure HMDA shows high positive charge at a wide pH range until -10.7 (being related to its complete deprotonation, pK) with a small band between pH 6.0-7.0 (representing the partial deprotonation stage of diamines, H2N-(CH2)6-NH2), thus confirming the high contribution of amino (CNF-NH2) groups. A gradual reduction of the titration curve for the CNF-ox-HMDA sample and shifting of HMDA’s pK value towards lower pH may, thus, be because of its binding to CNF-ox. In order to confirm the efficacy of the HMDA attachment on aldehydes, the aldehyde content was evaluated after both the oxidation and functionalization steps, being reduced from -16.4 mmol/g to -0.13 mmol/g. The non-stoichiometrically attachment of HMDA to CNF-ox might be related to preferentially a one-side (grafting) and rarely both-sides (crosslinking) reaction, being also supported by the good dispersibility of CNF-ald in aqueous media, although the attached HMDA resulted in the formation of CNF-HMDA aggregates, as revealed by the zeta-size analysis (Figure 11) and SEM images (Figure 12). Even higher charge (~1.8 mmol/g) at ~io.i pH and total charge (~6.62 mmol/g) for CNC-ox-HMDA might be related to its better dispersibility and thus primarily one-side grafting of HMDA.

[154] Table 14: Aldehyde groups, pKi, pK2, charge pKi, charge pK2 and total charge for analysed functionalized and native celluloses [155] Example 8: Antibacterial activity

[156] Antibacterial activity of native and functionalized CNF and CNC celluloses was determined using standard minimum inhibitory concentrations, minimum bactericidal concentrations and log reduction of Gram-negative E. coli (EXB-V127) and Gram-positive S. aureus (EXB-V54) after 24-h exposure to native an differently modified/functionalized CNCs (CNC; CNC-ox, CNC-ox-HMDA) and CNFs (CNF; CNF-ox, CNF-ox-HMDA) in dilution antibiogram.

[157] The results (Figure 13) show significant log reductions for CNF-ox, CNC-ox as well as CNF-ox-HMDA and CNC-ox-HMDA, wherein concentrations CNF-ox, CNC-ox as well as CNF- ox-HMDA and CNC-ox-HMDA lower than 1 wt% (for E. coli) and lower than 0.5 wt% (for S. aureus) already exhibit high efficiency.

[158] Table 15: Minimum inhibitory concentrations (MIC) and minimum bactericidal concentrations (MBC) of different CNF/CNC suspensions for E. coli (EXB- V127) and S. aureus (EXB-V54) determined by the dilution antibiogram method. Results are given as the average of two independent replicates. Legend: N/A - could not be determined because no concentration-dependent inhibitory and bactericidal response was observed.

[159] The results for MIC and MBC suggest superior antimicrobial activity of CNF-ox, while CNC-ox-HMDA showed lower minimal inhibitory and bacteirical concentrations than CNCox. [160] Taken together, obtained results indicate efficient antimicrobial activity of aCNC and aCNF against Gram negative and Gram positive model bacterial organisms.

[161] Example 9: Filtration of bacterial cells

[162] Figure 14 shows results for multiple filtration of S. aureus with aCNF and qCNF decontamination agents, wherein the qCNF shows significantly inferior bacterial filtration properties as the number of bacterial cells remains approximately the same in all experiments. On the contrary, aCNF (CNF-ox-HMDA) efficiently reduced the number of bacterial cells, thereby suggesting that aCNF is able to function as a filter for bacteria. [163] Example 10: Reduction of virus

Figure 15 shows the results of the reduction of Bacteriophage phi6 after being placed upon the visous (VIS) membrane surface containing aCNF and qCNF decontamination agents, wherein the qCNF-decorated membrane shows significantly inferior virus reduction properties after 2 h of incubation, while membrane containing also aCNF (CNF-ox-HMDA) efficiently reduced the virus, thereby suggesting that aCNF is able to function also as a filter for viruses.

[164] Example 11: Biodegradation in soil

[165] Figure 16 shows results of biodegradation properties in soil by analysing weight loss, wherein CNF-ox and CNC-ox are fully biodegradable (weight loss is increasing), while CNF-ox- HMDA and CNC-ox-HMDA are not (weigh loss is reduced) due capturing of soils microorganisms.

[166] Example 12: Filtration of microplastics:

[167] Prepared decontamination agents (CNF-ox-HMDA suspension) was mixed with 0.5 L of laundry wastewater containing an approximate 80 pm long synthetical microfibres. After 15 min of magnetic stirring the formed aggregates (A) were filtrated using commercial membranes of 180 pm pore size ( left column), followed by filtration using too pm pore size (middle column) and 10 pm pore size (right column) membranes, wherein filtration was performed sequentially (B). In parallel, qCNF was used showing much less efficiency. In case of control (using no CNF) the effect of microfibrils retention was insignificant.

REFERENCES

[i68] The references are:

1. CN105498733A

2. CN107138135A

3. CN107840895A

4. CN109608554A

5. CN109678972A

6. US2016010275A1

7. EP3272849A1

8. EP3272848A1

9. Liquiang et al., Cellulose, 2015, 22, 4, DOI: 10.1007/S10570-015-0649-4

10. Landrigan et al, The Lancet Commissions, 2018, 391, 10119, DOI : 10.1016/S0140-

6736(17)32345-0)

Claims

1. A decontamination agent, comprising aminated cellulose as an active agent, wherein:

- individual glucose units of the cellulose exhibiting three hydroxy groups are first oxidized to display aldehyde groups, and then said aldehyde groups are substituted with amino groups,

- the aminated cellulose exhibits a degree of substitution of 50% of its aldehyde groups or at least 33% of its original hydroxy groups, and

- said cellulose is selected from microfibrillated cellulose, cellulose nanocrystals, cellulose nanofibrils and combinations thereof.

2. The decontamination agent of claim 1, wherein oxidation is achieved with sodium periodate, potassium periodate or periodic acid.

3. The decontamination agent of any one of claims 1 or 2, wherein the amino groups are chosen from a list comprising primary, secondary and tertiary amino groups, wherein primary amino groups can be described with the formula (G-NH₂), secondary amino groups can be described with the formula (G-NHR¹), tertiary amino groups can be described with the formula (G- NRTi²), wherein G is the (modified) glucose unit of the functionalized cellulose and R¹, and R², are residual organic groups and wherein between the (modified) glucose and the N of the amino group maybe one or more bridging atoms.

4. The decontamination agent of claim 3, wherein the amine molecule is a linear primary diamine (H₂N-R-NH₂) with R being a C to C₆ alkyl , preferably C₃ to C₆ alkyl, most preferably C₆ alkyl (hexane 1,6 diamine).

5. The decontamination agent of any one of claims 1 to 4, wherein the aminated cellulose is further quarternized up to a degree of substition of 100% of original hydroxy groups.

6. The decontamination agent of claim 5, wherein the cellulose comprises at least two different substituents each selected from an amino group-containing substituent or a quaternary ammonium group-containing substituent.

7. The decontamination agent of any one of claims 1 to 6, wherein the decontamination agent comprises at least two different types of functionalization or functional cellulose as a mixture, preferably at least three types, for example aminated and native cellulose; aminated and quarternized cellulose; aminated and oxidized cellulose; native, aminated and oxidized cellulose; quarternized and oxidized cellulose; oxidized, aminated and quarternized cellulose; or oxidized, native, aminated and quarternized cellulose.

8. The decontamination agent of any one of claims l to 7, wherein the agent is provided is in a form selected in the group consisting of aqueous or non-aquenous suspension, dispersion, gel, thin film, non-woven mat, membrane, thin-layer coating, dried powder and composite.

9. The decontamination agent of any one of claims 1 to 8, wherein the decontamination agent further comprises at least one additional component selected from the group of surfactants, builders, anti-redeposition agents, corrosion inhibitors, processing aids, colorants, fragrances, bleaching agents, enzymes, suds control agents, opacifiers and/ or fabric softeners.

10. The decontamination agent of any one of claims 1 to 9, wherein the agent is a laundry treatment additive.

11. A use of the decontamination agent according to any of the preceding claims for the removal of chemical, particle-based and biological contaminants from a medium, wherein the chemical contaminants are atoms and/or molecules such as metal ions, dyes and pigments, ionic and hydrophobic molecules, the particle-based contaminants are nanoparticles and/or microparticles such as nano- and micro-plastics, and metal oxides, and the biological contaminants are microorganisms sich as bacteria and viruses.

12. The use of claim 11, wherein the medium is industrial or domestic wastewater such as in laundry treatment.

13. A method for the treatment of laundry in a laundry treating appliance that is operating to an automated cycle of operation, comprising the following steps in a subsequent order:

(i) A soaking phase,

(ii) Optionally, a prewashing phase, and (iii) A washing phase, wherein the decontamination agent of any one of claims 1 to 10 is used in at least one of the phases (i)-(iii), preferably in the soaking phase.

14. The method of claim 13, wherein the decontamination agents is used in a cellulose concentration from 0.1 g/L to 1 g/L, preferably from 0.1 g/L to 0.5 g/L, most preferably from 0.1 g/L to 0.2 g/L in soaking water or wastewater.

15. The method of claim 13 or 14, wherein the decontamination agent is contacted with the laundry for 1 to 240 min, preferably 1 to 120 min, most preferably 1 to 35 min.

16. The method of any one of claims 14 to 15, wherein the laundry is treated at water temperatures of 15 to 95°C, preferably 20 to 80 °C, more preferably 30 to 70 °C, most preferably at 20 to 40 °C.

17. A method for the treatment of wastewater formed during laundry washing with a laundry treating appliance, wherein the decontamination agent according to any claim from 1 to 10 is provided at the outlet from the drum, so as to clean the water prior to release into the environment.