Composite materials functionalized with protein fibers comprising at least one amyloid structure

Abstract

The present invention relates to a composite material comprising at least one textile commodity polymer and protein fibers comprising at least one amyloid structure. The invention also relates to a method for preparing such a material, as well as to the use of such a material for adsorbing a pollutant or extracting metal ions.

Description

DESCRIPTION TITLE OF THE INVENTION: Composite materials functionalized with protein fibers comprising at least one amyloid structure TECHNICAL FIELD

[0001] The present invention relates to composite materials comprising a textile commodity polymer and protein fibers comprising at least one amyloid structure. The invention also relates to a method for preparing these composite materials, the use of these materials for preparing textile yarns, and their use for capturing pollutants. PRIOR ART

[0002] Recently, the interest of protein fibers comprising amyloid structures for pollution control has been described (ref#l).

[0003] Application EP 2921 216 describes a composite material comprising amyloid fibers and activated carbon, with, optionally, a support material.

[0004] Protein fibers comprising amyloid structures, also called amyloid fibers, are generally obtained by self-assembly of proteins under partially denaturing physicochemical conditions. These fibers consist of “amyloid fiber” typology arrangements characterized by the stacking of 0 strands parallel to the fiber axis.

[0005] For decontamination tests, amyloid fibers are prepared in the form of aerogel (ref#2), deposited on filters (ref#3) or in the form of membranes (ref#4-6). Amyloid fibers are capable of extracting many pollutants, both inorganic and organic. Organic compounds are fixed in grooves that run through the amyloid fibers. These grooves are amphiphilic environments favorable to the stabilization of certain conformations of these compounds. The structural properties of the fibers give them excellent adsorption capacities for per- and polyfluoroalkyl substances (PF AS), pollutants described as perpetual and sources of great concern, in particular those with long chains (ref#7).

[0006] Regarding the capture of metals, several fixation modes are possible, depending on the chemical nature of the metals considered. Many proteins, for example metalloproteins, have metal binding sites that can remain partially structured after formation of amyloid fibers and therefore maintain the ability of the protein in the amyloid fiber to bind the metals usually partners of the protein in its native conformation. Moreover, many proteins have disulfide bridges which, under reducing conditions, make available thiol groups capable of binding many so-called soft metals in reference to the HSAB theory (Pearson classification), such as Cu(I), Pb(II), Hg(II), Au(III), etc. (ref#5). Finally, amyloid fibers are often surface charged, which allows the adsorption of many metals.

[0007] However, P-sheet protein fibers are organic materials with limitations in mechanical or physicochemical strength.

[0008] For example, amyloid fibers are sensitive to their environment, i.e., to physicochemical conditions. The vast majority of fibers used in the decontamination literature are formed under acidic conditions (pH < 4). When pH conditions change (pH rise), the fibers disassemble and lose their "amyloid" conformation, which gives them their pollutant capture properties. This leads to losses in binding / complexation / adsorption efficiency observed when the pH increases (ref#2,4-7).

[0009] In addition, the conditions / modalities of use of the decontamination systems / devices can be very harsh and incompatible with the use of protein materials. For example, the decontamination of industrial sites involves the use of geotextiles over which bulldozers will be driven to deposit the polluted soil. Also, the decontamination of groundwater requires that the filtration systems be subjected to high pressures.

[0010] The decontamination materials containing amyloid fibers currently available are aerogels, i.e. obtained by freeze-drying, and membranes. These materials are not compatible with applications in real conditions, i.e. outside the laboratory. Indeed, for their use on industrial sites, decontamination materials must be able to withstand high pressures (filtration), be resistant to extreme mechanical treatments (use of bulldozers, etc.), and retain their decontamination properties under very different physicochemical conditions.

[0011] These reasons probably explain why, to date, no pollution control system based on protein fibers has been tested or deployed in real conditions on industrial sites.

[0012] There is therefore a need for new materials that can be used as pollution control materials and can be used in a variety of environments.

[0013] There is a need for decontamination materials suitable for use in environments with high mechanical or physicochemical constraints.

[0014] There is a need for decontamination materials with a high adsorption capacity for polluting agents.

[0015] There is a need for decontamination materials that can reversibly capture pollutants so that they can be easily recycled and reused.

[0016] There is a need for decontamination materials that have good durability in varied environments.

[0017] There is a need for pollution control materials that are easy to implement in different environments.

[0018] The present invention aims to satisfy all or part of these needs. SUMMARY OF THE INVENTION

[0019] According to one of these first objects, the present description relates to a composite material comprising at least one textile commodity polymer and protein fibers comprising at least one amyloid structure.

[0020] According to another of these objects, the present description relates to a composite material comprising at least one textile commodity polymer and protein fibers comprising at least one amyloid structure, said material comprising approximately from 12% to 30% by weight of protein fibers comprising at least one amyloid structure relative to the total weight of the material.

[0021] As shown below in the Examples section, amyloid fibers, including α-lactalbumin amyloid fibers, were incorporated into a thermoplastic polymer matrix. The resulting composite material was found to be suitable for the manufacture of composite yarns by extrusion / spinning. Within these composite yarns, the protein fibers have retained their amyloid structure and therefore their capacity to fix different pollutants, in particular organic ones, whatever the physicochemical conditions. These composite threads are advantageously usable for the manufacture of robust woven or non-woven fabrics, in which the depollution properties are provided by the amyloid fibers.

[0022] As the examples show, amyloid fibers are incorporated into the polymer matrix during extrusion, but composite filaments allow pollutants to be accessible to the fibers. Advantageously, the fiber proteins are inserted into the polymer matrix, which makes it possible to inhibit conformational changes likely to be induced by changes in physicochemical conditions (pH, ionic strength, exposure to UV radiation, etc.) or by mechanical stresses. In addition, the mechanical properties of polymers in filament form allow the manufacture of textile fabrics (woven fabrics, knits and nonwovens) capable of withstanding mechanical (e.g. tension, pressure), physical (e.g. UV) and chemical (e.g. pH variations) stresses, linked to the conditions of use in industrial sites.

[0023] According to one embodiment, a composite material as described herein may comprise about 1% to 80% by weight of protein fibers comprising at least one amyloid structure relative to the total weight of the material, in particular about 3% to 70%, in particular 5% to 60%, in particular about 8% to 50%, in particular about 10% to 40%, in particular about 12% to 30%, and in particular about 15% to 20% by weight of protein fibers comprising at least one amyloid structure relative to the total weight of the material.

[0024] Protein fibers comprising at least one amyloid structure are also called amyloid fibers.

[0025] According to one embodiment, the amyloid fibers can be obtained with at least one protein comprising, or being capable of forming, at least one amyloid structure.

[0026] According to one embodiment, a protein comprising, or being capable of forming, at least one amyloid structure may further comprise at least one protein domain capable of adsorbing at least one metal ion.

[0027] According to one embodiment, the amyloid fibers can be obtained with at least one protein selected from α-zein, soy protein, arachin, conarachin, avenin, avenalin, sunflower globulin, sunflower albumin, α-lactalbumin, β-lactoglobulin, lysozyme, bovine serum albumin, and HET-s protein from filamentous fungus Podospora anserina, spidroin, silk fibroin, and mixtures thereof.

[0028] According to one embodiment, the amyloid fibers can be obtained with a mixture of proteins as defined above.

[0029] According to one embodiment, the amyloid fibers can be obtained with at least α-zein.

[0030] According to one embodiment, the amyloid fibers can be obtained with at least α-lactalbumin.

[0031] According to one embodiment, the polymer may be selected from ethylene vinyl acetate (EVA), polybutylene succinate (PBS), polycaprolactone (PCL), polyethylene (PE), polypropylene (PP), polystyrene (PS), polyvinyl chloride (PVC), polyamide (PA), polyester (PET), a cellulose polymer, a chitosan polymer, a casein polymer, and mixtures thereof.

[0032] A composite material described herein may be prepared by any method for assembling a textile commodity polymer and amyloid fibers into a polymer matrix incorporating the amyloid fibers.

[0033] According to another of its objects, the present description relates to a method for preparing a composite material as described herein, the method comprising at least one step of incorporating protein fibers comprising at least one amyloid structure into a textile commodity polymer matrix.

[0034] According to one embodiment, the incorporation step can be carried out by a method chosen from a melt spinning method, a solvent spinning method, an electrospinning method, a centrifugal spinning method, an extrusion-blowing (or meltblown) method, and a method for manufacturing a non-woven (spunbond).

[0035] According to another of its objects, the present description relates to a method for preparing a composite material, in which the incorporation step comprises at least the steps of: a) preparing a mixture comprising protein fibers comprising at least one amyloid structure and at least one textile commodity polymer, and b) extruding the mixture obtained in step (a) through a die to obtain a composite material.

[0036] According to another of its objects, the present description relates to a method for preparing a composite material comprising at least one textile commodity polymer and protein fibers comprising at least one amyloid structure, the method comprising at least one step of incorporating the protein fibers comprising at least one amyloid structure into a textile commodity polymer matrix, said incorporation step comprising at least the steps of: (a) preparing a mixture of protein fibers comprising at least one amyloid structure and at least one textile commodity polymer, and (b) extruding the mixture obtained in step (a) through a die to obtain a composite material.

[0037] According to one embodiment, the composite material can be extruded in the form of a wire or a film.

[0038] According to one embodiment, a composite material yarn obtained by a method as described above may be a monofilament yarn.

[0039] According to one embodiment, the mixture of amyloid fibers and the textile commodity polymer can be obtained (a-1) by dispersing the protein fibers in the molten polymer or (a-2) by dispersing the protein fibers in the polymer solubilized in an aqueous or organic solvent.

[0040] According to one embodiment, the protein fibers comprising at least one amyloid structure can be mixed with the polymer, in the form of a powder, a hydrogel or an aqueous dispersion.

[0041] According to one embodiment, at the mixing stage the polymer is in a solid form, for example in the form of granules or a powder.

[0042] According to one embodiment, in the mixing step the polymer and the amyloid protein fibers are in a solid form, for example in the form of polymer granules and an amyloid fiber powder.

[0043] According to one embodiment, the amyloid fibers are mixed with the polymer in the form of a powder.

[0044] According to one embodiment, in a melt extrusion process the polymer may be selected to have a melting temperature less than or equal to 160°C.

[0045] According to one embodiment, prior to the dispersion step, the amyloid fiber powder may be subjected to a drying step at a temperature varying from approximately 40°C to approximately 80°C, and for a period of time varying from approximately 6 hours to approximately 24 hours.

[0046] According to one embodiment, a method as described above may further comprise a step (c) of drying the extruded composite material obtained in step (b).

[0047] According to one embodiment, a method as described above may further comprise a step (d) of cutting into rods the dried composite material obtained in step (c).

[0048] According to another of its objects, the present description relates to a method for manufacturing a textile yarn of composite material by a melt spinning process comprising at least the steps of: a) continuously extruding a composite material described here to continuously obtain a monofilament or a plurality of monofilaments, and b) cooling the monofilament(s) obtained in step (a), c) optionally, assembling the monofilaments obtained in step (b) into a multifilament, and d) drawing the monofilament obtained in step (b) or the multifilament obtained in step (c).

[0049] According to another of its objects, the present description relates to a textile yarn comprising a composite material as described herein.

[0050] According to another of its objects, the present description relates to a textile yarn obtained by a method of manufacturing a textile yarn as described herein.

[0051] According to another of its objects, the present description relates to a textile yarn comprising a composite material comprising at least one textile commodity polymer and protein fibers comprising at least one amyloid structure or a textile yarn prepared by a method as described herein.

[0052] According to one embodiment, a composite material as described herein may be in the form of a monofilament yarn or a multifilament yarn.

[0053] According to another of its objects, the present description relates to a fabric comprising at least one yarn of a composite material as described herein, in particular a multifilament yarn.

[0054] According to another of its objects, the present description relates to a use of a composite material as described herein or prepared by a process as described herein, of a yarn as described herein, or of a fabric as described herein, for capturing a polluting agent.

[0055] According to another of its objects, the present description relates to a method for capturing a polluting agent comprising at least the step of bringing the agent into contact pollutant to be captured with a composite material as described herein or prepared by a method as described herein, or with a yarn as described herein, or with a fabric as described herein, under conditions sufficient to obtain the capture of the pollutant by the protein fibers comprising at least one amyloid structure of said composite material.

[0056] According to another of its objects, the present description relates to a method for capturing a polluting agent comprising at least the step of bringing the polluting agent to be captured into contact with a composite material comprising at least one textile commodity polymer and protein fibers comprising at least one amyloid structure or prepared by a method as described here, or with a yarn as described here, under conditions sufficient to obtain the capture of the polluting agent by the protein fibers comprising at least one amyloid structure of said composite material.

[0057] According to one embodiment, in such methods or textile yarn, the material may comprise about 1% to 80% by weight of protein fibers comprising at least one amyloid structure relative to the total weight of material, in particular about 3% to 70%, in particular about 5% to 60%, in particular about 8% to 50%, in particular about 10% to 40%, in particular about 12% to 30%, and in particular about 15% to 20% by weight of protein fibers comprising at least one amyloid structure relative to the total weight of the material.

[0058] According to one embodiment, in such methods, use or textile yarn, the protein fibers may comprise at least one amyloid structure are obtained with at least one protein selected from α-zein, soy protein, arachin, conarachin, avenin, avenalin, sunflower globulin, sunflower albumin, α-lactalbumin, β-lactoglobulin, lysozyme, bovine serum albumin, HET-s protein from the filamentous fungus Podospora anserina, spidroin, silk fibroin, and mixtures thereof.

[0059] According to one embodiment, in such methods, use or textile yarn, the polymer may be selected from ethylene vinyl acetate (EVA), polybutylene succinate (PBS), polycaprolactone (PCL), polyethylene (PE), polypropylene (PP), polystyrene (PS), polyvinyl chloride (PVC), polyamide (PA), polyester (PET), a cellulose polymer, a chitosan polymer, a casein polymer, and mixtures thereof.

[0060] According to another of its objects, the present description relates to a method for extracting a polluting agent, said method comprising at least the steps consisting of: a) contacting a composite material as described herein or prepared by a method as described herein, or a yarn as described herein, or a fabric as described herein, with a substrate comprising a polluting agent under conditions sufficient to obtain the capture of said polluting agent by the protein fibers comprising at least one amyloid structure, b) dissociating, under conditions sufficient, said polluting agent from the protein fibers comprising at least one amyloid structure, to obtain the extracted polluting agent.

[0061] A substrate comprising a polluting agent may be a solid or liquid substrate. A solid substrate may be a portion of soil polluted with the polluting agent to be extracted. A liquid substrate may be a portion of water, for example rain, having washed a soil polluted with the polluting agent to be extracted.

[0062] A pollutant can be a volatile organic compound (VOC), a polycyclic aromatic hydrocarbon (PAH), an organic solvent, such as benzene, toluene, or xylene, a pesticide, such as DDT, chlordecone, or glyphosate, a PCB (polychlorinated biphenyl), a dioxin, a furan, a per- and polyfluoroalkyl substance (PFAS), or a heavy metal, such as mercury, lead, cadmium, arsenic, nickel, copper, zinc, or chromium.

[0063] According to another of its objects, the present description relates to a method for extracting at least one metal ion, said method comprising at least the steps of: a) bringing into contact a composite material as described here or prepared by a method as described here, or with a thread as described here, or with a fabric as described here, with a substrate comprising at least one metal ion under conditions sufficient to obtain the capture of said metal ion by the protein fibers comprising at least one amyloid structure, b) dissociating, under sufficient conditions, said metal ion from the protein fibers comprising at least one amyloid structure, to obtain the extracted metal ion.

[0064] A metal ion can be a Cu, Ag, Pb, Hg, Au, Cd, As, Ni, Zn or Cr ion.

[0065] A step of dissociating a pollutant or a metal ion adsorbed by the amyloid fibers of a composite material described herein can be carried out by subjecting the composite material having adsorbed the pollutant or the metal ion to an acid solution. BRIEF DESCRIPTION OF THE FIGURES

[0066] [Fig 1] shows cross sections of ethylene vinyl acetate (EVA) polymer yarns comprising 0%, 3% or 20% by weight of oc-lactalbumin amyloid fibers relative to the total weight of material. The sections are observed by scanning electron microscopy.

[0067] [Fig. 2] shows the Young's moduli measured by Dynamic Mechanical Analysis (DMA) as a function of the α-lactalbumin amyloid fiber loading rate in an ethylene vinyl acetate (EVA) polymer yarn. The material comprises 0%, 3%, 10 and 20% α-lactalbumin amyloid fibers by weight / total material weight.

[0068] [Fig. 3] represents emission spectra (X e xc.: 640 ± 10 nm) in the near infrared (660 to 750 nm) of ethylene vinyl acetate (EVA) polymer yarns comprising 0%, 3%, or 20% by weight of α-lactalbumin amyloid fibers / total weight of composite material. The material is incubated in an aqueous buffer at pH 6.0 or pH 8.3.

[0069] [Fig. 4] is a photograph illustrating an experiment on the adsorption of rhodamine B by ethylene vinyl acetate (EVA) polymer yarns comprising 0% or 20% by weight of amyloid fibers / total weight of material. A rhodamine solution of 2 or 10 ppm is placed in the presence of an EVA yarn prepared in the absence (0%) or with 20% of amyloid fibers (weight / total weight of material) for 24 h at room temperature.

[0070] [Fig. 5] is a photograph illustrating the adsorption experiment of different textile dyes: Turquoise diazol LU.JRL*, Yellow Foron, Orange Erionyl 20* RD.4GRL*, and Red maxiion* Rhodamine B*, by polycaprolactone (PCL) polymer yarns comprising 0% (virgin PCL) or 20% weight / weight of amyloid fibers (PCL80 / Proteins 20). The dyes are prepared in aqueous solution at contents varying from 2 to 10 ppm and placed in the presence of a material comprising 0% or 20% of amyloid fibers for 24 hours at room temperature.

[0071] [Fig. 6] represents the proportion of Congo red dye remaining in an aqueous solution of distilled water (a) or in a solution of tap water (b) after 4 days of incubation in the presence of ethylene vinyl acetate (EVA) or polybutylene succinate (PBS) polymer yarns comprising 0%, 10% or 20% by weight of amyloid fibers (a) or 20% by weight of amyloid fibers (b) relative to the total weight of the material. The concentration of dye remaining in solution is measured by UV-visible absorbance spectrophotometry in a range of wavelengths from 400 to 800 nm, with a maximum absorbance value (À ma x) of 498 nm and expressed relative to to.

[0072] [Fig. 7] represents the evolution of the amount of Congo red dye adsorbed by a 100 mg ethylene vinyl acetate (EVA) composite yarn comprising 20% ​​by weight amyloid fibers / total weight of material. The composite yarn was kept in 15 mL of a solution of distilled water (pH 5.5) and 10 pM Congo red (i.e., 150 nmoles in solution at the beginning of the experiment). The measurements were carried out by UV-visible absorbance spectrophotometry in a wavelength range of 400 to 800 nm, with a maximum absorbance value (Xmax) of 498 nm over an eight-day incubation period at different time intervals.

[0073] [Fig. 8] represents an observation of cross sections of a 100 mg ethylene vinyl acetate (EVA) composite yarn comprising 20 wt% amyloid fibers / total material weight. The composite yarn was kept in a solution of distilled water (pH 5.5) and 10 μM Congo red. A series of scalpel cross sections were taken.

[0074] [Fig. 9] represents the percentage of PF As, by molecular weight category, in suspension after incubation of a mixture of PF As (233.5 pg / L) in the absence of composite yarn (o), in the presence of a yarn composed solely of polymer (A), or in the presence of a composite yarn of polymer and amyloid fibers (□) (20% w / w of material). The amount of polymer yarn or composite material was 400 mg + / - 20 mg per test. Left panel: EVA. Middle panel: PBS. Right panel: PCL.

[0075] [Fig. 10] represents the total percentage of suspended PFAs after incubation of a mixture of PFAs (233.5 pg / E) in the absence of composite yarn, in the presence of a yarn composed solely of polymer, or in the presence of a composite yarn of polymer and amyloid fibers (20% w / w of material). The amount of polymer yarn or composite material was 400 mg + / - 20 mg per test. The value obtained with EVA alone is not representative of the control experiment. Without wishing to be bound by any theory, it has been hypothesized at this stage that this observation reflects an experimental or data reporting problem. DETAILED DESCRIPTION Definitions

[0076] Unless otherwise defined in the specification, scientific and technical terms used have the meanings that are commonly understood in the technical field. In the event of a conflict, this specification shall prevail. Units, prefixes, and symbols are given in their accepted International System of Units (SI) form. The headings provided in the specification document are not limiting of the various aspects of the disclosure. The list of sources, ingredients, and components described herein is enumerated such that combinations and mixtures thereof are also contemplated and within the scope hereof. Exemplary methods and materials are described below, and methods and materials similar or equivalent to those described herein may also be used in practicing the present invention.It is appreciated that certain features of the invention, which are, for clarity, described in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the invention, which are, for brevity, described in the context of a single embodiment, may also be provided separately or in any suitable subcombination.

[0077] Numerical ranges include all numbers defining the range. Each maximum numerical limitation given throughout the description includes any lower numerical limitation, as if such lower numerical limitations were expressly written herein. Each minimum numerical limitation given throughout the description includes any higher numerical limitation, as if such higher numerical limitations were expressly written herein. Each numerical range given throughout the description includes any narrower numerical range that falls within such a broad numerical range, as if such narrower numerical ranges were all expressly written herein.

[0078] All lists of items, such as, for example, lists of ingredients, are intended and should be interpreted as Markush groups. Thus, all lists can be read and interpreted as items "selected from the group consisting of the list of items" and combinations and mixtures thereof.

[0079] Unless the context otherwise requires, terms in the singular include the plural and terms in the plural include the singular. The terms “a”, “one or more” and “at least one” may be used interchangeably in the description.

[0080] In the description, embodiments described herein with the terms "having" or "comprising" include embodiments described with the terms "comprising only", "consisting of" and / or "consisting essentially of". The expression “consisting of” implies the inclusion of the stated elements to the exclusion of any other elements. The expression “consisting essentially of” implies the inclusion of the stated elements, and possibly other elements where the other elements do not materially affect the fundamental characteristic(s) of the disclosure.

[0081] Furthermore, the expression "and / or" should be considered a specific disclosure of each of the two features with or without the other. Thus, the expression "and / or" used in an expression such as "A and / or B" is intended to include "A and B", "A or B", "A" (alone) and "B" (alone).

[0082] The terms "about" or "approximately" mean an acceptable measurement error for a particular value of a parameter determined by measurement methods customary in the field and which will depend in part on how the value is measured or determined, i.e., the limitations of the measurement system. For example, "about" may mean within a range of three or more standard deviations, depending on the practice of the art. Alternatively, "about" may mean a numerical range or deviation of up to 20%, e.g., up to 10%, e.g., up to 5%, and again up to 1% of a given value.

[0083] Composite material. In the description, the expression "composite material" is intended to designate a heterogeneous assembly or mixture of at least two components, having a high capacity for interpenetration and adhesion and together forming a new material. The material thus formed has properties that the components alone do not possess. A composite material described herein comprises a textile commodity polymer matrix incorporating amyloid fibers.

[0084] Polymer. In the description, the term "polymer" is intended to refer to a macromolecule made up of repeating small units called monomers. Monomers are assembled by chemical reactions.

[0085] Textile commodity polymer. In the description, the term "textile commodity polymer" is intended to refer to a synthetic polymer made from petrochemical or bio-based monomers and suitable for the manufacture of textile fibers. Textile commodity polymers are specifically designed for use in the production of textile fibers. These polymers have specific properties that make them suitable for use in textiles, such as their resistance to water, color fading, and wear, their light weight, and their durability. Examples of textile commodity polymers include polyethylene (PE), polypropylene (PP), polystyrene (PS), polyvinyl chloride (PVC), ethylene vinyl acetate (EVA), polybutylene succinate (PBS), and polycaprolactone (PCL).

[0086] Bio-based. In the description, the term "bio-based" is intended to describe a material or substance derived from renewable sources of biological origin, such as plants, microorganisms, or animals. An example of a bio-based polymer is polycaprolactone (PCL).

[0087] Amyloid structure. Amyloid structure refers to a structure composed of extended p-sheet hydrogen bonding networks that extend orthogonally to the backbone of a peptide or protein. Monomers or soluble peptide / protein molecules comprising amyloid structures self-assemble into oligomers, which give rise to protofibrils that then pack to form mature amyloid fibers. An amyloid structure can be characterized by the binding of thioflavin T (or S) and its enhanced fluorescence, the binding of Congo red with a shift in the optical absorbance maximum and birefringence, and a typical wide-angle X-ray diffraction pattern (as described in #11 - Dharmadana et al., Interface Focus 7: 20160160. http: / / dx.doi.org / 10.1098 / rsfs.2016.0160).

[0088] Protein fiber comprising at least one amyloid structure. The term "protein fiber comprising at least one amyloid structure" is understood to mean small fibers, generally from a few nanometers to several micrometers in length, consisting of proteins having, or comprising, at least one amyloid structure and forming aggregates of amyloid fibers. Such fibers may be obtained from proteins naturally comprising an amyloid structure or from proteins subjected to a chemical or physical process capable of conferring an amyloid structure on them. Examples of proteins whose structure may comprise or be modified to comprise an amyloid structure include α-zein, α-lactalbumin, β-lactoglobulin, lysozyme, or bovine serum albumin.The terms "amyloid fiber(s)", "amyloid protein fiber(s)", and "protein fiber(s) comprising at least one amyloid structure" are used interchangeably in the description.

[0089] Protein hydrogel. In the description, "protein hydrogel" means a three-dimensional network of protein chains containing water.

[0090] Freeze-drying. In the description, "freeze-drying" is intended to mean a sublimation drying process involving the conversion of water (or other solvents) from a solid or liquid material into a gas, avoiding the intermediate liquid step. The freeze-drying process includes steps of freezing the material, so as to transform the water or the solvent into ice, and sublimation by exposing the frozen material to low pressure allowing the ice to sublime into gas.

[0091] Atomization. In the description, "atomization" is understood to mean a process for reducing a material to powder comprising the steps of dispersing a liquid or gel into droplets and solidifying, generally by drying, the droplets.

[0092] Polluting agent. In the description, the term "polluting agent" is intended to mean a substance, material, or compound that may have a negative impact on the environment, human health, or animal health. Examples of polluting agents include volatile organic compounds (VOCs), polycyclic aromatic hydrocarbons (PAHs), organic solvents such as benzene, toluene, or xylene, pesticides such as DDT, chlordecone, or glyphosate, PCBs (polychlorinated biphenyls), dioxins and furans, per- and polyfluoroalkyl substances (PFAS), or heavy metals such as mercury, lead, cadmium, arsenic, nickel, copper, zinc, or chromium.

[0093] Captation. For the purposes of the description, the term "capture" or "capture" is understood to mean the process by which a polluting agent is retained or trapped by the amyloid fibers. Depending on the nature of the polluting agent, different types of interactions and bonds may be involved in the process of capturing the polluting agent by the amyloid fibers. Examples include physical adsorption, which may involve hydrophobic and / or hydrophilic interactions; chemical adsorption, which may involve acid-base, oxido-reductive reactions, or the formation of covalent bonds; selective retention, which may involve specific binding sites for the polluting agent, which may be ionic, steric, or by interaction of functional groups; complexation; or chelation.

[0094] Textile yarn. For the purposes of this description, "textile yarn" means, regardless of its structure, simple or complex, a long assembly of fibers, filaments (continuous yarn) or discontinuous fibers (fiber yarn), directly usable for textile manufacturing. A textile yarn may, in particular, be monofilament or multifilament.

[0095] Monofilament yarn or monofilament. The terms "monofilament yarn" or "monofilament" are used interchangeably and are intended to refer to a yarn made of a single filament with or without twist. This monofilament must be strong and flexible enough to be woven, knitted, braided, etc.

[0096] Multifilament yarn. The terms "multifilament yarn" or "multifilament" are used interchangeably and are intended to refer to a yarn made up of several filaments with or without twist. Composite material

[0097] The composite materials described herein are composed of a mixture of at least one textile commodity polymer and protein fibers comprising at least one amyloid structure.

[0098] According to one embodiment, in order to promote the homogeneity of the mixture intended to produce the composite material, the polymer(s) and the amyloid fibers can be selected to be of the same nature: polar or apolar.

[0099] A composite material may comprise hydrophilic amyloid fibers and a hydrophilic polymer.

[0100] Alternatively, a composite material may comprise hydrophobic amyloid fibers and a hydrophobic polymer.

[0101] Alternatively, a composite material may comprise hydrophilic amyloid fibers, or hydrophobic hydrophilic amyloid fibers, or a mixture of hydrophilic amyloid fibers and hydrophobic amyloid fibers and a copolymer of hydrophilic units and hydrophobic units.

[0102] According to one embodiment, a composite material may comprise approximately 1% to 80% by weight of protein fibers comprising at least one amyloid structure relative to the total weight of material, in particular approximately 3% to 70%, in particular approximately 5% to 60%, in particular approximately 8% to 50%, in particular approximately 10% to 40%, in particular approximately 12% to 30%, and in particular approximately 15% to 20% by weight of protein fibers comprising at least one amyloid structure relative to the total weight of material.

[0103] According to one embodiment, a composite material may comprise approximately 8% to 32% by weight of protein fibers comprising at least one amyloid structure relative to the total weight of material, in particular approximately 10% to 30%, in particular approximately 15% to 30%, in particular approximately 20% to 30%, in particular approximately 30% by weight of protein fibers comprising at least one amyloid structure relative to the total weight of material.

[0104] According to one embodiment, a composite material as described herein may comprise about 99% to 15% by weight of textile commodity polymer relative to the total weight of material, in particular about 99% to 20% by weight of textile commodity polymer relative to the total weight of material, in particular about 97% to 30%, in particular about 95% to 40%, in particular about 92% to 50%, in particular about 90% to 60%, in particular about 88% to 70%, and in particular about 85% to 80% by weight of textile commodity polymer relative to the total weight of material.

[0105] According to one embodiment, a composite material as described herein may comprise approximately 15% to 20% by weight of protein fibers comprising at least one amyloid structure relative to the total weight of the material.

[0106] According to one embodiment, a composite material may comprise at least one additional agent usually used in the textile field to give the composite material or a yarn or fabric comprising such a composite material specific textile properties such as abrasion resistance, breathability and weather resistance.

[0107] An additional agent may be present in a composite material described herein in a content ranging from about 1% to 25% by weight relative to the total weight of material, in particular from about 5% to 20%, and in particular from about 10% to 15% by weight relative to the total weight of composite material.

[0108] In one embodiment, a composite material may comprise about 74% to 19% by weight of textile commodity polymer, about 1% to 80% by weight of amyloid fibers, and about 1% to 25% by weight of at least one additional agent, based on the total weight of material.

[0109] Additional agents include silicones, fluorocarbons, epoxy resins, polyurethanes, waxes, antistatic agents, flame retardants, antimicrobial agents, UV stabilizers, plasticizers, such as glycerol, and softening agents. Textile commodity polymer

[0110] Textile commodity polymers are polymers used in the textile industry for their mechanical strength, abrasion resistance, lightness, flexibility, thermal stability, and resistance to discoloration. Textile commodity polymers can be composed of synthetic monomers or bio-based monomers.

[0111] A suitable textile commodity polymer may be a thermoplastic polymer. In one embodiment, a suitable polymer may be a biodegradable polymer.

[0112] A polymer may have a molecular weight ranging from about 5,000 to about 800,000 g / mol, for example from about 10,000 to about 200,000 g / mol.

[0113] A polymer may be a hydrophilic polymer, a hydrophobic polymer, or a copolymer of hydrophilic units and hydrophobic units. In one embodiment, a polymer suitable for the disclosure may be a copolymer of hydrophilic units and hydrophobic units.

[0114] In one embodiment, a polymer suitable for preparing a composite material described herein has physicochemical properties suitable for a spinning process.

[0115] In one embodiment, a polymer suitable for preparing a composite material described herein has physicochemical properties suitable for a melt spinning process, a solvent spinning process, an electrospinning process, a centrifugal spinning process, a meltblown spinning process, or a spunbond manufacturing process.

[0116] According to one embodiment, a polymer suitable for preparing a composite material described herein has physicochemical properties suitable for a melt spinning process and / or a solvent spinning process.

[0117] A polymer suitable for a melt spinning process may have a melting temperature of about 200°C or less, and in particular of about 160°C or less so that the temperature to which the polymer must be brought is not a temperature of degradation of amyloid fibers.

[0118] A polymer suitable for a solvent spinning process may be soluble in a solvent that does not denature or degrade amyloid fibers. A polymer suitable for solvent processing may be solubilized, depending on its solubility parameters, in an aqueous solvent or in an organic solvent.

[0119] A polymer suitable for a solvent spinning process may have a melting temperature higher than the degradation temperature of amyloid fibers.

[0120] A polymer, for example suitable for a melt spinning process, may have a melting temperature ranging from about 50°C to about 200°C, for example from about 55°C to about 160°C, and for example from about 60°C to about 130°C.

[0121] In one embodiment, a polymer suitable for a melt spinning process of a composite material described herein may be a thermoplastic polymer having a melting temperature ranging from about 50°C to about 300°C, and a molecular weight ranging from about 5,000 to about 800,000 g / mol.

[0122] A polymer may be a thermoplastic polymer, having a melting temperature ranging from about 55°C to about 160°C, and a molecular weight ranging from about 10,000 to about 200,000 g / mol.

[0123] According to one embodiment, a polymer may be a thermoplastic copolymer, comprising hydrophilic units and hydrophobic units, having a melting temperature ranging from about 55°C to about 160°C, and a molecular weight ranging from about 10,000 to about 200,000 g / mol.

[0124] A polymer suitable for solvent spinning may be soluble in an aqueous solvent or in an organic solvent, such as, for example, acetic acid, dimethylformamide (DMF), dimethylacetamide, acetone, carbon disulfide / acetone mixture, chloroform, dichloromethane, tetrachloromethane, benzene, toluene, cyclohexanone or 2-nitropropane.

[0125] According to one embodiment, a solvent suitable for the description may be chosen from acetic acid, dimethylformamide (DMF), dimethylacetamide, acetone, and a carbon disulfide / acetone mixture.

[0126] In one embodiment, a textile commodity polymer may be ethylene vinyl acetate (EVA), polybutylene succinate (PBS), polycaprolactone (PCL), polyethylene (PE), polypropylene (PP), polystyrene (PS), polyvinyl chloride (PVC), polyamide (PA), polyester (PET), a cellulose polymer, a chitosan polymer, a casein polymer, and mixtures thereof.

[0127] According to one embodiment, the polymer may be selected from ethylene vinyl acetate (EVA), polybutylene succinate (PBS), polycaprolactone (PCL), polyethylene (PE), polypropylene (PP), polystyrene (PS), polyvinyl chloride (PVC), polyamide (PA), polyester (PET), and mixtures thereof.

[0128] According to one embodiment, the polymer may be selected from ethylene vinyl acetate (EVA), polyethylene (PE), polybutylene succinate (PBS), polycaprolactone (PCL), and a mixture thereof, and in particular may be selected from ethylene vinyl acetate (EVA), polybutylene succinate (PBS), polycaprolactone (PCL), and mixtures thereof.

[0129] According to one embodiment, the polymer may be polycaprolactone (PCL).

[0130] Ethylene vinyl acetate (EVA) is a copolymer with a melting point between 70 and 130°C, with a molecular weight between 10,000 and 200,000 g / mol. EVA fibers are mainly used in the production of carpets, shoes, and bags. An example of commercial references for EVA is EVAFLEX™.

[0131] Polybutylene succinate (PBS) is a biodegradable polymer with a melting point between 105 and 115°C and a molecular weight between 10,000 and 50,000 g / mol. PB S fibers are primarily used in the production of clothing, duvets, and mattresses. Examples of commercially available PB S fibers include BIOSUCCINIUM™.

[0132] Polycaprolactone (PCL) is a biodegradable polymer with a melting point between 60 and 65°C and a molecular weight between 10,000 and 100,000 g / mol. PCL fibers are primarily used in the production of clothing, bags, and medical fabrics. Examples of commercial PCL fibers include TONE™.

[0133] Polyethylene (PE) is a thermoplastic polymer with a melting temperature between 110 and 130°C and a molecular weight between 10,000 and 200,000 g / mol. Polyethylene fibers are used in the production of protective clothing, bags, and flooring. Examples of commercial references are TYVEK™ and SPECTRA™.

[0134] Polypropylene (PP) is a polymer with a melting temperature between 160 and 170°C, with a molecular weight between 50,000 and 500,000 g / mol. Polypropylene fibers are used in the production of carpets, ropes, and geotextiles. Examples of commercial references are MARLEX™ and MOPLEN™.

[0135] Polystyrene (PS) is a polymer with a melting temperature between 240 and 260°C, and a molecular weight between 10,000 and 200,000 g / mol. Polystyrene fibers are mainly used in the production of carpets and felts. Examples of commercial references for PS include STYRON™.

[0136] Polyvinyl chloride (PVC) is a polymer with a melting temperature between 160 and 210°C, with a molecular weight between 10,000 and 200,000 g / mol. PVC fibers are mainly used in the production of carpets, floor coverings, and tents. An example of commercial references for PVC is GEON™.

[0137] Polyamide (PA) is a polymer with a melting temperature between 215 and 265°C, and a typical molecular weight between 10,000 and 30,000 g / mol. Polyamide fibers are used in the production of sportswear, underwear, socks, and tights. Examples of commercial references are NYLON™ 6 and NYLON™ 66.

[0138] Polyester (PET) is a polymer with a melting temperature between 245 and 255°C, with a typical molecular weight between 10,000 and 50,000 g / mol. Polyester fibers are used in the production of clothing, blankets, curtains, and upholstery fabrics. Examples of commercial references are TERYLENE™ and DACRON™.

[0139] Cellulose polymers can have a molecular weight ranging from 50,000 to 500,000 g / mol, and a melting temperature between 200 and 230°C. These fibers can be used to make clothing, sheets, or towels.

[0140] Casein polymers can have an average molecular weight of about 100,000 g / mol and a melting temperature of about 200 °C. These fibers can be used to make technical fabrics.

[0141] Chitosan polymers can have a molecular weight ranging from 100,000 to 1,000,000 g / mol and a melting temperature between 200 and 300°C. They can be solubilized in acetic acid. These fibers can be used to manufacture medical fabrics.

[0142] It is worth noting that these polymers can be used alone or in combination with other materials to achieve specific textile properties such as abrasion resistance, breathability and weather resistance.

[0143] Polyamide (PA) and polyester (PES) are hydrophilic polymers. Polypropylene (PP), polyethylene (PE), and polystyrene (PS) are hydrophobic polymers. Ethylene vinyl acetate (EVA), polybutylene succinate (PBS), and polycaprolactone (PCL) are copolymers of hydrophilic / hydrophobic units.

[0144] According to one embodiment, a polymer may be selected from ethylene vinyl acetate (EVA), polybutylene succinate (PBS), polycaprolactone (PCL), polyethylene (PE), and mixtures thereof. These polymers may advantageously be used in a melt spinning process and / or a solvent spinning process.

[0145] According to one embodiment, a polymer may be selected from ethylene vinyl acetate (EVA), polybutylene succinate (PBS), polycaprolactone (PCL), and mixtures thereof.

[0146] According to one embodiment, a polymer may be polycaprolactone (PCL). Protein fibers comprising at least one amyloid structure

[0147] According to one embodiment, a composite material as described herein may comprise about 1% to 80% by weight of protein fibers comprising at least one amyloid structure, relative to the total weight of material, in particular about 3% to 70%, in particular about 5% to 60%, in particular about 8% to 50%, in particular about 10% to 40%, in particular about 12% to 30%, and in particular about 15% to 20% by weight of protein fibers comprising at least one amyloid structure relative to the total weight of the material.

[0148] Amyloid fibers can be obtained with at least one protein comprising, or being capable of forming, at least one amyloid structure.

[0149] A protein comprising, or being capable of forming, at least one amyloid structure may further comprise at least one protein domain capable of adsorbing at least one metal ion.

[0150] Protein fibers comprising or being capable of forming at least one amyloid structure may be obtained with at least one protein selected from α-zein, soy protein, arachin, conarachin, avenin, avenalin, sunflower globulin, sunflower albumin, α-lactalbumin, β-lactoglobulin, lysozyme, bovine serum albumin, HET-s protein from the filamentous fungus Podospora anserina, spidroin, silk fibroin, and mixtures thereof.

[0151] According to one embodiment, amyloid fibers can be obtained with a-zein, arachin, conarachin, avenin, avenalin, sunflower globulin, sunflower albumin, a-lactalbumin, 0-lactoglobulin, and mixtures thereof.

[0152] In one embodiment, fibers may be obtained with α-zein, sunflower globulin, sunflower albumin, α-lactalbumin, β-lactoglobulin, and mixtures thereof.

[0153] According to one embodiment, amyloid fibers can be obtained with α-zein, α-lactalbumin, β-lactoglobulin, and mixtures thereof.

[0154] According to one embodiment, amyloid fibers can be obtained with oc-zein, oc-lactalbumin, and mixtures thereof.

[0155] According to one embodiment, amyloid fibers can be obtained with oc-zein.

[0156] Proteins suitable for the preparation of amyloid fibers may be obtained by any method known in the art, such as extraction from a biological source naturally expressing that protein or as recombinant proteins obtained by heterologous expression in a host cell, for example Escherichia coli or CHO cells, and amplification of the host cell in a bioincubator. The recombinant proteins thus obtained are then purified by any method known in the art.

[0157] For the preparation of amyloid fibers, proteins can be used in purified or unpurified forms.

[0158] A purified protein is a protein obtained from a mixture that has undergone a method of removing impurities, contaminants, or unwanted substances from the mixture. As a result of the purification method, the protein may be obtained at a high concentration and be free of, or in the presence of a minimal amount of, unwanted substances. A purification method may involve steps such as filtration, distillation, or extraction.

[0159] An unpurified protein is a protein extracted from its natural environment and accompanied by other compounds, for example proteins, sugars, lipids, from the protein's natural environment. For example, an unpurified protein may be contained in an extraction residue from milk, for example whey, or from a plant, for example corn or sunflower meal. According to one embodiment, the amyloid fibers may be obtained with whey, for example comprising α-lactalbumin and / or β-lactoglobulin, a corn flour or meal, for example comprising α-zein, or a sunflower flour or meal, for example comprising sunflower globulin and / or sunflower albumin, or a peanut meal. Preparation of amyloid fibers

[0160] Protein fibers comprising at least one amyloid structure can be prepared by any method known in the art and adapted to the nature of the protein.

[0161] A composite material described herein may be prepared by any method for assembling a textile commodity polymer and amyloid fibers into a polymer matrix incorporating the amyloid fibers.

[0162] Amyloid fibers are highly stable fibrillar structures formed by self-assembly of proteins organized into O-sheets. The formation of amyloid fibers follows a nucleation-elongation process. Thus, a protein acquires a secondary structure rich in O-strands that associate via hydrogen bonds to form O-sheets. The protein subunits self-assemble by successive stacking perpendicular to the elongation axis of the fiber. The structure is stabilized by a dense network of hydrogen bonds with an orientation parallel to the fibrillar axis.

[0163] The formation of amyloid fibers can be dependent on various parameters such as pH, ionic strength of the solution containing the proteins, protein concentration, the presence of other molecules or impurities, temperature, or even stirring speed, which can lead to different fibrillation kinetics and organizations. It is within the practice of those skilled in the art to adapt the operating conditions according to the nature of the proteins used.

[0164] Amyloid fibers can be about 1 pm to 10 pm in length and about 5 nm to 50 nm in diameter.

[0165] Amyloid fibers can be prepared by chemical treatment leading to self-assembly of proteins into amyloid fibers or by electrospinning (electrospinning technique).

[0166] Advantageously, the amyloid fibers can be prepared in the form of aqueous fiber dispersions, hydrogels or even in dry forms, for example in the form of powders.

[0167] An aqueous dispersion of amyloid fibers may be obtained by any method known in the art. The preparation of an amyloid fiber dispersion generally comprises the steps of: a) dissolving the proteins in an aqueous phase, optionally comprising an organic phase, for example ethanol, and b) denaturing the proteins into amyloid fibers, for example by heating, for example at a temperature ranging from about 35°C to about 110°C, at acidic pH, for example at a pH ranging from 1 to 3, or at basic pH, for example at a pH ranging from 8 to 12, for a time ranging from about 10 h to about 168 h.

[0168] After the denaturation step, the amyloid fibers can be obtained in the form of an aqueous dispersion of amyloid fibers or in the form of an amyloid fiber hydrogel.

[0169] Prior to the heating step, the aqueous solution can be filtered. The filtration step can be performed before the heating step. Filtration can be carried out, for example, with a 0.5 pm or 0.22 pm filter to purify the solution and remove any contaminants.

[0170] The heating and pH conditions are adapted according to the protein(s) considered so as to allow the structuring of the proteins into O-sheets and amyloid fibers. Optionally, an aqueous dispersion of amyloid fibers can be transformed into a hydrogel by means of an additional crosslinking step, chemically, for example with a glutaraldehyde or carbodiimide-based crosslinking agent, or by physical treatment, such as heating, freezing-thawing or lyophilization.

[0171] The aqueous phase may be a saline solution. An aqueous solution may have an ionic strength less than or equal to approximately 60 mM, for example less than approximately 50 mM, or even approximately 30 mM. The ionic strength may be obtained and / or adjusted by adding a salt which may be chosen from alkali or alkaline earth metal halides, such as for example NaCl, KCl, MgCl, CaCl, etc.; alkali or alkaline earth metal carbonates or their mixture; phosphates, such as for example sodium or potassium phosphate or sulfates such as for example sodium or magnesium sulfate.

[0172] The preparation of the solution may include a stirring step. A stirring step may be carried out using any device known in the art.

[0173] As an example of a process for preparing amyloid fibers, we can cite the process described by #12 - Soon et al., (Chemical Engineering Journal, 445, 2022, 136513, https: / / doi.Org / 10.1016 / j.cej.2022.136513).

[0174] In this method, the proteins, for example sunflower or peanut proteins, may be dissolved in an aqueous phase at an acidic pH, for example at pH 2 or 3. The solution may be heated to a temperature ranging from about 50°C to about 110°C, for example at 90°C or 100°C, and in particular at 90°C, for a period of time ranging from about 10 to 48 hours, for example 24 hours to induce the formation of amyloid fibers. The reaction may be stopped by lowering the temperature, for example by quenching in ice.

[0175] As another example of a method for preparing amyloid fibers, we can cite the method for preparing amyloid fibers described by #13 - Sanchez-Iglesias et al. (ACS Nano 2012 6 (12), 11059-11065, doi: 10.1021 / nn3047605).

[0176] In this method, the proteins, for example α-zein, may be dissolved in an aqueous phase comprising from 50% to 90%, for example 70%, of an organic phase, for example ethanol. The pH of the solution may be adjusted to a basic pH, for example ranging from pH 8 to pH 12, and for example to pH 8. The solution may be heated to a temperature ranging from about 50°C to about 90°C, for example to about 60°C, for a time ranging from about 10h to 96h, for example 72 hours, to induce the formation of amyloid fibers.

[0177] It is possible to obtain an amyloid fiber hydrogel by using high concentrations of α-zein, for example greater than or equal to 2% by weight of protein relative to the weight of the solution, for example 3% or 5%, and high contents of ethanol, for example greater than 80% by weight relative to the weight of the aqueous phase.

[0178] α-Zein is an amphiphilic protein, and α-Zein amyloid fibers can be implemented with hydrophilic polymers, hydrophobic polymers, or hydrophilic / hydrophobic copolymers. For example, amyloid fibers prepared from zein can be implemented with polyethylene.

[0179] An amyloid fiber hydrogel can be obtained by any method known in the art. The preparation of an amyloid fiber hydrogel generally comprises the steps of: dissolving the proteins in an aqueous solvent, followed, if necessary, by denaturing the proteins allowing the formation of amyloid fibers, for example by heating at acidic or basic pH, then by crosslinking the fibers, chemically, by for example with a glutaraldehyde or carbodiimide crosslinking agent, or by physical treatment, such as heating, freezing-thawing or lyophilization.

[0180] As an example of a process for preparing amyloid fibers, in particular in the form of a hydrogel, mention may be made of the process described in WO 2012 / 136909.

[0181] In this method, proteins, for example α-lactalbumin or α-zein, may be dissolved in an aqueous phase in a content of at least about 5 mg / ml of protein. The protein concentration may vary from about 5 mg / ml to the solubility limit of the protein. For example, the protein concentration may vary from about 5 mg / ml to about 200 mg / ml, for example 40 mg / ml.

[0182] The pH of the aqueous solution can be an acidic pH. For example, the pH can be less than 3. The pH can be less than 2.5. The pH can be adjusted using a strong acid, for example HCl. The pH is adjusted before adding and solubilizing the protein.

[0183] The preparation of the aqueous solution may include a heating step, for example at a temperature selected from a range of about 35°C to about 60°C. The solution may be stirred. The heating step and the stirring step may be carried out simultaneously. The heating step may last at least 10 hours, or even a week (or 168 hours). For example, the heating step may last from 48 hours to 96 hours.

[0184] According to one embodiment, a method for preparing an amyloid fiber hydrogel may comprise at least the steps of: solubilizing proteins capable of self-assembling into amyloid fibers, in a content varying from at least 5 g / L to the solubility limit, for example from 20 to 200 g / L, in an acidic saline solution with a pH varying from approximately 1.5 to 2.5, then heating the solution obtained at a temperature varying from approximately 35°C to 60°C, for a period of at least 10 hours.

[0185] A process for preparing a hydrogel is carried out, for example, in the absence of water evaporation.

[0186] According to one embodiment, the amyloid fibers are prepared in the form of a hydrogel.

[0187] Electrospinning uses an electric field to create a jet of protein solution, which is then collected on a substrate to form a fibrous mat. The resulting fibers can be aligned or randomly distributed. By controlling processing parameters such as solution concentration, flow rate, and electric field strength, it It is possible to adapt the morphology, diameter and mechanical properties of amyloid fibers. Amyloid fiber powder

[0188] In preparing a composite material as described herein, the amyloid fibers may be mixed with the textile commodity polymer in the form of an aqueous dispersion, in the form of a hydrogel, or in the form of a powder.

[0189] Advantageously, the amyloid fibers can be mixed with the textile commodity polymer in powder form.

[0190] An aqueous dispersion or hydrogel of protein fibers comprising at least one amyloid structure may be reduced to powder by any means known in the art.

[0191] Examples of processes for preparing a powder from a hydrogel or an aqueous dispersion of amyloid fibers include freeze-drying or atomization processes.

[0192] Freeze-drying, or sublimation drying, involves freezing the hydrogel or aqueous dispersion and then drying it under vacuum at a temperature below the sublimation point of water. Water is removed from the hydrogel or aqueous dispersion in the form of vapor. The process produces a dry, porous powder.

[0193] According to one embodiment, the reduction of a hydrogel or an aqueous dispersion into powder by lyophilization may comprise at least the steps of freezing the hydrogel or aqueous dispersion, for example at a temperature below -40°C, and placing the frozen hydrogel under vacuum, for example at 0.1 or 0.001 mbar, to obtain the sublimation of the frozen water. Optionally, the sublimation may be accompanied by a heating step, for example at -20°C or -15°C.

[0194] Atomization involves spraying a jet of liquid hydrogel into a stream of hot air, causing the water to evaporate and form small solid particles.

[0195] According to one embodiment, the reduction of a hydrogel into powder by atomization may comprise at least the steps of forming a jet of liquid hydrogel, spraying the resulting jet into a hot air stream, in order to evaporate the water, and obtaining solid particles of the hydrogel. The size and shape of the particles may depend on the size of the spray nozzle and the air velocity.

[0196] An amyloid fiber powder can be subjected to a grinding step.

[0197] Advantageously, a grinding step makes it possible to obtain a powder of amyloid fiber particles that are homogeneous in size and distribution.

[0198] Grinding of amyloid fiber powder can be carried out by any method known in the field, for example with a ball mill or a centrifugal mill. The grinding technique and parameters are adapted according to the nature of the amyloid proteins.

[0199] As an example of a ball mill, it is possible to use a BB1L porcelain ball mill with 20 g of balls.

[0200] As an example of a centrifugal mill, it is possible to use a UT 6000 rpm ultracentrifugal mill.

[0201] Advantageously, grinding can be carried out with a centrifugal grinder.

[0202] Advantageously, after grinding, the amyloid fiber powder comprises particles having a size varying from approximately at least 1 pm to at least 100 pm, in particular varying from approximately at least 5 pm to at least 90 pm, from approximately at least 10 pm to approximately 70 pm, from approximately 20 pm to approximately 50 pm.

[0203] The size and size distribution of an amyloid fiber powder can be measured by any method known in the field, including Dynamic Light Scattering (DLS).

[0204] An amyloid fiber powder, ground or unground, may optionally be subjected to a drying step. The drying step may be carried out in an oven, at a temperature varying from approximately 40°C to approximately 80°C, in particular from approximately 40°C to approximately 60°C, for example at a temperature of approximately 45°C. The drying time may vary from approximately 6 hours to approximately 24 hours, and may be, for example, approximately 12 hours.

[0205] The residual water content in the powder after the drying step may be less than or equal to 3% by weight.

[0206] A powder of ground amyloid fibers can advantageously be used in a process for preparing a composite material by solvent spinning. The use of a homogeneous powder allows for a homogeneous distribution of amyloid fibers in the solubilized polymer.

[0207] According to one embodiment, amyloid fibers suitable for the preparation of a composite material described herein may be prepared by means of a method comprising at least the steps of: a) dissolving proteins capable of forming amyloid fibers in an aqueous phase, optionally comprising an organic phase, for example ethanol, b) adjusting the pH of the solution obtained in step to an acidic pH, for example to a pH ranging from 1 to 3, or to a basic pH, for example, to a pH ranging from 8 to 12, c) heating the solution obtained in step (b), for example to a temperature ranging from about 40°C to about 110°C, for a time ranging from about 10 hours to about 168 hours, to obtain a dispersion or a hydrogel of amyloid fibers, d) optionally, crosslinking the dispersion obtained in step (c) to obtain a hydrogel of amyloid fibers, e) reducing the dispersion obtained in step (c) to powder or the hydrogel obtained in step (c) or (d),for example by an atomization or freeze-drying process, f) optionally, drying the powder obtained in step (e), and g) optionally, grinding the powder obtained in step (e) or (f).,

[0208] The method further comprises a step of incorporating the powder obtained in step (e), (f) or (g), comprising protein fibers comprising at least one amyloid structure, into a textile commodity polymer matrix. Process for preparing composite materials Preparation of composite materials

[0209] A composite material described herein may be prepared by any method for assembling a textile commodity polymer and amyloid fibers into a polymer matrix incorporating the amyloid fibers.

[0210] According to another of its objects, the present description relates to a method for preparing a composite material as described herein, the method comprising at least one step of incorporating protein fibers comprising at least one amyloid structure into a textile commodity polymer matrix.

[0211] According to one embodiment, the incorporation step can be carried out by a method chosen from a spinning method.

[0212] According to one embodiment, the incorporation step can be carried out by a method chosen from a melt spinning method, a solvent spinning method, an electrospinning method, a centrifugal spinning method, an extrusion-blowing (or meltblown) method, and a method for manufacturing a non-woven (spunbond).

[0213] These methods are known to those skilled in the art who can apply them to the preparation of a composite material described here on the basis of their general knowledge.

[0214] A melt spinning process involves melting at least one thermoplastic polymer mixed with amyloid fibers, extruding the material through a spinneret, and cooling the material to form continuous filaments.

[0215] A solvent spinning process involves dissolving the polymer in a solvent, mixing it with amyloid fibers, extruding the material, and precipitating the material in a non-solvent bath to form fibers.

[0216] An electrospinning process involves using an electric field to draw and deposit fine fibers of material from a solution of a mixture of polymer and amyloid fibers.

[0217] A centrifugal spinning process involves injecting a mixture of molten polymer and amyloid fibers into a rotating chamber, the centrifugal force creates spun fibers of material which are solidified upon cooling.

[0218] A meltblown process involves extruding a mixture of polymer and amyloid fibers through a fine die, followed by a hot air blower to stretch and form fine fibers of material.

[0219] A process for manufacturing a nonwoven (spunbond) fabric involves extruding a mixture of thermoplastic polymer and amyloid fibers into continuous filaments, randomly depositing the filaments onto a rotating drum, and then mechanically or thermally bonding them to form a cohesive nonwoven fabric.

[0220] A method of preparing a composite material may be a method in which the step of incorporating protein fibers comprising at least one structure amyloid in a textile commodity polymer matrix may comprise at least the steps of: a) preparing a mixture comprising protein fibers comprising at least one amyloid structure and at least one textile commodity polymer, and b) extruding the mixture obtained in step (a) through a die to obtain a composite material.

[0221] The extrusion step allows the mixture of polymer and amyloid fibers to be conveyed continuously, the polymer to be melted, and the mixture, and in particular the polymer, to be put under pressure.

[0222] According to one embodiment, the composite material can be extruded in the form of a wire or a film.

[0223] According to one embodiment, a composite material yarn obtained by a method as described above may be a monofilament yarn.

[0224] A spinning process can be carried out using melt or solvent processes.

[0225] The mixture of step (a) can be obtained (a-1) by dispersing the protein fibers in the molten polymer or (a-2) by dispersing the protein fibers in the polymer solubilized in an aqueous or organic solvent, in particular as described previously.

[0226] Protein fibers comprising at least one amyloid structure may be mixed with the molten or solubilized polymer in the form of a powder, a hydrogel or an aqueous dispersion.

[0227] Advantageously, the amyloid fibers are mixed with the molten polymer or solubilized in the form of a powder. The powder can be ground and dried as described above.

[0228] A melt spinning process may comprise at least the steps of melting a blend of textile commodity polymer and protein fibers comprising at least one amyloid structure, and extruding the melt by compressing and passing it through a spinneret.

[0229] A method of preparing a composite material as described herein by a melt spinning process may comprise at least the steps of: a) mixing protein fibers comprising at least one amyloid structure and at least one textile commodity polymer, b) heating the mixture obtained in step (a) to a temperature allowing the polymer to melt, and c) extruding the molten mixture obtained in step (b) through a die, or a nozzle, to obtain a composite material.

[0230] The person skilled in the art knows how to adapt the parameters of a melt spinning process to make it compatible with the sensitivity of the proteins to the conditions used, in particular to the temperature for the melt process, but also to the dimensions of the proteins, and to the compatibility between the matrix polymer and the proteins in order to avoid any agglomeration, and to the pressure induced by the passage through the die.

[0231] Depending on the nature of the polymer, the nature and proportion of amyloid fibers, the person skilled in the art knows how to adapt the parameters of melting temperature, extrusion pressure, rotation speed of the extrusion screw, diameter and shape of the die, and cooling speed of the extruded composite material.

[0232] According to one embodiment, in a melt spinning process, the polymer may be selected to have a melting temperature less than or equal to 160°C.

[0233] According to one embodiment, in a melt spinning process, the mixture comprising the polymer and the amyloid fibers can be melted at a temperature less than or equal to 160°C.

[0234] According to one embodiment, in step (a), the protein fibers comprising at least one amyloid structure can be provided in the form of a powder and the polymer can be provided in the form of granules.

[0235] According to one embodiment, a temperature gradient may be applied during step (b). The temperature gradient is adapted according to the nature of the polymer and the amyloid fibers.

[0236] The temperature gradient can range from about 60°C to about 160°C, for example from about 80°C to about 110°C.

[0237] According to one embodiment, the extrusion step (c) can be carried out at a temperature below 160°C. Such a temperature makes it possible to avoid negatively impacting the protein fibers.

[0238] According to one embodiment, during step (b), the mixing can be carried out with a co-rotating twin-screw conveyor and mixer. The rotation speed of the twin-screw can vary from approximately 40 rpm to approximately 150 rpm, or even from approximately 50 rpm to approximately 100 rpm, and be for example approximately 100 rpm.

[0239] According to one embodiment, a method for preparing a composite material may comprise a step (c) of cooling the resulting composite material. The cooling step may be air or water cooling, advantageously air cooling. The cooling step may be carried out by subjecting the extruded composite material to an air flow maintained at a temperature of approximately 20°C.

[0240] A solvent spinning process may comprise at least the steps of mixing an amyloid fiber powder with a textile commodity polymer solution and extruding the resulting mixture by compressing and passing it through a spinneret.

[0241] The solvent used for dissolving the polymer is adapted according to the nature of the textile commodity polymer considered. A solvent suitable for the preparation of a composite material described here is chosen from aqueous or organic solvents which allow solubilization of the targeted polymer(s) and which do not affect the integrity and structure of the protein fibers. It is within the skill of the person skilled in the art to select the appropriate solvent with regard to the polymer considered. For example, solvents such as acetic acid, dimethylformamide (DMF), dimethylacetamide, acetone, a carbon disulfide / acetone mixture, chloroform, dichloromethane, tetrachloromethane, benzene, toluene, cyclohexanone or 2-nitropropane may be used.

[0242] The polymer is dissolved in a suitable solvent to form a homogeneous solution. The dissolution step may be accompanied by a step of stirring the mixture to obtain a homogeneous solution. The temperature, stirring speed and polymer / solvent ratio are adapted according to the polymer and the expected viscosity properties of the solution.

[0243] The amyloid fiber powder is added, with stirring, to the polymer solution to obtain a homogeneous mixture of polymer and amyloid fibers.

[0244] The resulting mixture is fed into extrusion equipment, such as a screw extruder. The extruder maintains controlled pressure and temperature to facilitate the extrusion of the mixture.

[0245] The mixture is extruded through a die or nozzle in the extruder. The speed, temperature and pressure conditions in the extruder are adapted to the properties of the mixture, the geometry of the die and the final properties of the extruded composite material.

[0246] Once the composite material has been extruded, the solvent is removed, for example by drying. The drying step can be carried out, for example, by using a stream of hot air.

[0247] A method of preparing a composite material as described herein by a solvent spinning process may comprise at least the steps of: a) dissolving at least one textile commodity polymer in a solvent, b) mixing, with stirring, protein fibers comprising at least one amyloid structure with the textile commodity polymer solubilized in step (a), c) extruding the mixture obtained in step (b) through a spinneret, or a nozzle, to obtain a composite material, and d) evaporating the solvent.

[0248] At the end of the preparation process, a composite material may be in the form of granules or filaments. The filaments obtained at the end of an extrusion preparation process may have an average diameter of approximately 300 to 700 μm, and in particular approximately 500 μm.

[0249] The filaments or granules can be subjected to a spinning process in order to prepare a textile yarn, which can then be used in the manufacture of fabrics. Spinning of composite materials

[0250] According to another of its objects, the present description relates to a method of manufacturing a textile yarn comprising at least one step of spinning a composite material as described here.

[0251] According to one embodiment, a composite material suitable for a spinning step may be in the form of pellets or filaments.

[0252] Prior to implementing the spinning process, the composite material may be subjected to a drying step. The drying step may be carried out in an oven. The residual moisture content may be reduced to a content less than or equal to approximately 3%, for example less than or equal to approximately 2%, or else be approximately 0%, in particular from 0.01% to 0.5%, or even be 0%.

[0253] A composite material can be dried, depending on the nature of the polymer, for about 2 to 20 hours, for example for about 4 to 12 hours. The drying temperature can be, depending on the nature of the polymer, about 40°C to 140°C.

[0254] For example, for a composite material comprising PET as a polymer, drying can be approximately 4 hours at approximately 140°C.

[0255] According to one embodiment, the drying temperature and time of a composite material described herein may be, respectively, approximately 40°C and approximately 12 hours.

[0256] A method for preparing a composite material textile yarn may be a method selected from a melt spinning method, a solvent spinning method, an electrospinning method, a centrifugal spinning method, an extrusion-blowing (or meltblown) method, and a method for manufacturing a non-woven (spunbond).

[0257] A method for preparing a textile yarn of composite material by a melt spinning process may comprise at least the steps of: a) extruding the composite material through a spinneret to continuously obtain a monofilament or a plurality of monofilaments, b) cooling the monofilament(s) obtained in step (a), c) optionally, assembling the monofilaments obtained in step (b) into a multifilament, and d) drawing the monofilament obtained in step (b) or the multifilament obtained in step (c).

[0258] The extrusion step allows the composite material to be conveyed continuously, the material to be melted, and it to be put under pressure.

[0259] The extrusion step can be performed using an extruder. An extruder may include a heated cylinder, a screw for pushing the molten composite material, and a die. The heated cylinder may be divided into several individually controlled temperature zones. The die may be a ring die or a flat die.

[0260] For example, the composite material, in the form of granules or rods, can be introduced into a feed hopper of a single-screw extruder which may comprise 5 temperatures set independently of each other. The molten material is pushed through dies whose geometry can be chosen (section, diameter, and number of filaments) by means of a volumetric pump to ensure a constant flow rate.

[0261] The cooling step may be performed by immersing the filament(s) in a cold water bath or by passing them through an air cooling system. The cold water bath may be a solution of water and surfactant. An air cooling system may include a set of fans or air nozzles blowing cold air onto the moving wire. The cooling step may be performed by subjecting the filaments to an airflow maintained at a temperature of approximately 20°C.

[0262] Monofilaments can be assembled into multifilaments. Multifilaments or monofilaments can be subjected to a drawing step.

[0263] The stretching step can be performed hot or cold. Hot stretching is performed at a temperature above the melting temperature of the polymer. Cold stretching is performed at a temperature below the melting temperature of the polymer.

[0264] For example, the filaments obtained in the extrusion stage are then cooled under an air flow and then assembled during passage through the sizing gudulette. The multifilament thus obtained undergoes stretching during passage over a succession of different rollers heated beyond the glass transition temperature, to then be wound.

[0265] A method for preparing a textile yarn of composite material may further comprise a step of winding the yarn. A winding step may be performed by a winding machine that winds the yarn onto a rotating bobbin. The yarn may be wound in continuous layers or in cross layers.

[0266] According to one embodiment, a composite material as described herein may be in the form of a textile yarn, for example in the form of a reel of textile yarn.

[0267] A yarn of a composite material as described herein may be composed of a plurality of filaments, about 60 to 100 filaments, particularly about 80 filaments. The filaments may have an average unit diameter of about 10 to 50 μm, and particularly about 30 μm in diameter.

[0268] According to another of its objects, the present description relates to a wire comprising a composite material as described herein or prepared according to a method as described herein. Uses and methods

[0269] A composite material textile yarn as described herein may be used to prepare a fabric, woven or non-woven, with pollutant capture properties.

[0270] According to another of its objects, the present description relates to a use of a composite material as described herein or prepared by a process as described herein, of a filament or a thread as described herein, or of a fabric as described herein, for capturing a polluting agent.

[0271] A fabric of a composite material as described herein may be obtained by any method known in the art, such as weaving, knitting, warp and weft weaving, felting, spunbond, meltblown, or needle punching.

[0272] A composite material fabric used to capture pollutants may be arranged in roll form for large-scale use in air, water, or waste treatment facilities, in sheet form for use in air, water, or gas filters, in pleated filter media, in bag filters, or in filter cartridge form.

[0273] As polluting agents considered in the present description, mention may be made of volatile organic compounds (VOCs), polycyclic aromatic hydrocarbons (PAHs), organic solvents, such as benzene, toluene, or xylene, pesticides, such as DDT, chlordecone, or glyphosate, PCBs (polychlorinated biphenyls), dioxins and furans, per- and polyfluoroalkyl substances (PFAS), or heavy metals, such as mercury, lead, cadmium, arsenic, nickel, copper, zinc, or chromium.

[0274] According to one embodiment, a composite material, in particular comprising PBS, EVA and / or PCL, and, for example, 20% amyloid fibers by weight / weight of material, can absorb from about 0.5 to 2.5 mg of per- and polyfluoroalkyl substances per gram of amyloid fibers, or from about 1.0 to 2.0 mg / g, or even about 1.5 mg of per- and polyfluoroalkyl substances per gram of amyloid fibers.

[0275] According to another of its objects, the present description relates to a method for capturing a polluting agent comprising at least the step of bringing the polluting agent to be captured into contact with a composite material as described here or prepared by a method as described here, or with a filament or a thread as described here, or with a fabric as described here, under conditions sufficient to obtain the capture of the polluting agent by the protein fibers comprising at least one amyloid structure of said composite material.

[0276] According to another of its objects, the present description relates to a method for extracting a polluting agent, said method comprising at least the steps of: a) bringing into contact a composite material as described here or prepared by a method as described here, or a filament or a thread as described here, or a fabric as described here, with a substrate comprising a polluting agent under conditions sufficient to obtain the capture of the polluting agent by the protein fibers comprising at least one amyloid structure, b) dissociating, under sufficient conditions, said polluting agent from the protein fibers comprising at least one amyloid structure, to obtain the extracted polluting agent.

[0277] A substrate comprising a polluting agent may be a solid or liquid substrate. A solid substrate may be a portion of soil polluted with the polluting agent to be extracted. A liquid substrate may be a portion of water, for example rain, having washed a soil polluted with the polluting agent to be extracted.

[0278] A pollutant can be a volatile organic compound (VOC), a polycyclic aromatic hydrocarbon (PAH), an organic solvent, such as benzene, toluene, or xylene, a pesticide, such as DDT, chlordecone, or glyphosate, a PCB (polychlorinated biphenyl), a dioxin, a furan, a per- and polyfluoroalkyl substance (PFAS), or a heavy metal, such as mercury, lead, cadmium, arsenic, nickel, copper, zinc, or chromium.

[0279] According to another of its objects, the present description relates to a method for extracting at least one metal ion, said method comprising at least the steps of: a) bringing into contact a composite material as described here or prepared by a method as described here, or with a thread as described here, or with a fabric as described here, with a substrate comprising at least one metal ion under conditions sufficient to obtain the capture of said metal ion by the protein fibers comprising at least one amyloid structure, b) dissociating, under sufficient conditions, said metal ion from the protein fibers comprising at least one amyloid structure, to obtain the extracted metal ion.

[0280] A metal ion can be a Cu, Ag, Pb, Hg, Au, Cd, As, Ni, Zn or Cr ion.

[0281] A step of dissociating a pollutant or a metal ion captured by the amyloid fibers of a composite material described herein can be carried out by subjecting the material composite having adsorbed the polluting agent or the metal ion at a washing step with an acid solution.

[0282] The pollutant or metal ion is removed with the acid solution.

[0283] After the washing step with an acid solution, the composite material can be subjected to a rinsing step, for example with water, before reuse.

[0284] According to one of its objects, the present description provides a method for recycling a composite material described herein or a manufactured product comprising such a material, for example a filter. A recycling method may comprise at least the steps of: a) contacting a composite material as described herein, said material comprising at least one captured pollutant or metal ion, with a solution under conditions sufficient to dissociate said pollutant or metal ion from said material, b) separating the solution comprising said pollutant or metal ion and said composite material, c) contacting the composite material obtained in step (b) with a rinsing solution, and d) drying the composite material obtained in step (c).

[0285] Steps (a) to (c) may be repeated 1 to 10 times, for example 2, 3, 4, or 5 times before implementing step (d).

[0286] A composite material as described here can be subjected to a recycling process at least 2, or even 3, 4, 5 or 10 times while retaining its properties of capturing polluting agents or metal ions.

[0287] In step (a), a suitable solution may be an acid solution or a v / v water / ethanol mixture.

[0288] An acid solution that can be used is hydrochloric acid solution. A hydrochloric acid solution can be 1 M hydrochloric acid solution.

[0289] A suitable water-ethanol mixture might be a mixture of about 20 / 80 v / v to about 80 / 20 v / v of water and ethanol.

[0290] The contact time between the acid solution and the composite material can vary from about 1 hour to about 10 hours, or even from about 2 hours to about 5 hours.

[0291] Step (a) may be carried out at a temperature ranging from about 15°C to about 30°C. Optionally, step (a) may be accompanied by a heating step, for example from about 45°C to about 60°C, for example to about 50°C.

[0292] The rinse solution can be an aqueous solution.

[0293] The aqueous rinse solution can be water, for example distilled water or tap water.

[0294] The composite material may be dried in step (d) at room temperature, from about 20°C to about 30°C, or placed in an oven or under a flow of hot air, for example at a temperature ranging from about 45°C to about 60°C. EXAMPLES Example 1 Materials & Methods Preparation of amyloid fibers

[0295] Composite material yarns containing about 20% of their weight in amyloid protein fibers (amyloid fibers) in textile commodity polymers of elastomer and thermoplastic type were manufactured according to the process described below.

[0296] Amyloid fibers were prepared from a whey protein: alpha-lactalbumin (α-lactalbumin). The α-lactalbumin amyloid fibers were obtained in a hydrogel by incubation at 45°C of a protein suspension (40 mg / ml) whose pH was adjusted to pH 2 according to the method described in Example 2 of application WO 2012 / 136909 A1.

[0297] Measured by electron microscopy, the amyloid fibers obtained have an average length of 2 pm for an average diameter of 30 nm. In addition, they carry a relatively large positive electrical charge (ref#8).

[0298] The resulting hydrogel was freeze-dried to reduce the amyloid fibers to powder. The freeze-drying of the hydrogel was carried out with the following parameters:

[0299] [Table 1]

[0300] The lyophilized hydrogel was then ground in a UT ultracentrifugal mill at 6000 rpm. The powder was then dried in an oven at 45°C for 12 h. The measured residual moisture was less than 3% by weight. Preparation of composite material filaments

[0301] The commodity polymers tested are ethylene vinyl acetate (EVA P33015C: Repsol), polybutylene succinate (PBS) and polycaprolactone (PCL).

[0302] The amyloid fibers were mixed with the polymers by an extrusion (compounding) process as described below.

[0303] Amyloid protein fiber powder is mixed with polymer granules in a fiber weight ratio to the total composite material weight of 0%, 3% and 20%.

[0304] In the extruder, mixing was carried out with a co-rotating twin-screw conveyor and mixer. The rotation speed of the twin-screw was set at 50 rpm or 100 rpm.

[0305] For EVA, the polymer / amyloid fiber mixture was subjected to a temperature gradient ranging from 60°C to 110°C in order to melt the mixture.

[0306] For PCL, the polymer / amyloid fiber mixture was subjected to a temperature gradient ranging from 58°C to 100°C in order to melt the mixture.

[0307] For PB S, the polymer / amyloid fiber mixture was subjected to a temperature gradient ranging from 125°C to 135°C in order to melt the mixture.

[0308] At the extruder outlet, the monofilament is cooled in air (temperature of around 20°C), then wound onto a reel or cut into granules (or rods). Spinning of composite filaments

[0309] The monofilaments (approximately 500 pm in diameter) obtained at the compounding stage (extrusion of the polymer with the amyloid protein fibers) were cut into granules in order to feed a semi-industrial spinning pilot plant to produce multifilaments (80 monofilaments of 30 pm unit diameter).

[0310] The adjustment of the process parameters (extrusion and spinning stages) is carried out according to the polymer considered and the polymer / protein ratio, taking into account the thermal properties, measured by thermogravimetric analysis (TGA: Thermal Gravimetric Analysis) and by differential scanning calorimetry (DSC: Differential scanning calorimetry), and the rheological properties measured by the melt flow index (MFI: Melt Flow Index).

[0311] The screw rotation speed was established between 30 and 100 rotations per minute (rpm). The temperature ranges are those indicated above for the polymers used. Measurement of mechanical resistance

[0312] The mechanical strength of composite material yarns and filaments is measured using a tensile testing machine with jaws set for a gap of 50 mm. The gap speed is set at 100 mm / min. A preload of 0.1 N is applied to the yarn. The load applied to the yarn is measured until it breaks.

[0313] Tensile strength is defined as the maximum load applied before failure, divided by the cross-sectional area of ​​the wire. UV-visible absorbance spectrometry

[0314] The spectra are recorded in a wavelength range of 400 to 800 nm, with a maximum absorbance wavelength value (À ma x) of 498 nm. Measurements of pollution control capacities

[0315] The decontamination capabilities of composite yarns were tested with dyes used in textiles (considered as pollutants; ref#l). The different dyes tested were first prepared in the form of a 20 ppm stock solution. During decontamination tests, the solutions were diluted to 10 ppm or 2 ppm.

[0316] The experimental protocol is illustrated in Figure 4.

[0317] In a first experiment, a single EVA yarn and a composite EVA yarn containing 20% ​​w / w amyloid protein fibers were incubated for 24 hours in an aqueous solution of rhodamine B of 2 to 10 ppm, at 40°C.

[0318] The color of the solution and polymer threads was visually observed after incubation.

[0319] In a second experiment, polycaprolactone (PCL) yarns comprising 0% or 20% w / w amyloid fibers were immersed in dye baths containing textile dyes: Diazol Turquoise LU.JRL*, Foron Yellow, Erionyl Orange 20* RD.4GRL*, and Maxiion Red* Rhodamine B*.

[0320] Dye solutions were prepared in aqueous solution from the stock solution diluted to 10 or 2 ppm.

[0321] The composite material filaments were incubated in the different dye solutions for 24 hours at room temperature.

[0322] In a third experiment, Congo red uptake measurements were performed to test the properties of textile commodity polymers: EVA (Ethylene vinyl acetate) and PB S (polybutylene succinate) comprising 0%, 10% or 20% w / w of amyloid protein fibers. Congo red dye was prepared at 7 ppm in an aqueous solution prepared with distilled water or tap water.

[0323] The filaments were incubated in Congo red solutions for 4 days at 37°C.

[0324] In a first series of experiments, the ability of EVA or PBS filaments comprising 0%, 10% or 20% by weight of amyloid fibers relative to the total weight of material, to capture Congo red dye from a solution prepared with distilled water was evaluated (Fig. 6 (a)). Prior to the incubation step, the yarns were washed at least 3 times and at most 5 times for 2 hours with distilled water.

[0325] In a second series of experiments, the ability of EVA or PBS filaments comprising 20% ​​by weight of amyloid fibers relative to the total weight of material to capture Congo red dye from a solution prepared with tap water was evaluated (Fig. 6(b)). In this series of experiments, the threads were not pre-washed before incubation with the Congo red solution.

[0326] The capture of the Congo red dye in solution by the polymer threads was monitored by measuring, after 4 days of incubation, the concentration of the dye remaining in solution by absorbance spectrophotometry by performing UV-visible spectra from 400 to 800 nm (max 498 nm).

[0327] In a fourth experiment, the change in the amount of Congo red dye adsorbed by a 100 mg EVA composite yarn comprising 20% ​​w / w amyloid protein fibers was measured. The yarn was kept in 15 mL of a distilled water solution (pH 5.5) of Congo red at 10 pM or 7 ppm (i.e., 150 nmoles in solution at the start of the experiment). Measurements were made over an eight-day incubation period by absorbance spectrophotometry, performing UV-visible spectra from 400 to 800 nm (À m ax 498 nm). The amount of dye attached to the composite yarn over time was deduced from measurements of the amount of dye remaining in solution. Results Characterization of composite yarns

[0328] The homogeneity of the distribution of amyloid fibers within the monofilament composite yarns was verified by scanning electron microscopy (Fig. 1). The diameter of the yarns is a few hundred microns and the visualized objects are regularly distributed within the yarn when protein fibers were added. The size of the observed elements is consistent with the size of the amyloid fibers (average length of a few pm: ref#8).

[0329] The effect of the presence of protein fibers on the mechanical properties of monofilament composite yarns was measured by Dynamic Mechanical Analysis (DMA). An increase in Young's modulus appears to be induced by the addition of protein fibers (Fig. 2). This effect appears to be accompanied by a slight decrease in the elongation at break of the polymer yarns.

[0330] The results obtained demonstrate that the addition of amyloid fibers does not deteriorate the mechanical properties of the polymer threads.

[0331] The persistence of the amyloid structure of fiber proteins under physicochemical conditions that normally induce the return of proteins to their monomeric form (the fibers disassemble) was verified by taking advantage of the spectroscopic properties of amyloid fibers recently highlighted (ref#9).

[0332] In particular, amyloid fibers have a near-infrared signal that is absent for proteins in the monomeric state. Fig. 3 shows near-infrared emission spectra (À ex : 640 ± 10 nm, At em: 660 to 750 nm) of different EVA composite yarns comprising 0% or 3% w / w of monomeric proteins or comprising 20% ​​w / w of amyloid fibers previously incubated in aqueous solution at pH 6 (distilled water) or 8.3 (tap water) for 24 hours at 40°C, then dried.

[0333] For EVA alone, a weak signal is observed and the same type of signal is observed with threads containing 3% w / w monomeric protein.

[0334] At pH 6 (i.e., greater than 4), α-lactalbumin amyloid fibers disassemble within minutes when suspended in aqueous solvent, leading to loss of the near-infrared signal.

[0335] In contrast, composite yarns containing 20% ​​w / w protein fibers have an intense signal after incubation for several hours in a buffered solution at pH 6. Thus, in composite yarns, the persistence of the amyloid structure of the fiber proteins is confirmed by the constancy of the signal in the near infrared after incubation for several hours of the composite yarns at pH 6 or in tap water at pH 8.3.

[0336] High pH, ​​combined with high concentrations of divalent metal cations, especially Ca 2+ , are normally incompatible with the structuring of alpha-lactalbumin into amyloid fibers in solution. Measurements of pollution control capacities

[0337] Experiment 1

[0338] After incubation for 24 hours in a 2 ppm Rhodamine B solution, the EVA yarn comprising 0% amyloid fibers remained transparent and the solution pink (no color change observed). On the other hand, in the case of the EVA composite yarn comprising 20% ​​w / w amyloid fibers, the yarn came out pink (which is the color of Rhodamine B) and the solution discolored, demonstrating that the composite yarn captured the majority of the pollutant (Fig. 4).

[0339] Experiment 2

[0340] Observation of polycaprolactone (PCL) yarns comprising 0% or 20% w / w amyloid protein fibers after immersion in dye baths containing textile dyes: Diazol Turquoise LU.JRL*, Foron Yellow, Erionyl Orange 20* RD.4GRL*, and Maxiion Red* Rhodamine B*, at 10 or 2 ppm, shows that the composite yarns are loaded with dyes, whereas the polymer yarns without amyloid fibers remained colorless (Fig. 5).

[0341] Experiment 3-1

[0342] Congo red capture experiments using different commodity polymer yarns: EVA (Ethylene vinyl acetate) and PBS (polybutylene succinate) comprising 0%, 10% or 20% amyloid fibers were carried out.

[0343] With the composite yarns prepared with EVA or PBS and distilled water aqueous solution, almost all of the dye was attached to the composite yarns after 4 days of incubation (Fig. 6(a)).

[0344] Experiment 3-2

[0345] The experiment carried out with an aqueous solution of Congo red dye prepared with tap water and polymer threads containing 0% or 20% amyloid protein fibers shows that the amount of Congo red dye in solution decreased very significantly (Fig. 6 (b)), but in lesser proportions than in distilled water.

[0346] Several reasons can be considered to explain this phenomenon: (i) the capture capacities of the wires are lower in tap water due to the latter's ion charge, or (ii) the rinsing step which was added for the experiments in distilled water, makes it possible to increase the capture capacities of the wires.

[0347] Experiment 4

[0348] The change in the quantity (number of moles) of Congo red dye in aqueous solution (distilled water) in the presence of 100 mg of a composite EVA yarn comprising 20% ​​weight / weight of amyloid fibers was measured as a function of time (over 8 days).

[0349] Under the experimental conditions used, the data show that the kinetics is not complete after 7 days of incubation (Fig. 7).

[0350] The amount of dye attached to the composite yarn over time was deduced from the measurements of the amount of dye remaining in solution. The weight of the yarn used allows the capture capacity of the fibers within the composite yarns to be estimated. At the end of the experiment, a value of 4 mg / g was obtained. This value is of the same order as that reported in the literature for dyes (ref#l). Materials & Methods

[0351] A textile yarn was prepared as detailed in Example 1 with ethylene vinyl acetate (EVA) and 20% by weight relative to the mass of amyloid fiber material of alpha-lactalbumin.

[0352] The resulting composite yarn was incubated in a 10 pM Congo red solution, prepared as detailed in Example 1. The incubation time was 24 hours at room temperature.

[0353] After incubation, the composite yarn impregnated with Congo red was recovered, dried and sectioned transversely with a scalpel into 3 sections. Results

[0354] Visual observation (Fig. 8) revealed that Congo red was fixed on the surface and inside the yarn, demonstrating that all the amyloid proteins in the composite material are involved in the process of capturing polluting agents. Materials & Methods

[0355] Textile yarns were prepared as detailed in Example 1 with polybutylene succinate (PBS), ethylene vinyl acetate (EVA), or polycaprolactone (PCL) and 20% by weight relative to the mass of material of alpha-lactalbumin amyloid fibers.

[0356] Control threads comprising only the polymers, without amyloid fibers, were prepared in a similar manner.

[0357] Samples of composite yarns and control yarns were incubated in a mixture of per- and polyfluoroalkyl substances (PFAs) (see Table 2).

[0358] [Table 2]: PFAS used for the experiment and their molecular weights

[0359] ). The total PF AS concentration was 233.5 |Jg / L, with individual concentrations ranging from 4 |Jg / L to 21 |Jg / L.

[0360] Yarn samples (400 + / - 20 mg) were incubated for 24 hours in 1 mL of PFAS cocktail. Compounds remaining in suspension after incubation were detected and quantified by LC-MS / MS (Liquid Chromatography-Tandem Mass Spectrometry) analysis.

[0361] Experiments with EVA and PBS were performed at pH 2, those with PCL at pH 6 in distilled water. Results

[0362] Strange behavior was observed in the wire control in the "EVA" experiment, with two distinct populations observed. Without wishing to be bound by any theory, it has been hypothesized at this stage that this observation reflects an experimental or data reporting problem.

[0363] Overall, the same behavior was observed with the three polymers: appearance of non-specific fixation with the increase in the size of the PFAs; the latter being more marked with EVA.

[0364] A significant decrease in PFAS concentration was systematically observed in the presence of composite material (Fig. 9).

[0365] A size-dependent profile was observed for all three polymers with binding of low molecular weight compounds (optimum between 300g and 400g), disappearance of the effect for intermediate molecular weights (400-550g), then binding again for high molecular weights (> 550g). Without wishing to be bound by any theory, it has been hypothesized at this stage that this observation reflects a competition / inhibition effect between the PFAS present.

[0366] With EVA and PBS, the experiments were carried out at pH 2 to promote the fixation of low molecular weight PFAS. It was hypothesized that PCE, which is an intrinsically highly acidic matrix, would not require working in an acidic solution. This hypothesis appears to be confirmed, at least for low molecular weights.

[0367] The presence of amyloid protein fibers allows the fixation of approximately 50% of the mass of compounds present (Fig. 10), which corresponds to a fixation capacity of 1.5 mg / g of protein, thus revealing a particularly significant capacity for capturing polluting agents. LIST OF CITED DOCUMENTS

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Claims

CLAIMS

1. A composite material comprising at least one textile commodity polymer and protein fibers comprising at least one amyloid structure, said material comprising approximately 12% to 30% by weight of protein fibers comprising at least one amyloid structure relative to the total weight of the material.

2. The composite material of claim 1, comprising about 15% to 20% by weight of protein fibers comprising at least one amyloid structure relative to the total weight of the material.

3. The composite material according to claim 1 or 2, wherein the protein fibers comprising at least one amyloid structure are obtained with at least one protein selected from α-zein, soy protein, arachin, conarachin, avenin, avenalin, sunflower globulin, sunflower albumin, α-lactalbumin, β-lactoglobulin, lysozyme, bovine serum albumin, HET-s protein from the filamentous fungus Podospora anserina, spidroin, silk fibroin, and mixtures thereof.

4. The composite material according to one of claims 1 to 3, wherein the polymer is selected from ethylene vinyl acetate (EVA), polybutylene succinate (PBS), polycaprolactone (PCL), polyethylene (PE), polypropylene (PP), polystyrene (PS), polyvinyl chloride (PVC), polyamide (PA), polyester (PET), a cellulose polymer, a chitosan polymer, a casein polymer, and mixtures thereof.

5. A method of preparing a composite material comprising at least one textile commodity polymer and protein fibers comprising at least one amyloid structure, the method comprising at least one step of incorporating the protein fibers comprising at least one amyloid structure into a textile commodity polymer matrix, said incorporation step comprising at least the steps of: (a) preparing a mixture of protein fibers comprising at least one amyloid structure and at least one textile commodity polymer, and (b) extruding the mixture obtained in step (a) through a die to obtain a composite material.

6. The method of claim 5, wherein the protein fibers are mixed with the polymer in the form of a powder, a hydrogel, or an aqueous dispersion.

7. Textile yarn comprising a composite material comprising at least one textile commodity polymer and protein fibers comprising at least one amyloid structure or prepared by a process as defined in claim 5 or 6.

8. Use of a composite material comprising at least one textile commodity polymer and protein fibers comprising at least one amyloid structure or prepared by a process as defined according to claim 5 or 6, or of a yarn as defined in claim 7, for capturing a polluting agent.

9. A method of capturing a polluting agent comprising at least the step of bringing the polluting agent to be captured into contact with a composite material comprising at least one textile commodity polymer and protein fibers comprising at least one amyloid structure or prepared by a method as defined according to claim 5 or 6, or with a yarn as defined in claim 7, under conditions sufficient to obtain the capture of the polluting agent by the protein fibers comprising at least one amyloid structure of said composite material.

10. A method according to claim 5 or 6, a textile yarn according to claim 7, a use according to claim 8, or a method according to claim 9, wherein the material comprises about 1% to 80% by weight of protein fibers comprising at least one amyloid structure relative to the total weight of the material, in particular about 3% to 70%, in particular about 5% to 60%, in particular about 8% to 50%, in particular about 10% to 40%, in particular about 12% to 30%, and in particular about 15% to 20% by weight of protein fibers comprising at least one amyloid structure relative to the total weight of the material.

11. A method according to claim 5, 6 or 10, a textile yarn according to claim 7 or 10, a use according to claim 8 or 10, or a method according to claim 9 or 10, wherein the protein fibers comprising at least one amyloid structure are obtained with at least one protein selected from α-zein, soy protein, arachin, conarachin, avenin, avenalin, sunflower globulin, sunflower albumin, α-lactalbumin, β-lactoglobulin, lysozyme, bovine serum albumin, HET-s protein from the filamentous fungus Podospora anserina, spidroin, silk fibroin, and mixtures thereof.

12. A method according to claim 5, 6, 10 or 11, a textile yarn according to claim 7, 10 or 11, a use according to claim 8, 10 or 11, or a method according to claim 9, 10 or 11, wherein the polymer is selected from ethylene vinyl acetate (EVA), polybutylene succinate (PBS), polycaprolactone (PCL), polyethylene (PE), polypropylene (PP), polystyrene (PS), polyvinyl chloride (PVC), polyamide (PA), polyester (PET), cellulose polymer, chitosan polymer, casein polymer, and mixtures thereof.

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