Voltage generator based on a material comprising glycosylated proteins and amyloid fibres

Abstract

The invention relates to a method for electrochemically activating a material comprising hydronium ion-conducting amyloid fibres and glycosylated proteins, the method comprising at least one step that consists in placing at least part of said material in contact with a water vapour, electrolysing at least part of the water vapour which is in contact with said material, and obtaining an activated material. The invention also relates to an activated material obtained in this way and to the use thereof for generating electrical energy.

Description

DESCRIPTION Title: Voltage Generator Based on Material Comprising Glycosylated Proteins and Amyloid Fibers technical field

[0001] The present invention relates to a voltage generator. More specifically, it describes a material, activated by an electrochemical process, comprising glycosylated proteins and amyloid fibers, for producing electrical energy from ambient humidity or any atmosphere containing water vapor. The use of such a material for producing electrical energy and its preparation process are also described. Previous technique

[0002] Energy demand, particularly for electricity, is constantly increasing, making it essential to develop renewable energy sources to mitigate the negative environmental impacts associated with fossil fuel consumption. Water, covering 71% of the Earth's surface, represents the world's largest energy reservoir. Water absorbs approximately 35% of the solar energy received by Earth, equivalent to 60 petawatts (10¹² kWh). 15 W) (Stephens et al., Nature Geosci 5, 691-696 (2012)).

[0003] Numerous efforts have been made to harness energy from water in various forms: rivers and oceans, tides, and even raindrops. Energy recovery from water, or hydroelectricity, is primarily achieved through the construction of hydroelectric dams or tidal power plants. These plants mainly utilize electromagnetic generators, which are heavy, bulky, and dependent on the available water supply.

[0004] Very recently, hydrovoltaics has been proposed as an alternative means of producing electrical energy from water (Zhang et al., Nature Nanotech 13, 1109-1119 (2018)). Unlike current technologies that recover the kinetic energy (in the case of streams and rivers) or potential energy (in the case of basins and lakes) of water, hydrovoltaic technology allows for the direct generation of energy from the interaction between water and the material. However, hydrovoltaics developed so far mainly uses inorganic materials. The materials currently used are made from starting from silicon nanowires, Ni / Al hydroxide or even from carbon (graphene or carbon nanotubes) (Yang et al. (2018) J. Am. Chem. Soc. 140, 13746-13752; Tang et al., (2016), Angew. Chem. Int. Ed. 55, 14412-14416; Yin et al., (2014), Nat. Commun. 5, 3582; Xu et al., Nature 578, 392-396 (2020)).

[0005] Water vapor in the ambient atmosphere could also be used to recover energy.

[0006] Electrical energy production from ambient humidity using biological materials has been reported (Liu et al., Nature 578, 550-554 (2020); WO 2020 / 069523).

[0007] However, this device, composed of bionanofila derived from Geobacter sulfurreducens, must be exposed to a water vapor gradient to generate energy. These filaments do not result from spontaneous self-assembly but require the internal machinery of the bacterium for their formation. Furthermore, the bionanofila used are derived from a recombinant protein, necessitating the use of Escherichia coli as a scaffold for their production; this is a significant obstacle to mass production and large-scale industrialization of the process.

[0008] Fish of the hagfish family (Myxinidae) are eel-like aquatic animals lacking a backbone and true jaws. These animals produce a rapidly expanding mucus, or hydrogel, which clogs the gills of any predator attempting to eat them, causing them to immediately spit out their prey. This mucus is formed from dry mucin fibers, glycosylated proteins that instantly hydrate into mucus, and fibrous threads rich in intermediate filaments (IFs). These filamentous elements are only 12 nanometers thick and can reach up to 15 centimeters in length. Under the action of mechanical stress, for example stretching, the proteins of intermediate filament fibers can undergo a transition from α-helices to |3-sheets and leading to the formation of amyloid fibers (Boni et al., Sci Rep. 2016;6:30371; Fu et al., Biomacromolecules. 2015;16(8):2327-2339; Fudge et al., Biophys J. 2003;85(3):2015-2027).

[0009] The particular properties of F hydrogel from Myxinidae are of interest to many companies wishing to take advantage of them.

[0010] For example, the company Benthic Labs is developing a biodegradable polymer made from components of mucus that could be used in the manufacture of tissues for protective clothing, food packaging, elastic cords, bandages or airbags.

[0011] There is a need for a material that can generate electrical energy from a humid surrounding atmosphere that is low cost and readily available, particularly on an industrial scale.

[0012] There is also a need for such a material that is biodegradable and renewable.

[0013] There is also a need for such a material that can produce a quantity of electrical energy that can be modulated according to the relative humidity level in the surrounding atmosphere.

[0014] There is also a need for such a material to enable the creation of different electrical configurations.

[0015] There is also a need for a material capable of supplying electrical energy to various electrical or electronic devices by generating electrical energy from a humid surrounding atmosphere.

[0016] The present invention aims to satisfy all or part of these needs. Summary of the invention

[0017] According to one of its objects, the present invention relates to a method for preparing a material activated by electrochemical activation, said material comprising hydronium ion-conducting amyloid fibers and glycosylated proteins, said method comprising at least the steps of:

[0018] (a) to bring at least a part of said material into contact with water vapor,

[0019] (b) electrolyze at least a portion of the water vapor in contact with said material, and

[0020] (c) obtain an activated material.

[0021] For the purposes of this invention, the term "electrochemical activation" refers to a process comprising a step in which a material is exposed to an electric current in order to modify the chemical structure of that material, the material being suitable for such a process, and enabling that material to be given the property of generating electrical energy from the water vapor from the surrounding atmosphere. A material produced by an electrochemical activation process described herein is referred to in this description as an "activated material".

[0022] For the purposes of this invention, the term "activated material" refers to a material resulting from an electrochemical activation process in which the material's structure is modified to give it voltage-generating properties. An activated material is a material capable of producing electrical energy when brought into contact with water vapor in a humid surrounding atmosphere, through the conduction of hydronium ions.

[0023] The electrochemical activation of a material described here can, for example, be monitored by chronoamperometry. This method allows the measurement of the amount of electrical charge flowing through the material during its electrochemical activation. Activation can be verified by generating an open-circuit electrical potential difference when the material is exposed to a humid atmosphere.

[0024] For the purposes of this invention, the terms "humid atmosphere" or "humid surrounding atmosphere" refer to an atmosphere containing water molecules in a vapor state. The water vapor content of a humid atmosphere suitable for this invention can vary from approximately 30% to approximately 100%, or from approximately 35% to approximately 99%, or from approximately 40% to approximately 95%, or from approximately 45% to approximately 90%, or from approximately 50% to approximately 85%. A humid surrounding atmosphere is an atmosphere in contact with a material as described herein.

[0025] For the purposes of this invention, "generating electrical energy from a humid surrounding atmosphere" refers to the ability of an activated material, as described herein, to react with at least some of the water vapor, or humidity, contained in the surrounding atmosphere, i.e., in contact with it, and to generate electrical energy. The water vapor content of such an atmosphere is sufficient to allow the generation of hydronium ions. The hydronium ions can circulate within the structure of the activated material. A sufficient water vapor content can range from approximately 30% to approximately 100%.

[0026] The term "electrical energy" refers to the potential energy of an electric charge in an electric field or an electric current in a magnetic field. The electrical energy generated during the use of an activated material according to the invention is a potential difference created between two ends of the material. This potential difference can be used to generate an electric current.

[0027] According to another of its objects, the present invention relates to an activated material comprising hydronium ion-conducting amyloid fibers and glycosylated proteins and being activated by an electrochemical activation process.

[0028] According to another of its objects, the present invention relates to an activated material obtained by a process described herein, said material comprising hydronium ion-conducting amyloid fibers and glycosylated proteins.

[0029] Unexpectedly, as detailed in the Examples below, the inventors observed that it was possible to impart to a material comprising hydronium ion-conducting amyloid fibers and glycosylated proteins, for example in the form of intermediate filaments and mucins, respectively, prepared by dehydrating a hagfish hydrogel or mucus, properties enabling it to generate an electric current from ambient humidity, or water vapor. Advantageously, such a material is 100% bio-based and renewable. It allows for the extraction of an electrical potential difference from the surrounding humid atmosphere, thus producing low-cost, green energy based on ambient humidity.

[0030] Advantageously, compared with inorganic materials, an activated material is biodegradable, non-toxic, and biocompatible.

[0031] According to another of its advantages, an activated material described here makes it possible to obtain an electrical potential difference at ambient humidity and at very high humidity (for example from 40 to 85%), thus allowing the voltage obtained to be adjusted and modulated up to a target value.

[0032] According to another advantage, an activated material described here can exhibit high internal resistance (~50 kΩ). In an electrical power generation device incorporating such an activated material, the resistance can be modulated by varying the amount of material, for example, in the form of films that can be connected in series or parallel.

[0033] According to another of its advantages, an activated material described here can exhibit high stability.

[0034] According to another of its advantages, an activated material described here naturally possesses adhesion properties that can be exploited to prepare electrical power generation devices simply and at low cost. For example, a material configured as a film, it can be cut into pieces, the pieces then being moistened and glued onto and between electrodes.

[0035] An activated and dried material can be used in various textile production processes to prepare textile fibers and fabrics. The fibers and fabrics thus obtained can be used in devices that generate electricity from ambient humidity. For example, an activated material described here can be dried and carded, and the resulting fibers can then be spun. The yarns from fibers of this activated material can advantageously be woven using any textile forming technique to produce woven or nonwoven fabrics. Combining the fibers or yarns of an activated material with fibers or yarns of a second electrically conductive material, such as carbon fibers, can enable the manufacture, using weaving techniques, of devices that generate electricity from steam over large areas.

[0036] In an electrochemical activation process described here, step (b) of electrolysis of water vapor in contact with a material to be activated can be carried out by exposing the material to an electrical potential difference.

[0037] An electrical potential difference can be obtained by means of two electrodes electrically connected to the material.

[0038] An electrical potential difference suitable for the invention is an electrical potential difference capable of inducing electrolysis of at least a portion of the water vapor.

[0039] The difference in electrical potential can be fixed or variable.

[0040] For the purposes of the invention, the term "fixed" refers to an electrical potential difference that remains substantially constant during the period of time required for the electrochemical activation of a material as described herein.

[0041] For the purposes of the invention, the term "variable" refers to a difference in electrical potential which changes over the period of time required for the electrochemical activation of a material as described herein and which maintains for a sufficient period of time a value allowing the electrolysis of water.

[0042] An electrical potential difference can be at least 1.23 V.

[0043] In step (b), an electrical potential difference is applied for a period of time sufficient to generate an electric current in the material. The generation of such an electric current can be measured by chronoamperometry at 0 V vs E oc (open circuit electrical potential).

[0044] The water vapor used in a process described here may originate from a humid atmosphere surrounding the material.

[0045] A suitable humid surrounding atmosphere for an electrochemical activation process described herein may include a relative humidity ranging from at least 60% to 100%, and in particular may range from about 65% to about 85%.

[0046] The surrounding atmosphere can be humid and neutral.

[0047] The water vapor used in a process described here can come from a humid and neutral atmosphere.

[0048] For the purposes of this invention, the term "neutral atmosphere" refers to a chemically neutral atmosphere, meaning one that does not react with the elements in contact with it, such as the material to be activated or the electrodes. A neutral atmosphere is an atmosphere devoid of oxygen.

[0049] A neutral atmosphere can be an atmosphere of nitrogen or argon, and for example is a nitrogen atmosphere.

[0050] In a material of the invention, hydronium ion-conducting amyloid fibers can be obtained from intermediate filaments. These intermediate filaments are capable of conforming to amyloid fibers after exposure to mechanical stress, such as stretching. Thus, hydronium ion-conducting amyloid fibers can be obtained from stretched intermediate filaments.

[0051] Intermediate filaments can be composed of proteins selected from roc-keratin, lamin, vimentin, desmin, peripherin, syncoilin, oc-intemexin, neurofilament, synemin, thread keratins a, |3 and y, variants of these proteins, and mixtures thereof.

[0052] A protein variant, or protein isoform, is a member of a set of very similar proteins that originate from a single gene or gene family and are the result of genetic differences. Variants within a protein family generally have similar biological functions.

[0053] The intermediate filaments can be associated, or organized, into fibers or threads.

[0054] Glycosylated proteins can be mucins, including mucins capable of forming mucus in the presence of water.

[0055] According to one embodiment, a material comprising hydronium ion-conducting amyloid fibers and glycosylated proteins can be obtained from a hydrogel produced by a fish selected from the fish of the Myxinidae family, and in particular from the subfamilies Myxininae and Eptatretinae.

[0056] According to one embodiment, a material suitable for the invention can be obtained from a hydrogel produced by a fish selected from fish of the genus Myxine or Eptatretus.

[0057] According to one embodiment, a material suitable for the invention can be obtained from a hydrogel produced by a Myxina glutinosa.

[0058] The intermediate filaments of a hydrogel produced by a fish of the Myxinidae family can undergo a stretching step to transform at least some of the α-helices of the intermediate filament proteins into γ-sheets and confer upon the intermediate filaments, at least partially, a structure and properties of amyloid fibers. These amyloid fibers are notably conductors of hydronium ions.

[0059] The material used in a process such as the one described here can be dehydrated.

[0060] A dehydrated, or dried, material is a material whose water content has been reduced by drying. The water content of a dehydrated material can be reduced from at least 10% to at least 99% of its initial water content. The amount of water removed from a dehydrated material can be measured, for example, by measuring the mass of the material before and after drying, the difference in mass representing the amount of water removed. The residual water content in the dehydrated material can be measured, for example, by near-infrared spectroscopy.

[0061] A material used in the invention can be implemented in the form of a fiber, a yarn, or a film. The shaping of the material can be carried out before or after its activation by a process of the invention.

[0062] The term "fiber" refers to a structure whose longitudinal dimension is significantly greater than its lateral dimension. The term "thread" refers to an assembly of fibers. The term "film" refers to a structure whose longitudinal and lateral dimensions are significantly greater than its lateral dimension. Lateral dimensions are significantly greater than transverse dimensions. A film can be composed of a collection of fibers or threads.

[0063] An activated material is a conductor of hydronium ions.

[0064] By "hydronium ion" we mean the H3Cl cation resulting from the protonation of a water molecule.

[0065] By "hydronium ion conductive material" we mean the ability of a material to ensure ionic and proton conduction allowing the movement of hydronium ions or protons.

[0066] An activated material as described here may include at least one additional electrically conductive material.

[0067] An additional electrically conductive material can be a carbon fiber, a metallic fiber, conjugated polymers, or nanoparticles.

[0068] An activated material as described can be configured as a woven or non-woven textile.

[0069] According to one aspect, the present invention relates to the use of an activated material as defined herein, in particular obtained by a process as defined herein, to generate electrical energy from a humid surrounding atmosphere.

[0070] The material thus used can be electrically connected to a first and a second electrode. The first and / or second electrodes can be chosen from gold, silver, platinum, aluminum, or carbon electrodes.

[0071] According to another aspect, the present invention relates to an electrical energy production device comprising:

[0072] (a) at least one activated material as defined herein, in particular obtained by a process as defined herein,

[0073] (b) at least one pair of electrodes comprising a first electrode and a second electrode, said electrodes being electrically connected to said material,

[0074] said material being intended to, or configured to, be exposed at least partially to a humid surrounding atmosphere.

[0075] An energy production device such as described here is configured to ensure that at least a portion of the activated material as described here is exposed to a humid surrounding atmosphere.

[0076] According to another of its aspects, the invention relates to the use of an energy production device as described herein to supply electrical energy to an electrical or electronic device intended to, or configured to, be supplied with electrical energy.

[0077] According to another aspect, the present invention relates to a method for supplying electrical energy to an electrical or electronic device intended to be supplied with electrical energy, the method comprising at least one step of exposing to a humid surrounding atmosphere, at least partially, at least one activated material as defined herein, in particular obtained by a process as defined herein, said material being arranged in an electrical energy production device as described herein, said device being electrically connected to said electrical device.

[0078] According to another aspect, the present invention relates to a method for supplying electrical energy to an electrical or electronic device intended to, or configured to, be supplied with electrical energy, the method comprising at least the steps of:

[0079] a) to electrically connect a device, as described herein, to an electrical or electronic apparatus intended to be supplied with electrical power, and

[0080] b) expose said material, at least partially, to a humid surrounding atmosphere.

[0081] According to another aspect, the present invention relates to a method of manufacturing a device as described herein, in particular obtained by a method as defined herein, comprising at least one step of electrically connecting an activated material as described herein to a first and a second electrode of a pair of electrodes.

[0082] According to another aspect, the present invention relates to an electrical or electronic device powered by electrical energy through a device as described herein.

[0083] According to another aspect, the present invention relates to a humidity sensor comprising at least one device, as described herein.

[0084] According to another aspect, the present invention relates to a moisture-sensitive electrical circuit breaker comprising at least one device, as described herein.

[0085] According to another aspect, the present invention relates to an electric charger comprising at least one device, as described herein.

[0086] These objects, features and advantages, as well as other aspects of the present invention, will be set forth in detail in the following description. Brief description of the drawings

[0087] [Fig 1] shows (A) a schematic of the device for the electrochemical activation of a film of amyloid fibers and glycosylated proteins composed of mucins and intermediate filament proteins (mucin film) obtained by dehydration of a hydrogel secreted by a hagfish. The mucin film is electrically connected to two electrodes connected to an electrical power source, and the entire assembly is mounted on a support; and (B) a schematic of the enclosure containing the device. The enclosure is a three-necked flask sealed with airtight stoppers to ensure the electrical connection of the electrodes and the maintenance of a neutral atmosphere (N2) for the device. The atmospheric vapor is obtained using a saturated KCl solution. Electronic characterization of the mucin films was performed using a Biologie SP-200 potentiostat equipped with a low-current probe.Humidity control was performed with a saturated solution of KC1 and a Sensirion humidity sensor.

[0088] [Fig 2] represents (A) the IV curves between 0 V and 3 V at 5 mV / s under nitrogen (N2) and 85% relative humidity (RH) immediately after degassing (dashed line) and after 2h at 3 V vs E re f (dotted line); (B) the chronoamperometry curves at 3V vs E re f) the curves of the mucin film at 85% RH and under N2: (solid line) applied voltage, (dashed line) measured current; and (C) the chronoamperometry curves at 0 V vs Eoc on the mucin film at 85% RH and under N2: (solid line) measured voltage (Eoc), (dashed line) measured current. The value of Eoc during degassing is also shown.

[0089] [Fig 3] represents (A) the evolution of the voltage across the mucin film in open circuit before the capacitor is charged and the influence of the direction of connection on the electrodes demonstrating a polarization of the mucin film; and (B) the charging of a capacitor with a capacitance of 470 pF and a voltage of 16 V.

[0090] [Fig 4] represents (A) a typical power curve obtained for an electrochemically activated hagfish mucus film and (B) a discharge curve in a 31 kOhms resistor which corresponds to the load allowing maximum power delivery. Detailed description Definitions

[0091] Unless otherwise defined in the description, the scientific and technical terms used in connection with the present invention have the meanings commonly understood in the technical field. In case of conflict, this description shall prevail. Units, prefixes, and symbols are given in their accepted form in the International System of Units (SI). The headings provided in the description document are not exhaustive of the various aspects of disclosure. The list of sources, ingredients, and components described below is enumerated in such a way that combinations and mixtures thereof are also envisaged and fall within the scope of this description. Examples of processes and materials are described below, and processes and materials similar or equivalent to those described herein may also be used in implementing the present invention.It is appreciated that certain features of the invention, which are, for clarity, described in the context of separate embodiments, can also be provided in combination in a single embodiment. Conversely, various features of the invention, which are, for the sake of brevity, described in the context of a single embodiment, can also be provided separately or in any appropriate sub-combination.

[0092] Numerical ranges include all numbers defining the range. Each maximum numeric limit given throughout the description includes any lower numeric limit, as if those lower numeric limits were expressly stated. Each minimum numeric limit given throughout the description includes any upper numeric limit, as if those higher numeric limits were expressly stated herein. Each numeric range given throughout the description includes any narrower numeric range that falls within such a wide numeric range, as if all those narrower numeric ranges were expressly stated herein.

[0093] All lists of items, such as ingredient lists, are intended to be and should be interpreted as Markush groups. Thus, all lists can be read and interpreted as items "selected from the group constituted by the list of items" and combinations and mixtures thereof.

[0094] Reference may be made to the trade names of components, including various ingredients used in this disclosure. The inventors do not intend to be limited to materials under any particular trade name. Equivalent materials (e.g., those obtained from a different source under a different name or reference number) to those mentioned by trade name may be substituted and used in the descriptions below.

[0095] All publications and other references mentioned in the description are incorporated by reference in their entirety.

[0096] Unless the context otherwise indicates, singular terms include the plural and plural terms include the singular. The terms "a," "one or more," and "at least one" may be used interchangeably in the description.

[0097] In this description, the embodiments described herein with the terms "having" or "comprising" include the 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 all other elements. The expression "consisting essentially of" implies the inclusion of the stated elements, and possibly other elements when the other elements do not materially affect the fundamental characteristic(s) of the disclosure.

[0098] Furthermore, the expression "and / or" should be considered a specific disclosure of each of the two characteristics 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).

[0099] The terms "about" or "approximately" mean an acceptable measurement error for a particular value of a parameter determined by the usual measurement methods in the field, and which will depend in part on how the value is measured or determined—that is, on the limitations of the measurement system. For example, "about" may mean within a range of three or more standard deviations, according to best practice. Alternatively, "about" may mean a range or numerical deviation of up to 20%, for example, up to 10%, for example, up to 5%, and even up to 1% of a given value.

[0100] The expression "significantly" used with respect to a change or difference is intended to signify that the observed change or difference is noticeable and / or that it has statistical significance.

[0101] In the description, the terms "substantially" or "substantially identical" used in conjunction with a feature are intended to define a set of embodiments related to that feature which are largely, but not entirely, similar to that feature. Material comprising hydronium ion-conducting amyloid fibers and glycosylated proteins

[0102] A material suitable for an electrochemical activation process of the invention is a material comprising amyloid fibers and glycosylated proteins, and capable of being activated by a process as described herein. Such a material is said to be "electro-activatable" or "activatable by an electrochemical activation process". Amyloid fibers

[0103] The term "amyloid fiber" refers to a fiber composed of proteins structured in J3 sheets and organized into fibers. The fiber may consist entirely of J3-sheeted proteins, or it may consist primarily of J3-sheeted proteins, i.e., in sufficient quantity to give the fiber the properties of an amyloid fiber.

[0104] Amyloid fibers suitable for the invention are hydronium ion conductors.

[0105] According to one embodiment, amyloid fibers can be prepared from intermediate filaments.

[0106] For the purposes of the invention, the term "intermediate filament" is intended to designate an assembly of proteins associated in filaments of approximately 10 nm in diameter comprising the cytoskeleton structure of many cells in most metazoan taxa or of the defensive mucus produced by Myxinidae.

[0107] Intermediate filaments (IFs) are made up of a set of proteins organized into filaments about 10 to 12 nm in diameter and several micrometers long and constitute a component of the cytoskeleton in most metazoan taxa or of the defensive mucus produced by Myxinidae.

[0108] Intermediate filaments share a common architecture characterized by a central α-helical coiled domain, flanked by a largely amorphous N-terminal "head" domain and a C-terminal "tail" domain of variable length and sequence. Given their open molecular architecture and unique assembly plane, intermediate filaments possess mechanical properties combining extreme extensibility, flexibility, and toughness (Boni et al., ACS Appl Mater Interfaces. 2018; 10(47):40460-40473), as well as a very strong hydration capacity.

[0109] Intermediate filaments are composed of proteins rich in α-helices that can be converted into γ-sheets when subjected to mechanical deformations such as stretching (Litvinov et al., Biophys J. 2012; 103(5): 1020-1027).

[0110] An intermediate filament suitable for the invention is a filament comprising helical domains of a length at least greater than 3.8 nm.

[0111] According to one embodiment, amyloid fibers are stretched intermediate filaments. A "stretched intermediate filament" is a filament that has undergone sufficient mechanical deformation to convert all or part of the α helices of the proteins constituting the intermediate filaments into γ-sheets. The conversion of α helices into γ-sheets can be measured or monitored by FITR spectroscopy (Fourier transform infrared spectroscopy) or by colorimetry with the Congo Red dye (Litvinov et al., Biophys J. 2012; 103(5):1020-1027; Fudge et al., Biophys J. 2003; 85(3):2015-2027).

[0112] As an example of intermediate filaments suitable for the invention, one may cite intermediate filaments composed of proteins selected from F oc-keratin, lamin, vimentin, desmin, peripherin, syncoilin, F oc-internexin, neurofilament, synemin, thread keratins a, |3 and y, for example from the defensive mucus produced by Myxinidae, variants of these proteins, and mixtures thereof.

[0113] According to one embodiment, the intermediate filaments suitable for the invention may be composed of thread keratin proteins (“thread keratins”) a, |3, and y, and mixtures thereof. The thread keratin proteins a, |3, and y, and mixtures thereof, may be derived from the defensive mucus produced by hagfish (Myxinidae).

[0114] The intermediate filaments can be associated together into fibers or threads.

[0115] The intermediate filament fibers or threads can have a diameter ranging from about 0.5 to about 5 pm, or from about 1 to about 3 pm, or from about 1.5 to about 2 pm.

[0116] The intermediate filament fibers or threads can vary in length from approximately 1 to approximately 20 cm, or from approximately 2 to approximately 18 cm, or from approximately 5 to approximately 15 cm.

[0117] Intermediate filaments can be extracted from natural sources or produced recombinantly in fermenters using genetically modified recombinant microorganisms to produce the proteins that make up the intermediate filaments.

[0118] For example, intermediate filaments can be obtained recombinantly according to the process described by Oliveira et al. (Microb Biotechnol. 2021; 14(5):1976-1989) or in US patent applications 2019 / 0002529 A1 or 2005 / 0034280 A1

[0119] As an example, intermediate filaments can be prepared from the mucus or hydrogel produced by fish of the Myxinidae family, such as the hagfish. Hagfish threads consist of axially aligned intermediate filaments, which condense into a solid fiber approximately 1 to 3 pm in diameter and up to approximately 15 cm long (Bôcker et al., ACS Biomater. Sci. Eng., vol. 2, no. 1, pp. 90-95, 2016).

[0120] When the hagfish is attacked by a predator, it releases, via glands, dry fibers of mucin and intermediate filaments. These fibers instantly hydrate into mucus and fibrous threads rich in intermediate filaments (IF) (Bôcker et al., ACS Biomater. Sci. Eng., vol. 2, no. 1, pp. 90-95, 2016).

[0121] Hagfish intermediate filaments comprise three thread keratin proteins (TK) (α, β, and γ). Hagfish intermediate filaments are termed "keratins" because of features in their head and tail domains that are similar to keratin. Tα is a homolog of type II keratin, and TKγ possesses features of type I keratins but also contains structural similarities with type III intermediate filaments, which include desmin and vimentin (Boni et al., ACS Appl Mater Interfaces. 2018;10(47):40460-40473).

[0122] The intermediate filaments of a hydrogel from a fish of the family Myxinidae can be configured into amyloid fibers by exposing the hydrogel to mechanical deformation, such as stretching. This deformation can be applied during handling, for example, manually, of the hydrogel during its recovery from the fish, or by any mechanical device that allows such stretching. Alternatively, the deformation mechanical force, for example stretching, can be exerted on the intermediate filaments of a dry material. Glycosylated proteins

[0123] According to one embodiment, a material suitable for the invention comprises glycosylated proteins.

[0124] A glycosylated protein is a protein to which sugar (or glycosylated) groups are attached. This attachment can occur to nitrogen atoms – N-glycosylation – or oxygen atoms – O-glycosylation. Glycosylated proteins suitable for the invention are capable of forming mucus in the presence of water.

[0125] Glycosylated proteins suitable for the invention are glycosylated proteins capable of forming a hydrogel in the presence of an aqueous phase.

[0126] The term "hydrogel" refers to a system comprising networks of physically or chemically bonded polymers that trap water in the intermolecular spaces. Glycosylated proteins capable of forming hydrogels are known to those skilled in the art.

[0127] Glycosylated proteins suitable for the invention may be mucins.

[0128] For the purposes of this invention, the term "mucin" refers to a highly glycosylated protein that is a component of many mucus substances. Mucins are characterized, in particular, by the tandem repetition of serine and threonine-rich amino acid sequences, which serve as attachment points for glycosylated structures.

[0129] Mucin-like proteins exist in virtually all animals and many microorganisms. The mucins suitable for the invention are those capable of forming a hydrogel.

[0130] Mucins suitable for the invention are highly glycosylated proteins with multiple domains whose structure gives them the property of forming gels by homo-oligomerization contributing to the creation of protein networks.

[0131] Examples of mucin suitable for the invention include human mucins such as MUC2, MUC5AC, MUC5B, MUC6 or MUC19, or mucins from fish of the Myxinidae family.

[0132] According to one embodiment, glycosylated proteins suitable for the invention can be mucins from fish of the Myxinidae family, for example from Myxine glutinosa.

[0133] Mucins can be extracted from natural sources or produced recombinantly in fermenters using genetically modified recombinant microorganisms to produce mucin proteins.

[0134] For example, mucins can be obtained recombinantly according to the process described by Shurer et al. (Biotechnol Bioeng. 2019;116(6): 1292-1303. Doi: 10.1002 / bit.26940) or in US applications 2012 / 0165272 Al, or US 2021 / 0246176 Al.

[0135] As an example, mucins can be prepared from the mucus or hydrogel produced by fish of the Myxinidae family, such as the hagfish.

[0136] Mucins from fish of the Myxinidae family, such as hagfish, can be composed of approximately 80% protein and 20% sugars. They can oligomerize through the formation of disulfide bridges and sulfonated structures. Preparation of a material comprising amyloid fibers and glycosylated proteins

[0137] A material that can be activated by an electrochemical activation process described here and comprising hydronium ion-conducting amyloid fibers and glycosylated proteins can be obtained by any method known in the field.

[0138] Such a material can be obtained through synthetic routes, through biotechnological processes enabling the production of hydronium ion-conducting amyloid fibers and recombinant glycosylated proteins, or from animals producing such materials.

[0139] Recombinant proteins can be obtained by heterologous expression in a host cell, for example Escherichia coli or CHO cells, and amplification of the host cells in a bioincubator. The recombinant proteins thus obtained are then purified by any known method in the field.

[0140] According to one embodiment, a material comprising hydronium ion-conducting amyloid fibers and glycosylated proteins can be obtained from a hydrogel produced by a fish selected from the fish of the Myxinidae family, and in particular from the subfamilies Myxininae and Eptatretinae.

[0141] According to one embodiment, a material activatable by an electrochemical process and suitable for the invention can be prepared from a mucus or hydrogel secreted by a fish selected from the Myxinidae family, and in particular from the Myxininae and Eptatretinae subfamilies. The fish can be selected from the genera Myxine, Nemamyxine, Neomyxine, Notomyxine, Eptatretus, Eleptatretus, or Rubicundus.

[0142]

[0140] A material suitable for the invention can be obtained from a fish selected from Myxine affinis, Myxine australis, Myxine capensis, Myxine circifrons, Myxine debueni, Myxine dorsum, Myxine fernholmi, Myxine formosana, Myxine garmani, Myxine glutinosa, Myxine hubbsi, Myxine hubbsoides, Myxine ios, Myxine jespersenae, Myxine knappi, Myxine kuoi, Myxine limosa, Myxine mccoskeri, Myxine mcmillanae, Myxine paucidens, Myxine pequenoi, Myxine robinsorum, Myxine sotoi, Eptatretus bischoffii, Eptatretus burgeri, Eptatretus caribbeaus, Eptatretus carlhubbsi, Eptatretus chinensis, Eptatretus cirrhatus, Eptatretus deani, Eptatretus decatrema, Eptatretus eos, Eptatretus fernholmi, Eptatretus fritzi, Eptatretus goliath, Eptatretus grouseri, Eptatretus hexatrema, Eptatretus indrambaryai, Eptatretus lakeside, Eptatretus laurahubbsae, Eptatretus longipinnis, Eptatretus mcconnaugheyi, Eptatretus mccoskeri, Eptatretus mendozai, Eptatretus menezesi, Eptatretus minor, Eptatretus multidens,Eptatretus nanii, Eptatretus octatrema, Eptatretus okinoseanus, Eptatretus polytrema, Eptatretus profundus, Eptatretus sinus, Eptatretus springeri, Eptatretus stoutii, Eptatretus strahani, Eptatretus wayuu, and Eptatretus wisneri.

[0143] According to one embodiment, a material suitable for the invention can be obtained from the fish Myxine glutinosa.

[0144] According to one embodiment, a material suitable for the invention can be prepared from a hydrogel comprising amyloid fibers and glycosylated proteins, for example from mucus or hydrogel obtained from a fish of the Myxinidae family.

[0145] According to one embodiment, a hydrogel obtained from a fish of the Myxinidae family can be subjected to a mechanical deformation step, in particular stretching, in order to allow the conversion of the α helices of the intermediate filament proteins into β sheets. This step can be carried out mechanically or manually, for example by manipulating the hydrogel when it is taken from a fish of the Myxinidae family or by using a device to stretch the hydrogel.

[0146] A mechanical deformation process suitable for converting helices of intermediate filament proteins into sheets may include a stretching step.

[0147] Stretching can be achieved by manual traction.

[0148] Alternatively, stretching can be achieved by means of a mechanical device, for example an extruder, a carding machine, or a loom.

[0149] The stretching force required to convert the α-helices of intermediate filament proteins into γ-sheets is adjusted by those skilled in the art to achieve the desired conversion without material rupture. The conversion of α-helices into γ-sheets can be determined by any method known in the field, for example as described by Litvinov et al. (Biophys J. 2012; 103(5): 1020-1027) or Fudge et al. (Biophys J. 2003; 85(3): 2015-2027).

[0150] A stretching force suitable for converting the helices of intermediate filament proteins into μ-sheets can be at least 1 MPa, in particular at least 10 MPa, or even at least 20 MPa. According to one embodiment, a stretching force can be in a range from about 10 to about 20 MPa.

[0151] The mechanical deformation step can be performed on a dehydrated material.

[0152] A material suitable for the invention may comprise glycosylated proteins, for example mucins, for example mucins from fish of the Myxinidae family, and amyloid fibers, for example in the form of intermediate filaments, for example from fish of the Myxinidae family. The intermediate filaments are stretched.

[0153] According to one embodiment, a material suitable for the invention may be in the form of a fiber, a yarn, or a film. A material suitable for the invention may be in the form of a film. A material suitable for the invention may be in the form of a yarn.

[0154] According to one embodiment, a material suitable for the invention can be dehydrated.

[0155] According to one embodiment, a hydrogel or mucus comprising amyloid fibers and glycosylated proteins, used to prepare a material suitable for the invention, is subjected to a dehydration step. This dehydration step can be carried out by any method known in the field.

[0156] The dehydration step can precede or follow the electrochemical activation step. For example, the dehydration step precedes the electrochemical activation step.

[0157] The temperature and duration conditions are selected so as to allow the evaporation of the water contained in the hydrogel or mucus, without alteration of the amyloid fibers and glycosylated proteins.

[0158] A hydrogel or mucus comprising amyloid fibers and glycosylated proteins can be arranged into a film, membrane, fibers, or threads.

[0159] According to one embodiment, after collection from a fish of the Myxinidae family, a hydrogel can be formed into a membrane by membrane casting or into filaments by extrusion. Immediately after collection, a hydrogel has not yet released much water and has a transparent appearance.

[0160] According to another embodiment, after partial drying, a hydrogel obtained from a fish of the Myxinidae family can be formed into sheets by spreading and drying. Partial drying can be achieved by simply releasing a significant proportion of water. A hydrogel that has begun to dry also begins to whiten.

[0161] Alternatively, a material activatable by a process described here and prepared from a hydrogel or mucus comprising hydronium ion-conducting amyloid fibers and glycosylated proteins, can be arranged into film, fibers or threads subsequent to the dehydration step.

[0162] A hydrogel comprising amyloid fibers and glycosylated proteins, for example a hydrogel obtained from a fish of the family Myxinidae, for example a Myxina glutinosa, can be dehydrated by any method known in the field as described above.

[0163] According to one embodiment, a film of a dehydrated material suitable for a process of the invention can be prepared from a hydrogel comprising amyloid fibers and glycosylated proteins, for example, a hydrogel obtained from a fish of the Myxinidae family, for example, Hagfish (Myxina glutinosa), spread in a thin layer on a suitable support and exposed to a temperature and for a duration sufficient to reduce the water content of the hydrogel. A hydrogel layer can have a thickness ranging from about 10 to about 900 µm, for example, from about 50 to about 600 µm, or even, for example, from about 100 to about 500 µm.

[0164] A substrate suitable for spreading a hydrogel film must prevent the hydrogel from adhering to the substrate. Such a substrate may be hydrophobic.

[0165] A support for spreading a hydrogel into a film can be, for example, parchment paper or something made of TEFLON®.

[0166] A dehydration temperature can be from about 40°C to about 70°C, or from about 45°C to about 60°C, or be about 50°C.

[0167] For example, the dehydration of a hydrogel can be carried out in an oven or by exposure to air or a stream of dry air.

[0168] An activated material as described here may comprise at least one additional electrically conductive material.

[0169] An additional electrically conductive material can be a carbon or graphite wire or fiber, a metallic wire or fiber, conjugated polymers, or nanoparticles. The metal in a metallic wire or fiber can be copper, silver, gold, aluminum, zinc, or iron.

[0170] An additional electrically conductive material may be combined with a material described here before or after its activation by an electro-chemical activation process described here.

[0171] For example, an additional electrically conductive material can be added to a hydrogel obtained from a hagfish before the hydrogel is dehydrated. Alternatively, the hagfish hydrogel can be dehydrated and prepared into a film, fibers, or yarn, and the additional electrically conductive material is added to the film, fibers, or yarns.

[0172] A material suitable for the invention can be formed into films, fibers or threads.

[0173] Film shaping of a material can be achieved by dehydrating a hydrogel obtained from a fish of the Myxinidae family.

[0174] A material can be formed into yarns or fibers by any known textile fiber or yarn production process, for example, by carding and spinning. The fibers and yarns thus obtained can then be used in any fabric production process, whether woven or non-woven. Weaving operations can enable the production of steam-generating devices over large areas. Weaving operations can also enable the production of films of activated material according to the invention.

[0175] The shaping of a material into film, yarn or fiber can be carried out before or after activation by a process as described here.

[0176] The shaping of a material into film, yarn or fiber can be carried out before or after dehydration of the material obtained in the form of a hydrogel.

[0177] An activated material described here can be manufactured as a woven or non-woven fabric. An activated material can be prepared in the form of yarns or fibers. The resulting yarns or fibers can then be assembled, for example, into woven or non-woven textiles.

[0178] When an activated material described here is prepared in the form of a woven or non-woven textile, an additional electrically conductive material may be added at the textile assembly stage.

[0179] Any process for preparing woven or non-woven textiles can be implemented. Electrochemical activation process

[0180] According to one of its objects, the invention relates to a method for the electrochemical activation of a material comprising amyloid fibers and glycosylated proteins, the method comprising at least the steps of:

[0181] (a) to bring at least a part of said material into contact with water vapor,

[0182] (b) electrolyze at least a portion of the water vapor in contact with said material, and

[0183] (c) obtain an activated material.

[0184] Step (b) is carried out by exposing the material to an electrical potential difference.

[0185] Without wishing to be bound to any particular theory, the inventors hypothesize that electrochemical activation leads to the modification of intermediate filament proteins and glycosylated proteins through water vapor redox reactions occurring during exposure to an electrical potential difference, which induce the creation of a charge gradient. This charge gradient allows the establishment of an electrical potential difference in the presence of water vapor.

[0186] The electrical potential difference can be applied by means of two electrodes electrically connected to the material.

[0187] A material that can be activated by an electrochemical activation process described herein can be brought into contact with, or attached to, the electrodes by any method known in the appropriate field. to enable an electrical connection and the application of an electrical potential difference to the material.

[0188] For example, when the material activatable by an electrochemical activation process is prepared from a dehydrated hydrogel of hagfish mucus, it can be fixed to the electrodes by simply moistening the region of the material that will be in contact with the electrodes.

[0189] The electrodes can be arranged so that each electrode is in contact with a point on the material. A first electrode is in contact with a first point on the material, and a second electrode is in contact with a second point on the material.

[0190] For example, the first and / or second electrode(s) can be chosen from gold, silver, platinum, aluminum or carbon electrodes.

[0191] The electrical potential difference is capable of inducing electrolysis of at least some of the water vapor in contact with the material. The electrical potential difference can be at least 1.23 V. For example, the electrical potential difference can be in a range from approximately 1.3 to approximately 10 V, or from approximately 1.5 to approximately 8 V, or from approximately 2 to approximately 5 V, or be approximately 3 V.

[0192] The difference in electrical potential can be fixed or variable.

[0193] A fixed electrical potential difference is an electrical potential difference that remains substantially constant throughout the electrochemical activation step. The electrical potential difference is applied at the selected value to achieve water electrolysis and then remains substantially constant during the electrochemical activation step.

[0194] A variable electrical potential difference is an electrical potential difference whose value changes over time during the electrochemical activation step. A variable electrical potential difference includes electrical potential values ​​that allow for the electrolysis of water.

[0195] A variable electrical potential difference can extend over a range from about 0 to about 10 V, or from about 1.23 to about 10 V, or from about 1.5 to about 8 V, or from about 3 to about 4 V.

[0196] For example, a variable electrical potential difference can span a range from approximately 1.23 V to approximately 3 V.

[0197] A fixed or variable electrical potential difference is applied at a value and for a duration sufficient to electrolyze the water vapor in contact with a material described here and obtain the electrochemical activation of this material.

[0198] The electrochemical activation of the material can be characterized by its ability to generate an electric current in the presence of water vapor. Such an electric current can be measured by chronoamperometry at 0 V vs. Eoc.

[0199] Chronoamperometry is an electrochemical technique in which the electrical potential of the working electrode is stepped and the current resulting from faradaic processes occurring at the electrode is monitored as a function of time.

[0200] The electrochemical activation of the material can also be characterized by any method of measuring the change in the chemical structure of a material, such as mass spectrometry for example or analytical chemistry methods.

[0201] Step (a) of bringing the material into contact with water vapor can be carried out by placing the material in a humid atmosphere.

[0202] A humid surrounding atmosphere for an electrochemical activation process described herein may have a relative humidity ranging from approximately 60% to approximately 100%, or from approximately 65% ​​to approximately 99%, or from approximately 70% to approximately 95%, or from approximately 75% to approximately 90%, or from approximately 80% to approximately 85%, or be approximately 85%. A humid surrounding atmosphere for an electrochemical activation process described herein may have a relative humidity of at least 60%, or at least 65%, or at least 70%, or at least 75%, or at least 80%, or at least 85%, or at least 90%, or at least 95%, or at least 99%.

[0203] According to one embodiment, a humid atmosphere surrounding the material may include a relative humidity ranging from at least about 70% to about 90%, and be, for example, about 85%.

[0204] A humid ambient atmosphere can be obtained by any method known in the field. For example, a humid ambient atmosphere can be obtained using a saturated salt solution, such as KCl.

[0205] The relative humidity of an atmosphere can be measured by all known methods, for example by means of a hygrometer.

[0206] An atmosphere used in the process described here can be a neutral atmosphere. A neutral atmosphere is one that does not react chemically or physically with the elements in contact with it.

[0207] A humid and neutral atmosphere is an atmosphere comprising water vapor and a neutral gas that does not react chemically or physically with the elements in contact with it during the execution of the process described here. However, in accordance with the process described here, the water vapor in contact with the material to be electro-activated can undergo electrolysis under appropriate conditions.

[0208] A neutral atmosphere may include nitrogen, helium, neon, argon, or a mixture thereof as neutral gases. In one embodiment, a neutral atmosphere may include nitrogen or argon as neutral gases, and for example may include nitrogen.

[0209] When an electro-activatable material is prepared from a hydrogel, for example hagfish mucus, the electrochemical activation process may include, prior to step (a), a hydrogel dehydration step.

[0210] The hydrogel dehydration step can be carried out using any method known in the field, for example, as detailed previously. One usable method is to expose the material to a temperature and for a sufficient duration to allow the evaporation of the water contained in the hydrogel.

[0211] When an electro-activatable material is prepared from a hydrogel comprising intermediate filaments, for example hagfish mucus, the electrochemical activation process may include, prior to the hydrogel dehydration step, a mechanical deformation step, for example stretching, of the hydrogel to achieve a conversion of all or part of the α helices into γ sheets.

[0212] According to one embodiment, a process for preparing an electrochemically activated material, the material comprising glycosylated proteins and intermediate filaments, may include at least the steps of:

[0213] (i) obtaining an activation material in the form of a hydrogel comprising glycosylated proteins and intermediate filaments, the intermediate filaments comprising proteins comprising α-helices,

[0214] (ii) mechanically deform the material obtained in step (i), for example by stretching, to obtain a conversion of at least part of the α helices of the intermediate filament proteins into P-sheets (amyloid fibers),

[0215] (iii) dehydrate at least partially the material obtained in step (ii),

[0216] (iv) bring at least a part of the material obtained in step (iii) into contact with water vapor,

[0217] (v) electrolyze at least a portion of the water vapor in contact with said material, and

[0218] (vi) obtain an activated material.

[0219] According to one embodiment, a process for preparing a material activated by electrochemical activation,

[0220] the material being in the form of a hydrogel comprising glycosylated proteins and intermediate filaments, the intermediate filaments comprising proteins comprising P-sheets (amyloid fibers) resulting from all or part of the conversion of the a-helices of said proteins,

[0221] and the process comprising at least the steps of:

[0222] (i) dehydrate the material at least partially,

[0223] (ii) bring at least a portion of the material obtained in step (i) into contact with water vapor,

[0224] (iii) electrolyze at least a portion of the water vapor in contact with said material, and

[0225] (iv) obtain an activated material.

[0226] An activated material obtained through an electrochemical activation process described herein, capable of generating an electric current by contact with water vapor.

[0227] An activated material obtained through an electrochemical activation process described here is a conductor of hydronium ions. Uses of an activated material

[0228] An activated material, comprising hydronium ion-conducting amyloid fibers and glycosylated proteins, as described herein, can be used to generate electrical energy by contact with a humid surrounding atmosphere.

[0229] In such an application, the material can be electrically connected to a first and a second electrode. The pair of electrodes can be placed on the surface of materials of various types and shapes. The choice of the type and shape of the materials used to support the electrodes is determined by a person skilled in the art, according to the intended use of the electrodes. Suitable materials include polymers or plastic resins, vitreous materials, and fabrics.

[0230] The first and / or second electrode(s) can be chosen from gold, silver, platinum, aluminum or carbon electrodes.

[0231] An activated material, for example in the form of a wire, fiber, or film, can be electrically connected to a first and a second electrode. The first electrode is electrically connected, for example via one of its tips, to a first point on the material, and the second electrode is electrically connected, for example via one of its tips, to a second point on the material. The first and second electrodes can form an electrode pair.

[0232] A wire or fiber of an activated material may comprise a first end and a second end. In one embodiment, a first electrode may be electrically connected, for example by a point, to a first end of the wire or fiber, and a second electrode may be electrically connected, for example by a point, to a second end of said wire or fiber.

[0233] An activated material, such as the one described here, can be implemented in an electrical power generation device.

[0234] An electrical power generation device may include:

[0235] (a) at least one activated material as described herein,

[0236] (b) at least one pair of electrodes comprising a first electrode and a second electrode, said electrodes being electrically connected to said material,

[0237] said material being intended to be exposed (brought into contact), at least partially, with a humid surrounding atmosphere.

[0238] The intensity of the electrical energy generated by a device such as the one described here can depend on the humidity content of the surrounding atmosphere in contact with the activated material. The intensity can also depend on the surface area of ​​the film or the number of fibers or wires present in the device.

[0239] According to one embodiment, a device as described may include an activated material in the form of threads. The threads may or may not be woven.

[0240] According to one embodiment, a device as described may comprise a plurality of wires or films each electrically connected to a first and a second electrode.

[0241] According to one embodiment, a device may comprise a plurality of wires or films arranged in parallel.

[0242] According to another embodiment, a device may comprise a plurality of wires or films arranged in series.

[0243] According to one embodiment, a device as described herein may comprise a plurality of pairs of first and second electrodes, each of said pairs of electrodes being electrically connected to a wire or film, or to a plurality of at least 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 500, 1000, or more, wires or films. In such an embodiment, the wires or films are then electrically connected in parallel.

[0244] A device such as the one described here may comprise a plurality of first and second electrode pairs. These electrode pairs may be electrically connected to each other in series or in parallel.

[0245] According to one embodiment, a device as described herein may comprise a pair of first and second electrodes, or a plurality of at least 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 500, 1000, or more, pairs of first and second electrodes, each pair of first and second electrodes being electrically connected to a wire or film, or a plurality of wires or films, at least 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 500, 1000, or more, as described here. When at least two, or more, pairs of electrodes are present, these can be electrically connected to each other in series or in parallel.

[0246] A parallel architecture advantageously allows for a reduction in internal resistance.

[0247] A series architecture advantageously allows for increasing the circuit's electrical load potential to several volts. Furthermore, a series architecture allows for high internal resistance and enables the custom design and fabrication of a device with a precisely defined final resistance.

[0248] According to one embodiment, a device may comprise a plurality of wires or films arranged in parallel and a plurality of wires or films arranged in series.

[0249] According to one embodiment, a device may include a plurality of pairs of electrodes electrically connected to one or a plurality of wires or films and arranged in parallel and a plurality of pairs of electrodes electrically connected to one or a plurality of wires or films and arranged in series.

[0250] The plurality of wires or pairs of electrodes can be arranged to form a planar, two-dimensional, or three-dimensional configuration.

[0251] According to one embodiment, a device includes at least one film, fiber or at least one yarn of an activated material arranged so that at least 50%, for example at least 60%, at least 70%, at least 80%, at least 90% or even 100% of the surface of the film or the length of the fiber or yarn is exposed to the surrounding humid atmosphere.

[0252] A device such as the one described here could be an electrical power supply device, for example a battery.

[0253] An electrical power generation device described here can be used to supply electrical power to an electrical or electronic device intended to be supplied with electrical power.

[0254] An electrical power generation device described here can be implemented in a process to supply electrical power to an electrical or electronic device.

[0255] A method for supplying electrical energy to an electrical or electronic device intended for, or configured to be supplied with electrical energy may include at least one step of exposing to a humid surrounding atmosphere, at least partially, at least one activated material as described herein, said material being disposed in an electrical energy production device as described herein, said device being electrically connected to said electrical or electronic device.

[0256] According to another embodiment, this disclosure relates to a method for supplying electrical energy to an electrical or electronic device intended to be supplied with electrical energy, the method comprising at least the steps of:

[0257] a) electrically connect a device as described to an electrical or electronic appliance intended to be supplied with electrical power, and

[0258] b) expose, at least partially, the activated material to a humid surrounding atmosphere.

[0259] An electrical energy production device described herein can be prepared by a manufacturing process comprising at least one step of placing an activated material as described herein between a first and a second electrode of a pair of electrodes to electrically connect said electrodes with said material.

[0260] A device such as the one described herein can be prepared by a process further comprising at least the steps of:

[0261] - to bring into contact a material activatable by an electrochemical activation process, the material comprising hydronium ion-conducting amyloid fibers and glycosylated proteins, with a first and a second electrode of a pair of electrodes to electrically connect said electrodes to the material, and

[0262] - to expose at least a part of said material to water vapor,

[0263] - to electrolyze at least a portion of the water vapor in contact with said material, and

[0264] - to obtain an activated material.

[0265] A device such as the one described herein can be prepared with a material in the form of a hydrogel comprising glycosylated proteins and intermediate filaments, the intermediate filaments comprising proteins comprising λ3 sheets resulting from all or part of the conversion of the helices of said proteins, and by a process further comprising at least the steps of:

[0266] - electrically connect said material with a first and a second electrode of a pair of electrodes,

[0267] - dehydrate the material at least partially, and

[0268] - expose at least part of the material obtained in the previous step to water vapor,

[0269] - electrolyze at least part of the water vapor in contact with said material.

[0270] A device such as the one described herein can be prepared by a process further comprising at least the steps of:

[0271] - to obtain a material in the form of a hydrogel comprising glycosylated proteins and intermediate filaments, the intermediate filaments comprising proteins comprising λ3 sheets resulting from all or part of the conversion of the helices to said proteins,

[0272] - electrically connect said material with a first and a second electrode of a pair of electrodes,

[0273] - dehydrate the material at least partially, and

[0274] - expose at least part of the material obtained in the previous step to water vapor,

[0275] - electrolyze at least part of the water vapor in contact with said material.

[0276] The material can be in the form of films, yarns, or fibers.

[0277] A device described here can advantageously be implemented in an area with high humidity, for example a marine environment, to recharge small electrical or electronic devices, such as smartphones, sensors, for example humidity sensors, beacons, electric chargers, or lamps.

[0278] An electrical power generation device described here can be installed in a humidity sensor, a humidity-sensitive electrical circuit breaker, or an electrical charger.

[0279] It is understood that this description encompasses all variations, combinations, and permutations in which at least one limitation, element, clause, descriptive term, etc., of at least one of the claims is introduced into another dependent claim of the same basic claim (or, where applicable, into any other claim), unless otherwise stated or it is obvious to a person skilled in the art that a contradiction or inconsistency would arise. Where elements are presented in list form, for example in a Markush group or in a similar form, it is understood that Each subgroup of elements is also disclosed, and any element may be removed from the group. It should be understood that, in general, when the disclosure, or aspects of the disclosure, is / are designated as comprising particular elements, features, etc., they also encompass embodiments consisting of, or essentially consisting of, such elements, features, etc. For the sake of simplicity and conciseness, these elements have not always been specifically disclosed in this document. It should also be understood that any embodiment or aspect of the disclosure may be explicitly excluded from the claims, whether or not the specific exclusion is mentioned in the description. Publications and other reference materials cited in the description to describe the background of the invention and to provide further details concerning its implementation are incorporated by reference.

[0280] Without limiting the present description of the invention, various embodiments of the invention are described below for illustrative purposes. Examples Example 1: Preparation of an electro-activatable material film

[0281] A film of hydronium-conducting amyloid fibers and glycosylated proteins was created from a hydrogel secreted by the hagfish (Myxine glutinosa) through dehydration. The hydrogel secreted by the hagfish is composed of mucins, glycosylated proteins, and intermediate filaments. During manipulation of the hydrogel, the intermediate filaments are stretched, and at least some of the proteins composing them undergo a transition from their α-helices to P-sheets, conferring upon the intermediate filaments a structure and properties of amyloid fibers. These amyloid fibers are notably hydronium-conductive.

[0282] The hydrogel was isolated directly after the hagfish were captured. It was spread onto parchment paper placed on a grid. Oven drying at 50°C resulted in the dehydration of a film of mucins and intermediate filament proteins in the form of a sheet. Example 2: Electrochemical activation of the material comprising glycosylated proteins and amyloid fibers.

[0283] A piece of glycosylated protein and amyloid fiber film (i.e., mucins and intermediate filament proteins) (1 cm x 2 mm) was connected to two glassy carbon electrodes (6 mm diameter). The connection between the film and the glassy carbon was made by moistening the film at the contact points. A 1 mm gap separates the two glassy carbon electrodes (Figure 1(A)). This device was then placed in a sealed chamber. A saturated KCl solution was placed in the sealed chamber to maintain a relative humidity (RH) of 85% (Figure 1(B)). The protein film was placed in the high-humidity (85%) climate chamber, and the chamber was degassed with nitrogen (N2) for 18 h.

[0284] The open-circuit electrical potential difference (Eoc) between the two electrodes was recorded during degassing (Fig. 2 (C)).

[0285] We can observe that the Eoc during degassing is unstable for the first 7 hours. Subsequently, a stabilization can be seen at around 10 mV.

[0286] Once degassing was complete, an initial current-potential (IV) curve was obtained between 0 and 3 V at a rate of 5 mV / s (Fig. 2 (A), dashed line). This curve can be broken down into 3 phases: - Phase 1: between 0 V and 1.4 V, a very low current is observed, - Phase 2: between 1.4 V and 2.6 V, a slight increase in current is observed, which corresponds to the beginning of water electrolysis which occurs from 1.23 V. - Phase 3: between 2.6 V and 3 V, an increase in current up to 80 pA which corresponds to the electrolysis of water since the electrical potential is greater than 1.23 V.

[0287] Next, a chronoamperometry at 3 V vs E reThe experiment was conducted for 2 hours to observe the evolution of the current over time (Fig. 2 (B)). Initially, a decrease in current can be observed during the first few minutes. This corresponds to the stabilization of the system following curve IV, which was previously plotted. Subsequently, the current increases over time, rising from 40 pA to 120 pA. During this stage, the oxidation of water occurs at the anode and the reduction of protons to hydrogen occurs at the cathode.

[0288] A new chronoamperometry was then performed at 0 V vs E oc (Fig 2 (O). The current and the E O c have been recorded.

[0289] The observed current is stable at 2.5 pA, which is consistent with the values ​​obtained with IV. Furthermore, it is clear that an electrical potential difference has been established at 1.46 V and has remained stable over a period of 16 hours.

[0290] A second IV curve between 0 V and 3 V at a rate of 5 mV / sa was then obtained (Fig. 2 (A), dashed line). It can be seen that the current values ​​are higher than those observed during the first IV. Therefore, there was electrochemical activation of the hagfish film.

[0291] Without claiming to be supported by a specific mechanism, the inventors hypothesize that electro-activation results from protein modifications due to redox reactions occurring on either side of the film during exposure to a 3V electrical potential difference. These reactions induce the creation of a charge gradient within the film, allowing the establishment of an electrical potential difference in the presence of water vapor. A mechanism of this nature has been used to modify the charge distribution in graphene sheets and thus generate electricity from water vapor (Wang et al., J. Mater. Chem. A9, 8870-8895, 2021). Example 3: Energy production by an activated film of hydronium ion-conducting amyloid fibers and glycosylated proteins from ambient humidity

[0292] The open-circuit electrical potential was then recorded over time (Fig. 3 (A)). It was observed that the open-circuit potential remained stable at 1.30 V for several hours. During this experiment, the connections to the glassy carbon electrodes were reversed. It can be noted that the open-circuit potential became negative (-1.30 V), indicating that the mucin and intermediate filament protein film is naturally polarized in the presence of moisture. The direction of this polarization can be attributed to the polarizations performed at the beginning of the experiment (IV and chronoamperometry).

[0293] An electrolytic capacitor was connected to the terminals of the glassy carbon electrodes to be charged using the Eoc (Fig. 3 (B)). The capacitor used had a capacitance of 470 pF and a voltage rating of 16 V. It was charged twice, with the Eoc recorded between the two charges. This recording was consistent with previous observations, as the voltage obtained was 1.25 V. Between the two charging tests, the capacitor was discharged through a resistor until zero voltage was reached. It can be observed that the charging kinetics, followed by the evolution of the voltage across the capacitor, does not start at 0 V. This is directly related to the experimental setup and the very short charging time constant observed (r = RC = 40 s). Indeed, a few seconds elapsed between the time the capacitor was connected to the terminals of the mucin film and the start of the recording. A limiting voltage of 1.A voltage of 25 V was reached after 2 minutes during the first charge and 3 minutes during the second charge. This limiting voltage corresponded well to the observed operating voltage (Eoc) for the hagfish film. The determination of the capacitor's charging time constant r yielded a value of 40 s. Considering that a capacitor is fully charged after 4 r, we indeed obtain values ​​of 4 and 5 minutes. Finally, from the charging time constant, we can determine an internal resistance of the film on the order of 50 kΩ.

[0294] These results demonstrate proof of concept that activated films of glycosylated proteins and amyloid fibers, for example mucins and intermediate filament proteins prepared from a hydrogel obtained from fish such as hagfish, are capable of recharging a capacitor in the presence of moisture.

[0295] Here, the experiments were conducted at a relative humidity (RH) of 85%, resulting in quick and easy operation. It is, of course, possible to work at lower humidity levels (40%).

[0296] It can be observed that the capacitor's charging time is very short, due to the film's internal resistance. It is conceivable to develop an architecture comprising several films with a mixture of films connected in parallel and series to increase the electrical charging potential (several volts). Example 4: Power curve and discharge curve obtained with a hagfish mucus film

[0297] An electrochemically activated hagfish mucus film was prepared as described above. The film was placed in a humid atmosphere (85% RH) and connected to a decade resistor box, allowing the load resistance to be varied over several orders of magnitude. The potential (V) across the resistor was measured with a voltmeter. The current (pA) was calculated using the formula I = V / R, and the electrical power (pW) using the formula P = V x I.

[0298] A power curve was obtained for an electrochemically activated hagfish mucus film ([Fig 4], panel (A)).

[0299] The curve shows that a resistance of 31 k is the load that delivers the maximum power.

[0300] An electrochemically activated hagfish mucus film was prepared as described above. The film was placed in a humid atmosphere (85% RH) and connected to a 31 kΩ resistor. A voltmeter was used to monitor the change in potential over time.

[0301] A discharge curve in a 31 kOhms resistance was obtained which corresponds to the load allowing the maximum power to be delivered ([Fig 4], panel (B)). List of documents cited

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[0303] Boni L, Fischer P, Bôcker L, Kuster S, Rühs PA. Hagfish slime and mucin flow properties and their implications for defense. SciRep. 2016;6:30371. Published 2016 Jul 27. doi:10.1038 / srep30371

[0304] Boni LJ, Sanchez-Ferrer A, Widmer M, et al. Structure and Nanomechanics of Dry and Hydrated Intermediate Filament Films and Fibers Produced from Hagfish Slime Fibers. ACS Appl Mater Interfaces . 2018;10(47):40460-40473. doi:10.1021 / acsami.8bl7166

[0305] Fu J, Guerette PA, Miserez A. Self-Assembly of Recombinant Hagfish Thread Keratins Amenable to a Strain-Induced a-Helix to P-Sheet Transition. Biomacromolecules. 2015 ; 16(8) :2327-2339. Doi :10.1021 / acs.biomac.5b00552

[0306] Fudge DS, Gardner KH, Forsyth VT, Riekel C, Gosline JM. The mechanical properties of hydrated intermediate filaments : insights from hagfish slime threads. Biophys J. 2003 ;85(3) :2015-2027. Doi :10.1016 / S0006-3495(03)74629-3

[0307] Litvinov RI, Faizullin DA, Zuev YF, Weisel JW. The a-helix to P-sheet transition in stretched and compressed hydrated fibrin clots. Biophys J. 2012 ; 103(5) : 1020-1027. Doi : 10.1016 / j.bpj.2012.07.046

[0308] Oliveira PE, Chen D, Bell BE, et al. The next generation of protein super-fibres: robust recombinant production and recovery of hagfish intermediate filament proteins with fibre spinning and mechanical-structural characterizations. Microb Biotechnol. 2021;14(5):1976- 1989. doi:10.1111 / 1751-7915.13869

[0309] Shurer CR, Wang Y, Feeney E, et al. Stable recombinant production of codon- scrambled lubricin and mucin in human cells. Biotechnol Bioeng. 2019; 116(6): 1292-1303. doi: 10.1002 / bit.26940

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Claims

DEMANDS

1. A process for preparing an electrochemically activated material, said material comprising hydronium ion-conducting amyloid fibers and glycosylated proteins, said process comprising at least the steps of: (a) to bring at least a part of said material into contact with water vapor, (b) electrolyze at least a portion of the water vapor in contact with said material, and (c) obtain an activated material.

2. A method according to claim 1, wherein the water vapor comes from a humid and neutral atmosphere.

3. A method according to claim 2, wherein the humid atmosphere comprises a relative humidity ranging from at least 60 to 100%.

4. A method according to any one of claims 1 to 3, wherein hydronium ion-conducting amyloid fibers are obtained from intermediate filaments.

5. A method according to any one of claims 1 to 5, wherein the glycosylated proteins are mucins.

6. A method according to any one of claims 1 to 6, wherein the material is obtained from a hydrogel produced by a fish selected from the fish of the family Myxinidae, in particular from a hydrogel produced by a Myxine glutinosa.

7. Activated material comprising hydronium ion-conducting amyloid fibers and glycosylated proteins and being activated by an electrochemical activation process.

8. Use of an activated material obtained by the process according to any one of claims 1 to 6 or of an activated material according to claim 7, to generate electrical energy from a humid surrounding atmosphere.

9. Electrical power generation device comprising: (a) at least one activated material obtained by the process according to any one of claims 1 to 6 or an activated material according to claim 7, (b) at least one pair of electrodes comprising a first electrode and a second electrode, said electrodes being electrically connected to said material, said material being intended to be exposed, at least partially, to a humid surrounding atmosphere.

10. Humidity sensor, humidity-sensitive electrical circuit breaker, or electrical charger comprising at least one device according to claim 9.

Images