Stable vitreous materials based on histidine, arginine and glutamic acid amino acids

Abstract

The invention relates to a vitreous material comprising at least one compound of formula (I) or a salt thereof, and at least one polar solvent in a total content ranging from 0.1% to 30% by weight relative to the total weight of the vitreous material. The invention also relates to a method for producing said vitreous material, and to the use thereof as glues, as cryoprotectants and / or thermal protectants for molecular and / or biological elements when temperatures are below the glass transition temperature of said vitreous material, and for moulding water-soluble glass structures with micro-to nano-precision. The invention also relates to a method for producing said vitreous material, and to the use thereof as glues, as cryoprotectants and / or thermal protectants for molecular and / or biological elements when temperatures are below the glass transition temperature of said vitreous material. The invention also relates to a microneedle comprising a vitreous material according to the invention.

Description

Technical Field

[0001] This invention relates to a vitreous material comprising at least one compound of formula (I) or a salt thereof, and at least one polar solvent in a total content of 0.1% to 30% by weight relative to the total weight of the vitreous material. The invention also relates to a method for preparing the vitreous material, and its use as an adhesive, as a cryoprotectant and / or thermal protectant for molecular and / or biological elements when the temperature is below the glass transition temperature of the vitreous material, and for molding water-soluble glass structures with micron to nanometer precision. The invention further relates to a microneedle comprising the vitreous material according to the invention, wherein the total content of the at least one polar solvent is greater than or equal to 0.1% and less than 10% by weight relative to the total weight of the vitreous material. Background Technology

[0002] Glassy materials like silica glass are composed of molecular networks linked by covalent bonds. In contrast, some glassy materials are formed from molecules or polymers linked by non-covalent interactions. These are called supramolecular glasses. Among these, some low-molecular-weight supramolecular glasses are noteworthy because they are easier to purify than polymers. Furthermore, their structures can be more easily modified to tune the material's properties. However, they tend to have lower glass stability and therefore crystallize more quickly over time. This drawback hinders their application in fields requiring long-lived amorphous phases, such as organic electronics, photonics, and drug delivery.

[0003] Vitreous materials made from biological or biocompatible molecules are rare. Among glasses made from biomolecules, the most common molecules are sugars, such as sucrose or trehalose. These materials have been used in nutrition, pharmaceutical formulations, cryoprotection, and, in rare cases, as encapsulation media for active ingredients and in the formation of soluble microneedles for transdermal or intradermal administration. Intradermal administration may be superior to subcutaneous administration, which can be painful and impractical for patients. Furthermore, using microneedles as drug carriers allows for the controlled release of bioactive molecules. However, the biocompatibility and solubility of non-biopolymer-based microneedles remain major obstacles to their development. In addition, the inorganic monomers used are often not bioavailable.

[0004] On March 17, 2023, Xing Ruirui et al. disclosed examples of bio-derived glasses manufactured using bio-derived amino acids or peptides through a heat-quenching process. However, their examples of vitreous materials were limited to peptides and amino acids with specific C-terminal modifications, amino acids modified with acetyl (Ac-) and 9-fluorenylmethoxycarbonyl (Fmoc-) groups, and amino acids and peptides modified with benzyloxycarbonyl (Cbz-) groups.

[0005] Therefore, there is an urgent need to develop a novel glassy material based on natural molecules that exhibits high biocompatibility, ease of customization, and a time-stable glass structure.

[0006] The inventors of this invention have surprisingly discovered a novel vitreous material made from amino acids, thus exhibiting superior biocompatibility. The vitreous nature of this material allows for precise shaping and the creation of sharper edges to improve the penetration of microneedles. A sharp edge refers to an edge with a tip as low as 300 nm. The vitreous material according to the invention is also water-soluble and possesses a time-stable supramolecular glass structure, particularly stable for at least one week, or even at least one month, or even at least six months, or even longer, up to at least one year, even at a low molecular weight, thereby allowing it to be used as a long-lived amorphous phase in a variety of applications. The vitreous material according to the invention comprises: a) at least one compound of formula (I) or a salt thereof, X1-B-X2 (Equation (I)) in, - X1 and X2 may be the same or different, representing an amino acid selected from histidine (L-His or D-His), glutamic acid (L-Glu or D-Glu), arginine (L-Arg or D-Arg), lysine (L-Lys or D-Lys), aspartic acid (L-Asp or D-Asp), serine (L-Ser or D-Ser), threonine (L-Thr or D-Thr), glutamine (L-Gln or D-Gln), asparagine (L-Asn or D-Asn), tyrosine (L-Tyr or D-Tyr), glycine (L-Gly or D-Gly), citrulline (L-Cit or D-Cit), ornithine (L-Orn or D-Orn), and cysteine ​​(L-Cys or D-Cys), or its derivatives, and methionine. Sulfoxide (L-Met-SO or D-Met-SO); preferably selected from histidine (L-His or D-His), glutamic acid (L-Glu or D-Glu), arginine (L-Arg or D-Arg), lysine (L-Lys or D-Lys), aspartic acid (L-Asp or D-Asp), serine (L-Ser or D-Ser), threonine (L-Thr or D-Thr), glutamine (L-Gln or D-Gln), asparagine (L-Asn or D-Asn), tyrosine (L-Tyr or D-Tyr), glycine (L-Gly or D-Gly), citrulline (L-Cit or D-Cit), ornithine (L-Orn or D-Orn), and cysteine ​​(L-Cys or D-Cys); - At least one of X1 and X2 is selected from histidine (L-His or D-His), arginine (L-Arg or D-Arg), and glutamic acid (L-Glu or D-Glu), or derivatives thereof; preferably selected from histidine (L-His or D-His), arginine (L-Arg or D-Arg), and glutamic acid (L-Glu or D-Glu); more preferably selected from histidine (L-His or D-His) and glutamic acid (L-Glu or D-Glu); - B is absent, or represents a straight-chain sequence of an additional amino acid or at least two identical or different additional amino acids, which may be the same as or different from X1 and X2; - Optionally, at least one amino acid of the compound of formula (I) is connected to another non-adjacent amino acid of the compound of formula (I) via an intramolecular bridge, preferably via a disulfide bond; The conditions are: - The compound of formula (I) contains at least 33% of acidic, basic or polar uncharged amino acids, based on amino acids; - When X1 and / or X2 represent lysine (L-Lys or D-Lys) or arginine (L-Arg or D-Arg), B must be present; and - The compound of formula (I) is different from the homopolymer of poly-γ-glutamic acid; and b) At least one polar solvent, in a total content ranging from 0.1% to 30% by weight relative to the total weight of the vitreous material.

[0007] Furthermore, the vitreous material according to the invention is versatile because it can be viscoelastic or solid, depending on the total content of the at least one polar solvent present in the vitreous material. By weight, when the total content of the at least one polar solvent ranges from 10% to 30% relative to the total weight of the vitreous material, the vitreous material is viscoelastic, exhibiting self-healing properties. When this viscoelastic vitreous material is stretched at low speeds, it can form fibers. It can also be used as a water-soluble adhesive when dry. When this viscoelastic vitreous material is stretched at high speeds, it solidifies and can be used to form microneedles or rods. By weight, when the total content of the at least one polar solvent is greater than or equal to 0.1% and less than 10% relative to the total weight of the vitreous material, the vitreous material is solid. In this case, it can be used to mold water-soluble glass structures with micron to nanometer precision, such as microneedles, hooks, pointed microspheres, finely granulated powders, and optical lenses, or it can be spread as nano-precision thin films by spin coating. When the temperature is below the glass transition temperature of the vitreous material, it can be used as a cryoprotectant and / or thermal protectant for molecular and / or biological elements. The material can be stored at ambient temperature and humidity. Preferably, for better preservation and storage, it can be stored in a dry and cool environment away from light. Summary of the Invention

[0008] This invention relates to a vitreous material comprising: a) at least one compound of formula (I) or a salt thereof, X1-B-X2 (Equation (I)) in, - X1 and X2 may be the same or different, representing an amino acid selected from histidine (L-His or D-His), glutamic acid (L-Glu or D-Glu), arginine (L-Arg or D-Arg), lysine (L-Lys or D-Lys), aspartic acid (L-Asp or D-Asp), serine (L-Ser or D-Ser), threonine (L-Thr or D-Thr), glutamine (L-Gln or D-Gln), asparagine (L-Asn or D-Asn), tyrosine (L-Tyr or D-Tyr), glycine (L-Gly or D-Gly), citrulline (L-Cit or D-Cit), ornithine (L-Orn or D-Orn), and cysteine ​​(L-Cys or D-Cys), or its derivatives, and methionine. Sulfoxide (L-Met-SO or D-Met-SO); preferably selected from histidine (L-His or D-His), glutamic acid (L-Glu or D-Glu), arginine (L-Arg or D-Arg), lysine (L-Lys or D-Lys), aspartic acid (L-Asp or D-Asp), serine (L-Ser or D-Ser), threonine (L-Thr or D-Thr), glutamine (L-Gln or D-Gln), asparagine (L-Asn or D-Asn), tyrosine (L-Tyr or D-Tyr), glycine (L-Gly or D-Gly), citrulline (L-Cit or D-Cit), ornithine (L-Orn or D-Orn), and cysteine ​​(L-Cys or D-Cys); - At least one of X1 and X2 is selected from histidine (L-His or D-His), arginine (L-Arg or D-Arg), and glutamic acid (L-Glu or D-Glu), or derivatives thereof; preferably selected from histidine (L-His or D-His), arginine (L-Arg or D-Arg), and glutamic acid (L-Glu or D-Glu); more preferably selected from histidine (L-His or D-His) and glutamic acid (L-Glu or D-Glu); - B is absent, or represents a straight-chain sequence of an additional amino acid or at least two identical or different additional amino acids, which may be the same as or different from X1 and X2; - Optionally, at least one amino acid of the compound of formula (I) is connected to another non-adjacent amino acid of the compound of formula (I) via an intramolecular bridge, preferably via a disulfide bond; The conditions are: - The compound of formula (I) contains at least 33% of acidic, basic or polar uncharged amino acids, based on amino acids; - When X1 and / or X2 represent lysine (L-Lys or D-Lys) or arginine (L-Arg or D-Arg), B must be present; and - The compound of formula (I) is different from the homopolymer of poly-γ-glutamic acid; and b) At least one polar solvent, in a total content ranging from 0.1% to 30% by weight relative to the total weight of the vitreous material.

[0009] According to one embodiment, the vitreous material comprises: a) at least one compound of formula (I) or a salt thereof, X1-B-X2 (Equation (I)) in, - X1 and X2 may be the same or different, representing an amino acid selected from histidine (L-His or D-His), glutamic acid (L-Glu or D-Glu), arginine (L-Arg or D-Arg), lysine (L-Lys or D-Lys), aspartic acid (L-Asp or D-Asp), serine (L-Ser or D-Ser), threonine (L-Thr or D-Thr), glutamine (L-Gln or D-Gln), asparagine (L-Asn or D-Asn), tyrosine (L-Tyr or D-Tyr), glycine (L-Gly or D-Gly), citrulline (L-Cit or D-Cit), and cysteine ​​(L-Cys or D-Cys), or derivatives thereof; - At least one of X1 and X2 is selected from histidine (L-His or D-His), arginine (L-Arg or D-Arg) and glutamic acid (L-Glu or D-Glu), or derivatives thereof; - B is absent, or represents a straight-chain sequence of an additional amino acid or at least two identical or different additional amino acids, which may be the same as or different from X1 and X2; The conditions are: - The compound of formula (I) contains at least 33% of acidic, basic or polar uncharged amino acids, based on amino acids; - When X1 and / or X2 represent lysine (L-Lys or D-Lys) or arginine (L-Arg or D-Arg), B must be present; and - The compound of formula (I) is different from the homopolymer of poly-γ-glutamic acid; and b) At least one polar solvent, in a total content ranging from 0.1% to 30% by weight relative to the total weight of the vitreous material.

[0010] Advantageously, at least one amino acid of the compound of formula (I) is linked to another non-adjacent amino acid of the compound of formula (I) via an intramolecular bridge. The intramolecular bridge according to the invention differs from a cyclic structure.

[0011] Advantageously, the glass transition temperature of the glassy material is in the range of 50°C to 150°C, preferably 70°C to 130°C.

[0012] Advantageously, the at least one polar solvent is selected from water, polar organic solvents and mixtures thereof; preferably selected from water, acetone, dimethyl sulfoxide and mixtures thereof; more preferably, the polar solvent is water.

[0013] In one embodiment, the total content of the at least one polar solvent, by weight, ranges from 10% to 30% relative to the total weight of the vitreous material.

[0014] In another embodiment, the total content of the at least one polar solvent, by weight, is greater than or equal to 0.1% and less than 10% relative to the total weight of the vitreous material.

[0015] Advantageously, X1 and X2 may be the same or different, representing a combination of histidine (L-His or D-His), glutamic acid (L-Glu or D-Glu), arginine (L-Arg or D-Arg), lysine (L-Lys or D-Lys), aspartic acid (L-Asp or D-Asp), serine (L-Ser or D-Ser), threonine (L-Thr or D-Thr), glutamine (L-Gln or D-Gln), asparagine (L-Asn or D-Asn), tyrosine (L-Tyr or D-Tyr), glycine (L-Gly or D-Gly), and citrulline. Amino acids of L-Cit or D-Cit, ornithine (L-Orn or D-Orn) and cysteine ​​(L-Cys or D-Cys); preferably selected from histidine (L-His or D-His), arginine (L-Arg or D-Arg) and glutamic acid (L-Glu or D-Glu), ornithine; more preferably selected from histidine (L-His or D-His), arginine (L-Arg or D-Arg) and glutamic acid (L-Glu or D-Glu), and even more preferably selected from histidine (L-His or D-His) and glutamic acid (L-Glu or D-Glu).

[0016] In another embodiment, X1 and X2 may be the same or different, representing a combination selected from histidine (L-His or D-His), glutamic acid (L-Glu or D-Glu), arginine (L-Arg or D-Arg), lysine (L-Lys or D-Lys), aspartic acid (L-Asp or D-Asp), serine (L-Ser or D-Ser), threonine (L-Thr or D-Thr), glutamine (L-Gln or D-Gln), and asparagine (L-Asn or D-Asn). The amino acids are selected from L-Asn, tyrosine (L-Tyr or D-Tyr), glycine (L-Gly or D-Gly), citrulline (L-Cit or D-Cit), and cysteine ​​(L-Cys or D-Cys); preferably selected from histidine (L-His or D-His), arginine (L-Arg or D-Arg), and glutamic acid (L-Glu or D-Glu); more preferably selected from histidine (L-His or D-His) and glutamic acid (L-Glu or D-Glu).

[0017] In one embodiment, B represents a linear sequence of at least two identical or different additional amino acids, which may be the same as or different from X1 and X2, and the number of additional amino acids in the linear sequence of B ranges from 2 to 200; preferably from 2 to 150; more preferably from 2 to 100.

[0018] In another embodiment, B represents a linear sequence of at least two identical or different additional amino acids, which may be the same as or different from X1 and X2, and the number of additional amino acids in the linear sequence of B ranges from 201 to 700; preferably from 201 to 634.

[0019] In one embodiment, the additional amino acid of B is selected from alanine (L-Ala or D-Ala), arginine (L-Arg or D-Arg), asparagine (L-Asn or D-Asn), aspartic acid (L-Asp or D-Asp), cysteine ​​(L-Cys or D-Cys), glutamic acid (L-Glu or D-Glu), glutamine (L-Gln or D-Gln), glycine (L-Gly or D-Gly), histidine (L-His or D-His) or derivatives thereof, isoleucine (L-Ile or D-Ile), leucine (L-Leu or D-Leu), and lysine (L-Lys or D-L ... ys), methionine (L-Met or D-Met), phenylalanine (L-Phe or D-Phe), proline (L-Pro or D-Pro), pyrrolidone (L-Pyl or D-Pyl), selenocysteine ​​(L-Sec or D-Sec), serine (L-Ser or D-Ser), threonine (L-Thr or D-Thr), tryptophan (L-Trp or D-Trp), tyrosine (L-Tyr or D-Tyr), valine (L-Val or D-Val), carnitine (L-carnitine or D-carnitine), γ-aminobutyric acid, hydroxyproline (Hyp), methionine sulfoxide (L-Met-SO or D- Met-SO), selenomethionine (L-SeMet or D-SeMet), citrulline (L-Cit or D-Cit), ornithine (L-Orn or D-Orn), β-alanine, α-aminoisobutyric acid (Aib), α-aminobutyric acid (L-Abu or D-Abu), 3-aminomethylbenzoic acid, anthranilic acid, high arginine (L-Har or D-Har), δ-hydroxylysine (Hyl), 3-mercaptophenylalanine (L-3-mercaptophenylalanine or D-3-mercaptophenylalanine), 2-hydroxyphenylalanine (L-2-hydroxyphenylalanine or D-2-hydroxyphenylalanine), 3-hydroxyphenylalanine (L-3-hydroxyphenylalanine) β-(2-pyridyl)-alanine (L-Phg or D-Phg), β-(3-pyridyl)-alanine (L-2Pal or D-2Pal), β-(3-pyridyl)-alanine (L-3Pal or D-3Pal), 4-methyl-phenylalanine (L-4-methyl-phenylalanine or D-4-methyl-phenylalanine), 4-amino-phenylalanine (L-4-amino-phenylalanine or D-4-amino-phenylalanine), 2,3-diaminopropionic acid (L-Dap or D-Dap), 2,4-diaminobutyric acid (L-Dab or D-Dab), 3,4-Dihydroproline (L-Dhp or D-Dhp), thioproline (L-thioproline or D-thioproline), α-methylproline (L-α-methylproline or D-α-methylproline), pipercoic acid (L-pipercoic acid or D-pipercoic acid), α-aminohexanoic acid (L-Aad or D-Aad), 2-aminopimelic acid (L-2-aminopimelic acid or D-2-aminopimelic acid), 2-aminopimelic acid (L-2-aminopimelic acid or D-2-aminopimelic acid), α-aminooctanoic acid (L-ASU or D-ASU), and 3,4-dihydroxyphenylalanine (L-DOPA or D-D-D-dihydroxyproline) -DOPA), 4-(phenylazo)-phenylglycine (L-4-(phenylazo)-phenylglycine or D-4-(phenylazo)-phenylglycine), (4-phenylazo)-phenylalanine (L-(4-phenylazo)-phenylalanine or D-(4-phenylazo)-phenylalanine), (4-(4'-tert-butoxycarbonyl)phenylazo)phenylalanine (L-(4'-tert-butoxycarbonyl)phenylazo)phenylalanine or D-(4'-tert-butoxycarbonyl)phenylazo)phenylalanine), azobenzyl-lysine (L-azobenzyl-lysine or D-azobenzyl-lysine), or derivatives thereof.

[0020] Advantageously, the additional amino acid of B is selected from alanine (L-Ala or D-Ala), arginine (L-Arg or D-Arg), asparagine (L-Asn or D-Asn), aspartic acid (L-Asp or D-Asp), cysteine ​​(L-Cys or D-Cys), glutamic acid (L-Glu or D-Glu), glutamine (L-Gln or D-Gln), glycine (L-Gly or D-Gly), histidine (L-His or D-His) or derivatives thereof, isoleucine (L-Ile or D-Ile), leucine (L-Leu or D-Leu), lysine (L-Lys or D-Ala), and arginine (L-Arg or D-Arg). D-Lys, methionine (L-Met or D-Met), phenylalanine (L-Phe or D-Phe), proline (L-Pro or D-Pro), pyrrolidone (L-Pyl or D-Pyl), selenocysteine ​​(L-Sec or D-Sec), serine (L-Ser or D-Ser), threonine (L-Thr or D-Thr), tryptophan (L-Trp or D-Trp), tyrosine (L-Tyr or D-Tyr), valine (L-Val or D-Val), carnitine (L-carnitine or D-carnitine), γ-aminobutyric acid, hydroxyproline (Hyp), selenomethionine ( L-SeMet or D-SeMet), citrulline (L-Cit or D-Cit), ornithine (L-Orn or D-Orn), β-alanine, α-aminoisobutyric acid (Aib), α-aminobutyric acid (L-Abu or D-Abu), 3-aminomethylbenzoic acid, anthranilic acid, arginine (L-Har or D-Har), δ-hydroxylysine (Hyl), 3-mercaptophenylalanine (L-3-mercaptophenylalanine or D-3-mercaptophenylalanine), 2-hydroxyphenylalanine (L-2-hydroxyphenylalanine or D-2-hydroxyphenylalanine), 3-hydroxyphenylalanine (L-3-hydroxyphenylalanine or D-... 3-Hydroxyphenylalanine), phenylglycine (L-Phg or D-Phg), homophenylalanine (L-Hph or D-Hph), β-(2-pyridyl)-alanine (L-2Pal or D-2Pal), β-(3-pyridyl)-alanine (L-3Pal or D-3Pal), 4-methyl-phenylalanine (L-4-methyl-phenylalanine or D-4-methyl-phenylalanine), 4-amino-phenylalanine (L-4-amino-phenylalanine or D-4-amino-phenylalanine), 2,3-diaminopropionic acid (L-Dap or D-Dap), 2,4-diaminobutyric acid (L-Dab or D-Dab), 3,4-Dihydroproline (L-Dhp or D-Dhp), thioproline (L-thioproline or D-thioproline), α-methylproline (L-α-methylproline or D-α-methylproline), pipercoic acid (L-pipercoic acid or D-pipercoic acid), α-aminohexanoic acid (L-Aad or D-Aad), 2-aminopimelic acid (L-2-aminopimelic acid or D-2-aminopimelic acid), 2-aminopimelic acid (L-2-aminopimelic acid or D-2-aminopimelic acid), α-aminooctanoic acid (L-ASU or D-ASU), and 3,4-dihydroxyphenylalanine (L-DOPA or D-D-D-dihydroxyproline) -DOPA), 4-(phenylazo)-phenylglycine (L-4-(phenylazo)-phenylglycine or D-4-(phenylazo)-phenylglycine), (4-phenylazo)-phenylalanine (L-(4-phenylazo)-phenylalanine or D-(4-phenylazo)-phenylalanine), (4-(4'-tert-butoxycarbonyl)phenylazo)phenylalanine (L-(4'-tert-butoxycarbonyl)phenylazo)phenylalanine or D-(4'-tert-butoxycarbonyl)phenylazo)phenylalanine), azobenzyl-lysine (L-azobenzyl-lysine or D-azobenzyl-lysine), or derivatives thereof.

[0021] Advantageously, the vitreous material further comprises at least one additional component that is different from the at least one compound of formula (I) or its salt, and also different from the at least one polar solvent, the additional component being selected from active ingredients, pH control agents, surfactants, transition metal salts or post-transition metal salts and mixtures thereof.

[0022] The present invention also relates to a method for preparing a vitreous material according to the present invention, the method comprising the following steps: i) Dissolving at least one compound of formula (I) or a salt thereof, and optionally at least one additional component, in at least one polar solvent, wherein the total amount of said at least one polar solvent is sufficient to completely dissolve the compound to form a single-phase solution. ii) Dry the single-phase solution of step i) to partially remove the at least one polar solvent until the total content of the at least one polar solvent by weight ranges from 0.1% to 30% relative to the total weight of the vitreous material, to obtain the vitreous material according to the invention, then iii) Optionally, when the total content of the at least one polar solvent in the vitreous material obtained in step ii) is between 10% and 30% by weight relative to the total weight of the vitreous material, the material is stretched to obtain fibers, rods, or microneedles.

[0023] Furthermore, the present invention relates to a method for preparing a vitreous material according to the present invention, wherein, by weight, the total content of the at least one polar solvent is greater than or equal to 0.1% and less than 10% relative to the total weight of the vitreous material, and the method comprises the following steps: i) A mixture of at least one compound of formula (I) or a salt thereof, and optionally at least one additional ingredient, ii) Heating the mixture from step i) until the mixture melts to obtain a molten material, wherein the heating temperature is greater than or equal to the glass transition temperature of at least one compound of formula (I) or a salt thereof, then iii) Cool the molten material obtained in step ii) to ambient temperature to obtain the vitreous material according to the invention, wherein the total content of the at least one polar solvent is greater than or equal to 0.1% and less than 10% by weight relative to the total weight of the vitreous material.

[0024] The present invention also relates to the use of a vitreous material according to the invention, wherein the total content of the at least one polar solvent, by weight, ranges from 10% to 30% relative to the total weight of the vitreous material, as an adhesive.

[0025] The present invention also relates to the use of the vitreous material according to the invention, wherein the total content of the at least one polar solvent, by weight, ranges from 0.1% to 30% relative to the total weight of the vitreous material, and is used as a cryoprotectant and / or thermal protectant for molecular and / or biological elements when the temperature is below the glass transition temperature of the vitreous material.

[0026] Furthermore, the present invention relates to the use of a vitreous material according to the invention, wherein the total content of the at least one polar solvent is greater than or equal to 0.1% and less than 10% by weight relative to the total weight of the vitreous material, for molding water-soluble glass structures with micron to nanometer precision.

[0027] Finally, the present invention relates to a microneedle comprising the vitreous material of the present invention, wherein, by weight, the total content of the at least one polar solvent is greater than or equal to 0.1% and less than 10% relative to the total weight of the vitreous material.

[0028] definition In this invention, the following terms have the following meanings: "Ambient temperature" refers to a temperature ranging from 20°C to 25°C.

[0029] "Ambient humidity" refers to a relative humidity ranging from 20% to 50%.

[0030] "Acidic amino acids" refers to amino acids with acidic side chains. In this invention, the acidic amino acids are preferably selected from aspartic acid (L-Asp or D-Asp) and glutamic acid (L-Glu or D-Glu), or their derivatives; more preferably selected from aspartic acid (L-Asp or D-Asp) and glutamic acid (L-Glu or D-Glu).

[0031] "Active ingredient" refers to photo-switching molecules, pigments, organic compounds with optical effects, cryoprotectants, thermal protectants, molecules or biological elements that require cryoprotection or thermal protection, or any ingredient that provides biological activity or other direct effects in the diagnosis, cure, relief, treatment or prevention of disease, or affects the structure or any function of the human or animal body.

[0032] "Amino acid" refers to an organic compound containing both a carboxylic acid (COOH) group and an amino group. The amino acid can be α- (i.e., the carboxylic acid group and the amino group are located on adjacent carbon atoms) or β- (i.e., the amino group is attached to the second carbon atom of the carboxylic acid group). The amino acid can have an L-configuration or a D-configuration. In this invention, the amino acid "AA" with the L-configuration will be referred to as "L-AA" or simply "AA" by default, while the amino acid "AA" with the D-configuration will always be referred to as "D-AA" or "AA". d In this invention, the term "amino acid" includes standard amino acids, such as histidine or glutamic acid, as well as modified versions of said standard amino acids (referred to as "derivatives").

[0033] "Basic amino acids" refer to amino acids with basic side chains. In this invention, the basic amino acids are preferably selected from histidine (L-His or D-His), arginine (L-Arg or D-Arg), and lysine (L-Lys or D-Lys), or their derivatives; more preferably selected from histidine (L-His or D-His), arginine (L-Arg or D-Arg), and lysine (L-Lys or D-Lys).

[0034] "consisting of" or "consist" should be interpreted as having a closed, non-inclusive meaning, limited only to the features following the term.

[0035] "Comprising" or "comprise" should be interpreted as having an open and inclusive meaning, but is not limited to this.

[0036] "Derivative" refers to a modified version of a standard amino acid. In one embodiment, the derivative of the standard amino acid is N-alkylated, N-acetylated, PEGylated, lipid-modified, and / or a β-version of the standard amino acid, and / or the α-carbon of the amino acid is linked to a structure selected from the following: (i) H2N-(CH2)-; (ii) H2N- (iii) H(acetyl)N-(CH2) 0-1 ;and (iv) H- or CH3-; The C-terminus and / or the N-terminus are modified to incorporate a blocking group, a type of group commonly used in peptide chemistry, to protect the peptide terminus from unwanted biochemical attacks and degradation in vivo; and / or the N-terminus are modified to incorporate a blocking group, a type of group commonly used in peptide chemistry, to protect the peptide terminus from unwanted biochemical attacks and degradation in vivo. Suitable conventional C-terminal modifications include, for example, forming a ketone or amide group on the carbon atom of the C-terminal carboxyl group, or forming an ester group on the oxygen atom of the carboxyl group. Suitable conventional N-terminal modifications include, for example, N-acetylation or N-alkylation, such as N-methylation. As for histidine (L-His or D-His), its derivatives further include 3,4-dihydroxyphenylalanine (L-DOPA or D-DOPA) and vinylimidazole, imidazole. The histidine (L-His or D-His) derivative may be selected from 3,4-dihydroxyphenylalanine (L-DOPA or D-DOPA), vinylimidazole, imidazole, 3-methyl-L-histidine, 3-methyl-D-histidine, deaminohistidine, 2-amino-histidine, β-hydroxy-histidine, homohistidine, α-fluoromethylhistidine, and α-methylhistidine.

[0037] "From X to Y" refers to the numerical range between X and Y, with the endpoints X and Y included within the range.

[0038] The glass transition temperature refers to the gradual and reversible transition of an amorphous material from a hard and relatively brittle glassy state to a viscous or rubbery state as temperature increases. Glass transition temperature can be measured, for example, by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), dilatational expansion (DIL), and thermomechanical analysis (TMA). The temperature is measured internally within the instrument.

[0039] "Glassy materials" refers to amorphous, non-crystalline materials that lack long-range structural order and exhibit a glass transition when heated to a liquid state.

[0040] "Fatty acid" refers to a carboxylic acid having a straight or branched chain, and a saturated, unsaturated, or polyunsaturated carbon chain. The number of carbon atoms in a fatty acid is preferably in the range of 10 to 20, more preferably 14 to 18.

[0041] In this invention, "lipidization" refers to the covalent bonding of fatty acid groups to molecules. This bonding can be achieved via spacer groups.

[0042] In this invention, "microneedle" refers to a micrometer-sized medical device used for the application of active ingredients in cosmetics or pharmaceuticals. For example, microneedles can be used for intraocular, vaginal, cardiac, vascular, gastrointestinal, cochlear, intradermal, and / or transdermal delivery of active ingredients.

[0043] "Polar uncharged amino acids" refers to amino acids with polar uncharged side chains. In this invention, the polar uncharged amino acids are preferably selected from serine (L-Ser or D-Ser), threonine (L-Thr or D-Thr), glutamine (L-Gln or D-Gln), asparagine (L-Asn or D-Asn), and cysteine ​​(L-Cys or D-Cys), or their derivatives; more preferably selected from serine (L-Ser or D-Ser), threonine (L-Thr or D-Thr), glutamine (L-Gln or D-Gln), asparagine (L-Asn or D-Asn), and cysteine ​​(L-Cys or D-Cys).

[0044] "PEGylation" refers to the covalent bonding of polyethylene glycol (PEG) polymer chains to molecules. This bonding can be achieved through spacer groups.

[0045] The "salt" of the compound of formula (I) of the present invention refers to the combination of the compound of formula (I) with a counterion selected to maintain electroneutrality.

[0046] A “sequence” refers to a series of at least two elements.

[0047] When referring to an amino acid, the term "side chain" refers to a chemical group attached to the α-carbon atom of a carboxylic acid for α-amino acids, or to a chemical group attached to the β-carbon atom of a carboxylic acid skeleton for β-amino acids; the chemical group is different from the amino functional group present on the α or β carbon atom.

[0048] A "spacer group" refers to a single covalent bond or a group containing a series of stable covalent bonds, typically comprising 1-40 multivalent atoms selected from the group consisting of C, N, O, S, and P, which covalently link two molecules together. The number of multivalent atoms in a spacer group can be, for example, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 25, 30, or more, up to 40 or more. Spacer groups can be straight-chain or non-straight-chain; some spacer groups have dangling side chains or dangling functional groups (or both). For example, spacer groups can be composed of alkyl groups, -C(O)NH-, -C(O)O-, -NH-, -S-, -O-, -C(O)-, -S(O). n The combination of groups, where n is 0, 1 or 2, -O-, 5 or 6-membered monocyclic rings and optional pendant functional groups, such as sulfonyl, hydroxyl and carboxyl groups.

[0049] "Stable over time" when referring to glassy materials means that the material retains its amorphous and amorphous properties when stored at ambient temperature and humidity for at least one month, more preferably at least six months, or even more preferably at least one year.

[0050] "Supramolecular glass" refers to glassy materials whose structure is formed through non-covalent interactions, preferably through hydrogen bonds. Attached Figure Description

[0051] Figure 1a A photograph showing the self-healing behavior of the fibers obtained after the glassy material obtained in step ii) of the first method for preparing a glassy material according to the present invention is stretched, broken and bonded together, wherein the stretching is carried out at a low stretching speed (i.e., 0.01 m / s to 0.3 m / s) and at an ambient humidity of 50% to 90%. Figure 1b A photograph showing the viscoelastic and self-stretching behavior of the fibers obtained after stretching in step ii) of the first method for preparing a vitreous material according to the present invention, wherein the stretching is carried out at a low stretching speed (i.e., 0.01 m / s to 0.3 m / s) and at an ambient humidity of 50% to 90%.

[0052] Figure 2 A photograph shows a borosilicate tube bonded to a Teflon block using the glassy material of Example 4.

[0053] Figure 3 A photograph showing tweezers holding the lens-shaped glass material of Example 21.

[0054] Figure 4 The scattering intensity of the vitreous material in Example 7 after one year of storage at ambient temperature and humidity, as obtained by wide-angle X-ray scattering analysis, is compared with the wide-angle (Å) value. -1 A graph showing the functional relationship between .

[0055] Figure 5 A) through C) show photographs of the vitreous materials of Examples 29, 15 and 34, respectively.

[0056] Figure 6 This shows a scanning electron microscope (SEM) image (scale bar: 1 µm) of a 300 nm thick section of the vitreous material from Example 21.

[0057] Figure 7 Images A) through C) show photographs of glassy materials from Examples 23, 25, and 30 molded into microneedles with a height of 600 µm.

[0058] Figure 8The material in Comparative Example 6, after being stored at ambient temperature and humidity for 12 hours, showed a scattering intensity obtained by wide-angle X-ray scattering analysis compared to the wide-angle (Å) scattering intensity. -1 A graph showing the functional relationship between .

[0059] Figure 9 This shows a photograph of a three-year-old glassy material (bead) from Example 25. Detailed Implementation

[0060] glassy materials This invention relates to a vitreous material comprising: a) at least one compound of formula (I) or a salt thereof, X1-B-X2 (Equation (I)) in, - X1 and X2 may be the same or different, representing an amino acid selected from histidine (L-His or D-His), glutamic acid (L-Glu or D-Glu), arginine (L-Arg or D-Arg), lysine (L-Lys or D-Lys), aspartic acid (L-Asp or D-Asp), serine (L-Ser or D-Ser), threonine (L-Thr or D-Thr), glutamine (L-Gln or D-Gln), asparagine (L-Asn or D-Asn), tyrosine (L-Tyr or D-Tyr), glycine (L-Gly or D-Gly), citrulline (L-Cit or D-Cit), ornithine (L-Orn or D-Orn), and cysteine ​​(L-Cys or D-Cys), or its derivatives, and methionine. Sulfoxide (L-Met-SO or D-Met-SO); preferably selected from histidine (L-His or D-His), glutamic acid (L-Glu or D-Glu), arginine (L-Arg or D-Arg), lysine (L-Lys or D-Lys), aspartic acid (L-Asp or D-Asp), serine (L-Ser or D-Ser), threonine (L-Thr or D-Thr), glutamine (L-Gln or D-Gln), asparagine (L-Asn or D-Asn), tyrosine (L-Tyr or D-Tyr), glycine (L-Gly or D-Gly), citrulline (L-Cit or D-Cit), ornithine (L-Orn or D-Orn), and cysteine ​​(L-Cys or D-Cys); - At least one of X1 and X2 is selected from histidine (L-His or D-His), arginine (L-Arg or D-Arg), and glutamic acid (L-Glu or D-Glu), or derivatives thereof; preferably selected from histidine (L-His or D-His), arginine (L-Arg or D-Arg), and glutamic acid (L-Glu or D-Glu); more preferably selected from histidine (L-His or D-His) and glutamic acid (L-Glu or D-Glu); - B is absent, or represents a straight-chain sequence of an additional amino acid or at least two identical or different additional amino acids, which may be the same as or different from X1 and X2; - Optionally, at least one amino acid of the compound of formula (I) is connected to another non-adjacent amino acid of the compound of formula (I) via an intramolecular bridge, preferably via a disulfide bond; The conditions are: - The compound of formula (I) contains at least 33% of acidic, basic or polar uncharged amino acids, based on amino acids; - When X1 and / or X2 represent lysine (L-Lys or D-Lys) or arginine (L-Arg or D-Arg), B must be present; and - The compound of formula (I) is different from the homopolymer of poly-γ-glutamic acid; and b) At least one polar solvent, in a total content ranging from 0.1% to 30% by weight relative to the total weight of the vitreous material.

[0061] In this invention, the term "additional amino acid" always refers to the amino acid of B when B is present.

[0062] According to the present invention, "a straight-chain sequence of at least two identical or different additional amino acids" can be understood as a short chain of at least two identical or different additional amino acids linked by peptide bonds.

[0063] In the sequence X1-B-X2 of the compound of formula (I), X1, B, and X2 are linked by peptide bonds in this order. If B is absent, then X1 and X2 in sequence X1-X2 are linked by peptide bonds.

[0064] Advantageously, the glass transition temperature (Tg) of the glassy material according to the invention ranges from 50°C to 150°C, preferably from 70°C to 130°C.

[0065] Preferably, the vitreous material according to the invention has maximum absorbance at a wavelength of 280 nm or less.

[0066] Advantageously, the glassy material according to the invention is soluble in the at least one polar solvent when the total content of the at least one polar solvent is greater than 30% relative to the total weight of the glassy material.

[0067] The vitreous material according to the invention is made of amino acids, thus exhibiting increased biocompatibility. It is also water-soluble.

[0068] Surprisingly, the glassy material according to the invention has a time-stable supramolecular glass structure, preferably stable for at least one week, more preferably one month, more preferably at least six months, and even more preferably at least one year.

[0069] At least one compound of formula (I) The total content of at least one compound of formula (I) or its salt relative to the total weight of the vitreous material is preferably 40% to 99.9%, more preferably 40% to 95%, and even more preferably 59% to 88%.

[0070] The compound of formula (I) comprises at least 33% of acidic, basic, or polar uncharged amino acids, particularly when B is present. Preferably, the compound of formula (I) comprises at least 39% of acidic, basic, or polar uncharged amino acids. More preferably, the compound of formula (I) comprises at least 50% of acidic, basic, or polar uncharged amino acids.

[0071] The compound of formula (I) according to the invention comprises at least one terminal (X1 or X2) selected from histidine (L-His or D-His), arginine (L-Arg or D-Arg), and glutamic acid (L-Glu or D-Glu), or derivatives thereof; preferably selected from histidine (L-His or D-His), arginine (L-Arg or D-Arg), and glutamic acid (L-Glu or D-Glu); more preferably selected from histidine (L-His or D-His) and glutamic acid (L-Glu or D-Glu). The vitreous material according to this embodiment has been found to have a supramolecular glass structure stable for at least one month.

[0072] Preferably, the additional amino acid in B is selected from alanine (L-Ala or D-Ala), arginine (L-Arg or D-Arg), asparagine (L-Asn or D-Asn), aspartic acid (L-Asp or D-Asp), cysteine ​​(L-Cys or D-Cys), glutamic acid (L-Glu or D-Glu), glutamine (L-Gln or D-Gln), glycine (L-Gly or D-Gly), histidine (L-His or D-His) or its derivatives, isoleucine (L-Ile or D-Ile), leucine (L-Leu or D-Leu), and lysine (L-Lys or D-Lys). Methionine (L-Met or D-Met), Phenylalanine (L-Phe or D-Phe), Proline (L-Pro or D-Pro), Pyrrolidone (L-Pyl or D-Pyl), Selenocysteine ​​(L-Sec or D-Sec), Serine (L-Ser or D-Ser), Threonine (L-Thr or D-Thr), Tryptophan (L-Trp or D-Trp), Tyrosine (L-Tyr or D-Tyr), Valine (L-Val or D-Val), Carnitine (L-Carnitine or D-Carnitine), Gamma-aminobutyric acid, Hydroxyproline (Hyp), Methionine sulfoxide (L-Met-SO or D-Met-SO) t-SO), selenomethionine (L-SeMet or D-SeMet), citrulline (L-Cit or D-Cit), ornithine (L-Orn or D-Orn), β-alanine, α-aminoisobutyric acid (Aib), α-aminobutyric acid (L-Abu or D-Abu), 3-aminomethylbenzoic acid, anthranilic acid, arginine (L-Har or D-Har), δ-hydroxylysine (Hyl), 3-mercaptophenylalanine (L-3-mercaptophenylalanine or D-3-mercaptophenylalanine), 2-hydroxyphenylalanine (L-2-hydroxyphenylalanine or D-2-hydroxyphenylalanine), 3-hydroxyphenylalanine (L-3-hydroxyphenylalanine) Phenylalanine or D-3-hydroxyphenylalanine), phenylglycine (L-Phg or D-Phg), homophenylalanine (L-Hph or D-Hph), β-(2-pyridyl)-alanine (L-2Pal or D-2Pal), β-(3-pyridyl)-alanine (L-3Pal or D-3Pal), 4-methyl-phenylalanine (L-4-methyl-phenylalanine or D-4-methyl-phenylalanine), 4-amino-phenylalanine (L-4-amino-phenylalanine or D-4-amino-phenylalanine), 2,3-diaminopropionic acid (L-Dap or D-Dap), 2,4-diaminobutyric acid (L-Dab or D-Dab), 3,4-Dihydroproline (L-Dhp or D-Dhp), thioproline (L-thioproline or D-thioproline), α-methylproline (L-α-methylproline or D-α-methylproline), pipercoic acid (L-pipercoic acid or D-pipercoic acid), α-aminohexanoic acid (L-Aad or D-Aad), 2-aminopimelic acid (L-2-aminopimelic acid or D-2-aminopimelic acid), 2-aminopimelic acid (L-2-aminopimelic acid or D-2-aminopimelic acid), α-aminooctanoic acid (L-ASU or D-ASU), and 3,4-dihydroxyphenylalanine (L-DOPA or D-D-D-dihydroxyproline) -DOPA), 4-(phenylazo)-phenylglycine (L-4-(phenylazo)-phenylglycine or D-4-(phenylazo)-phenylglycine), (4-phenylazo)-phenylalanine (L-(4-phenylazo)-phenylalanine or D-(4-phenylazo)-phenylalanine), (4-(4'-tert-butoxycarbonyl)phenylazo)phenylalanine (L-(4'-tert-butoxycarbonyl)phenylazo)phenylalanine or D-(4'-tert-butoxycarbonyl)phenylazo)phenylalanine), azobenzyl-lysine (L-azobenzyl-lysine or D-azobenzyl-lysine), or derivatives thereof.

[0073] More preferably, the additional amino acid of B is selected from alanine (L-Ala or D-Ala), arginine (L-Arg or D-Arg), asparagine (L-Asn or D-Asn), aspartic acid (L-Asp or D-Asp), cysteine ​​(L-Cys or D-Cys), glutamic acid (L-Glu or D-Glu), glutamine (L-Gln or D-Gln), glycine (L-Gly or D-Gly), histidine (L-His or D-His), and isoleucine (L-Ile or D-Gly). D-Ile), leucine (L-Leu or D-Leu), lysine (L-Lys or D-Lys), phenylalanine (L-Phe or D-Phe), proline (L-Pro or D-Pro), serine (L-Ser or D-Ser), threonine (L-Thr or D-Thr), tryptophan (L-Trp or D-Trp), tyrosine (L-Tyr or D-Tyr), valine (L-Val or D-Val), and citrulline (L-Cit or D-Cit), or their derivatives.

[0074] Even more preferably, the additional amino acid of B is selected from alanine (L-Ala or D-Ala), arginine (L-Arg or D-Arg), asparagine (L-Asn or D-Asn), aspartic acid (L-Asp or D-Asp), cysteine ​​(L-Cys or D-Cys), glutamic acid (L-Glu or D-Glu), glutamine (L-Gln or D-Gln), glycine (L-Gly or D-Gly), histidine (L-His or D-His), and isoleucine (L-... The following amino acids are listed: Ile or D-Ile, leucine (L-Leu or D-Leu), lysine (L-Lys or D-Lys), phenylalanine (L-Phe or D-Phe), proline (L-Pro or D-Pro), serine (L-Ser or D-Ser), threonine (L-Thr or D-Thr), tryptophan (L-Trp or D-Trp), tyrosine (L-Tyr or D-Tyr), valine (L-Val or D-Val), and citrulline (L-Cit or D-Cit).

[0075] The compound of formula (I) is preferably selected from His-His (H2), His-Ser (HS), His-Glu (HE), His-His-His (H3), His-His-Lys (HHK), His d -His-Lys(H dHK), Lys-His-His (KHH), His-Lys-His (HKH), Lys-Lys-His (KKH), His-Lys-Lys (HKK), His-His-Cys (HHC), His-His-Arg (HHR), His-His-His-His (H4), His-Gly-His-Lys (HGHK), His-Lys-Lys-His (HKKH), His-His-His-Lys (HHHK), His-His-His-His-His (H5), His-His-Glu-His-His (HHEHH), His-His-Arg-His-His (HHRHH), His-Lys-Lys-Lys-His (HKKKH), His-His-Cit-His-His (HHCitHH), His-His-His-His-His-His (H6), His-His-His-His-His-His-His (H7), His-His-His-Cys-Tyr-Ile-Gln-Asn-Cys-Pro-Leu-Gly-His-His-His (HHHCYIQNCPLGHHH) single disulfide bridge, His-His-His-His-His-His-His-His-His-His (H10), His-Ala-Glu-Gly-Thr-Phe-Thr-Ser-Asp-Val-Ser-Ser-Tyr-Leu-Glu-Gly-Gln-Ala-Ala-Lys-Glu-Phe-Ile-Ala-Trp-Leu-Val-Lys-Gly-Arg-Gly (HAEGTFTSDVSSYLEGQAAKEFIAWLVKGRG), histidine copolymer 2500 g / mol, Glu-Glu (E2), Glu-Glu-Glu-Glu-Glu (E5), glutamic acid copolymer 15000 g / mol,and mixtures thereof, acetyl-Glu-Glu-Met-Gln-Arg-Arg-NH2 (acetyl-EEMQRR-NH2), acetyl-Glu-Glu-Met-Gln-Arg-Arg-Ala-Asp-NH2 (acetyl-EEMQRRAD-NH2), Arg-His-His-His (RHHH), Glu-His-His-His (EHHH), Arg-His-His-His-Arg (RHHHR), His -His-His-Ser (HHHS), Glu-Glu-Glu-Asp (EEED), His-His-His-Thr (HHHT), His-His-His-Gln (HHHQ), His-His- His-Orn, His-His-His-Cit, EEAAEAKYKAAKAYKKAAAKKAKYAAKAKAAYKKAKAEKAEE, His-His-His (HHH) {N-Me-His}. ,

[0076] The compound of formula (I) is more preferably selected from His-His (H2), His-Ser (HS), His-Glu (HE), His-His-His (H3), His-His-Lys (HHK), His d -His-Lys(H dHK), Lys-His-His (KHH), His-Lys-His (HKH), Lys-Lys-His (KKH), His-Lys-Lys (HKK), His-His-Cys (HHC), His-His-Arg (HHR), His-His-His-His (H4), His-Gly-His-Lys (HGHK), His-Lys-Lys-His (HKKH), His-His-His-Lys (HHHK), His-His-His-His-His (H5), His-His-Glu-His-His (HHEHH), His-His-Arg-His-His (HHRHH), His-Lys-Lys-Lys-His (HKKKH), His-His-Cit-His-His (HHCitHH), His-His-His-His-His-His (H6), His-His-His-His-His-His-His (H7), His-His-His-Cys-Tyr-Ile-Gln-Asn-Cys-Pro-Leu-Gly-His-His-His (HHHCYIQNCPLGHHH) single disulfide bridge, His-His-His-His-His-His-His-His-His-His (H10), His-Ala-Glu-Gly-Thr-Phe-Thr-Ser-Asp-Val-Ser-Ser-Tyr-Leu-Glu-Gly-Gln-Ala-Ala-Lys-Glu-Phe-Ile-Ala-Trp-Leu-Val-Lys-Gly-Arg-Gly (HAEGTFTSDVSSYLEGQAAKEFIAWLVKGRG), histidine copolymer 2500 g / mol, Glu-Glu (E2), Glu-Glu-Glu-Glu-Glu (E5), glutamic acid copolymer 15000 g / mol, and mixtures thereof.

[0077] Optionally, when B represents an additional amino acid or a straight-chain sequence of at least two identical or different additional amino acids (which may be the same as or different from X1 and X2), at least one amino acid (an amino acid of X1, X2, or B) contained in the compound of formula (I) is connected to another non-adjacent amino acid of the compound of formula (I) via an intramolecular bridge, preferably a disulfide bond. Preferably, the compound of formula (I) contains at least two cysteine ​​residues (L-Cys or D-Cys), and at least one cysteine ​​residue (L-Cys or D-Cys) is connected to another cysteine ​​residue (L-Cys or D-Cys) via a disulfide bond. Preferably, at least two amino acids contained in the compound of formula (I) are connected to another non-adjacent amino acid of the compound of formula (I) via an intramolecular bridge; more preferably, at least three amino acids contained in the compound of formula (I) are connected to another non-adjacent amino acid of the compound of formula (I) via an intramolecular bridge. In other words, the compound of formula (I) preferably contains at least two intramolecular bridges, more preferably at least three.

[0078] According to one embodiment, the compound of formula (I) is selected from the compound of formula (Ia): X1-B-X2 (Equation (Ia)), in, - X1 and X2 may be the same or different, representing an amino acid selected from histidine (L-His or D-His), arginine (L-Arg or D-Arg), and glutamic acid (L-Glu or D-Glu), or derivatives thereof; preferably selected from histidine (L-His or D-His), arginine (L-Arg or D-Arg), and glutamic acid (L-Glu or D-Glu); more preferably selected from histidine (L-His or D-His) and glutamic acid (L-Glu or D-Glu); - B is absent, or represents a straight-chain sequence of an additional amino acid or at least two identical or different additional amino acids, which may be the same as or different from X1 and X2; - Optionally, at least one amino acid of the compound of formula (I) is connected to another non-adjacent amino acid of the compound of formula (I) via an intramolecular bridge, preferably via a disulfide bond; The conditions are: - The compound of formula (Ia) contains at least 33% acidic, basic, or polar uncharged amino acids, based on amino acid content; and - When X1 and / or X2 represent arginine (L-Arg or D-Arg), B must be present; and - The compound of formula (Ia) is different from the homopolymer of poly-γ-glutamic acid.

[0079] The glassy material according to this embodiment has been found to have a stable supramolecular glass structure for at least 6 months.

[0080] According to this embodiment, the compound of formula (Ia) is preferably selected from His-His (H2), His-Glu (HE), His-His-His (H3), His-Lys-His (HKH), His-His-His-His (H4), His-Lys-Lys-His (HKKH), His-His-His-His-His (H5), His-His-Glu-His-His (HHEHH), His-His-Arg-His-His (HHRHH), and His-Lys-Lys-Lys-His (HKKKH). His-His-Cit-His-His (HHCitHH), His-His-His-His-His-His (H6), His-His-His-His-His-His-His (H7), His-His-His-Cys-Tyr-Ile-Gln-Asn-Cys-Pro-Leu-Gly-His-His-His (HHHCYIQNCPLGHHH) monodisulfide bridge, His-His-His-His-His-His-His-His-His-His (H10), histidine copolymer 2500 g / mol, Glu-Glu (E2), Glu-Glu-Glu-Glu-Glu (E5), glutamic acid copolymer 15000 g / mol, and mixtures thereof.

[0081] According to one embodiment, the compound of formula (I) is selected from the compounds of formula (Ib): X1-B-X2 (Equation (Ib)), in, - X1 and X2 are different, each representing a combination of histidine (L-His or D-His), glutamic acid (L-Glu or D-Glu), arginine (L-Arg or D-Arg), lysine (L-Lys or D-Lys), aspartic acid (L-Asp or D-Asp), serine (L-Ser or D-Ser), threonine (L-Thr or D-Thr), glutamine (L-Gln or D-Gln), asparagine (L-Asn or D-Asn), tyrosine (L-Tyr or D-Tyr), glycine (L-Gly or D-Gly), citrulline (L-Cit or D-Cit), and cysteine ​​(L-Cys or D-Cys). Amino acids, or their derivatives, preferably selected from histidine (L-His or D-His), glutamic acid (L-Glu or D-Glu), arginine (L-Arg or D-Arg), lysine (L-Lys or D-Lys), aspartic acid (L-Asp or D-Asp), serine (L-Ser or D-Ser), threonine (L-Thr or D-Thr), glutamine (L-Gln or D-Gln), asparagine (L-Asn or D-Asn), tyrosine (L-Tyr or D-Tyr), glycine (L-Gly or D-Gly), citrulline (L-Cit or D-Cit), and cysteine ​​(L-Cys or D-Cys). - At least one of X1 and X2 is selected from histidine (L-His or D-His), arginine (L-Arg or D-Arg), and glutamic acid (L-Glu or D-Glu), or derivatives thereof; preferably selected from histidine (L-His or D-His), arginine (L-Arg or D-Arg), and glutamic acid (L-Glu or D-Glu); more preferably selected from histidine (L-His or D-His) and glutamic acid (L-Glu or D-Glu); - B is absent, or represents a straight-chain sequence of an additional amino acid or at least two identical or different additional amino acids, which may be the same as or different from X1 and X2; - Optionally, at least one amino acid of the compound of formula (I) is connected to another non-adjacent amino acid of the compound of formula (I) via an intramolecular bridge, preferably via a disulfide bond; The conditions are: - The compound of formula (Ib) contains at least 33% acidic, basic, or polar uncharged amino acids, based on amino acid content; and - B must be present when X1 and / or X2 represent lysine (L-Lys or D-Lys) or arginine (L-Arg or D-Arg).

[0082] In other words, in this embodiment, the two ends X1 and X2 must be different from each other. The glassy material according to this embodiment has been found to have a supramolecular glass structure that is stable for at least one month.

[0083] According to this embodiment, the compound of formula (Ib) is preferably selected from His-Ser (HS), His-Glu (HE), His-His-Lys (HHK), His d -His-Lys(H d HK), Lys-His-His (KHH), Lys-Lys-His (KKH), His-Lys-Lys (HKK), His-His-Cys (HHC), His-His-Arg (HHR), His-Gly-His-Lys (HGHK), His-His-His-Lys (HHHK), His-Ala-Glu-Gly -Thr-Phe-Thr-Ser-Asp-Val-Ser-Ser-Tyr-Leu-Glu-Gly-Gln-Ala-Ala-Lys-Glu-Phe-Ile-Ala-Trp-Leu-Val-Lys-Gly-Arg-Gly (HAEGTFTSDVSSYLEGQAAKEFIAWLVKGRG), and mixtures thereof.

[0084] According to a first variant of this embodiment, one of X1 and X2 is histidine (L-His or D-His) or a derivative thereof, preferably histidine (L-His or D-His); the other of X1 and X2 is selected from glutamic acid (L-Glu or D-Glu), arginine (L-Arg or D-Arg), lysine (L-Lys or D-Lys), aspartic acid (L-Asp or D-Asp), serine (L-Ser or D-Ser), threonine (L-Thr or D-Thr), glutamine (L-Gln or D-Gln), asparagine (L-Asn or D-Asn), tyrosine (L-Tyr or D-Tyr), glycine (L-... Amino acids of Gly or D-Gly, citrulline (L-Cit or D-Cit) and cysteine ​​(L-Cys or D-Cys), or derivatives thereof; preferably selected from arginine (L-Arg or D-Arg), lysine (L-Lys or D-Lys), serine (L-Ser or D-Ser), threonine (L-Thr or D-Thr) and cysteine ​​(L-Cys or D-Cys), or derivatives thereof; more preferably selected from arginine (L-Arg or D-Arg) and lysine (L-Lys or D-Lys), or derivatives thereof; even more preferably selected from arginine (L-Arg or D-Arg) and lysine (L-Lys or D-Lys).

[0085] According to a second variant of this embodiment, one of X1 and X2 is glutamic acid (L-Glu or D-Glu) or a derivative thereof, preferably glutamic acid (L-Glu or D-Glu); the other of X1 and X2 is selected from histidine (L-His or D-His), arginine (L-Arg or D-Arg), lysine (L-Lys or D-Lys), aspartic acid (L-Asp or D-Asp), serine (L-Ser or D-Ser), threonine (L-Thr or D-Thr), glutamine (L-Gln or D-Gln), asparagine (L-Asn or D-Asn), tyrosine (L-Tyr or D-Tyr), glycine (L-Gly or D-Gly), citrulline (L-Cit or D-Gly), and glutamine (L-Gln or D-Gln). The amino acids X1 and X2 are aspartic acid (L-Asp or D-Asp) and cysteine ​​(L-Cys or D-Cys), or derivatives thereof; preferably selected from aspartic acid (L-Asp or D-Asp), serine (L-Ser or D-Ser), threonine (L-Thr or D-Thr), glutamine (L-Gln or D-Gln), asparagine (L-Asn or D-Asn), tyrosine (L-Tyr or D-Tyr), glycine (L-Gly or D-Gly) and cysteine ​​(L-Cys or D-Cys), or derivatives thereof; more preferably, the other of X1 and X2 is aspartic acid (L-Asp or D-Asp) or a derivative thereof; even more preferably, the other of X1 and X2 is aspartic acid (L-Asp or D-Asp).

[0086] According to a third variant of this embodiment, one of X1 and X2 is arginine (L-Arg or D-Arg) or a derivative thereof, preferably arginine (L-Arg or D-Arg); the other of X1 and X2 is selected from histidine (L-His or D-His), glutamic acid (L-Glu or D-Glu), lysine (L-Lys or D-Lys), aspartic acid (L-Asp or D-Asp), serine (L-Ser or D-Ser), threonine (L-Thr or D-Thr), glutamine (L-Gln or D-Gln), asparagine (L-Asn or D-Asn), tyrosine (L-Tyr or D-Tyr), glycine (L-Gly or D-Gly), citrulline (L-Cit or D-Gly), and citrulline (L-Cit or D-Gly). The amino acids X1 and X2 are aspartic acid (L-Asp or D-Asp) and cysteine ​​(L-Cys or D-Cys), or derivatives thereof; preferably selected from aspartic acid (L-Asp or D-Asp), serine (L-Ser or D-Ser), threonine (L-Thr or D-Thr), glutamine (L-Gln or D-Gln), asparagine (L-Asn or D-Asn), tyrosine (L-Tyr or D-Tyr), glycine (L-Gly or D-Gly) and cysteine ​​(L-Cys or D-Cys), or derivatives thereof; more preferably, the other of X1 and X2 is aspartic acid (L-Asp or D-Asp) or a derivative thereof; even more preferably, the other of X1 and X2 is aspartic acid (L-Asp or D-Asp).

[0087] According to one embodiment, the compound of formula (I) is selected from the compounds of formula (Ic): X1-X2 (Equation (Ic)), in, - X1 and X2 may be the same or different, representing a combination selected from histidine (L-His or D-His), glutamate (L-Glu or D-Glu), aspartic acid (L-Asp or D-Asp), serine (L-Ser or D-Ser), threonine (L-Thr or D-Thr), glutamine (L-Gln or D-Gln), asparagine (L-Asn or D-Asn), tyrosine (L-Tyr or D-Tyr), glycine (L-Gly or D-Gly), citrulline (L-Cit or D-Cit), and cysteine ​​(L-Cys or D-Cys). Amino acids, or their derivatives, preferably selected from histidine (L-His or D-His), glutamic acid (L-Glu or D-Glu), aspartic acid (L-Asp or D-Asp), serine (L-Ser or D-Ser), threonine (L-Thr or D-Thr), glutamine (L-Gln or D-Gln), asparagine (L-Asn or D-Asn), tyrosine (L-Tyr or D-Tyr), glycine (L-Gly or D-Gly), citrulline (L-Cit or D-Cit), and cysteine ​​(L-Cys or D-Cys). - At least one of X1 and X2 is selected from histidine (L-His or D-His) and glutamic acid (L-Glu or D-Glu), or derivatives thereof; preferably selected from histidine (L-His or D-His) and glutamic acid (L-Glu or D-Glu); The conditions are: - The compound of formula (Ic) contains at least 50% acidic, basic, or polar uncharged amino acids, based on amino acid content; and - The compound of formula (Ic) is different from the homopolymer of poly-γ-glutamic acid.

[0088] In other words, according to this embodiment, the compound of formula (Ic) consists of two amino acids: X1 and X2 as previously defined. The amino acids X1 and X2 are linked by peptide bonds.

[0089] The glassy material according to this embodiment has been found to have a supramolecular glass structure that is stable for at least one month. Therefore, even the low molecular weight supramolecular glassy material according to the present invention exhibits good glass stability.

[0090] According to this embodiment, the compound of formula (Ic) is preferably selected from His-His (H2), His-Ser (HS), His-Glu (HE), Glu-Glu (E2), and mixtures thereof.

[0091] According to one embodiment, the compound of formula (I) is selected from the compound of formula (Id): X1-B-X2 (Formula (Id)), in, - X1 and X2 may be the same or different, representing a selection from histidine (L-His or D-His), glutamic acid (L-Glu or D-Glu), arginine (L-Arg or D-Arg), lysine (L-Lys or D-Lys), aspartic acid (L-Asp or D-Asp), serine (L-Ser or D-Ser), threonine (L-Thr or D-Thr), glutamine (L-Gln or D-Gln), asparagine (L-Asn or D-Asn), tyrosine (L-Tyr or D-Tyr), glycine (L-Gly or D-Gly), citrulline (L-Cit or D-Cit), and cysteine ​​(L-Cys or D-Cys). Amino acids, or their derivatives, preferably selected from histidine (L-His or D-His), glutamic acid (L-Glu or D-Glu), arginine (L-Arg or D-Arg), lysine (L-Lys or D-Lys), aspartic acid (L-Asp or D-Asp), serine (L-Ser or D-Ser), threonine (L-Thr or D-Thr), glutamine (L-Gln or D-Gln), asparagine (L-Asn or D-Asn), tyrosine (L-Tyr or D-Tyr), glycine (L-Gly or D-Gly), citrulline (L-Cit or D-Cit), and cysteine ​​(L-Cys or D-Cys). - At least one of X1 and X2 is selected from histidine (L-His or D-His), arginine (L-Arg or D-Arg), and glutamic acid (L-Glu or D-Glu), or derivatives thereof; preferably selected from histidine (L-His or D-His), arginine (L-Arg or D-Arg), and glutamic acid (L-Glu or D-Glu); more preferably selected from histidine (L-His or D-His) and glutamic acid (L-Glu or D-Glu); - B represents an additional amino acid that may be the same as or different from X1 and X2; - Optionally, at least one amino acid of the compound of formula (I) is connected to another non-adjacent amino acid of the compound of formula (I) via an intramolecular bridge, preferably via a disulfide bond; The conditions are: - The compound of formula (Id) contains at least 33% acidic, basic, or polar uncharged amino acids, based on amino acid content; and - The compound of formula (Id) is different from the homopolymer of poly-γ-glutamic acid.

[0092] In other words, according to this embodiment, the compound of formula (Id) consists of three amino acids: X1, B, and X2 as previously defined. The amino acids X1, B, and X2 are linked by peptide bonds in this order.

[0093] The glassy material according to this embodiment has been found to have a supramolecular glass structure that is stable for at least one month. Therefore, even the low molecular weight supramolecular glassy material according to the present invention exhibits good glass stability.

[0094] According to this embodiment, the compound of formula (Id) is preferably selected from His-His-His (H3), His-His-Lys (HHK), His d -His-Lys(H d HK), Lys-His-His (KHH), His-Lys-His (HKH), Lys-Lys-His (KKH), His-Lys-Lys (HKK), His-His-Cys (HHC), His-His-Arg (HHR), and mixtures thereof.

[0095] According to one embodiment, the compound of formula (I) is selected from the compounds of formula (Ie): X1-B-X2 (Equation (Ie)), in, - X1 and X2 may be the same or different, representing a selection from histidine (L-His or D-His), glutamic acid (L-Glu or D-Glu), arginine (L-Arg or D-Arg), lysine (L-Lys or D-Lys), aspartic acid (L-Asp or D-Asp), serine (L-Ser or D-Ser), threonine (L-Thr or D-Thr), glutamine (L-Gln or D-Gln), asparagine (L-Asn or D-Asn), tyrosine (L-Tyr or D-Tyr), glycine (L-Gly or D-Gly), citrulline (L-Cit or D-Cit), and cysteine ​​(L-Cys or D-Cys). Amino acids, or their derivatives, preferably selected from histidine (L-His or D-His), glutamic acid (L-Glu or D-Glu), arginine (L-Arg or D-Arg), lysine (L-Lys or D-Lys), aspartic acid (L-Asp or D-Asp), serine (L-Ser or D-Ser), threonine (L-Thr or D-Thr), glutamine (L-Gln or D-Gln), asparagine (L-Asn or D-Asn), tyrosine (L-Tyr or D-Tyr), glycine (L-Gly or D-Gly), citrulline (L-Cit or D-Cit), and cysteine ​​(L-Cys or D-Cys). - At least one of X1 and X2 is selected from histidine (L-His or D-His), arginine (L-Arg or D-Arg), and glutamic acid (L-Glu or D-Glu), or derivatives thereof; preferably selected from histidine (L-His or D-His), arginine (L-Arg or D-Arg), and glutamic acid (L-Glu or D-Glu); more preferably selected from histidine (L-His or D-His) and glutamic acid (L-Glu or D-Glu); - B represents a straight-chain sequence of at least two identical or different additional amino acids, which may be the same as or different from X1 and X2; - Optionally, at least one amino acid of the compound of formula (I) is connected to another non-adjacent amino acid of the compound of formula (I) via an intramolecular bridge, preferably via a disulfide bond; The conditions are: - The compound of formula (Ie) contains at least 33% acidic, basic, or polar uncharged amino acids, based on amino acid content; and - The compound of formula (Ie) is different from the homopolymer of poly-γ-glutamic acid.

[0096] In other words, in this embodiment, the compound of formula (Ie) comprises at least four amino acids in total: amino acid X1 as previously defined, at least two identical or different additional amino acids of B, and amino acid X2. The linear sequence of amino acid X1, at least two identical or different additional amino acids of B, and amino acid X2 are linked by peptide bonds in this order.

[0097] It has been found that the vitreous material according to this embodiment has a supramolecular glass structure that is stable for at least one month.

[0098] According to this embodiment, the compound of formula (Ie) is preferably selected from the group consisting of His-His-His-His (H4), His-Gly-His-Lys (HGHK), His-Lys-Lys-His (HKKH), His-His-His-Lys (HHHK), His-His-His-His-His (H5), His-His-Glu-His- His (HHEHH), His-His-Arg-His-His (HHRHH), His-Lys-Lys-Lys-His (HKKKH), His-His-Cit-His-His (HHCitHH), His-His-His-His-His-His (H6), His-His-His-His-His-His-His (H7), His-His-His-Cys-Tyr-Ile-Gln-Asn-Cys-Pro-Leu-Gly-His-His-His (HHHCYIQNCPLGHHH) single disulfide bridge, His-His-His-His-His-His-His-His-His-His (H10), His-Ala-Glu-Gly-Th r-Phe-Thr-Ser-Asp-Val-Ser-Ser-Tyr-Leu-Glu-Gly-Gln-Ala-Ala-Lys-Glu-Phe-Ile-Ala-Trp-Leu-Val-Lys-Gly-Arg-Gly (HAEGTFTSDVSSYLEGQAAKEFIAWLVKGRG), histidine copolymer (2500 Glu-Glu-Glu-Glu-Glu-Glu (E5), Glutamic Acid Copolymer (15000 g / mol), and mixtures thereof.

[0099] Advantageously, the number of additional amino acids (which may be the same as or different from X1 and X2) in the straight-chain sequence of B ranges from 2 to 700.

[0100] Advantageously, X1 and X2 may be the same or different, representing an amino acid selected from histidine (L-His or D-His), arginine (L-Arg or D-Arg) and glutamic acid (L-Glu or D-Glu), or derivatives thereof; preferably selected from histidine (L-His or D-His), arginine (L-Arg or D-Arg) and glutamic acid (L-Glu or D-Glu); more preferably selected from histidine (L-His or D-His) and glutamic acid (L-Glu or D-Glu).

[0101] In a first preferred embodiment, the number of additional amino acids (which may be the same as or different from X1 and X2) in the straight-chain sequence of B ranges from 2 to 200; preferably from 2 to 150; more preferably from 2 to 100. According to the first preferred embodiment, the compound of formula (Ie) is preferably selected from His-His-His-His (H4), His-Gly-His-Lys (HGHK), His-Lys-Lys-His (HKKH), His-His-His-Lys (HHHK), His-His-His-His-His (H5), His-His-Glu-His-His (HHEHH), His-His-Arg-His-His (HHRHH), His-Lys-Lys-Lys-His (HKKKH), His-His-Cit-His-His (HHCitHH), His-His-His-His-His-His (H6), His-His-His-His-His-His-His (H7), and His-His-His-Cy s-Tyr-Ile-Gln-Asn-Cys-Pro-Leu-Gly-His-His-His (HHHCYIQNCPLGHHH) monodisulfide bridge, His-His-His-His-His-His-His-His-His-His (H10), His-Ala-Glu-Gly-Thr-Phe-Thr-Ser-Asp-Val-Ser-Ser-Tyr-Leu-Glu-Gly-Gln-Ala-Ala-Lys-Glu-Phe-Ile-Ala-Trp-Leu-Val-Lys-Gly-Arg-Gly (HAEGTFTSDVSSYLEGQAAKEFIAWLVKGRG), Glu-Glu-Glu-Glu-Glu (E5), histidine copolymer (2500 g / mol), glutamic acid copolymer (15000 g / mol), and mixtures thereof.

[0102] In a second preferred embodiment, the number of additional amino acids (which may be the same as or different from X1 and X2) in the straight-chain sequence of B ranges from 201 to 700; preferably from 201 to 634. According to this second preferred embodiment, the compound of formula (Ie) is preferably selected from histidine copolymers, glutamic acid copolymers, and mixtures thereof.

[0103] The compound of formula (I) in this invention may be in salt form, comprising at least one counterion. Advantageously, said at least one counterion is selected from anionic counterions, cationic counterions, and mixtures thereof.

[0104] In one embodiment, when the vitreous material of the present invention comprises a salt of a compound of formula (I), the at least one counterion is an anionic counterion, preferably selected from acetates, halides, phosphates, nitrates, sulfates or sulfonates, more preferably selected from acetates, halides, nitrates or sulfates, even more preferably selected from trifluoroacetates, acetates or chlorides, and even more preferably selected from trifluoroacetates and acetates.

[0105] In another embodiment, when the vitreous material of the present invention comprises a salt of a compound of formula (I), the at least one counterion is a cationic counterion, preferably selected from cationic counterions derived from alkali metals or alkaline earth metals, ammonium ions or ions derived from organic amines, more preferably selected from sodium, potassium or cesium.

[0106] In one embodiment, when the vitreous material of the present invention comprises a salt of a compound of formula (I), the at least one counterion is a mixture of at least one anionic counterion and at least one cationic counterion, wherein the at least one anionic counterion is preferably selected from acetates, halides, phosphates, nitrates, sulfates or sulfonates, more preferably from acetates, halides, nitrates or sulfates, even more preferably from trifluoroacetates, acetates or chlorides, and even more preferably from trifluoroacetates and acetates; wherein the at least one cationic counterion is preferably selected from cationic counterions derived from alkali metals or alkaline earth metals, ammonium ions or ions derived from organic amines, more preferably from sodium, potassium or cesium.

[0107] When the vitreous material contains a salt of a compound of formula (I), the molar ratio R1 of the content of the at least one counterion to the content of the at least one compound of formula (I) is equal to N multiplied by the number of polar charged amino acids contained in the at least one compound of formula (I), wherein N ranges from 1 to 2.

[0108] At least one polar solvent Advantageously, the at least one polar solvent is selected from water, polar organic solvents and mixtures thereof; preferably selected from water, acetone, dimethyl sulfoxide and mixtures thereof; more preferably, the vitreous material according to the invention comprises a polar solvent, wherein the polar solvent is water.

[0109] In one embodiment, the total content of the at least one polar solvent ranges from 10% to 30% by weight relative to the total weight of the vitreous material. According to this embodiment, the vitreous material is viscoelastic and exhibits self-healing properties.

[0110] In another embodiment, the total content of the at least one polar solvent, by weight, is greater than or equal to 0.1% and less than 10% relative to the total weight of the vitreous material. According to this embodiment, the vitreous material is preferably a solid.

[0111] Therefore, the vitreous material according to the invention is versatile because it can be viscoelastic or solid, depending on the total content of the at least one polar solvent.

[0112] Additional ingredients The vitreous material according to the invention may optionally further comprise at least one additional component that is different from the previously described compound (i.e., the at least one compound of formula (I) or a salt thereof, and the at least one polar solvent), said additional component being selected from active ingredients, pH control agents, surfactants, transition metal salts or post-transition metal salts and mixtures thereof.

[0113] The vitreous material according to the invention may optionally further contain at least one active ingredient.

[0114] Advantageously, at least one of the optional active ingredients used in this invention is selected from analgesics, vaccines, anti-wrinkle agents, depigmenting agents, collagen promoters, botulinum toxin, anti-inflammatory drugs, anti-Alzheimer's drugs, antidotes, antibodies, allergens, neurotransmitters, contraceptives, progestins, estrogens, nicotine, mannitol, magnetite, chitosan, morphine, ibuprofen, naproxen, diclofenac, indomethacin, celecoxib, lidocaine, tetracaine, benzocaine Adrenaline, bupivacaine, phenobarbital, amiodarone, digoxin, mitefosine, mycophenolic acid, alendronate, zolmitriptan, hepatitis B surface antigen, Japanese encephalitis virus antigen, adalimumab, ustekinumab, pembrolizumab, cassicimarab, imdevimab, lenalidomide, ibrutinib, apixaban, bis-p-(iodoacetamido)azobenzene, 3,3′-bis(sulfonyl)-4, 4′-Bis(chloroacetamido)azobenzene, tetra-o-methoxyazobenzene, piperazine-tetra-o-methoxyazobenzene, 2-amino-3-(4-((3-vinylphenyl)diazeninyl)phenyl)propionic acid, 1-(b-carboxyethyl)-3,3-dimethyl-60-nitrospiro(indoline-2,20[2H-1]benzopyran), ketamine, gentamicin, penicillin V, tranexamic acid, kanamycin, metformin, besylate Fibrocin, sodium nitroprusside, amifostine, doxorubicin, caffeine, donepezil hydrochloride, phenylephrine, diphtheria and tetanus toxoids, A-CGRP peptide, dihydroergotamine mesylate, minoxidil, finasteride, triamcinolone, retinoid, methotrexate, rapamycin, buspirone, tacrolimus, vemodilide, aflibercept, nestorone acetate, insulin, naphthalene diimide, water-soluble perylenediimides, phenol, pigments, trehalose, sucrose, propylene glycol, glycerin, ethylene glycol, propylene glycol, and mixtures thereof.

[0115] When present in the vitreous material according to the invention, the total content of the at least one active ingredient, by weight, is preferably from 0.001% to 60% relative to the total weight of the vitreous material, more preferably from 0.1% to 50%.

[0116] The vitreous material according to the invention may optionally further contain at least one surfactant.

[0117] Advantageously, the optional at least one surfactant used in this invention is selected from cationic surfactants, anionic surfactants, nonionic surfactants, and mixtures thereof; preferably, the optional at least one surfactant is a nonionic surfactant; more preferably, the optional at least one surfactant is selected from glyceryl caprylate, polysorbate 20 to 80, poly(ethylene oxide)-poly(propylene oxide)-block copolymers, and mixtures thereof. Regarding polysorbate 20 to 80, an example is Tween® 20 to 80. Regarding poly(ethylene oxide)-poly(propylene oxide)-block copolymers, examples are Lutrol® F68, Lutrol® F108, and Pluronic® F88.

[0118] The vitreous material according to the invention may optionally further comprise at least one transition metal salt or post-transition metal salt.

[0119] Advantageously, the cation of any one of the optional transition metal salts or post-transition metal salts is a divalent cation of the transition metal or post-transition metal; preferably, the transition metal or post-transition metal is selected from zinc, copper, iron, cobalt, nickel, and cadmium; more preferably, the optional one of the transition metal salts or post-transition metal salts used in the present invention is selected from zinc sulfate, zinc chloride, zinc nitrate, nickel sulfate, nickel chloride, copper chloride, cobalt chloride, ferric chloride, cadmium chloride, and mixtures thereof.

[0120] The vitreous material according to the invention may optionally further contain at least one pH control agent.

[0121] Advantageously, at least one pH control agent that can be used in this invention is selected from organic acids, inorganic acids, organic bases, inorganic bases and mixtures thereof; preferably selected from hydrochloric acid, trifluoroacetic acid, citric acid, malic acid, acetic acid, sodium hydroxide, potassium hydroxide and mixtures thereof; more preferably selected from hydrochloric acid, trifluoroacetic acid, acetic acid, sodium hydroxide and mixtures thereof.

[0122] When present in the vitreous material according to the invention, the total content of the at least one pH control agent, by weight, is preferably 0.001% to 30% relative to the total weight of the vitreous material, more preferably 0.01% to 5%.

[0123] If the preparation of the vitreous material according to the invention is carried out by the following steps: dissolving at least one compound of formula (I) or a salt thereof, optionally at least one active ingredient, optionally at least one surfactant and optionally at least one transition metal salt or post-transition metal salt in at least one polar solvent, wherein the total amount of at least one polar solvent is sufficient to completely dissolve to form a single-phase solution, and then optionally adding at least one pH control agent to the mixture to ensure: - When the compound of formula (I) is positively charged as a whole, the pH of the single-phase solution is acidic or neutral, preferably below 6.5, more preferably 2 to 5. as well as - When the compound of formula (I) is negatively charged as a whole, the pH of the single-phase solution is alkaline or neutral, preferably, the pH is 7 to 10.

[0124] In one embodiment, the vitreous material according to the invention further comprises at least one active ingredient and at least one surfactant; preferably, the at least one active ingredient is selected from analgesics, vaccines, anti-wrinkle agents, freckle-removing agents, collagen promoters, botulinum toxin, anti-inflammatory drugs, anti-Alzheimer's drugs, antidotes, antibodies, allergens, neurotransmitters, contraceptives, progestins, estrogens, nicotine, mannitol, magnetite, chitosan, morphine, ibuprofen, naproxen, diclofenac, indomethacin, celecoxib, lidocaine, and butyl... Cacaine, Benzocaine, Epinephrine, Bupivacaine, Phenobarbital, Amiodarone, Digoxin, Mitefocin, Mycophenolic Acid, Alendronate, Zolmitriptan, Hepatitis B Surface Antigen, Japanese Encephalitis Virus Antigen, Adalimumab, Ustekinumab, Pembrolizumab, Cassirhizoma, Imdevimab, Lenalidomide, Ibrutinib, Apixaban, Bis-p-(iodoacetamido)azobenzene, 3,3′-bis(sulfonyl)-4,4′-bis(chloroacetamido)azobenzene, Tetra-o-methoxy Piperazinyl-tetra-o-methoxy-azobenzene, 2-amino-3-(4-((3-vinylphenyl)diazeninyl)phenyl)propionic acid, 1-(b-carboxyethyl)-3,3-dimethyl-60-nitrospiro(indoline-2,20[2H-1]benzopyran), ketamine, gentamicin, penicillin V, tranexamic acid, kanamycin, metformin, besifloxacin, sodium nitroprusside, amifostine, doxorubicin, caffeine, donepezil hydrochloride, phenylephrine, diphtheria and tetanus toxoids, A-CGRP Peptides, dihydroergotamine mesylate, minoxidil, finasteride, triamcinolone, retinoic acid, methotrexate, rapamycin, buspirone, tacrolimus, vemodilide, aflibercept, enorgestrel acetate, insulin, naphthalenediimide, water-soluble perylenediimide, phenol, pigments, trehalose, sucrose, propylene glycol, glycerol, ethylene glycol, propylene glycol, and mixtures thereof; wherein the at least one surfactant is selected from glyceryl caprylate, polysorbate 20 to 80, poly(ethylene oxide)-poly(propylene oxide)-block copolymers, and mixtures thereof.

[0125] Preferred vitreous material In one embodiment, the vitreous material comprises: a) at least one compound of formula (Ia) as previously defined, or a salt thereof, wherein the total content by weight is preferably 40% to 99.9% relative to the total weight of the vitreous material, more preferably 40% to 95%, and even more preferably 59% to 88%; and b) At least one polar solvent, by weight, comprising 0.1% to 30% of the total weight of the vitreous material.

[0126] In another embodiment, the vitreous material comprises: a) at least one compound of formula (Ib) as previously defined, or a salt thereof, wherein the total content by weight is preferably 40% to 99.9% relative to the total weight of the vitreous material, more preferably 40% to 95%, and even more preferably 59% to 88%; and b) At least one polar solvent, by weight, comprising 0.1% to 30% of the total weight of the vitreous material.

[0127] In one embodiment, the vitreous material comprises: a) at least one compound of formula (Ic) as previously defined, or a salt thereof, wherein the total content by weight is preferably 40% to 99.9% relative to the total weight of the vitreous material, more preferably 40% to 95%, and even more preferably 59% to 88%; and b) At least one polar solvent, by weight, comprising 0.1% to 30% of the total weight of the vitreous material.

[0128] In one embodiment, the vitreous material comprises: a) at least one compound of formula (Id) as previously defined, or a salt thereof, wherein the total content by weight is preferably 40% to 99.9% relative to the total weight of the vitreous material, more preferably 40% to 95%, and even more preferably 59% to 88%; and b) At least one polar solvent, by weight, comprising 0.1% to 30% of the total weight of the vitreous material.

[0129] In one embodiment, the vitreous material comprises: a) at least one compound of formula (Ie) as previously defined, or a salt thereof, wherein the total content by weight is preferably 40% to 99.9% relative to the total weight of the vitreous material, more preferably 40% to 95%, and even more preferably 59% to 88%; and b) At least one polar solvent, by weight, comprising 0.1% to 30% of the total weight of the vitreous material.

[0130] First method for preparing vitreous material according to the present invention The present invention also relates to a first method for preparing a vitreous material according to the present invention, comprising the following steps: i) Dissolving at least one compound of formula (I) or a salt thereof, and optionally at least one additional component, in at least one polar solvent, wherein the total amount of said at least one polar solvent is sufficient to completely dissolve the compound to form a single-phase solution. ii) Dry the single-phase solution of step i) to partially remove the at least one polar solvent until the total content of the at least one polar solvent by weight ranges from 0.1% to 30% relative to the total weight of the vitreous material, to obtain the vitreous material according to the invention, then iii) Optionally, when the total content of the at least one polar solvent in the vitreous material obtained in step ii) is between 10% and 30% by weight relative to the total weight of the vitreous material, the material is stretched to obtain fibers, rods, or microneedles.

[0131] Steps i) to iii) of the first method for preparing the vitreous material according to the present invention are performed in this order.

[0132] In a first embodiment, the first method for preparing the vitreous material according to the present invention comprises the following steps: i) Dissolve at least one compound of formula (I) or a salt thereof, and optionally at least one additional component, in at least one polar solvent, wherein the total amount of said at least one polar solvent is sufficient to completely dissolve the compound to form a single-phase solution, and then... ii) Dry the single-phase solution of step i) to partially remove the at least one polar solvent until the total content of the at least one polar solvent by weight is in the range of 0.1% to 30% relative to the total weight of the vitreous material, to obtain the vitreous material according to the invention.

[0133] In a second embodiment, the first method for preparing the vitreous material according to the present invention comprises the following steps: i) Dissolving at least one compound of formula (I) or a salt thereof, and optionally at least one additional component, in at least one polar solvent, wherein the total amount of said at least one polar solvent is sufficient to completely dissolve the compound to form a single-phase solution. ii) Dry the single-phase solution of step i) to partially remove the at least one polar solvent until the total content of the at least one polar solvent, by weight, ranges from 10% to 30% relative to the total weight of the vitreous material, to obtain a vitreous material, wherein the total content of the at least one polar solvent in the vitreous material ranges from 10% to 30% by weight relative to the total weight of the vitreous material, and then... iii) Stretching step ii) The material obtained is used to obtain fibers, rods or microneedles.

[0134] When at least one compound of formula (I) is positively charged as a whole, at least one pH control agent is optionally added to ensure that the pH of the single-phase solution of step i) is acidic or neutral, preferably below 6.5, more preferably 2 to 5.

[0135] When at least one compound of formula (I) is negatively charged as a whole, at least one pH control agent is optionally added to ensure that the pH of the single-phase solution of step i) is alkaline or neutral, preferably, the pH is 7 to 10.

[0136] The total amount of the at least one polar solvent in step i) is selected to completely dissolve the at least one compound of formula (I) or a salt thereof, and optionally at least one additional component, wherein the complete dissolution is carried out in the at least one polar solvent. A single-phase solution is thus obtained.

[0137] Advantageously, the weight ratio R2 of the content of the at least one polar solvent in step i) to the content of the at least one compound of formula (I) or its salt is greater than 0.5, preferably 1 to 10.

[0138] Step ii) is preferably performed directly after the at least one compound of formula (I) or a salt thereof and optionally at least one additional component have been dissolved in the at least one polar solvent (i.e., after step i), without any intermediate waiting time.

[0139] Advantageously, the single-phase solution in step ii) of drying step i) is dehydrated, heated, or subjected to other drying techniques known to those skilled in the art. Heating can be performed, for example, by microwaves or magnetic induction thermotherapy.

[0140] The single-phase solution in drying step i) of step ii) will first result in the formation of a viscous material (i.e., according to the invention, a glassy material having a total content of the at least one polar solvent in the range of 10% to 30% by weight relative to the total weight of the glassy material), and after a longer drying time, form a solid glass (i.e., according to the invention, a glassy material having a total content of the at least one polar solvent in the range of 0.1% to less than 10% by weight relative to the total weight of the glassy material).

[0141] In one embodiment, the drying of the single-phase solution in step ii) of step i) can be carried out in a mold to give the resulting vitreous material a shape.

[0142] In one embodiment, in step ii), a glassy material having a total content of the at least one polar solvent relative to the total weight of the glassy material of greater than or equal to 0.1% and less than 10% by weight is obtained, and it is spread as a nano-precision thin film by spin coating.

[0143] Optional step iii) is preferably performed directly after drying the single-phase solution of step i) in step ii) (i.e., after step ii), without any intermediate waiting time. Furthermore, it is performed only in step ii) if a glassy material having a total content of the at least one polar solvent in the range of 10% to 30% by weight relative to the total weight of the glassy material is obtained. In other words, optional step iii is performed only if drying the single-phase solution of step i) in step ii) is stopped before the formation of solid glass (i.e., according to the invention, a glassy material having a total content of the at least one polar solvent in the range of 0.1% to less than 10% by weight relative to the total weight of the glassy material).

[0144] The properties of the obtained material can be altered depending on the stretching rate of the material obtained in stretching step ii) used in optional step iii), and the humidity conditions of 50% to 90%. In practice, if the stretching rate in step iii) is high, rods or microneedles are obtained in optional step iii) that are solid and brittle (i.e., the total content of each of the at least one polar solvent is greater than or equal to 0.1% and less than 10% by weight relative to their total weight). If the stretching rate in step iii) is low, fibers are obtained in optional step iii) that are viscoelastic (i.e., the total content of each of the at least one polar solvent is 10% to 30% by weight relative to their total weight), and they exhibit self-healing properties, such as... Figure 1a and Figure 1b As shown in the photo.

[0145] "High" stretching speed refers to 1 m / s to 3 m / s.

[0146] "Low" stretching speed refers to 0.01 m / s to 0.3 m / s.

[0147] The tensile speed can be determined using particle tracking or tensile testing methods.

[0148] The second method for preparing the vitreous material according to the present invention The present invention also relates to a second method for preparing a vitreous material according to the present invention, wherein, by weight, the total content of the at least one polar solvent is greater than or equal to 0.1% and less than 10% relative to the total weight of the vitreous material, the method comprising the following steps: i) A mixture of at least one compound of formula (I) or a salt thereof, and optionally at least one additional ingredient, ii) Heating the mixture from step i) until the mixture melts to obtain a molten material, wherein the heating temperature is greater than or equal to the glass transition temperature (Tg) of at least one compound of formula (I) or a salt thereof, then iii) Cool the molten material obtained in step ii) to ambient temperature to obtain the vitreous material according to the invention, wherein the total content of the at least one polar solvent is greater than or equal to 0.1% and less than 10% by weight relative to the total weight of the vitreous material.

[0149] Steps i) to iii) of the second method for preparing the vitreous material according to the present invention are carried out in this order, wherein, by weight, the total content of the at least one polar solvent is greater than or equal to 0.1% and less than 10% relative to the total weight of the vitreous material.

[0150] Step ii) is preferably performed directly after the mixing of at least one compound of formula (I) or a salt thereof, and optionally at least one additional ingredient (i.e., after step i), without any intermediate waiting time. Step ii) allows the mixing to be increased by achieving the viscoelastic state of the at least one compound of formula (I) or a salt thereof.

[0151] Step iii) is preferably performed directly after the mixture in step i) has been heated until it melts (i.e., after step ii), without any intermediate waiting time.

[0152] Advantageously, the cooling in step iii) includes allowing the molten material from step ii) to stand at ambient temperature and atmospheric pressure, with or without controlled humidity.

[0153] The cooling of the molten material obtained in step ii) in step iii) will result in the formation of a glassy material, wherein the total content of the at least one polar solvent in the glassy material is greater than or equal to 0.1% and less than 10% by weight relative to the total weight of the glassy material.

[0154] In one embodiment, cooling the molten material from step ii) in step iii) can be performed in a mold to give the resulting vitreous material a shape.

[0155] In one embodiment, cooling the molten material from step ii) in step iii) can be performed simultaneously with spreading the molten material by spin coating to obtain the vitreous material according to the invention, as a nano-precision film, wherein the total content of the at least one polar solvent is greater than or equal to 0.1% and less than 10% by weight relative to the total weight of the vitreous material.

[0156] In another embodiment, cooling the molten material from step ii) in step iii) can be performed simultaneously with depositing the molten material onto a surface using a 3D printer.

[0157] The at least one polar solvent present in the material may be due to air humidity through hygroscopic action, or may be a residue from peptide synthesis.

[0158] Uses of the vitreous material according to the present invention The present invention also relates to the use of a vitreous material according to the invention, wherein the at least one polar solvent is present, by weight, in a total content of 10% to 30% relative to the total weight of the vitreous material, as an adhesive. The material, wherein the at least one polar solvent is present, by weight, in a total content of 10% to 30% relative to the total weight of the vitreous material, is a viscoelastic substance. When dried, it can be used as a water-soluble adhesive having specific biological or chemical properties. Examples of materials that can be bonded by the above-described viscoelastic material in a dry environment are Teflon and borosilicate glass. A photograph of a borosilicate tube bonded to a Teflon block using the vitreous material of Example 4 can be seen in… Figure 2 .

[0159] The present invention also relates to the use of the vitreous material according to the invention, wherein the total content of the at least one polar solvent, by weight, ranges from 0.1% to 30% relative to the total weight of the vitreous material, and is used as a cryoprotectant and / or thermal protectant for molecular and / or biological elements when the temperature is below the glass transition temperature of the vitreous material.

[0160] The present invention also relates to the use of a vitreous material according to the invention, wherein the total content of the at least one polar solvent, by weight, is greater than 0.1% and less than 10% relative to the total weight of the vitreous material, for molding water-soluble glass structures with micrometer (at least 20 µm) to nanometer precision. For example, possible water-soluble glass structures include: - Microneedles with rapid or slow release for transdermal or intradermal injection in cosmetics or medicine. -Crochet hook, - Tipped microspheres for oral capsule absorption and intragastric or intestinal injection. - Powder for intranasal administration, and - Optical lenses with specific chemical and biological properties, serving as bio-optical biomaterials that can be used as ocular medications.

[0161] A photograph of the lens-shaped glass material of Example 21 held by tweezers can be seen in Figure 3 .

[0162] The molding can be performed by depositing or spraying a viscous or liquid vitreous material into a mold. Preferably, the mold has a hydrophilic surface to allow for better filling. The filled mold can be centrifuged to improve filling. The liquid vitreous material can be pre-degassed to remove tiny air bubbles.

[0163] The vitreous material according to the invention exhibits high biocompatibility, which is advantageous when used to form microneedles for transdermal or intradermal drug delivery. Furthermore, the vitreous material according to the invention, wherein the total content of the at least one polar solvent is greater than 0.1% and less than 10% by weight relative to the total weight of the vitreous material, can be used to mold microneedles, preferably microneedles with sharp edges, to improve penetration.

[0164] The present invention also relates to the use of a vitreous material according to the invention, wherein the total content of the at least one polar solvent, by weight, is greater than or equal to 0.1% and less than 10% relative to the total weight of the vitreous material, for use as a mask in photolithography. The vitreous material, wherein the total content of the at least one polar solvent, by weight, is greater than or equal to 0.1% and less than 10% relative to the total weight of the vitreous material, can be spread as a nano-precision thin film by spin coating.

[0165] microneedles The present invention also relates to a microneedle comprising the above-mentioned vitreous material, wherein, by weight, the total content of the at least one polar solvent is greater than 0.1% and less than 10% relative to the total weight of the vitreous material.

[0166] Preferably, the microneedles have sharp edges.

[0167] Preferably, the microneedles are composed of the aforementioned vitreous material, wherein, by weight, the total content of the at least one polar solvent is greater than 0.1% and less than 10% relative to the total weight of the vitreous material.

[0168] The microneedles according to the invention exhibit high biocompatibility and improved penetration when used for transdermal or intradermal injection in cosmetics or pharmaceuticals.

[0169] Example The present invention is further illustrated in a non-limiting manner through the following embodiments.

[0170] Example 1: Material Preparation Materials and methods The material was prepared using the following steps: i) Dissolving: - A compound of formula (I) (the present invention) or a compound containing at least one amino acid (comparative example), or a salt thereof, In water, the total amount of water is sufficient to completely dissolve and form a single-phase solution; ii) In a dryer containing a desiccant (e.g., calcium carbonate), at 20% relative humidity and ambient temperature, dry the single-phase solution of step i) until the total water content in the material by weight is greater than or equal to 0.1% and less than 10% relative to the total weight of the vitreous material.

[0171] result The compounds of formula (I) used (in this invention) or compounds containing at least one amino acid (comparative examples), or salts thereof, are shown in Table 1.

[0172] Table 1

[0173] Example 2: Assessment of material aging and measurement of glass transition temperature (Tg) of glassy materials Materials and methods The appearance of the material prepared in Example 1 was evaluated immediately after its preparation, after it was stored in a sealed transparent container at ambient temperature and humidity for one month, and after it was stored under the same conditions for six months.

[0174] In addition, the glass transition temperature (Tg) of the vitreous material prepared in Example 1 was measured by differential scanning calorimetry (DSC). The measurement method is as follows: A liquid, viscous, or solid peptide sample was inserted into a platinum cup for measurement. The sample cup and an empty cup (as a reference) were placed together in the calorimeter. The instrument was started and run for 1 to 4 heating / cooling cycles, and DSC measurements were performed in the temperature range of 25°C to 140°C.

[0175] result The appearance of the above materials immediately after preparation, after 1 month, and after 6 months, as well as the measured potential glass transition temperature (Tg), are presented in Table 2.

[0176] Table 2

[0177] Examples 1-51 correspond to the vitreous material according to the invention. The results presented in Table 2 show that the vitreous material according to the invention is solid immediately after the drying step (i.e., immediately after step ii) and remains solid after one month of storage in a sealed transparent container at ambient temperature and humidity. No crystallization was observed. Therefore, this result demonstrates that the vitreous material according to the invention has a stable supramolecular structure for at least one month. The vitreous material of Example 7 remains solid even after one year of storage in a sealed transparent container at ambient temperature and humidity, and its amorphous structure after one year of storage in a sealed transparent container at ambient temperature and humidity can... Figure 4 The images were observed in wide-angle X-ray scattering diagrams. Photographs of the vitreous materials in Examples 29, 15, and 34 can be found in […]. Figure 5 A) to C). Scanning electron microscope (SEM) images of a 300 nm thick section of the vitreous material from Example 21 are visible. Figure 6 Photographs of the vitreous materials shaped into microneedles of 600 µm height in Examples 23, 25, and 30 can be found in [the respective text is missing]. Figure 7 (A) to (C).

[0178] Specifically, Examples 1, 3-6, 11, 17, 19, 22-31, and 33-51 correspond to the vitreous material according to the invention, which includes a compound of formula (Ia) or a salt thereof, wherein X1 and X2 may be the same or different, representing an amino acid selected from histidine (L-His or D-His), arginine (L-Arg or D-Arg), and glutamic acid (L-Glu or D-Glu), or derivatives thereof; preferably selected from histidine (L-His or D-His), arginine (L-Arg or D-Arg), and glutamic acid (L-Glu or D-Glu); more preferably selected from histidine (L-His or D-His) and glutamic acid (L-Glu or D-Glu). The results presented in Table 2 indicate that the specific vitreous material remains solid for at least 6 months.

[0179] Comparative Examples 1-7 are materials comprising compounds containing at least one amino acid. However, these compounds differ from compounds of formula (I) or their salts as defined in this invention. The results presented in Table 2 show that all materials of Comparative Examples 1-7 were crystalline immediately after the drying step (i.e., immediately after step ii). The crystal structure of the material of Comparative Example 6 after storage at ambient temperature and humidity for 12 hours was [missing information]. Figure 8 These results were observed in wide-angle X-ray scattering patterns. These results demonstrate that at least one compound of formula (I) or a salt thereof, as defined in this invention, is required in the material to obtain a solid glassy material. Figure 9 This shows a photograph of the glass beads from Example 25 over a three-year period. This result demonstrates the long-term stability of the material.

Claims

1. A vitreous material, said vitreous material comprising: a) at least one compound of formula (I) or a salt thereof, X1-B-X2 (Equation (I)) in, - X1 and X2 may be the same or different, representing amino acids selected from histidine (L-His or D-His), glutamic acid (L-Glu or D-Glu), arginine (L-Arg or D-Arg), lysine (L-Lys or D-Lys), aspartic acid (L-Asp or D-Asp), serine (L-Ser or D-Ser), threonine (L-Thr or D-Thr), glutamine (L-Gln or D-Gln), asparagine (L-Asn or D-Asn), tyrosine (L-Tyr or D-Tyr), glycine (L-Gly or D-Gly), citrulline (L-Cit or D-Cit), ornithine (L-Orn or D-Orn), and cysteine ​​(L-Cys or D-Cys), or their derivatives, and methionine sulfoxide (L-Met-SO or D-Met-SO). - At least one of X1 and X2 is selected from histidine (L-His or D-His), arginine (L-Arg or D-Arg) and glutamic acid (L-Glu or D-Glu), or derivatives thereof; - B is absent, or represents a straight-chain sequence of one additional amino acid or at least two identical or different additional amino acids, which may be the same as or different from X1 and X2; The conditions are: - The compound of formula (I) contains at least 33% of acidic, basic or polar uncharged amino acids, based on amino acids; - When X1 and / or X2 represent lysine (L-Lys or D-Lys) or arginine (L-Arg or D-Arg), B must be present; and - The compound of formula (I) is different from the homopolymer of poly-γ-glutamic acid; and b) At least one polar solvent, wherein the total content of the at least one polar solvent, by weight, ranges from 0.1% to 30% relative to the total weight of the vitreous material.

2. The vitreous material according to claim 1, wherein at least one amino acid of the compound of formula (I) is connected to another non-adjacent amino acid of the compound of formula (I) via an intramolecular bridge.

3. The glassy material according to claim 1 or 2, wherein the glass transition temperature of the glassy material is in the range of 50°C to 150°C, preferably 70°C to 130°C.

4. The vitreous material according to any one of the preceding claims, wherein the at least one polar solvent is selected from water, polar organic solvents and mixtures thereof; preferably selected from water, acetone, methanol, ethanol, dimethyl sulfoxide and mixtures thereof; more preferably, the polar solvent is water.

5. The vitreous material according to any one of the preceding claims, wherein the total content of the at least one polar solvent, by weight, ranges from 10% to 30% relative to the total weight of the vitreous material.

6. The vitreous material according to any one of claims 1-4, wherein, by weight, the total content of the at least one polar solvent is greater than or equal to 0.1% and less than 10% relative to the total weight of the vitreous material.

7. The vitreous material according to any one of the preceding claims, wherein X1 and X2 are the same or different, representing a subset selected from histidine (L-His or D-His), glutamic acid (L-Glu or D-Glu), arginine (L-Arg or D-Arg), lysine (L-Lys or D-Lys), aspartic acid (L-Asp or D-Asp), serine (L-Ser or D-Ser), threonine (L-Thr or D-Thr), glutamine (L-Gln or D-Gln), asparagine (L-Asn or D-Asn), tyrosine (L-Tyr or D-Tyr), and glycine (L-Glycine). Amino acids selected from histidine (L-Gly), citrulline (L-Cit or D-Cit), ornithine (L-Orn or D-Orn), and cysteine ​​(L-Cys or D-Cys); preferably selected from histidine (L-His or D-His), arginine (L-Arg or D-Arg), glutamic acid (L-Glu or D-Glu), and ornithine; more preferably selected from histidine (L-His or D-His), arginine (L-Arg or D-Arg), and glutamic acid (L-Glu or D-Glu), and even more preferably selected from histidine (L-His or D-His) and glutamic acid (L-Glu or D-Glu).

8. The vitreous material according to any one of the preceding claims, wherein B represents at least two identical or different linear sequences of additional amino acids, the additional amino acids being identical or different from X1 and X2, and the number of additional amino acids in the linear sequence of B ranging from 2 to 200; preferably from 2 to 150; more preferably from 2 to 100.

9. The vitreous material according to any one of claims 1-7, wherein B represents at least two identical or different linear sequences of additional amino acids, the additional amino acids being identical or different from X1 and X2, and the number of additional amino acids in the linear sequence of B ranging from 201 to 700; preferably from 201 to 634.

10. The vitreous material according to any one of the preceding claims, wherein the additional amino acid of B is selected from alanine (L-Ala or D-Ala), arginine (L-Arg or D-Arg), asparagine (L-Asn or D-Asn), aspartic acid (L-Asp or D-Asp), cysteine ​​(L-Cys or D-Cys), glutamic acid (L-Glu or D-Glu), glutamine (L-Gln or D-Gln), glycine (L-Gly or D-Gly), histidine (L-His or D-His) or derivatives thereof, isoleucine (L-Ile or D-Ile), leucine (L-Leu or D-Leu). Lysine (L-Lys or D-Lys), Methionine (L-Met or D-Met), Phenylalanine (L-Phe or D-Phe), Proline (L-Pro or D-Pro), Pyrrolidone (L-Pyl or D-Pyl), Selenocysteine ​​(L-Sec or D-Sec), Serine (L-Ser or D-Ser), Threonine (L-Thr or D-Thr), Tryptophan (L-Trp or D-Trp), Tyrosine (L-Tyr or D-Tyr), Valine (L-Val or D-Val), Carnitine (L-Carnitine or D-Carnitine), Gamma-aminobutyric acid, Hydroxyproline (Hyp), Methionine sulfoxide (L- Met-SO or D-Met-SO), selenomethionine (L-SeMet or D-SeMet), citrulline (L-Cit or D-Cit), ornithine (L-Orn or D-Orn), β-alanine, α-aminoisobutyric acid (Aib), α-aminobutyric acid (L-Abu or D-Abu), 3-aminomethylbenzoic acid, anthranilic acid, high arginine (L-Har or D-Har), δ-hydroxylysine (Hyl), 3-mercaptophenylalanine (L-3-mercaptophenylalanine or D-3-mercaptophenylalanine), 2-hydroxyphenylalanine (L-2-hydroxyphenylalanine or D-2-hydroxyphenylalanine), 3-hydroxyphenylalanine (L... -3-hydroxyphenylalanine or D-3-hydroxyphenylalanine), phenylglycine (L-Phg or D-Phg), homophenylalanine (L-Hph or D-Hph), β-(2-pyridyl)-alanine (L-2Pal or D-2Pal), β-(3-pyridyl)-alanine (L-3Pal or D-3Pal), 4-methyl-phenylalanine (L-4-methyl-phenylalanine or D-4-methyl-phenylalanine), 4-amino-phenylalanine (L-4-amino-phenylalanine or D-4-amino-phenylalanine), 2,3-diaminopropionic acid (L-Dap or D-Dap), 2,4-diaminobutyric acid (L-Dab or D-Dab), 3,4-Dihydroproline (L-Dhp or D-Dhp), thioproline (L-thioproline or D-thioproline), α-methylproline (L-α-methylproline or D-α-methylproline), pipercoic acid (L-pipercoic acid or D-pipercoic acid), α-aminohexanoic acid (L-Aad or D-Aad), 2-aminopimelic acid (L-2-aminopimelic acid or D-2-aminopimelic acid), 2-aminopimelic acid (L-2-aminopimelic acid or D-2-aminopimelic acid), α-aminooctanoic acid (L-ASU or D-ASU), and 3,4-dihydroxyphenylalanine (L-DOPA or D-D-D-dihydroxyproline) -DOPA), 4-(phenylazo)-phenylglycine (L-4-(phenylazo)-phenylglycine or D-4-(phenylazo)-phenylglycine), (4-phenylazo)-phenylalanine (L-(4-phenylazo)-phenylalanine or D-(4-phenylazo)-phenylalanine), (4-(4'-tert-butoxycarbonyl)phenylazo)phenylalanine (L-(4'-tert-butoxycarbonyl)phenylazo)phenylalanine or D-(4'-tert-butoxycarbonyl)phenylazo)phenylalanine), azobenzyl-lysine (L-azobenzyl-lysine or D-azobenzyl-lysine), or derivatives thereof.

11. The vitreous material according to any one of the preceding claims, wherein the vitreous material further comprises at least one additional component, the component being different from the at least one compound of formula (I) or a salt thereof, and also different from the at least one polar solvent, the additional component being selected from active ingredients, pH control agents, surfactants, transition metal salts or post-transition metal salts and mixtures thereof.

12. A method for preparing the vitreous material according to any one of claims 1-11, comprising the following steps: i) Dissolving at least one compound of formula (I) or a salt thereof, and optionally at least one additional component, in at least one polar solvent, wherein the total amount of said at least one polar solvent is sufficient to completely dissolve the compound to form a single-phase solution. ii) Dry the single-phase solution of step i) to partially remove the at least one polar solvent until the total content of the at least one polar solvent by weight ranges from 0.1% to 30% relative to the total weight of the vitreous material, to obtain the vitreous material according to any one of claims 1-11, then iii) Optionally, when the total content of the at least one polar solvent in the vitreous material obtained in step ii) is between 10% and 30% by weight relative to the total weight of the vitreous material, the material is stretched to obtain fibers, rods, or microneedles.

13. A method for preparing the vitreous material according to any one of claims 1-4 and 6-11, comprising the following steps: i) A mixture of at least one compound of formula (I) or a salt thereof, and optionally at least one additional ingredient, ii) Heating the mixture from step i) until the mixture melts to obtain a molten material, wherein the heating temperature is greater than or equal to the glass transition temperature of at least one compound of formula (I) or a salt thereof, then iii) Cool the molten material obtained in step ii) to ambient temperature to obtain the vitreous material according to any one of claims 1-4 and 6-11.

14. Use of the vitreous material according to any one of claims 1-5 and 7-11 as an adhesive.

15. Use of the vitreous material according to any one of claims 1-11 as a cryoprotectant and / or thermal protectant for molecular and / or biological elements at temperatures below the glass transition temperature of the vitreous material.

16. Use of the vitreous material according to any one of claims 1-4 and 6-11 for molding water-soluble glass structures with micron to nanometer precision.

17. A microneedle comprising a vitreous material according to any one of claims 1-4 and 6-11.

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