Coffee melanoidin nanoparticles and nanofibers

Abstract

The present invention relates to a method for preparing a melanoidin product comprising: a) an extraction step, in which coffee grounds are treated with an extractant having a pH value above 7 to extract melanoidin-containing solutes in a fluid phase of the extractant; b) a first separation step, in which the fluid phase is separated from the coffee grounds; c) a precipitation step, in which the fluid phase is contacted (i) with an acid to obtain an acidic mixture having a pH value below 4 or (ii) with an organic phase separating agent and an acid to obtain a mixture having a pH value in the range of 4 to 8, thereby forming a precipitate containing melanoidins; and d) a second separation step, in which the formed precipitate is separated from the acidic mixture. The present invention further relates to melanoidin nanoparticles and melanoidin nanofibers obtained from coffee grounds.

Description

[Technical field]

[0001] The present invention relates to nanoparticles and nanofibers containing coffee melanoidin. The present invention further relates to a method for producing coffee melanoidin nanoparticles and nanofibers. [Background technology]

[0002] Melanoidins are a class of brown, hydrophilic nitrogen-containing polymers that are produced during the heat treatment of foods such as coffee, cocoa, bread, malt, barley, Brewers Spent Grain (BSG), soy, meat and honey. During the heat treatment of such foods, amino acids and reducing sugars, such as aldoses and d-xylose, react to form what are called initial Maillard reaction products. On continued heating, melanoidins are formed by cyclization, dehydration, retro-aldolization, rearrangement, isomerization and condensation of these initial Maillard reaction products. Due to the complexity of the Maillard reaction pathway, the final reaction products are varied and, among other things, the heating time, type of heating, temperature, initial chemical composition of the system, moisture content, water activity and pH value determine the final composition.

[0003] As an example, the roasting process of green coffee beans can be represented as a two-stage change: i) evaporation of free moisture from the beans, and ii) pyrolysis inside the beans, resulting in swelling and darkening of the beans and loss of dry weight. Oligosaccharides, polysaccharides and proteins present in the green coffee beans are decomposed and then participate in the Maillard reaction. As a result, the chemical composition of the beans changes significantly during roasting, and melanoidins are the main products, although caffeine and chlorogenic acid are also present in the final roasted coffee beans.

[0004] The chemical composition of coffee also varies depending on the variety. The major components of roasted beans are carbohydrates (about 38 to about 42% by weight), melanoidins (about 25 to about 28% by weight), lipids (about 11 to about 17% by weight), and proteins (about 8% by weight). Trace components include minerals, chlorogenic acid, aliphatic acids, caffeine, and trigonelline.

[0005] The extraction of melanoidins from coffee grounds has been known in the art for several decades. UK Patent Application No. GB ​​1,073,738 discloses a method for producing instant coffee. This industrial scale process includes an extraction step, an acidification step, and an optional drying step.

[0006] Document IT MI20 132 040 A1 discloses a method for extracting melanoidins from freshly ground roasted coffee using ethanol and water as extractants. The resulting particles are suitable for various applications in the food and pharmaceutical sectors.

[0007] Document US 2020 / 0367487 A1 discloses a coffee extract-based agent and a method for preserving organs, tissues or cells of a living body. After the extraction process, the pH of the coffee extract is adjusted and extracted with an organic solvent.

[0008] Melanoidins and their potential use in food, medical or technological applications have been attracting attention in recent years. For example, in the paper "Coffee melanoidin-based multipurpose film formation: application to single-cell nanoencapsulation" by Ji Yup Kim et al. (ChemNanoMat 10.1002 / cnma.202000004), melanoidins extracted from soluble coffee powder are utilized as a material-independent multipurpose coating material. Coffee melanoidins and ferric ions (Fe 3+Instantaneous complexation with coffee melanoidin leads to surface-adherent aggregates, triggering sequential film deposition. The authors further disclosed a coffee melanoidin-based coating applied to single-cell nanocapsules of Saccharomyces cerevisiae.

[0009] So far, academia and industry have focused mainly on synthetic melanoidins based on the Maillard reaction of glucose with the amino acid glycine. The possibility of obtaining nanoscale melanoidins from other sources has not been explored so far. Summary of the Invention [Problem to be solved by the invention]

[0010] The object of the present invention is to provide a method for obtaining melanoidins in nanoscale. A further object of the present invention is to provide melanoidin products which can be used in many applications, said nanoscale melanoidins being obtainable by an environmentally friendly and efficient method. [Means for solving the problem]

[0011] This problem is solved by providing a method for preparing a melanoidin product according to claim 1 and by providing a melanoidin product according to claims 8 to 11. Advantageous embodiments and applications of the subject matter of the invention are given in claims 2 to 7 and 12 to 15. [Brief description of the drawings]

[0012] [Figure 1] FIG. 1 shows a photograph of the obtained fibers taken with a scanning electron microscope (SEM). [Diagram 2] FIG. 2 shows a photograph of the obtained fibers taken with a scanning electron microscope (SEM). [Diagram 3] FIG. 3 shows a photograph of the obtained particles taken with a scanning electron microscope (SEM).

[0013] definition

[0014] In the following, any reference to one (including the articles "a" and "the"), two or any other number of objects is meant to be understood as not excluding the presence of further such objects in the present invention, unless something else is explicitly mentioned.

[0015] As used herein, the words "comprising," "comprises," and "comprised of" are synonymous with "including," "includes," "containing," or "contains," are inclusive or open-ended, and do not exclude additional, unrecited materials, elements, or method steps. When used, the phrase "consisting of" is closed and excludes all additional elements. Furthermore, the phrase "consisting essentially of" excludes additional material elements but allows for the inclusion of non-material elements that do not materially alter the nature of the invention.

[0016] When amounts, concentrations, dimensions, and other parameters are expressed in the form of ranges, preferred ranges, upper values, lower values, or preferred upper and lower values, it is to be understood that the range obtained by combining any upper value or preferred value with any lower value or preferred value is also specifically disclosed, regardless of whether any resulting range is expressly stated in the context.

[0017] Furthermore, in accordance with standard understanding, a weight range expressed as being "from x to x" specifically includes x weight %, and the component defined by the range may be absent from the composition, or may be present in the composition in an amount up to x weight %.

[0018] The terms "weight percent," "weight %," and "wt%" are used interchangeably.

[0019] The words "preferable," "preferred," "preferably," "particularly," and "desirably" are frequently used herein to refer to embodiments of the present disclosure that may offer certain advantages, under certain circumstances. However, the recitation of one or more preferred, preferred, particular or desirable embodiments does not imply that other embodiments are not useful, and is not intended to exclude such other embodiments from the scope of the present disclosure.

[0020] As used throughout this application, the word "may" is used in its permissive, i.e. possible, rather than mandatory, sense.

[0021] As used herein, room temperature is 23°C ± 2°C.

[0022] As used herein, number average molecular weight (Mn) and weight average molecular weight (Mw) are determined by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as the eluent according to DIN 556721:2007-08.

[0023] The term "micronized" when used in reference to food products means a powder having a particle size of 1 to 1500 microns, typically 100 to 1250 microns. The term "micronized" is intended to refer both to particles produced through finely dividing a material originally provided in bulk form, as well as to particles obtained by formation in solution with or without seeding, as well as other mechanical, chemical or physical methods mentioned above, including comminution by one or more of pulverization, milling, grinding, homogenization and sonication.

[0024] The words "micrometer", "micron" and "μm" are used interchangeably.

[0025] Grinding can be carried out, for example, using a planetary ball mill, which has a grinding chamber equipped with a rotor shaft that is used to rotate the grinding media. Reference may be made to the following document: Le Caer et al. Mechanical Alloying and High Energy Ball-Milling: Technical Simplicity and Physical Complexity for the Synthesis of New Materials www.ademe.fr / recherche / manifestations / materiaux-2002 / .

[0026] The grinding may be carried out in any high energy mill, examples of which include centrifugal mills, planetary ball mills, jet mills (e.g., spinning air flow jet mills), and fluid energy mills. Desirably, the high energy mill should be capable of imparting an impact force of at least 0.5 G, e.g., 0.5 to 25 G, to the milling media. Non-limiting examples of grinding mills that may be useful in the present invention are disclosed in U.S. Pat. Nos. 5,522,558, 5,232,169, 6,126,097, and 6,145,765. Moreover, it should be noted that the present invention does not preclude milling from being carried out under heat, e.g., as described in WO 00 / 56486 A1, and / or in the presence of additives, such as lubricants, surfactants, dispersants and solvents.

[0027] As used herein, "d 50 By "particle size" is meant a particle size distribution such that at least 50% by weight of the particles have a particle size diameter less than a specified value. Unless otherwise specified, the particle size is determined by dynamic light scattering.

[0028] The viscosity of the compositions described herein is measured under standard conditions of 25° C. and 50% relative humidity (RH) using a Brookfield Viscometer according to ASTM D3236, unless otherwise specified. The calibration method, spindle type and rotation speed of the Brookfield Viscometer are selected according to the manufacturer's instructions appropriate for the composition to be measured.

[0029] Methods for preparing melanoidin products

[0030] In a first aspect of the invention, the problem is a method for preparing a melanoidin product, comprising the steps of: an extraction step in which the coffee grounds are treated with an extractant having a pH value greater than 7 to extract melanoidin-containing solutes in the fluid phase of the extractant; a first separation step in which said fluid phase is separated from said coffee grounds; a precipitation step in which the fluid phase is contacted (i) with an acid to obtain an acidic mixture having a pH value of less than 4, or (ii) with an organic phase separating agent and an acid to obtain a mixture having a pH value in the range of 4 to 8, thereby forming a precipitate containing melanoidins; and a second separation step in which the formed precipitate is separated from the acidic mixture. The above problem is solved by providing the above method, which includes the steps of:

[0031] In the context of the present invention, "coffee grounds" are either fresh coffee grounds or coffee grounds remaining after brewing coffee, the latter also being referred to as "spent coffee grounds".

[0032] According to the invention, it can be exploited that used coffee grounds can still contain a significant amount of melanoidins. Used coffee grounds are usually accumulated during coffee preparation. In hotels and restaurants, large amounts of used coffee grounds are regularly disposed of as waste. Advantageously, according to the invention, valuable raw materials can be extracted from the discarded used coffee grounds.

[0033] Generally, other melanoidin-containing foods, such as cocoa, bread, malt, barley, Brewers Spent Grain (BSG), soy, meat or honey, can be used as well for the preparation of the melanoidin product according to the invention. However, coffee grounds are preferred since they have a higher melanoidin content than other food sources. Among coffee grounds, spent coffee grounds are particularly preferred as the raw material from which melanoidins are extracted.

[0034] In the context of the present invention, a solute is a substance that is present in dissolved and / or dispersed form in the fluid phase of the extractant.

[0035] Extraction process

[0036] In the extraction process, the coffee grounds are treated with an extractant to extract melanoidin-containing solutes, which may be present in a dissolved and / or dispersed form in a liquid phase.

[0037] Suitable extraction methods include, but are not limited to, reflux extraction, pressurized liquid extraction, ultrasound assisted extraction, microwave assisted extraction, pulsed electric field extraction, and / or hydro-distillation.

[0038] Preferably, the extraction step is carried out at a pressure between 1 and 8 bar (abs). More preferably, the pressure ranges from 2 to 5 bar (abs). In a preferred variant, the pressure is adjusted by heating the extractant in a closed apparatus.

[0039] In a preferred embodiment, the extraction step comprises pressurized liquid extraction. Preferably, the pressurized liquid extraction is carried out at a temperature of 100° C. or more, more preferably at a temperature of 120° C. or more. Preferably, the temperature is below 140° C. The preferred duration of the pressurized liquid extraction is more than 10 minutes and less than 1 hour, for example 30-40 minutes. It is an achievable advantage of the liquid extraction method as described above that a high solute extraction yield can be realized.

[0040] Preferably, the extractant is or comprises a liquid phase, where the solute is dissolved and / or dispersed in the liquid phase. More preferably, the extractant or the liquid phase of the extractant is aqueous, and the solute is dissolved and / or dispersed in the aqueous extractant or the aqueous phase of the extractant. The use of water as the extractant or as part of the extractant has the advantage that the extraction process can be carried out in an environmentally friendly manner. Moreover, it has been found that the use of water in the extraction process results in high melanoidin recovery.

[0041] Suitable extractants are sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate and ammonia (NH 3(水性) ), but are not limited to. The extractant may contain one or more water-miscible solvents. The extractant is considered "aqueous" in the sense of the present invention if the one or more water-miscible solvents do not exceed 20% by weight of the extractant. Preferably, the extractant is aqueous and contains at least sodium hydroxide or potassium hydroxide. More preferably, the aqueous extractant has the following composition: 1-5% by weight, more preferably 2-4% by weight, particularly preferably 3% by weight of sodium hydroxide or potassium hydroxide, and the remainder is water.

[0042] The advantages of using an aqueous extractant include high dissociation constant, low dynamic viscosity, good diffusivity into the solid matrix of the coffee grounds, good wetting of the solutes, as well as short extraction times due to high solubility of the solutes from the coffee grounds.

[0043] The extractant has a pH value above 7, preferably above 8, more preferably above 10. Preferably, the pH value is below 14, for example 12-14.

[0044] First separation step

[0045] In the first separation step, the fluid phase containing solutes is separated from the coffee grounds. Suitable separation methods include, but are not limited to, centrifugation, maceration, percolation, filtration, and / or decoction.

[0046] In a suitable centrifugation method, the centrifugal force is more than 100 G (corresponding to gravity), preferably more than 500 G. The centrifugal force is preferably less than 10000 G, more preferably less than 5000 G, for example between 600 G and 800 G. Preferably, the centrifugation is carried out at a temperature above 0° C., more preferably above 5° C. Preferably, the temperature is less than 50° C., more preferably less than 30° C., for example between 10° C. and 20° C. The preferred duration of the centrifugation is more than 1 minute, preferably more than 5 minutes. The duration is preferably less than 4 hours, preferably less than 1 hour, for example between 10 minutes and 30 minutes. Preferably, at the end of the centrifugation, the supernatant containing the melanoidins is collected.

[0047] Precipitation process

[0048] In a first variant of the precipitation step, the fluid phase from the first separation step is contacted with an acid to obtain an acidic mixture having a pH value of less than 4, thereby forming a precipitate containing melanoidins. Preferably, the pH value is greater than 1 and less than 4, for example between 2 and 3.5.

[0049] Suitable acids include, but are not limited to, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and methanesulfonic acid. Preferably, the acid used in the precipitation step is hydrochloric acid.

[0050] In a second variant of the precipitation process, the fluid phase is contacted with an organic phase separating agent and with an acid to obtain a mixture having a pH value in the range of 4 to 8, thereby forming a precipitate containing melanoidins.

[0051] The mixture has a pH value of equal to or greater than 4. Preferably, the pH value is greater than 5, more preferably greater than 6. The mixture has a pH value of equal to or less than 8. Preferably, the pH value is less than 8, for example between 6.5 and 7.5.

[0052] Suitable organic phase separating agents include, but are not limited to, ethanol, ethyl acetate, tetrahydrofuran, and 2-methyltetrahydrofuran. Preferably, the organic phase separating agent is ethyl acetate.

[0053] The weight ratio of the organic phase separating agent to the fluid phase is preferably less than 1: 3. The weight ratio of the organic phase separating agent to the fluid phase is preferably greater than 1: 5, for example from 1: 3.5 to 1: 4.5.

[0054] Suitable acids for the second variant of the precipitation step include, but are not limited to, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, methanesulfonic acid. Preferably, the acid used in the second variant of the precipitation step is hydrochloric acid.

[0055] Preferably, the precipitation is carried out at a temperature below 50° C., more preferably below 40° C. Preferably, the precipitation is carried out at a temperature above 20° C.

[0056] Second Separation Step

[0057] In the second separation step, the formed precipitate is separated from the acidic mixture. Suitable separation methods include, but are not limited to, centrifugation, maceration, percolation, filtration, and / or decoction.

[0058] The process for preparing a melanoidin product according to the present invention is environmentally friendly and gives a high quality melanoidin product from coffee grounds. The melanoidin product obtained by the process according to the present invention is already nanoscale or can be easily converted into a nanoscale product.

[0059] Fractionation process

[0060] In a preferred embodiment of the method for preparing a melanoidin product, the second separation step comprises or follows a fractionation step in which the melanoidin-containing precipitate is separated by molecular weight fractionation.

[0061] In a preferred embodiment of the method, the fractionation is carried out by ultrafiltration, preferably using a membrane with the required molecular weight cut-off. Advantageously, ultrafiltration can give multiple retentates which can then be further processed.

[0062] In a preferred embodiment of the method, the fractionation is carried out by centrifugation or size exclusion chromatography. It is an achievable advantage of this embodiment of the invention that by appropriately selecting the minimum molecular weight of the compounds to be fractionated, caffeine (molecular weight 194 Daltons) can be substantially removed from the obtained retentate.

[0063] Liquid phase removal process

[0064] The product of the second separation or fractionation step, e.g., precipitate or residue, can be subjected to a liquid phase removal step to obtain the melanoidin fraction in solid form. In the case of aqueous extractants, suitable dehydration methods include, but are not limited to, freeze drying, spray drying, convection drying, radiation drying and vacuum drying. Preferably, the water removal step provides the melanoidin product as a powder. Preferred powder particles have an average particle size (mass-median-diameter D) of 1 nm (nanometer) or more, more preferably 10 nm or more. 50Preferably, the particles of the powder have an average particle size (D) of 50 μm (micrometers) or less, more preferably 5 μm or less, for example 10 nm to 1 μm. 50 ).

[0065] Nanoparticle manufacturing process / nanofiber manufacturing process

[0066] The product of the second separation step, the fractionation step or the liquid phase removal step, e.g. a precipitate or a residue, may be subjected to a nanoparticle production process in which nanoparticles are produced. Preferably, the nanoparticle production process comprises at least one method selected from the group of electrospraying, laser ablation, freeze drying, spray drying, convection drying, radiation drying, vacuum drying and ultrasonic particulation.

[0067] The product of the second separation step, the fractionation step or the liquid phase removal step, e.g., precipitate or residue, may be subjected to a nanofiber production process where nanofibers are produced. Preferably, the nanofiber production process comprises electrospinning. The nanofiber production process may comprise the addition of one or more auxiliary ingredients to the melanoidin fraction. These auxiliary ingredients may improve processability or fiber formation. In a preferred embodiment, polyvinyl alcohol is added as an auxiliary ingredient.

[0068] In one preferred embodiment, the second separation step comprises or is a step following a fractionation step in which a low molecular weight fraction of the formed precipitate is obtained, the average molecular weight of which is less than 10 kDa, and the second separation step is followed by a nanoparticle production step in which nanoparticles are produced from the low molecular weight fraction.Preferably, the nanoparticle production step comprises at least one method selected from the group consisting of electrospraying, laser ablation, freeze drying, spray drying, convection drying, radiation drying, vacuum drying and ultrasonic atomization.

[0069] In another preferred embodiment, the second separation step includes or is a step following a fractionation step in which a high molecular weight fraction of the formed precipitate is obtained having an average molecular weight of at least 10 kDa, where the second separation step is followed by a nanofiber production step in which nanofibers are produced from the high molecular weight fraction. Preferably, the nanofiber production step includes electrospinning. The nanofiber production step may include the addition of one or more auxiliary components to the melanoidin fraction. These auxiliary components may improve processability or fiber formation. In a preferred embodiment, polyvinyl alcohol is added as an auxiliary component.

[0070] Pretreatment

[0071] In another preferred embodiment of the method for preparing a melanoidin product, the extraction step is preceded by one or more pretreatment steps.

[0072] A preferred pretreatment is the micronization of the coffee grounds. In the context of the present invention, "micronization" is a process that reduces the average diameter of the particles of the coffee grounds. Preferably, the micronization is carried out by milling or grinding. A preferred mill is a ball mill. The average diameter of the coffee grounds after micronization is preferably less than 1500 μm, more preferably less than 1250 μm. The average diameter is preferably greater than 1 μm, more preferably greater than 100 μm.

[0073] Another preferred pretreatment is drying the coffee grounds. Preferably, during drying, the coffee grounds are exposed to a temperature of more than 50° C., more preferably more than 70° C. Preferably, the drying temperature is less than 110° C., for example between 70° C. and 90° C. The moisture content of the coffee grounds after drying is preferably less than 5%, more preferably less than 2%. The preferred drying time is more than 1 hour and less than 2 hours.

[0074] Another preferred pretreatment is the defatting of the coffee grounds. In a preferred defatting method, at least a portion of the lipids and / or oils present in the coffee grounds are extracted with a suitable solvent, such as carbon dioxide. Preferably, the carbon dioxide is applied at a pressure and temperature such that it becomes a supercritical fluid.

[0075] In another preferred degreasing method, which is particularly suitable for used coffee grounds, at least a portion of the lipids and / or oils present in the coffee grounds is extracted with an organic solvent, such as ethanol, diethyl ether or chloroform.

[0076] The lipid content of the coffee grounds after defatting is preferably less than 2%, more preferably less than 1%, which advantageously achieves an increased yield in the subsequent extraction step and prevents the potential formation of oil-extraction solvent emulsions.

[0077] The above and other pretreatments can be carried out alone or in any combination. Preferably, micronization is carried out before drying and / or degreasing, rather than after the latter steps.

[0078] Melanoidin nanoparticles and nanofibers

[0079] In a second aspect of the invention the problem is solved by providing melanoidin nanoparticles and melanoidin nanofibers obtainable by the method according to the invention.

[0080] In one preferred embodiment, the melanoidin product is nanoparticles having an average diameter of between 1 nm and 800 nm.

[0081] Preferably, the nanoparticles have an average diameter of more than 1 nm, more preferably more than 10 nm. Preferably, the nanoparticles have an average diameter of less than 1000 nm, more preferably less than 800 nm, for example between 40 nm and 600 nm.

[0082] Preferably, the melanoidin nanoparticles comprise more than 70% by weight melanoidin, more preferably more than 80% by weight melanoidin, even more preferably more than 90% by weight melanoidin, especially more than 95% by weight melanoidin.

[0083] It is further preferred that the melanoidin contains 1% to 15% by weight of phenolic compounds. Preferably, the melanoidin contains more than 2% by weight of phenolic compounds, more preferably more than 3% by weight of phenolic compounds. Preferably, the melanoidin contains less than 14% by weight of phenolic compounds, more preferably less than 13% by weight of phenolic compounds, for example 4 to 12% by weight of phenolic compounds.

[0084] The term "phenolic compounds" means the sum of all phenols and polyphenols present in the melanoidin product, including, but not limited to, phenols, polyphenols, and phenolic acids, such as gallic acid, chlorogenic acid, caffeic acid, and salicylic acid.

[0085] Quantitative analysis of the phenolic compounds can be performed using the Folin-Ciocalteu reagent, which is well established in the art and is a mixture of phosphomolybdate and phosphotungstate, typically used for the in vitro colorimetric analysis of phenolic and polyphenolic antioxidants.

[0086] More preferably, the melanoidin contains 1% to 40% by weight of protein. Preferably, the melanoidin contains more than 5% by weight of protein, more preferably more than 10% by weight of protein. Preferably, the melanoidin contains less than 35% by weight of protein, for example 20 to 30% by weight of protein.

[0087] Quantitative analysis of protein content can be performed using the Bradford protein assay, which is a spectrophotometric method used to measure protein concentration in a solution and is well established in the art.

[0088] In another preferred embodiment, the melanoidin product is a nanofiber.

[0089] Preferably, the nanofibers have an average diameter of more than 1 nm, more preferably more than 10 nm. Preferably, the nanofibers have an average diameter of less than 1000 nm, more preferably less than 800 nm, for example between 40 nm and 600 nm.

[0090] Preferably, the melanoidin nanofibers comprise more than 50% by weight melanoidin, more preferably more than 70% by weight melanoidin, even more preferably more than 90% by weight melanoidin, especially more than 95% by weight melanoidin.

[0091] It is further preferred that the melanoidin contains 1% to 15% by weight of phenolic compounds. Preferably, the melanoidin contains more than 2% by weight of phenolic compounds, more preferably more than 3% by weight of phenolic compounds. Preferably, the melanoidin contains less than 14% by weight of phenolic compounds, more preferably less than 13% by weight of phenolic compounds, for example 4 to 12% by weight of phenolic compounds.

[0092] More preferably, the melanoidin contains 1% to 40% by weight of protein. Preferably, the melanoidin contains more than 5% by weight of protein, more preferably more than 10% by weight of protein. Preferably, the melanoidin contains less than 35% by weight of protein, for example 20 to 30% by weight of protein.

[0093] The melanoidin nanoparticles and nanofibers obtained from coffee grounds according to the present invention have been found to have advantageous properties that enable a wide range of applications, including, but not limited to, good solubility in water and other solvents, a wide light absorption range, and antibacterial and antioxidant properties.

[0094] Moreover, it has been found that the melanoidin nanoparticles and melanoidin nanofibers obtained from coffee grounds according to the present invention have high heat conversion efficiency and excellent electrical conductivity compared to known melanoidin products.

[0095] Uses of melanoidin nanoparticles and nanofibers

[0096] A further aspect of the invention is an electronic component comprising a melanoidin product according to the invention, which may comprise melanoidin nanoparticles and / or melanoidin nanofibers.

[0097] The electrical conductivity of nanoscale melanoidin products according to the present invention enables the development and provision of environmentally friendly and sustainable electronic components, including but not limited to computers, memory storage, displays, optoelectronic devices, printed circuits, conductive liquids, solar collectors, solar heating, and solar evaporation.

[0098] A further aspect of the invention is a conductive liquid comprising a melanoidin product according to the invention, which may comprise melanoidin nanoparticles and / or melanoidin nanofibers.

[0099] In a preferred embodiment, the conductive liquid is a conductive ink. The conductive ink according to the present invention can be used in a variety of applications in printed electronics, such as flexible circuits, resistors, heating elements, displays, sensors, RFID antennas, smart tattoos.

[0100] A further aspect of the invention is the use of the melanoidin product according to the invention in photothermal applications, in particular in photothermal therapy, photodynamic therapy, photothermal catalysis, photothermal antibacterial treatment, solar collectors, solar heating, solar evaporation, which melanoidin product may comprise melanoidin nanoparticles and / or melanoidin nanofibers.

[0101] A further aspect of the invention is the use of a melanoidin product according to the invention, which may comprise melanoidin nanoparticles and / or melanoidin nanofibers, for drug delivery applications.

[0102] In a preferred embodiment, the melanoidin product is used for topical drug delivery. In another preferred embodiment, the melanoidin product is used for transdermal drug delivery. In both embodiments, a controlled release of a drug or other active ingredient can be achieved. Due to its favorable biocompatibility, the melanoidin product can be degraded through natural pathways in the body.

[0103] Preferably, the melanoidin nanoparticles and / or nanofibers according to the invention are used to provide a matrix in which a drug or active ingredient is placed, and when applied to the skin, for example as a cream, lotion, ointment or adhesive tape, the melanoidin nanoparticles and / or nanofibers can penetrate the skin and deliver the drug or active ingredient into the body.

[0104] In a further embodiment for drug delivery, the melanoidin product is used in a medical product for subcutaneous injection applications. In a preferred medical product of this type, the melanoidin product is combined with a drug or active ingredient. The medical product is placed under the skin, for example as a wound tissue after surgery, or as a drug depot that continuously delivers a drug amount to the body for a controlled medical treatment over a period of time.

[0105] In a further embodiment for drug delivery, the melanoidin product is used in a medical product for oral use. In a preferred medical product of this type, it is foreseen that the drug or active ingredient is delivered to the intestine. By using the melanoidin product as a carrier, the drug or active ingredient can then penetrate the intestinal wall.

[0106] The melanoidin nanoparticles and nanofibers according to the invention are particularly well suited for medical applications due to their good biocompatibility and beneficial properties, such as antibacterial properties.

[0107] A further aspect of the invention is the use of the melanoidin products according to the invention, which may comprise melanoidin nanoparticles and / or melanoidin nanofibers, for bioelectronic applications. The melanoidin products according to the invention are particularly well suited for these applications due to their conductive properties.

[0108] In one variation, the melanoidin products are used for neural biointerface applications, particularly implant applications, including but not limited to bioelectrodes, neural interfaces, neural electrode-tissue interfaces, cardiac interfaces, bone tissue biomaterials, artificial tissue biomaterials, tissue regeneration, stretchable bioelectronics, conductive hydrogels for neural interfaces.

[0109] In a further variation, the melanoidin products are used for bio-actuator applications, for example, neurostimulation, mechanical actuation, bioactuators, dynamic actuation such as e-skin, e-muscle applications, artificial joints.

[0110] For all medical applications, the terms "skin" and "body" may refer to human skin and body, as well as animal skin and body.

[0111] A further field of application of the melanoidin nanoparticles and melanoidin nanofibers of the invention obtained from coffee grounds is cosmetic compositions. A further subject of the invention therefore includes, but is not limited to, the following list of cosmetic embodiments, where the term "nanoscale melanoidin product" means melanoidin nanoparticles having an average diameter between 1 nm and 1000 nm and / or melanoidin nanofibers having an average diameter between 1 nm and 1000 nm.

[0112] As used herein, the term "cosmetic" is used in accordance with the definition applicable in the US Federal Food, Drug and Cosmetic Act (amended December 19, 2002 by PL 107-377) as "articles intended to be rubbed, poured, sprinkled, or sprayed on, introduced into, or otherwise applied to the human body...for cleansing, beautifying, promoting attractiveness, or altering the appearance." In its broadest disclosure, the form of the cosmetic composition of the present invention is not particularly limited and may be a liquid, emulsion, paste, gel, solid powder, or compact powder. Specific examples of such cosmetic compositions include face washes, facial treatments such as skin lotions, skin milks, creams, gels, serums and facial masks, preparations of facial and eye make-up such as face powders, foundations, lip rouge, blush, eyeliner, mascara, eyeshadow and eyebrow pencils, tattoos including permanent make-up, hair cosmetic compositions such as shampoos, rinses, conditioners, hair styling products, hair treatments and hair colorants. Particularly included within this definition are preparations of eye and facial make-up, tattoos including permanent make-up, and hair colorants.

[0113] The term "solid" as used herein with respect to a cosmetic composition refers to the state of the composition at room temperature and atmospheric pressure: the composition has a high consistency that retains its form during storage and does not flow under its own weight.

[0114] As used herein, the term "structurant" refers to any material known or otherwise effective to provide suspending, gelling, thickening, solidifying and / or thickening properties to the composition, or to otherwise provide structure to the final product form. These solid structurants include one or more solid crystals or other non-polymeric suspending agents suitable for topical application to human skin. Suitable suspending agents are those capable of forming a crystalline or other matrix in the composition in which volatile solvents, non-volatile solvents, or other liquid components of the composition are included. Such materials are typically solid under ambient conditions and include organic solids, waxes, crystalline or other gelling agents, or combinations thereof. The structurant provides uniform distribution of particulate actives throughout the product, and also controls the hardness or rheology of the product. For completeness, suitable crystalline structurants for use in the solid compositions disclosed herein are described in, inter alia, U.S. Pat. No. 5,552,136 (Motley), U.S. Pat. No. 5,976,514 (Guskey et al.), and U.S. Pat. No. 5,891,424 (Bretzler et al.).

[0115] The term "compact powder" refers to a mass of product that has at least partially received its cohesive strength through compression or pressure during manufacture. In particular, compact powders should have a pressure resistance of 0.1 to 2.5 kg relative to the surface area of ​​the spindle used, as measured using a TA.XT.plus Texture Analyser texturometer available from Stable Micro Systems. This resistance measurement was performed using an SMS P / 3 flat head cylindrical spindle (7.07 mm2 ) over a distance of 1.5 mm and at a speed of 0.5 mm / s.

[0116] The term "tattoo" refers to an indelible mark or design on a mammalian body obtained through the insertion of pigment under the skin using a needle, scalpel, or other related instrument. The term is intended to encompass both intraepidermal and intradermal tattoos, which are distinguished, inter alia, by the degree of permanence of the tattoo.

[0117] As used herein, "keratinous tissue" refers to the keratin-containing layer that is disposed as the outermost protective covering of a mammal, including, but not limited to, the skin, hair, nails, and cuticles. There is no particular intention to limit the sites of keratinous tissue to which the cosmetic composition of the present invention may be applied, and reference may be made to keratinous tissue exposed on the face, neck, chest, back, arms (including armpits), hands, legs, feet, buttocks, and scalp.

[0118] As used herein, the term "epidermis" refers to the outer layer of the skin in which the predominant cell type is keratinocytes. As understood by those skilled in the art, the epidermis is conventionally divided into five strata: stratum corneum; stratum granulosum; stratum spinosum; and stratum basale. The stratum corneum is often referred to as non-viable and contains many layers of dead, anucleated keratinocytes that are substantially filled with keratin. The stratum corneum contains 2-3 layers of anucleated cells. The stratum granulosum contains 2-4 layers of cells that are connected by desmosomes that contain keratohyaline granules. The stratum spinosum contains 8-10 layers of moderately actively dividing cells that are held together by desmosomes. The stratum basale contains a single layer of columnar cells, which actively divide by mitosis and provide the cells that migrate through the upper epidermis into the stratum corneum.

[0119] As used herein, the term "dermis" refers to the layer of skin between the epidermis and the subcutaneous tissue. The dermis provides structural support to the skin and contains acellular collagen fibers derived from fibroblasts.

[0120] As used herein, the term "hair" refers to mammalian keratin fibers and includes scalp, facial and body hair. In addition, the term includes both hair that is attached to a living subject and hair that has been removed therefrom. For the avoidance of doubt, "hair shaft" or "hair fiber" refers to an individual strand of hair.

[0121] The expression "proximal to the scalp" refers to an extended or substantially straightened hair shaft, that portion of the hair that is closer in distance to the scalp than the end of the hair. Hereby, 50% of the length of the hair fiber is considered to be proximal to the scalp, and 50% of the length of the hair fiber is considered to be distal to the scalp. When used proximal to the scalp, "x cm" refers to the distance "x" along an extended or substantially straightened hair, measured with the scalp as the end point.

[0122] By "cosmetically acceptable" it is meant that the compositions, formulations or ingredients described herein are suitable for use in contact with human keratinous tissue without undue toxicity, incompatibility, instability, allergic reaction, etc. All compositions and formulations described herein that are intended to be applied directly to keratinous tissue are limited to being cosmetically acceptable.

[0123] As used herein, the term "topical application" means applying or spreading the compositions of the present invention onto the surface of the skin.

[0124] Water for use as a (co)solvent herein is intended to mean water with a low solids content, as would be understood by one of ordinary skill in the art. The water may be, for example, distilled water, demineralized water, deionized water, reverse osmosis water, boiler condensate water, or ultrafiltered water. Tap water, although acceptable in some circumstances, is not acceptable within the tattoo ink compositions described herein.

[0125] As used herein, a "solvent" is a substance that can dissolve other substances to form a homogeneous solution, where neither the solvent nor the dissolved substances undergo chemical changes during dissolution. Solvents may be polar or non-polar. The term "alcohol solvent" includes solvents that are water-soluble monoalcohols, diols, or polyols that are liquid at 25° C. under atmospheric pressure.

[0126] If the organic liquid product has a boiling range, the beginning (minimum temperature) of the boiling range at atmospheric pressure is treated as the nominal boiling point. If necessary, measurements of the initial boiling point of the material should be made in accordance with ASTM Standard Test Method D1078-95 or its latest edition.

[0127] As used herein, the term "water-miscible organic solvent" refers to an organic solvent that is completely miscible with water at room temperature. In this regard, organic solvents that are soluble, freely soluble or highly soluble in water and are thereby characterized by requiring ≦30 ml of water to dissolve 1 g of the organic solvent at room temperature are particularly preferred (https: / / www.sigmaaldrich.com / united-kingdom / technical-services / solubility.html).

[0128] As used herein, the term "water-immiscible organic solvent" refers to an organic solvent that forms a two-phase system with water. In this regard, organic solvents that are slightly soluble, very slightly soluble, or substantially insoluble in water and thereby characterized by requiring ≧100 ml of water to dissolve 1 g of the organic solvent at room temperature are particularly preferred (https: / / www.sigmaaldrich.com / united-kingdom / technical-services / solubility.html).

[0129] As used herein, the term "dispersion" refers to a composition that includes discrete particles dispersed throughout a continuous liquid medium.

[0130] As used herein, the term "surface tension" refers to the force required to increase the surface area of ​​a liquid, the interface between two liquids, or the interface between a liquid and a gas, typically measured in dynes / cm. Surface tension as described herein is measured by the Du Nouy ring method using an EasyDyne Tensiometer Model K20 sold by Kruss USA, Matthews, NC.

[0131] As used herein, "C1-C n An "alkyl" group refers to a monovalent group containing 1 to n carbon atoms, which is a radical of an alkane, and includes linear and branched organic groups. Thus, a "C1-C6 alkyl" group refers to a monovalent group containing 1 to 6 carbon atoms, which is a radical of an alkane, and includes linear and branched organic groups. Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl. In the present invention, such alkyl groups may be unsubstituted or substituted with one or more halogen atoms. If applicable, the priority for a given substituent will be described in the specification.

[0132] As used herein, the term "C2-C6 alkylene" is defined as a saturated divalent hydrocarbon radical having two to six carbon atoms.

[0133] The compositions of the present invention are defined herein as being "substantially free" of a certain compound, element, ion, or other similar component. The term "substantially free" is intended to mean that the compound, element, ion, or other similar component is not intentionally added to the composition and is present at most in trace amounts that do not (adversely) affect the desired properties of the composition. An exemplary trace amount is less than 1000 ppm by weight of the composition. The term "substantially free" encompasses those embodiments in which a particular compound, element, ion, or other similar component is completely absent from the composition or is absent in any amount that can be measured by techniques commonly used in the art.

[0134] Cosmetic embodiment 1 is a cosmetic composition comprising a nanoscale melanoidin product.

[0135] Cosmetic embodiment 2 is a cosmetic composition comprising a nanoscale melanoidin product, wherein the nanoscale melanoidin product has a weight average molecular weight of 200 Daltons (Da) to 300 kilodaltons (kDa), preferably 1 to 300 kDa, more preferably 1 to 100 kDa, and most preferably 10 to 100 kDa.

[0136] Cosmetic embodiment 3 are cosmetic compositions comprising nanoscale melanoidin products having a more narrowly defined molecular weight, e.g., 10-30 kDa, 30-50 kDa, 50-100 kDa, or 100-200 kDa, where, for example, a particular pigmentary or light absorption effect is desired. It is also envisaged that there may be two or more nanoscale melanoidin product fractions: for example, a first fraction based on nanoscale melanoidin products having a weight average molecular weight of 10-30 kDa may be combined in the cosmetic composition with a second fraction based on nanoscale melanoidin products having a weight average molecular weight of 50-100 kDa or 100-200 kDa.

[0137] Cosmetic embodiment 4 is a cosmetic composition comprising a nanoscale melanoidin product, wherein the cosmetic composition is a non-powder solid cosmetic composition, a compact powder cosmetic composition, or an aqueous liquid cosmetic composition.

[0138] Cosmetic embodiment 5 is a cosmetic composition comprising an essentially caffeine-free nanoscale melanoidin product.

[0139] Cosmetic embodiment 6 teeth, a) a nanoscale melanoidin product, wherein the nanoscale melanoidin product has a weight average molecular weight of 200 Daltons to 300 kDa, preferably 1 to 300 kDa, more preferably 1 to 100 kDa; and b) at least one auxiliary selected from the group consisting of wetting agents, swelling agents, penetrating agents, pH adjusting agents, surfactants, thickening agents, antibacterial agents, and fragrances; The aqueous hair dye composition comprises:

[0140] Cosmetic embodiment 7 is based on the weight of the composition, a) 5-20% by weight of a nanoscale melanoidin product, wherein the nanoscale melanoidin product has a weight average molecular weight of 200 Daltons to 300 kDa, preferably 1-300 kDa, more preferably 1-100 kDa; and b) 5 to 40% by weight of at least one auxiliary selected from the group consisting of wetting agents, swelling agents, penetrating agents, pH adjusters, surfactants, thickening agents, antibacterial agents, and fragrances; and c) 40 to 90% by weight of water The aqueous hair dye composition comprises:

[0141] With regard to the aqueous hair dye composition, it is preferred that the composition contains 40-90% by weight, preferably 40-80% by weight, more preferably 55-75% by weight of water, based on the weight of the composition, where the sum of the above components a), b) and c) is always 100% by weight. In an alternative, but not mutually exclusive characterization, the aqueous hair dye composition may be defined by a viscosity of 0.005-50 Pa.s, as measured using a Brookfield viscometer at 25°C.

[0142] Ingredient b) in embodiment 7 of the cosmetic product represents a classification based on the benefit provided by the agent or based on the assumed mode of action of the agent. This classification is made for convenience, for example, a given chemical ingredient, e.g., ammonia, may provide multiple benefits or act via multiple modes of action.

[0143] Exemplary humectants that may be used alone or in combination include, but are not limited to, glycerin, propylene glycol, sorbitol, 1,3-butylene glycol, polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), polypropylene glycol (PPG), PEG / PPG-block copolymers, and PEG / PPG-random copolymers. An exemplary PEG / PPG-random copolymer is PEG / PPG-8 / 17.

[0144] Exemplary swelling agents include ammonia and monoethanolamine (MEA). Ammonia, if included, will be present in the aqueous compositions of the present invention as an ammonia solution, NH3 (aqueous). This includes a weakly basic solution of ammonia in water that may be referred to in the art as ammonium hydroxide, aqueous ammonia, ammonia liquor, aqua ammonia, aqueous ammonia, or simply ammonia. The term "ammonium hydroxide" refers to a solution of ammonia having the composition [NH4 + ][OH - [1,2], it is virtually impossible to isolate a sample of NHOH, since except in extremely dilute aqueous ammonia solutions, these ions do not constitute a significant proportion of the total amount of ammonia in the aqueous ammonia solution.

[0145] Exemplary penetrants that may be used alone or in combination include monohydric alcohols having C1 to C6 alkyl groups, such as ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol; polyhydric alcohols having 3 to 8 carbon atoms, such as propanediol, butanediol, pentanediol, hexanediol, hexanetriol, heptanediol, heptanetriol, octanediol, octanetriol, isoprene glycol, propylene glycol, glycerin, and diethylene glycol monoethyl ether; esters of the above polyhydric alcohols; These include certain N-alkylpyrrolidones, such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-butyl-2-pyrrolidone and N-cyclohexyl-2-pyrrolidone; C2-C6 alkylene carbonates, such as ethylene carbonate and propylene carbonate; aromatic alcohols, such as benzyl alcohol, benzyloxyethanol, cinnamyl alcohol, p-anisyl alcohol, p-methylbenzyl alcohol, phenoxyethanol, phenoxyisopropanol, 2-benzylethanol, β-phenylethyl alcohol. 2-Propanol, 1,2-hexanediol and benzyl alcohol may be mentioned as being preferred.

[0146] Examples of pH adjusters include mineral acids, such as phosphoric acid; hydroxycarboxylic acids, such as lactic acid, glycolic acid, citric acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 2-hydroxybutanedioic acid, 2,3-dihydroxybutanedioic acid, 3-hydroxyvaleric acid, 5-hydroxyvaleric acid, 6-hydroxycaproic acid and alkali metal or alkaline earth metal salts thereof; ammonia; alkali metal hydroxides; alkali metal carbonates; alkali metal hydrogen carbonates; alkaline earth metal hydroxides; alkaline earth metal carbonates; and alkaline earth metal hydrogen carbonates.

[0147] The aqueous hair dye composition of the present invention typically comprises up to 10% by weight of surfactant, for example up to 5% by weight or up to 3% by weight, based on the weight of the composition. A wide variety of surfactants may be used herein. Desirable surfactants for emulsifying the dispersed phase and for providing acceptable spreading of the applied composition are selected from the group consisting of anionic surfactants, nonionic surfactants, amphoteric surfactants, non-lathering surfactants, emulsifiers, and combinations thereof. U.S. Patent No. 6,280,757 (McAtee et al.) provides a useful disclosure of suitable surfactants.

[0148] Anionic surfactants: Non-limiting examples of anionic surfactants useful in the compositions of the present invention are disclosed in US Patent No. 3,929,678 (Laughlin et al.) and US Patent No. 4,557,853. Mention may be made of anionic surfactants selected from the group consisting of: i) fatty acid soaps based on fatty acids having 8 to 36 or 8 to 24 carbon atoms; ii) monoalkyl, dialkyl and trialkyl phosphate salts; iii) sarcosinates, such as sodium lauroyl sarcosinate, sodium myristoyl sarcosinate and sodium cocoyl sarcosinate; iv) sulfates, such as the sulfates of the above, including alkyl sulfates and alkyl ether sulfates, such as sodium lauryl sulfate, ammonium lauryl sulfate, ammonium laureth sulfate, sodium laureth sulfate, tridecane sulfate, ammonium lauryl sulfate, ammonium laureth sulfate, sodium laureth sulfate, tridecane sulfate, ammonium lauryl sulfate, ammonium laureth sulfate, sodium laureth sulfate, tridecane sulfate, ammonium lauryl sulfate, ammonium lauryl sulfate, sodium laureth sulfate, tridecane ... Mention may be made of sodium cetyl sulfate, ammonium cetyl sulfate and sodium cetyl sulfate; v) isethionates, such as sodium lauroyl isethionate and ammonium cocoyl isethionate; vi) taurates, such as sodium lauroyl methyl taurate and sodium cocoyl methyl taurate; vii) lactylates, such as sodium lauroyl lactylate, triethanolamine lauroyl lactylate and sodium caproyl lactylate; viii) glutamate, such as sodium lauroyl glutamate, sodium myristoyl glutamate and sodium cocoyl glutamate; and mixtures thereof.

[0149] Nonionic Surfactants: Suitable nonionic surfactants having utility in the present disclosure include alkyl glucosides; alkyl polyglucosides; polyhydroxy fatty acid amides; alkoxylated fatty acid esters; sucrose esters; amine oxides; and mixtures thereof. For example, C8-C 14 Glucose amide, C8-C 14 Mention may be made of alkyl polyglucosides, sucrose cocoate, sucrose laurate, lauramine oxide, cocoamine oxide and combinations thereof.

[0150] Amphoteric surfactants: as used herein, the term "amphoteric surfactants" is also intended to include zwitterionic surfactants. Useful amphoteric surfactants that can be used alone or in combination include, but are not limited to, derivatives of aliphatic secondary and tertiary amines, preferably where the nitrogen is in a cationic state and where at least one aliphatic radical has an ionizable water-soluble group, such as carboxyl, sulfonate, sulfate, phosphate or phosphonate, betaine, sultaine, hydroxysultaine, alkyliminoacetate, iminodialkanoate, and aminoalkanoate.

[0151] Non-lathering surfactants: Considering that the hair dye compositions of the present invention are not conventionally intended to have a cleansing function, therefore, they do not need to be lathering systems and can include non-lathering surfactants. Exemplary non-lathering surfactants having utility herein include polyethylene glycol 20 sorbitan monolaurate (polysorbate 20); polysorbate 60; polysorbate 80; polyoxyethylene 20 sorbitan trioleate (polysorbate 85); steareth 20; ceteth-10; ceteareth-20; cetyl phosphate; potassium cetyl phosphate; cetyl diethanolamine phosphate; glyceryl stearate; PPG-2-methyl glucose ether distearate; and PEG-100 stearate.

[0152] Emulsifier systems: In addition to the above, the use of one or more emulsifiers is not excluded in this disclosure. The following emulsifier mixtures may be mentioned: PROLIPID available from ISP 登録商標 141 (glyceryl stearate, behenyl alcohol, palmitic acid, stearic acid, lecithin, lauryl alcohol, myristyl alcohol and cetyl alcohol); PROLIPID available from ISP 登録商標151 (Glyceryl stearate, Cetearyl alcohol, Stearic acid, 1-propanamide, 3-amino-N-(2-(hydroxyethyl)-N-N-dimethyl, N-C(16-18) acyl derivative, chloride); POLAWAX available from Croda 登録商標 NF (emulsifying wax NF); INCROQUAT available from Croda 登録商標 BEHENYL TMS (behentrimonium sulfate and cetearyl alcohol); and EMULLIUM available from Gattefosse 登録商標 DELTA (Cetyl Alcohol, Glyceryl Stearate, PEG-75 Stearate, Ceteth-20 and Steareth-20).

[0153] The aqueous hair dye compositions of the present disclosure may contain 0-10% by weight, for example 0-5% by weight, of one or more thickening agents, based on the weight of the composition. The thickening agents may be selected from: i) carboxylic acid polymers, such as CARBOPOL available from BFGoodrich. 登録商標 900 series; ii) Acrylate / C 10 ~C 30 Alkyl acrylate crosspolymers, such as CARBOPOL available from BFGoodrich 登録商標 1342, CARBOPOL 登録商標 1382, PEMULEN 登録商標 TR-1 and PEMULEN 登録商標TR-2; iii) crosslinked polyacrylate polymers which may be cationic or nonionic; iv) polyacrylamide polymers, particularly nonionic polyacrylamide polymers; iv) multiblock copolymers of acrylamide and substituted acrylamide with acrylic acid and substituted acrylic acid; v) polysaccharides such as those listed above, including scleroglucans, cellulose and cellulose derivatives such as carboxymethylcellulose and alkylhydroxyalkylcellulose ethers; vi) modified starches; vii) gums such as xantham gum, acacia gum, arginine, sodium alginate, locust bean gum and guar gum; viii) proteins such as collagen, albumin and gelatin; and combinations thereof.

[0154] The aqueous hair dye composition of the present disclosure may contain 0-5% by weight, preferably 0-2% by weight, of at least one antimicrobial agent based on the weight of the composition. The or each antimicrobial agent contained in the composition is preferably a crystalline particle that is insoluble in water. Exemplary antimicrobial agents include, but are not limited to, sulfur; piroctone olamine; selenium sulfide as described in U.S. Pat. Nos. 2,694,668, 3,152,046, and 4,089,945; and pyridinethione salts as described in U.S. Pat. Nos. 3,753,196, 4,345,080, 4,323,683, and 4,470,982.

[0155] Examples of fragrances that may be included in the aqueous hair dye composition include vanillin, cinnamic alcohol, heliotropin, coumarin, 2-methyl-3-(3,4-methylenedioxy-phenyl)-propanal, 4-(4-hydroxyphenyl)-2-butanone, benzaldehyde, anisyl alcohol, 3,4-dimethoxybenzaldehyde, heliotropyl acetate, phenylacetaldehyde dimethyl acetal, phenoxyethyl alcohol, phenylacetaldehyde glyceryl acetal, benzyl alcohol, phenylethyl alcohol, furaneol, sugar lactone, menthol, ethyl diglycol, benzyl acetate, linalool, camphor, terpineol, citronellol, geraniol, 2,6-nonadienol, methyl octyl 20 carbonate, 3,7-dimethyl-2,6-octadienal, and nonanal.

[0156] The hair dye compositions of the present invention may be applied to at least a portion of the hair shaft using conventional means, including, for example, by finger, by hand, by brush or by another implementation, optionally in conjunction with a means for providing thermal energy or suitable electromagnetic radiation. One or more of the compositions may be applied to wet hair or to dry hair 25. The amount applied will vary depending on the thickness and length of the hair and the desired effect.

[0157] One or more hair dye compositions may be applied to substantially all of the hair, or alternatively, to a portion of the hair. In one embodiment, the compositions may be applied to a portion of the hair adjacent to the scalp, for example, 0-10 cm or 0-5 cm adjacent to the scalp. This may be desirable for a user to modify the color of the roots 30 of newly grown hair.

[0158] Cosmetic embodiment 8 is a water-based tattoo ink composition, a) at least one colorant, wherein the at least one colorant comprises a nanoscale melanoidin product, the nanoscale melanoidin product having a weight average molecular weight of 200 Daltons to 300 kDa, preferably 1 to 300 kDa, more preferably 1 to 100 kDa; and b) at least one adjuvant selected from the group consisting of binders, thickeners, pH adjusters, surfactants, humectants, antibacterial agents, anti-inflammatory agents, antioxidants, preservatives, and local anesthetics; Includes.

[0159] Optionally, the water-based tattoo ink can further include at least one co-solvent.

[0160] Cosmetic embodiment 9 is an aqueous tattoo ink composition in which the sum of the following components of the composition is 100% by weight, based on the weight of the composition: a) 10-40% by weight of water; b) 30-60% by weight of at least one colorant, wherein the at least one colorant comprises a nanoscale melanoidin product, the nanoscale melanoidin product having a weight average molecular weight of 200 Daltons to 300 kDa, preferably 1 to 300 kDa, more preferably 1 to 100 kDa; c) 0 to 15% by weight of at least one co-solvent; and d) 5-15% by weight of at least one adjuvant selected from the group consisting of binders, thickeners, pH adjusters, surfactants, humectants, antibacterial agents, anti-inflammatory agents, antioxidants, preservatives, and local anesthetics.

[0161] Ingredient d) in embodiment 9 of the cosmetic product represents a classification based on the benefit provided by the auxiliary or based on the assumed mode of action of the auxiliary. This classification is made for convenience, and a given chemical ingredient, such as polyethylene glycol, may provide multiple benefits or act through multiple modes of action. In this regard, it is reiterated here that nanoscale melanoidin products themselves provide pigment function and act as antibacterial, anti-inflammatory and antioxidant, thereby minimizing the need to provide auxiliary ingredients with these functionalities.

[0162] The aqueous tattoo ink composition of the present invention may contain, in addition to the melanoidins described above, further colorants. The colorants are necessarily water-soluble or water-dispersible and may be selected from: inorganic pigments; organic pigments; natural dyes; synthetic dyes; and combinations thereof. The use of organic pigments, lacquered pigments or lacquer pigments ("lake pigments"), obtained by precipitating natural or synthetic dyes with metal salts, is also envisaged. However, it is preferred that the formulation is substantially free of metal particles or substantially free of microencapsulated colorants.

[0163] For completeness, exemplary inorganic pigments include, but are not limited to, metal oxides such as iron oxide red, iron oxide yellow, iron oxide black, anatase, brookite, rutile, aluminum oxide, zirconium oxide, cobalt oxide, cerium oxide, nickel oxide, chromium oxide, nickel chromium oxide, zinc oxide, and composite oxides; metal hydroxides such as calcium hydroxide, iron hydroxide, aluminum hydroxide, chromium hydroxide, magnesium hydroxide, and composite metal hydroxides; Prussian blue; iron sulfide; manganese violet; carbon black; mica; and kaolin.

[0164] The aqueous tattoo ink composition may include at least one water-miscible organic co-solvent. If present, the water and the at least one water-miscible organic solvent should be mixed in a weight ratio of 20:80 to 80:20, such as 30:70 to 70:30. In preferred additional descriptions of the weight ratios described above, which are not intended to be mutually exclusive, the water-miscible organic solvent or mixture of water-miscible organic solvents included in this section are preferably selected and added to the water in an amount sufficient to reduce the surface tension of the water / solvent combination to less than 64 dynes / cm at room temperature.

[0165] The at least one water-miscible organic solvent of the present invention may be selected from the group consisting of: 1~6 Alkanols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-pentanol; cyclopentanol; cyclohexanol; diols, in particular diols having 2 to 12 carbon atoms, such as ethylene glycol, propylene glycol, butylene glycol, 1,5-pentanediol, pentylene glycol, hexylene glycol, but including thiodiglycol, and oligo- and polyalkylene glycols, such as diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol and polypropylene glycol; triols, such as 1,2,6-hexanetriol; ketones and ketone alcohols, such as acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, methyl isobutyl ketone, cyclohexanone and diacetone alcohol; tetrahydrofuran; dioxane; mono-C diols having 2 to 12 carbon atoms. 1~4-alkyl ethers, such as ethylene glycol mono-(C1-C4)-alkyl ethers, propylene glycol mono-(C1-C4)-alkyl ethers, in particular ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether; diethylene glycol mono(C1-C4)-alkyl ethers, such as diethylene glycol monomethyl ether and diethylene glycol monobutyl ether; dipropylene glycol mono(C1-C4)-alkyl ethers, ethers, such as dipropylene glycol N-propyl ether, dipropylene glycol monopropyl ether and dipropylene glycol monobutyl; propylene glycol phenyl ether; linear amides, such as N,N-dimethylformamide and N,N-dimethylacetamide; cyclic amides, such as 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, caprolactam and 1,3-dimethylimidazolidone; sugar esters, such as dimethyl isosorbide; cyclic esters, such as caprolactone; and sulfoxides, such as dimethyl sulfoxide and sulfolane.

[0166] The at least one water-miscible solvent is preferably selected from acetone, diacetone alcohol, isopropyl alcohol, and combinations thereof.

[0167] While the presence of water-immiscible organic solvents in the formulation is not strictly excluded, it is not intended to represent a preferred embodiment, rather it is preferred that the formulation is essentially free of water-immiscible organic solvents and is present as a single continuous aqueous phase.

[0168] With regard to component d) above, binders or binding agents are conventional components of aqueous tattoo ink compositions, which may be present in an amount of up to 5% by weight, based on the weight of the composition. The binder is a non-volatile component that binds the particulate colorants together, thereby facilitating the introduction of the ink into the skin or into the epidermis using an injection means, such as a needle. Polyvinylpyrrolidone (PVP), particularly polyvinylpyrrolidone having a weight average molecular weight of 1 to 3000 kDa, polyethylene glycol (PEG), particularly polyethylene glycol having a weight average molecular weight of 0.2 to 6 kDa, polypropylene glycol (PPG), particularly polypropylene glycol having a weight average molecular weight of 0.2 to 6 kDa, PEG / PPG block copolymers, particularly PEG / PPG block copolymers having a weight average molecular weight of 5 to 15 kDa, PEG / PPG random copolymers, and shellac resins.

[0169] The aqueous tattoo ink composition typically comprises up to 5% by weight, such as up to 3% by weight, of a surfactant based on the weight of the composition. A wide variety of surfactants can be used herein. Desirable surfactants for emulsification of the dispersed phase and for providing acceptable spreading of the applied composition are selected from the group consisting of anionic surfactants, nonionic surfactants, amphoteric surfactants, non-foaming surfactants, emulsifiers, and combinations thereof. The disclosure regarding surfactants provided for the aqueous hair dye composition described above is believed to be applicable and is incorporated herein by reference.

[0170] Examples of pH adjusters: mineral acids, such as phosphoric acid; hydroxycarboxylic acids, such as lactic acid, glycolic acid, citric acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 2-hydroxybutanedioic acid, 2,3-dihydroxybutanedioic acid, 3-hydroxyvaleric acid, 5-hydroxyvaleric acid, 6-hydroxycaproic acid, and their alkali metal or alkaline earth metal salts; ammonia; alkali metal hydroxides; alkali metal carbonates; alkali metal hydrogen carbonates; alkaline earth metal hydroxides; alkaline earth metal carbonates and alkaline earth metal hydrogen carbonates.

[0171] The formulations of this embodiment may contain 0-5% by weight, for example 0-3% by weight, of one or more thickening agents based on the weight of the composition. Such thickening agents may be selected from: i) carboxylic acid polymers, such as CARBOPOL available from BFGoodrich. 登録商標 900 series; ii) Acrylate / C 10 ~C 30 Alkyl acrylate crosspolymers, such as CARBOPOL available from BFGoodrich 登録商標 1342, CARBOPOL 登録商標 1382, PEMULEN 登録商標 TR-1 and PEMULEN 登録商標 TR-2; iii) crosslinked polyacrylate polymers which may be cationic or nonionic; iv) polyacrylamide polymers, in particular nonionic polyacrylamide polymers; iv) multiblock copolymers of acrylamide and substituted acrylamide with acrylic acid and substituted acrylic acid; v) polysaccharides such as scleroglucan, cellulose and cellulose derivatives such as carboxymethylcellulose and alkylhydroxyalkylcellulose ethers; vi) modified starches; vii) gums such as xantham gum, acacia gum, arginine, sodium alginate, locust bean gum and guar gum; viii) proteins such as collagen, albumin and gelatin; and mixtures thereof.

[0172] As known in the art, humectants are cosmetic ingredients that have water-binding properties, and can hold a large amount of water relative to their weight.Humectants are usually more soluble in water than in oil.References for suitable humectants for use in the present formulation include WO98 / 22085, WO98 / 18444 and WO97 / 01326.And exemplary humectants for use herein include amino acids, collagen amino acids or peptides, keratin amino acids, silk amino acids, urea, glycosaminoglycans, N-acetylglucosamine, glycerin, polyethylene glycol ether of glycerin, and alkali metal salts of hyaluronic acid, acetyl hyaluronic acid, aspartic acid, glucuronic acid and glutamic acid.

[0173] The formulation of this embodiment may contain 0-5% by weight, preferably 0-2% by weight, of at least one antimicrobial agent based on the weight of the composition. The or each antimicrobial agent contained in the composition is preferably a crystalline particle that is insoluble in water. Exemplary antimicrobial agents include, but are not limited to, sulfur; piroctone olamine; selenium sulfide as described in U.S. Pat. Nos. 2,694,668, 3,152,046, and 4,089,945, and pyridinethione salts as described in U.S. Pat. Nos. 3,753,196, 4,345,080, 4,323,683, and 4,470,982.

[0174] The formulation of this embodiment may contain 0-2% by weight of at least one anti-inflammatory agent based on the weight of the composition. Suitable anti-inflammatory agents that may be used alone or in combination include: vitamin F, vitamin E, unsaturated fatty acids, rutin, bioflavonoids, caffeic acid phenethyl ester, sea buckthorn oil, olive oil, jojoba oil, chamomile essential oil, chamomile extract, witch hazel (also known as Hamamelis virginiana) extract, beetroot extract, wasabi extract, dandelion extract, Chrysanthemum indicum extract, Scutellaria extract, betamethasone, dexamethasone, and mixtures thereof. The aforementioned extracts may be obtained by known methods, such as those described above, including a hot water or alcohol extraction step. It may be mentioned that witch hazel extract is preferred.

[0175] Exemplary antioxidants include vitamin E, vitamin F, vitamin C, rutin, resveratrol, carnosic acid, chitosan, flavonoids, gallates, anthocyanins, and carotenoids. Exemplary preservatives include captan, chlorhexidine, hexachlorophene, triclosan, triacetin, and mixtures thereof.

[0176] In some embodiments, the formulations of this embodiment may contain up to 1% by weight of at least one local anesthetic, based on the weight of the composition. As is known in the art, local anesthetics reduce the excitability of sensitive nerve fibers and block the influx of sodium ions through interactions with binding sites on the inner side of the membrane of sodium ion channels, thus preventing the generation of action potentials necessary for the conduction of excitation. In this specification, the preferred local anesthetic is selected from the group consisting of lidocaine, mepivacaine, prilocaine, articaine, bupivacaine, dibucaine, ropivacaine, etidocaine, dyclonine, procaine, benzocaine, 2-chloroprocaine, oxybuprocaine, tetracaine, fomocaine, etidocaine, pramocaine, levobupivacaine, oxyprocaine, hexylcaine, dibucaine, piperocaine, butamben, butamben picrate, dimethisoquin hydrochloride, diperodone, dyclonine, ketamine, p-butylaminobenzoic acid, pramoxine, and their pharmaceutically acceptable salts, and their mixtures. It may be mentioned that lidocaine and benzocaine are preferred. This preference is intended to include the pharmaceutically acceptable salts of these compounds.

[0177] The tattoo ink compositions of the present disclosure may be applied by any conventional technique. As will be appreciated by those skilled in the art, application of the tattoo may be preceded by preparation of the skin by cleansing to remove surface contaminants, and / or application of an anesthetic to provide local and temporary pain relief. The prior application of a local anesthetic may supplement any anesthetic included in the ink composition itself, as described above.

[0178] Intradermal tattoos may be considered "semi-permanent colorants" in that the colorant is located within the epidermis but does not diffuse out of the skin and cannot be removed from the skin without either physical destruction or natural desquamation of the skin. In particular, intraepidermal tattoos do not wash off under the action of water, soap, alcoholic solvents, or combinations thereof.

[0179] Epidermal administration of the compositions of the present disclosure may be performed, for example, by needles, microneedles, jet injection, thermal microporation, electroporation, sonoporation, or combinations thereof. Additionally, the site of epidermal administration may be one or more of the stratum corneum, the stratum lucidum immediately beneath the stratum corneum in the skin of the palms of the hands and soles of the feet, the stratum granulosum, the stratum spinosum, and the stratum basale.

[0180] Without intending to limit the present disclosure, the technique for intradermal application includes at least three fine points, the points being spaced apart by 50 to 5,000 minutes. -1 It is believed that the ink should be characterized by introducing the ink into the dermis under capillary action with a needle that moves axially back and forth at a frequency of 100 rpm. Under such a method of introduction, macrophages are released into the dermis as a defense reaction. However, considering that the ink particles are much larger than macrophages, the ink particles are surrounded by phagocytes, resulting in the ink particles being fixed in the dermis. Under such a method of introduction, it has also been demonstrated that some of the ink particles are taken up by fibroblasts, and some are retained in the extracellular matrix of collagen fibers in the dermis. However, the ink deposited in the epidermis will be lost as the epidermal cells are shed both naturally and as a healing reaction to the needle injury.

[0181] Exemplary tattoo needles for intradermal application include, but are not limited to, those described in European Patent Application Publication EP 2454966 A1; U.S. Patent Application Publication No. 2007 / 0038181 A (Melamud); U.S. Patent Application Publication No. 2004 / 0186501 A (Kuei); U.S. Patent No. 8,764,784 (Crockett); U.S. Design Patent No. 866950 S1 (Schubert); and U.S. Design Patent No. 888240 S1 (Importla).

[0182] It is recognized that although tattoos are intended to be permanent, people often seek to remove them from the body. It is believed that the use of melanoidins as pigments has the advantage that these compounds can be broken down through the targeted action of enzymes and chemicals, such as hydrogen peroxide and ozone, introduced into the dermis or epidermis. The breakdown of melanoidins makes the pigment "removable."

[0183] Cosmetic embodiment 10 is a solid cosmetic composition, wherein the composition comprises: a) at least one colorant, wherein the at least one colorant comprises a nanoscale melanoidin product, the nanoscale melanoidin product having a weight average molecular weight of 200 Daltons to 300 kDa, preferably 1 to 300 kDa, more preferably 1 to 100 kDa; b) at least one structuring agent; and c) at least one thickening agent Includes.

[0184] Cosmetic embodiment 11 is based on the weight of the composition, a) 2-30% by weight of at least one colorant, wherein the at least one colorant comprises a nanoscale melanoidin product, wherein the nanoscale melanoidin product has a weight average molecular weight of 200 Daltons to 300 kDa, preferably 1-300 kDa, more preferably 1-100 kDa; b) 4-50 wt. % of at least one structuring agent; c) 4 to 50% by weight of at least one thickening agent; and d) 0 to 90% by weight of at least one auxiliary agent selected from the group consisting of carriers, stabilizers, surfactants, and preservatives. A solid cosmetic composition comprising:

[0185] Ingredient d) in cosmetic embodiment 11 represents a classification based on the benefit provided by the agent or the agent's postulated mode of action. This classification is made for convenience. A given chemical ingredient may provide multiple benefits or act via multiple modes of action.

[0186] The solid cosmetic composition may comprise from 4 to 50% by weight, for example from 5 to 40% or 5 to 30% by weight, based on the weight of the composition, of one or more structuring agents. Without intending to limit the invention, the structurant having utility in the present invention should comprise or consist of a wax having a softening point of 50-150°C and may include one or more of the following: i) polyethylene having a number average molecular weight of 500-7500; ii) petroleum waxes such as paraffin wax, ozokerite wax, ceresin wax, ader wax, earth wax, and microcrystalline wax; iii) synthetic waxes made by polymerizing carbon monoxide and hydrogen such as Fischer-Tropsch wax; iv) polyolefin waxes; v) hydrogenated animal, fish or vegetable oils; vi) waxes of animal or vegetable origin such as beeswax, carnauba wax, candelilla wax, spermeceti wax, and baysberry wax.

[0187] The solid cosmetic composition may comprise from 4 to 50% by weight, for example from 5 to 40% by weight or from 5 to 30% by weight, based on the weight of the composition, of one or more thickening agents. Such thickening agents may be selected from: i) carboxylic acid polymers, such as CARBOPOL available from BFGoodrich. 登録商標 900 series members; ii) Acrylate / C 10 ~C 30 Alkyl acrylate crosspolymers, such as CARBOPOL available from BFGoodrich登録商標 1342, CARBOPOL 登録商標 1382, PEMULEN 登録商標 TR-1 and PEMULEN 登録商標 TR-2; iii) crosslinked polyacrylate polymers which may be cationic or nonionic polymers; iv) polyacrylamide polymers, particularly nonionic polyacrylamide polymers; iv) multiblock copolymers of acrylamide and substituted acrylamide with acrylic acid and substituted acrylic acid; v) polysaccharides such as those mentioned above, including scleroglucan, cellulose and cellulose derivatives such as carboxymethylcellulose and alkylhydroxyalkylcellulose ethers; vi) modified starches; vii) gums such as xantham gum, acacia gum, arginine, sodium alginate, locust bean gum and guar gum; viii) proteins such as collagen, albumin and gelatin; and combinations thereof. A mixture of.

[0188] The solid cosmetic composition may contain up to 50% by weight of a carrier that has the functionality of leaving a film containing nanoscale melanoidin products as coloring agents when applied.Exemplary carriers include water; water-miscible solvents; water-immiscible solvents; volatile silicones as described in Todd et al., "Volatile Silicone Fluids for Cosmetics", Cosmetics and Toiletries, 91:27-32 (1976); non-volatile organic fluids; and non-volatile silicone fluids.The term "volatile silicone" refers to silicone materials that have a measurable vapor pressure under ambient conditions.Cyclomethicone is an important example.

[0189] For the sake of completeness, non-limiting examples of non-volatile organic fluids include mineral oil, PPG-14 butyl ether, isopropyl myristate, petrolatum, butyl stearate, cetyl octanoate, butyl myristate, myristyl myristate, C 12 ~C 15These include alkyl benzoates (e.g., Finsolv.TM), dipropylene glycol dibenzoate, PPG-15 stearyl ether benzoate and blends thereof (e.g., Finsolv TPP), neopentyl glycol diheptanoate (e.g., Lexfeel 7 by Inolex), octyldodecanol, isostearyl isostearate, octododecyl benzoate, isostearyl lactate, isostearyl palmitate, isononyl / isononate, isoeicosane, octyldodecyl neopentanoate, hydrogenated polyisobutane, and isobutyl stearate. U.S. Patent No. 6,013,248 (Luebbe et al.) and U.S. Patent No. 5,968,489 (Swaile et al.) are believed to provide useful references in this context.

[0190] The solid cosmetic composition typically comprises up to 5% by weight, for example up to 3% by weight, of a surfactant based on the weight of the composition. A wide variety of surfactants may be used herein. Desirable surfactants for emulsifying the dispersed phase and for providing acceptable spreading of the applied composition are selected from the group consisting of anionic surfactants; nonionic surfactants; amphoteric surfactants; non-lathering surfactants; emulsifiers; and combinations thereof. The disclosures on surfactants provided for the aqueous hair dye composition above are considered applicable and are incorporated herein by reference.

[0191] Preservatives may also be present in the solid cosmetic composition. Examples include phenoxyethanol; C1-C6 alkyl parabens; imidazolinyl urea; dimethylmethoylhydantoin; N-(3-chloroallyl)hexaminium chloride; cetrimonium bromide; trisodium ethylenediaminetetraacetate; and butylated hydroxyanisole (BHA). When present, the preservatives are typically added in an amount of up to 0.5% by weight, for example 0.01-0.1% by weight, based on the weight of the composition. However, considering the preservative function of melanoidins, it is also envisaged that the solid cosmetic composition may be substantially free of preservatives.

[0192] The solid cosmetic compositions of the present invention can be formulated as any known or other effective product form for providing topical application of melanoidin activity to the desired area of ​​the skin. Non-limiting examples of such product forms include cakes, sticks, pencils, and roll-ons, provided that the selected form includes all essential elements as defined herein. The solid compositions are generally stored in and dispensed from a suitable package or applicator device, which should be closable to prevent loss of any of the constituent volatile compounds prior to and during application.

[0193] The solid cosmetic compositions according to cosmetic embodiments 10 and 11 are particularly well suited as facial make-up.

[0194] The use of melanoidin nanoparticles or nanofibers in cosmetic compositions has several advantages over known cosmetic compositions.

[0195] By directly incorporating nanoscale melanoidins into cosmetic compositions, said melanoidins can replace all or part of commonly used organic pigments, mineral pigments and synthetic dyes, which is beneficial in view of the potential health issues and harmful effects associated with known pigments and dyes, such as carbon black.

[0196] Nanoscale melanoidins obtained from coffee grounds, especially spent coffee grounds, are environmentally friendly and a renewable and sustainable source for cosmetic composition ingredients.

[0197] Nanoscale melanoidins in cosmetic compositions have the ability to penetrate into the skin and adhere better to the skin, an effect that can be advantageously used for example for sunscreen, skin colorant or hair colorant applications.

[0198] DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS OF THE PRESENTINVENTION

[0199] In the following, further preferred embodiments of the present invention are illustrated by the following examples, but the present invention is not limited to these examples. The features described in the above description, the following examples and the appended claims can be relevant individually or in any combination to realize various embodiments of the present invention.

[0200] Unless otherwise stated, the following analytical methods were used: concentration in solution was determined by absorbance at 405 nm and at various wavelengths by UV-VIS, molecular weight distribution was determined by gel permeation chromatography and / or gas chromatography and mass spectrometry, and stability related to electrical surface, surface pH, and surface charge was determined by zeta potential measurements.

[0201] Example 1

[0202] A melanoidin product was prepared by a process according to the present invention comprising an extraction step, a first separation step, a precipitation step and a second separation step.

[0203] Extraction process

[0204] The extraction process was carried out in a stainless steel reactor with an internal volume of 1.2 liters. The reactor was equipped with a mechanical stirrer, external electrical heating within the reactor volume, and a serpentine cooling coil within the reactor. The reactor was preheated to 80° C. by electrical heating. 100 g of spent coffee grounds were placed in the reactor.

[0205] The extractant was prepared by dissolving 30 g of sodium hydroxide (NaOH) in 1 liter of distilled water. The pH value of the extractant was 13.9. The extractant was preheated to a temperature of 80° C. and placed in the reactor immediately after the coffee grounds. The reactor was sealed and the contents were stirred at a speed of 50-100 rpm. The reactor was heated for 15 minutes until a temperature of 120° C. was reached. The pressure in the reactor was increased to 3 bar (absolute). The temperature was maintained for another 30 minutes. The heat was then turned off and liquid cooling was allowed to flow through the cooling coil. The liquid contents of the reactor were rapidly cooled to 40° C. in 10 minutes. The reactor was opened and the resulting melanoidin-containing solute was obtained in the fluid phase of the extractant.

[0206] First separation step

[0207] The reactor contents were fed to a filter press with a cut-off at 200 μm. The fluid phase containing the melanoidin-containing solutes was separated from the discharged coffee grounds.

[0208] Precipitation process

[0209] The fluid phase separated in the first separation step was fed into a 2 liter glass beaker. Hydrochloric acid (HCl) with a concentration of 37% (w / v) was added dropwise to the fluid phase until the pH value was 2. The pH value was continuously measured by a pH electrode. During acidification, an increase in the turbidity of the acid mixture was observed, indicating the formation of a precipitate.

[0210] Second Separation Step

[0211] The acid mixture was left to stand for about 12 hours. The acid mixture was then homogenized by stirring and fed into a centrifuge (Eppendorf Model 5810R). After centrifugation at 10,000 rpm for 10 minutes, the solid particles were collected in a 50 ml flask. The liquid phase was drained. The solid particles in the flask were resuspended in 50 ml of acid water and centrifuged a second time. The solid particles obtained from the second centrifugation were resuspended in water and freeze-dried. The resulting powder was dark brown in color and reached 21% by weight of the original coffee grounds powder.

[0212] Example 2

[0213] 1 g of powder obtained by the method according to Example 1 was dissolved in 50 ml (milliliters) of demineralized water. The weakly acidic solution was neutralized to a pH value of 7 with sodium hydroxide. The neutralized mixture was fed to an ultrafiltration membrane, where a fraction of particles with a molecular weight of more than 300 kDa was separated from a fraction with a low molecular weight. The high molecular weight fraction was mixed with an aqueous solution of ethanol. The aqueous liquid contained 75% by volume of ethanol and 25% by volume of water. An 80% by weight aqueous solution of ethanol was mixed with 20% by weight of the melanoidin-containing mixture.

[0214] The resulting mixture was fed into an electrospinning apparatus. The target was aluminum foil. The distance between the needle and the target was 15 cm. The applied voltage was varied from 10 kV to 20 kV. This method yielded melanoidin-containing nanofibers with diameters of 300 to 400 nm (nanometers).

[0215] Example 3

[0216] 1 g of powder obtained by the method according to Example 1 was dissolved in 50 ml of demineralized water. The weakly acidic solution was neutralized to a pH value of 7 with sodium hydroxide. The neutralized mixture was fed to an ultrafiltration membrane, where the fraction of particles with a molecular weight of more than 100 kDa was separated from the fraction with a lower molecular weight. The high molecular weight fraction was mixed with an aqueous solution of ethanol. The aqueous liquid contained 50% by volume of ethanol and 50% by volume of water. An 84.15% by weight aqueous solution of ethanol was mixed with 15% by weight of the melanoidin-containing mixture and 0.85% by weight of pure polyvinyl alcohol (Sigma Aldrich) with a molecular weight (Mw) of 85000-124000 and hydrolyzed to 87-89%.

[0217] The resulting mixture was fed into an electrospinning tool at a flow rate of 0.3 ml / h. The target was an aluminum foil. The distance between the needle and the target was 12 cm. The applied voltage was 13.5 kV. By this method, a multilayer fiber mat was obtained. Figure 1 shows a photograph of the obtained fibers taken with a scanning electron microscope (SEM). The scale is given as 1 μm in the lower left corner of Figure 1. The diameter of the fibers ranged from 200 nm to 500 nm.

[0218] Example 4

[0219] 1 g of powder obtained by the method according to Example 1 was dissolved in 50 ml (milliliters) of demineralized water. The weakly acidic solution was neutralized to a pH value of 7 with sodium hydroxide. The neutralized mixture was fed to an ultrafiltration membrane, where the fraction of particles with a molecular weight of more than 100 kDa was separated from the fraction with a lower molecular weight. The high molecular weight fraction was mixed with an aqueous solution of ethanol. The aqueous liquid contained 50% by volume of ethanol and 50% by volume of water. An 82.45% by weight aqueous solution of ethanol was mixed with 15% by weight of the melanoidin-containing mixture and 2.55% by weight of pure polyvinyl alcohol (Sigma Aldrich) with a molecular weight (Mw) of 85000-124000 and 87-89% hydrolyzed.

[0220] The resulting mixture was fed into an electrospinning tool at a flow rate of 0.3 ml / h. The target was an aluminum foil. The distance between the needle and the target was 12 cm. The applied voltage was 11.7 kV. By this method, a multilayer fiber mat was obtained. Figure 2 shows a photograph of the obtained fibers taken with a scanning electron microscope (SEM). The scale is given as 1 μm in the lower left corner of Figure 2. The diameter of the fibers ranged from 250 nm to 450 nm.

[0221] Example 5

[0222] 1 g of powder obtained by the method according to Example 1 was dissolved in 50 ml of demineralized water. The weakly acidic solution was neutralized to a pH value of 7 with sodium hydroxide. The neutralized mixture was fed to an ultrafiltration membrane, where a fraction of particles with a molecular weight of more than 100 kDa was separated from a fraction with a low molecular weight. The high molecular weight fraction was mixed with an aqueous solution of ethanol. The aqueous liquid contained 50% by volume of ethanol and 50% by volume of water. An 80% by weight aqueous solution of ethanol was mixed with a 20% by weight melanoidin-containing mixture.

[0223] The resulting mixture was fed into an electrospinning tool. The target was an aluminum foil. The distance between the needle and the target was 16 cm. The applied voltage was 24.7 kV. This method resulted in spherical melanoidin-containing nanoparticles. Figure 3 shows a photograph of the resulting particles taken with a scanning electron microscope (SEM). The scale is given as 200 nm in the lower left corner of Figure 3. The diameter of the particles was less than 400 nm and had a smooth surface.

[0224] Example 6

[0225] A melanoidin product was prepared by a process according to the present invention comprising an extraction step, a first separation step, a precipitation step and a second separation step.

[0226] The extraction step and the first separation step were the same as those in Example 1.

[0227] Precipitation process

[0228] The fluid phase separated in the first separation step was fed into a vessel equipped with a mechanical stirrer within the vessel volume. The fluid phase was at ambient temperature (about 25°C). The stirrer was operated at 400-500 rpm. The fluid phase was contacted with ethyl acetate as an organic phase separating agent. Ethyl acetate was added to the fluid phase in an amount equivalent to 25% of the volume of the fluid phase. The stirring was continued until an emulsion of two immiscible liquids was formed. Hydrochloric acid (HCl) with a concentration of 37% (w / v) was slowly added to the emulsion until a pH value of 7 was reached. The pH value was continuously measured by a pH electrode. During acidification, an increase in the turbidity of the mixture was observed, indicating the formation of a precipitate.

[0229] Second Separation Step

[0230] The mixture was then fed into a centrifuge (Eppendorf Model 5810R). After centrifugation at 2,000 rpm for 5 minutes, the mixture was filled into a flask. After settling, three phases were separated: an aqueous phase at the bottom of the flask, an ethyl acetate phase at the top, and an intermediate phase containing melanoidin-containing precipitate. The solid particles were removed from the intermediate phase by filtration and subsequently dried in an oven. The resulting powder had a dark brown color and amounted to 21% by weight of the original coffee grounds. The powder was analyzed for its particle size distribution. The particle size was between 40 and 600 nm (nanometers), with the majority of the particles being between 200 and 400 nm.

[0231] Example 7

[0232] A melanoidin product was prepared by the method according to Example 1. The obtained product was further processed by ultrafiltration, resulting in the following fractions of different molecular weights: 300 kDa, 100 kDa, 30 kDa, 10 kDa, 3 kDa, 1 kDa and less than 1 kDa. The membranes used (Ultracel by Merck) 登録商標 ) was made of regenerated cellulose and had a diameter of 76 mm. Various fractions were recovered from the solution by freeze-drying. The yield was calculated as a percentage of the total melanoidin content.

[0233] The total phenolic content (TPC) of each melanoidin fraction was determined by the Folin-Ciocalteu method. Each extract was first diluted in deionized water or in 0.01 M NaOH solution if the extract was not soluble in pure water. 50 μL of sample and 500 μL of Folin-Ciocalteu reagent aliquots were mixed for 15 seconds and incubated at room temperature for 30 minutes. Then, 450 μL of 75 g / L sodium carbonate was added to the mixture. After being stored in the dark at room temperature for 1 hour, the absorbance of the mixture at 760 nm was measured using a microplate reader. Standard solutions of trihydroxybenzoic acid containing known concentrations of gallic acid were used to determine a calibration curve, and the results were expressed in mg gallic acid equivalents per mass (mg GAeq). Each analysis was performed in triplicate and averaged.

[0234] Total protein content was determined using the Bradford protein assay. 10 μl of filtered extract, appropriately diluted in the same solvent used for extraction, was mixed with 300 μl of Coomassie Blue reagent in a 96-well microplate. The microplate was then agitated for 30 seconds, and after 10 minutes at room temperature, the absorbance was measured at 595 nm in a spectrophotometer microplate reader (Sunrise Tecan, Grodig, Austria) with a blank prepared in distilled water. A calibration curve was prepared using an aqueous solution of BSA (bovine serum albumin). Protein content was expressed as milligrams per mass of material (mg BSA / g).

[0235] Table 1 below shows the yield, total phenolic content (TPC) and total protein content of the different fractions.

[0236] [Table 1]

[0237] Example 8

[0238] The conductivity of the melanoidin nanoparticles as an electrolyte solution was measured at room temperature. Demineralized water was used as the base for the solution. The conductivity of the base solution without melanoidin nanoparticles was 15 μS / cm (10 -6 The conductivity was measured in siemens / centimeter. Melanoidin nanoparticles in weight fractions ranging from 10 kDa to 300 kDa were added to the base solution. The solution was thoroughly stirred prior to conductivity measurement. Table 2 below shows the measured conductivity for different concentrations of melanoidin nanoparticles in solution.

[0239] [Table 2]

Claims

1. A method for adjusting melanoidin products, comprising: a) an extraction step of treating coffee grounds with an extractant having a pH value of more than 7 to extract melanoidin-containing solutes in the fluid phase of the extractant; b) a first separation step of separating the fluid phase from the coffee grounds; c) a precipitation step of contacting the fluid phase with (i) an acid to obtain an acidic mixture having a pH value of less than 4, or (ii) an organic phase separating agent and an acid to obtain a mixture having a pH value in the range of 4 to 8, thereby forming a precipitate containing melanoidin; and d) a second separation step of separating the formed precipitate from the acidic mixture The method as described above.

2. The method according to claim 1, wherein the extractant is aqueous and contains sodium hydroxide or potassium hydroxide.

3. The method according to claim 1 or 2, wherein the organic phase separating agent is selected from the group consisting of ethanol, ethyl acetate, tetrahydrofuran, and 2-methyltetrahydrofuran.

4. The method according to claim 1 or 2, wherein the second separation step includes a fractionation step of obtaining a low molecular weight fraction of the formed precipitate having an average molecular weight of less than 10 kDa, and here, after the second separation step, a nanoparticle production step of producing nanoparticles from the low molecular weight fraction is included.

5. The method according to claim 4, wherein the nanoparticle production step includes at least one method selected from the group consisting of electrospraying, laser ablation, freeze drying, spray drying, convective drying, radiation drying, vacuum drying, and ultrasonic atomization.

6. The method according to claim 1 or 2, wherein the second separation step includes a fractionation step of obtaining a high molecular weight fraction of the formed precipitate having an average molecular weight of at least 10 kDa, and here, after the second separation step, a nanofiber production step of producing nanofibers from the high molecular weight fraction is included.

7. The method according to claim 6, wherein the nanofiber production step includes electrospinning.

8. A melanoidin product extracted from coffee grounds, wherein the melanoidin product is melanoidin nanoparticles having an average diameter of 1 nm to 800 nm.

9. The melanoidin product according to claim 8, wherein the melanoidin nanoparticles contain more than 70% by weight of melanoidin, and wherein the melanoidin contains 1% to 15% by weight of a phenolic compound and / or 1% to 40% by weight of a protein.

10. A melanoidin product extracted from coffee grounds, wherein the melanoidin product is melanoidin nanofibers.

11. The melanoidin product according to claim 10, wherein the melanoidin nanofibers have an average diameter of 1 nm to 1000 nm and contain more than 50% by weight of melanoidin, and wherein the melanoidin contains 1% to 15% by weight of a phenolic compound and / or 1% to 40% by weight of a protein.

12. An electronic component comprising the melanoidin product according to any one of claims 8 to 11.

13. A conductive liquid comprising the melanoidin product according to any one of claims 8 to 11.

14. A method of using the melanoidin product according to any one of claims 8 to 11 for photothermal applications.

15. A cosmetic composition comprising the melanoidin product according to any one of claims 8 to 11.

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