Extraction process for plant-based proteins and cosmetic compositions based thereon
Patent Information
- Authority / Receiving Office
- EP · EP
- Patent Type
- Applications
- Current Assignee / Owner
- SYMRISE GMBH & CO KG
- Filing Date
- 2023-09-01
- Publication Date
- 2026-07-08
AI Technical Summary
Existing methods for extracting native proteins like Zein from plant materials are laborious and require harsh conditions, leading to poor solubility and stability issues in cosmetic compositions.
A simplified extraction process using water or aqueous ethanol as solvents, heated to specific temperatures for extended periods, followed by filtration and stabilization with cosmetic solvents like propylene glycol and pentylene glycol, to enhance solubility and stability of native Zein proteins.
The process achieves a stable, aqueous-soluble Zein protein extract that can be easily formulated into cosmetic compositions, improving their efficacy and stability for hair and skin care applications.
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Abstract
Description
Extraction process for plant-based proteins and cosmetic compositions based thereonTechnical field
[0001] The present invention relates to a simplified extraction process for obtaining an extract rich in proteins from plant materials, and preferably rich in Zein proteins from plant materials such as corn (maize, Zea mays) plant materials, the corresponding protein extract, a process for preparing a stabilized protein extract solution, the corresponding, stabilized protein extract solution as such, and a process for the preparation of a cosmetic composition prepared based on the extraction, as well as cosmetic compositions as such comprising the extract or the stabilized protein extract solution of the present invention.Background art
[0002] Proteins are large biomolecules and macromolecules that comprise one or more long chains of amino acid residues. They perform a vast variety of important functions within organisms such as e.g. providing structure to cells, catalyzing metabolic reactions, responding to stimuli and as storage proteins to serve as biological reserves of metal ions and amino acids.
[0003] Proteins play an important role in food, nutrition and feed in form of animal or plant proteins. As a consequence of the vegetarian and vegan trend and the consumer demand for vegetarian and vegan products which continue to grow all around the world plant derived proteins become more and more important for the food sector. This trend meanwhile becomes also more and more relevant for non-food applications such as e.g. cosmetic products or also cleansing or cleaning compositions. In contrast to food applications where proteins are mostly present in solid or suspended form, non-food liquid products such as e.g. tonics, emulsions, balms, creams, shampoos or detergent cleansers which are applied on living or dead tissue such as e.g. skin, scalp, hair, nail, oral cavity, fur, wool, silk, cashmere, cotton, viscose, modal or other surfaces require the proteins to be dissolved and thereby in a readily available form to provide their effects.
[0004] Broadly, based on the structure, proteins can be classified as globular (albumins, globulins, prolamins, glutelins, nucleoproteins, glycoproteins, phosphoproteins, and hemoglobins), fibrous (keratin, myosin fibrin, and collagen), or flexible (casein), depending on their physicochemical properties such as amino acid residue quantity and sequence on the polymer chain.
[0005] Plant proteins are mainly made of globular proteins, present as multimers that are covalently linked together, and are classified as albumins (soluble in water), globulins (soluble in dilute salt solutions), prolamins (soluble in aqueous ethanol solutions), and glutelins (soluble in dilute acid / alkaline solutions or insoluble in water). For the transition from animal- to plant- derived dietary proteins, plant proteins are normally processed into extracts, and due to the type of process, proteins from the globulin class are mainly extracted. Such extractions have several waste streams, containing other protein classes: albumins and prolamins. Also plant albumins and prolamins have good functionality and their extraction and use in food but also in non-food applications is therefore objective of recent investigations and upcycling or circular economy projects.
[0006] Albumins are found in various plants and are also known as 2S albumin and typically show high levels of cysteine residues. Albumin and globulins are predominately present in all pulses (>50 %) and some pseudocereals (e.g. quinoa, and amaranth), but also e.g. in potato, whereas prolamins (seeds of the Poaceae plants e.g. wheat, corn, barley, oat, rice, millet, sorghum and rye) and glutelins (wheat) make up about 85 % of the total protein in the cereal and pseudocereal family. Various plants that produce seeds contain 2S albumins in the seeds, such as sunflower and other plants from the Asteraceae (Compositae) family, nuts (e.g. peanuts, almonds, cashew), passion fruit, sesame, buckwheat, chia, lupin, jackfruit, castor bean, seeds of Brassicaceae plants (e.g. black mustard, canola (rapeseed), mustard) and pulses (e.g. chickpea, pea, beans, kidney beans, mung beans).
[0007] Albumins are described to have various valuable benefits like support of active ingredient or drug delivery, acceleration of wound healing, action as antioxidant and radical scavenger.
[0008] Prolamins are characterized by a high glutamine and proline content and are also described to have various benefits amongst these also action as antioxidant and radical scavenger. Cereal prolamins are furthermore broadly classified into cysteine (Cys)-poor and Cys-rich species with e.g. wheat, barley, rice and corn being Cys-rich species.
[0009] Plant proteins in cosmetics are considered to be particularly skin-friendly. Papain, obtainable by water extraction of Papaya (Car / ca papaya), is used in cosmetic formulation e.g. as non-irritating exfoliant (specially for individuals with sun-damaged skin) and it also contributes to attenuating freckles and brown spots due to exposure to sunlight and smoothing the skin. Bromelain, obtainable by water extraction of Pineapple (Ananas comosus), also hasbeen used in cosmetic applications for application such as tooth whitening, acne, wrinkles, dry skin treatment, and post-injection bruising and swelling reduction. Other plant derived proteins which have raised interest include Zingipain from ginger (Zingiber officinale), Actidin from kiwifruit (Actinidia deliciosa), Cardosin from Cardoon (Cynara cardunculus), Cucumisin from Melon (Cucumis melo), Ficin from Fig (Ficus genus), Gliadin from Triticum sp. such as wheat (Triticum aestivum), spelt (Triticum spelta), and Wrightin from Wrightia tinctoria.
[0010] Also macroalgae or seaweeds (Rhodophyta or red seaweeds e.g. Palmaria palmata, Phaeophyta or brown seaweeds (e.g. Undaria sp., Fucus sp. and Sargassum sp.) and Chlorophyta or green seaweeds e.g. lllva lactuca, lllva rigida) and unicellular organisms such as microalgae (e.g. Tetraselmis sp., Chlorella sp., Isochrysis sp., Nannochloropsis sp.) and cyanobacteria (e.g. spirulina) are known non-animal alternative protein sources and contain water and aqueous ethanol soluble proteins. The protein content in microalgae spans from 20 % to 70 % depending on the species and cultivation parameters.
[0011] The corn (Zea mays) or maize kernel is for example commonly used for nutritional purposes; however, it also has great medicinal value, since corn kernel is a good source of bioactive phytochemical compounds, such as polyphenols, phenolic acids, flavonoids, carotenoids, anthocyanins, vitamins and other compounds like sugars, polysaccharides, and proteins.
[0012] Zein is the major storage protein in corn, accounting for 45-50 wt.-% of the total protein content. Zein is considered a non-allergenic protein and corn gluten-free plant material. It has been exclusively found in the endosperm and due to its characteristic solubility is considered a prolamin. Zein is generally insoluble in water, however, a certain concentration of alcohol, high concentrations of urea, extreme alkaline conditions (pH > 11), and / or anionic detergents can render it soluble under aqueous conditions to a low extent. Known extraction processes for Zein protein mainly involve alkaline conditions rendering these extraction processes rather harsh, thereby negatively influencing the product yield and quality as well as the stability of accompanying beneficial secondary metabolites such as phenols.
[0013] Zein is a relatively low molecular weight protein. Based on the solubility and the sequence homology, Zein is divided into four different classes: alpha-Zein (19 and 22 kDa), beta-Zein (14 kDa), gamma-Zein (16 and 27 kDa) and delta-Zein (10 kDa). Alpha-, beta- and gamma-Zein constitute 75-80 %, 10-15 % and 10-15 % by weight of the total Zein, respectively, whereas delta-Zein only accounts for a small proportion of the total Zein. Commercial Zein ismainly composed of alpha-Zein and only contains small amounts of beta- and gamma-Zein, which in turn include more cysteines than alpha-Zein.
[0014] Zein can be extracted from corn or more preferably from corn-protein-containing raw material, such as corn gluten meal. Corn gluten meal is the principal protein of corn endosperm consisting mainly of Zein and glutelin. It is a byproduct of corn processing such as e.g. corn starch production and is often used as an animal feed. Despite the name, corn gluten does not contain true gluten, which is formed by the interaction of gliadin and glutenin proteins. Accordingly, Zein can be considered “gluten-free”.
[0015] In another aspect, hair has a great social significance for human beings since it is important for our self-confidence and constitutes a part of appearance and self-concept. Hair is mainly composed of keratin proteins. The main amino acids that make up keratin are: cystine (17.5 %), serine (11.7 %), glutamic acid (11.1 %), threonine (6.9 %), glycine (6.5 %) and lastly arginine (5.6 %). During the life cycle of a human hair, the hair structure changes, particularly because of mechanical stress or chemical treatment, for example due to bleaching, coloring, or perming. Particularly damage impairs the surface properties of the hair. Damaged hair breaks more easily than undamaged hair. The same is true for animal hair.
[0016] An important indicator of hair health and strength is its resistance to fatigue and fracture breakage. Day-to-day grooming and styling processes damage the cuticle layers, which are decisive for giving hair a healthy or unhealthy look. The deterioration of hair properties can be noticed in the form of poor manageability, dryness, brittleness, loss of shine, fatigue and decrease strength (fiber breakage). The change in physical properties and the wearing down of the fiber weaken it structurally, i.e. these damages to hair lead to changes in the fiber properties.
[0017] Also fur and hair of pets such as e.g. of dogs and horses (horsetail and horsemain) are often regularly washed and pet care products are applied to maintain and improve the visual appearance and manageability of the animal hair. Animal fur and human hair are made up of the same protein, keratin. Therefore, mechanical stress also impacts the hair structure of pet fur, and the deterioration of hair properties can be noticed by the same characteristics such as poor manageability, dryness, brittleness, loss of shine, fatigue and decreased strength (fiber breakage).
[0018] In another aspect, skin of face, body and scalp, is impacted by reactive oxygen species and radicals and thereby oxidative stress. It is well known in the literature that oxidativestress is damaging to skin and that antioxidants can provide a protective effect from various sources of oxidative damage. The formation of free radicals is a widely accepted mechanism leading to skin aging and damage. Free radicals are highly reactive molecules with unpaired electrons that can directly damage various cellular structural membranes, lipids, proteins, and DNA. The damaging effects of these reactive oxygen species are induced internally during normal metabolism and immune response and externally through various oxidative stressors like sun exposure, first- or secondhand cigarette smoke, environmental toxins, poor diet, stress, etc. These various reactive oxygen species must be continually removed from cells to maintain healthy metabolic function.
[0019] To make proteins suitable for use in cosmetics, normally it is necessary to convert them into an aqueous soluble form, which is easier to manipulate and is more practical for formulating purposes. This form is obtained by the hydrolysis procedure, i.e., by cleavage of the protein macromolecule by disruption of some of the peptide bonds by e.g., proteases. Protein hydrolysates are known to be very beneficial to hair and skin, imparting increased moisturization, enhancing softness and flexibility. Therefore, hydrolyzed proteins, which can be prepared by degradation of native proteins, as well as their derivatives have been widely incorporated in hair care and skin care products. The protein hydrolysates largely contain peptides having a molecular weight in the range from 2 to 3 kDa and are obtainable from various protein sources, for example cereals. However, cutting native proteins into smaller pieces will produce water-soluble peptides that can be expected to have different cosmetic effects than native proteins.
[0020] However, native proteins in cosmetics ingredients are not common, and very difficult to solubilize and formulate. To make these proteins suitable for use in cosmetics normally is necessary to convert them into a soluble form, which is easier to manipulate and is more practical for formulating purposes. Moreover, the liquid form allows for an improved uptake by e.g. skin or hair and thus for an improved efficacy o the proteins. This form is obtained by the hydrolysis procedure, i.e. by cleavage of the protein macromolecule by disruption of some of the peptide bonds by e.g., proteases, this however, changes the properties and effects of the protein as explained above.
[0021] For example, in WO 2004039340 A1 , the use of native Zein for improving the condition of hair is generally described. The native Zein used therein is either obtained by standard extraction methods or is commercially available.
[0022] The methods of the state of the art for extracting (natural) proteins such as Zein proteins are generally rather laborious requiring a plurality of process steps ad specific conditions using many different chemicals at different pH values.Technical problem
[0023] It is commonly known that the use of native, i.e. non-hydrolyzed proteins in cosmetic compositions is rather problematic, which is due to formulation issues, mainly because of their very poor solubility and / or the limited stability of the native proteins.
[0024] Moreover, the known extraction methods of proteins such as Zein proteins from plant materials require rather harsh conditions, which are likely to have a negative impact on the final composition, the protein properties and the yield of the protein extract.
[0025] The present invention has been made in view of the problems mentioned above and an object of the present invention is to provide a simplified and more gentle extraction method of native proteins such as albumins and prolamins, preferably native Zein proteins as well as to provide a stable cosmetic composition comprising the (natural) proteins such as albumins and prolamins, preferably native Zein protein extract. Preferably this cosmetic composition is suitable for both, human and animal hair / fur and skin.
[0026] Accordingly, the present invention provides for a process and the provision of proteinbased compositions, wherein the plant proteins show an improved solubility and are thus more suitable for the incorporation into various consumer product formulations and that are readily available for uptake by skin, hair etc.
[0027] Preferably, the plant proteins are selected from the group of water soluble (albumin type) and aqueous ethanol soluble (prolamin type) proteins to obtain solutions easy to handle and formulate.
[0028] Based on the process disclosed herein, it is possible to extract proteins such as Zein proteins in a chemically facilitated manner. The process according to the present invention is very simple and requires only few steps without negatively influencing the yield or product quality / protein properties. The resulting protein-rich extract, e.g. extract rich in Zein, allows for the preparation of cosmetic compositions such as protein extract solutions with 5 to 8 wt- % Zein that are easy to formulate and can be provided in liquid form taking full advantage ofthe beneficial protein properties for hair and skin in various cosmetic products, and preferably in hair or fur care and skin care products.
[0029] Natural or native proteins and natural or native protein extracts are to be understood as proteins and extracts derived from naturally occurring sources such as from plant materials, i.e. proteins and extracts which are not synthetically created.
[0030] Preferably the proteins used within the scope of the present invention are plant-based and therefore vegetarian and vegan.Solution to the problem and advantages of the invention
[0031] In one aspect, the present invention relates to an extraction process for proteins from plant materials, preferably for albumins and prolamins, preferably Zein protein extracted from plant materials comprising the steps of: a) adding an extraction solvent, preferably water or aqueous ethanol to said plant material to form a mixture, preferably wherein the amount of ethanol in the extraction solvent is from 20 to 99 wt.-%, preferably from 50 to 90 wt.-%, more preferably from 60 to 80 wt- %, and most preferably from 68 to 72 wt.-%; b) heating the mixture under a), preferably up to a temperature of between 40 to 90 °C, preferably between 50 to 80 °C, more preferably from 60 to 75 °C and more preferably from 65.5 to 72.5 °C; c) maintaining said temperature for a period of at least 30 minutes, preferably, wherein the period is between 1 to 6 hours, more preferably, from 1.5 to 5 hours and more preferably, from 2 to 3.5 hours; d) preferably cooling the obtained mixture to room temperature; e) submitting the mixture to filtration.
[0032] Preferably, these proteins are from natural sources. Accordingly, the present invention also relates to an extraction process for natural proteins preferably from plant materials, more preferably natural albumin and prolamin preferably from plant materials, most preferably natural Zein protein extract from plant materials.
[0033] In a preferred variant, the present invention relates to an extraction process for (natural) Zein protein extract from plant materials comprising the steps of: a) adding an extraction solvent, preferably water or aqueous ethanol to said plant material to form a mixture, preferably wherein the amount of ethanol in the extraction solvent isfrom 20 to 99 wt.-%, preferably from 50 to 90 wt.-%, more preferably from 60 to 80 wt- %, and most preferably from 68 to 72 wt.-%; b) heating the mixture under a), preferably up to a temperature of between 40 to 90 °C, preferably between 50 to 80 °C, more preferably from 60 to 75 °C and most preferably from 65.5 to 72.5 °C; c) maintaining said temperature for a period of at least 30 minutes, preferably, wherein the period is between 1 to 6 hours, more preferably from 1.5 to 5 hours and most preferably, from 2 to 3.5 hours; d) preferably cooling the obtained mixture to room temperature; e) submitting the mixture to filtration.
[0034] Surprisingly, the aforementioned extraction process enables the extraction or provision of extracts rich in protein content such as in (natural) Zein content, which show a significantly different composition profile for the protein extract compared to state-of-the-art extraction processes. In particular, the extraction process of the present invention allows for obtaining an increased ratio of beta- and gamma-Zein, comprising both a relative high number of cysteine functions. As keratin is especially rich in cystine which is composed of two cysteine molecules joined by a disulfide bond, increased contents of beta- and gamma-Zein in the Zein protein extract is of high value for treatment of keratin-containing tissues such as hair, skin and nails.
[0035] Moreover, the process disclosed herein allows for the facilitated extraction of (natural) proteins such as Zein proteins. The process according to the present invention is very simple and requires only few steps. The resulting protein-rich extract, e.g. extract rich in Zein, allows for the preparation of cosmetic compositions (such as protein extract solutions) with 5 to 8 wt- % Zein that are easy to formulate and can be provided in liquid form. Said liquid form is advantageous for the preparation of cosmetic formulations, rendering the overall process of the preparation of cosmetic formulations easier. Furthermore, the extracted protein is stabilized in the form of a liquid, not requiring further stabilization steps or additives. The extracted protein can directly and stably be incorporated into various cosmetic preparations.
[0036] Besides water and ethanol also other extraction solvents might be suitable depending on the protein to be extracted. Further commonly used extraction solvents are for example methanol, n-propanol and iso-propanol and mixtures thereof with water.
[0037] Preferably, the extraction solvent is ethanol in water, wherein the amount of ethanol in the extraction solvent is from 20 to 99 wt.-% and preferably from 50 to 90 wt.-%, morepreferably from 60 to 80 wt.-%, and most preferably from 68 to 72 wt.-%. This extraction solvent was found to be particularly suitable for the extraction of prolamin-based proteins.
[0038] In another preferred embodiment, the extraction solvent is water. This extraction solvent was found to be particularly suitable for the extraction of albumin-based proteins.
[0039] The proteins are preferably selected from plant materials preferably select from the group consisting of albumins, prolamins, or mixtures of the aforementioned proteins, and more preferably Zein proteins.
[0040] In a preferred aspect of the invention, the mixture formed under step a) is a suspension. Preferably, this mixture is obtained using an extraction solvent comprising 60 to 80 wt.-% ethanol in an aqueous solution, more preferably the ethanol content is from 65 to 75 wt.-%, most preferably the ethanol content ranges from 68 to 72 wt.-%. These ranges are particularly suitable for the extraction of prolamin-based proteins such as Zein.
[0041] In another preferred aspect, the extraction temperature in step b) preferably ranges from 40 to 90 °C, preferably from 50 to 80 °C, more preferably from 60 to 75 °C, and most preferably from 65.5 to 72.5 °C.
[0042] Surprisingly, it was found that the aforementioned extraction process works best if it is carried out within said temperature ranges. At lower temperatures, the amount of extracted protein material is significantly lower. In addition, when using extraction temperatures of less than 40 °C, this leads to the problem that bacteria and other microbial species are not efficiently killed during the extraction process, so that they may be carried into the extract, which is to be avoided in order to achieve a high product quality and stability. At higher temperatures, i.e. above 90 °C, more preferably above 80 °C, the protein profile of the extract does not show the unique composition anymore. Moreover, the overall yield of extracted proteins was found to decrease if higher extraction temperatures are applied.
[0043] The period during which the extraction temperature is maintained as mentioned under step c) amounts to at least 30 minutes. Preferably, the temperature is maintained for a period of 1 hours to 6 hours and even more preferred from 1.5 to 5 hours. Most preferably, the temperature is maintained for a period of 2 to 4 hours, ultimately preferably the temperature is maintained for 2 to 3.5 hours.
[0044] Surprisingly, it was found that the best results are obtained, if the extraction temperature is maintained for the periods indicated above. In general, shorter heating results in only partial extraction of the protein mixture from the plant material and therefore in inefficient extraction processes. However, if the extraction temperature is maintained for too long times, i.e. more than 6 hours, it was found that the yield of extracted protein material as well as the protein profile are negatively affected.
[0045] The solubility of non-hydrolyzed proteins is a challenge in the application of native proteins in cosmetics. Surprisingly, it was found that the addition of specific further solvents (so-called cosmetic solvents) as specified herein enhances the solubility of non-hydrolyzed proteins.
[0046] Thus, in a further aspect, the present invention relates to a process for extracting and simultaneous preparing a stable solution of (natural) proteins such as (natural) Zein proteins extracted from plant materials further comprising the steps of: f) i) adding at least one further solvent to the extract solution obtained in step e); ii) further removing the extraction solvent by distillation, preferably at elevated temperature and reduced pressure, preferably wherein the temperature is in the range of from 40 to 80 °C, and preferably, wherein the pressure is in the range of from 0.01 to 950 mbar; iii) optionally further filtering the distillation residue, preferably by using a tissue or paper filter; and iv) obtaining a solution of the protein extract (protein extract solution), in the at least one further solvent; or g) alternatively to f), obtaining a dry extract, preferably using lyophilization or spray-drying.
[0047] The proteins are preferably selected from plant materials select from the group consisting of albumins, prolamins, or mixtures of the aforementioned proteins, and preferably (natural) Zein proteins.
[0048] The process according to step f) allows for the preparation of stable solutions of non- hydrolyzed, native proteins e.g. from corn (Zeins), in a liquid form which is advantageous for the preparation of cosmetic formulations, mainly for hair care and skin care.
[0049] In a further preferred aspect, the present invention relates to a process for the extraction and simultaneous preparation of a stable solution of (natural) Zein proteins extracted from plant materials further comprising the steps of:f) i) adding at least one further solvent to the extract solution obtained in step e); ii) further removing the extraction solvent by distillation, preferably at elevated temperature and reduced pressure, preferably wherein the temperature is in the range of from 40 to 80 °C, and preferably, wherein the pressure is in the range of from 0.01 to 950 mbar; iii) optionally further filtering the distillation residue, preferably by using a tissue or paper filter; and iv) obtaining a solution of the Zein protein extract (protein extract solution), in the at least one further solvent; or g) alternatively to f), obtaining a dry extract, preferably using lyophilization or spray-drying.
[0050] This allows for the preparation of stabilized extracts of non-hydrolyzed, native proteins from e.g. corn (Zeins), in a liquid form which is advantageous for the preparation of cosmetic formulations in general, and preferably for hair (or fur) care and skin care preparations.
[0051] Surprisingly, the procedure under f) significantly improves the handling of the (natural) protein extracts such as the (natural) Zein protein extract and further enhances its stability and solubility by adding a further solvent. In case a dry extract is needed, lyophilization can be applied as mentioned under step g), i.e. the lyophilization step, it is done after the extraction process to get a dry extract. In this case, the lyophilization is done without the addition of further solvents (so-called cosmetic solvents (such as pentylene glycol and propylene glycol)). However, the extract can also be dried by other state of the art methods, e.g by spray-drying.
[0052] Also surprisingly, the dry extracts obtained by the aforementioned extraction process show a significantly different composition than commercial Zein or those obtained by state-of- the-art extraction processes. This again indicates the advantages of the simple mild extraction process which is disclosed by the present invention.
[0053] Preferably, the further solvent added in step f) i) for the preparation of the protein extract solution is a so-called cosmetic solvent. This means, that the at least one further solvent is selected from a group consisting of solvents, that are suitable for the formulation of cosmetic products. Thus, cosmetic solvents comprise solvents which are preferably non-toxic and admitted for the use in cosmetics. In addition, cosmetic solvents are preferably hydrophilic and thus easy to formulate in aqueous compositions. Preferably, cosmetic solvents are selected from the group consisting of water, glycerol and 1 ,2-alkandiols having 3 to 12 carbon atoms as well as the corresponding 2,3-alkandiol and 3,4-alkandiol isomers, or mixtures of the aforementioned solvents.
[0054] While the extraction solvent (i.e. water or a mixture of water and ethanol as specified herein) is removed, the cosmetic solvent remains in the composition to give a stable solution of the protein in the cosmetic solvent. This protein extract solution can already be considered a cosmetic composition.
[0055] Preferred alkanediols for the use as cosmetic solvents (at least one further solvent) in the stabilizing and solubilizing process of step f) are selected from the group consisting of linear1 .2-diols, 2,3-diols or 3,4-diols having 3 to 12 carbon atoms. Preferably, the alkanediol is selected from the group consisting of 1 ,2-propanediol, 1 ,2-butanediol, 1 ,2-pentanediol, 1 ,2- hexanediol, 1 ,2-heptanediol, 1 ,2-octanediol, 1 ,2-nonanediol, 1 ,2-decanediol, 1 ,2- undecanediol and 1 ,2-dodecanediol, also preferably the alkanediol is 2,3-hexanediol and / or2.3-heptanediol and / or 2,3-octanediol. Further preferably the alkanediol is a combination of 1 ,2-hexanediol and 2,3-hexanediol, or 1 ,2-heptanediol and 2,3-heptanediol, or 1 ,2-octanediol and 2,3-octanediol. More preferably, the alkanediol comprises 1 ,2-octanediol or 1 ,2- decanediol, also preferably 1 ,2-hexanediol, 1 ,2-octanediol and / or 1 ,2-decanediol. Most preferably, the 1 ,2-alkandiol comprises 1 ,2-propanediol, 1 ,2-pentanediol or a mixture thereof. These cosmetic solvents (such as pentylene glycol and propylene glycol) are added to the extracted solution, i.e. after the finished extraction according to steps a) to e), in order to obtain stabilized non-hydrolyzed proteins in a liquid form, i.e. a protein extract solution, suitable for the preparation of cosmetic formulations. These substances can be considered as cosmetically acceptable carriers.
[0056] The 1 ,2-alkanediols and / or 2,3-alkanediols have the advantage of improving the formulability of the liquid in cosmetic compositions, i.e. the incorporation of the liquid protein compositions in cosmetic product compositions. These components were found to increase the solubility of the (natural) protein extract and at the same time can stabilize the as-obtained extracts and formulations (stabilized protein extract solution).
[0057] Suitable alkanediols are: at least one linear alkanediol having a carbon chain of 3 to 12 carbon atoms or a mixture comprising at least one first linear alkanediol having a carbon chain of 3 to 12 carbon atoms and one or more second linear alkanediols having a carbon chain of 3 to 12 carbon atoms which is different from the first linear alkanediol. The phrase “different from each other means” that the first linear alkanediols and the second linear alkanediols in the mixture are either different with regard to the length of their carbon chain, i.e. number of the carbon atoms, or with regard to their constitutional isomerism. The at least one linear alkanediol or the at least one first linear alkanediol having a carbon chain of 3 to 12carbon atoms in the textile treatment composition according to the second aspect of the present invention is selected from the group consisting of propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, undecanediol, and dodecanediol. The at least one second linear alkanediol having a carbon chain of 3 to 12 carbon atoms in the textile treatment composition according to the second aspect of the present invention is selected from the group consisting of propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, undecanediol, and dodecanediol.
[0058] In a preferred variant, the alkanediols used within the scope of the present invention have a carbon chain of 3 to 8 carbon atoms, even more preferred from 3 to 7 and most preferred from 3 to 5 carbon atoms.
[0059] In a preferred variant of the present invention, the linear alkanediol or the first linear alkanediol is selected from the group consisting of: 1 ,2-propanediol, 2,3-propanediol, 3,4- propanediol, 1 ,2-butanediol, 2,3-butanediol, 3,4-butanediol, 1 ,2-pentanediol, 2,3-pentanediol, 3,4-pentanediol, 1 ,2-hexanediol, 2,3-hexanediol, 3,4-hexanediol, 1 ,2-heptanediol, 2,3- heptanediol, 3,4-heptanediol, 1 ,2-octanediol, 2,3-octanediol, 3,4-octanediol, 1 ,2-nonanediol,2.3-nonanediol, 3,4-nonanediol, 1 ,2-decanediol, 2,3-decanediol, 3,4-decanediol, 1 ,2- undecanediol, 2,3-undecanediol, 3,4-undecanediol, 1 ,2-dodecanediol, 2,3-dodecanediol, 3,4- dodecanediol, 1 ,2-tridecanediol, 2,3-tridecanediol, 3,4-tridecanediol, 1 ,2-tetradecanediol, 2,3- tetradecanedioll, 3,4-tetradecanediol, and any mixture thereof.
[0060] In a further preferred variant, the at least one alkanediol is a 1 ,2-alkanediol and / or a2.3-alkanediol.
[0061] The as-obtained compositions or formulations allow for efficiently stabilizing by solubilizing and formulating non-hydrolyzed proteins for the development of cosmetic products such as hair and / or skin actives. In addition, the use such preparations on hair formulations demonstrates the effectiveness of the formulation on the hair fiber’s caring, improving the mechanical properties and helping in the recovery of its structural physical properties.
[0062] Especially good results were achieved when using 1 ,2-pentanediol, 1 ,2-propandiol or a combination of 1 ,2-pentanediol and 1 ,2-propandiol which both are commonly used cosmetic compliant ingredients as well as preservative boosters for proteins such as e.g. albumins (water soluble) and prolamins (soluble in aq. ethanol). These proteins were preferably extracted according to steps a) to e). The addition of these alkanediols to the crude extractsresults in clear solutions. The improved solubility of the resulting composition and its clear appearance are beneficial for preparing stable cosmetic formulations.
[0063] Preferably, the distillation as mentioned in step f) ii) is carried out at a temperature in the range between 40 to 80 °C, more preferably between 50 to 75 °C and most preferably between 60 to 70 °C. Preferably, the corresponding pressure during the distillation is in the range between 0.01 to 950 mbar, more preferably between 1 to 900 mbar, more preferably between 5 to 800 mbar, more preferably between 10 to 700 mbar, more preferably between 25 to 600 mbar, more preferably between 40 to 500 mbar, more preferably between 55 to 400 mbar and most preferably between 80 to 300 mbar. The preferred temperature and pressure ranges of the distillation have the effect of allowing an efficient removal of the extraction solvents while at the same time providing relatively mild conditions which are not detrimental to the (natural) protein extracts such as the (natural) Zein protein extract.
[0064] Preferably, the recovery of the extraction solvents in the distillation step under f) ii) ranges from between 50 to 100 %, more preferably from 75 to 100 % and most preferably from 95 to 100 %. In a further preferred variant, 98 to 100 % of ethanol and 80 to 90 % of water are recovered.
[0065] Preferably, the extraction process is carried out at relatively lower pH values compared to state-of-the-art extraction processes. In particular, the present extraction method avoids pH values of 10 and higher, as they are present during alkaline protein extraction processes. An extraction process at lower pH is advantageous for maintaining certain properties of the proteins, such as their conformation. In addition, a lower pH was found to be beneficial to the stability of phenolics and allows for the extraction of unsaturated fatty acids such as linoleic acid, which also form part of the obtained extract and thus were found to contribute interesting properties to the protein extract.
[0066] In another aspect, the present invention relates to an extraction and stabilization / solubilizing process for the preparation of protein extracts and solutions thereof, wherein the proteins from plant materials are select from the group consisting of albumins, prolamins, or mixtures of the aforementioned proteins, and preferably Zein proteins.
[0067] In another aspect, the present invention relates to an extraction process for (natural) Zein proteins from Zea mays, preferably from corn kernel material, more preferably from corn gluten meal.
[0068] In a further aspect, the present invention relates to an extraction process for proteins, and preferably Zein proteins, from plant materials, wherein the weight ratio of plant material and extraction solvent in step a) in the mixture is 1 :3 to 1 :100, preferably in the range of 1 :5 to 1 :25, more preferably wherein the weight ratio of plant material and solvent is in the range of 1 : 10 to 1 :20, and most preferably wherein the weight ratio of plant material and solvent is 1 : 15. These ranges provide for a high yield and allow for a facilitated handling. For example, extract solutions in a ratio of 1 :1 cannot be handled anymore, and no extract solution can be pressed out anymore.
[0069] The extraction process was found to be most efficient, if the weight ratio of plant material and extraction solvent in the mixture is about 1 :15. If less extraction solvent is used, the (natural) proteins undergo side-reactions during the extraction process, which is detrimental to the quality and the composition of the extract. In addition, the yield will drop, and less protein content can be extracted. Simultaneously, too low amounts of solvent result in different protein profiles, with is likewise not desired. On the other hand, using more extraction solvent increases the costs of the extraction process, since firstly, more solvent needs to be provided for the process, and secondly, the removal of the extraction solvent, as preferably described under step f), requires more time and thus resources.
[0070] In a further aspect, the present invention relates to an extraction process with an additional stabilizing / solubilizing step f) for (natural) proteins, and preferably (natural) Zein proteins, from plant materials, wherein the at least one further (cosmetic) solvent is selected from the group consisting of water, glycerol, and 1 ,2-alkanediols and / or 2, 3-alkanediols having 3 to 12 carbon atoms (preferably 3 to 8 and most preferred 3 to 5 carbon atoms), preferably the at least one further solvent is propylene glycol or pentylene glycol, more preferably the at least one further solvent is a mixture comprising propylene glycol and pentylene glycol, preferably the at least one further solvent is a mixture comprising propylene glycol and pentylene glycol in a ratio of 1 :1 to 1 :20. These so-called cosmetic solvents (such as pentylene glycol and propylene glycol) are added to the extracted solution, i.e. after the finished extraction according to steps a) to e), in order to obtain stabilized non-hydrolyzed proteins in a liquid form suitable for the preparation of cosmetic formulations.
[0071] However, depending on the protein also other ranges might be suitable such as wherein the mixture comprising propylene glycol and pentylene glycol is present in a ratio of 20: 1 to 1 :20, preferably in a ratio of 10: 1 to 1 : 10 or 1 : 1 to 20: 1 .
[0072] In a preferred variant, the ratio between propylene glycol and pentylene glycol is from 20: 1 to 1 :20. Alternatively, pentylene glycol is used in at least equal amount of propylene glycol or in excess, so that a further preferred ratio between propylene glycol and pentylene glycol is from 1 :1 to 1 :20. More preferably, the ratio between propylene glycol and pentylene glycol is from 1 :2 to 1 :10. Most preferably, the ratio between propylene glycol and pentylene glycol is from 1 :3 to 1 :5. The choice of the further solvents propylene glycol and pentylene glycol is advantageous, since they are capable of dissolving the natural protein extracts such as the (natural) Zein extracts while at the same time being suitable for the use in cosmetic compositions. The appropriate ratio between propylene glycol and pentylene glycol leads to clear solutions which are stable for periods of at least 24 hours. Thus, a mixture of propylene glycol and pentylene glycol, preferably in a ratio between 1 :3 to 1 :5, has the surprising effect of simultaneously dissolving and stabilizing the (natural) Zein protein extract while at the same time allowing the solution to be used in cosmetic compositions.
[0073] In another aspect, the present invention comprises an extract, which is obtained from the aforementioned extraction process.
[0074] According to another aspect the present invention relates to an extract comprising proteins from plant materials, preferably wherein the proteins from plant materials are select from the group consisting of albumins, prolamins, or mixtures of the aforementioned proteins, and preferably Zein proteins, and at least one further solvent selected from the group consisting of water, glycerol, and 1 ,2-alkanediols and / or 2, 3-alkanediols having 3 to 12 carbon atoms (preferably 3 to 8 and most preferred 3 to 5 carbon atoms), or mixtures of the aforementioned solvents.
[0075] In a further aspect, the present invention comprises an extract comprising 45 to 85 wt.-% (natural) Zein proteins, preferably from 50 to 80 wt.-% (natural) Zein proteins, and more preferably 55 to 75 wt.-% based on the weight of the dried extract, wherein the protein portion of the extract comprises:30 to 80 wt.-% alpha-Zein, preferably 45 to 70 wt.-% alpha-Zein,1 to 30 wt.-% beta-Zein, preferably 7 to 20 wt.-% beta-Zein,0.1 to 20 wt.-% gamma-Zein, preferably 5 to 15 wt.-% gamma-Zein, and0.001 to 5 wt.-% delta-Zein, preferably 0.01 to 1wt.-% delta-Zein, based on the dry weight of the extract.
[0076] The extracts according to the present invention advantageously comprise a further solvent to give a stabilized extract solution, which is preferably selected from the groupconsisting of water, glycerol, and 1 ,2-alkanediols and / or 2, 3-alkanediols having 3 to 12 carbon atoms, preferably 1 ,2-alkanediols and / or 2, 3-alkanediols having 3 to 8 carbon atoms and even more preferred from 3 to 5 carbon atoms, more preferably the at least one further solvent is propylene glycol or pentylene glycol, more preferably the at least one further solvent is a mixture comprising propylene glycol and pentylene glycol, preferably the at least one further solvent is a mixture comprising propylene glycol and pentylene glycol in a ratio of 1 :1 to 1 :20. However, depending on the protein the ratio of propylene glycol and pentylene glycol can also range from 1 :1 to 20:1.
[0077] Surprisingly, the resulting protein extract solution (proteins solubilized and stabilized in liquid form) disclosed by the present invention comprises an increased amount of beta- and gamma-Zeins. In addition, the present final and stabilized extract solution was found to improve the efficacy in hair restoration and thus gives rise to more efficient hair-care products. This protein extract solution can already be considered a cosmetic composition.
[0078] Preferably, the amount of alpha-, beta-, gamma- and delta-Zein in the extract is determined using LC-MS analysis or other suitable analysis method allowing the separation of the alpha-, beta-, gamma- and delta-Zein.
[0079] In another preferred aspect, the present invention comprises an extract, which is obtainable by the abovementioned extraction process, wherein the extract comprises 45 to 85 wt.-% (natural) Zein proteins, preferably from 50 to 80 wt.-% (natural) Zein proteins, more preferably 55 to 75 wt.-% based on the weight of the dried extract, and wherein the extract further comprises:30 to 80 wt.-% alpha-Zein, preferably 45 to 70 wt.-% alpha-Zein,1 to 30 wt.-% beta-Zein, preferably 7 to 20 wt.-% beta-Zein,0.1 to 20 wt.-% gamma-Zein, preferably 5 to 15 wt.-% gamma-Zein, and0.001 to 5 wt.-% delta-Zein, preferably 0.01 to 1 wt.-% delta-Zein, based on the dry weight of the extract.
[0080] In another variant, the extract of the present invention further comprises a further solvent, which is preferably selected from the group consisting of water, glycerol, and 1 ,2- alkanediols and / or 2, 3-alkanediols having 3 to 12 carbon atoms and preferably 3 to 8 carbon atoms and even more preferred 3 to 5 carbona atoms, preferably the at least one further solvent is propylene glycol or pentylene glycol, more preferably the at least one further solvent is a mixture comprising propylene glycol and pentylene glycol, preferably the at least onefurther solvent is a mixture comprising propylene glycol and pentylene glycol in a ratio of 1 :1 to 1 :20.
[0081] However, depending on the protein the ratio of propylene glycol and pentylene glycol can also range from 1 :1 to 20: 1.
[0082] More preferably, the at least one solvent or solvent mixture comprises at least one further cosmetic solvent or a mixture of cosmetic solvents.
[0083] The presence of at least one further solvent as specified herein, preferably at least one further cosmetic solvent, has been found to increase the stability of the (natural) protein extract such as the (natural) Zein protein extract in solution (stabilized extract solution). In particular, the further solvent delays the degradation of the protein extract and thus delays the protein unfolding and consequently the loss of quaternary, tertiary and even secondary structures and keeps the stabilized extract in a liquid form easy to handle for the preparation of homogeneous product formulations of the protein extract. Overall, the further solvent helps to maintain a homogeneous and clear extract over an increased period of time.
[0084] In another aspect the present invention relates to the use of the protein extract or the stabilized protein extract solutions for the preparation of cosmetic compositions.
[0085] Accordingly, the present invention also relates to a process for the preparation of cosmetic composition based on the protein extract or the (stabilized) protein extract solutions according to the present invention as well as the cosmetic compositions or formulations as such comprising the protein extract or the (stabilized) protein extract solutions according to the invention.
[0086] In another aspect, the present invention includes a cosmetic composition comprising an extract or extract solution according to the present invention.
[0087] According to a preferred aspect, the present invention relates to a cosmetic composition comprising a Zein extract or a stabilized Zein extract solution according to the present invention.
[0088] In a preferred variant, the cosmetic composition comprises an extract, which is obtainable by the extraction (and solution stabilization) process disclosed above.
[0089] In a further preferred variant, the extract composition comprises proteins from plant materials, preferably wherein the proteins from plant materials are select from the group consisting of albumins, prolamins, or mixtures of the aforementioned proteins, and preferably Zein proteins, and at least one further solvent selected from the group consisting of water, glycerol, and 1 ,2-alkanediols and / or 2, 3-alkanediols having 3 to 12 carbon atoms (preferably3 to 8 and most preferred 3 to 5 carbon atoms), or mixtures thereof.
[0090] In a further aspect, the invention is related to a cosmetic composition comprising: from 2 to 12 wt.-% Zein proteins, preferably wherein the Zein content is from 4 to 10 wt.-%, more preferably wherein the overall Zein content is from 5 to 8 wt.-%, a further solvent or solvent mixture comprising a further solvent selected from the group consisting of 1 ,2-alkanediols and / or 2, 3-alkanediols having 3 to 12 carbon atoms (preferably 3 to 8 and most preferred 3 to 5 carbon atoms), preferably pentylene glycol, further preferably comprising propylene glycol, or preferably a mixture of pentylene glycol and propylene glycol.
[0091] Preferably the ranges of the mixture of cosmetic solvents are as specified above.
[0092] In a further preferred variant, the invention is related to a cosmetic composition comprising: from 2 to 12 wt.-% (natural) Zein proteins, preferably wherein the (natural) Zein content is from4 to 10 wt.-%, more preferably wherein the overall Zein content is from 5 to 8 wt.-%, wherein the Zein proteins are preferably selected from Zea mays, a further solvent or solvent mixture comprising a further solvent selected from the group consisting of 1 ,2-alkanediols and / or 2, 3-alkanediols having 3 to 12 carbon atoms (preferably 3 to 8 and most preferred 3 to 5 carbon atoms), preferably pentylene glycol, further preferably comprising propylene glycol, or preferably a mixture of pentylene glycol and propylene glycol.
[0093] Preferably the ranges of the mixture of cosmetic solvents are as specified above.
[0094] It has been found that the extract according to the invention, i.e. comprising an increased amount of beta- and gamma-Zeins, tends to undergo gelation upon storage especially when exposed to higher temperatures for a longer period of time. Surprisingly, the gelation has been found to be delayed, if alkali or earth alkali salts, and preferably calcium chloride or sodium chloride, and / or L-arginine are present in the extract solution. Thus, bothcalcium chloride and L-arginine are capable of increasing the stability of as-obtained protein extracts.
[0095] Accordingly, in another aspect the present invention relates to an extract or extract solution or cosmetic composition comprising an additive selected from the group consisting of inorganic alkali or earth alkali salts such as calcium chloride or sodium chloride, L-arginine, sugar such as sucrose, or mixtures of the aforementioned substances.
[0096] Additionally, it was found that these substances efficiently suppress the gelation of the protein extract.
[0097] However, also other additives such as selected from the group consisting of amino acids such as L-arginine, inorganic alkali or earth alkali salts, such as NaCI, KCI, MgCl2 and CaCl2, and sugars such as sucrose, or mixtures of the aforementioned substances showed the advantageous effects and are thus suitable additives.
[0098] Preferably said additives are added in an amount of from 0.01 to 5 wt.-%, more preferably each in amount of from 0.2 to 1.2 wt.-%, based on the protein extract solution or the final cosmetic composition.
[0099] Preferably the additive is selected from calcium chloride, sodium chloride, L-arginine, or a mixture of calcium chloride or sodium chloride and L-arginine.
[0100] More preferably the additive is selected from calcium chloride, L-arginine, or a mixture of calcium chloride and L-arginine.
[0101] According to another aspect, the protein extract or the corresponding stabilized extract solution may also comprise other additives which prevent and / or delay gelation upon storage.
[0102] In another aspect, the (natural) protein extract or the (natural) Zein protein extract or the corresponding stabilized extract solution may also comprise other additives which prevent and / or delay gelation upon storage. Preferably, these additives are selected from the group consisting of amino acids such as L-arginine, inorganic alkali or earth alkali salts, such as NaCI, KCI, MgCl2 and CaCh, and sugars such as sucrose, or mixtures of the aforementioned substances.
[0103] In another preferred aspect, the extract, the stabilized extract solution or the cosmetic composition further comprises calcium chloride or sodium chloride or L-arginine, preferably each in an amount of from 0.01 to 5 wt.-%, more preferably each in amount of from 0.2 to 1.2 wt.-%, based on the protein extract solution or the final cosmetic composition.
[0104] In another preferred variant of the present invention, the (natural) protein extract, the (natural) Zein protein extract, the stabilized extract solution or the cosmetic composition further comprises calcium chloride or sodium chloride and L-arginine, preferably each in an amount of from 0.01 to 5 wt.-%, more preferably each in an amount of from 0.2 to 3 wt.-%, and most preferred each in an amount 0.5 to 1.5% wt.-% based on the protein extract solution or the final cosmetic composition.
[0105] In a further preferred variant, the protein extract, the (natural) Zein protein extract, the stabilized extract solution or the cosmetic composition further comprises calcium chloride or sodium chloride in an amount of from 0.1 to 1.0 wt.-%, more preferably from 0.25 to 0.75 wt.- % and most preferably from 0.45 to 0.55 wt.-%, based on the protein extract solution or the final cosmetic composition.
[0106] In another aspect, the protein extract, the Zein protein extract, the stabilized extract solution or the cosmetic composition further comprises L-arginine in an amount of from 0.1 to 2.0 wt.-%, more preferably from 0.5 to 1 .5 wt.-% and most preferably from 0.85 to 0.95 wt.-%, based on the protein extract solution or the final cosmetic composition.
[0107] Moreover, it was surprisingly found that the further solvents as specified herein considerably improve the solubility of proteins, preferably (natural) proteins. This makes the proteins easier to handle and to incorporate into various consumer product formulations without negatively influencing the protein characteristics and properties.
[0108] Therefore, the present invention also relates to the use of further solvents as specified herein for increasing the solubility of proteins, preferably albumins, prolamins, or mixtures of the aforementioned proteins, and preferably (natural) Zein proteins, wherein the (natural) Zein proteins are extracted from Zea mays, preferably from corn kernel material, more preferably from corn gluten meal.
[0109] Additionally, it was found that the additives as specified herein stabilize the as- obtained solutions and avoid gelation, thus providing for a stabilized protein extract solution which can be used as or in cosmetic compositions and formulations.
[0110] Surprisingly it was found that the specific extract composition composed by a group of specific native proteins, and preferably Zein proteins, (preferably with a molecular weight range from 10kDa to 25 kDa) has the capability to deposit and interact with the surface of the hair fiber due to electric charges, which assists the interaction with damaged regions (negatively charged), anchoring the active ingredient and improving fiber surface conditions and mechanical properties of damaged hair.
[0111] Surprisingly it was also found that the specific extract composition composed by a group of specific native proteins, and preferably Zein proteins, (preferably with molecular weight range from 10kDa to 25 kDa) has the capability to scavenge radicals and reduce oxidative stress, more preferably cutaneous oxidative stress.
[0112] Additionally, it was found that the compositions according to the present invention have beneficial properties as or in skin care formulations.
[0113] Preferably said composition comprises both, the cosmetic solvent(s) and the additives specified above such as calcium chloride and / or L-arginine.
[0114] Thus in another preferred variant, the present invention relates to the (natural) protein extract, the (natural) Zein protein extract, the stabilized extract solution or the cosmetic composition further comprising at least one further solvent selected from the group consisting of water, glycerol, and 1,2-alkanediols and / or 2, 3-alkanediols having 3 to 12 carbon atoms, or mixtures thereof (preferably selected from selected from the group consisting of 1,2- alkanediols and / or 2, 3-alkanediols having 3 to 8 and even more preferred from 3 to 5 carbon atoms, preferably pentylene glycol, further preferably comprising propylene glycol, or preferably a mixture of pentylene glycol and propylene glycol) and at least one additive selected from the group consisting of amino acids such as L-arginine, inorganic alkali or earth alkali salts, such as NaCI, KCI, MgCl2 and CaCh, and sugars such as sucrose, or mixtures of the aforementioned substances (preferably the additive is calcium chloride and / or L-arginine).
[0115] Native proteins such as e.g. albumins (water soluble) and prolamins (soluble in aq. ethanol) can be used in personal care or home care formulations in purified form or enriched or as a constituent of a plant, mushroom, algae or microalgae extract. These proteins have many benefits for cosmetic applications for skin and hair care, however, they are rarely used so far as they are extremely difficult to formulate and prevent from precipitation in common cosmetic formulations as explained above. Instead of native proteins, hydrolyzed proteins aretherefore used which have the benefit of easy formulation but due to processing and smaller molecular size of course possess different efficacies than the respective native protein. However, surprisingly it was found that the use of at least one further solvent such as a 1 ,2- alkanediol and / or a 2,3-alkanediol alone or in combination with other solvents allows for obtaining clear protein solutions (especially albumins e.g. albumin and prolamins e.g. zeins from corn). Completely dissolved proteins are easier to formulate and stay or remain for a longer period in dissolved form in typical cosmetic formulations compared to not clearly dissolved (= suspended) or solid proteins. Only dissolved proteins are readily bioavailable and can exhibit their beneficial effect(s).
[0116] Accordingly, the abovementioned processes and compositions are not only suitable in respect of prolamins such as Zein proteins but also beneficially improve the properties and applicability of other types of proteins such as albumins, e.g. from plant derived raw material.
[0117] Proteins such as lipases and proteases are water soluble and are also used in home care products, especially laundry and dish washing products. Based on the beneficial effects on hair of these proteins, these protein formulations will likewise have a beneficial effect on other keratin- or protein-containing fibers such as wool, silk and cashmere as well as animal fur. Consequently, the compositions according to the present invention are not only applicable in cosmetic preparations but also for home care preparations.
[0118] Thus, in another aspect the present invention also relates to a composition comprising or consisting of (a) at least one water soluble (albumin type) and aqueous ethanol soluble (prolamin type) protein, (b) at least one alkanediol, preferably a C3-C12 alkanediol, more preferably a 1 ,2- or 2,3- or 3,4-C3-C12 alkanediol, most preferably 1 ,2-C3-C10 alkanediol and (c) optionally a salt, preferably selected from the group of salts containing an alkali or alkaline earth metal cation, more preferably Na, K, Mg or Ca.
[0119] Moreover, it was found that albumin and prolamin proteins could efficiently be extracted based on the process disclosed herein.
[0120] Furthermore, the as-obtained extracts could successfully be dried or combined with alkanediols as specified herein in order to give a stabilized solution of proteins which could successfully be incorporated into various consumer product formulations.
[0121] Therefore, different solvents were used, first in pure form and or in form of combinations, to investigate the solubility of corn protein extract. Solubility tests wereconducted with water, glycerol, 1 ,3-butanediol (INCI: butylene glycol), 1 ,2-propanediol (INCI: propylene glycol) and 1 ,2-pentanediol (INCI: pentylene glycol) as well as with longer homologues and combinations of the aforementioned substances resulting in improved solubilities and clear solutions suitable for the incorporation into various consumer product preparations. The results clearly show that surprisingly 1 ,2-alkanediols alone or in combination with other 1 ,2-alkanediols are very good solvents for proteins of the prolamin type. Moreover, the addition of alkanediols could significantly improve the solubility in other solvents such as glycerol. Also 2,3-alkanediols were found to be suitable either alone or in combination with the other solvents mentioned above.
[0122] Generally, it was found that the protein extract can be dissolved in form of the dry protein extract as described above or the cosmetic solvent such as the 1 ,2-alkanediol solvent or a 1 ,2-alkanediol comprising solvent system can be added to the extract solution obtained from the extraction process after the removal of insoluble components. This can be done either directly or after partial removal of the extracting solvent.
[0123] Moreover, likewise the gelatin delaying additives as specified herein can be added during any of the process steps disclosed herein. Preferably, the additives as specified herein are added before, together with, or after the addition of the cosmetic solvents, and before or after the removal of insoluble components.
[0124] The same is true for the corresponding 2,3-alkanediols and mixtures of 1 ,2- alkanediols and 2,3-alkanediols as specified herein.
[0125] To allow bioavailability, the protein extract needs to be homogeneously dissolved in the formulation.
[0126] Compositions comprising the protein extract (solution) as well as a cosmetic ingredient as specified herein could successfully be incorporated into emulsions with excellent formulation properties and emulsion stabilities. No precipitations were observed under the microscope, and the ingredient was homogeneously distributed within the emulsion. The emulsions comprising the protein extract were observed to have a higher viscosity than the placebo, showing an additional thickening effect of the extract in emulsion. After 6 months, no change in color or odor were recognized nor precipitations were observable. Therefore, these results show that the protein solution is easy to formulate and dissolves in typical cosmetic formulations, such as emulsions.
[0127] The samples comprising proteins other than the Zein protein (for the Zein protein see experimental section) likewise showed excellent hair care properties in fatigue tests, stress tests and swelling test as well as excellent skin care properties.
[0128] In still another preferred variant, the present invention is related to the use of the disclosed extract or cosmetic composition in scalp and hair care products and / or in skin care products, preferably in water-based scalp and hair care products and / or in skin care products, more preferably in shampoos and / or conditioners, emulsions, serums, tonics and cleansers, preferably in shampoos and / or conditioners.
[0129] Preferably, the water content in these formulations is at least 50 wt.-% based on the total weight of the formulation, preferably at least 50 wt.-% and more preferably at least 70 wt.- %.
[0130] The cosmetic composition according to the present invention can advantageously be combined with other cosmetically or pharmaceutically active agents and / or adjuvants and / or additives or auxiliaries, such as are customarily used in such compositions, such as for example abrasives, anti-acne agents, agents against ageing of the skin, anti-cellulitis agents, anti-dandruff agents, anti-inflammatory agents, anti-microbial agents, irritation-preventing agents, irritation-inhibiting agents, antioxidants, astringents, odor absorbers, perspirationinhibiting agents, antiseptic agents, anti-statics, binders, buffers, carrier materials, chelating agents, cell stimulants, cleansing agents, depilatory agents, surface-active substances, deodorizing agents, antiperspirants, softeners, emulsifiers, enzymes, enzyme inhibitors, essential oils, fibers, film-forming agents, fixatives, foam-forming agents, foam stabilizers, substances for preventing foaming, foam boosters, gelling agents, gel-forming agents, hair care agents, hair-setting agents, hair-straightening agents, moisture-donating agents, moisturizing substances, moisture-retaining substances, bleaching agents, strengthening agents, stain-removing agents, optically brightening agents, impregnating agents, dirtrepellent agents, dyes, friction-reducing agents, lubricants, moisturizing creams, ointments, opacifying agents, plasticizing agents, covering agents, polish, preservatives, gloss agents, green and synthetic polymers, powders, proteins, re-oiling agents, abrading agents, silicones, skin-soothing agents, skin-cleansing agents, skin care agents, skin-healing agents, skinlightening agents, skin-protecting agents, skin-softening agents, hair promotion agents, cooling agents, skin-cooling agents, warming agents, skin-warming agents, stabilizers, surfactants, UV-absorbing agents, UV filters, primary sun protection factors, secondary sun protection factors, detergents, fabric conditioning agents, suspending agents, skin-tanning agents, actives modulating skin or hair pigmentation, matrix-metalloproteinase inhibitors, skinmoisturizing agents, glycosaminoglycan stimulators, TRPV1 antagonists, desquamating agents, anti-cellulite agents or fat enhancing agents, hair growth activators or inhibitors, thickeners, rheology additives, vitamins, oils, waxes, pearlizing waxes, fats, phospholipids, saturated fatty acids, mono- or polyunsaturated fatty acids, a-hydroxy acids, polyhydroxy fatty acids, liquefiers, dyestuffs, color-protecting agents, pigments, anti-corrosives, fragrances or perfume oils, aromas, flavoring substances, odoriferous substances, polyols, electrolytes, organic solvents, and mixtures of two or more of the aforementioned substances.
[0131] Accordingly, the present invention also relates to the use of the extracts and composition according to the present invention for the preparation of the corresponding cosmetic products as well as to the resulting cosmetic products as such.
[0132] Suitable products are for example: solid and liquid soaps, shower gels, shampoos, shaving soaps, shaving foams, bath oils, cosmetic emulsions, skin creams and lotions, face creams and lotions, sun protection creams and lotions, after-sun creams and lotions, hand creams and hand lotions, foot creams and lotions, depilatory creams and lotions, after-shave creams and lotions, tanning creams and lotions, hair sprays, hair gels, hair lotions, hair conditioners, permanent and semi-permanent hair dyes, hair deforming agents, hair tonics, hair creams and lotions, deodorants, underarm sprays, roll-ons, deodorant sticks, deodorant cremes and decorative cosmetic products as well as perfume extracts, eau de parfums, eau de toilettes, shaving lotions, eau de colognes, preshave products, splash-colognes and the like.
[0133] In a further preferred variant, the present invention is related to the use of the disclosed extract or cosmetic composition in scalp and hair care products and / or in skin care products, preferably in shampoos and / or conditioners, wherein the extract or cosmetic composition is directed to hair restoration, preferably wherein the cosmetic composition is directed to the improvement of the tensile strength of hair, the treatment of hair fatigue and / or the avoidance of hair swelling.
[0134] It was surprisingly found that the protein compositions according to the present invention have a repairing and protecting effect on chemically damaged hair fibers. The extracts according to the present invention and the corresponding stabilized extract solutions and compositions / formulations result in a significantly reduced water intake of damaged hair, restoring part of its natural hydrophobicity, which contributed to the general health of the hair. Moreover, a beneficial impact on the elastic modulus and break stress of bleached hair was found, thus improving the mechanical properties of these fibers. Moreover, productscomprising the inventive compositions showed a better performance in mitigating fractures and avoiding the formation of new ones in hair, resulting in a bigger number of cycles necessary to have 63.2 % of the fibers broken (characteristic life parameter).
[0135] In a further preferred variant, the present invention is related to the use of the disclosed extract or cosmetic composition in skin care preparations, preferably, the extract or cosmetic composition is directed to skin care for reduction of oxidative stress.Surprisingly, it was found that the extracted proteins according to the present invention significantly decreased the UVA-induced ROS level versus untreated UVA-irradiated as well as vehicle treated UVA-irradiated samples, even when used in small amounts. The results indicate that these protein extracts efficiently reduce UV-induced ROS induction and oxidative stress and can therefore be expected to also clearly decrease ROS and oxidative stress associated tissue damages leading to e.g. premature skin aging. Accordingly, it was surprisingly found, that the extracts, compositions and formulations according to the present invention also have a positive skin treating effect and thus can advantageously be used for skin treatment and as or in cosmetic skin care preparations.
[0136] The mixtures according to the present invention may incorporate also at least one hair conditioning agent. In the context of the present invention a conditioning agent is a compound capable of coating on the surface and / or penetrating into a keratin fiber when applied to human hair. Typical examples encompass quaternary surfactants, cationic polymers and silicones and binary and ternary mixtures of these compounds.CATIONIC SURFACTANTS
[0137] Tetraalkyl ammonium salts. Cationically active surfactants comprise the hydrophobic high molecular group required for the surface activity in the cation by dissociation in aqueous solution. A group of important representatives of the cationic surfactants are the tetraalkyl ammonium salts of the general formula: (R1R2R3R4N+) X-. Here R1 stands for Ci-Cs alk(en)yl, R2, R3and R4, independently of each other, for alk(en)yl radicals having 1 to 22 carbon atoms. X is a counter ion, preferably selected from the group of the halides, alkyl sulfates and alkyl carbonates. Cationic surfactants, in which the nitrogen group is substituted with two long acyl groups and two short alk(en)yl groups, are particularly preferred.
[0138] Esterquats. A further class of cationic surfactants particularly useful as co-surfactants for the present invention is represented by the so-called esterquats. Esterquats are generally understood to be quaternized fatty acid triethanolamine ester salts. These are known compounds which can be obtained by the relevant methods of preparative organic chemistry.Reference is made in this connection to International patent application WO 91 / 01295 A1 , according to which triethanolamine is partly esterified with fatty acids in the presence of hypophosphorous acid, air is passed through the reaction mixture and the whole is then quaternized with dimethyl sulphate or ethylene oxide. In addition, German patent DE 4308794 C1 describes a process for the production of solid esterquats in which the quaternization of triethanolamine esters is carried out in the presence of suitable dispersants, preferably fatty alcohols.
[0139] Typical examples of esterquats suitable for use in accordance with the invention are products of which the acyl component derives from monocarboxylic acids corresponding to formula RCOOH in which RCO is an acyl group containing 6 to 10 carbon atoms, and the amine component is triethanolamine (TEA). Examples of such monocarboxylic acids are caproic acid, caprylic acid, capric acid and technical mixtures thereof such as, for example, so- called head-fractionated fatty acid. Esterquats of which the acyl component derives from monocarboxylic acids containing 8 to 10 carbon atoms, are preferably used. Other esterquats are those of which the acyl component derives from dicarboxylic acids like malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, sorbic acid, pimelic acid, azelaic acid, sebacic acid and / or dodecanedioic acid, but preferably adipic acid. Overall, esterquats of which the acyl component derives from mixtures of monocarboxylic acids containing 6 to 22 carbon atoms, and adipic acid are preferably used. The molar ratio of mono and dicarboxylic acids in the final esterquat may be in the range from 1 :99 to 99:1 and is preferably in the range from 50:50 to 90:10 and more particularly in the range from 70:30 to 80:20. Besides the quaternized fatty acid triethanolamine ester salts, other suitable esterquats are quaternized ester salts of mono- / dicarboxylic acid mixtures with diethanolalkyamines or 1 ,2-dihydroxypropyl dialkylamines. The esterquats may be obtained both from fatty acids and from the corresponding triglycerides in admixture with the corresponding dicarboxylic acids. One such process, which is intended to be representative of the relevant prior art, is proposed in European patent EP 0750606 B1. To produce the quaternized esters, the mixtures of mono- and dicarboxylic acids and the triethanolamine - based on the available carboxyl functions - may be used in a molar ratio of 1.1 :1 to 3:1. With the performance properties of the esterquats in mind, a ratio of 1.2:1 to 2.2:1 and preferably 1.5:1 to 1.9:1 has proved to be particularly advantageous. The preferred esterquats are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9.CATIONIC POLYMERS AND SILICONES
[0140] Suitable cationic polymers are, for example, cationic cellulose derivatives such as, for example, the quaternized hydroxyethyl cellulose obtainable from Amerchol under the name of Polymer JR 400®, cationic starch, copolymers of diallyl ammonium salts and acrylamides, quaternized vinyl pyrrolidone / vinyl imidazole polymers such as, for example, Luviquat® (BASF), condensation products of polyglycols and amines, quaternized collagen polypeptides such as, for example, Lauryldimonium Hydroxypropyl Hydrolyzed Collagen (Lamequat® L, Grunau), quaternized wheat polypeptides, polyethyleneimine, cationic silicone polymers such as, for example, amodimethicone, copolymers of adipic acid and dimethylaminohydroxypropyl diethylenetriamine (Cartaretine®, Sandoz), copolymers of acrylic acid with dimethyl diallyl ammonium chloride (Merquat®550, Chemviron), polyaminopolyamides and crosslinked water- soluble polymers thereof, cationic chitin derivatives such as, for example, quaternized chitosan, optionally in microcrystalline distribution, condensation products of dihaloalkyls, for example dibromobutane, with bis-dialkylamines, for example bis-dimethylamino-1 ,3-propane, cationic guar gum such as, for example, Jaguar®CBS, Jaguar®C-17, Jaguar®C-16 of Celanese, quaternized ammonium salt polymers such as, for example, Mirapol® A-15, Mirapol® AD-1, Mirapol® AZ-1 of Miranol and the various polyquaternium types (for example 6, 7, 32 or 37) which can be found in the market under the tradenames Rheocare® CC or Ultragel® 300.
[0141] Suitable silicone compounds are, for example, dimethyl polysiloxanes, methylphenyl polysiloxanes, cyclic silicones and amino-, fatty acid-, alcohol-, polyether-, epoxy-, fluorine-, glycoside- and / or alkyl-modified silicone compounds which may be both liquid and resin-like at room temperature. Other suitable silicone compounds are simethicones which are mixtures of dimethicones with an average chain length of 200 to 300 dimethylsiloxane units and hydrogenated silicates.
[0142] In another aspect, the cosmetic composition further comprises at least one additive selected from the groups consisting of UV filters, radical scavengers or other antioxidants, moisturizers, and / or anti-aging agents.
[0143] Oxidative stress in skin plays a major role in the aging process. The source of reactive oxygen species (ROS), enzymatic as well as non-enzymatic ones, in skin cells are manifold. As the skin is at the interface between the exterior and the interior, external factors, such as UV-irradiation, also contribute to ROS production in the skin.
[0144] Accordingly, a combination of the cosmetic composition with UV filters (organic and / or inorganic ones) is especially advantageous as it helps to reduce ROS formation induced by the UVA radiation even more. UV filters are mostly not absorbing the UVA radiation completely,i.e. to 100 %, but a certain extent of UVA is remaining and then penetrating the skin, reaching also the dermis and leading there to tissue damage.
[0145] Surprisingly, the extract in combination with other hair or skin actives give a better overall effect. Also, the extract as such possesses antioxidant and radical scavenging activity as shown by the ABTS results and the reduction of UVA-induced oxidative stress. Therefore, it is especially beneficial to combine the products of the present invention with other antioxidants and / or UV filters to obtain a much better overall activity in the final cosmetic preparation. This can be particularly relevant for scalp, but also face and body care, sun care product for skin and hair, anti-aging products, and the like.
[0146] UV filters which are optionally contained in the cosmetic composition are preferably selected from the group consisting of UVA filters, UVB filters, broadband filters and mixtures thereof.
[0147] The UV filters cited below are preferred but non-limiting examples which can be used within the context of the present invention. UV filters which are preferably used are selected from the group consisting of one, two, three, four, five or more of the following species:
[0148] Table 1 : Suitable U V filters.
[0149] In another preferred variant, the cosmetic composition additionally comprises at least one additive selected from the group consisting of radical scavengers and antioxidants. Such a combination shows an overall better and more pronounced effect in reduction of ROS formation and is therefore especially advantageous.
[0150] In general, antioxidants interrupt the photochemical reaction chain which is triggered when UV radiation penetrates the skin. Preferably, radical scavengers and antioxidants are selected from the group consisting of amino acids (e.g. glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (e.g. urocanic acid) and their derivatives, peptides like D,L- carnosine, D-carnosine, L-carnosine and their derivatives (e.g. anserine), carotenoids, carotenes (e.g. carotene, lycopene) and their derivates, chlorogenic acid and its derivatives,lipoic acid and its derivatives (e.g. dihydrolic acid), aurothioglucose, propylthiouracil and other thiols (e.g. thioredoxin, glutathione, cysteine, cystine, cystamin and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, linoleyl, cholesteryl and glyceryl esters) and their salts dilaurylthiodipropionate, ditearylthiodipropionate, thiodipropionic acid and its derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) as well as sulfoximine compounds (e.g. buthionine sulfoximines, homocysteine sulfoximines, butionine sulfones, penta-, hexa-, heptathionine sulfoximines) in very low tolerated dosages (e.g. pmol to mol / kg), furthermore (metal) chelators (e.g. hydroxy fatty acids, palmitic acid, phytinic acid, lactoferrin), hydroxy acids (e.g. citric acid, lactic acid, malic acid), humic acid, gallic acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives (e.g. linolenic acid, linoleic acid, oleic acid), folic acid and its derivatives, ubiquinone and ubiquinol and their derivatives, vitamin C and its derivatives (e.g. ascorbyl palmitate, Mg-ascorbyl phosphate, ascorbylacetate), tocopherols and derivatives (e.g. vitamin E acetate), vitamin A and derivates (vitamin A palmitate) as well as conifer aryl benzoate of benzoic resin, rutinic acid and its derivatives, glycosylrutin, ferulic acid, furfurylidene glucitol, carnosine, butyl hydroxytoluene, butylhydroxyanisole, nordihydroguaiac resin acid, nordihydroguajaretic acid, trihydroxybutyrophenone, uric acid and its derivatives, mannose and its derivatives, superoxide dismutase, zinc and its derivatives (e.g. ZnO, ZnSC ) selenium and its derivatives (e.g. selenium-methionine), stilbenes and their derivatives (e.g. styrene oxide, trans-stilbene oxide) and the derivatives suitable for the invention (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of these named active substances.
[0151] Anti-aging agents, moisturizers and further additives:
[0152] In another preferred variant, the cosmetic composition additionally comprises at least one additive selected from the group consisting of anti-aging.
[0153] The selection of anti-ageing agents and antioxidants overlaps to a certain extent, namely when ageing particular of skin is triggered by oxidative stress. Additional anti-agents encompass for example, tocopherol, tocopherol acetate, tocopherol palmitate, ascorbic acid, (deoxy)ribonucleic acid and its fragmentation products, p-glucans, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essential oils, plant extracts, such as such as prunus extract, bambaranus extract and vitamin complexes.
[0154] In a further preferred variant, the cosmetic composition additionally comprises at least one additive selected from the group consisting of actives modulating hair pigmentation.
[0155] Preferred active ingredients for hair lightening are selected from the group consisting of: kojic acid (5-hydroxy-2-hydroxymethyl-4-pyranone), kojic acid derivatives, preferably kojic acid dipalmitate, arbutin, ascorbic acid, ascorbic acid derivatives, preferably magnesium ascorbyl phosphate, hydroquinone, hydroquinone derivatives, resorcinol, resorcinol derivatives, preferably 4-alkylresorcinols and 4-(1-phenylethyl)-1 ,3-dihydroxybenzene (phenylethyl resorcinol), cyclohexylcarbamates, sulphur-containing molecules, preferably glutathione or cysteine, alpha-hydroxy acids (preferably citric acid, lactic acid, malic acid), salts and esters thereof, N-acetyl tyrosine and derivatives, undecenoyl phenylalanine, gluconic acid, chromone derivatives, preferably aloesin, flavonoids, 1-aminoethyl phosphinic acid, thiourea derivatives, ellagic acid, nicotinamide (niacinamide), zinc salts, preferably zinc chloride or zinc gluconate, thujaplicin and derivatives, triterpenes, preferably maslinic acid, sterols, preferably ergosterol, benzofuranones, preferably senkyunolide, vinyl guiacol, ethyl guiacol, dionic acids, preferably octodecene dionic acid and / or azelaic acid, inhibitors of nitrogen oxide synthesis, preferably L-nitroarginine and derivatives thereof, 2,7-dinitroindazole or thiocitrulline, metal chelators (preferably alpha-hydroxy fatty acids, phytic acid, humic acid, bile acid, bile extracts, EDTA, EGTA and derivatives thereof), retinoids, soy milk and extract, serine protease inhibitors or lipoic acid or other synthetic or natural active ingredients for skin and hair lightening, the latter preferably used in the form of an extract from plants, preferably bearberry extract, rice extract, papaya extract, turmeric extract, mulberry extract, bengkoang extract, nutgrass extract, liquorice root extract or constituents concentrated or isolated therefrom, preferably glabridin or licochalcone A, artocarpus extract, extract of rumex and ramulus species, extracts of pine species (pinus), extracts of vitis species or stilbene derivatives isolated or concentrated therefrom, saxifrage extract, scutelleria extract, grape extract and / or microalgae extract, in particular Tetraselmis suecica Extract.
[0156] Advantageous skin and hair tanning active ingredients in this respect are substrates or substrate analogues of tyrosinase such as L-tyrosine, N-acetyl tyrosine, L-DOPA or L- dihydroxyphenylalanine, xanthine alkaloids such as caffeine, theobromine and theophylline and derivatives thereof, proopiomelanocortin peptides such as ACTH, alpha-MSH, peptide analogues thereof and other substances which bind to the melanocortin receptor, peptides, pyrimidines, folic acid, copper salts such as copper gluconate, chloride or pyrrolidonate, 1 ,3,4- oxadiazole-2-thiols such as 5-pyrazin-2-yl-1 ,3,4-oxadiazole-2-thiol, curcumin, zinc diglycinate (Zn(Giy)2), manganese(ll) bicarbonate complexes (“pseudocatalases”), tetrasubstituted cyclohexene derivatives, isoprenoids, melanin derivatives such as Melasyn-100 and MelanZe, diacyl glycerols, aliphatic or cyclic diols, psoralens, prostaglandins and analogues thereof, activators of adenylate cyclase and compounds which activate the transfer of melanosomes tokeratinocytes such as serine proteases or agonists of the PAR-2 receptor, extracts of plants and plant parts of the chrysanthemum species, sanguisorba species, walnut extracts, urucum extracts, rhubarb extracts, micro-algae extracts, in particular Isochrysis galbana, trehalose, erythrulose and dihydroxyacetone. Flavonoids which bring about skin and hair tinting or browning (e.g. quercetin, rhamnetin, kaempferol, fisetin, genistein, daidzein, chrysin and apigenin, epicatechin, diosmin and diosmetin, morin, quercitrin, naringenin, hesperidin, phloridzin and phloretin) can also be used.
[0157] In a further preferred variant, the cosmetic composition additionally comprises at least one additive selected from the group consisting of hair growth activators or inhibitors.
[0158] Hair growth activators are preferably selected from the group consisting of pyrimidine derivatives such as 2,4-diaminopyrimidine-3-oxide (Aminexil), 2,4-diamino-6- piperidinopyrimidine-3-oxide (Minoxidil) and derivatives thereof, 6-amino-1 ,2-dihydro-1- hydroxy-2-imino-4-piperidinopyrimidine and its derivatives, xanthine alkaloids such as caffeine, theobromine and theophylline and derivatives thereof, quercetin and derivatives, dihydroquercetin (taxifolin) and derivatives, potassium channel openers, antiandrogenic agents, synthetic or natural 5-reductase inhibitors, nicotinic acid esters such as tocopheryl nicotinate, benzyl nicotinate and C1-C6 alkyl nicotinate, proteins such as for example the tripeptide Lys-Pro-Val, diphencypren, hormons, finasteride, dutasteride, flutamide, bicalutamide, pregnane derivatives, progesterone and its derivatives, cyproterone acetate, spironolactone and other diuretics, calcineurin inhibitors such as FK506 (Tacrolimus, Fujimycin) and its derivatives, Cyclosporin A and derivatives thereof, zinc and zinc salts, polyphenols, procyanidins, proanthocyanidins, phytosterols such as for example betasitosterol, biotin, eugenol, (±)-beta-citronellol, panthenol, glycogen for example from mus-sels, extracts from microorganisms, algae, plants and plant parts of for example the genera dandelion (Leontodon or Taraxacum), Orthosiphon, Vitex, Coffea, Paullinia, Theobroma, Asiasarum, Cucurbita or Styphnolobium, Serenoa repens (saw palmetto), Sophora flavescens, Pygeum africanum, Panicum miliaceum, Cimicifuga racemosa, Glycine max, Eugenia caryophyllata, Cotinus coggygria, Hibiscus rosa-sinensis, Camellia sinensis, Ilex paraguariensis, Isochrysis galbana, licorice, grape or apple.
[0159] Hair growth inhibitors are preferably selected from the group consisting of activin, activin derivatives or activin agonists, ornithine decarboxylase inhibitors such as alphadifluoromethylornithine or pentacyclic triterpenes like for example ursolic acid, betulin, betulinic acid, oleanolic acid and derivatives thereof, 5-alpha-reductase inhibitors, androgen receptor antagonists, S-adenosylmethionine decarboxylase inhibitors, gamma-glutamyl transpeptidaseinhibitors, transglutaminase inhibitors, soybean-derived serine protease inhibitors, extracts from microorganisms, algae, different microalgae or plants and plant parts of for example the families Leguminosae, Solanaceae, Graminae, Asclepiadaceae or Cucurbitaceae, the genera Chondrus, Gloiopeltis, Ceramium, Durvillea, Glycine max, Sanguisorba officinalis, Calendula officinalis, Hamamelis virginiana, Arnica montana, Salix alba, Hypericum perforatum or Gymnema sylvestre.
[0160] In another preferred variant, the cosmetic composition additionally comprises at least one additive selected from the group consisting of skin care agents.
[0161] Preferred examples for skin moisture retention regulators an skin repair agents are selected from the group consisting of sodium lactate, urea and derivatives, glycerol, propylene glycol, 1 ,2-pentanediol, 1 ,2-hexanediol and 1 ,2-octanediol, collagen, elastin or hyaluronic acid, diacyl adipates, petrolatum, urocanic acid, lecithin, allantoin, panthenol, phytantriol, lycopene, (pseudo-)ceramides (preferably Ceramide 2, hydroxypropyl bispalmitamide ME A, cetyloxypropyl glyceryl methoxypropyl myristamide, N-(1-hexadecanoyl)-4-hydroxy-L-proline (1-hexadecyl) ester, hydroxyethyl palmityl oxyhydroxypropyl palmitamide), glycosphingolipids, cholesterol, phytosterols, chitosan, chondroitin sulfate, lanolin, lanolin esters, amino acids, vitamin E and derivatives (preferably tocopherol, tocopheryl acetate), alpha-hydroxy acids (preferably citric acid, lactic acid, malic acid) and derivatives thereof, mono-, di- and oligosaccharides, preferably glucose, galactose, fructose, mannose, laevulose and lactose, polysugars, such as b-glucans, in particular 1 ,3-1 ,4-p-glucan from oats, alpha-hydroxy-fatty acids, triterpenic acids, such as betulic acid or ursolic acid, and algae extracts or single active compounds thereof, physiological cooling agents, preferably selected from the group consisting of menthone glycerol acetal, menthyl lactate preferably l-menthyl lactate, in particular l-menthyl l-lactate), menthyl ethyl oxamate, substituted menthyl-3-carboxylic acid amides (e.g. menthyl-3-carboxylic acid N-ethylamide, Na-(L-menthanecarbonyl)glycine ethyl ester, 2-isopropyl-N-2,3-trimethyl-butanamide, substituted cyclohexanecarboxylic acid amides, 3-menthoxypropane-1 ,2-diol, 2-hydroxyethyl menthyl carbonate, 2-hydroxypropyl menthyl carbonate, N-acetylglycine menthyl ester, isopulegol, menthyl hydroxycarboxylic acid esters (e.g. menthyl 3-hydroxybutyrate), monomenthyl succinate, monomenthyl glutarate, 2- mercaptocyclodecanone, menthyl 2-pyrrolidin-5-onecarboxylate, 2,3-dihydroxy-p-menthane, 3,3,5-trimethylcyclohexanone glycerol ketal, 3-menthyl 3,6-di- and -trioxaalkanoates, 3- menthyl methoxyacetate and icilin.
[0162] In another preferred aspect, the cosmetic composition additionally comprises at least one additive selected from the group consisting of anti-dandruff agents.
[0163] Preferably, the at least one antidandruff agent is selected from the group consisting of Pirocton Olamin (1-hydroxy-4-methyl-6-(2,4,4-trimethyhpentyl)-2-(1 H)-pyridinone monoethanolamine salt), Baypival® (Climbazole), Ketoconazol® (4-acetyl-1-{4-[2-(2,4- dichlorophenyl) r-2-(1 H-imidazol-1-ylmethyl)-1 ,3-dioxylan-c-4-ylmethoxyphenyl}-piperazine, ketoconazole, elubiol, selenium disulfide, colloidal sulfur, sulfur polyethylene glycol sorbitan monooleate, sulfur ricinol polyethoxylated, sulfur tar distillate, salicylic acid (or in combination with hexachlorophene), undecylenic acid, monoethano-lamide sulfosuccinate Na salt, Lamepon® UD (protein / undecylenic acid condensate), zinc pyrithione, aluminium pyrithione and magnesium pyrithione / dipyrithione magnesium sulfate.
[0164] Preferred compositions according to the present inventions are selected from the group of products for treatment, protecting, care and cleansing of the skin and / or hair or as a make-up product, preferably as a leave-on product (meaning that the one or more compounds of formula (I) stay on the skin and / or hair for a longer period of time, compared to rinse-off products, so that the moisturizing and / or anti-ageing and / or wound healing promoting action thereof is more pronounced).
[0165] The formulations according to the invention are preferably in the form of an emulsion, e.g. W / O (water-in-oil), O / W (oil-in-water), W / O / W (water-in-oil-in-water), O / W / O (oil-in-water- in-oil) emulsion, PIT emulsion, Pickering emulsion, emulsion with a low oil content, micro- or nanoemulsion, a solution, e.g. in oil (fatty oils or fatty acid esters, in particular C6-C32 fatty acid C2-C30 esters) or silicone oil, dispersion, suspension, creme, lotion or milk, depending on the production method and ingredients, a gel (including hydrogel, hydrodispersion gel, oleogel), spray (e.g. pump spray or spray with propellant) or a foam or an impregnating solution for cosmetic wipes, a detergent, e.g. soap, synthetic detergent, liquid washing, shower and bath preparation, bath product (capsule, oil, tablet, salt, bath salt, soap, etc.), effervescent preparation, a skin care product such as e.g. an emulsion (as described above), ointment, paste, gel (as described above), oil, balsam, serum, powder (e.g. face powder, body powder), a mask, a pencil, stick, roll-on, pump, aerosol (foaming, non-foaming or post-foaming), a deodorant and / or antiperspirant, mouthwash and mouth rinse, a foot care product (including keratolytic, deodorant), an insect repellent, a sunscreen, after-sun preparation, a shaving product, aftershave balm, pre- and aftershave lotion, a depilatory agent, a hair care product such as e.g. shampoo (including 2-in-1 shampoo, anti-dandruff shampoo, baby shampoo, shampoo for dry scalps, concentrated shampoo), conditioner, hair tonic, hair water, hair rinse, styling creme, pomade, perm and setting lotion, hair spray, styling aid (e.g. gel or wax), hair smoothing agent (detangling agent, relaxer), hair dye such as e.g. temporary direct-dyeing hairdye, semi-permanent hair dye, permanent hair dye, hair conditioner, hair mousse, eye care product, make-up, make-up remover or baby product.
[0166] The formulations according to the invention are particularly preferably in the form of an emulsion, in particular in the form of a W / O, O / W, W / O / W, O / W / O emulsion, PIT emulsion, Pickering emulsion, emulsion with a low oil content, micro- or nanoemulsion, a gel (including hydrogel, hydrodispersion gel, oleogel), a solution e.g. in oil (fatty oils or fatty acid esters, in particular C6-C32 fatty acid C2-C30 esters)) or silicone oil, or a spray (e.g. pump spray or spray with propellant).
[0167] Auxiliary substances and additives can be included in quantities of 5 to 99 wt.-%, preferably 10 to 80 wt.-%, based on the total weight of the formulation. The amounts of cosmetic or dermatological auxiliary agents and additives and perfume to be used in each case can easily be determined by the person skilled in the art by simple trial and error, depending on the nature of the particular product.
[0168] Additionally, the present invention relates to the use of the (stabilized) extract or extract solution or cosmetic composition according to the invention in scalp and hair care products and / or in skin care products, preferably in shampoos and / or conditioners.
[0169] Moreover, the present invention relates to the use of the (stabilized) extract or extract solution or cosmetic composition according to the invention in cosmetic compositions is directed to hair restoration, preferably wherein the cosmetic composition is directed to the improvement of the tensile strength of hair, the treatment of hair fatigue and / or the avoidance of hair swelling.Brief description of drawings
[0170] Fig. 1 shows the profile of Zein protein types in commercial Zein material (left bars) as well as in extracts using 70 % aqueous ethanol (according to the invention, middle bars) and 90 % aqueous ethanol (comparative experiment, right bars) as determined by LC-MS.
[0171] Fig. 2 provides a visual evaluation of the solubility of 1 wt.-% of the extract in different cosmetic solvents after 24 hours (protein extract solution).
[0172] Fig. 3 provides a visual evaluation of the solubility of 5 wt.-% of the extract in mixtures of propylene glycol and pentylene glycol (hydrolite-5) after 24 hours.
[0173] Fig. 4 shows the profile of Zein protein types as determined by LC-MS in extracts obtained by using different aqueous ethanol extraction solvents.
[0174] Fig. 5 shows the profile of Zein protein types as determined by LC-MS in extracts obtained by using different extraction temperatures.
[0175] Fig. 6 shows the emulsion as described in Tab. 6 without containing the cosmetic composition (protein extract solution) containing the Zein extract (placebo, left picture) and with the aforementioned cosmetic composition (right picture).
[0176] Fig. 7 shows images of a shampoo formulation prepared according to different methods.
[0177] Fig. 8 shows elastic modulus and break stress parameters of hair tresses treated with formulations comprising a Zein protein extract in comparison to placebo formulations. The parameters are extracted from a tensile test.
[0178] Fig. 9 shows the diameter variation during a swelling test of hair treated with formulations comprising a Zein protein extract in comparison to placebo formulations.
[0179] Fig. 10 shows the results of a fatigue test at 5 % strain, where the characteristic life (a) results are shown for hair treated with formulations comprising a Zein protein extract in comparison to placebo formulations.
[0180] Fig. 11 shows the visual evaluation of the effectiveness of CaCl2 and L-arginine additives in increasing the stability against jellification.
[0181] Fig. 12 shows the LC-MS protein profile for commercial Zein and the Zein extract according to Example 1.
[0182] Fig. 13 shows the stability of a solution of commercial Zein in diols at 50 °C.
[0183] Fig. 14 shows the electrophoresis analysis (SDS-PAGE) protein profile for the Zein extract according to Example 1.Experimental part
[0184] Example 1 : Zea mays Kernel extraction process
[0185] The maize kernel raw material used is a by-product of maize starch production, also called Corn Gluten Meal. Beside the name gluten, maize is a gluten-free cereal with a prolamintype protein called Zein, which consists of alpha-, beta-, gamma- and delta- sub-types.
[0186] Extraction: In a 1 L two-neck round bottom flask, 73.35 g of Corn Kernel raw material were extracted with 1100 g of extraction solvent (w / w-ratio of plant material : solvent of 1 :15). As the extraction solvent, 70 % aqueous ethanol was used (w / w-ratio of ethanol : water of 7:3), i.e. the plant material was extracted using as a solvent the mixture of ethanol and distilled water, in a solution of ethanol 70 % (w / w). The extraction was carried out for a period of 3 hours at a temperature of 70 °C under gentle stirring (100 to 150 rpm). The suspension was then cooled to ambient temperature and insoluble components were removed by filtration, i.e. the extract solution was vacuum-filtered to remove the solid residue. The extract solution drying process was initiated first by distillation of ethanol on rotavapor. After distillation, the extract solution with residual distilled water was frozen in a freezer at -20 °C and subsequently freeze- dried. The dry matter of the extract solution was measured with an IR Dryer machine (Sartorius), resulting in 3.2 ± 0.4 % of dry matter (pH ~5.2, BRIX 22.9 %), and the average yield of dry extract based on the plant material was 59.5 ± 4.5 %.
[0187] The extraction surprisingly gives a unique protein profile as determined by LC-MS. Due to the above process, the composition of the dry natural Zein protein extract (dried by lyophilization after ethanol removal by use of evaporator) can be differentiated from other processes according to the state of the art. Comparing the protein profile of the dry natural Zein protein extract from the process disclosed herein with commercially available Zein (Sigma-Aldrich) and the dried extract produced in a comparative experiment using a different extraction solvent (90 % aqueous ethanol) but the same process parameters, a clear difference is observed, as can be seen in Fig. 1 and in Tab. 2 below. In particular, the extraction process disclosed herein results in extracts, which contain significantly more beta- and gamma-Zein, and thus a higher protein content having cysteine functions. Accordingly, the Zein extracts differ in their molecular composition.
[0188] Table 2: Profiles of natural Zein protein extracts and commercial Zein.
[0189] Example 2: Composition characterization of the natural Zein protein extract
[0190] Based on Example 1 , the extraction was repeated using four other batches of maize kernel raw material giving comparable results. For analytical characterization, the obtained extract solutions were dried under vacuum using an evaporator to remove the ethanol followed by lyophilization to give a dry extract and different analyses were performed. The results are summarized in Tab. 3 below.
[0191] Table 3: Results from chemical characterization of dried natural Zein protein extracts (according to Example 1).
[0192] The results in Tab. 3 represent the composition variation, which is normally found in natural ingredients.
[0193] Linoleic acid is a polyunsaturated fatty acid. It is contained in vegetables like corn, sunflower, safflower, soybean, and canola. Sometimes referred to as Vitamin F, linoleic acid is an effective ingredient in skin care, strengthening the skin’s protective barrier while providing excellent moisturizing and healing properties. It was surprisingly found that the presence of linoleic acid in the formulations according to the present invention provides additional benefits to the skin, i.e. body and scalp skin. Such additives provide for further benefits to the pure protein.
[0194] Example 3: Solubility assessment for natural Zein protein extract
[0195] The solubility of natural Zein protein extract in cosmetic solvents (further solvent as specified herein) was also evaluated. For these tests, different cosmetic solvents were used, first in pure form and afterwards in mixtures, where the cosmetic solvents were used in different proportions. Solubility tests were conducted with water, glycerol, propylene glycol, 1 ,2- hexanediol (e.g. Hydrolite® 6, Symrise), butylene glycol, pentylene glycol (e.g. Hydrolite® 5, Symrise), 1 ,2-octanediol (e.g. Hydrolite® 8, Symrise) and 1 ,2-heptanediol (e.g. Hydrolite® ?, Symrise). The aforementioned products are also available from different sources and suppliers.
[0196] Some examples of test solutions are depicted in Fig. 2. Each sample contains 1 wt- % of the dried natural Zein protein extract (according to Example 1) in the corresponding cosmetic solvent or solvent mixture. As can be seen, most of the samples were at least slightly turbid after 24 hours.
[0197] The solubility of natural Zein protein extract was better in pentylene glycol and propylene glycol (cosmetic solvents as specified herein), with a clear solution even after 24 hours. The solubility was also investigated in mixtures with different proportions of both solvents, pentylene glycol and propylene glycol (Fig. 3). The maize extract was soluble in mixtures with higher content of pentylene glycol, and visually turbid in mixtures with more content of propylene glycol.
[0198] Based on the results of the solubility test, the most preferred ratio of pentylene glycol and propylene glycol in the mixture is 8:2 (w / w).
[0199] Example 4: Process for production of a cosmetic composition (incorporation of cosmetic solvents and distillation process, meaning “the product”, i.e. the protein extract solution)
[0200] For the production of the cosmetic composition (or the protein extract solution), it is not necessary to carry out the drying step (to obtain a dry extract). Instead, cosmetic solvents are directly added to the extract solution after the first filtration step or the partly removal of the extraction solvents. Subsequently, the residual extraction solvent, i.e. ethanol and water, is removed by distillation.
[0201] Generally, after the extraction process, the extract solution is left for 1 hour (without agitation) to allow decanting of the solid residue and cooling to room temperature. The supernatant is filtered through a paper filter to remove the solid residue. The residual plant material was discharged. To the extract a mixture of diols in a specific ratio was added at room temperature and the resultant protein extract solution was distilled on a rotavapor to remove residual ethanol and water, and a final filtration was done (corresponding to step f) of the process of the process according to the present invention).
[0202] More specifically, to the volume of extract solution obtained as described in Example 1 , a mixture of the cosmetic solvents pentylene glycol and propylene glycol is added in a specific ratio. The protein content in the dry extract is around 64.9 ± 5.2 % determined by using the DUMAS method. In order to have around 5.5 % protein content in the cosmetic composition as analyzed by the DUMAS method, the dry matter on the cosmetic composition needs to be around 8.05 ± 0.5 %. The extraction solvent (70 % aqueous ethanol, w / w) was removed by distillation at a maximum temperature of 70 °C under reduced pressure of from 300 to 80 mbar, resulting in a recovery range of 98 to 100 % of ethanol and 80 to 90 % of water. After the distillation process, a final filtration is carried out using a tissue filter and the cosmetic composition or protein extract solution is obtained. Examples of the process for the preparation of protein extract solutions for cosmetic compositions with higher protein content (9 to 11 %) and lower protein content (5 to 8 %) are given below. The latter (5 to 8 % protein content) was used in the subsequent examples and experiments.
[0203] Process example for protein extract solution with 9 to 11 wt.-% protein content:
[0204] Firstly, 40 g of maize kernel raw material were extracted using 600 g of a 70 % ethanolic solution during 3 hours at 70 °C. The extract solution was left undisturbed for 1 hour to allow decanting of the solids, followed by cooling of the extract solution to room temperature.The supernatant (extract solution) was filtered through a paper filter to remove the solid residue, which was discarded. The extraction process had a yield of 530 g of aqueous- ethanolic extract solution, where an amount of 113 g pentylene glycol and 28 g of propylene glycol were added (cosmetic solvents), to give a total of 141 g of a cosmetic solvent mixture (protein extract solution). After adding the mixture of the cosmetic solvents, the extraction solvent was removed by distillation process under reduced pressure and high temperature, and a final filtration step was carried out through a tissue filter used for viscous products to remove the remaining small solids. At the end of the process 152 g of a cosmetic composition (protein extract solution) comprising natural Zein protein extract were obtained, containing a content of 9.8 % protein as measured by DUMAS method. The obtained cosmetic composition is a viscous liquid with dark yellow-orange color.
[0205] Process example for cosmetic composition with 5 to 8 wt.-% protein content:
[0206] Firstly, 40 g of maize kernel raw material were extracted using 600 g of a 70 % ethanolic solution during 3 hours at 70 °C. The extract solution was left undisturbed for 1 hour to allow decanting of the solids, followed by cooling of the extract solution to room temperature. The supernatant (extract solution) was filtered through a paper filter to remove the solid residue, which is discarded. The extraction process had a yield of 530 g of aqueous-ethanolic extraction solvent, where an amount of 155.2 g pentylene glycol and 38.8 g of propylene glycol were added (cosmetic solvents), to give a total of 194 g of a cosmetic solvent mixture (protein extract solution). After adding the mixture of the cosmetic solvents, the extraction solvent was removed by distillation process under reduced pressure and high temperature, and a final filtration step was carried out through a tissue filter used for viscous products to remove the remaining small solids. At the end of the process around 199 g of a cosmetic composition (protein extract solution) comprising natural Zein protein extract were obtained, containing a content of 5.8 % protein as measured by DUMAS method. The obtained cosmetic composition is a viscous liquid with light yellow-orange color.
[0207] Example 5: Extraction parameters variation and protein profiles
[0208] The usual extraction process uses 70 % aqueous ethanol (w / w) as extraction solvent, wherein the extraction is carried out over 3 hours at a temperature of 70 °C. In the standard process, the ratio of plant material and solvent is 1 :15, based on weight.
[0209] Some variations on the extraction process parameters were done to verify the protein profile related to each variation to justify the specificity of the developed extraction process andthe corresponding protein profiles. Based on the extraction process described above a variation of the extraction parameters was performed and the protein profiles of the natural Zein protein extracts were analyzed by LC-MS.
[0210] As a first variant, the extraction solvent was changed, while keeping the other extraction parameters (3 hours, 70 °C) constant. The extraction was performed using different aqueous ethanol mixtures, having 60 % (CP_60), 70 % (CP_70) and 80 % (CP_80) ethanol content, respectively. The results are summarized in Fig. 4 and in Tab. 4 below. In particular, it is shown that the amount of isolated beta- and gamma-Zeins decreases with increasing ethanol content. At the same time, the overall amount of isolated Zein proteins also decreases.
[0211] Table 4: Profiles of natural Zein protein extracts obtained with different extraction solvents.
[0212] As a second variant the parameter of extraction temperature was changed, while keeping the other extraction parameters (3 hours, 70 % aqueous ethanol) constant. The extraction was performed at room temperature, 60 °C, 70 °C and 80 °C and the results are summarized in Fig. 5 and in Tab. 5 below. As can be seen, the extraction temperature has a less significant impact on the protein profile, however, there are still differences. While all extraction temperatures result in comparable protein overall yields of close to 90 %, the extraction performed at 70 °C results in the highest amount of both beta- and gamma-Zein, and the extraction at room temperature did not extract the desired proteins.
[0213] Table 5: Profiles of natural Zein protein extracts obtained at different extraction temperatures.
[0214] Example 6: Formulation of a cosmetic composition (Example 4) on O / W emulsion basis, and stability evaluation
[0215] The protein extract solution according to Example 4 (5 to 8 % protein content) was used to evaluate and compare the formulation properties. The ingredients of a sample formulation are summarized in Tab. 6 below. To allow bioavailability, the cosmetic composition needs to be homogeneously dissolved in the final product formulation.
[0216] Table 6: Ingredients of sample formulation (O / W emulsion).
[0217] The formulation was produced according to the following protocol. Phases A and C were separately heated up to 80 °C. Then, Phase B was dispersed in A, and C was added to AB and emulsified using an UltraTurrax Stirrer (5 min, 6000 rpm). Afterwards, Phase D was added, and the formulation was neutralized and allowed to cool by using a vane stirrer (15 min at 150 rpm and then 20 min at 100 rpm). Hydrolite-5 Green, propylene glycol and lauric-acid- propanediol-ester were then added to the finished emulsion and stirred (10 min, 100 rpm).
[0218] The formulation properties of the extract solution according to Example 4 were evaluated in the O / W emulsion as described in Tab. 6. The protein extract solution of Example 4 comprising the natural Zein protein extract was used at 1 wt.-% and showed very good solubility at this concentration (see Fig. 6). No precipitations were observed, and the ingredient was homogeneously distributed within the emulsion.
[0219] The cosmetic composition comprising the natural Zein protein extract was visually noticed to have a higher viscosity than the placebo, showing an additional thickening effect of the extract in emulsion.
[0220] With respect to the O / W emulsion without the protein extract solution of Example 4 comprising the natural Zein protein extract (placebo, Fig. 6 left), no color change was recognized for the emulsion containing the protein extract solution of Example 4 comprising the natural protein Zein extract (Fig. 6 right). Emulsions were stored for 6 months at either 5 °C, 40 °C or room temperature and exposed to light but did not show any changes in color or odor over time. Therefore, these results show that the protein extract solution comprising natural Zein protein extract is easy to formulate and dissolves in typical cosmetic formulations, such as emulsions. The protein extract can stably be incorporated into the final cosmetic formulation and provides for improved long-term shelf-storage properties.
[0221] Example 7: Optimization of formulation of protein extract solution (Example 4) in shampoo
[0222] The protein extract solution according to Example 4 (5 to 8 % protein content) was used to evaluate and compare formulation properties. Upon adding the protein extract solution I the cosmetic formulation to the finished shampoo formulation of Tab. 7, precipitation occurred.
[0223] Table 7: Formulation of a standard shampoo.
[0224] The formulation of a standard shampoo as set out in Tab. 7 was produced by four different methods as further specified below.
[0225] Standard production method (Std.): Ucare™ Polymer JR-400 was stirred in water at 50 °C until it was clearly dissolved. Then, Plantacare PS10 and citric acid were slowlyblended, and SymDiol® 68 followed by sodium gluconate and sodium chloride were sequentially added. Phase B was then added stepwise while stirring with a vane stirrer at a stirring speed of 50 rpm. Then, Phases C, D and E were added by stirring.
[0226] Production Method I: Phase F (cosmetic composition comprising Zein extract) was pre-blended in neutralized Plantacare®. Then the additional components of Phase A were added into Phase B, which was then stirred in water at 50 °C until it was clearly dissolved. Afterwards, Phase B was added stepwise while stirring with a vane stirrer at a stirring speed of 50 rpm. Then, Phases C, D and E were added by stirring.
[0227] Production method II: llcare™ Polymer JR-400 was stirred in water at 50 °C until it was clearly dissolved. Then, Plantacare PS10 and citric acid were slowly blended, and SymDiol® 68 followed by sodium gluconate and sodium chloride were sequentially added. Phase B was then added stepwise while stirring with a vane stirrer at a stirring speed of 50 rpm. Then, Phases C and E were added by stirring. Phase F was pre-blended in D and then added to the shampoo base.
[0228] Production method III: llcare™ Polymer JR-400 was stirred in water at 50 °C until it was clearly dissolved. Then, Plantacare PS10 and citric acid were slowly blended, and SymDiol® 68 followed by sodium gluconate and sodium chloride were sequentially added. Phase B was then added stepwise while stirring with a vane stirrer at a stirring speed of 50 rpm. Then, Phases C and E were added by stirring. Phase F was added under the same stirring conditions and finally Phase D was added.
[0229] For the production methods, several general observations have been made. When the extract solution comprising the natural Zein protein extract (Phase F) was added to the finished formulation, precipitation occurred (see Fig. 7). Similarly, precipitation was observed when the shampoo was prepared according to method II. However, no precipitation occurred when the shampoo was produced according to production methods I or III (Fig. 7). Moreover, when using procedures I or III, no crystals have been observed when the shampoo formulation was analyzed by microscopy.
[0230] Example 8: Formulation of protein extract solution (Example 4) in shampoo (adapted formulation method according to Example 7)
[0231] The protein extract solution according to Example 4 (5 to 8 % protein content) was used to evaluate and compare formulation properties. To allow bioavailability, the proteinextract solution I the cosmetic composition comprising the natural Zein protein extract must be homogeneously dissolved in the formulation. The composition of the formulation is shown inTab. 8.
[0232] Table 8: Formulation of a standard shampoo, prepared according to adapted method.
[0233] The formulation of a sample standard shampoo as shown in Tab. 8 was prepared according to an adapted production method described below.
[0234] Production Method: llcare™ Polymer JR-400 was stirred in water at 50 °C until it was clearly dissolved. Then, Plantacare PS10 and citric acid were slowly blended, and SymDiol® 68 followed by sodium gluconate and sodium chloride were sequentially added. Phase B was then added stepwise while stirring with a vane stirrer at a stirring speed of 50 rpm. Then, Phases C and E were added by stirring. Phase F was added under the same stirring conditions and finally Phase D was added.
[0235] The formulation properties of the cosmetic composition / the protein extract solution comprising the natural Zein protein extract according to Example 4 were evaluated in theshampoo formulation described in Tab. 8. The cosmetic composition I the protein extract solution comprising the natural Zein extract was used at 1 wt.-% and showed very good solubility at this concentration. No precipitations were observed and the cosmetic composition I the protein extract solution comprising the natural Zein extract was homogeneously distributed in the shampoo formulation.
[0236] After one month of storage at room temperature (RT) and 40 °C, no change in viscosity was observed. Slight discoloration at light and heat conditions was observed with no odor change during storage indicating a stable incorporation into the product formulation.
[0237] Example 9: Hair tresses, bleaching procedure and treatment
[0238] Six Caucasian hair tresses per group (1 g, 25 cm long - International Hair Importers & Products, USA) were previously cleaned using 10 % (w / w) sodium lauryl ether sulphate solution (SLES) and bleached for 30 minutes at 45 °C using a mixture of 1 part of commercially available bleaching powder (Yama, BRL) and 2 parts of hydrogen peroxide emulsion (12 % (w / w), Yama, BRL) in proportion of 5 g of the mixture to 1 g of hair. After bleaching, the tresses were washed three times with 10 % SLES solution and left for drying overnight under controlled conditions (22 ± 2 °C; 50 ± 5 % RH).
[0239] The concentration of the protein extract solution comprising the natural Zein protein extract (according to Example 4, 5 to 8 % protein content) applied in the hair care formulations (shampoo and conditioner) was 1 wt.-%.
[0240] Three bleached Caucasian hair tresses were subject to an application of shampoo and conditioner formulations containing 1.0 wt.-% of the cosmetic composition / the protein extract solution comprising the natural Zein protein extract, corresponding to 0.01 g protein extract solution per 1 g of hair. Afterwards, the tresses were left for drying overnight under controlled conditions (22 ± 2 °C; 50 ± 5 % RH). Tresses subjected to the same application protocol but using formulations without the composition according to the invention (placebo) were used as references.
[0241] Example 10: Tensile assessment of protein extract solution (Example 4) in hair care formulations
[0242] The tensile test measures mechanical properties of the hair fiber during a constant speed forced extension, providing information about the physical-chemical conditions of the hair cortex.
[0243] The evaluated parameters are the Elastic Modulus and thus the stiffness of a material, where a high elastic module corresponds with a high stiffness, and the Break Stress, which is a measure of the necessary mechanical tension that is required to lead the hair fiber to breakage.
[0244] Initially, the hair tresses were treated according to Example 9 and then the tensile test was performed as follows: 45 fibers from each treatment were collected randomly and fixed in 16 metallic crimps one by one. Then, the fibers were soaked in water for 1 hour and diameter measurements were executed using an instrument ALS1500 / FDAS770 (Dia-Stron, UK) and a Laser Scan Micrometer (Mitutoyo). Moreover, the tresses soaked in water for 1 h were subject to a tensile test which was performed using the Miniature Tensile Tester instrument MTT680 (Dia-Stron, UK) using a constant stretching rate of 15 mm / min. The elastic modulus and the break stress for each fiber were calculated using the UVWin software (Dia- Stron, UK). Comparisons among the treatments were performed using Student’s T-test at a 95 % confidence interval.
[0245] The results of the elastic modulus and break stress tests are depicted in Fig. 8. Performing the tensile test at 100 % relative humidity, it was possible to observe an increase of the bleached hair elastic modulus and break stress (p < 0.05) for the group treated with shampoo and hair conditioner formulations containing 1.0 wt-% of the cosmetic composition according to Example 4 (protein extract solution containing 5 to 8 % protein content) comprising the natural Zein protein extract, when compared to the group treated with placebo formulations (not containing the formulation according to Example 4). When using the cosmetic composition comprising the natural Zein protein extract, a 7 % improvement was observed for both parameters, the elastic modulus and the break stress. Consequently, the composition according to the present invention increases the bleached hair's elastic modulus and break stress (p < 0.05), at 100 % relative humidity, which were spoiled after the chemical damage, thus improving the mechanical properties of these fibers, compared to those treated with formulations without this ingredient.
[0246] Example 11 : Swelling assessment of protein extract solution (Example 4) in hair care formulations
[0247] Through diameter measurements, it is possible to determine the level of swelling of a fiber of hair over time when in contact with water. According to the fiber condition or the film covering its surface, the level of swelling may change. The more damaged the hair, the more hydrophilic it is, since most of the hair damages remove the lipids, ceramides and other hydrophobic substances from the hair, and, consequently, more swelling is noticed.
[0248] The evaluated parameters are the variation in hair diameter (%), in particular the percentage of change in fiber diameter and the swelling rate (pm / s) and thus the speed of the change in fiber diameter.
[0249] Initially, the hair tresses were treated according to Example 9 and then the swelling test was performed as follows: 45 fibers from each treatment were subjected to diameter measurement while soaked in water for 180 seconds using a Fiber Dimensional Analysis System FDAS770 with a Dynamic Swelling Module (DSM 770, Dia-Stron, UK). The diameter variation of the fibers was calculated using the UVWin software (Dia-Stron, UK). Comparisons among treatments were performed using Student’s T-test at a 95 % confidence interval.
[0250] The results of the swelling test are depicted in Fig. 9 and demonstrate that when added at 1.0 wt.-% in shampoo and hair conditioner formulations, the cosmetic composition (Example 4, protein extract solution having a 5 to 8 % protein content) comprising the natural Zein protein extract was able to reduce the variation of the diameter of the hair fibers induced by the water intake. Compared to the placebo group, fibers treated with formulations comprising the Zein extract presented a 6 % smaller diameter variation after 180 seconds soaked in water (p < 0.05). Consequently, the composition according to the present invention significantly reduces the damaged hair’s water intake, restoring part of its natural hydrophobicity, probably by depositing on the hair fibers’ surface, which contributes to the general health of the hair.
[0251] Example 12: Fatigue assessment of protein extract solution (Example 4) in hair care formulations
[0252] Fatigue is the weakening of a hair fiber caused by repeatedly applied loads. A crack will reach critical size, then will propagate, and the structure will finally fracture. Fatigue testing represents a more realistic simulation of real-life hair grooming since the hair is subjected to a level of stress similar to the one of daily manipulations.
[0253] The evaluated parameters are the survival probability, in particular the probability of a fiber to survive a certain number of cycles, and the characteristic life (a), which indicates the number of cycles at which 63.2 % of the fibers have broken, where a high value corresponds to a high survival probability and consequently a high resistance of the fiber.
[0254] Initially, the hair tresses were treated according to Example 9 and then the fatigue tests were performed as follows: 50 fibers from each group were collected randomly and fixed in metallic crimps one by one. Then, diameter measurements were executed followed by a fatigue test using an instrument ALS1500 / CYC801 (Dia-Stron, UK) and applying a constant stress of 5 % to all fibers. Comparison among treatments was performed using the characteristic life (a) parameter from Weibull distribution analysis obtained using UVWin software (Dia-Stron, UK) and Kaplan-Meier survival analysis followed by log-rank test.
[0255] The results of the fatigue test are shown in Fig. 10. The group treated with hair formulations (shampoo and conditioner) containing 1.0 wt.-% of the cosmetic composition according to Example 4 (protein extract solution having a 5 to 8 % protein content) comprising the natural Zein protein extract presented higher survival probabilities over the stretch cycles (survival probability curve). The characteristic life parameter a was 42 % higher for this group (a = 3827) than for the group using placebo hair formulations (a = 2705). Accordingly, the group treated with the composition according to Example 4 presented higher survival probabilities over the stretch cycles.
[0256] The fatigue results are intimately associated with the way how the existing fractures propagate, culminating in hair breakage. With a higher alpha value, the group treated with the composition according to the present invention presented a better performance in mitigating these fractures and avoiding the formation of new ones, resulting in a bigger number of cycles necessary to have 63.2% of the fibers broken (characteristic life parameter) in comparison to the placebo-treated group.
[0257] Example 13: Gelation of cosmetic composition / protein extract solution comprising natural Zein protein extract and increasing stability properties with additives
[0258] The stability of the neat cosmetic composition comprising the natural Zein protein extract according to Example 4 (protein extract solution having a 5 to 8 % protein content) was evaluated. After 1 month at 50 °C, complete gelation was observed, and after 3 months at 40 °C, an increase in viscosity was observed. For the improvement of stability of the neat cosmetic composition and thus to delay or even avoid gelation, tests were carried out with differentadditives. Among the main additives tested were used amino acid L-arginine, inorganic salts (NaCI, KCI, MgCh and CaCh) and sucrose. Many experiments have been carried out with the addition of additives in the cosmetic composition and also later in the formulation process.
[0259] The results of the tests revealed that CaCl2 at 0.5 wt.-% and L-arginine at 0.9 wt.-% were the best additives for improvement of stability delaying gelation when incorporated during the production process. The visual evaluation of the effectiveness of these two additives during storage for 1 month at 50 °C is shown in Fig. 11. In addition to CaCh and L-arginine, sodium chloride was also effective in delaying gelation.
[0260] Example 14: ABTS assay
[0261] The radical scavenging properties of the natural Zein protein extract described in Example 1 (test substance) were measured with the aid of the ABTS assay. 2,2’-Azino-bis(3- ethylbenzothiazoline-6-sulphonic acid) (ABTS) was transformed by potassium persulphate into the blue-green radical cation ABTS’*. The radical cations were reduced by antioxidants (test substances), and discoloration took place which was determined photometrically at 734 nm based on the following formula:Inhibition [%] = 100wherein A test substance means absorption of the wells with the test substance and A control means absorption of the wells without the test substance.
[0262] The IC50 was calculated from the inhibition of radical formation [%] in a series of dilutions of the tested sample. The IC50 value is the concentration at which radical formation is inhibited by 50 %. The results are summarized in Tab. 9 below.
[0263] Table 9: Results of radical-scavenging activity.
[0264] The results in Tab. 9 show that at the tested concentrations the natural Zein protein extract according to Example 1 showed activity, in particular direct radical-scavenging activity. The IC50 value of the extract was 0.0045 %, which is considered a strong antioxidant potential and is similarly found for commercial Zein (Sigma-Aldrich, IC50 = 0.0044 %).
[0265] A particular attention in the comparison of the results shown in Tab. 9 for the natural Zein protein extract according to Example 1 and the commercial Zein protein should be drawn to the fact, that the natural Zein protein extract is not a pure protein mixture but also contains other components in minor amounts while at the same time showing a similar antioxidant potential as pure commercial Zein, which only consists of proteins.
[0266] Example 15: UV-induced ex vivo oxidation of natural Zein protein extract
[0267] Since the natural Zein protein extract according to Example 1 was shown to exhibit antioxidant activity, its ability to reduce UVA radiation-induced stress was also evaluated. As positive control, alpha-tocopherol (vitamin E) was used.
[0268] Organ culture of human skin (phototype: light, ITA°: 43°) was performed starting from a skin sample, exciding pieces of approximately 8x3 mm (diameter x thickness). Skin samples (6 per treatment) were cultured in an air-liquid interface in a perforated ring of stainless steel in contact with culture medium (modified Williams’ E medium). The natural Zein protein extract was characterized as given in Example 1.
[0269] At start of the skin culture, in parallel to untreated, vehicle DMSO, 0.5 and 5 ppm natural Zein protein extract dissolved in DMSO and 100 % alpha-tocopherol were applied topically on the skin samples and afterwards they were cultivated overnight. On the next day, the topical treatments were renewed for 1 hour. In parallel, culture medium with 100 pM of 2’,7’-dichlorofluorescin diacetate (DCFH-DA, Sigma #D6883) was prepared. After 1 hour of incubation, of the skin samples, the culture medium was replaced by the medium containing DCFH-DA and the skin samples were incubated for 30 minutes. Then, the skin samples were washed in PBS buffer and UVA irradiation (lamp: Bio Sun by Vilber Lourmat, 60 J / cm2= 8 BED UVA) was performed.
[0270] Afterwards, the skin samples were harvested, cryo-fixed and cut at the cryostat for image acquisition and analysis. The image acquisition was performed using an Olympus BX51 microscope and an Olympus DP70 camera. Two skin sections for each skin sample were cut and the related images were acquired and analyzed. Doing so, 12 images were obtained foreach formulation for analysis. Image analysis was performed within the dermis area selected from the upper part by following the perimeter of the basal lamina to the deep dermis. The obtained values were normalized upon the dimension of the selected area. The results are summarized in Tab. 10.
[0271] Table 10: Comparison of mean fluorescence score in UV-induced ex vivo oxidation of natural Zein protein extract.
[0272] As expected, the comparison of UVA- irradiated untreated skin samples versus non- UVA-irradiated untreated skin samples proved a significant increase in fluorescence score, i.e. ROS (reactive oxygen species), from 0.09 to 3.30. The positive control 100 % tocopherol exhibited a significant reduction of UVA-induced ROS versus untreated UVA- irradiated samples by 79 %, which was also expected.
[0273] The vehicle DMSO had a non-significant effect on the UVA-induced ROS (0 % versus untreated UVA-irradiated) whereas the two natural Zein protein extract concentrations of 0.5 and 5 ppm significantly decreased the UVA-induced ROS level versus untreated UVA- irradiated as well as vehicle treated UVA-irradiated samples.
[0274] The results clearly show that the natural Zein protein extract reduces UV-induced ROS induction and oxidative stress and can therefore be expected to also clearly decrease ROS and oxidative stress associated tissue damages leading to e.g. premature skin aging. Accordingly, it was surprisingly found, that the extracts, compositions and formulations according to the present invention also have a positive skin treating effect and thus can advantageously be used for skin treatment and as or in cosmetic skin care preparations.
[0275] Example 16: Comparative LC-MS proteomic analysis and gelation behavior of commercial Zein
[0276] Zein is commercially available from Sigma-Aldrich (Z3625, CAS 9010-66-6). The material was analyzed by LC-MS for comparison of its protein profile with that of the natural Zein protein extract obtained according to Example 1. The results are shown in Fig. 12.
[0277] As can be seen from the LC-MS protein profile shown in Fig. 12, commercial Zein mainly consists of alpha-Zein. Most importantly, commercial Zein comprises significantly smaller amounts of beta- and gamma-Zein when compared to the natural Zein protein extract profile obtained according to Example 1.
[0278] The different Zein protein profiles of commercial Zein and natural Zein protein extracts according to example 1 can be further verified.
[0279] Example 17: Electrophoresis Analysis
[0280] Polyacrylamide gel electrophoresis (SDS-PAGE) was used for the general evaluation of the profile of proteins present in the dried extract samples of the raw material. Approximately 50 g of each sample was resuspended in XT 1X electrophoresis buffer (Bio-Rad, cod. 161- 0791) containing 5 % b-mercaptoethanol (v / v, Sigma) for protein disulfide bonds reduction. After incubation at 100 °C for 5 min, samples were applied to 8-16 % polyacrylamide gels (Genescript). Electrophoresis was performed at 40 V / gel for 30 min then 150 V for 1 hour in a Mini-PROTEAN II Electrophoresis System (Bio-Rad, USA). Five microliters of a duo color molecular weight standard (Bioread) were loaded. To visualize the proteins, the gels were stained with Coomassie Gel Code Blue Stain Reagent (Thermo, code 24590) according to the manufacturer's recommendations.
[0281] For this example, the natural Zein protein extract solution according to Example 4 was used.
[0282] The determination of the general profile of the proteins present in the samples analyzed indicates the presence of proteins with a molecular weight from 10 kDa to 25 kDa (Fig. 14). The results show the E qualitative total protein profile of dried extract. At the left and right ends the standards (ST) with 10KDa to 250KDa. The dried extracts from different batches of plant material are described as 1 , 2 and 3.
Claims
Claims1. An extraction process for proteins from plant materials, preferably Zein proteins from plant materials comprising the steps of: a) adding an extraction solvent, preferably water or aqueous ethanol to said plant material to form a mixture, preferably wherein the amount of ethanol in the extraction solvent is from 20 to 99 wt.-%, preferably from 50 to 90 wt.-%, more preferably from 60 to 80 wt.-%, and most preferably from 68 to 72 wt.-%; b) heating the mixture under a), preferably up to a temperature of between 40 to 90 °C, preferably between 50 to 80 °C, more preferably between 60 and 75, and most preferably from 65.5 to 72.5 °C; c) maintaining said temperature for a period of at least 30 minutes, preferably, wherein the period is between 1 to 6 hours, more preferably from 1.5 to 5 hours and most preferably from 2 to 3.5 hours; d) preferably cooling the obtained mixture to room temperature; e) submitting the mixture to filtration.
2. The process of claim 1, further comprising the steps of: f) i) adding at least one further solvent to the extract solution obtained in step e); ii) further removing the extraction solvent by distillation, preferably at elevated temperature and reduced pressure, preferably wherein the temperature is in the range of from 40 to 80 °C, and preferably, wherein the pressure is in the range of from 0.01 to 950 mbar; iii) optionally further filtering the distillation residue, preferably by using a tissue or paper filter; and iv) obtaining a solution of the protein extract, in the at least one further solvent; or g) alternatively to f), obtaining a dry extract, preferably using lyophilization or spraydrying.
3. The process of claim 1 or 2, wherein the proteins from plant materials are select from the group consisting of albumins, prolamins, or mixtures of the aforementioned proteins, and preferably Zein proteins, wherein the Zein proteins are extracted from Zea mays, preferably from corn kernel material, more preferably from corn gluten meal.
4. The process of any one of the preceding claims 1 to 3, wherein in step a) the weight ratio of plant material and extraction solvent in the mixture is 1:3 to 1:100, preferably in the range of 1:5 to 1:25, more preferably wherein the weight ratio of plant material and solventis in the range of 1 : 10 to 1 :20, and most preferably wherein the weight ratio of plant material and solvent is 1:15.
5. The process of any one of the preceding claims 1 to 4, wherein the at least one further solvent is selected from the group consisting of water, glycerol, and 1 ,2-alkanediols and / or 2,3-alkanediols having 3 to 12 carbon atoms, preferably the at least one further solvent is selected from the group consisting of 1 ,2-alkanediols and / or 2,3-alkanediols having 3 to 8 carbon atoms, more preferably the at least one further solvent is propylene glycol or pentylene glycol, more preferably the at least one further solvent is a mixture comprising propylene glycol and pentylene glycol, preferably the at least one further solvent is a mixture comprising propylene glycol and pentylene glycol in a ratio of 1:1 to 1:20.
6. An extract obtained from the process according to any one of the preceding claims 1 to 5.
7. An extract comprising proteins from plant materials, preferably wherein the proteins from plant materials are select from the group consisting of albumins, prolamins, or mixtures of the aforementioned proteins and at least one further solvent selected from the group consisting of water, glycerol, and 1,2-alkanediols and / or 2,3-alkanediols having 3 to 12 carbon atoms, and mixtures thereof.
8. An extract comprising 45 to 85 wt.-% Zein proteins, preferably from 50 to 80 wt.-% Zein proteins, more preferably 55 to 75 wt.-% based on the weight of the dried extract, wherein the extract comprises:30 to 80 wt.-% alpha-Zein, preferably 45 to 70 wt.-% alpha-Zein,1 to 30 wt.-% beta-Zein, preferably 7 to 20 wt.-% beta-Zein,0.1 to 20 wt.-% gamma-Zein, preferably 5 to 15 wt.-% gamma-Zein, and 0.001 to 5 wt.-% delta-Zein, preferably 0.01 to 1 wt.-% delta-Zein, based on the dry weight of the extract.
9. The extract of any one of the claims 6 to 8, comprising a further solvent, which is preferably selected from the group consisting of water, glycerol, and 1,2-alkanediols and / or 2,3-alkanediols having 3 to 12 carbon atoms, preferably the at least one further solvent is selected from the group consisting of 1,2-alkanediols and / or 2,3-alkanediols having 3 to 8 carbon atoms, more preferably the at least one further solvent is propylene glycol or pentylene glycol, more preferably the at least one further solvent is a mixture comprising propylene glycol and pentylene glycol, preferably the at least one furthersolvent is a mixture comprising propylene glycol and pentylene glycol in a ratio of 1 :1 to 1 :20.
10. The extract of any one of the claims 6 to 9, further comprising inorganic alkali or earth alkali salts such as calcium chloride or sodium chloride, L-arginine, sugar such as sucrose, or mixtures of the aforementioned substances, preferably calcium chloride and / or L-arginine.
11. Use of the extract according to any one of the claims 6 to 10 in or for the preparation of cosmetic compositions.
12. A cosmetic composition comprising an extract according to any one of the claims 6 to 11.
13. A cosmetic composition comprising proteins from plant materials, preferably wherein the proteins from plant materials are select from the group consisting of albumins, prolamins, or mixtures of the aforementioned proteins, preferably Zein proteins, and at least one further solvent selected from the group consisting of water, glycerol, and 1,2-alkanediols and / or 2, 3-alkanediols having 3 to 12 carbon atoms, and mixtures thereof.
14. A cosmetic composition comprising: from 2 to 12 wt.-% Zein proteins, preferably wherein the Zein content is from 4 to 10 wt.- %, more preferably wherein the overall Zein content is from 5 to 8 wt.-%, a solvent or solvent mixture comprising a solvent selected from the group consisting of 1,2-alkanediols having 3 to 12 carbon atoms, preferably pentylene glycol, further preferably comprising propylene glycol, or preferably a mixture of pentylene glycol and propylene glycol.
15. The cosmetic composition according to any one of the claims 12 to 14 comprising at least one further solvent selected from the group consisting of water, glycerol, and 1,2- alkanediols and / or 2, 3-alkanediols having 3 to 12 carbon atoms, preferably the at least one further solvent is selected from the group consisting of 1 ,2-alkanediols and / or 2,3- alkanediols having 3 to 8 carbon atoms, more preferably the at least one further solvent is propylene glycol or pentylene glycol, more preferably the at least one further solvent is a mixture comprising propylene glycol and pentylene glycol, preferably the at least one further solvent is a mixture comprising propylene glycol and pentylene glycol in a ratio of 1:1 to 1:20.
16. The cosmetic composition according to any of the claims 12 to 15, further comprising inorganic alkali or earth alkali salts such as calcium chloride or sodium chloride, L- arginine, sugar such as sucrose, or mixtures of the aforementioned substances, preferably each in an amount of from 0.01 to 5 wt.-%, more preferably each in an amount of from 0.2 to 3 wt.-%, based on the final cosmetic composition.
17. Use of the extract or cosmetic composition of any one of the preceding claims 6 to 10 or 12 to 16 in scalp and hair care products and / or in skin care products, preferably in waterbased scalp and hair care products and / or in skin care products, more preferably in shampoos and / or conditioners, emulsions, serums, tonics and cleansers.
18. The use of the extract or cosmetic composition of claim 17, wherein the extract or cosmetic composition is directed to hair restoration, preferably wherein the cosmetic composition is directed to the improvement of the tensile strength of hair, the treatment of hair fatigue and / or the avoidance of hair swelling.
19. The use of the extract or cosmetic composition of claim 17, wherein the extract or cosmetic composition is directed to skin care for reduction of oxidative stress.
20. The cosmetic composition of any one of the preceding claims 12 to 16, further comprising at least one additive selected from the groups consisting of UV filters, radical scavengers or other antioxidants, moisturizers, and / or anti-aging agents.
21. Use of the further solvents according to claim 5 for increasing the solubility of proteins, preferably albumins, prolamins, or mixtures of the aforementioned proteins, and preferably Zein proteins, wherein the Zein proteins are extracted from Zea mays, preferably from corn kernel material, more preferably from corn gluten meal.