Patent Application
20250066991
In general, in the leather industry, fatliquors affect the leather matrix by reducing frictional forces, improving tensile strength, introducing softness, and protecting the leather against cracking. The physical characteristics of the leather, such as flexibility, feel, and stitch tear resistance, are generally influenced by the nature of the fatliquors used. As an environmentally friendly (e.g., “green”) alternative, the use of vegetable oils (also referred to as vegetable-based oils) as fatliquoring agents has been suggested: e.g., sulfated castor oil, beeswax, coconut oil, vegetable oil, linseed oil, oleic acid, sulfated fish oil, sulfated canola oil, soybean oil, palm oil, fatty acids, etc. These may be advantageous because they are environmentally friendly and cost-effective compared to other petrochemical alternatives of fatliquoring. However, the disadvantage is that they are a complex mixture of different components that can change with the origin, so any formulation derived from them may vary in its properties and strength, making them difficult and expensive to use. As a result, these compounds have not been widely adopted by the leather industry.
In the context of mycelium-based textiles, in particular, only a few fatliquoring materials have been proposed, and most are transferred, with little adaptation, from more traditional leather treatments. Thus, there is a need for materials, particularly fatliquoring materials, that may be used with mycotextiles. Ideally, such materials would be environmentally friendly and efficient. Described herein are compositions and methods of using and making such nanoemulsion-based fatliquoring materials that may address these needs.
Described herein are formulations of oil-in-water (O/W) nanoemulsions based on fatty acids of vegetable origin using non-ionic surfactants that may be used as fatliquoring solutions in animal leather and leather-like materials, and in particular in leather materials based on fungal mycelium, protein, and/or other substitutes for animal leather. Also described herein are leather materials and mycelium-based textiles (also referred to herein as mycoleather or mycotextiles) that may include such formulations and methods and compositions for making and using these formulations. The methods described herein may be particularly advantageous for scaling up manufacture and processing, recovering, and reusing these materials.
As mentioned above, it may be highly beneficial or necessary to hydrate natural and bio-based leather materials, and in particular mycelium-based textiles. To obtain a mycelium-based textile resistant to peeling-off and cracking, specific steps may be carried out after the fermentation stage, i.e., the aerial mycelium formation on a scaffold. These steps mainly involve hydration with a plasticizing agent such as glycerol, crosslinking between the mycelium fibers to provide greater mechanical strength, pressing, drying, and, in some cases, embossing. However, depending on factors such as the fungal strain used or the post-fermentation operations, the resulting material may become brittle as soon as it loses its internal moisture. For this reason, it may be beneficial to increase wetting by incorporating different additives to increase flexibility. The patent application titled “Penetration and adhesion of finishes for fungal materials through solubilization, emulsion, or dispersion in water-soluble materials and the use of surfactants” (WO2020087033A1) describes a method for preparing a finish based on polylactic acid (PLA) as a plasticizer, directed by an emulsion system towards the inner layers of a mycelium-supported composite fabric. The polymer concentration is less than 50%, and the surfactant includes at least one polyurethane binder, isopropyl alcohol, and 2-butoxyethanol. Additionally, a polyurethane or acrylic layer is incorporated to promote adhesion, followed by additional layers containing color pigment, other acrylics, silicones, or resins.
The oil-in-water (O/W) nanoemulsions (e.g., fatliquoring compositions) described herein may be based on a vegetable-based oil. Any appropriate natural or synthetic vegetable oil may be used. For example, Table 1 shows the approximate composition of some vegetable oils that may be used as fats to be incorporated into mycotextile. In particular, the oil may be comprised of 85% or more saturated fatty acids (e.g., 85% or more, 86% or more, 87% or more, 88% or more, 89% or more, 90% or more, etc.). In the case of mycotextiles, where the material's main component is polysaccharides, the primary chemical interaction that can be handled to incorporate additives are Van der Waals forces. However, an important parameter may be the stability of the oil against oxidation to prevent it from accelerating the decomposition process of the material.
Unlike other fats, coconut oil is composed mainly of saturated fatty acids; its composition is more homogeneous regarding the chemical nature of the components, which facilitates the formulation because possible interferences or uncontrolled interactions with some other components may be avoided. U.S. patent application U.S. Pat. No. 11,993,068B2 (titled “MYCOTEXTILES INCLUDING ACTIVATED SCAFFOLDS AND NANO-PARTICLE CROSS-LINKERS AND METHODS OF MAKING THEM,” granted on May 28, 2024), herein incorporated by reference in its entirety, described the application of a coconut oil-based oil in water emulsion as a convenient step to incorporate fats into the material and hence, avoid brittleness. Likewise, waxes such as beeswax and lanonil are also strong candidates for wetting and fat incorporation since they usually contain cholesterol and fatty acid esters that maintain hydration. In addition, other effective emollients could also be considered as candidates as many of them give a dry feel and form films. Some examples are cetearyl ethylhexanoate, Octanoic acid, 1,3-propanediol ester, Decanoic acid, ester with 2,2′-[oxybis(methylene)]bis [2-(hydroxymethyl)-1,3-propanediol] octanoate pentanoate.
Most of these oils and fats are liquids with a considerably high viscosity. Some of them solidify at low temperatures, thus, their incorporation into the material cannot be direct because there is a risk that the fat of interest will not penetrate sufficiently and/or will not be adequately dispersed on the surface. For this reason, the most appropriate way to transport it to the fibers is through oil-in-water (O/W) emulsions.
An emulsion is a thermodynamically unstable dispersion of two immiscible liquids, usually of apolar and polar nature, in which one of them forms droplets of small size (from 0.1 to 100 microns), which is called dispersed or internal phase and the other, continuous, or external phase. It must contain an emulsifier, an amphiphilic substance that facilitates the formation of the emulsion by reducing the interfacial tension between the apolar (oil) and polar (aqueous) phases and also provides at least a specific physical stability for a period of time, which can be more or less long. Depending on the nature of the dispersed and continuous phases, emulsions are classified as O/W, W/O, or multiple W/O/W and O/W/O types. For example, see
The hydrophilic-lipophilic balance, HLB, may be useful for selecting an emulsifier or an optimal emulsifier blend, at least for low molecular mass emulsifiers. Emulsifiers are amphiphilic in nature but may have a greater or lesser tendency to solubilize in oily or aqueous media, depending on the relative importance of their hydrophilic (polar heads or ethoxylated groups) and hydrophobic (long hydrocarbon chains, C≥12) groups. If the emulsifier tends to be soluble in water, it will be useful for forming O/W emulsions. On the contrary, if its apolar part is dominant, it will preferentially dissolve in an oily medium and, consequently, will be more beneficial for forming W/O emulsions. The compositions described herein may formulate the mixture so that the oil can be delivered to the inner layers of the textile more easily; therefore, these compositions may be formulated as oil-in-water O/W emulsions. In this case, the distribution of the surfactant in the dispersed droplets may be as shown schematically in
Due to the complexity of the active matrix, the ideal candidates for formulation include nonionic surfactants, e.g., polyoxyethylene derivatives, polyoxypropylene derivatives, and derivatives of sorbitan anhydrides, alkanol amides, fats, and others of a nonionic nature. Non-ionic surfactants have the advantage that they are stable with most chemicals at the usual concentrations of use. Since they do not ionize in water, they do not form salts with metal ions and are equally effective in soft and hard water. The selection criteria for the nonionic surfactant may also include: (1) compatible with products in direct contact with the skin; (2) non-toxic; (3) the ability to provide fluid and stable emulsions at room temperature for high shelf life; (4) easily and economically available; and (5) compatible with the chemical components of the mycelium wall. Table 2 shows some examples of nonionic surfactants that may be used as part of the surfactant mixtures for the oil-in-water (O/W) nanoemulsions based on fatty acids of vegetable origin as described herein:
Other examples of nonionic surfactants may include alkyl polyglycoside, cetomacrogol 1000, cetostearyl alcohol, cetyl alcohol, cocamide DEA, cocamide MEA, decyl glucoside, decyl polyglucose, glycerol monostearate, IGEPAL CA-630, ioceteth-20, lauryl glucoside, maltoside, monolaurin, mycosubtilin, narrow-range ethoxylate, nonidet P-40, nonoxynol-9, nonoxynols, NP-40, octaethylene glycol monododecyl ether, N-Octyl beta-D-thioglucopyranoside, octyl glucoside, oleyl alcohol, pentaethylene glycol monododecyl ether, polidocanol, poloxamer, poloxamer 407, polyethoxylated tallow amine, polyglycerol polyricinoleate, polysorbate, polysorbate 20, polysorbate 80, sorbitan, sorbitan monolaurate, sorbitan monostearate, sorbitan tristearate, stearyl alcohol, surfactin, Triton X-100, and Tween 80.
Emulsions may be classified as “conventional” emulsions or macroemulsions, microemulsions, and nanoemulsions according to both their droplet size and stability (see, e.g., m and are thermodynamically metastable; they break down over time due to various destabilizing factors and are optically turbid since the droplet size is like the wavelength of light, scattering incident light and appearing opaque. On the other hand, microemulsion droplets have a size of <100 nm diameter (e.g., counterintuitively smaller than nanoemulsions) and are thermodynamically stable. Even slight variations in environmental conditions affect their stability, such as composition and temperatures. The microemulsion forms spontaneously as its free energy is lower than its phase-separated components. They are optically transparent since the particle size is smaller than the wavelength, and they weakly scatter light. In contrast, nanoemulsions have droplet dimensions similar to or overlapping with microemulsions including <200 nm and, in some cases, <100 nm. Like conventional emulsions, nanoemulsions are thermodynamically metastable as phase separation occurs over time. However, nanoemulsions are kinetically stable as there is no gravitational separation or droplet aggregation due to the reduced attractive force between tiny droplets. Unlike thermodynamically stable microemulsions, nanoemulsions are not affected by physical and chemical variations, including temperature and pH. They require less surfactant for their preparation. The droplet size of the nanoemulsion, in addition to determining its optical property and stability, also influences its rheological and release behavior. Therefore, nanoemulsions are more suitable than microemulsions for various applications because they can provide greater bioavailability and efficacy for delivering a range of bioactive compounds.
Since nanoemulsions are thermodynamically unstable systems, external energy is required for their preparation. Two generation processes are reported in the literature: high and low energy. In the first case, a high mechanical energy is applied during emulsification, generally using high shear agitation, high-pressure homogenizers, and/or ultrasonic generators. In contrast, the low-energy method, or condensation method, relies on the phase transitions that take place during the emulsification process. Low-energy methods are based on the spontaneous formation of tiny oil droplets within oil-water-emulsifier mixtures when their composition or environmental conditions are altered. Examples are spontaneous emulsification (SE), phase inversion temperature (PIT), phase inversion by composition (PIC), and emulsion inversion point (EIP) μm and are thermodynamically metastable. They break down over time due to various destabilizing factors and are optically turbid since the droplet size is similar to the wavelength of visible light, scattering incident light and appearing opaque.
Furthermore, these systems may allow the nanoencapsulation of several compounds of interest such as essential oils or other oil-based fragrances. This process enhances the solubility, stability, and controlled release of several water-insoluble compounds. The emulsification reduces the size of oil droplets, increasing their surface area and allowing for better interaction with the surrounding environment. Likewise, nanoemulsions offer benefits such as improved bioavailability, reduced volatility, and enhanced aroma retention. The encapsulation within nanoemulsions shields components from degradation caused by external factors like light, heat, and oxygen. Moreover, nanoemulsions provide a platform for targeted delivery, enabling the controlled release of these compounds at specific sites. Infinite possibilities could be opened to impart other functionalities to the materials that involve the different senses of the consumers using the fatliquoring formulations as vehicles inside the porous matrices of the biobased-textiles.
For example, described herein are nanoemulsions, e.g., nanoemulsion composition for fatliquoring a textile material, and in particular nanoemulsion composition for fatliquoring a mycotextile material. In some examples the nanoemulsion composition may be an oil-in-water nanoemulsion composition for fatliquoring a textile material, the composition comprising: between about 0.1% and 5% of a vegetable-based oil; and between about 1% and 10% of a nonionic surfactant, wherein the nanoemulsion comprises droplets of the vegetable-based oil surrounded by the nonionic surfactant and dispersed within a continuous water phase. In other examples, these nanoemulsions were used as carriers of essential oils and/or fragrances either mixing the essential oil/fragrance with the vegetable oil or not.
The vegetable-based oil may comprise more than 85% saturated fatty acids. The vegetable-based oil may comprise one or more of: coconut oil, soybean oil, canola oil, corn oil, avocado oil, and olive oil. For example, the vegetable coil may comprise a coconut oil. In some examples the vegetable-based oil phase comprises one or more of synthetic derivatives of vegetable oils including: cetearyl ethylhexanoate; octanoic acid, 1,3-propanediol ester; 2,2′-[oxybis(methylene)]bis [2-(hydroxymethyl)-1,3-propanediol] decanoate. In other examples, the vegetable-based oil phase comprises one or more natural waxes including beeswax and/or lanolin.
Any appropriate nonionic surfactant may be used. For example, the nonionic surfactant may comprise one or more of: polyoxyethylene, a polyoxyethylene derivative, polyoxypropylene, a polyoxypropylene derivative, sorbitan anhydride, a sorbitan anhydride derivative, an alkanol amide, and a nonionic fat. In general, the derivatives of these substances may include the original substance and one or more modifications of the substance. For example, the nonionic surfactant may comprise one or more of: polysorbate 20, polyoxyethylene (20) sorbitan monolaurate, glyceryl monoolcate, polysorbate 80, sorbitan monolaurate, polysorbate 80, polyoxyethylene (20) sorbitan monooleate, hydrogenated and ethoxylated castor oil, and glyceryl monostearate. In some examples, the nonionic surfactant comprises Tween 80.
The nanoemulsion droplets may generally have a mean droplet diameter of between 20-35 nm. The ratio of surfactant to oil may generally be between 1:2 and 1:15.
For example, an oil-in-water nanoemulsion composition for fatliquoring a textile material may include: a vegetable-based oil comprising 85% or more saturated fatty acids; and a nonionic surfactant, wherein the surfactant to oil (O:S) ratio is between 1:2 and 1:15, and the composition comprises between 0.1% and 5% of vegetable-based oil, further wherein the nanoemulsion comprises droplets of the vegetable-based oil surrounded by the nonionic surfactant and dispersed within a continuous water phase.
Also described herein are methods of making any of these oil-in-water nanoemulsions. For example, the method of forming a nanoemulsion for use as a fatliquoring agent having a stable shelf life may include: homogenizing a concentrated mixture of a vegetable-based oil comprising 85% or more saturated fatty acids and a nonionic surfactant at between 60-90° C., wherein the ratio of nonionic surfactant to vegetable-based oil (O:S) is between 1:2 and 1:15 in water, and the concentrated mixture comprises less than 50% water, by weight; adding water, slowly by dripping, into the concentrated mixture at between 60-90° C. to dilute the concentrated mixture; and agitating the mixture to form the nanoemulsion comprising droplets of the vegetable-based oil surrounded by the nonionic surfactant and dispersed within a continuous water phase, wherein the nanoemulsion comprises between 0.1% and 5% of vegetable-based oil. In general, homogenizing may comprise homogenizing using high shear agitation, a high-pressure homogenizer, and/or an ultrasonic generator. For example, homogenizing may comprise manual agitation. Homogenizing may include stirring at greater than 2000 RPM (e.g., >=2100 RPM, 2500 RPM, 2800 RPM, 3000 RPM, 3100 RPM, 3500 RPM, etc. Homogenizing may comprise increasing the rate of stirring up to 4000 RPM or greater.
Any of these methods may comprise removing contamination from the nanoemulsion after its application to promote reusing. For example, the nanoemulsion may be filtered by one or more of: filtration with activated carbon, filtration using cellulose acetate filters having a pore size of greater than pores of 1 μm, and/or filtration with cellulose acetate filters of 0.45 μm and subsequent addition of sodium hypochlorite.
In general, agitating a mixture such as the nanoemulsion mixture may include agitating, e.g., with a magnetic plate and vortex.
The nanoemulsion may comprise droplets having an average droplet size of between about 15 and 40 nm and/or a mean droplet diameter of between 20-35 nm. The nanoemulsion may have a polydispersity index (PDI) of between, e.g., about 0.05 and 0.2.
In any of these methods and compositions, the nanoemulsion may have a stable shelf life of greater than 30 days. The vegetable-based oil comprises coconut oil. In some examples, vegetable-based oil comprises one or more of: coconut oil, soybean oil, canola oil, corn oil, avocado oil, and olive oil. In some examples, the vegetable-based oil phase comprises one or more of synthetic derivatives of vegetable oils including: cetearyl ethylhexanoate; octanoic acid, 1,3-propanediol ester; 2,2′-[oxybis(methylene)]bis [2-(hydroxymethyl)-1,3-propanediol] decanoate. In other examples, the vegetable-based oil phase comprises one or more natural waxes including beeswax and/or lanolin.
The nonionic surfactant may comprise one or more of: polyoxyethylene, a polyoxyethylene derivative, polyoxypropylene, a polyoxypropylene derivative, sorbitan anhydride, a sorbitan anhydride derivative, an alkanol amide, and a nonionic fat. The nonionic surfactant comprises one or more of: polysorbate 20, polyoxyethylene (20) sorbitan monolaurate, glyceryl monoolcate, polysorbate 80, sorbitan monolaurate, polysorbate 80, polyoxyethylene (20) sorbitan monooleate, hydrogenated and ethoxylated castor oil, and glyceryl monostearate. For example, the nonionic surfactant may comprise Tween 80. The vegetable-based oil may comprise coconut oil.
For example, a method of forming a nanoemulsion for use as a fatliquoring agent having a stable shelf life may include: homogenizing a concentrated mixture of a vegetable-based oil comprising 85% or more saturated fatty acids and a nonionic surfactant at between 60-90° C., wherein the ratio of nonionic surfactant to vegetable-based oil (O:S) is between 1:2 and 1:15 in water, and the concentrated mixture comprises less than 50% water, by weight; adding water, slowly, into the concentrated mixture at between 60-90° C. to dilute the concentrated mixture; and agitating the mixture to form the nanoemulsion comprising droplets of the vegetable-based oil surrounded by the nonionic surfactant and dispersed within a continuous water phase, wherein the nanoemulsion comprises between 0.1% and 4% of vegetable-based oil.
Also described herein are textiles (e.g., including but not limited to mycotextiles). For example, a mycotextile may include: one or more crosslinked mycelium layers having a plurality of nanoparticles within the one or more crosslinked mycelium layers, wherein the plurality of nanoparticles are functionalized to crosslink chitin/chitosan within hyphae of the one or more crosslinked mycelium layers; and an oil-in-water nanoemulsion coating the hyphae of the one or more crosslinked mycelium layers.
The oil-in-water nanoemulsion may comprise a vegetable-based oil surrounded by a nonionic surfactant. For example, the ratio of nonionic surfactant to vegetable-based oil may be between 1:2 and 1:15. The vegetable-based oil may comprise more than 85% saturated fatty acids. For example, the vegetable-based oil comprises coconut oil. For example, vegetable-based oil comprises one or more of: coconut oil, soybean oil, canola oil, corn oil, avocado oil, and olive oil. In some examples, the vegetable-based oil phase comprises one or more of synthetic derivatives of vegetable oils including: cetearyl ethylhexanoate; octanoic acid, 1,3-propanediol ester; 2,2′-[oxybis(methylene)]bis [2-(hydroxymethyl)-1,3-propanediol] decanoate. In other examples, the vegetable-based oil phase comprises one or more natural waxes including beeswax and/or lanolin. The nonionic surfactant may comprise one or more of: polyoxyethylene, a polyoxyethylene derivative, polyoxypropylene, a polyoxypropylene derivative, sorbitan anhydride, a sorbitan anhydride derivative, an alkanol amide, and a nonionic fat. The nonionic surfactant may comprise one or more of: polysorbate 20, polyoxyethylene (20) sorbitan monolaurate, glyceryl monooleate, polysorbate 80, sorbitan monolaurate, polysorbate 80, polyoxyethylene (20) sorbitan monooleate, hydrogenated and ethoxylated castor oil, and glyceryl monostearate. For example, the nonionic surfactant may comprise Tween 80. The vegetable-based oil may comprise coconut oil. In some examples, the droplets of the nanoemulsion have a mean droplet diameter of between 20-35 nm.
For example, a mycotextile may include a support scaffold layer, a first crosslinked mycelium layer extending adjacent to a first side of the support scaffold layer, and a second crosslinked mycelium layer extending adjacent to a second side of the support scaffold layer, a plurality of nanoparticles within the first and second crosslinked mycelium layers, wherein the plurality of nanoparticles are functionalized to crosslink chitin/chitosan within hyphae of the first crosslinked mycelium layer and the second crosslinked mycelium layer; and an oil-in-water nanoemulsion coating the hyphae of the first and second crosslinked mycelium layers.
All the methods and apparatuses described herein, in any combination, are herein contemplated and can be used to achieve the benefits as described herein.
A better understanding of the features and advantages of the methods and apparatuses described herein will be obtained by reference to the following detailed description that sets forth illustrative embodiments, and the accompanying drawings of which:
Described herein are nanoemulsions of oily phases in water using non-ionic surfactants that are stable over longer periods of time to improve the flexibility and moisture retention in materials of biotechnological origin, and in particular mycotextiles that may be used as substitutes for animal leather. The nanoemulsions described herein may have a droplet size of between about 20 and 500 nm, which is a thousand times smaller than droplets of a conventional emulsion. These nanoemulsions may be deposited in an oily phase through a fibrous and/or porous material more efficient than conventional emulsions, resulting in greater availability of the oil in the mycotextile, as well as in the stability (shelf life) of the solution, which would allow its reuse and lower scaling costs.
The vegetable oil nanoemulsions (in water) described herein may be formed using a biocompatible surfactant and may be used as a fatliquoring agent.
Nanoemulsions that may be used are described herein. Example protocols to prepare the different nanoemulsions, macroemulsions, and microemulsions for comparison are described below. These examples are not intended to be limiting but illustrate testing compositions used herein.
In a 250 mL beaker, 20 g of coconut oil, 12 grams of Tween 80, and 28 grams of Span 80 are weighed, heated to 80° C., and homogenized with manual agitation. In a 5 L capacity flask, weigh 1940 grams of distilled water and heat it to 80° C. Once the required temperatures are reached, the water flask is placed under mechanical agitation of 1200 RPM. The homogeneous mixture of coconut oil with both surfactants is added gradually (in thread) and continuously under agitation. Once the whole volume is added, it is kept stirring for 10 min. At the end of the 10 min, the agitation is decreased to 700 RPM, and it is left agitating for 10 min more, observing a white and homogeneous solution. It is taken to an Ultraturrax® homogenizer for 30 seconds at 10000 RPM. Once the agitation process is completed, the emulsion is transferred to a 2 L container which should be stored at a temperature between 3° and 35° C.
Weigh 12.5 grams of coconut oil and 58.35 grams of Tween 80 into a 250 ml beaker. Heated to 60° C. under magnetic stirring at 600 RPM. Weighed 429.15 grams of distilled water into another 1 Liter beaker and heated to 60° C. Once the temperature is reached in both cases, the water is added drop by drop over the oil and surfactant mixture, under constant agitation at 600 RPM and maintaining the temperature at 60° C. Once the addition is finished, the agitation is maintained for 5 min. This mixture can be kept at room temperature.
Weigh 15 grams of coconut oil and 70 grams of tween 80 in a glass beaker of 2 L capacity and proceed to heat, under mechanical agitation, on a hotplate, ensuring a temperature of 60° C. 15 grams of distilled water are placed in a 250 ml beaker and heated to 60° C. on a hotplate. Once the reaction temperature is reached, it proceeds to incorporate by dripping the water of the glass into the mixture, raising the agitation to 600 RPM. Once the incorporation of the water into the mixture is completed, the agitation is maintained for 20 min at the same conditions and speed.
Approach 1: Approximation 1 is performed by slowly incorporating the dilution water (in the form of drops). For this purpose, 1400 grams of distilled water at 85° C. are added to 100 grams of the concentrated sample at 85° C., drop by drop, under a mechanical agitation of 1000 RPM.
Approximation 2 was realized by the addition of water in two stages. The first ⅓ of the total mass (approximately 470 g) is slowly added and controlled, and the remaining ⅔ (approximately 930 g) is at three times the rate.
Example 1. A mixture of tween 80 with span 80 in a ratio (3:7) was made for conventional emulsions containing 1% oil phase (O:S=1:2). For this preparation, the corresponding proportions of both surfactants are mixed in the oil phase and brought to 80° C. Then, the aqueous phase is also brought to the same temperature. Both solutions are mixed with a magnetic stirrer at 1200 rpm for 10 minutes, adding the water to the oily phase as a thread, and then it is lowered to 700 rpm for 10 min. Finally, it is taken to an Ultraturrax® type homogenizer at 10000 RPM for 30 sec. The resulting mixture has a milky appearance and low viscosity with a tendency to cream after hours of rest. The droplet size distribution analysis was carried out in a Malvern Mastersizer 2000 model using the general purpose-normal sensitivity model and, as optical parameters, a refractive index of 1.47 and zero absorbance. The average size obtained for this mixture is 9.79 μm with a distribution d(0.1) of 1.46 μm, d(0.5) of 6.24 μm, and d(0.9) of 10.03 μm. This distribution justifies the creaming effect observed in this type of mixture. This formulation's typical droplet size distribution profile is shown in
Example 2. A preparation was made with tween 80 by the direct method using a 1:4.67 surfactant oil ratio for emulsions containing a 2.5% oil phase. A translucent low-viscosity mixture is obtained, suggesting a microemulsion is obtained.
Example 3. This system was made directly by mixing at 70° C. the different components in such a way as to obtain a final concentration of 15% Tween 80, 1% coconut oil, and 84% water. It instantly has a cloudy appearance with a slightly milky appearance, with creaming after 24 hours.
Example 4. Preparation of liquid crystals or bicontinuous microemulsions of tween 80 for indirect nanoemulsions (PIC method) starting from 75% tween 80, 5% coconut oil, and 20% water. This sample presents a transparent appearance and a viscous consistency maintained for up to 24 h.
Example 5. Preparation of liquid crystals or bicontinuous microemulsions of tween 80 for indirect nanoemulsions (PIC method) starting from 70% tween 80, 15% coconut oil, and 15% water, presenting a cloudy appearance and a viscous consistency. After 24 hours, the viscosity increased.
Example 6. In this system, 1 g of the preparation of example 4 was taken, and 4 g of water was added dropwise, resulting in a concentration of 15% Tween 80, 1% coconut oil, and 84% water. Initially, it has a transparent, fluid appearance; after 24 hours, the system maintains its appearance. The droplet size distribution analysis was carried out in a Malvern equipment model Zetasizer Nano ZS presenting an average size of 10.37 nm with a polydispersity index (PDI) of 0.268.
Example 7. A nanoemulsion was made by indirect method 8.75% of Tween 80, 1.875% of coconut oil, and 89.375% of water starting from the preparation of example 5. This means that an amount of the concentrated sample must be prepared and homogenized at a given temperature. In this case, an increase in fluidity is observed at 60° C. and above. Subsequently, at the same temperature, water is added by dripping. The system was prepared by taking 1.5 g of the concentrate of 70% Tween 80 and 15% coconut oil and diluted with 10.5 g of water dropwise. It exhibited a translucent appearance with low viscosity.
Example 8. From a sample prepared as the example 5, a sample containing 4.67% Tween 80, 1% coconut oil, and 94.33% water was prepared. A quantity of the concentrated sample is prepared, homogenized at a temperature of 70° C., and then, at that temperature, water is added to induce phase transition and subsequent dropwise dilution.
On the other hand, as shown in
Example 9. Formulations of liquid crystals or bicontinuous microemulsions of nonionic surfactant for indirect nanoemulsions (PIC method) with composition 65% nonionic surfactant, 20% coconut oil, 15% water or 70% nonionic surfactant, 15% coconut oil, 15% water. We started by making the water-surfactant-coconut oil samples based on the nonionic surfactant, to proceed in a second stage to dilute them with deionized water and thus prepare the nanoemulsions using the indirect method of phase inversion by concentration (PIC). They were briefly vortexed and briefly subjected to a temperature of 80° C. to homogenize; several cycles of this treatment were carried out until homogeneous samples were obtained.
Example 10. A composition of 8.125% nonionic surfactant, 2.5% coconut oil and 89.38% water was prepared by PIC. It started from one of the samples of example 9. A quantity of the concentrated sample with 65% oil phase is prepared and homogenized at a temperature of 60-85° C. Subsequently, at that temperature, water is added little by little (dripping). This process is necessary to be carried out at 60-85° C. so that the concentrated systems flow a little more, mainly at the beginning of the process, since we are starting from a system that is very viscous at room temperature. They were subjected to agitation with a magnet and vortex. The resulting mixture is translucent and fluid.
Example 11. Starting from a concentrated sample of composition: 65% nonionic surfactant, 20% coconut oil, and 15% water, a quantity of the concentrated sample is prepared and homogenized at a temperature of 60-70° C. Subsequently, at that temperature, water is added to dilute, and the water is added little by little (dripping) to reach a final composition of 3.25% nonionic surfactant, 1% coconut oil, and 95.75% water. This process needs to be carried out at 60-70° C. to allow the concentrated systems to flow a little more, mainly at the beginning of the process, since we are starting from a very viscous system at room temperature. They were subjected to agitation with a magnetic plate and vortex.
Example 12. A composition of 11.66% nonionic surfactant, 2.5% coconut oil, and 85.84% water is prepared. It starts from a concentrated sample of example 9, where the ratio of the oily to aqueous phase is 1. A quantity of the concentrated sample is prepared, homogenized at a temperature of 60-70° C., and then, at that temperature, water is added to dilute, and the water is added little by little (dripping). This process must be carried out at 60-85° C. so that the concentrated systems flow a little more, mainly at the beginning of the process, since the starting point is a medium viscous system at room temperature. They are subjected to agitation with a magnetic agitator and vortex.
Example 13. A composition of 4.67% nonionic surfactant, 1% coconut oil, and 94.33% water was prepared. It started from a concentrated composition sample: 70% nonionic surfactant, 15% coconut oil, and 15% water. A quantity of the concentrated sample is prepared, homogenized at a temperature of 60-85° C., and then, at that temperature, water is added to dilute, and the water is added little by little (dripping). This process must be carried out at 60-85° C. so that the concentrated systems flow a little more, mainly at the beginning of the process, since the starting point is a medium viscous system at room temperature. They were subjected to agitation with a magnet and vortex. Freshly prepared, it takes on a transparent, translucent appearance, bluish in color, very low viscosity, and without evidence of creaming. After one month at rest, the appearance remains the same, which confirms the stability of these preparations guaranteeing long shelf life.
Example 14. A composition consisting of 23.35% nonionic surfactant, 5% coconut oil, and 71.65% water was prepared by the PIC method starting from one of the samples of example 9. A mass of the concentrated sample was homogenized at a temperature ranging from 60 to 90° C. Subsequently, at the same temperature, water was dripped until the final concentration of the oil phase reached 5%. The resulting mixture is translucent and less fluid than the obtained in examples from 10 to 13 thus working temperature should be as high as possible.
Example 15. A sample prepared as example 13 replacing the oil phase by cetearyl ethylhexanoate (DUB LIQUIDE 85 by Stearinerie Dubois) presents similar optical characteristics and stability.
Example 16. A sample prepared as example 13 replacing the oil phase by octanoic acid, 1,3-propanediol ester (Propanediol dicaprylate, DUB ZENOAT® by Stearinerie Dubois) presents similar optical characteristics and stability.
Example 17. Lanolin nanoemulsion formulations started from bicontinuous microemulsions of nonionic surfactant with compositions of 50% nonionic surfactant, 25% lanolin, 25% water, or 50% nonionic surfactant, 12.5% coconut oil, 12.5% lanolin and 25% water. The concentrated samples were prepared under continuous stirring at temperatures ranging from 70 to 75° C. We started by making the water-surfactant-oil concentrated samples based on the nonionic surfactant (e.g., a PEG-based nonionic surfactant) to proceed in a second stage to dilute them with deionized water and thus prepare the nanoemulsions using the indirect method of phase inversion by concentration (PIC). This concentrate initially presented a slightly viscous appearance at the preparation temperature but after a few minutes. At room temperature, it behaves very viscous and milky in appearance. Therefore, the dilution must be done immediately after obtaining the concentrated mixture or it must be heated to a temperature between 7° and 75° C. before the PIC method.
Example 18. The PIC method prepared a composition consisting of 4% nonionic surfactant, 2% lanolin, and 94% water starting from one of the samples of example 15. This system appeared fluid but cloudy, with a milky appearance. After 1 hour, the nanoemulsion began to appear cloudier until it creamed.
Example 19. A composition with a 4:2 surfactant to oil ratio consisting of 4% nonionic surfactant, 1% lanolin, 1% coconut oil and 94% water was prepared by PIC method starting from one of the samples of example 15. This system presented a fluid and transparent appearance when first prepared, the same optical characteristics remain after several hours at room temperature and no creaming was observed in this system, suggesting that an oil-wax mixture is more efficient to emulsify the lanolin wax. The transparent appearance may indicate the presence of a microemulsion.
The improvement due to the use of these mixtures as fatliquoring agents in treating mycotextiles and/or leather-equivalent materials from biotechnological sources can be evidenced by increased flexibility and resistance to internal moisture loss (wetting).
Example 20. In other approaches including nanoemulsion encapsulating essential oils, T80 was used as a surfactant starting from a concentrated mixture consisting of 70% T80, 15% of orange or lemon essential oils, and 15% water. Both nanoemulsions were made at 80° C. by the PIC method slowly adding the necessary amount of water to achieve a final concentration of 4.66% T80, 1% AC, and 94.3% water. As observed in Table 3, using orange oil the average particle size result in 36.82 nm while using lemon oil the average particle size resulted in 158.50 nm. Comparing these values with the one obtained in Example 8 (24.05 nm) using only coconut oil with an equivalent composition, the droplet size increased significantly. The different type of oil affects the droplet size of the nanoemulsion and hence, the appearance of the nanoemulsion.
Example 21. Likewise, the nanoencapsulation at 80° C. of the essential oils using nonionic surfactant causes an increase in the droplet size (Table 3), and it occurs at a lower surfactant-to-oil ratio (3.25:1). For these formulations the concentrate mixture should be 65% PEG-based nonionic surfactant, 20% essential oil and 15% water. By diluting up to a final composition of 3.25% PEG-based nonionic surfactant, 1% essential oil and 94% water, the particle size for the orange oil is 112.20 nm and 98.67 for the lemon oil. In this case, the difference between both systems is less. However, the optical appearance of the lemon oil is closer to the expected for these systems. These first examples indicate that both essential oils could be nanoencapsulated.
Example 22. When mixed with other oil such as coconut oil to increase the solubility in the oil phase, a dramatic decrease in the particle size was observed. In this example, T80 was used as an emulsifier, and the PIC method started from a concentrated mixture of 55% T80, 12.5% coconut oil, 12.5% essential oil and 20% water under sitting at 80° C. According to Table 3, it is possible to achieve average droplet sizes of 49.22 nm for the orange oil and 76.72 nm for the lemon oil.
Example 23. By changing the emulsifier of Example 20 by nonionic surfactant and keeping constant the starting concentration and mixing conditions the obtained droplet sizes diminished dramatically to 69.98 nm for the orange oils and to 27.33 nm for the lemon oil. In both cases, the PDI also diminishes, confirming that a nonionic surfactant is more appropriate to achieve the desired properties of the nanoemulsions.
Comparing the distribution of the particle size in
Similarly, as shown in
Example 24. Using the formulation and procedures of Example 21, three different types of fragrances (e.g., MoodScentz® Givaudan fragrances) were nano encapsulated. These are examples of fragrances that blend psychological and neuroscientific measurement techniques that may provide emotional benefits. By combining this technology with mycotextiles (mycoleather), the customer's final experience is enhanced.
The quantification of the oil content in the material is carried out by calculating the ratio between the intensity of this C═O band with an internal standard. The internal standard is a signal that does not change in any sample and is not affected by the procedure. In this case, the stretching of C—O—C bond in the carbohydrates conforming the cell wall of the fungus, located around 1038 cm−1, is a good internal standard, as it does not change either the intensity or the position after adding the nanoemulsion. Moreover, to ensure that the oil was deposited throughout the thickness of the mycelium layer of the fabric, the mycelium layer was tested in both sides: at the top of the layer (front surface) and, at the bottom of the layer (back surface). To make a proper comparison, each sample should be compared with the control sample, which is the material before the incorporation of the oil. This strategy generates four FTIR spectra required for the quantification of the oil content for each analyzed sample, as observed in the
The collection of a typical spectrum could be done in an infrared spectrophotometer, equipped with an “attenuated total reflectance” accessory to analyze directly the samples with comparable thickness (e.g., 1 mm). The recording conditions could be 32 scans, and 4 cm−1 resolution in a spectral range of 800 to 1800 cm−1. the obtained spectrum should be baseline-corrected and normalized to the maximum absorbance, in this case is the one located in 1038 cm−1.
The absorbance values extracted from the spectra in
The industrialization of these formulations requires controlling parameters such as agitation, water addition, and temperature, mainly during the preparation of the concentrated mixture (liquid crystal or bicontinuous microemulsion). To obtain 15 Kg of the nanoemulsion of example 13, it is necessary to start with stirring at 2400 RPM and reach stirring at 3600 RPM while adding water. In this case, a higher temperature (e.g., 90° C.) is helpful to increase the system's fluidity. Once the system is entirely homogeneous (e.g., stirring for 30 minutes at 90° C.), the process of phase inversion and corresponding dilution is started. The agitation is increased up to 5000 RPM. The water is added, which can be according to two approaches: 1) slowly, in the form of droplet threads or, 2) in two parts, a first stage in the form of drops until the viscosity decreases and the phase inversion is just observed and, subsequently, the rest of the water until the desired final concentration is reached. In this case, it is recommended to use water near average boiling temperature (e.g., 95° C.). In
Taking into consideration the challenges regarding the scaling up not only for the preparation but also in the application on the mycotextiles (mycelium fabric), two different approximations were explored, both allowing in-line workflows: (i) a spray strategy vs (ii) an immersion strategy.
In the case of the immersion bath in
After its use in the immersion strategy, the nanoemulsion may take on a cloudy appearance with a specific yellowish coloration due to the remains of the fermentation medium. To facilitate its industrial application and extend its shelf life, this preparation can be treated to remove these “contaminating” agents. Three experiments were carried out to achieve recovery. First (1) filtration with activated carbon was used: for this, a column is filled with activated carbon, and the solution used is passed through the upper part of the column, allowing the liquid to pass through the carbon column by the effect of gravity to be collected at the bottom. The incorporation of finely divided material (activated carbon) into the liquid is observed. A second filtration using a column packed with cotton still yields a yellowish liquid, suggesting that the adsorption of the components causing the color was inefficient.
Second (2) vacuum filtration using cellulose acetate filters with pores of 1 μm was used: in this case, a vacuum filtration system is used with a Buchner-type ceramic funnel connected to a Kitasato-type flask, which in turn is connected to a vacuum pump. A piece of cellulose acetate paper with pores of 1 μm was placed in the funnel, covering the perforated section of the funnel. The solution was passed through this system, and a translucent, bluish-colored liquid was expected to be collected. However, with this system was impossible to eradicate the contaminants, and a slight turbidity and yellowish color were still observed.
Third (3) filtration with cellulose acetate filters of 0.45 μm and subsequent addition of sodium hypochlorite: the suspended particulate material was removed using pores of 0.45 m. It is observed that the solution becomes translucent, indicating the removal of suspended particles larger than 0.45 μm. However, due to the persistence of the yellowish color, sodium hypochlorite was added up to a final concentration of 0.02 wt. %, starting from a commercial chlorine solution for disinfection. The solution is repeatedly homogenized using vigorous manual agitation and allowed to stand for at least 10 min. Almost immediately, a considerable loss of the yellowish color begins to be observed, suggesting that this strategy is viable for recovering the excess nanoemulsion. DLS analysis confirmed that the strategy is suitable for nanoemulsion recovery since the filtered solution presented average droplet sizes of 23.8±0.6 nm with polydispersity indices of 0.331±0.009. Whereas, upon addition of sodium hypochlorite, average droplet size and polydispersity index values were 23.1±0.2 nm and 0.102±0.003, respectively. Three photographs can be seen in
All publications and patent applications mentioned in this specification are herein incorporated by reference in their entirety to the same extent as if each individual publication or patent application was specifically and individually indicated to be incorporated by reference. Furthermore, it should be appreciated that all combinations of the foregoing concepts and additional concepts discussed in greater detail below (provided such concepts are not mutually inconsistent) are contemplated as being part of the inventive subject matter disclosed herein and may be used to achieve the benefits described herein.
The various exemplary methods described and/or illustrated herein may also omit one or more of the steps described or illustrated herein or comprise additional steps in addition to those disclosed. Further, a step of any method as disclosed herein can be combined with any one or more steps of any other method as disclosed herein.
The processor, as described herein, can be configured to perform one or more steps of any method disclosed herein. Alternatively, or in combination, the processor can be configured to combine one or more steps of one or more methods as disclosed herein.
When a feature or element is herein referred to as being “on” another feature or element, it can be directly on the other feature or element, or intervening features and/or elements may also be present. In contrast, when a feature or element is referred to as being “directly on” another feature or element, no intervening features or elements are present. It will also be understood that when a feature or element is referred to as being “connected”, “attached” or “coupled” to another feature or element, it can be directly connected, attached or coupled to the other feature or element or intervening features or elements may be present. In contrast, when a feature or element is referred to as being “directly connected”, “directly attached” or “directly coupled” to another feature or element, there are no intervening features or elements present. Although described or shown concerning one embodiment, the features, and elements so described or shown can apply to other embodiments. It will also be appreciated by those of skill in the art that references to a structure or feature that is disposed of “adjacent” Another feature may have portions that overlap or underlie the adjacent feature.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting to the invention. For example, as used herein, the singular forms “a”, “an” and “the” are intended to include the plural forms as well, unless the context indicates otherwise. It will be further understood that the terms “comprises” and/or “comprising,” when used in this specification, specify the presence of stated features, steps, operations, elements, and/or components but do not preclude the presence or addition of one or more other features, steps, operations, elements, components, and/or groups thereof. As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed items and may be abbreviated as “/”.
Spatially relative terms, such as “under”, “below”, “lower”, “over”, “upper,” and the like, may be used herein for ease of description to describe one element or feature's relationship to another element(s) or feature(s) as illustrated in the figures. It will be understood that the spatially relative terms are intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the figures. For example, if a device in the figures is inverted, elements described as “under” or “beneath” other elements or features would then be oriented “over” the other elements or features. Thus, the exemplary term “under” can encompass both an orientation of over and under. The device may be otherwise oriented (rotated 90 degrees or at other orientations), and the spatially relative descriptors used herein are interpreted accordingly. Similarly, the terms “upwardly”, “downwardly”, “vertical”, “horizontal” and the like are used herein for the purpose of explanation only unless specifically indicated otherwise.
Although the terms “first” and “second” may be used herein to describe various features/elements (including steps), these features/elements should not be limited by these terms unless the context indicates otherwise. These terms may be used to distinguish one feature/element from another feature/element. Thus, a first feature/element discussed below could be termed a second feature/element. Similarly, a second feature/element discussed below could be termed a first feature/element without departing from the present invention's teachings.
In general, any of the apparatuses and methods described herein should be understood to be inclusive, but all or a subset of the components and/or steps may alternatively be exclusive and may be expressed as “consisting of” or alternatively “consisting essentially of” the various components, steps, sub-components or sub-steps.
As used herein in the specification and claims, including as used in the examples and unless otherwise expressly specified, all numbers may be read as if prefaced by the word “about” or “approximately,” even if the term does not expressly appear. The phrase “about” or “approximately” may be used when describing magnitude and/or position to indicate that the value and/or position described is within a reasonable expected range of values and/or positions. For example, a numeric value may have a value that is +/−0.1% of the stated value (or range of values), +/−1% of the stated value (or range of values), +/−2% of the stated value (or range of values), +/−5% of the stated value (or range of values), +/−10% of the stated value (or range of values), etc. Any numerical values given herein should also be understood to include about or approximately that value unless the context indicates otherwise. For example, if the value “10” is disclosed, then “about 10” is also disclosed. Any numerical range recited herein is intended to include all sub-ranges subsumed therein. It is also understood that when a value is disclosed that is “less than or equal to” the value, “greater than or equal to the value” and possible ranges between values are also disclosed, as appropriately understood by the skilled artisan. For example, if the value “X” is disclosed the “less than or equal to X” as well as “greater than or equal to X” (e.g., where X is a numerical value) is also disclosed. It is also understood that the throughout the application, data is provided in several different formats and that this data represents endpoints and starting points, and ranges for any combination of the data points. For example, if a particular data point “10” and a particular data point “15” are disclosed, it is understood that greater than, greater than or equal to, less than, less than or equal to, and equal to 10 and 15 are considered disclosed as well as between 10 and 15. It is also understood that each unit between two particular units are also disclosed. For example, if 10 and 15 are disclosed, then 11, 12, 13, and 14 are also disclosed.
Although various illustrative embodiments are described above, any of several changes may be made to various embodiments without departing from the scope of the invention as described by the claims. Optional features of various device and system embodiments may be included in some embodiments and not in others. Therefore, the foregoing description is provided primarily for exemplary purposes and should not be interpreted to limit the scope of the invention as it is set forth in the claims.
The examples and illustrations included herein show, by way of illustration and not of limitation, specific embodiments in which the subject matter may be practiced. As mentioned, other embodiments may be utilized and derived therefrom, such that structural and logical substitutions and changes may be made without departing from the scope of this disclosure. Such embodiments of the inventive subject matter may be referred to herein individually or collectively by the term “invention” merely for convenience and without intending to voluntarily limit the scope of this application to any single invention or inventive concept, if more than one is, in fact, disclosed. Thus, although specific embodiments have been illustrated and described herein, any arrangement calculated to achieve the same purpose may be substituted for the specific embodiments shown. This disclosure is intended to cover any and all adaptations or variations of various embodiments. Combinations of the above embodiments, and other embodiments not specifically described herein, will be apparent to those of skill in the art upon reviewing the above description.
This patent application claims priority to U.S. Provisional Patent Application No. 63/520,933, titled “NANOEMULSIONS FOR INTERNAL HUMECTATION OF MYCELIUM-BASED TEXTILES” and filed on Aug. 21, 2023, and herein incorporated by reference in its entirety.
| Number | Date | Country | |
|---|---|---|---|
| 63520933 | Aug 2023 | US |
