• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Nanoemulsions to prevent the biological colonization of surfaces. The invention describes a process for preparing a nanoemulsion comprising nanocapsules with essential oil comprising: preparing a solution of zein and essential oil in water-alcohol (solution A); a solution of casein in water (solution B) and a solution of pectin in water (solution C); add solution A on the mixture of solutions B and C, or alternatively add solution A and solution B on solution C. The invention also describes the nanoemulsion obtainable by said method whose nanocapsules comprise: a central core comprising a matrix of zein and the essential oil; a first coating layer of the core comprising casein and a second outer coating layer on the first comprising pectin, as well as the use of the nanoemulsion for the antimicrobial treatment of a contaminated substrate and/or for the prevention of biological colonization of a substrate. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2697301A1
    申请号:ES201730956
    申请日:2017-07-21
    公开日:2019-01-22
    发明作者:Marco Veneranda；Mota Juan Manuel Madariaga；Ortiz De Pinedo Kepa Castro
    申请人:Euskal Herriko Unibertsitatea；
    IPC主号:
    专利说明:

    [0001]
    [0002]
    [0003]
    [0004] Field of the invention
    [0005] The present invention relates to nanoemulsions with nanoencapsulated essential oils for the treatment and prevention of biological contamination of inorganic surfaces in general and their manufacture.
    [0006]
    [0007] BACKGROUND OF THE INVENTION
    [0008] Biological colonization represents one of the processes of deterioration that most affect mortar and mortar surfaces. When favorable environmental conditions are present (high humidity values, direct contact with sunlight), different types of fungi, bacteria, algae and molds can colonize the walls producing chemical, physical and aesthetic damages. Although most degradations can only be appreciated on a microscopic scale, this problem becomes very important when colonization takes place on surfaces of interest such as materials and structures belonging to immovable cultural heritage (wall paintings, archaeological sites, historical buildings, etc.). .).
    [0009] Protecting these and other surfaces in general from the attack of microorganisms is an extremely complicated task since, to date, there is no eco-compatible and reversible product capable of preventing colonization. For this reason, the only way currently available to limit the biodeterioration phenomena is to resort to the periodic elimination of the biological patinas that are developing cyclically.
    [0010] Nowadays, the most used treatment by the restorers is the application of antimicrobial products followed by the mechanical export of the treated patina. The most commonly used antimicrobial products for this purpose are acids, pyrimidines and organometallic compounds, while mechanical removal of the biological pads is usually carried out using scalpels and spatulas that cause damage to the substrates. However, using this cleaning technique to treat a mural surface of cultural interest can be very expensive, since the price of these treatments can vary from 450 to 700 euros per m2.
    [0011]
    [0012] Despite the effectiveness of the antimicrobial compounds currently used, the world of research is constantly searching for eco-compatible alternatives that respect the principles of green chemistry. In this context, several research groups are experimenting with the use of essential oils with antimicrobial properties as a biological alternative to the conventional chemical products mentioned above. The investigations carried out so far have produced very promising results. For example, essential oils extracted from aromatic plants such as Origanum vulgare, Rosmarinas officinalis and Lavandula angustifolia, have been shown to successfully neutralize some of the biodeteriogens that most commonly compromise the conservation of immovable cultural heritage.
    [0013] However, its use in its pure state does not allow to prevent biological colonization in the long term, mainly due to the high volatility of them, which means that this treatment can only be used to neutralize the biological patinas that have already colonized the mural surface. This limitation can be overcome through the encapsulation of the essential oil in intelligent nanoemulsions that prevent the evaporation of the active compound and allow its release to be controlled. In fact it is well known the use of biological compounds such as zein, casein, egg, pectin, alginate and chitosan, to form stable and biocompatible nanocapsules that are being used in medical and nutritional fields to prevent the degradation and evaporation of essential oils and at the same time control their release.
    [0014]
    [0015] In view of the above, and despite the progress made so far, there remains a need to provide effective alternative products for the treatment of contaminated surfaces and especially for the effective prevention of biological colonization, overcoming at least part of the disadvantages of the products of the current state of the art.
    [0016]
    [0017] Surprisingly, the inventors have discovered that it is possible to obtain a nanoemulsion in a simple way by encapsulating essential oils in nanocapsules, formed by a central core based on a zein matrix, in which the essential oil is embedded, and protected by two layers of pectin and casein coating respectively. This new nanoemulsion of nanocapsules is able to provide better results in the treatment and prevention of biological contamination, ensuring high durability and stability of the product at room temperature.
    [0018]
    [0019] Description of the figures
    [0020] Figure 1: optical image and characterization of the nanoemulsion using a Nano Zetasizer ZS system.
    [0021] Figure 2: Characterization of the structure of the nanocapsules by infrared Fourier transform spectroscopy (FTIR) in transmission mode or attenuated total reflectance (ATR)
    [0022] Figure 3: transmission electron microscopy (TEM) images taken after 6 months of aging at room temperature.
    [0023]
    [0024] Description of the invention
    [0025] In a first aspect the invention relates to a process for preparing a nanoemulsion comprising nanocapsules with essential oil. This method, hereinafter, the method of the invention comprises the following steps:
    [0026]
    [0027] (i) preparing a solution of zein and essential oil in water-alcohol (solution A); a solution of casein in water (solution B) and a solution of pectin in water (solution C);
    [0028] (ii) add solution A to the mixture of solutions B and C, or alternatively, add solution A and solution B simultaneously to solution C, and
    [0029] (iii) obtaining a nanoemulsion of nanocapsules.
    [0030]
    [0031] The method of the invention leads to the spontaneous formation of stable nanocapsules due to the physicochemical processes that take place when the solutions A, B and C are combined in the manner defined in step (ii). The resulting nanocapsules are characterized because they comprise:
    [0032] (a) a central core comprising a matrix of zein and an essential oil;
    [0033] (b) a first coating layer of the core comprising casein and
    [0034] (c) a second outer coating layer on the first coating layer comprising pectin.
    [0035]
    [0036] Solution A for practicing the invention is prepared from zein and essential oil which are dissolved in a water-alcohol mixture, where the alcohol is preferably ethanol. The amount of alcohol in solution A can vary between 50% and 99.5% v / vt (total volume / volume), preferably between 55 and 90% v / vt, more preferably between 60 and 85% v / vt and even more preferably between 65 and 75% v / vt. Solution A is prepared by stirring at room temperature. The concentration of zein and essential oil in solution A is not particularly limited. In general the concentration of zein is between 0.1 and 1.5% m / vt, preferably between 0.2 and 1.0% m / vt, more preferably between 0.3 and 0.8% m / vt and even more preferably between 0.4 and 0.6% m / vt (mass / total volume). In general, the concentration of essential oil is between 0.5 and 5% v / vt, preferably between 1.0 and 4.0% v / vt, more preferably between 1.7 and 3.0% v / vt and even more preferably between 2.3 and 2.7% v / vt. Solution B is prepared by dispersing a salt derived from the casein in water, for example sodium caseinate. The dispersion is carried out at room temperature under stirring. Solution C is prepared by dispersing pectin in water. The dispersion is carried out at room temperature under stirring. In a preferred embodiment the pH of solution C is adjusted to a value below pH 4.6 with a base, for example a basic solution, preferably a sodium hydroxide solution.
    [0037] The water used to prepare the solutions is preferably ultrapure water.
    [0038] In the context of the present invention, the ambient temperature should be understood as comprised between 20 ° C and 30 ° C, preferably around 25 ° C.
    [0039]
    [0040] The stage (ii) in which the 3 solutions are brought into contact can be carried out according to two different alternatives.
    [0041] According to a particular embodiment of the process, solutions B and C are first mixed, and solution A is added thereto. The mixture of B and C is preferably made under magnetic stirring and at room temperature. Typically the stirring is carried out for a time of 1 hour at 1000rpm. Solution A is then added to the mixture of solutions B and C. Preferably solution A is added dropwise manually (eg by micro pipette) or automatically (eg by peristaltic pump) and mixing As it turns out, it is subjected to magnetic stirring at room temperature. In general, the stirring is carried out for a time equal to or greater than 30 minutes, preferably for 1 hour, at 1000 rpm.
    [0042] According to another particular embodiment of the process, solutions A and B are added dropwise simultaneously (manually or, more preferably, automatically by peristaltic pumps) to solution C. The resulting mixture is subjected to magnetic stirring at room temperature. In general, the stirring is carried out for a time equal to or greater than 30 minutes, preferably for 1 hour, at 1000 rpm.
    [0043]
    [0044] In the process of the invention the spontaneous formation of the nanocapsules occurs because the concentration of alcohol in the mixture of solutions A, B and C decreases progressively. The essential oil and zein, becoming immiscible in the final solution, form (under agitation) drops of essential oil / zein of nanometric scale. Casein, being an amphiphilic protein, creates a first protective layer that coats the drops of essential oil / zein (through hydrophobic interactions), and provides steric and electrostatic repulsion between the nanoparticles (through the hydrophilic portion). Finally the pectin, having a net charge opposite to the casein, creates a complex of electrostatic nature with it. Being a surfactant substance, the outer layer of pectin stabilizes the nanoparticles in the aqueous solution.
    [0045]
    [0046] The inventors have observed that the formation of the nanocapsules takes place when the concentration of the alcohol in the mixture of the solutions becomes equal to or less than 15% v / vt, preferably equal to or less than 12% v / vt, more preferably equal to or less than 10% v / vt and even more preferably equal to or less than 7% v / vt. The person skilled in the art can calculate in each particular case the volume ratio in which the solutions A, B and C have to be mixed in order to reach said alcohol concentration and achieve the formation spontaneous of the nanoemulsion of the invention.
    [0047]
    [0048] The nanoemulsion of the invention has between 0.05% and 2.00% m / vt (mass / total volume) of zein, preferably between 0.05 and 0.5% m / vt, and more preferably between 0.05 and 0.25% m / vt; between 0.05 and 2.00% v / vt (volume / total volume) of essential oil preferably between 0.10 and 1.00% v / vt, and more preferably between 0.20 and 0.50% v / vt ; between 0.10 and 1.50% m / vt of pectin, preferably between 0.10 and 0.50% m / vt, more preferably between 0.20 and 0.40% m / vt; and between 0.10 and 1.50% m / vt of casein, preferably between 0.10 and 0.50% m / vt, more preferably between 0.20 and 0.40% m / vt. The rest up to 100% corresponds to the aqueous phase (water-alcohol).
    [0049]
    [0050] The essential oil that can be used in the invention can be one or a mixture of two or more essential oils with antimicrobial properties such as, for example, lavender, eucalyptus, oregano, cinnamon, clove and white thyme, rosemary, among others. Its use as an antimicrobial is very attractive because they are natural compounds that can be obtained from a wide variety of plants.
    [0051]
    [0052] Regardless of whether the process is carried out according to one or another particular embodiment, a nanoemulsion of nanocapsules with an average diameter around 300 nm and 200 nm is obtained spontaneously. In a particular embodiment, the average diameter is between 275 nm and 225 nm, preferably around 250 nm. The resulting nanocapsules present high stability which is important to ensure that they maintain their antimicrobial activity for a prolonged time after being applied on the surfaces to be treated.
    [0053]
    [0054] In a preferred embodiment of the method of the invention, once the nanoemulsion of nanocapsules is obtained in step (iii), the pH thereof is adjusted to a value close to the isoelectric point of the zein, preferably between 6.2 and 8, 2, and more preferably between 6.6 and 7.0 and a heat treatment is applied which comprises subjecting the nanoemulsion to a temperature, between 60 and 90 ° C, preferably between 65 and 85 ° C, and more preferably between 70 and 80 ° C. In this way, a nanoemulsion of even more stable nanocapsules is obtained and with a smaller average diameter comprised between 120 nm and 190 nm, preferably between 125 nm and 180 nm, more preferably between 130 nm and 160 nm. In a particular embodiment the mean diameter is equal to or less than 170 nm. In another particular embodiment it is equal to or less than 150 nm. The reduction in size that occurs is due, on the one hand, to the fact that the increase in temperature facilitates the denaturation of proteins, in this case caseinate, and causes its consequent compaction. On the other it is favored that the alcohol present (for example, ethanol) evaporates, causing a subsequent decrease in the solubility of the zein and the essential oil, with the consequent compaction of the nanocapsules.
    [0055] In a particular embodiment the heat treatment is done by placing the nanoemulsion resulting from step (iii) in a water bath. Generally the heat treatment is carried out for a time equal to or greater than 1 hour and under constant agitation.
    [0056]
    [0057] The nanoemulsion obtained in this process constitutes a further aspect of the present invention. The nanoemulsion comprises nanocapsules characterized because they comprise:
    [0058] (a) a central core comprising a matrix of zein and an essential oil;
    [0059] (b) a first coating layer of the core comprising casein and
    [0060] (c) a second outer coating layer on the first coating layer comprising pectin.
    [0061]
    [0062] The nanoemulsion has been characterized by various techniques that have shown that the nanocapsules are spherical, uniform with a polydispersity index between 0.18 and 0.25 (preferably between 0.21 and 0.23), have an average diameter which varies as defined above, and are stable with Z potentials much lower than -30 d.nm, values that also remain fairly constant over time (see Example 1, Table 1).
    [0063]
    [0064] Example 2 shows a comparative test in which a nanoemulsion was prepared following the method of Example 1, but without casein. The results shown in Table 2 of mean diameter, polydispersity index and Z potential indicate that the nanoemulsion nanocapsules, and the nanoemulsion itself are less stable in time than in the case of the present invention. In this regard it can be seen that while the mean diameter of the nanocapsules in Example 2 increases by 25% in Example 1 in two months the average diameter of the nanocapsules of the invention increases by 15% only. This data indicates that the nanoemulsion of the invention causes the latter to remain more compact and therefore more stable. On the other hand the Z potential data reflect the stability of the nanoemulsions. In this sense, although nanocapsules without casein at time 0 have a more negative value in Example 2 than in Example 1, it can be seen that with time the Z potential decreases more rapidly: in particular, in 8 weeks (56 days) the nanocapsules of Example 2 lose a 7.6% charge, while those of the invention with casein lose only 2.3%. This clearly indicates that in the long term the nanoemulsions in the nanoemulsion of the invention remain surprisingly stable for a longer time without precipitating.
    [0065] The antimicrobial essential oil is embedded in the zein matrix, and also protected by the first and second layers of the oxidation and evaporation phenomena, giving it high stability, and safeguarding its antimicrobial properties in the long term. On the other hand, the very nature and arrangement of the compounds of the nanocapsules is advantageous in that it allows the intelligent release of the essential oil, that is, the release only takes place in the presence of microorganisms such as fungi, algae, bacteria and molds. , they synthesize enzymes which depolymerize the compounds of the nanocapsules releasing the essential oil that can then act as an antimicrobial.
    [0066]
    [0067] Therefore in another additional aspect the invention relates to the use of the nanoemulsion of the invention for the antimicrobial treatment of a contaminated inorganic substrate and / or for the prevention of the biological colonization of an inorganic substrate.
    [0068]
    [0069] The use comprises placing the nanoemulsion in contact with the inorganic surface of said substrate. The nanoemulsion of the invention can be applied directly, or it can be previously diluted in a suitable solvent and in the proper proportion in each case. The contacting of the substrate surface and the nanoemulsion is carried out by any conventional method, for example by spraying. The appropriate amount in each case will depend on the particular particular embodiment, such as the type of substrate, the area of the surface of the substrate to be treated, etc.
    [0070]
    [0071] The use of nanoemulsion for the antimicrobial treatment of a substrate involves reducing or eliminating the biological colonization of the substrate. The use of nanoemulsion for the prevention of the biological colonization of a substrate means avoiding the biological colonization of a substrate. The use according to the invention also has the advantage that it does not affect the appearance or the chemical-physical properties of the treated substrate, which is especially advantageous in the case of substrates of cultural interest such as Cultural Heritage.
    [0072] The essential oils, being 100% volatile, do not leave deposits on the treated surface. Therefore, the nanoemulsion can be advantageous and potentially applied to any type of surface muraría, mortar and stone susceptible to the phenomenon of biological colonization.
    [0073]
    [0074] From an economic point of view, the low cost of the used compounds, and of the obtaining procedure allows to obtain an extremely economic product. In addition to being a nanoemulsion obtained from natural, ecological and biodegradable products, guarantees the safety of workers and respect for the environment. The procedure for obtaining the nanoemulsion is simple, and only requires simple agitation at room temperature.
    [0075]
    [0076] The present invention manages to provide a solution to a problem of great importance in the world of the conservation of cultural heritage, of surfaces in general and in particular of mortar surfaces, mortars and sculptures by biodeteriogens.
    [0077]
    [0078] Below are examples to illustrate the invention that should not be considered in any way as limiting the scope of the same.
    [0079]
    [0080] Examples
    [0081] Example 1: Preparation of a nanoemulsion
    [0082]
    [0083] A nanoemulsion was prepared with stable nanocapsules of size less than 150 nm using essential oil extracted from the clove plant (whose fungicidal and bactericidal capacity has been proven in numerous works). For this, solutions A, B and C were prepared as follows:
    [0084]
    [0085] • Solution A : 30mg of zein (type Z3625 Sigma Aldrich Corp) and 150pl of essential oil were dissolved in 5ml of 70% aqueous ethanol solution. The dispersion was subjected to magnetic stirring (1000 rpm) for 150 minutes at 25 ° C;
    [0086] • Solution B : 120 mg of casein (type C8654 Sigma Aldrich Corp) were dissolved in 5 ml of ultrapure water. The dispersion was subjected to magnetic stirring (1000 rpm) for 120 minutes at 25 ° C;
    [0087] • Solution C : 48mg of pectin (type P9135, Sigma-Aldrich Corp.) were dissolved in 20ml of ultrapure water. The dispersion was subjected to magnetic stirring (1000 rpm) for 240 minutes at 25 ° C; Next, the pH of the solution was adjusted to pH 4.0 using a 10mM HCl solution;
    [0088]
    [0089] 1 ml of solution A and 1 ml of solution B were simultaneously poured into 10 ml of solution C using a multichannel pipette (eppendorf). Next, the solution was stirred magnetically for 1 hour, at 1000 rpm and at a temperature of 25 ° C.
    [0090] In this way, an aqueous solution of 6.4% ethanol was obtained and composed of 0.05% m / vt of zein, 0.25% v / vt of essential oil, 0.20% m / vt of casein and 0.20% m / vt of pectin.
    [0091] Finally, the pH of the suspension was adjusted to a value equal to 6.6 by a 10mM NaOH solution. After 60 minutes of magnetic stirring at 1000 rpm and at room temperature, a heat treatment (water bath at 80 ° C) was applied for 60 minutes in order to induce the denaturation of the proteins and the evaporation of ethanol.
    [0092] Characterization of nanoemulsion and nanocapsules:
    [0093] Once the synthesis process is finished, the analytical techniques have been used in order to characterize the nanoemulsion.
    [0094] The analyzes carried out by means of the Nano Zetasizer ZS system (Malvern Instruments, Ltd., Worcestershire, UK) have allowed to verify that the nanoemulsion obtained is composed of nanocapsules, uniform (ie with a polydispersity index (PDI) = 0.229 ± 3 , 4), stable (Z potential: = -47.2 ± 2.6) and with a mean particle size of less than 150 nm (Z size: 133.2 ± 3.4 nm) (see Figure 1).
    [0095] A part of the nanoemulsion was spray dried by using a Nano Spray Dryer B-90 (BUCHI, Labortechnik Ag, Flawill, Switzerland) and the powder obtained was characterized with Fourier transform infrared spectroscopy (FTIR) in ATR mode.
    [0096] As shown in Figure 2, the main peaks of the compounds zein, casein and pectin have been detected in the spectrum of the sprayed sample (lowest spectrum: S1). The absence of the identifying peaks of the essential oil confirms that the active compound is located in the nucleus of the nanocapsules.
    [0097] It should also be noted that, in order to assess its stability over time, the nanoemulsion was analyzed weekly by the Nano Zetasizer team for a period of two months. As can be seen in the following Table 1, the nanoparticles have been shown to have excellent stability over time.
    [0098]
    [0099]
    [0100]
    [0101] Finally, thanks to the images captured through a transmission electron microscope (TEM) it was possible to observe that the nanocapsules, after 6 months of aging, still conserved a perfectly spherical shape (Figure 3, where a) is the image in time zero and b) is the image at 6 months).
    [0102] Comparative Example 2: Preparation of a nanoemulsion
    [0103] A nanoemulsion was prepared following exactly the method described in Example 1 except that solution B did not contain casein and was only ultrapure water. It was then characterized in the same way as in Example 1. The results are shown in the following Table 2:
    [0104]
    [0105]
    权利要求:
    Claims (13)
    [1]
    A process for preparing a nanoemulsion comprising nanocapsules with essential oil comprising the following steps:
    (i) preparing a solution of zein and essential oil in water-alcohol (solution A); a solution of casein in water (solution B) and a solution of pectin in water (solution C);
    (ii) adding solution A to the mixture of solutions B and C, or alternatively adding solution A and solution B simultaneously or sequentially to solution C, and (iii) obtaining a nanoemulsion of nanocapsules.
    [2]
    2. A process according to claim 1 wherein the alcohol of solution A is ethanol.
    [3]
    3. A process according to claim 1 or 2, wherein the alcohol in solution A is present in an amount between 50% and 99.5% v / vt, preferably between 55 and 90% v / vt , more preferably between 60 and 85% v / vt and even more preferably between 65 and 75% v / vt.
    [4]
    4. A process according to any one of claims 1 to 3 wherein the pH of solution C is adjusted to a value less than pH 4.6.
    [5]
    5. A process according to any one of claims 1 to 4 wherein the essential oil is one or more essential oils.
    [6]
    6. A method according to claim 5 wherein the essential oil is clove.
    [7]
    7. A process according to any one of claims 1 to 6 further comprising adjusting the pH of the nanoemulsion of nanocapsules obtained in step (iii) to a value between 6.2 and 8.2 and applying a heat treatment comprising subject the nanoemulsion to a temperature between 60 and 90 ° C.
    [8]
    8. A process according to claim 7 wherein the pH value is between 6.6 and 7.0.
    [9]
    9. A method according to claim 7 or 8 wherein the temperature is between 70 and 80 ° C.
    [10]
    10. A nanoemulsion comprising nanocapsules characterized in that they comprise:
    (a) a central core comprising a matrix of zein and an essential oil;
    (b) a first coating layer of the central core comprising casein and (c) a second outer coating layer on the first coating layer comprising pectin.
    [11]
    11. A nanoemulsion according to claim 10, wherein the nanocapsules have a mean diameter of between 300 nm and 200 nm.
    [12]
    12. A nanoemulsion according to claim 10, wherein the nanocapsules have a mean diameter between 120 nm and 190 nm.
    [13]
    13. Use of the nanoemulsion according to any one of claims 10 to 12 for the antimicrobial treatment of a contaminated substrate and / or for the prevention of the biological colonization of an inorganic substrate.
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