Compositions and methods

Abstract

Disclosed are compositions comprising extracts of kale and a number of other plants in synergistic mixtures. Methods of forming metal nanoparticles and nanoparticles formed using the methods are disclosed.

Description

Technical Field

[0001] This invention relates to a composition. The invention also relates to a method for preparing the composition, metal nanoparticles, a method for preparing the metal nanoparticles using the composition, and their applications. Background Technology

[0002] Metal nanoparticles are generally defined as particles with a diameter of less than 100 nm. These products have a wide range of commercial applications, including in pharmaceuticals and electronics.

[0003] Over the past 20 years, various processes, including chemical and physical manufacturing routes, have been developed to produce metal nanoparticles. However, some of these methods have raised environmental and safety concerns. There is a desire to manufacture these products in a more environmentally friendly way.

[0004] David L. Johnson et al. described the biosynthesis, purification, and characterization of silver nanoparticles using kaempferia galanga in Micro & Nano Letters, 2020, 15(2), 110-113. This process uses only kaempferia galanga as a source of antioxidants. The proportion of antioxidants used and the bioreactor used in this process differ from those of the present invention. In particular, the reaction efficiency is lower, requiring 6 hours at 37°C. Furthermore, different washing solutions are used for centrifugation, and the separation techniques are also different. Specifically, the process uses AgNO3 as the silver salt—nitrate leaching into water sources is known to be environmentally detrimental.

[0005] Mohammad Pourassan Moghadam et al. described gold nanoparticles based on watercress, their biosynthesis, formation mechanism, and in vitro biocompatibility in Micro & Nano Letters, 2014, 9(5), 345-350. The process used to produce gold nanoparticles was HAuCl4·3H2O, and watercress was used solely as a source of antioxidants. The bioreactor used differed from that of this invention and was less efficient.

[0006] US2012 / 0055873 describes a green synthesis of nano-metals using plant extracts. The process uses commercially available plant extracts (such as green tea / coffee) to produce nanoparticles. The main antioxidants used are polyphenols and caffeine, and the bioreactor differs from that of this invention. Furthermore, the process also uses AgNO3 as a source of silver ions.

[0007] US2011 / 0110723 describes a green synthesis of nanometals using fruit extracts. The process uses fruit (sugar-rich fruit) as a source of antioxidants, and the bioreactor differs from that of this invention. Furthermore, this process also uses AgNO3 as a source of silver ions. Summary of the Invention

[0008] According to one aspect of the invention, a composition comprising an extract obtained from:

[0009] (a) Kale (Brassica oleracea Acephala group); and

[0010] (b) at least one other plant selected from the following:

[0011] (i) Artichoke (Cyanara cardunculus),

[0012] (ii) Red cabbage (Brassica oleracea Capitata group var.rubra),

[0013] (iii)Origanum vulgare,

[0014] (iv) Rosemary (Salvia cormanus),

[0015] (v) Sage (Salvia officinalis),

[0016] (vi) Watercress (Nasturtium officinale),

[0017] (vii) Dog Rose (Rosa canina)

[0018] (viii) Peppermint (Mentha spp.),

[0019] (ix) Thyme (Thymus spp.),

[0020] (x) Basil (Osimum basilicum), and

[0021] (xi) Spinach (Spinacia oleracea).

[0022] According to another aspect of the present invention, a method for producing the composition of the present invention is provided, the method comprising one or more of the following steps:

[0023] (a) Combining plants to provide preparations of plants as defined herein; and

[0024] (b) Extracting bioactive components from the combined preparations using solvents.

[0025] According to another aspect of the present invention, a method for producing metal nanoparticles is provided, the method comprising:

[0026] (a) Provides dissolved metal ions; and

[0027] (b) Contact the dissolved metal ions with the composition of the present invention;

[0028] This allows dissolved metal ions to be reduced to form metal nanoparticles.

[0029] According to another aspect of the present invention, metal nanoparticles that are obtained or obtainable by the method of the present invention are provided.

[0030] According to another aspect of the invention, a metal nanoparticle having a coated biopolymer layer is provided.

[0031] According to another aspect of the present invention, a product comprising the metal nanoparticles of the present invention is provided. Brief description of the attached diagram

[0033] Figure 1 This is a process flow diagram showing the preferred method for producing the composition of the present invention and the metal nanoparticles of the present invention;

[0034] Figure 1A This is a process flow diagram showing an alternative preferred method for producing the composition of the present invention and the metal nanoparticles of the present invention;

[0035] Figure 2 The Pareto front analysis demonstrates the sensitivity of various constraint configurations for multiple compositions of the present invention.

[0036] Figure 3 The Pareto optimal frontier analysis results for nine blend compositions of the present invention are shown (antioxidant composition vs. cost per 100g of blend);

[0037] Figure 4 The Pareto optimal frontier analysis results show the relative antioxidant activity of the nine blend compositions of the present invention relative to paddy field mustard.

[0038] Figure 5 The composition of nine blend compositions of the present invention is shown;

[0039] Figure 6 The composition of five preferred blends of the present invention, subjected to the DPPH test described in Example 2, is shown;

[0040] Figure 7 The results show the variation of DPPH inhibition of the preferred composition of the present invention with antioxidant concentrations (concentrations of watercress and crested kale);

[0041] Figure 8 The variation of DPPH inhibition of the five preferred blend compositions of the present invention as a function of antioxidant concentration (blend) as tested in Example 2 is shown;

[0042] Figure 9 The DPPH inhibition of ascorbic acid was shown as a function of concentration;

[0043] Figure 10 Linear regression analysis showed the DPPH inhibition of ascorbic acid as a function of concentration.

[0044] Figure 11 Linear regression analysis showed that DPPH inhibition of paddy mustard was influenced by concentration.

[0045] Figure 12 Linear regression analysis showed that DPPH inhibition in curly kale varied with concentration.

[0046] Figure 13 It shows, as Figure 6 The composition of the present invention shown in "Blend 1" exhibits linear regression of DPPH inhibition as a function of concentration;

[0047] Figure 14 It shows, as Figure 6 The DPPH inhibition of the composition of the present invention shown in "Blend 2" is linearly regressed as a function of concentration;

[0048] Figure 15 It shows, as Figure 6 The DPPH inhibition of the composition of the present invention shown in "Blend 3" is linearly regressed as a function of concentration.

[0049] Figure 16 It shows, as Figure 6 The DPPH inhibition of the composition of the present invention shown in "Blend 4" is linearly regressed as a function of concentration.

[0050] Figure 17 It shows, as Figure 6 The "blend 5" in the figure shows the linear regression of the DPPH inhibition of the composition of the present invention as a function of concentration;

[0051] Figure 18 The UV-Vis spectrophotometer absorbance as a function of wavelength is shown for the reaction of Example 4 carried out at 35°C at t = 55 min.

[0052] Figure 19The UV-Vis spectrophotometer absorbance as a function of wavelength from 0 to 55 minutes is shown to illustrate the kinetics of the reaction in Example 4 carried out at 50°C;

[0053] Figure 20 The UV-Vis spectrophotometer absorbance as a function of wavelength from 0 to 55 minutes is shown to illustrate the kinetics of the reaction in Example 4 carried out at 60°C.

[0054] Figure 21 The UV-Vis spectrophotometer absorbance as a function of wavelength from 0 to 55 minutes is shown to illustrate the kinetics of the reaction in Example 4 carried out at 70°C.

[0055] Figure 22 The UV-Vis spectrophotometer absorbance as a function of wavelength is shown over time from 4 to 6.5 minutes to illustrate the kinetics of the reaction in Example 4 carried out at 85°C;

[0056] Figure 23 The UV-Vis spectrophotometer absorbance as a function of wavelength at t = 55 min is shown to compare the reaction kinetics of Example 4 at 50, 60 and 70 °C.

[0057] Figure 24 The UV-Vis spectrophotometer peak absorbance as a function of time at t = 55 min is shown to compare the reaction kinetics of Example 4 at 50, 60, and 70 °C.

[0058] Figure 25 The UV-Vis spectrophotometer absorbance as a function of wavelength is shown to illustrate the kinetics of the reaction in Example 4 at different blend concentrations;

[0059] Figure 26 These are scanning electron microscope (SEM) images of the organic polymer and metal nanoparticles prepared according to Example 4;

[0060] Figure 27 These are scanning electron microscope (SEM) images of the organic polymer and metal nanoparticles prepared according to Example 4;

[0061] Figure 28 These are scanning electron microscope (SEM) images of the organic polymer and metal nanoparticles prepared according to Example 4;

[0062] Figure 29 The image shows a scanning electron microscope (SEM) image of the metal nanoparticles prepared according to Example 4.

[0063] Figure 30The image shows a scanning electron microscope (SEM) image of the metal nanoparticles prepared according to Example 4.

[0064] Figure 31 The image shows a scanning electron microscope (SEM) image of the metal nanoparticles prepared according to Example 4.

[0065] Figure 32 The image shows a scanning electron microscope (SEM) image of the metal nanoparticles prepared according to Example 4.

[0066] Figure 33 The image shows a scanning electron microscope (SEM) image of the metal nanoparticles prepared according to Example 4.

[0067] Figure 34 The image shows a scanning electron microscope (SEM) image of the metal nanoparticles prepared according to Example 4.

[0068] Figure 35 The image shows a scanning electron microscope (SEM) image of the metal nanoparticles prepared according to Example 4.

[0069] Figure 36 The image shows a scanning electron microscope (SEM) image of the metal nanoparticles prepared according to Example 4.

[0070] Figure 37 The image shows a scanning electron microscope (SEM) image of the metal nanoparticles prepared according to Example 4.

[0071] Figure 38 The image shows a scanning electron microscope (SEM) image of the metal nanoparticles prepared according to Example 4.

[0072] Figure 39 These are scanning electron microscope (SEM) images of the organic polymer and metal nanoparticles prepared according to Example 4;

[0073] Figure 40 The image shows a scanning electron microscope (SEM) image of the metal nanoparticles prepared according to Example 4.

[0074] Figure 41 The image shows a scanning electron microscope (SEM) image of the metal nanoparticles prepared according to Example 4.

[0075] Figure 42 The image shows a scanning electron microscope (SEM) image of the metal nanoparticles prepared according to Example 4.

[0076] Figure 43 The image shows a scanning electron microscope (SEM) image of the metal nanoparticles prepared according to Example 4.

[0077] Figure 44This is an energy-dispersive X-ray spectral image of the metal nanoparticles prepared according to Example 4;

[0078] Figure 45 This is an energy-dispersive X-ray spectral image of the metal nanoparticles prepared according to Example 4;

[0079] Figure 46 This is an energy-dispersive X-ray spectral image of the metal nanoparticles prepared according to Example 4;

[0080] Figure 47 This is an energy-dispersive X-ray spectral image of the metal nanoparticles prepared according to Example 4;

[0081] Figure 48 This is an energy-dispersive X-ray spectral image of the metal nanoparticles prepared according to Example 4;

[0082] Figure 49 This is an energy-dispersive X-ray spectral image of the metal nanoparticles prepared according to Example 4;

[0083] Figure 50 This is an energy-dispersive X-ray spectral image of the metal nanoparticles prepared according to Example 4;

[0084] Figure 51 This is an energy-dispersive X-ray spectral image of the metal nanoparticles prepared according to Example 4;

[0085] Figure 52 This is an energy-dispersive X-ray spectral image of the metal nanoparticles prepared according to Example 4;

[0086] Figure 53 This is an energy-dispersive X-ray spectral image of the metal nanoparticles prepared according to Example 4;

[0087] Figure 54 This is an energy-dispersive X-ray spectral image of the metal nanoparticles prepared according to Example 4;

[0088] Figure 55 This is an energy-dispersive X-ray spectral image of the metal nanoparticles prepared according to Example 4;

[0089] Figure 56 The energy dispersive X-ray spectral images of the metal nanoparticles prepared according to Example 4 show evidence of a biopolymer protective layer (carbon + oxygen) on the silver nanoparticles.

[0090] Figure 57 The energy dispersive X-ray spectral images of the metal nanoparticles prepared according to Example 4 show evidence of a biopolymer protective layer (carbon) on the silver nanoparticles.

[0091] Figure 58The energy dispersive X-ray spectral images of the metal nanoparticles prepared according to Example 4 show evidence of a biopolymer protective layer (oxygen) on the silver nanoparticles.

[0092] Figure 59 These are scanning electron microscope (SEM) images showing the outlines of silver nanoparticles on the sampling area produced according to Example 4;

[0093] Figure 60 These are scanning electron microscope (SEM) images showing silver nanoparticles on the sampling area produced according to Example 4;

[0094] Figure 61 This is a graph showing the relationship between the frequency and diameter of nanoparticles. Figure 59 Particle size distribution of silver nanoparticles in the sampling region;

[0095] Figure 62 This is a graph showing the relationship between the frequency and diameter of nanoparticles, displaying the overall particle size distribution of silver nanoparticles across multiple sampling regions;

[0096] Figure 63 The sample color is shown as the blend concentration increases;

[0097] Figure 64 The color of the samples taken at different times (every 5 minutes) during a 55-minute reaction at 70°C is shown.

[0098] Figure 65 The comparison between the blend based on cruciferous kale (Group 1) and the blend based on paddy mustard (Group 6) according to Comparative Example 1 is shown;

[0099] Figure 66 The composition of the paddy field mustard-based blend composition according to Comparative Example 1 is shown;

[0100] Figure 67 The UV / VIS spectrum of silver nanoparticles produced according to batch S1 of Example 5;

[0101] Figure 68 The UV / VIS spectrum of silver nanoparticles produced according to batch S2 of Example 5;

[0102] Figure 69 The UV / VIS spectrum of silver nanoparticles produced according to batch S3 of Example 5;

[0103] Figure 70 The UV / VIS spectrum of silver nanoparticles produced according to batch S4 of Example 5;

[0104] Figure 71The UV / VIS spectra of gold nanoparticles produced according to batch S1 of Examples 6 and 7;

[0105] Figure 72 The UV / VIS spectra of gold nanoparticles produced according to batch S2 of Examples 6 and 7;

[0106] Figure 73 The UV / VIS spectra of gold nanoparticles produced in batch S3 according to Examples 6 and 7;

[0107] Figure 74 This is a graph showing the relationship between the frequency of nanoparticles and their diameter, illustrating the overall particle size distribution of the gold nanoparticles prepared according to Examples 6 and 7.

[0108] Figure 75 These are scanning electron microscope (SEM) images of gold nanoparticles prepared according to Examples 6 and 7;

[0109] Figure 76 These are scanning electron microscope (SEM) images of gold nanoparticles prepared according to Examples 6 and 7;

[0110] Figure 77 These are scanning electron microscope (SEM) images of gold nanoparticles prepared according to Examples 6 and 7;

[0111] Figure 78 These are scanning electron microscope (SEM) images of gold nanoparticles prepared according to Examples 6 and 7;

[0112] Figure 79 These are scanning electron microscope (SEM) images of gold nanoparticles prepared according to Examples 6 and 7;

[0113] Figure 80 These are scanning electron microscope (SEM) images of gold nanoparticles prepared according to Examples 6 and 7;

[0114] Figure 81 These are scanning electron microscope (SEM) images of gold nanoparticles prepared according to Examples 6 and 7;

[0115] Figure 82 These are scanning electron microscope (SEM) images of gold nanoparticles prepared according to Examples 6 and 7;

[0116] Figure 83 These are energy-dispersive X-ray spectral images of gold nanoparticles prepared according to Examples 6 and 7;

[0117] Figure 84 These are energy-dispersive X-ray spectral images of gold nanoparticles prepared according to Examples 6 and 7;

[0118] Figure 85 The images are energy-dispersive X-ray spectra of metal nanoparticles prepared according to Examples 6 and 7, depicting gold atoms on the nanoparticles.

[0119] Figure 86 The images are energy-dispersive X-ray spectra of metal nanoparticles prepared according to Examples 6 and 7, depicting carbon atoms on the biopolymer layer that capping the nanoparticles.

[0120] Figure 87 The images are energy-dispersive X-ray spectra of the metal nanoparticles prepared according to Examples 6 and 7, depicting oxygen atoms on the biopolymer layer coating the nanoparticles.

[0121] Figure 88 These are scanning electron microscope (SEM) images of gold nanoparticles prepared according to Examples 6 and 7; and

[0122] Figure 89 The images show the energy-dispersive X-ray spectra of gold nanoparticles prepared according to Examples 6 and 7. Invention Details

[0124] definition

[0125] In this specification, the term "extract" refers to a substance obtained by extraction from a raw material. Typically, the raw material is a naturally occurring substance. In one embodiment, the raw material is a plant, examples of which are described herein.

[0126] In this specification, the term "bioactive ingredient" refers to a substance obtained from a natural source (usually an extract as defined above, preferably a plant-based extract) that can act on metal ions to produce the metal nanoparticles described herein.

[0127] In one embodiment, the bioactive ingredient is a bioreducing agent (i.e., a substance obtained from a natural source, typically plant-based), as described herein, capable of reducing metal ions to produce metal nanoparticles.

[0128] In one embodiment, the bioactive ingredient is a biocoating agent or encapsulating agent. In one embodiment, the biocoating agent or encapsulating agent is a carbohydrate.

[0129] In this specification, the term "antioxidant" refers to a substance that inhibits oxidation. In one embodiment, an antioxidant is a substance capable of terminating a free radical-based chain reaction. In one embodiment, the antioxidant is a naturally occurring antioxidant, examples of which are described herein. In some respects, the term "antioxidant" is synonymous with "bioreducing agent" as defined above.

[0130] In this specification, "nanoparticle" refers to a particle of matter with a diameter between 1 nm and 1 μm. In one embodiment, the diameter of the nanoparticle is between 1 nm and 500 nm. In one embodiment, the diameter of the nanoparticle is between 1 nm and 200 nm. In one embodiment, the diameter of the nanoparticle is between 1 nm and 100 nm. In one embodiment, the diameter of the nanoparticle is between 1 nm and 50 nm. In one embodiment, the diameter of the nanoparticle is between 1 nm and 20 nm. In one embodiment, the diameter of the nanoparticle is measured using ultraviolet-visible (UV-Vis) spectroscopy. In one embodiment, the diameter of the nanoparticle is measured using scanning electron microscopy (SEM). In one embodiment, the diameter of the nanoparticle is measured using transmission electron microscopy (TEM).

[0131] Advantages and amazing discoveries

[0132] The inventors have surprisingly discovered that when the compositions of the present invention are used as reducing agents in the preparation of metal nanoparticles from the corresponding metal ions, they exhibit higher activity than expected from additive reduction activity (e.g., when tested using the DPPH assay), thus indicating a synergistic relationship between the different plants used in the compositions.

[0133] This remarkable discovery enables the production of metal nanoparticles using a method with a significantly lower environmental impact than known processes, including those described in the prior art above. Because the compositions of this invention possess far greater antioxidant activity (and therefore are effective as bioreducing agents) and lower cost than extracts from single plants, and exhibit the synergistic effects described above, the reduction of metal ions to metal nanoparticles requires far less material and energy. This is particularly important when the process is scaled up.

[0134] The method for producing metal nanoparticles according to the present invention, because it uses a bioreducing agent, enables the use of reagents that are less toxic and more environmentally friendly compared to current manufacturing routes. It also minimizes waste generation throughout the process by including a recycling loop around crystallization, thereby maximizing process conversion at the point of metal ion introduction and avoiding the release of large amounts of metal ions into the environment. Similarly, the addition of a recycling loop around the antioxidant extraction unit reduces waste and minimizes environmental impact.

[0135] Surprisingly, it was also found that forming nanoparticles according to the method of the present invention results in the formed nanoparticles having a protective bio-layer on them (as described herein). This protects the nanoparticles and eliminates the need for additional coating agents.

[0136] Composition

[0137] The compositions of this invention are made from plant extracts. Typically, these plants are naturally occurring varieties. However, in an alternative, the plants can be genetically modified plants. In another alternative, the plants can be genetically edited, for example, using a technology such as CRISPR-Cas9.

[0138] In one aspect of the invention, a composition comprising an extract obtained from:

[0139] (a) Kale (Brassica oleracea Acephala group); and

[0140] (b) At least one other plant capable of producing bioreducing agents.

[0141] Many plants can produce antioxidants. Examples of such plants include, but are not limited to, kale (Brassica oleracea Acephala group), artichoke (Cyanara cardunculus), red cabbage (Brassica oleracea Capitata group var. rubra), oregano (Origanum vulgare), rosemary (Salvia cormanus), sage (Salvia officinalis), watercress (Nasturtium officinale), dog rose (Rosa canina), mint (Mentha spp.), especially spearmint (Mentha spicata) and peppermint (Menthax piperita), thyme (Thymus spp., especially Thymus cirtodorus, Thymus hera-barona, Thymus praecox, Thymus pseudolanugionsus, Thymus seryllum and Thymus vulgaris), basil (Osimum basilicum), and spinach (Spinacia oleracea).

[0142] Therefore, in one embodiment, a composition comprising an extract derived from: (a) kale (Brassica oleracea Acephala group); and (b) at least one other plant selected from: (i) artichoke (Cyanara cardunculus), (ii) red cabbage (Brassica oleracea Capitata group var. rubra), (iii) oregano (Origanum vulgare), (iv) rosemary (Salvia cormanus), (v) sage (Salvia officinalis), (vi) watercress (Nasturtium officinale), (vii) dog rose (Rosacanina), (viii) mint (Mentha spp.), (ix) thyme (Thymus spp.), (x) basil (Osimum basilicum), and (xi) spinach (Spinacia oleracea).

[0143] In one embodiment, a composition comprising an extract derived from:

[0144] (a) Kale (Brassica oleracea Acephala group); and

[0145] (b) at least one other plant selected from the following: (i) artichoke (Cyanara cardunculus), (ii) red cabbage (Brassica oleracea Capitata group var. rubra), (iii) oregano (Origanum vulgare), (iv) rosemary (Salvia cormanus), and (v) watercress (Nasturtium officinale).

[0146] In one embodiment, a composition comprising an extract derived from:

[0147] (a) Kale (Brassica oleracea var. Acephala group); and

[0148] (b) At least two other plants selected from the following:

[0149] (i) Artichoke (Cyanara cardunculus),

[0150] (ii) Red cabbage (Brassica oleracea var.Capitata group var.rubra),

[0151] (iii)Origanum vulgare,

[0152] (iv) Rosemary (Salvia cormanus),

[0153] (v) Watercress (Nasturtium officinale), and

[0154] (vi) Sage (Salvia officinalis).

[0155] In one implementation, an extract derived from:

[0156] (a) Kale (Brassica oleracea var. Acephala group); and

[0157] (b) At least two other plants selected from the following:

[0158] (i) Artichoke (Cyanara cardunculus),

[0159] (ii) Red cabbage (Brassica oleracea var.Capitata group var.rubra),

[0160] (iii)Origanum vulgare,

[0161] (iv) Rosemary (Salvia cormanus), and

[0162] (v) Watercress (Nasturtium officinale).

[0163] In one implementation, an extract derived from:

[0164] (a) Kale (Brassica oleracea var. Acephala group); and

[0165] (b) At least two other plants selected from the following:

[0166] (i)Origanum vulgare,

[0167] (ii) Rosemary (Salvia cormanus),

[0168] (iii) Watercress (Nasturtium officinale), and

[0169] (iv) Sage (Salvia officinalis).

[0170] In one embodiment, a composition comprising an extract derived from:

[0171] (a) Kale (Brassica oleracea var. Acephala group);

[0172] (b) Artichoke (Cyanara cardunculus); and

[0173] (c) Red cabbage (Brassica oleracea var.Capitata group var.rubra).

[0174] In one embodiment, a composition comprising an extract is provided, said extract being derived from:

[0175] (a) Kale (Brassica oleracea var. Acephala group);

[0176] (b) Artichoke (Cyanara cardunculus); and

[0177] (c)Origanum vulgare.

[0178] In one embodiment, a composition comprising an extract derived from:

[0179] (a) Kale (Brassica oleracea var. Acephala group);

[0180] (b) Red cabbage (Brassica oleracea var. Capitata group var. rubra); and

[0181] (c)Origanum vulgare.

[0182] In one embodiment, a composition comprising an extract derived from:

[0183] (a) Kale (Brassica oleracea var. Acephala group); and

[0184] (b) At least two other plants selected from the following:

[0185] (i) Artichoke (Cyanara cardunculus),

[0186] (ii) Red cabbage (Brassica oleracea var.Capitata group var.rubra),

[0187] (iii)Origanum vulgare,

[0188] (iv) Rosemary (Salvia cormanus), and

[0189] (v) Watercress (Nasturtium officinale).

[0190] In one embodiment, a composition comprising an extract derived from:

[0191] (a) Kale (Brassica oleracea var. Acephala group); and

[0192] (b) At least three other plants selected from the following:

[0193] (i) Artichoke (Cyanara cardunculus),

[0194] (ii) Red cabbage (Brassica oleracea var.Capitata group var.rubra),

[0195] (iii)Origanum vulgare,

[0196] (iv) Rosemary (Salvia cormanus), and

[0197] (v) Watercress (Nasturtium officinale).

[0198] In one embodiment, a composition comprising an extract obtained from:

[0199] (a) Kale (Brassica oleracea var. Acephala group);

[0200] (b) Red cabbage (Brassica oleracea var.Capitata group var.rubra);

[0201] (c) Oregano (Origanum vulgare); and

[0202] (d) Rosemary (Salvia cormanus).

[0203] In one embodiment, a composition comprising an extract obtained from:

[0204] (a) Kale (Brassica oleracea var. Acephala group); and

[0205] (b) At least three other plants selected from the following:

[0206] (i) Artichoke (Cyanara cardunculus),

[0207] (ii) Red cabbage (Brassica oleracea var. Capitata group var. rubra), and

[0208] (iii) Rosemary (Salvia cormanus).

[0209] In one embodiment, a composition comprising an extract derived from:

[0210] (a) Kale (Brassica oleracea var. Acephala group); and

[0211] (b) At least four other plants selected from the following:

[0212] (i) Artichoke (Cyanara cardunculus),

[0213] (ii) Red cabbage (Brassica oleracea var.Capitata group var.rubra),

[0214] (iii)Origanum vulgare,

[0215] (iv) Rosemary (Salvia cormanus), and

[0216] (v) Watercress (Nasturtium officinale).

[0217] In one embodiment, a composition comprising an extract derived from:

[0218] (a) Kale (Brassica oleracea var. Acephala group);

[0219] (b) Artichoke (Cyanara cardunculus);

[0220] (c)Origanum vulgare;

[0221] (d) Rosemary (Salvia cormanus); and

[0222] (e) Watercress (Nasturtium officinale).

[0223] In one embodiment, a composition comprising an extract derived from:

[0224] (a) Kale (Brassica oleracea var. Acephala group); and

[0225] (b) Red cabbage (Brassica oleracea var.Capitata group var.rubra);

[0226] (c)Origanum vulgare;

[0227] (d) Rosemary (Salvia cormanus); and

[0228] (e) Watercress (Nasturtium officinale).

[0229] The compositions of the present invention typically contain an extract of kale (Brassica oleracea var. Acephala group). In one embodiment, the composition contains at least 5% by mass of kale extract as a percentage of the total mass of the composition. In one embodiment, the composition contains at least 10% by mass of kale extract as a percentage of the total mass of the composition. In one embodiment, the composition contains at least 15% by mass of kale extract as a percentage of the total mass of the composition. In one embodiment, the composition contains at least 20% by mass of kale extract as a percentage of the total mass of the composition. In one embodiment, the composition contains at least 25% by mass of kale extract as a percentage of the total mass of the composition. In one embodiment, the composition contains at least 30% by mass of kale extract as a percentage of the total mass of the composition. In one embodiment, the composition contains at least 35% by mass of kale extract as a percentage of the total mass of the composition. In one embodiment, the composition contains at least 40% by mass of kale extract as a percentage of the total mass of the composition. In one embodiment, the composition contains at least 45% by mass of kale extract as a percentage of the total mass of the composition. In one embodiment, the composition contains at least 50% by mass of kale extract as a percentage of the total mass of the composition. In one embodiment, the composition contains at least 55% by mass of kale extract as a percentage of the total mass of the composition. In one embodiment, the composition contains at least 60% by mass of kale extract as a percentage of the total mass of the composition. In one embodiment, the composition contains at least 65% by mass of kale extract as a percentage of the total mass of the composition. In one embodiment, the composition contains at least 70% by mass of kale extract as a percentage of the total mass of the composition. In one embodiment, the composition contains at least 75% by mass of kale extract as a percentage of the total mass of the composition. In one embodiment, the composition contains at least 80% by mass of kale extract as a percentage of the total mass of the composition.

[0230] In one embodiment, the composition contains up to 95% by mass of kale extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 90% by mass of kale extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 85% by mass of kale extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 80% by mass of kale extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 75% by mass of kale extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 70% by mass of kale extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 65% by mass of kale extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 60% by mass of kale extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 55% by mass of kale extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 50% by mass of kale extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 45% by mass of kale extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 40% by mass of kale extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 35% by mass of kale extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 30% by mass of kale extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 25% by mass of kale extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 20% by mass of kale extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 15% by mass of kale extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 10% by mass of kale extract as a percentage of the total mass of the composition.

[0231] In one embodiment, the composition contains 5% to 95% by mass of kale extract as a percentage of the total mass of the composition. In one embodiment, the composition contains 10% to 90% by mass of kale extract as a percentage of the total mass of the composition. In one embodiment, the composition contains 20% to 95% by mass of kale extract as a percentage of the total mass of the composition.

[0232] In one embodiment, the composition contains 30% to 90% by mass of kale extract as a percentage of the total mass of the composition. In one embodiment, the composition contains 35% to 85% by mass of kale extract as a percentage of the total mass of the composition. In one embodiment, the composition contains 40% to 80% by mass of kale extract as a percentage of the total mass of the composition.

[0233] In one embodiment, the composition contains 45% to 75% by mass of kale extract as a percentage of the total mass of the composition. In another embodiment, the composition contains 50% to 70% by mass of kale extract as a percentage of the total mass of the composition.

[0234] In one embodiment, the composition of the present invention comprises an extract of artichoke (Cyanara cardunculus). In one embodiment, the composition contains at least 1% by mass of artichoke extract as a percentage of the total mass of the composition. In one embodiment, the composition contains at least 2.5% by mass of artichoke extract as a percentage of the total mass of the composition. In one embodiment, the composition contains at least 5% by mass of artichoke extract as a percentage of the total mass of the composition. In one embodiment, the composition contains at least 7.5% by mass of artichoke extract as a percentage of the total mass of the composition. In one embodiment, the composition contains at least 10% by mass of artichoke extract as a percentage of the total mass of the composition. In one embodiment, the composition contains at least 12.5% ​​by mass of artichoke extract as a percentage of the total mass of the composition. In one embodiment, the composition contains at least 15% by mass of artichoke extract as a percentage of the total mass of the composition.

[0235] In one embodiment, the composition contains up to 40% by mass of artichoke extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 35% by mass of artichoke extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 30% by mass of artichoke extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 25% by mass of artichoke extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 20% by mass of artichoke extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 15% by mass of artichoke extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 12.5% ​​by mass of artichoke extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 10% by mass of artichoke extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 7.5% by mass of artichoke extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 5% by mass of artichoke extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 2.5% by mass of artichoke extract as a percentage of the total mass of the composition. In another embodiment, the composition contains up to 1% by mass of artichoke extract as a percentage of the total mass of the composition.

[0236] In one embodiment, the composition contains 0.5% to 40% by mass of artichoke extract as a percentage of the total mass of the composition. In another embodiment, the composition contains 10% to 90% by mass of artichoke extract as a percentage of the total mass of the composition. In yet another embodiment, the composition contains 1% to 35% by mass of artichoke extract as a percentage of the total mass of the composition.

[0237] In one embodiment, the composition contains 2.5% to 30% by mass of artichoke extract as a percentage of the total mass of the composition. In another embodiment, the composition contains 5% to 25% by mass of artichoke extract as a percentage of the total mass of the composition. In yet another embodiment, the composition contains 10% to 20% by mass of artichoke extract as a percentage of the total mass of the composition.

[0238] In one embodiment, the composition of the present invention comprises an extract of red cabbage (Brassica oleracea Capitatagroup var. rubra). In one embodiment, the composition contains at least 1% by mass of red cabbage extract as a percentage of the total mass of the composition. In one embodiment, the composition contains at least 2.5% by mass of red cabbage extract as a percentage of the total mass of the composition. In one embodiment, the composition contains at least 5% by mass of red cabbage extract as a percentage of the total mass of the composition. In one embodiment, the composition contains at least 10% by mass of red cabbage extract as a percentage of the total mass of the composition. In one embodiment, the composition contains at least 15% by mass of red cabbage extract as a percentage of the total mass of the composition. In one embodiment, the composition contains at least 20% by mass of red cabbage extract as a percentage of the total mass of the composition. In one embodiment, the composition contains at least 25% by mass of red cabbage extract as a percentage of the total mass of the composition.

[0239] In one embodiment, the composition contains up to 50% by mass of red cabbage extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 45% by mass of red cabbage extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 40% by mass of red cabbage extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 35% by mass of red cabbage extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 30% by mass of red cabbage extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 25% by mass of red cabbage extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 20% by mass of red cabbage extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 15% by mass of red cabbage extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 10% by mass of red cabbage extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 5% by mass of red cabbage extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 2.5% by mass of red cabbage extract as a percentage of the total mass of the composition. In another embodiment, the composition contains up to 1% by mass of red cabbage extract as a percentage of the total mass of the composition.

[0240] In one embodiment, the composition contains 0.5% to 50% by mass of red cabbage extract as a percentage of the total mass of the composition. In one embodiment, the composition contains 1% to 40% by mass of red cabbage extract as a percentage of the total mass of the composition. In one embodiment, the composition contains 1% to 35% by mass of red cabbage extract as a percentage of the total mass of the composition. In one embodiment, the composition contains 2.5% to 30% by mass of red cabbage extract as a percentage of the total mass of the composition. In one embodiment, the composition contains 5% to 25% by mass of red cabbage extract as a percentage of the total mass of the composition. In one embodiment, the composition contains 10% to 20% by mass of red cabbage extract as a percentage of the total mass of the composition.

[0241] In one embodiment, the composition of the present invention comprises oregano (Origanum vulgare) extract. In one embodiment, the composition contains at least 0.5% by mass of oregano extract as a percentage of the total mass of the composition. In one embodiment, the composition contains at least 1% by mass of oregano extract as a percentage of the total mass of the composition. In one embodiment, the composition contains at least 2% by mass of oregano extract as a percentage of the total mass of the composition. In one embodiment, the composition contains at least 3% by mass of oregano extract as a percentage of the total mass of the composition. In one embodiment, the composition contains at least 5% by mass of oregano extract as a percentage of the total mass of the composition. In one embodiment, the composition contains at least 7.5% by mass of oregano extract as a percentage of the total mass of the composition. In one embodiment, the composition contains at least 10% by mass of oregano extract as a percentage of the total mass of the composition.

[0242] In one embodiment, the composition contains up to 30% by mass of oregano extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 25% by mass of oregano extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 20% by mass of oregano extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 15% by mass of oregano extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 10% by mass of oregano extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 5% by mass of oregano extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 2.5% by mass of oregano extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 1% by mass of oregano extract as a percentage of the total mass of the composition.

[0243] In one embodiment, the composition contains 0.5% to 30% by mass of oregano extract as a percentage of the total mass of the composition. In one embodiment, the composition contains 1% to 20% by mass of oregano extract as a percentage of the total mass of the composition. In one embodiment, the composition contains 2% to 15% by mass of oregano extract as a percentage of the total mass of the composition. In one embodiment, the composition contains 5% to 10% by mass of oregano extract as a percentage of the total mass of the composition.

[0244] In one embodiment, the composition of the present invention comprises rosemary (Salvia cormanus) extract. In one embodiment, the composition contains at least 1% by mass of rosemary extract as a percentage of the total mass of the composition. In one embodiment, the composition contains at least 2.5% by mass of rosemary extract as a percentage of the total mass of the composition. In one embodiment, the composition contains at least 5% by mass of rosemary extract as a percentage of the total mass of the composition. In one embodiment, the composition contains at least 10% by mass of rosemary extract as a percentage of the total mass of the composition. In one embodiment, the composition contains at least 15% by mass of rosemary extract as a percentage of the total mass of the composition. In one embodiment, the composition contains at least 20% by mass of rosemary extract as a percentage of the total mass of the composition. In one embodiment, the composition contains at least 25% by mass of rosemary extract as a percentage of the total mass of the composition.

[0245] In one embodiment, the composition contains up to 50% by mass of rosemary extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 45% by mass of rosemary extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 40% by mass of rosemary extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 35% by mass of rosemary extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 30% by mass of rosemary extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 25% by mass of rosemary extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 20% by mass of rosemary extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 15% by mass of rosemary extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 10% by mass of rosemary extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 5% by mass of rosemary extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 2.5% by weight of rosemary extract as a percentage of the total mass of the composition. In another embodiment, the composition contains up to 1% by weight of rosemary extract as a percentage of the total mass of the composition.

[0246] In one embodiment, the composition contains 0.5% to 50% by mass of rosemary extract as a percentage of the total mass of the composition. In one embodiment, the composition contains 1% to 40% by mass of rosemary extract as a percentage of the total mass of the composition. In one embodiment, the composition contains 1% to 35% by mass of rosemary extract as a percentage of the total mass of the composition. In one embodiment, the composition contains 2.5% to 30% by mass of rosemary extract as a percentage of the total mass of the composition. In one embodiment, the composition contains 5% to 25% by mass of rosemary extract as a percentage of the total mass of the composition. In one embodiment, the composition contains 10% to 20% by mass of rosemary extract as a percentage of the total mass of the composition.

[0247] In one embodiment, the composition of the present invention comprises an extract of *Nasturtium officinale*. In one embodiment, the composition contains at least 0.5% by mass of *Nasturtium officinale* extract as a percentage of the total mass of the composition. In one embodiment, the composition contains at least 1% by mass of *Nasturtium officinale* extract as a percentage of the total mass of the composition. In one embodiment, the composition contains at least 2% by mass of *Nasturtium officinale* extract as a percentage of the total mass of the composition. In one embodiment, the composition contains at least 3% by mass of *Nasturtium officinale* extract as a percentage of the total mass of the composition. In one embodiment, the composition contains at least 5% by mass of *Nasturtium officinale* extract as a percentage of the total mass of the composition. In one embodiment, the composition contains at least 7.5% by mass of *Nasturtium officinale* extract as a percentage of the total mass of the composition. In one embodiment, the composition contains at least 10% by mass of *Nasturtium officinale* extract as a percentage of the total mass of the composition.

[0248] In one embodiment, the composition contains up to 30% by mass of *Miscanthus sinensis* extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 25% by mass of *Miscanthus sinensis* extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 20% by mass of *Miscanthus sinensis* extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 15% by mass of *Miscanthus sinensis* extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 10% by mass of *Miscanthus sinensis* extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 5% by mass of *Miscanthus sinensis* extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 2.5% by mass of *Miscanthus sinensis* extract as a percentage of the total mass of the composition. In one embodiment, the composition contains up to 1% by mass of *Miscanthus sinensis* extract as a percentage of the total mass of the composition.

[0249] In one embodiment, the composition contains 0.5% to 30% by mass of *Miscanthus sinensis* extract as a percentage of the total mass of the composition. In one embodiment, the composition contains 1% to 20% by mass of *Miscanthus sinensis* extract as a percentage of the total mass of the composition. In one embodiment, the composition contains 2% to 15% by mass of *Miscanthus sinensis* extract as a percentage of the total mass of the composition. In one embodiment, the composition contains 5% to 10% by mass of *Miscanthus sinensis* extract as a percentage of the total mass of the composition.

[0250] In one embodiment, the composition comprises an extract obtained from:

[0251] (i) kale (Brassica oleracea var. Acephala group), in an amount of 60% to 90% by mass of the total mass of the composition;

[0252] (ii) Artichoke (Cyanara cardunculus), in an amount of 10% to 20% by mass of the total composition; and

[0253] (iii) Oregano (Origanum vulgare), in an amount of 5% to 15% by mass of the total composition.

[0254] In one embodiment, the composition comprises an extract obtained from:

[0255] (i) kale (Brassica oleracea var. Acephala group), in an amount of 60% to 90% by mass of the total mass of the composition;

[0256] (ii) Red cabbage (Brassica oleracea var. Capitata group var. rubra), in an amount of 5% to 15% by mass of the total composition; and

[0257] (iii) Origanum vulgare, in an amount of 5% to 15% by mass of the total composition.

[0258] In one embodiment, the composition comprises an extract obtained from:

[0259] (i) kale (Brassica oleracea var. Acephala group), in an amount of 50% to 80% by mass of the total composition;

[0260] (ii) Artichoke (Cyanara cardunculus), in an amount of 15% to 25% by mass of the total composition;

[0261] (iii) Origanum vulgare, in an amount of 5% to 20% by mass of the total composition;

[0262] (iv) Rosemary (Salvia cormanus), in an amount of 0.5% to 5% by mass of the total composition; and

[0263] (v) Watercress (Nasturtium officinale), in an amount of 1% to 10% by mass of the total mass of the composition.

[0264] In one embodiment, the composition comprises an extract obtained from:

[0265] (i) kale (Brassica oleracea var. Acephala group), in an amount of 50% to 70% by mass of the total composition;

[0266] (ii) Red cabbage (Brassica oleracea var. Capitata group var. rubra), in an amount of 5% to 15% by mass of the total composition;

[0267] (iii) Origanum vulgare, in an amount of 1% to 15% by mass of the total composition;

[0268] (iv) Rosemary (Salvia cormanus), in an amount of 15% to 35% by mass of the total composition; and

[0269] In one embodiment, the composition comprises an extract obtained from:

[0270] (i) kale (Brassica oleracea var. Acephala group), in an amount of 10% to 50% by mass of the total composition;

[0271] (ii) Red cabbage (Brassica oleracea var. Capitata group var. rubra), in an amount of 5% to 30% by mass of the total composition;

[0272] (iii) Origanum vulgare, in an amount of 0.5% to 10% by mass of the total composition;

[0273] (iv) Rosemary (Salvia cormanus), in an amount of 2.5% to 25% by mass of the total composition; and

[0274] (v) Watercress (Nasturtium officinale), in an amount of 10% to 30% by mass of the total composition.

[0275] The compositions of the present invention contain antioxidants as bioreducing agents. In one embodiment, the antioxidant is selected from ascorbic acid, β-carotene; retinol (vitamin A); phenolic compounds (especially polyphenols, such as flavonoids or epicatechin); lutein; all-trans β-carotene; 9-cis-β-carotene; neoxanthin; auroxin; rutin; apigenin-7-rutinoside; cynarin; 1-caffeoylquinic acid; luteolin; 7-apigenin-(1->2)-glucoside; luteolin; caffeic acid; tannin; chlorogenic acid; luteolin-7-rutinoside; anthocyanins, such as anthocyanin-3-diglucoside-5-glucoside; kaempferol; p-coumaric acid; ferulic acid. Myricetin; Resveratrol; Rosmarinic acid; Salicerol; Hesperidin; Rosmarinic acid; Epirosmarinic acid; Rosmarinic dialdehyde; Salicerol; Methyl salicate; Gallic acid; Quercetin-3-O-rutin; Dicaffeoyl tartaric acid; Isorhamnetin; Anthocyanin-3-glucoside; Luteolin-7-O-glucoside; Quercetin-3-O-rhamnoside; and Watercress glycoside.

[0276] When the composition contains kale, the composition may contain any or all of the following antioxidants in varying proportions: ascorbic acid (vitamin C); beta-carotene; retinol (vitamin A); phenolic compounds (polyphenols); lutein; all-trans beta-carotene; 9-cis-beta-carotene; neoxanthin; azathioprine.

[0277] When the composition contains artichokes, the composition may contain any or all of the following antioxidants in different proportions: naringin; apigenin 7-rutin; cynarin; 1-caffeoylquinic acid; luteolin 7-apigenin-(1->2)-glucoside; luteolin; flavonoids; caffeic acid; tannins; chlorogenic acid; luteolin-7-rutin.

[0278] When the composition contains red cabbage, the composition may contain any or all of the following antioxidants in different proportions: anthocyanins, such as anthocyanin-3-diglucoside-5-glucoside; kaempferol; vitamin C; vitamin A; lutein.

[0279] When the composition contains oregano, the composition may contain any or all of the following antioxidants in different proportions: chlorogenic acid; epicatechin; p-coumaric acid; caffeic acid; ferulic acid; rosmarinic acid; myricetin; resveratrol.

[0280] When the composition contains rosemary, the composition may contain any or all of the following antioxidants in varying proportions: rosmarinic acid; carrageenan; carrageenan; hesperidin.

[0281] When the composition contains sage, the composition may contain any or all of the following antioxidants in varying proportions: rosmarinicol; epirosmarinicol; sagelol; rosmarinic dialdehyde; sagelic acid; methyl sage.

[0282] When the composition contains watercress, the composition may contain any or all of the following antioxidants in different proportions: gallic acid; chlorogenic acid; caffeic acid; quercetin-3-O-rutinoside; dicaffeoyl tartaric acid; isorhamnetin; anthocyanin-3-glucoside; luteolin-7-O-glucoside; quercetin-3-O-rhamnoside; and lecithin.

[0283] In one implementation, the antioxidant is ascorbic acid.

[0284] In one embodiment, each 100g of the composition contains at least 5 mmol of antioxidant. In another embodiment, each 100g of the composition contains at least 15 mmol of antioxidant.

[0285] Method for preparing the composition

[0286] The composition of the present invention can be prepared by treating plants such that the active bioreducing agent (antioxidant) component of the composition is extracted from the plants into a solution.

[0287] In one implementation, the method includes one or more of the following steps:

[0288] (a) Provide the plant preparation as described above; and

[0289] (b) Extracting bioactive components from the combined preparation using solvents.

[0290] In one embodiment, the plant preparation step includes drying the plants. In one embodiment, the plants are mixed prior to the drying step. In one embodiment, the individual plants are dried prior to the particle size reduction step.

[0291] The temperature for the drying step is typically between room temperature and 80°C, preferably between 30°C and 50°C, and more preferably 40°C.

[0292] The pressure for the drying step is typically 0.2 to 10 bar, preferably 0.5 to 2 bar, and more preferably 0.9 to 1.1 bar.

[0293] The drying process typically takes from 10 minutes to 72 hours, preferably from 1 to 48 hours, and more preferably from 12 to 36 hours.

[0294] In one embodiment, the plant preparation step includes reducing the particle size of the dried plants. This step can be performed using any method or equipment suitable for carrying out the task. It is typically carried out in a mixer. Generally, the plants are reduced to a particle size range of 10 μm to 1 mm, preferably 20 to 200 μm, more preferably 100 μm.

[0295] In one embodiment, the extraction step is performed by filtration. The filtration process allows for the extraction of the bioactive ingredient. Typically, the method involves dissolving the bioactive ingredient from dried plant particles into a solvent. The active ingredient typically undergoes mass diffusion from the pores of the particles to the solid-liquid interface, and then from the solid-liquid interface to the bulk solution.

[0296] The solvent used in the extraction step can include any solvent capable of dissolving the bioactive ingredient. Examples of suitable solvents include water; ethers, such as diethyl ether and 1,2-dimethoxyethane; hydrocarbons, such as hexane; halogenated hydrocarbons, such as dichloromethane and chloroform; and mixtures thereof. However, water is preferred as the solvent used in the extraction step because it can dissolve oxidized active ingredients such as ascorbic acid present in many blends, while avoiding the toxicity and environmental impact of some organic solvents.

[0297] The temperature at which the extraction step is performed depends on the nature of the plant, the solvent, and the biological agent to be extracted. However, the temperature is generally from room temperature to the boiling point of the solvent, preferably 30 to 70°C, and more preferably 40 to 60°C.

[0298] The pressure used for the extraction step depends on the nature of the plant, the solvent, and the biological agent to be extracted. However, the pressure is typically 0.2 to 10 bar, preferably 0.5 to 2 bar, and more preferably 0.9 to 1.1 bar.

[0299] The extraction process typically takes from 1 minute to 72 hours, preferably from 2 minutes to 4 hours, and more preferably from 5 minutes to 60 minutes.

[0300] Typically, the extraction process is carried out with stirring.

[0301] In one implementation, after the extraction step, the solution can be decanted to separate the solution from the solids. The decanter can form three phases (scum, clarified liquid, and slurry). The slurry can be recycled back to the mixer for further processing to extract the maximum amount of bioactive components until the concentration in the solid particles is reduced to a minimum. At this point, the depleted plant particles can be discharged from the process.

[0302] In one implementation, after decantation but before filtration, bioactive components and / or broken cells can be recovered by passing the filtrate through a hydrocyclone. This also uses centrifugal force to remove solids, but is done continuously.

[0303] In one embodiment, the composition may be filtered after the extraction step or after the decantation step to produce a filtrate and residue. Depending on the solids content, filtration may be carried out under pressure, vacuum, or a combination thereof. The pressure at which the filtration step is performed depends on the nature of the plant, the solvent, and the bio-agent to be extracted. The pressure at which the filtration step is performed is typically 0.1 to 100 bar, preferably 0.3 to 10 bar, more preferably 0.3 to 5 bar. In one embodiment, the filtration step is carried out at a pressure of 0.001 to 0.1 bar.

[0304] In one embodiment, after the extraction step or after the decanting step, the composition can be filtered through a sieve to remove larger particles.

[0305] In one embodiment, the filtrate may be centrifuged after the filtration step. Centrifugation can further break down cells, remove smaller particles, and thus allow a greater amount of bioactive components to dissolve. In one embodiment, centrifugation is performed at 500 to 20,000 rpm. In another embodiment, centrifugation is performed at 500 to 15,000 rpm. In yet another embodiment, centrifugation is performed at 300 to 5,000 rpm. In yet another embodiment, centrifugation is performed at 100 to 3,000 rpm.

[0306] In one embodiment, centrifugation is performed at 2500 rpm. This centrifugation speed is particularly preferred because it allows for the removal of many broken cells from the precipitate, which would otherwise interfere with the nucleation of nanoparticles and allow for a large number of impurities in the crystals. By removing cells from the filtrate, nanoparticles with a certain particle size distribution and a more spherical shape can be obtained.

[0307] In one embodiment, centrifugation is performed for 10 seconds to 1 hour. In one embodiment, centrifugation is performed for 30 seconds to 30 minutes. In one embodiment, centrifugation is performed for 1 to 20 minutes. In one embodiment, centrifugation is performed for 10 minutes.

[0308] In alternative embodiments, the bioactive component can be recovered from the solution by chromatography. This can be thin-layer chromatography, column chromatography, liquid chromatography (especially high-performance liquid chromatography), or gas chromatography.

[0309] In alternative implementations, bioactive components can be recovered from a solution by passing the solution through a membrane. Examples of such technologies include microfiltration and nanofiltration.

[0310] In alternative embodiments, the bioactive ingredient can be recovered from the solution by precipitation or crystallization. In alternative embodiments, the bioactive ingredient can be recovered from the solution by liquid-liquid extraction. In alternative embodiments, the bioactive ingredient can be recovered from the solution by drying. In alternative embodiments, the bioactive ingredient can be recovered from the solution by osmotic pressure shock. In alternative embodiments, the bioactive ingredient can be recovered from the solution by electrophoresis. All of these techniques are well known to those skilled in the art.

[0311] Metal nanoparticles

[0312] The present invention also includes metal nanoparticles that are obtained or obtainable by the method of the present invention.

[0313] Surprisingly, it has been found that forming nanoparticles according to the method of the present invention results in the formed nanoparticles having a protective bio-layer on them. This protects the nanoparticles without the need for additional coating agents.

[0314] Therefore, in another aspect, a coated metal nanoparticle is provided. In one embodiment, the coating comprises carbon. In one embodiment, the coating comprises oxygen. In one embodiment, the coating comprises nitrogen. In one embodiment, the coating comprises sulfur. In one embodiment, the coating comprises a biopolymer. In one embodiment, the coating comprises carbohydrates. In one embodiment, the coating comprises a bioreducing agent identified as an antioxidant compound, or a compound derived therefrom, of the bioreducing agents of the compositions of the present invention described and exemplified above.

[0315] Nanoparticles may comprise a single metal or a mixture of metals. In one embodiment, the nanoparticles comprise a single metal. In another embodiment, the nanoparticles comprise a mixture of metals.

[0316] The metal that forms the nanoparticles can be any metal capable of forming nanoparticles and stable to the methods described above. Examples of suitable metals include, but are not limited to, gold, silver, copper, nickel, platinum, iron, zinc, gadolinium, titanium, cerium, thallium, manganese, aluminum, zirconium, chromium, palladium, and cobalt, or any combination thereof.

[0317] In one embodiment, the metal is selected from silver, gold, platinum, aluminum, zirconium, and iron, or any combination thereof.

[0318] In one embodiment, the metal is selected from silver, gold, and copper, or any combination thereof. In one embodiment, the metal is silver. In one embodiment, the metal is gold.

[0319] In one embodiment, the nanoparticles are multilayer nanoparticles. Typically, such multilayer nanoparticles include an inner core and a outer shell. The metals constituting the core and shell can be the same or different, and can be any metal listed above. As an example, the nanoparticles may include an iron core and a silver shell.

[0320] The metal nanoparticles of this invention can be formed into a variety of shapes, depending on the precise nature of the process used to form them and their intended use. Typical examples of suitable shapes include spheres, ovals, cylinders, rods, cubes and cuboids, prisms (e.g., triangles, pentagons or hexagons), cones and pyramids.

[0321] Methods for preparing metal nanoparticles

[0322] In another aspect, the present invention provides a method for producing metal nanoparticles, the method comprising:

[0323] (a) Provides dissolved metal ions; and

[0324] (b) Contact the dissolved metal ions with the composition of the present invention, such that the dissolved metal ions are reduced to form metal nanoparticles.

[0325] Typically, dissolved metal ions exist in the form of a metal salt solution. Preferably, the salt contains counterions with low toxicity to humans and low environmental impact. Examples of suitable salts include chlorides, sulfates, carbonates, gluconates, and acetates. In one embodiment, the metal salt is an organometallic salt. In another embodiment, the metal salt is an acetate.

[0326] In one embodiment, the dissolved metal ions are present as a solvate of a metal salt. Preferably, the solvent forming the solvate has low toxicity to humans and low environmental impact. In another embodiment, the dissolved metal ions are present as a hydrate, wherein the solvent is water.

[0327] When the metal is silver, preferred salts include silver chloride, silver carbonate, and silver acetate, or solvates of any of them. When the metal is copper, preferred salts include copper(II) sulfate and copper(II) gluconate, or solvates of any of them. When the metal is gold, preferred salts include gold(I) chloride and gold(III) chloride, or solvates of any of them.

[0328] The solvent used in the contact step can include any solvent capable of dissolving the bioactive ingredient. Examples of suitable solvents include water; and alcohols such as methanol, ethanol, and isopropanol; and mixtures thereof. However, water is preferred as the solvent for use in the contact step because it can dissolve metal ions and oxidized bioreducing agents such as ascorbic acid present in many mixed products, while avoiding the toxicity and environmental impact of some organic solvents.

[0329] The contact step can be performed by any method known to those skilled in the art capable of generating metal nanoparticles from dissolved metal ions. Preferably, the composition of the present invention is added to a solution of metal ions. In an alternative embodiment, a solution of metal ions is added to the composition of the present invention.

[0330] In one embodiment, a smaller volume of the higher concentration of the composition of the present invention is added to a larger volume of a lower concentration of metal ion solution. In one embodiment, the volume of the metal ion solution used is 2 to 50 times the volume of the composition of the present invention. In another embodiment, the volume of the metal ion solution used is 5 to 20 times the volume of the composition of the present invention.

[0331] Preferably, the metal ion solution is preheated before the addition of the composition of the present invention. It has been found that nucleation for the generation of nanoparticles is substantially instantaneous when using the method steps described. In one embodiment, the metal ion solution is preheated to a temperature of 40 to 100°C. In another embodiment, the metal ion solution is preheated to a temperature of 60 to 80°C.

[0332] Typically, the concentration of metal ions used in the contact step is between 0.1 and 5 g / L, preferably between 0.5 and 1.5 g / L.

[0333] Typically, the concentration of the composition of the present invention used in the contact step is between 0.5 and 7 g / L, preferably 5 to 7 g / L.

[0334] In one embodiment, the contact step is performed at a temperature ranging from room temperature to the solvent's boiling point. In one embodiment, the contact step is performed at a temperature between 25 and 90°C. In one embodiment, the contact step is performed at a temperature between 35 and 70°C.

[0335] In one embodiment, the contacting step is performed at a pressure of 0.3 to 1.2 bar. In another embodiment, the contacting step is performed at a pressure of 0.9 to 1.15 bar.

[0336] In one embodiment, the contact step lasts from 30 seconds to 2 hours. In another embodiment, the contact step lasts from 1 minute to 1 hour. In yet another embodiment, the contact step lasts from 5 minutes to 40 minutes.

[0337] In one embodiment, the contact step is carried out at a pH of 2 to 12. It is not desirable to be bound by theory, as the pH of the reaction is believed to affect the size of the resulting metal nanoparticles. Preferably, the contact step is carried out at a pH of 5 to 8.

[0338] In one embodiment, the contact step is carried out under stirring. In one embodiment, stirring is performed at 200 to 1000 rpm.

[0339] In one embodiment, a seed solution of metal nanoparticles (typically prepared using the method of the present invention) is added to the solution of metal ions before the addition of the composition of the present invention in the contact step. It is not desired to be bound by theory, but it is believed that adding the seed solution of metal nanoparticles allows for better control of nanoparticle growth. Typically, a volume of 500 nL to 1 mL of seed solution is added before the contact step.

[0340] In one embodiment, the contact step is followed by quenching of the reaction mixture. This can be done in any manner known in the art. Typically, it is done by cooling, for example using a jacketed reactor, which allows heat transfer around the reactor without direct contact with the product solution.

[0341] Following the contact step, the reaction mixture is post-treated to purify the metal nanoparticles. This can be done using methods known to those skilled in the art.

[0342] In one embodiment, the product is purified by ion-exchange chromatography. As known to those skilled in the art, ion-exchange chromatography separates molecules based on their respective charged groups by passing them through a matrix (typically a column) capable of ion exchange (typically an ion-exchange resin). Ion-exchange chromatography retains analyte molecules on the column based on coulombic (ion) interactions. The ion-exchange chromatographic matrix consists of positively and negatively charged ions. Essentially, the molecules interact electrostatically with opposite charges on the stationary phase matrix. The stationary phase consists of a stationary matrix containing charged ionizable functional groups or ligands.

[0343] In one embodiment, the product is purified by crystallization. As those skilled in the art will know, this typically involves forming a crystalline solid phase from a solution (typically a supersaturated solvent).

[0344] In one implementation, a portion of the output from the crystallization step is recycled to the input of the contact step. It has been found that including a recycling loop around the contact step minimizes waste generation throughout the process, thereby maximizing process conversion at the point where metal ions are introduced, thus avoiding the release of large amounts of metal ions into the environment.

[0345] In one embodiment, the product is purified by centrifugation. Centrifugation can be performed in a single centrifugation step or in multiple centrifugation steps (e.g., 2, 3, 4, or 5 steps). When centrifugation is performed in multiple centrifugation steps, the centrifugation rate and the centrifugation time in each step can be the same or different.

[0346] In one embodiment, centrifugation is performed at 500 to 100,000 rpm. In one embodiment, centrifugation is performed at 500 to 16,000 rpm. In one embodiment, centrifugation is performed at 100 to 5,000 rpm. In one embodiment, centrifugation is performed at 2,000 to 3,000 rpm. In one embodiment, centrifugation is performed at 1,000 rpm. In one embodiment, centrifugation is performed at 2,500 rpm. In one embodiment, centrifugation is performed at 5,000 rpm. In one embodiment, centrifugation is performed at 7,000 rpm.

[0347] Differential centrifugation can be used to adjust the size of nanoparticles based on the centrifugation speed. Multiple rounds of centrifugation can be used to improve the purity of metal nanoparticles.

[0348] In one embodiment, centrifugation is performed in two steps. In one embodiment, the first centrifugation step is performed at 500 to 100,000 rpm, and the second centrifugation step is performed at 500 to 100,000 rpm. In one embodiment, the first centrifugation step is performed at 500 to 2000 rpm, and the second centrifugation step is performed at 5000 to 20000 rpm. In one embodiment, the first centrifugation step is performed at 1000 rpm, and the second centrifugation step is performed at 10000 rpm. In one embodiment, the first centrifugation step is performed at 10000 rpm, and the second centrifugation step is performed at 1000 rpm.

[0349] In one embodiment, centrifugation is performed for 20 seconds to 2 hours. In another embodiment, centrifugation is performed for 1 minute to 1 hour.

[0350] In one embodiment, centrifugation is performed for 10 to 30 minutes. In one embodiment, centrifugation is performed for 20 minutes. In one embodiment, centrifugation is performed for 2 minutes. In one embodiment, centrifugation is performed for 5 minutes. In one embodiment, centrifugation is performed for 10 minutes.

[0351] In one embodiment, the product is purified by ultrasonic treatment. In one embodiment, the ultrasonic treatment is performed at 30 to 50 kHz. In one embodiment, the ultrasonic treatment is performed at 35 to 45 kHz. In one embodiment, the ultrasonic treatment is performed at 0 to 50°C. In one embodiment, the ultrasonic treatment is performed at 15 to 40°C. In one embodiment, the ultrasonic treatment lasts for 1 to 30 minutes. In one embodiment, the ultrasonic treatment lasts for 10 to 20 minutes. In one embodiment, the ultrasonic treatment lasts for 15 minutes.

[0352] In one embodiment, the ultrasonic treatment is performed in two steps. The frequency, temperature, and time of each step follow the general ultrasonic treatment procedure described above. In one embodiment, the first ultrasonic treatment step lasts for 2 to 15 minutes, and the second ultrasonic treatment step lasts for 1 to 10 minutes. In one embodiment, the first ultrasonic treatment step lasts for 10 minutes, and the second ultrasonic treatment step lasts for 5 minutes.

[0353] In one embodiment, the method includes an oscillation step following the ultrasound treatment step or each ultrasound treatment step. In one embodiment, the oscillation lasts from 10 seconds to 30 minutes. In another embodiment, the oscillation lasts from 30 seconds to 15 minutes.

[0354] In one embodiment, the method includes two ultrasound processing steps, each followed by an oscillation step. The conditions for each ultrasound processing step and each oscillation step follow the general ultrasound and oscillation procedures described above.

[0355] In one embodiment, the method includes a step of raising the pH between a centrifugation step and an ultrasonic treatment step. Typically, the pH is raised to between 10 and 14. This operation can be performed using any suitable alkali, as long as it does not affect the nanoparticles. Examples include alkali metal hydroxides, such as sodium hydroxide.

[0356] In one embodiment, the product is purified by microfiltration, ultrafiltration, and / or nanofiltration. As known to those skilled in the art, microfiltration is a membrane filtration-based method that uses a membrane with pores of the micrometer size to filter particulate material. Furthermore, as known to those skilled in the art, ultrafiltration is a variety of membrane filtration methods in which forces such as pressure or concentration gradients cause separation through a semi-permeable membrane. Additionally, as known to those skilled in the art, nanofiltration is a membrane filtration-based method that uses nanometer-sized pores permeating the membrane. The pore size of microfiltration membranes is typically 1-100 μm, while the pore size of nanofiltration membranes is typically 1-100 nm, for example, 1-10 nm. In one embodiment, the product is purified by microfiltration. In one embodiment, the product is purified by microfiltration followed by ultrafiltration. In one embodiment, the membrane pore size is between 1 nm and 1 μm. In one embodiment, the membrane pore size is between 100 nm and 500 nm.

[0357] In one embodiment, the method includes a pH adjustment step following the sonication step. Typically, the pH is adjusted to between 7 and 9. Any suitable acid can be used for this operation, as long as it does not affect the nanoparticles. Weak acids are preferred, particularly organic acids, and acetic acid is especially preferred.

[0358] In one embodiment, the method includes the step of drying the nanoparticles. In one embodiment, drying is performed by vacuum drying. In a preferred embodiment, drying is performed by vacuum distillation.

[0359] Figure 1 The preferred process is described in more detail. A plant solution mixed in appropriate proportions enters the drying unit 10 through line 12. Air is pumped into the compressor 16 through line 14, and then sent to the heater 20 through line 18. The heated air then enters the drying unit 10 through line 22 and exits the drying unit through line 24.

[0360] The dried plants leave the drying unit 10 and enter the mixer 28 via line 26. The mixed plant solution leaves the mixer and is sent to the impregnation unit 32 via line 30. Water is heated in the heater 34, leaves the heater via line 36, and is pumped to the heating jacket 41 surrounding the impregnation unit 32 via pump 38 and line 40. Deionized water is introduced into the top of the impregnation unit 32 via line 42.

[0361] The solution exits the bottom of the immersion filter unit 32 and is pumped into the decanter unit 44 via pump 48 and line 46, where it forms a separated blend solution and a blend slurry. Some of the slurry exits the decanter unit and is recirculated back to the immersion filter unit 32 via line 49. The blend slurry is removed via line 51.

[0362] The decanting solution of the mixed plants is fed from the decanting unit 44 into the filtration unit 54 via line 50 and pump 52. Additional sludge is removed via line 53 into line 51. The solution exits the filtration unit 54 via line 56 and pump 58 into the centrifuge 60, where it separates the solution and removes any additional solids. The precipitated waste exits the centrifuge unit 60 via line 62.

[0363] The solution of mixed plants exits the centrifuge 60 through line 64 and enters the reactor 66. A solution of metal ions is introduced to the top of the reactor 66 through line 68, where the bio-reducing agent in the mixed plant solution reacts with the metal ions to form metal nanoparticles.

[0364] Water is introduced into heater 63 via line 61. The heated water is then pumped into heating jacket 59 surrounding reactor 66 via pump 65 and line 67. Water exits reactor 66 via line 69 into cooler 71 and is recirculated back into reactor 66 via line 73. Water also exits jacket 59 via line 75 into heater 63 and is recirculated back into jacket 59 via pump 65 and line 67.

[0365] The metal nanoparticles exit reactor 66 and are fed into centrifuge 72 via line 70 and pump 74. In centrifuge 72, the reaction mixture is separated into nanoparticles and a metal ion solution.

[0366] The metal ion solution exits centrifuge 72 and is fed into ion exchange chromatography unit 78 via line 76. An acid solution is fed into unit 78 via line 80 to regenerate the ion exchange resin. The purified metal ions exit ion exchange chromatography unit 78 and are recycled back into reactor 66 via line 82. Waste liquid exits ion exchange chromatography unit 78 via line 84 and is removed.

[0367] The metal nanoparticles exit the centrifuge 72 and are fed into the mixer 83 via line 86 and pump 88. An alkali (preferably a sodium hydroxide solution) is introduced into the mixer 83 via line 90. The pH is adjusted in the mixer 83, and the metal nanoparticles exit the mixer 83 via line 94 and are fed into the ultrasonic transducer 92.

[0368] After ultrasonic treatment, the metal nanoparticles leave the ultrasonic instrument 92 and are fed into the membrane 96 through the line 98 and the pump 100. Oversized nanoparticles (typically larger than 200 nm) are removed by the membrane 96 and discharged through the line 102.

[0369] Metal nanoparticles passing through membrane 96 are fed into mixer 104 via line 106. An acid solution is introduced into mixer 104 via line 108 to adjust the pH. Colloidal nanoparticles are removed from mixer 104 via line 110.

[0370] The metal nanoparticles exit the mixer 104 and are fed into the dryer 112 through line 114. Water is removed in the dryer 112 and exits the dryer 112 through line 116 and pump 118. The finished nanoparticle powder exits the dryer 112 through line 120.

[0371] Figure 1A An alternative process is illustrated. The process implementation scheme is similar to... Figure 1 The difference is that unit 92 is a hybrid unit in which ultrasonic processing and mixing are performed.

[0372] application

[0373] The metal nanoparticles of this invention can be incorporated into a variety of products and methods.

[0374] Therefore, in another aspect of the present invention, a product comprising the metal nanoparticles of the present invention is provided.

[0375] In one embodiment, a cosmetic comprising the metal nanoparticles of the present invention is provided.

[0376] In one embodiment, a battery comprising the metal nanoparticles of the present invention is provided.

[0377] In one embodiment, a pharmaceutical product comprising the metal nanoparticles of the present invention is provided (which may be an active pharmaceutical ingredient, a pharmaceutical excipient, or a pharmaceutical delivery agent).

[0378] In one embodiment, a plant protection product comprising the metal nanoparticles of the present invention is provided, such as an agricultural chemical product (which may be an active agrochemical ingredient, an agrochemical excipient, or an agrochemical delivery agent).

[0379] In one embodiment, a building material comprising the metal nanoparticles of the present invention is provided.

[0380] In one embodiment, a detergent or cleaning product comprising the metal nanoparticles of the present invention is provided.

[0381] In one embodiment, a textile product or garment, footwear, or accessory (e.g., jewelry, bag, or other fashion item) comprising the metal nanoparticles of the present invention is provided.

[0382] In one embodiment, a biosensor comprising the metal nanoparticles of the present invention is provided.

[0383] In one embodiment, a lubricant comprising the metal nanoparticles of the present invention is provided.

[0384] In one embodiment, an optical or optoelectronic device comprising the metal nanoparticles of the present invention is provided.

[0385] In one embodiment, a conductive ink comprising the metal nanoparticles of the present invention is provided.

[0386] In one embodiment, an antimicrobial agent comprising the metal nanoparticles of the present invention is provided.

[0387] In one embodiment, a biocide (including an insecticide) comprising the metal nanoparticles of the present invention is provided.

[0388] In one embodiment, a catalyst comprising the metal nanoparticles of the present invention is provided.

[0389] In one embodiment, a reinforcing material is provided (e.g., a polymer comprising the metal nanoparticles of the present invention, which may be a polymer with embedded nanoparticles, or a functionalized material or derivative thereof).

[0390] In one embodiment, a preservative (e.g., a food preservative) comprising the metal nanoparticles of the present invention is provided.

[0391] In one embodiment, a filter comprising the metal nanoparticles of the present invention is provided (e.g., a filter for air and / or water purification).

[0392] In one embodiment, a machine (e.g., a robot, which may be a nanorobot) comprising the metal nanoparticles of the present invention is provided.

[0393] In one embodiment, the use of the metal nanoparticles of the present invention in biomedical imaging is provided.

[0394] In one embodiment, the use of the metal nanoparticles of the present invention in gene sequencing is provided.

[0395] In one embodiment, the use of the metal nanoparticles of the present invention in information storage and processing (including nanocomputing and quantum computing applications) is provided.

[0396] In one embodiment, the use of the metal nanoparticles of the present invention in nanoelectronics is provided. Example

[0397] Overview

[0398] UV / VIS spectra were recorded on a visible spectrophotometer (721LDC Digital LabSpectrophotometer). Scanning electron microscopy (SEM) measurements were performed using Hitachi SU8230 and SU8200 field emission SEMs. Energy-dispersive X-ray (EDX) spectra were recorded on Hitachi SU8230 and SU8200 SEMs using a Bruker XFlash detector.

[0399] Example 1 - Developing Optimal Blends Using GAMS Modeling

[0400] The optimal blend composition was obtained by constructing a Pareto boundary in GAMS using a multi-objective linear optimization procedure employing the ε-constraint method. The two variables optimized were the antioxidant capacity per 100g and the cost per 100g.

[0401] Antioxidant capacity was used as an environmentally friendly variable. If the antioxidant capacity of the same mass of blend is higher, then less plant material is needed to biosynthesize metal nanoparticles, thus reducing material and energy consumption. As outlined in the article “Design Through the 12 principles of Green Engineering” (Paul T. Anastas et al., Environ. Sci. Technol., 2003, 37(5), 94A-101A), this will generate environmental benefits in the following ways: less direct and indirect resource consumption, and reduced CO2 and SO2 emissions from energy production. x This reduces emissions and water usage for plant growth, thus minimizing upstream environmental impact. The entire process and its environmental impact were assessed within a life cycle analysis framework. The content of water, sugar, zinc, iron, and carbohydrates per 100 grams was used as lower optimization constraints, while the content of vitamin C (ascorbic acid), lutein, zeaxanthin, and carotene per 100 grams was used as upper constraints. Since the first step in the production process is drying, the amount of water in the mixture was minimized to reduce downstream energy costs. Considering the high enthalpy of vaporization of water (40.65 kJ / mol), this resulted in a significant reduction in energy requirements after process scale-up.

[0402] The amount of sugar and carbohydrates can be reduced to inhibit potential microbial growth in the blend, thus extending its shelf life. The amounts of zinc and iron are minimized to avoid the formation of other metal nanoparticles (MNPS) and zeta potential disturbances after nanoparticle production, which could otherwise lead to MNPS aggregation and render them unusable. Finally, considering economic cost constraints, water-soluble antioxidants (ascorbic acid, lutein) and fat-soluble antioxidants (carotene) are rationally maximized.

[0403] The basic constraints of development are shown in Table 1.

[0404] Constraints Quantity (g / 100g) water 85 sugar 1.5 iron 0.01 Zinc 0.001 carbohydrate 20 ascorbic acid 0.02 Carotene 0.003 Lutein + Zeaxanthin 0.001

[0405] Table 1

[0406] The mixed model includes plants and spices readily available in the UK: artichokes, curly kale, red cabbage, oregano, rosemary, sage, and watercress. Their nutritional composition was obtained from various online databases, with myfoodata.com being the primary one. Due to the use of a linear procedure, values ​​are considered globally optimal if all optimal values ​​(minimum in this case) belong to the feasible set. Cost per 100 grams is based on local supermarket pricing. Results are as follows...

[0407] As shown in Table 2.

[0408]

[0409] Table 2

[0410] Finally, nine blends were obtained using programming software, which allowed for the construction of Pareto fronts, such as... Figure 3 As shown. From Figure 5 It can be seen that the main component of each blend is curly kale, with artichoke or red kale used as "filler" and flavoring; oregano, sage, and rosemary are used as rich sources of antioxidants. Antioxidants have been used to reduce metal ions into nanoparticles. It can be noted that the greater the increase in the antioxidant capacity of the blend, the higher the cost per 100 grams. Finally, from... Figure 4 As can be understood from Table 2, almost all blends, except for blend 9, are superior to the watercress-only scheme widely used in the prior art (from an economic point of view). This is because blend 9 contains a uniform distribution of each plant species, rather than the preferred configuration [rich in the main filler]. Therefore, it is recommended to test blends that are both economically and chemically advantageous for reactive synthesis. However, it must be noted that a uniform distribution of plant varieties allows for the highest antioxidant potential, thus requiring less material in processing and saving overall economic resources.

[0411] Example 2 - DPPH Determination - Experimental Verification and Synergistic Effect

[0412] To validate the results obtained from the optimization algorithm, the antioxidant content of the produced blends was experimentally verified. For this purpose, individual plant extracts and blend extracts were tested, and their relative strengths in reducing the free radical 2,2-diphenyl-1-picrylhydrazine (DPPH) were evaluated. Pure ascorbic acid was used as the baseline antioxidant. A colorimetric assay using DPPH was developed and used to assess antioxidant activity. For each blend and individual plant, the corresponding 50% inhibition concentration of the free radical in solution was determined. The 50% inhibition point (IC50) was determined by linear regression. 50 This allows for the prediction of IC. 50 concentration( Figures 7 to 17 Each experiment was repeated once, and the average value was taken. The following equation was used for calculation:

[0413] DPPH scavenging activity (%) = [(Ab–At) / Ab] × 100

[0414] Ab: Blank absorbance

[0415] At: Measured absorbance of the sample

[0416] Relative intensity = IC 50 (Sample) / IC 50 (ascorbic acid)

[0417] (It can also be compared with other antioxidants such as watercress-WC)

[0418]

[0419] Table 3

[0420]

[0421]

[0422] Table 4

[0423] As can be observed from Table 4, Figure 5 In the test blends, the DPPH IC of all blends 50 All were superior to watercress. Notably, curly kale performed worst when used alone, but performed better when used as a primary source of antioxidants in blends. All blends had higher relative strength than most single components, with blend 4 (without watercress) having a higher relative strength than oregano, which has the second highest single IC50 after ascorbic acid. 50 Concentration, although oregano and rosemary are minor components.

[0424] This was unexpected. Therefore, it was decided to calculate the theoretical IC. 50 The concentrations were calculated and compared with experimental concentrations. Table 3 shows that the reducing power of almost every blend was higher than predicted using linear programming. This is likely more than 150% stronger than the reducing power predicted using mathematical modeling theory, as seen in blend 4.

[0425] Therefore, based on these results, it can be concluded that a synergistic potential mechanism exists in the reduction of DPPH when using blends, compared to individual plants. This is surprising, as the deviation from the expected theoretical model is less than 5%. (IC) 50 Based on these variations, the fact that curly kale can exhibit stronger reducing activity in these specific combinations than when it is alone (even though it remains the main component in blends) can only point to enhancements and optimizations according to the present invention.

[0426] Example 3 – Method for producing the composition

[0427] The selected plants were then dried at 40°C and 1 bar for 24 hours. The dried plants were then collected and mixed in varying proportions using a mixer until particles smaller than 100 μm were obtained. After mixing, the powder was recovered and impregnated in a tank by adding deionized water for 20 minutes under continuous stirring at 50°C and 1 bar. The stirred tank was connected to a decanter, which itself formed a three-phase mixture (scum, clarified liquid, and slurry). The slurry was recycled back to the mixer for further processing to extract the maximum amount of antioxidants until the concentration in the solid particles was reduced to a minimum. At this point, the depleted plant particles were removed from the process. The clarified liquid was then recovered and filtered under pressure through different grades of filter membranes (microfiltration) to remove particles in the suspension down to 1 μm. The filtrate was then differentially centrifuged (also at 2500 RPM for 10 minutes) to discard the smaller particles in the precipitate.

[0428] Example 4 – Method for preparing silver metal nanoparticles

[0429] An ionic solution was prepared at a desired concentration of 0.5 g / L to 1.5 g / L and preheated to 70 °C for 1 hour at 1 bar in a reactor with continuous stirring. When a stable temperature was reached, a blend concentration of 0.5 g / L to 7 g / L was added to the reactor, and nucleation immediately began.

[0430] Silver acetate (AgCH3COO) is used as a substitute for silver nitrate (AgNO3). This avoids the presence of NO3 in the solution. - The presence of ions, the NO3 -The ions are toxic and harmful to the environment. Crystallization takes 5 minutes to 2 hours, depending on the desired conversion rate and nanoparticle size. It can be noted that the nanoparticles grow over time, therefore it is recommended to adjust the nanoparticle size according to the reaction time. Bioreduction occurs at this point, and the metal nanoparticles grow through primary heterogeneous nucleation. A color change from transparent to brown / black can be observed during this period.

[0431] The reaction was then quenched using cooling water at 4°C until the internal temperature of the mixture reached 10°C. The mixture of nanoparticles and plant extracts was subsequently recovered and centrifuged differentially (2500 RPM for 20 minutes). The supernatant was recycled back to the reactor to improve conversion. It was then passed through a cation exchange resin to recover the maximum amount of pure metal ions that could be recycled. Deactivated antioxidants were removed during the process. The precipitate (containing trace amounts of water) was recovered and NaOH was added to raise the pH to 10-14. The precipitate was then sonicated at 25°C at 40 kHz for 15 minutes.

[0432] The colloid is then passed through a micromembrane filter to remove any large agglomerates or deformed particles, ensuring high-quality functional nanoparticles with a high surface area to volume ratio. This is a particularly useful property for antibacterial applications, conductive inks, and catalysis. Prior to shipment, the solution pH is adjusted to neutral or slightly alkaline (pH 7 to pH 9) using a weak organic acid (such as acetic acid) to ensure the solution is non-corrosive to the user.

[0433] The colloid can also be fed into a vacuum dryer, where water is removed under vacuum (3000 Pa) at room temperature. This allows for the formation of nanoparticles, which can then be dissolved to produce other nanoscale products, such as conductive inks that require higher concentrations to conduct electricity.

[0434] Silver nanoparticles were ultimately obtained in a colloidal solution. The presence of naturally occurring bioactive agents (possibly including carbohydrates) in the extract as encapsulating agents for the nanoparticles was highlighted in the energy-dispersive X-ray spectroscopy results (see [link to original text]). Figures 56-58 ).

[0435] It can be confirmed that the chemical reaction likely begins at room temperature (25°C). Experiments were conducted at 35°C, 40°C, 50°C, 60°C, 70°C, and 85°C. Figure 18-22 Atmospheric pressure and above allows for the production of metal nanoparticles. Sufficient nanoparticles were produced in each case and identified using spectroscopic analysis (UV / VIS). The effect of blend concentration on nanoparticle formation could also be tested. Figure 25 It can be observed that the blend at 500 mg / L is Ag. + The threshold concentration at which full reduction occurs and nanoparticles are formed.

[0436] exist Figure 24 In this study, a cyclical crystallization property following the LaMer nucleation mechanism can be observed. After nucleation, the size of the nanoparticles increases, thereby increasing the concentration of nanoparticles in the solution until a critical concentration is reached. The critical concentration is reached 30 minutes after the start of the reaction. Subsequently, the concentration decreases until a stable value is reached, corresponding to the thermodynamic stability achieved by the colloidal solution. This can be explained by the complex balance of attractive and repulsive forces acting on the nanoparticles (reaching Gibbs free energy equilibrium).

[0437] UV-Vis analysis (using the method of Paramelle et al. Analyst, 2014, 139, 4855-4861) determined that the diameter of the nanoparticles generated at the reactor outlet was between 38 and 50 nm.

[0438] Following the reactor, nanoparticles were filtered using microfiltration. A 200 nm membrane was used to discard any large agglomerates that might remain after sonication. SEM analysis of the filtered sample revealed nanoparticles ranging in size from 5 nm to 30 nm. Figures 26 to 43 and Figures 59 to 62 As shown. From Figure 62 It can be observed that a normal distribution was obtained on a large sample of nanoparticles, with an average diameter of 12.59 nm and a standard deviation of 5.64 nm. The nanoparticles are uniformly distributed, without agglomeration, and have good sphericity (>70%).

[0439] Based on energy-dispersive X-ray spectroscopy ( Figures 44-58 This allows for further verification of the formation of silver nanoparticles. Even more interestingly, biopolymers, such as..., were discovered in solution. Figures 56 to 58 Highlighted in the image, carbon and oxygen atoms are noticeably present both within and between the particles. This indicates the presence of carbohydrates coating the nanoparticles in solution, preventing their aggregation through steric hindrance and electrostatic repulsion. No other polymers or organic stabilizers were added to the solution, meaning these molecules are derived from the original blend. This offers the advantage of saving materials and production costs in the process, as no additional stabilizers are required when using our blends.

[0440] Finally, Tables 5 and 6 illustrate several key advantages of the process of this invention compared to other chemical reduction routes. First, using the cost-optimized blends disclosed herein, considerable cost savings can be achieved on the reducing agent, as outlined in Table 6. Furthermore, the blends are non-toxic to humans and pose no flammability or reactivity hazard, making the product for end-users inherently safer than current market alternatives. Another key advantage is that, using the process of this invention, up to five times the commercial concentration can be produced in less than 30 minutes.

[0441] temperature Concentration (M) of this invention Market concentration (M) This invention: Market 50℃ 3.73E-10 9.47E-11 3.9 60℃ 3.64E-10 9.47E-11 3.8 70℃ 5.27E-10 9.47E-11 5.6

[0442] Table 5

[0443]

[0444] Table 6

[0445] In UV-Vis spectroscopy, absorbance can be detected from t=0 min. Therefore, it can be inferred that the reaction is quasi-instantaneous upon reagent contact, thus enabling continuous flow crystallization, rather than the current industry standard of batch flow. Converting a previously known batch process into a continuous process presents significant scale-up advantages. Furthermore, our process does not use any VOCs (volatile organic compounds) or organic matter as solvents or for liquid-liquid extraction.

[0446] The process of this invention is a greener and safer biochemical process that can replace existing market products, whether they are products from the inorganic reduction route in the prior art or products from the current plant-based reducing agent route in the prior art.

[0447] Comparative Example 1

[0448] The possibility of using another plant to replace crucian carp was evaluated. Watercress was chosen as a possible alternative because its nutritional characteristics are similar to those of crucian carp. Figure 65 and 66 As shown, the blends based on watercress used sage, oregano, and rosemary as high-quality antioxidant carriers, with red cabbage as a filler. However, it can be observed that to obtain the same results (in terms of antioxidant activity) as shown, the cost increases by 30%–70% compared to the kale-leaf model (see Table 7). This further validates the superiority of kale-leaf compared to watercress, compared to existing literature results.

[0449]

[0450] Table 7

[0451] Example 5 – Further methods for preparing silver metal nanoparticles

[0452] The method generally described in Example 4 was repeated to produce four batches of silver nanoparticles. The precise conditions are referred to as S1 to S4 in Table 8 below, with concentrations varying between 0.25 g / L and 0.9 g / L. Stirring was performed at 600 RPM. Figure 6Any of the blends 1 to 5 shown are suitable for carrying out the method.

[0453] After reaction at 70°C and 600 RPM with stirring, the reaction mixtures S1, S2, and S3 were quenched with ice-cooled water after 5 minutes, while the reaction mixture S4 was quenched after 30 minutes. It should be noted that the reaction rate was extremely fast—silver ions in the reaction mixtures S1, S2, and S3 were observed to transform into silver nanoparticles in less than 5 minutes.

[0454] After recovering the precipitate, it was first treated with ultrasound at 40 kHz at 25°C for 10 minutes, then oscillated for 5 minutes, then treated with ultrasound at 40 kHz at 25°C for 5 minutes, and then oscillated again for 5 minutes.

[0455] Batch Name Silver acetate concentration (g / L) Blend concentration (g / L) S1 0.9 7.00E+00 S2 0.7 7.00E+00 S3 0.5 7.00E+00 S4 0.25 7.00E+00

[0456] Table 8

[0457] The diameter of the nanoparticles was estimated by UV-VIS spectroscopy using the same method detailed in Example 4. The UV-VIS spectra are as follows: Figures 67 to 70 As shown in the figure. The molar concentration of the nanoparticles was also measured and compared with that of commercially available nanoparticles. The estimated diameters and concentrations are shown in Table 9.

[0458]

[0459] Table 9

[0460] This embodiment demonstrates that silver nanoparticles with a concentration greater than 2.9 times (and in some cases more than 4.5 times) of commercially available concentrations can be manufactured using the process of the present invention.

[0461] Example 6 – General Method for Producing Gold Metal Nanoparticles

[0462] An ionic solution was prepared at a desired concentration of 0.1 g / L to 1.5 g / L and preheated to 70 °C for 1 hour at 1 bar in a reactor with continuous stirring at 600 rpm. Upon reaching the steady-state temperature, a blend concentration of 0.5 g / L to 10 g / L was added to the reactor, and nucleation immediately commenced. Figure 6 Any of the blends 1 to 5 shown are suitable for this purpose. Gold(III) chloride hydrate (HAuCl4·H2O) is used.

[0463] Crystallization takes 5 minutes to 2 hours, depending on the desired conversion rate and nanoparticle size. It can be noted that the nanoparticles grow over time, therefore it is recommended to adjust the nanoparticle size according to the reaction time. Bioreduction occurs at this point, with the metal nanoparticles growing through primary heterogeneous nucleation. During this period, a color change from transparent to wine-red / purple can be observed.

[0464] The reaction was then quenched using 4°C cooling water until the internal temperature of the mixture reached 10°C. The mixture of nanoparticles and plant extracts was subsequently recovered and centrifuged (10,000 rpm, 20 min). The supernatant was recycled back to the reactor to improve conversion. It was passed through a cation exchange resin to recover the maximum amount of pure metal ions available for recycling. Deactivated antioxidants from the process were removed. The precipitate (containing trace amounts of water) was recovered and NaOH was added to raise the pH to 10-14. The precipitate was then first sonicated at 25°C and 40 kHz for 10 min, followed by agitation for 5 min, then sonicated at 25°C and 40 kHz for another 5 min, followed by agitation again for 5 min.

[0465] Subsequently, the colloid is passed through a micromembrane filter to remove any large agglomerates or deformed particles, ensuring high-quality functional nanoparticles with a high surface area to volume ratio. This property is particularly useful for medical, pharmaceutical, antimicrobial, conductive ink, and catalysis applications. Prior to shipment, the solution pH is adjusted to neutral or slightly alkaline (pH 7 to pH 9) using a weak organic acid (such as acetic acid) to ensure the solution is non-corrosive to the user.

[0466] Gold nanoparticles were ultimately obtained in colloidal solution. Sufficient nanoparticles were produced in each case and identified using spectroscopic analysis (UV / VIS). UV-Vis analysis allowed for identification using known methods (described in...) https: / / www.sigmaaldrich.com / GB / en / technical-documents / technical-article / materials-science-and-engineering / biosensors-and-imaging / gold-nanoparticles It was determined that the diameter of the nanoparticles generated at the reactor outlet was between 40 and 60 nanometers.

[0467] After the reactor, nanoparticles are filtered using microfiltration. A 200 nm membrane is used to remove any large agglomerates that may remain after sonication.

[0468] Example 7 – A specific method for producing gold metal nanoparticles

[0469] The method generally described in Example 6 was used to produce gold nanoparticles in three batches. The precise conditions are referred to as S1 to S3 in Table 11 below. Figure 6 Any of the blends 1 to 5 shown are suitable for carrying out the method.

[0470] Particles were prepared in three batches (S1 to S3), and their concentrations are shown in Table 10 below:

[0471] Batch Name Gold(III) chloride hydrate concentration (g / L) Blend concentration (g / L) S1 0.9 7.00E+00 S2 0.7 7.00E+00 S3 0.25 7.00E+00

[0472] Table 10

[0473] After reaction at 70°C and 600 RPM with stirring, the S1 and S2 reaction mixtures were quenched with ice-cooled water after 3 minutes, and the S3 reaction mixture was quenched after 30 minutes. Notably, the reaction rate was extremely fast—gold ions in the S1 and S2 reaction mixtures were observed to transform into gold nanoparticles in less than 3 minutes.

[0474] The diameter of the nanoparticles was estimated by UV-VIS spectroscopy using the same method detailed in Example 6. The UV-VIS spectra are as follows: Figures 71 to 73 As shown.

[0475] The particle size distribution of gold nanoparticles is as follows Figure 74 As shown in the figure, a normal distribution was obtained on a large sample of nanoparticles, with an average diameter of 21.65 nm and a standard deviation of 10.49 nm.

[0476] pass Figure 75-82 The scanning electron microscope (SEM) shown and Figure 83 and 84 The energy-dispersive X-ray spectroscopy (EDX) shown examined the gold nanoparticles. EDX allows for further verification of the formation of the gold nanoparticles and also enables the superposition of the gold nanoparticles with the positions of carbon and oxygen atoms, such as... Figures 85 to 88 As shown, this further confirms the presence of at least a carbohydrate bio-coating layer on the gold nanoparticles. Figure 89 The EDX spectrum of the gold nanoparticles further supports the presence of elemental gold, as well as carbon and oxygen on the nanoparticles. This further confirms the presence of a bio-coating agent on the metal nanoparticles.

[0477] The molar concentration of the nanoparticles was also measured and compared with that of commercially available nanoparticles. The estimated diameters and concentrations are shown in Table 11.

[0478]

[0479] Table 11

[0480] This embodiment demonstrates that the process of the present invention can be used to manufacture gold nanoparticles with a concentration more than 3 times that of commercially available products.

[0481] All publications mentioned in the foregoing specification are incorporated herein by reference. Various modifications and variations of the invention will be apparent to those skilled in the art without departing from the scope and spirit of the invention. While the invention has been described in conjunction with specific preferred embodiments, it should be understood that the claimed invention should not be unduly limited to such specific embodiments. Indeed, various modifications to the described modes of carrying out the invention that will be apparent to those skilled in the chemistry or related fields are intended to be within the scope of the following claims.

Claims

1. A method of producing metal nanoparticles having a diameter of between 1 nm and 1 μm, the method comprising: (a) providing dissolved metal ions; and (b) contacting the dissolved metal ions with a composition comprising an extract derived from: (a) Brassica oleracea Acephala group and Origanum vulgare; and (b) at least one other plant selected from: (i) Cyanara cardunculus, (ii) Brassica oleracea Capitata group var. rubra, (iii) Salvia cormanus, (iv) Salvia officinalis, (v) Nasturtium officinale, such that the dissolved metal ions are reduced to form metal nanoparticles.

2. The method of claim 1, wherein the metal is selected from gold, silver, copper, nickel, platinum, iron, zinc, gadolinium, titanium, cerium, thallium, manganese, aluminium, zirconium, chromium, palladium and cobalt, or any combination thereof.

3. The method of claim 1, wherein the metal is silver.

4. The method of claim 1, wherein the metal is gold.

5. The method of any one of claims 1 to 4, wherein the dissolved metal ions are present in the form of a solution of a metal salt.

6. The method of claim 5, wherein the metal salt is an acetate salt.

7. The method of any one of claims 1 to 6, wherein the composition comprises an extract derived from: (a) Brassica oleracea Acephala group and Origanum vulgare; and (b) at least one other plant selected from: (i) Cyanara cardunculus, (ii) Brassica oleracea Capitata group var. rubra, (iii) Salvia cormanus, and (iv) Nasturtium officinale.

8. The method of any one of claims 1 to 6, wherein the composition comprises an extract derived from: (a) Brassica oleracea var. Acephala group and Origanum vulgare; and (b) at least two other plants selected from: (i) Cyanara cardunculus, (ii) Brassica oleracea Capitata group var. rubra, (iii) Salvia cormanus, and (iv) Nasturtium officinale. (ii) red cabbage (Brassica oleracea var. Capitata group var. rubra), (iii) rosemary (Salvia cormanus), and (iv) watercress (Nasturtium officinale).

9. The method according to any one of claims 1 to 6, wherein the composition comprises an extract obtained from: (i) kale (Brassica oleracea var. Acephala group) in an amount of 30 to 90 mass-% of the total mass of the composition; (ii) artichoke (Cyanara cardunculus) in an amount of 0 to 20 mass-% of the total mass of the composition; (iii) red cabbage (Brassica oleracea var. Capitata group var. rubra) in an amount of 0 to 30 mass-% of the total mass of the composition; (iv) oregano (Origanum vulgare) in an amount of 1 to 20 mass-% of the total mass of the composition; (v) rosemary (Salvia cormanus) in an amount of 0 to 30 mass-% of the total mass of the composition; and (vi) watercress (Nasturtium officinale) in an amount of 0 to 30 mass-% of the total mass of the composition.

10. The method according to any one of claims 1 to 9, wherein a metal ion solution is added to the composition.

11. The method according to claim 10, wherein the metal ion solution is pre-heated before being added to the composition.

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