• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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  • 优先权
    • 专利摘要:
    Industrial method for the synthesis of metal nanoparticles of adjustable size. A method for obtaining metallic nanoparticles comprising: obtaining an infusion of at least one plant selected from the group consisting of: Camellia sinensis, Tilia, Chameamelum nobile, Equisetum arvense and a combination of the above; mixing the infusion obtained in the previous step with a precursor containing at least one metallic element, in an aqueous medium; adjust the pH of the mixture between 5 and 12, and the temperature equal to or less than 60ºC; and d) applying UV radiation to the mixture and stirring by ultrasound until a solution of metallic nanoparticles is obtained that comprises an amount equal to or greater than 100 ppm of metallic nanoparticles. As well as, the metallic nanoparticles with micellar structure that are obtained by this synthesis method and their use as antimicrobials. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2778948A1
    申请号:ES201930108
    申请日:2019-02-12
    公开日:2020-08-12
    发明作者:Gil Jesus Martin；Ramos Pablo Martin；Lebena Eduardo Perez；Juan Celia Andres
    申请人:Universidad de Valladolid；
    IPC主号:
    专利说明:

    [0002] INDUSTRIAL METHOD OF SYNTHESIS OF METALLIC NANOPARTICLES OF SIZE
    [0004] TECHNICAL SECTOR
    [0006] The present invention falls within the field of Inorganic Chemistry and has a direct application in the health sector. More specifically, it provides a biosustainable method to synthesize metal nanoparticles of adjustable size, in particular nanoparticles of a metal or metal oxide with antimicrobial characteristics (eg: Ag, Au, Pt, Cu, Cu20, CuO, ZnO). Thus, the nanoparticles obtained by this method can be used to treat and reduce pathogens (such as viruses, fungi and bacteria) that affect human and animal health, agriculture and, in general, Nature.
    [0008] The metallic nanoparticles obtained by the method of the present invention are micellar, which is a significant advantage, since it guarantees their bioavailability and, consequently, their antimicrobial activity in vivo.
    [0010] STATE OF THE ART
    [0012] In the state of the art the antimicrobial properties of metals such as, for example, silver, gold, platinum and copper are known; as well as various metal oxides such as Cu20, CuO, ZnO.
    [0014] On the other hand, the field of nanotechnology is growing by leaps and bounds due to the appearance of so-called nanomaterials, in particular inorganic nanoparticles (NP) with unique functions and physicochemical properties that are dependent on their size and geometry. The potential of inorganic nanoparticles has been explored in applications of nanomedicine, drug delivery and biomedical devices, cosmetics, electronics, as well as in the energy sector and environmental protection.
    [0016] In particular, metal or metal oxide nanoparticles (NP-M) have distinctive physical and chemical properties, for example, high thermal and electrical conductivity, improved Raman scattering at the surface, chemical stability, catalytic activity, and non-linear optical behavior. Due to these properties, NP-M can be used in a wide range of range of applications in industry, in particular in the preparation of consumer products (e.g. inks, plastics, food packaging, soaps, pastes, food and textiles) and in biomedical sectors, especially due to its effectiveness against microbes ( bacteria, fungi and viruses), its anti-inflammatory activity, and its ability to heal wounds and burns.
    [0018] Another additional advantage of NP-Ms is that they can be used in various forms (liquid or solid). For example, nanoparticles can be mixed with solid material for the synthesis of polymers, allowing the obtaining of enamels, coatings or paints; they can be found suspended in materials such as soap; or in the composition of fabrics.
    [0020] In relation to the synthesis of metallic nanoparticles, in the state of the art there are chemical, physical, photochemical and biological methods described to synthesize this type of nanoparticles. Each method has its advantages and disadvantages, commonly associated with issues related to the procedure (in particular, cost of production and scalability), or to the characteristics of the nanoparticles obtained (in particular, stability, size and concentration).
    [0022] Chemical methods are generally preferred due to ease of synthesis. These methods are generally based on three factors: (a) a metal precursor; (b) a reducing agent; and (c) a stabilizing agent. The synthesis and geometry of the metallic nanoparticles obtained by this method is based on the nucleation and subsequent stacking of the metal nuclei.
    [0024] Along with chemical methods, several alternative physical techniques have been described. In particular, evaporation and condensation processes have been implemented. One of the most common drawbacks of these methods is the increased energy requirement and the time required. In parallel, a thermal decomposition process has also been developed in which, by forming a complex between Ag and oleate at elevated temperature, NP-Ag with a particle size less than 10 nm are obtained.
    [0026] Another very common technique is electrolysis, in which high purity silver electrodes are used, greater than 99.99%. However, cost is considered to be the main obstacle to adopting such a method as it requires expensive consumables.
    [0027] In photochemical techniques, metal nanoparticles are synthesized by photoreduction of metal precursors or ions, using photochemically activated intermediates. In one of these methods, the NP-Ms are achieved using UV radiation, and an aqueous solution with the nonionic surfactant Triton-X 100, a chemical compound that acts as a stabilizing agent. This surfactant helps maintain the stability, monodispersity and uniform size of the synthesized NP-M. In another method using a photochemical technique, Ag nanoparticles are synthesized from an aqueous alkali solution containing AgN03 and carboxymethylated chitosan (CMCTS), using UV radiation. In this method, CMCTS is used as a stabilizing agent for the particles, with a diameter less than 10 nm.
    [0029] Analogous to chemical methods, the biological synthesis of metal nanoparticles and, in particular, of NP-Ag also requires a precursor (preferably AgN03), a reducing agent and a stabilizing or capping agent, for example: PVP (polyvinyl pyrrolidone ) or PVA (polyvinyl alcohol), to avoid agglomeration of the particles that are obtained. However, in this type of method, the nanoparticles are synthesized using active principles obtained from plants, algae, yeasts, fungi and / or bacteria as reducing agents and stabilizers. The size of the NP-Ag obtained by these methods can be less than 15 nm, with uniform dispersion characteristics, spherical shape, improved stability and large surface area. This procedure is economical, reproducible and consumes less energy compared to conventional ones.
    [0031] In particular, patent application W02005120173 A2 describes a method for obtaining silver nanoparticles (NP-Ag) using an extract of plant tissue. However, the procedure described in this document has several drawbacks. The first of these is that the concentration of NP-Ag obtained in this method is very low (it does not exceed 6 ppm), which makes commercial exploitation of this procedure unfeasible, since a minimum concentration of 100 ppm is necessary for that the method is competitive. The second drawback is derived from the fact that the reaction time in the method described in this document can be prolonged for several hours. Finally, many of the plants mentioned in the application W02005120173 are difficult to access, which makes it difficult for the described method to be carried out in an industrial way.
    [0033] On the other hand, in the scientific publication "Synthesis and characterization of novel silver nanoparticles using Chamaemelum nobile extract for antibacterial application", Hoda Erjaee et al., 2017, Adv. Nat. Sci: Nanosci. Nanotechnol. 8025004, a method is described in which chamomile, Chamaemelum nobile, is used for the first time to obtain NP-Ag. However, the reaction times described in this publication exceed 8 hours, going even between 16 and 24 hours. This drawback is important to ensure the success of industrial scalability.
    [0035] In the publication "Green Tea as Biological System for the Synthesis of Silver Nanoparticles", Elbossaty WF, J Biotechnol Biomater 7: 269., A method similar to the previous one is proposed, but it suffers from the same drawbacks: an excessive reaction time and a very low concentration of NP-Ag in ppm in the medium.
    [0037] DESCRIPTION OF THE INVENTION
    [0039] The present invention provides a method of synthesis of metallic nanoparticles, preferably NP-Ag, with micellar structure and dispersed in an aqueous medium. In the method described here, the synthesis of metallic nanoparticles takes place very quickly, preferably in a period of less than 10 min, and makes it possible to obtain a concentration of nanoparticles in solution of at least 100 ppm. Consequently, the method of the present invention makes it possible to obtain metallic nanoparticles, in particular NP-Ag, on an industrial scale.
    [0041] As mentioned above, the nanoparticles obtained by the synthesis method described in this document have a micellar structure. This is a great advantage for the use of metallic nanoparticles as antimicrobial agents, since it significantly increases their bioavailability. In general, it is preferred that antimicrobial compounds (CAMs) are water-soluble, since thus the benefits they provide are significantly greater, allowing complete absorption by the host.
    [0043] Thus, a first aspect of the present invention is a method for obtaining metallic nanoparticles that comprises:
    [0044] a) obtain an infusion of at least one plant selected from the group consisting of: Camellia sinensis (tea), Tilia (linden), Chameamelum nobile (chamomile), Equisetum arvense (horsetail), and a combination of the above;
    [0045] b) mixing the infusion obtained in the previous step with a precursor containing at least one metallic element, in an aqueous medium;
    [0046] c) adjust the pH of the mixture between 5 and 12, and the temperature equal to or less than 60 ° C; and d) applying UV radiation to the mixture, preferably between 400 nm and 320 nm, and stirring by ultrasound until obtaining a solution of metallic nanoparticles, preferably of metal or metallic oxide, which comprises an amount equal to or greater than 100 ppm of metallic nanoparticles. and a micellar structure.
    [0048] Unlike other methods described above, the method for obtaining metallic nanoparticles described here can take place in an aqueous medium, preferably water, without the need to add alcohols such as, for example, polyvinyl alcohol, nor is it necessary to use of alcohol / water mixtures for the synthesis of nanoparticles to take place. Furthermore, the inventors have observed that the use of water as a solvent improves the stability of the solutions and the micellar structure, while the presence of alcohol favors the formation of colloidal structures.
    [0050] As mentioned above, the nanoparticles obtained by the method described here have a micellar structure. This structure remains stable and without the formation of colloids or suspensions, even when working with concentrations of metallic nanoparticles of up to 2000 ppm, preferably between 500 and 750 ppm. Additionally, the method makes it possible to control the size of metallic nanoparticles as a function of the time that the UVA illumination and the application of ultrasound are maintained. The longer the exposure time, the larger the nanoparticles.
    [0052] The combined use of UV radiation and ultrasound significantly reduces the reaction time, allowing the production of metallic nanoparticles in a period of less than 10 min, in particular between 2 and 5 min. Thus, the procedure described here makes it possible to obtain metal nanoparticles in solution in a stable way and with a micellar structure even for a concentration of nanoparticles in solution of 2000 ppm. In particular, the inventors have observed that under these conditions the method of the present invention makes it possible to obtain micellar structures stable over time, for at least 15 days, preserved at 4 ° C and in an inert atmosphere.
    [0054] Unless expressly indicated otherwise, in the present invention it should be understood that the concentration of nanoparticles in solution is expressed in weight / volume, that is, the ppm indicated correspond to the milligrams of metal nanoparticles per liter of solution (mg / L).
    [0055] Additionally, the method for obtaining metallic nanoparticles described here may comprise an additional stage, for example for characterization studies, where the solution of metallic nanoparticles from stage d) is subjected to a treatment to eliminate the solvent, for example, lyophilization, simple evaporation or elimination under vacuum, to obtain metallic nanoparticles in solid state with a particle size equal to or less than 400 nm, and more preferably less than 50 nm.
    [0057] In the method of the present invention, NP-M with different morphology and different particle size can be obtained, especially when working with NP-Au due to the characteristic variability of this type of nanoparticle. This is because, over time, some of the NPs can stabilize by increasing in size.
    [0059] The metal nanoparticles obtained in the process described here can be metal nanoparticles or metal oxides with antimicrobial or antitumor properties. Preferably, nanoparticles of Ag, Au, Pt, Cu, Cu20, CuO, ZnO or a combination of the above.
    [0061] The method proposed in the present invention uses an infusion of at least one plant selected from the group consisting of Camellia sinensis (tea), Tilia (linden), Chameamelum nobile (chamomile), Equisetum arvense (horsetail), and a combination of the above. The use of any of these four plants is advantageous due to its innocuousness, ease of commercial access and its special relevance when it comes to achieving the synthesis of nanoparticles.
    [0063] Step a) of the method described herein may comprise performing an infusion, a procedure also called extraction, of one or more of the plants specified above, either separately or mixed together in any proportion. To make this infusion, any part of the plant can be used, that is, the stem, leaves and even the root or, alternatively, the whole plant can be used. The common denominator of these plants is that they comprise alkaloids, terpenes, flavonoids and polyphenols in general that play a decisive role in the process of reducing the corresponding metal ions (for example: from Ag + to metallic Ag), as well as in stabilization of the nanoparticles obtained. In particular, polyphenols are oxidized to form quinones that are absorbed on the surface of NPs, contributing decisively to their stabilization.
    [0064] The infusion or extraction of step a) can be obtained by mixing one or more of the plants specified above in an aqueous medium, heating to a boil and maintaining stirring for a minimum period of 10 min. The concentration of the plant in the mixture to be infused can vary, it being preferable that this concentration is around 50 g / l, in particular between 30 g / l and 70 g / l, expressed in grams of plant with respect to the volume of solvent added to obtain the mixture to be infused. Preferably the solvent used is water, the addition of alcohol or water / alcohol mixtures is neither necessary nor recommended. It has been found that the use of only water improves the stability of the solutions and the micellar structure of the nanoparticles over time, while the presence of alcohol / water favors the formation of colloidal structures. In this way the dissolution of the active principles of the plant in the water is obtained. The final infusion, once filtered or centrifuged, can be used separately or mixed with one or more infusions of another of the mentioned plants.
    [0066] Additionally, the precursor containing at least one metal element can be an inorganic salt (preferably a nitrate or chloride) containing the corresponding metal cation. In the particular case of obtaining copper nanoparticles, the inventors have observed that the use of copper sulfate as a precursor does not give good results, while the use of copper nitrate does allow to obtain copper nanoparticles, obtaining a mixture of Cu , Cu20 and CuO. Something similar occurs in relation to obtaining zinc nanoparticles, which is why the use of zinc nitrate is also preferred to obtain nanoparticles, in this case ZnO nanoparticles. On the other hand, to obtain gold or platinum nanoparticles (antitumor properties), it is preferred to use a chloride of the corresponding metal as precursor, in particular, salts of AuCl3xH20 and Na2PtCl4.
    [0068] The amount of metal precursor is added as a function of the concentration of metal nanoparticles in solution to be obtained, preferably in a 1: 1 molar ratio between precursor and metal nanoparticles. For example, to obtain approximately 1 liter of a solution with 500 ppm of NP-Ag, 780 mg of AgN03 can be used.
    [0070] Preferably, the method of the present invention comprises mixing an aqueous solution comprising the metallic precursor, with the infusion obtained from at least one plant selected from the group consisting of Camellia sinensis (tea), Tilia (linden), Chameamelum nobile (chamomile), Equisetum arvense (horsetail) and a combination of the above.
    [0072] In particularly preferred embodiments, the method described here comprises using 50 ml of the plant infusion extract (50 g / l) and, once filtered, adding it drop by drop to a solution comprising the necessary amount of metallic precursor (at 1: 1 molar ratio) to obtain 1 liter of 500 ppm NP-M. In this way, a sufficiently concentrated extract is available to produce the stabilized metallic nanoparticles.
    [0074] In preferred embodiments, the method of the present invention comprises adjusting the pH of the mixture between 7 and 10, before the simultaneous application of UV radiation and ultrasound. Likewise, it is also preferred that the temperature of the mixture is kept between 20 ° C and 60 ° C during the nanoparticle formation process. Unexpectedly, by adjusting the pH between 7-10, ionized complexes are formed in the polyphenols from the plant that help stabilize the nanoparticles. However, temperatures of 60 ° C should not be exceeded during sonication.
    [0076] The method for obtaining metallic nanoparticles described in this document comprises applying radiation in the UVA range as a catalyst. Preferably, this radiation has a wavelength between 400 nm and 320 nm, and more preferably around 370 nm. In this way the reaction is completed in a very few minutes (less than 10 min). The size of the particle obtained is adjustable depending on the time of application of the UV radiation and, in any case, less than 100 nm.
    [0078] Simultaneously with the application of UVA radiation, the reaction mixture is stirred by ultrasound, preferably at a frequency between 20,000 and 60,000 Hz.
    [0080] The proposed method uses the combined and simultaneous use of ultrasound and UVA light to accelerate reaction times and adjust the size of the PN to the desired parameters. Executing the procedure in this way, NP-M are obtained in a reduced time, less than 10 minutes, not described so far.
    [0082] Another object of protection of the present invention are the metallic nanoparticles obtained by the method described in this document, in particular NP-Ag. These nanoparticles are characterized by presenting a micellar structure in solution and, preferably a particle size equal to or less than 400 nm, more preferably a particle size less than 50 nm.
    [0084] Likewise, the present invention also refers to the use of nanoparticles, with micellar structure, obtained by the method described here with an antimicrobial agent.
    [0086] Brief description of the figures
    [0088] Figure 1: Images made by transmission electron microscopy (TEM), made with a 200kV field emission TEM microscope model JEOL JEM-FS2200 HRP, of a micellar extract obtained by reduction of HAuCl4 in the presence of chamomile ( Chameamelum nobile) (solution 500 ppm of NP-Au), where AuNPs of different morphologies and sizes are observed: Fig. 1 (a) and Fig. 1 (b) Triangular, hexagonal (truncated triangular) and spheroidal AuNPs at two magnifications (100000 * and 250,000 *); Fig. 1 (c) 360 * 240 nm hexagonal particle, accompanied by small spheroidal particles, 30 nm in diameter; Fig. 1 (d) two triangular-looking nanoparticles, one of 60 nm and the other of 110 nm; and a decahedral, 40 nm, located in the lower left.
    [0090] EXAMPLES
    [0092] Example 1: Obtaining a solution comprising 500 ppm of NP-Ag
    [0094] First, an infusion of camolina ( Chameamelum nobile) is obtained in the following way: 50 g of this plant are weighed and added to 1 liter of demineralized water. The mixture is heated to boiling and is kept stirring for 10 min under these conditions. Subsequently, the mixture is cooled and filtered.
    [0096] On the other hand, 780 mg of AgNO3 are weighed and added to 1 liter of deionized and distilled water. This solution is stirred until total homogenization is achieved. To this solution of the metallic precursor 50 ml of the infusion of chamomile ( Chamaemelum nobile) prepared above are added. Once this mixture is made, the pH is adjusted with phosphate buffer 7.4 and subjected to the action of ultrasound (20kHz) under the illumination of a 370 nm UVA light lamp. The simultaneous application of UVA light and ultrasound agitation was applied during 6 periods of 5 minutes of sonication, and not allowing the temperature of the sonicated mixture to exceed 60 ° C, obtaining a solution with a concentration 500 ppm of NP-Ag with micellar structure. Subsequently, the solvent was removed from this solution to obtain NP-Ag with a particle size between 20 and 100 nm.
    [0098] Example 2: Obtaining a solution comprising 750 ppm of NP-Ag
    [0100] First, an infusion of tea ( Camellia sinensis) is obtained in the following way: 50 g of this plant are weighed and added to 1 liter of demineralized water. The mixture is heated to boiling and is kept stirring for 10 min under these conditions. Subsequently, the mixture is cooled and filtered.
    [0102] On the other hand, 1170 mg of AgN03 are weighed and added to 1 liter of deionized and distilled water. This solution is stirred until total homogenization is achieved. To this solution of the metallic precursor 50 ml of the tea infusion ( Camellia sinensis) prepared above are added. Once this mixture has been carried out, the pH is adjusted with phosphate buffer 7.4. Once this mixture is made, it is subjected to the action of ultrasound (20 kHz) under the illumination of a 370 nm UVA light lamp. The simultaneous application of UVA light and ultrasound agitation was applied during a 5-minute period of sonication, and not allowing the temperature of the sonicated mixture to exceed 60 ° C, obtaining a solution with a concentration of 500 ppm of NP-Ag with micellar structure. Subsequently, the solvent was removed from this solution to obtain NP-Ag with a particle size between 20 and 100 nm.
    [0104] Example 3: Obtaining a solution comprising 500 ppm of NP-Au
    [0106] First, an infusion of camoline ( Chameamelum nobile) is obtained in the same way as in the previous examples.
    [0108] On the other hand, 868 mg of HAuCl4 are weighed and added to 1 liter of deionized and distilled water. This solution is stirred until total homogenization is achieved. To this solution of the metallic precursor 50 ml of the infusion of chamomile ( Chamaemelum nobile) prepared above are added. Once this mixture is made, the pH is adjusted with phosphate buffer 7.4 and subjected to the action of ultrasound (20kHz) under the illumination of a 370 nm UVA light lamp. The simultaneous application of UVA light and ultrasound shaking was applied during 6 periods of 5 minutes of sonication, and not allowing the temperature of the sonicated mixture to exceed 60 ° C, obtaining a solution with a concentration of 500 ppm of NP-Au with micellar structure.
    [0109] Subsequently, the solvent was removed from this solution to obtain NP-Au with different morphologies and sizes (see figure 1) and solid state metallic nanoparticles with a particle size equal to or less than 400 nm, and more preferably less than 50, are observed. nm.
    [0111] It has also been observed that when working with concentrated solutions of 500 ppm of AuNPs, hexagonal particles and flavonoids can also appear in the form of glucosides.
    [0113] As can be seen in the different images in Figure 1, the method described here allows obtaining NP-Au with different morphologies and sizes (30 nm spheroidal and 30 nm triangular and, in some cases, 110 nm). This is because some of the NP-Au tend to stabilize by increasing in size, as a function of time, especially for concentrated solutions of 500 ppm of NP-Au.
    [0115] As mentioned above, the method for obtaining NP-M of the present invention makes it possible to obtain metallic nanoparticles in solid state with a particle size equal to or less than 400 nm, and more preferably less than 50 nm.
    [0117] Thus, although it is particularly preferred that the nanoparticles have a size less than 50 nm, over time the size of the particles may grow, giving rise to the appearance of aggregates or precipitates with a particle size equal to or less than 400 nm. In the particular case of the NP-Au solution, it has been observed that the solution is stable for at least 15 days and that its properties remain unchanged for at least this period of time.
    权利要求:
    Claims (12)
    [1]
    1. - A method for obtaining metallic nanoparticles that comprises:
    a) obtain an infusion of at least one plant selected from the group consisting of: Camellia sinensis, Tilia, Chameamelum nobile, Equisetum arvense and a combination of the above;
    b) mixing the infusion obtained in the previous step with a precursor containing at least one metallic element, in an aqueous medium;
    characterized in that the method additionally comprises:
    c) adjust the pH of the mixture between 5 and 12, and the temperature equal to or less than 60 ° C; and d) applying UV radiation to the mixture and stirring using ultrasound until a solution of metallic nanoparticles is obtained that comprises an amount equal to or greater than 100 ppm of metallic nanoparticles and a micellar structure.
    [2]
    2. - The method according to claim 1, wherein the solution of metallic nanoparticles comprises at least up to 500 ppm of metallic nanoparticles.
    [3]
    3. - The method according to any one of claims 1 and 2, comprising an additional step e) where the solution of metallic nanoparticles is subjected to a treatment to eliminate the solvent, obtaining metallic nanoparticles in solid state with an equal particle size or less than 400 nm.
    [4]
    4. - The method according to any one of claims 1 to 3, wherein nanoparticles of a metal or metal oxide selected from the group consisting of Ag, Au, Pt, Cu, Cu20, CuO, ZnO and a combination of the above are obtained .
    [5]
    5. - The method according to any one of claims 1 to 4, wherein step a) comprises mixing at least one of the plants in an aqueous medium, heating to a boil and stirring for a minimum period of 10 min.
    [6]
    6. - The method according to any one of claims 1 to 5, wherein the metallic precursor is selected from the group consisting of silver nitrate, copper nitrate, zinc nitrate, gold chloride and platinum chloride.
    [7]
    7. - The method according to any one of claims 1 to 6, wherein step c) comprises adjusting the pH of the mixture between 7 and 10.
    [8]
    8. The method according to any one of claims 1 to 7, wherein the temperature is maintained between 20 ° C and 60 ° C during step d).
    [9]
    9. The method according to any one of claims 1 to 8, wherein the UVA radiation has a wavelength between 400 nm and 320 nm.
    [10]
    10. - The method according to any one of claims 1 to 9, wherein the stirring by ultrasound takes place at a frequency between 20,000 and 60,000 Hz.
    [11]
    11. - Metallic nanoparticles obtained by the method described in any one of claims 1 to 10, where these nanoparticles have micellar structure.
    [12]
    12. Use of the metallic nanoparticles described in claim 11 as an antimicrobial agent.
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    同族专利:
    公开号 | 公开日
    WO2020165476A1|2020-08-20|
    ES2778948B2|2021-08-13|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO2005120173A2|2004-05-12|2005-12-22|Kishore Madhukar Paknikar|Anti-microbial activity of biologically stabilized silver nano particles|
    AU2015101419A4|2015-09-29|2015-11-12|Ghotekar, Suresh MR|A process for bio-synthesizing metal nano-particles|
    CN107671305A|2017-09-22|2018-02-09|鲁东大学|The method that nano silver antibacterial agent is quickly prepared using Ligustrum quihoui fruit extracting solution|
    KR0155608B1|1995-07-14|1998-12-01|박홍기|The preparation of far-infrared radiating polyester fiber|
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    PCT/ES2020/070066| WO2020165476A1|2019-02-12|2020-01-30|Industrial method of synthesis of metal nanoparticles with adjustable size|
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