KR102292488B1 - Manufacturing method of silver nanoparticles using citrus fruits - Google Patents

Abstract

The present invention relates to a manufacturing method of silver nanoparticles which can synthesize silver nanoparticles by using a natural reducing agent extracted from tangerine and a plant having a high advantage related to production cost and harmfulness. The manufacturing method comprises: a step (a) of preparing a natural extract of the tangerine and the plant; and a step (b) of mixing the natural extract and a silver salt compound to synthesize the silver nanoparticles. Therefore, the present invention has significantly high industrial validity since the present invention enables mass production and uses an eco-friendly method.

Description

Manufacturing method of silver nanoparticles using citrus fruits

The present invention relates to a method for producing silver nanoparticles using a plant of the citrus family, and in particular, silver nanoparticles that can be synthesized using a natural reducing agent extracted from a plant of the citrus family, which has high advantages in terms of production cost and harm. It relates to a manufacturing method of

In general, silver nanoparticles (silver nonoparticles, AgNPs) have been known to have useful antibacterial properties and are being used in a wide variety of related fields. That is, silver nanoparticles can be applied to a wide range of fields such as food, cosmetics, detergents, electronic products, and quasi-drugs due to their excellent conductivity, catalyst and optical activity as well as intrinsic sterilization and antibacterial properties.

As a manufacturing technology of such silver nanoparticles, there are chemical, physical, and biological synthesis methods.

That is, the physical method is a method of manufacturing silver nanoparticles by pulverizing bulk materials with mechanical force. It requires a large space and a lot of energy, and it is inefficient in terms of energy and economics because it requires maintaining thermal stability.

In addition, the chemical method is a method of manufacturing by chemically reducing silver ions in a solution with organic and inorganic reducing agents. Compared to the physical method, the maintenance cost is reduced and mass production is possible within a short time, but the chemical and There are disadvantages in that the toxicity and harmfulness of the generated by-products and the need for a dispersion stabilizer of nanoparticles are required. In particular, chemical toxicity is a major hindrance to the application of silver nanoparticles to life and bio fields.

On the other hand, as a manufacturing technology that can solve the disadvantages of physical and chemical manufacturing methods, the biological synthesis method uses microorganisms, strains, and plant extracts. However, the method of utilizing microorganisms and bacteria has no industrial feasibility as it requires highly sterile conditions and cell culture conditions.

An example of a technique for solving this problem is disclosed in Documents 1 to 3 and the like.

For example, in Patent Document 1 below, camellia, citron, gom pine, tea tree, maple, wild mulberry, bumblebee, mugwort, cedar, pine, persimmon, chestnut, ginkgo, cypress, fern, 1ml~10ml of a plant extract extracted from at least one plant tissue selected from the group of red pepper tree, jujube, holy basil, betel and juniper tree, 1mM water-soluble metal compound, 1ml~10ml and KCl, NaCl, NaBr, NaNO ₃ , NaH ₂ PO ₄ , Na ₂ SO ₄ , KF, KI, KBr, KNO ₃ , KH ₂ PO ₄ One or more adjuvants selected from the group 1 mM, 1 ml to 10 ml are mixed, and at least one of reaction time, temperature and pH is adjusted. Disclosed is a method for manufacturing metal nanoparticles for controlling the size and shape of metal nanoparticles produced by

In Patent Document 2, 5 g of G jasminoides Ellis seed powder is dissolved in 100 ml of distilled water, boiled for 10 minutes, centrifuged at 10,000 rpm and filtered through filter paper to prepare a gardenia seed extract, the gardenia seed extract Preparation of silver nanoparticles using gardenia seed extract, which includes adding 10 ml to 90 ml of an aqueous solution containing silver ions (Ag+) and reacting at room temperature for 24 hours, centrifuging the synthesized green and freeze-drying A method is disclosed.

On the other hand, in Patent Document 3 below, a turnip green comprising the steps of preparing a turnip extract obtained by extracting turnip green on a water bath at 80 to 100 ° C. Disclosed is a method for preparing silver nanoparticles using the same.

Republic of Korea Patent Publication No. 10-1144416 (registration of 2012.05.02) Republic of Korea Patent Publication No. 10-2091166 (registered on March 13, 2020) Republic of Korea Patent Publication No. 10-1456390 (Registered on October 23, 2014)

As described above, Patent Document 1 discloses a technology for controlling the size or shape of nanoparticles, and Patent Document 2 discloses an ecologically sustainable and economically producible technology, but productivity and production rate, etc. Mass production was not disclosed.

In addition, Patent Document 3 discloses a technology for synthesizing silver nanoparticles safely, effectively and environmentally friendly using turnip green, but Patent Document 3 also discloses technology for mass production such as productivity and production speed, and silver nanoparticles as the final product. The dispersion stability of the solution was not disclosed.

It is an object of the present invention to solve the above problems, and to provide a method for producing silver nanoparticles using citrus fruits and plants using natural citrus extracts having high advantages in terms of production cost and harmfulness.

Another object of the present invention is to provide a method for producing silver nanoparticles using citrus fruits that can be mass-produced by a rapid reduction reaction.

Another object of the present invention is to provide a method for producing silver nanoparticles using citrus fruits, which can prevent the toxicity of by-products generated during the synthesis of silver nanoparticles in advance.

Another object of the present invention is to provide a method for producing silver nanoparticles using citrus fruits, in which the formed silver nanoparticles do not agglomerate in an aqueous solution and the dispersion stability is maintained for 30 days or more.

In order to achieve the above object, a method for producing silver nanoparticles using a citrus fruit plant according to the present invention comprises the steps of (a) preparing a natural extract of a citrus plant, (b) mixing the natural extract and a silver salt compound to obtain silver nanoparticles. It is characterized in that it comprises the step of synthesizing the particles.

In addition, in the method for producing silver nanoparticles using a citrus plant according to the present invention, the citrus plant is any one of lemon, lime, orange, mandarin, grapefruit, yuzu, bergamot, and kumquat.

In addition, in the method for producing silver nanoparticles using a citrus fruit plant according to the present invention, the silver salt compound is silver nitrate (AgNO ₃ ), silver perchlorate (AlClO ₄ ), silver chlorate (AgClO ₃ ), silver carbonate (Ag ₂ CO ₃ ) , silver sulfate (Ag ₂ SO ₄ ), silver chloride (AgCl), silver bromide (AgBr), silver acetate or silver fluoride (AgF).

In addition, in the method for producing silver nanoparticles using a citrus plant according to the present invention, the citrus plant is citron, and the silver salt compound is silver nitrate (AgNO ₃ ).

In addition, in the method for producing silver nanoparticles using a citrus plant according to the present invention, the natural extract in step (a) is vacuum-dried at 50° C. for 48 hours in a dryer after the first pulverization of the citrus plant, 2 It is characterized in that it is prepared by dispersing the tea finely in distilled water to prepare a dispersion solution, and stirring the dispersion solution at 60 to 80° C. for 1 hour.

In addition, in the method for producing silver nanoparticles using citrus fruits according to the present invention, the mixing in step (b) is prepared by dissolving the silver nitrate in distilled water to a concentration of 1 to 5 mM, and using 0.1 M NaOH to pH It is characterized in that a mixed solution is prepared by mixing a basic aqueous solution of about 9 to 11 and the natural extract.

In addition, in the method for producing silver nanoparticles using a citrus plant according to the present invention, the citrus plant is characterized in that it is a natural reducing agent having a high content of phenolic compounds and flavonoids.

In addition, in the method for producing silver nanoparticles using a citrus plant according to the present invention, the citrus plant is characterized in that it contains a large amount of reducing agents of caffeic acid, ferulic acid, rutin and kaempferol.

Further, in the method for producing silver nanoparticles using citrus fruits according to the present invention, the size of the silver nanoparticles is between 1 and 100 nm.

As described above, according to the method for producing silver nanoparticles using a citrus fruit plant according to the present invention, silver nanoparticles are produced using a natural reducing agent derived from citrus fruits, so the production rate, production and yield of silver nanoparticles, etc. can be quantified, no separate maintenance cost is required, mass production is possible through rapid reduction reaction, and the effect of very high industrial feasibility is obtained in an environmentally friendly method.

In addition, according to the method for producing silver nanoparticles using citrus fruits according to the present invention, it is possible to provide an eco-friendly method for synthesizing silver nanoparticles by blocking the toxicity of by-products generated during the synthesis of silver nanoparticles in advance.

In addition, according to the method for producing silver nanoparticles using a citrus fruit plant according to the present invention, an aqueous silver nanoparticle aqueous solution is synthesized in an environmentally friendly manner using a natural reducing agent extracted from the citrus fruit plant. It has a size between the two and is free from chemical toxic substances, so it is advantageous for pharmaceutical, cosmetic and food industry applications.

1 is a schematic diagram for explaining a method for producing silver nanoparticles using a citrus fruit extract according to the present invention;
2 is a UV-Vis spectrophotometer graph of silver nanoparticles prepared with citrus extract;
3 is a UV-Vis spectrophotometer graph for each hour of silver nanoparticles prepared with a citron extract;
4 is an ultraviolet-visible spectrophotometer graph for each pH of silver nanoparticles prepared with a citron extract;
5 is a graph of component analysis (HPLC quantitative, qualitative analysis) of the yuja extract;
6 is a graph showing the content table of natural reducing agent and dispersing agent of citrus extract;
7 is a UV-Vis spectrogram of the dispersion stability of silver nanoparticles prepared with yuja extract;
8 is a graph showing the results of measuring silver nanoparticles prepared from citron extract according to the present invention by a dynamic light scattering (DLS) method;
9 is a TEM (Transmission Election Microscopy) photograph of silver nanoparticles prepared with a citron extract.

The above and other objects and novel features of the present invention will become more apparent from the description of the present specification and accompanying drawings.

As used herein, the term “citrus fruits” refers to fruits with sweet and sour taste, and refers to any one of tangerine, citron, tangja, lemon, lime, orange, mandarin, grapefruit, bergamot, and kumquat.

Citrus plants applied to the present invention are, for example, any one of lemon, lime, orange, mandarin, grapefruit, citron, bergamot, and kumquat, and synthesized by reducing silver ions of a silver salt compound with a natural reducing agent extracted from citrus fruits. Based on the results of productivity, production speed, and stability of silver nanoparticles, silver nanoparticles prepared using a synthesis method using a natural extract and a citron extract with the highest content of effective reducing agent were prepared.

Examples of citrus fruits applied to the present invention are briefly described as follows.

The lemon (Citrus limon) is an evergreen arboreous tree of the dicotyledonous plant Russinaceae, the fruit has an oval shape, the outer skin is green, but turns yellow when ripe, and has a strong sour taste due to a lot of vitamin C and citric acid, making it a drink or flavoring agent. is used as

Lime (Citrus aurantifolia) is an evergreen shrub of the dicotyledonous rutaceae family, the fruit flesh is yellow-green, soft, succulent and sour, sweeter and more sour than lemon, and used as a flavoring or seasoning.

Orange is one of the fruits belonging to the citrus family. It is round in shape, orange in color, and has a thick and succulent skin.

Mandarin is a generic name for dicotyledonous rutaceae and mandarin-based tangerines, and is a related species of mandarin orange/Citrus reticulata, and is eaten as it is or used as juice, vinegar, etc.

Grapefruit is a fruit of the grapefruit tree belonging to the genus Citrus. It has a strong sweet taste and a little bitter taste.

Citron is the fruit of the citron tree, which is yellow, ball-shaped, has a rough skin and has a sour taste, and is used as a tea.

Bergamot (Citrus bergamia) is an evergreen shrub of the rutaceae family of dicotyledonous plants, dicotyledonous plants, mainly cultivated in Italy. The fruit is 7.5-10 cm in diameter, in the shape of a flat ball, an upside down egg, or a pear-shaped, strong sour taste and flavoring. is used as

Kumquat is an evergreen shrub of the rutaceae family. The fruit peel is orange, smooth, and sweet, and the flesh is sweet and sour.

As described above, the natural reducing agent is extracted from the citrus plant according to the present invention and silver nanoparticles are synthesized in an eco-friendly manner using the same.

For example, silver nanoparticles synthesized from citron extract exhibited a fast production rate and high yield, and were stably dispersed in an aqueous solution as a natural capsule of citron extract for a long time.

In addition, the silver salt compound applied to the present invention is silver nitrate (AgNO ₃ ), silver perchlorate (AlClO ₄ ), silver chlorate (AgClO ₃ ), silver carbonate (Ag ₂ CO ₃ ), silver sulfate (Ag ₂ SO ₄ ), silver chloride ( AgCl), silver bromide (AgBr), silver acetate or silver fluoride (AgF) may be applied.

Hereinafter, an embodiment according to the present invention will be described with reference to the drawings.

1 is a schematic diagram illustrating a method for manufacturing silver nanoparticles using a citrus fruit extract according to the present invention.

As shown in FIG. 1 , in the method for synthesizing silver nanoparticles according to the present invention, natural product extraction is first performed.

Natural product extraction applied to the present invention is a plant of the citrus family, and any one of tangerine, citron, tangja, lemon, lime, orange, mandarin, grapefruit, bergamot, and kumquat can be applied. 1 shows, for example, citron, but is not limited thereto, and any one of lemon, lime, orange, mandarin, grapefruit, bergamot, and kumquat may be applied.

After pulverizing natural citrus fruits and plants with a grinder, vacuum-drying at 50° C. for 48 hours in a dryer.

After the dried natural product is secondarily pulverized more finely, 1 g of the finely pulverized natural product is dispersed in 20 ml of distilled water to prepare a dispersion solution. The natural reducing agent was sufficiently extracted by stirring the dispersion solution at 60-80° C. for 1 hour, and the extract was cooled to room temperature to prepare an extract. The extract was analyzed for components through High-Performance Liquid Chromatography (HPLC)-MS. As natural products, extracts were prepared through the above-described processes for yuzu, lemon, lime, orange, mandarin, grapefruit, bergamot, and kumquat, respectively.

Next, silver nanoparticle synthesis was performed.

_{It is prepared by dissolving silver nitrate (AgNO 3} ), a starting material of silver nanoparticles, in 10 ml of distilled water to a concentration of 1 to 5 mM. A mixed solution is prepared by mixing 10 ml of a basic aqueous solution prepared at pH 9 to 11 using 0.1 M NaOH and 10 ml of a natural extract. The prepared silver nitrate aqueous solution is slowly added to this mixed solution. Ensure that the pH of the mixed solution remains constant during the addition.

After mixing and stirring at room temperature for 1 to 24 hours, silver nanoparticles are prepared. The initial reaction rate and production volume of the prepared silver nanoparticles were analyzed by Gage R&R analysis of UV-Vis spectrophotometer.

As described above, when the synthesis of silver nanoparticles is finished, the unreacted starting material remains mixed with the nanoparticle dispersion. Therefore, after separating the nanoparticles through centrifugation, it was possible to separate pure nanoparticles by washing with distilled water 2 to 3 times the amount of the mixed solution.

After the nanoparticles of the final product were dried at room temperature, the size and production of silver nanoparticles were analyzed using DLS and ICP_OES.

2 is a UV-Vis spectrophotometer graph of silver nanoparticles prepared from citrus extracts.

That is, the silver nanoparticle aqueous solution prepared using citrus (citron, lemon, kumquat, grapefruit) extracts was measured with a spectrophotometer after 1 hour. As can be seen in FIGS. 2 and 1, the citron extract was used The production rate of silver nanoparticles was the highest.

extract Citron lemon kumquat grapefruit Production rate (mg/h) 320.65 110.95 106.70 123.43

3 is a UV-Vis spectrophotometer graph of silver nanoparticles prepared with a citron extract over time. Table 2 is a table of hourly production of silver nanoparticles prepared using citron extract. As can be seen from Figure 3 and Table 2, the maximum production was obtained in 24 hours.

Citron 1h 6h 18h 24h Production (mg) 320.65 365.78 374.57 380.00

4 is a UV-visible spectrophotometer graph for each pH of silver nanoparticles prepared from citron extract. As can be seen from FIG. 4 , the synthesis of silver nanoparticles was best performed at a pH of 10.

5 is a graph of component analysis (HPLC quantitative, qualitative analysis) of the yuja extract.

The results of quantitative analysis of gallic acid, catechin, caffeic acid, ferulic acid, coumaric acid, rutin, myricetin, quecetin, apigenin, and kaempferol of the natural reducing agent contained in the citron extract using LC-MS/MS were performed. It was measured to contain a large amount of the four reducing agents shown in Table 3.

Chemicals Area Sample content per mg (ug) Caffeic acid ^a) 81400 0.011 Ferulic acid ^b) 31114 0.014 Rutin ^c) 213010 0.026 Kaempferol ^d) 175323 0.002

6 is a graph showing the content of natural reducing agent and dispersing agent in citrus extracts.

As a result of quantitative analysis of lemon, kumquat, and grapefruit in addition to the citron extract, as can be seen in FIGS. 6 and 4, it was found that phenolic compounds and flavonoid compounds were detected the most in citron.

extract Citron lemon kumquat grapefruit total phenolic compounds
(caffeic acid, ferulic acid)
(mg/L) 25 6.25 8.57 6.87 total flavonoid compounds
(rutin, kaempferol)
(mg/L) 28 5.76 9.40 15.7

Table 5 shows the characteristics table of the total amount of silver nanoparticles (per 1 g of natural product) according to the citrus extract according to the present invention. That is, lemon, lime, orange, mandarin, grapefruit, yuzu, bergamot, kumquat, each natural extract 1㎖, 0.1M NaOH 3.3㎖, AgNO ₃ 5mM (total volume) 6㎖ scale shows the experimental results. As can be seen from Table 5, it was found that citron was overwhelmingly superior in production speed and final production.

natural product production speed
(mg/h) final production
(mg/day) yield rate
(%) dispersion stability
(day) granularity
(nm) Orange 92.65 121.5 30 10 20 grapefruit 123.43 120.8 29.8 14 26-28 mandarin 117.13 119.4 29.8 7 50 lemon 110.95 106.1 26.5 2 32 kumquat 106.70 120.4 29.6 18 28-30 Citron 320.65 380.0 85 35 32 Lime 90.23 116.7 25 3 52 Bergamot 200.77 120.4 29.6 5 40

FIG. 7 is a UV-Vis spectrogram showing the dispersion stability of silver nanoparticles prepared from a citron extract. As shown in FIG. 7 , in the citron extract with a high content of natural dispersant, it was found that silver nanoparticles were not agglomerated and dispersed well even after 30 days.

8 is a graph showing the results of measuring silver nanoparticles prepared from a citron extract according to the present invention by a dynamic light scattering (DLS) method. As shown in FIG. 8 , the average particle size of the silver nanoparticles prepared from the citron extract according to the present invention was 32 nm.

9 is a TEM (Transmission Election Microscopy) photograph of silver nanoparticles prepared with a citron extract. As can be seen from FIG. 9 , it was found that silver nanoparticles did not aggregate even after 30 days had elapsed.

Although the invention made by the present inventors has been described in detail according to the above embodiments, the present invention is not limited to the above embodiments and various modifications can be made without departing from the gist of the present invention.

By using the method for producing silver nanoparticles using citrus fruits according to the present invention, mass production is possible and the industrial feasibility is very high as an environmentally friendly method.

Claims (9)

(a) preparing a natural extract of citrus and plants;
(b) mixing the natural extract with a silver salt compound to synthesize silver nanoparticles,
The method for producing silver nanoparticles using a citrus plant, characterized in that the citrus plant is citron. delete In claim 1,
The silver salt compound is silver nitrate (AgNO ₃ ), silver perchlorate (AlClO ₄ ), silver chlorate (AgClO ₃ ), silver carbonate (Ag ₂ CO ₃ ), silver sulfate (Ag ₂ SO ₄ ), silver chloride (AgCl), silver bromide (AgBr) ), silver acetate or silver fluoride (AgF), a method for producing silver nanoparticles using a citrus plant, characterized in that any one. delete In claim 3,
In step (a), the natural extract is first pulverized and vacuum dried at 50° C. in a dryer for 48 hours, and secondly finely pulverized and dispersed in distilled water to prepare a dispersion solution, and the dispersion solution is mixed with 60~ A method for producing silver nanoparticles using citrus fruits, characterized in that it is prepared by stirring at 80° C. for 1 hour. In claim 5,
The mixing in step (b) is prepared by dissolving the silver nitrate in distilled water to a concentration of 1 to 5 mM, and preparing a mixed solution by mixing a basic aqueous solution of about pH 9 to 11 and the natural extract using 0.1 M NaOH A method for producing silver nanoparticles using citrus fruits, characterized in that In claim 1,
The method for producing silver nanoparticles using citrus fruits, characterized in that the citron is a natural reducing agent having a higher content of phenolic compounds and flavonoids than lemon, kumquat or grapefruit. In claim 1,
The method for producing silver nanoparticles using citrus fruits, characterized in that the citron contains a large amount of reducing agents of caffeic acid, ferulic acid, rutin and kaempferol. In claim 1,
The method for producing silver nanoparticles using citrus fruits, characterized in that the size of the silver nanoparticles is between 1 and 100 nm.

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