KR102250304B1 - Method of preparing ultrasmall nano complex - Google Patents

Abstract

The present application relates to a method for manufacturing an ultrafine nanocomposite. The present invention relates to a method for manufacturing an ultrafine nanocomposite that can be uniformly and continuously, predictably manufactured to be applied efficiently according to a pre-designed direction in an application field.

Description

Manufacturing method of ultrafine nanocomposite {METHOD OF PREPARING ULTRASMALL NANO COMPLEX}

The present application relates to a method of manufacturing an ultrafine nanocomposite, and a method of producing an ultrafine nanocomposite that can be efficiently applied according to a predesigned direction in the application field by uniformly and continuously predictable manufacturing of the ultrafine nanocomposite. It is about.

Attaching or growing bacteria is a major problem in human health, biotechnology, and bioindustry. In addition, as resistance to conventional antibiotics is increasing, there is a continuing need for alternative substances for inhibiting a broad spectrum of bacteria and microorganisms.

In response to this demand, several technologies have been proposed, and among them, materials having excellent antimicrobial properties against microorganisms including multidrug-resistant (MDR) bacteria have been developed. However, the procedure for removing such substances is quite complicated, and the input time is also excessively large, so that the economic feasibility is remarkably deteriorated.

In addition, inorganic nanoparticles ranging from 10 nanometers to 100 nanometers have been proposed as a new alternative. These inorganic nanoparticles are applicable to a wide spectrum of bacteria and have excellent economic efficiency. Applications of these nanoparticles include water treatment, prevention of bioadhesiveness, and treatment of infectious diseases. In particular, silver or copper nanoparticles can be applied to a wide spectrum of bacteria by interacting with silver ions or copper ions emitted from the surface of the nanoparticles and membrane proteins of bacteria. These interactions act to alter cell membranes and DNA, disrupt cell metabolism, and prevent bacterial replication. However, these inorganic nanoparticles have limitations in the aforementioned applications due to inherent toxicity and side effects. In addition, since the method of preparing such a nanocomposite uses hazardous chemicals and is based on a complex multi-step reaction, its application is limited. In addition, these nanoparticles have a problem in that they aggregate during storage or are deformed by a hydrolysis reaction.

Therefore, there is a need for research on a method that minimizes toxicity and can predictably produce ultrafine nanocomposites with a simple method.

Korean Patent Registration No. 10-1777975 Korean Patent Registration No. 10-1879510

According to an exemplary embodiment of the present application, it is intended to provide a method of manufacturing an ultrafine nanocomposite of less than 3 nm with less variation by preventing aggregation of nanoparticles.

According to an embodiment of the present application, it is intended to provide a method of manufacturing an ultrafine nanocomposite applicable to bacteria having a broad spectrum.

According to an embodiment of the present application, it is intended to provide a method of manufacturing an ultrafine nanocomposite having excellent antimicrobial properties by combining ultrafine nanoparticles with a hydrogel, minimizing toxicity of metal nanoparticles, and improving adhesion to a substrate. .

An aspect of the present application provides a method of manufacturing an ultrafine nanocomposite.

As an example, the manufacturing method comprises the steps of preparing a carrier gas; Supplying unipolar ions to the carrier gas to mount the unipolar ions on the carrier gas; The carrier gas on which the unipolar ions are mounted is supplied into the chamber in which the spark is generated, is separated by a predetermined distance, and passed through a fluid passage between a pair of metal electrodes to which a voltage is applied, and between the pair of electrodes. , Forming a metal nanoparticle; And forming an ultrafine nanocomposite by supplying the formed metal nanoparticles to the outside of the chamber and combining with the hydrogel material.

As an example, the carrier gas is nitrogen or an inert gas.

As an example, gas and metal nanoparticles in the fluid passage are unipolarly charged.

As an example, the concentration of unipolar ions in the carrier gas on which the unipolar ions are mounted is 1 x 10 ⁶ ions/cm 3 to 1 x 10 ⁷ ions/cm 3.

As an example, the average diameter of the formed metal nanoparticles is 3 nm or less (excluding 0), and the number of atoms of the metal nanoparticles is 200 or less.

As an example, the hydrogel contains at least one selected from the group consisting of proteins, peptides, lipids, biomolecules, and synthetic polymers.

As an example, the metal nanoparticles are immersed in a hydrogel solution to form a hydrogel coating layer on the surface of the metal nanoparticles, thereby bonding with the hydrogel material.

Another aspect of the present application provides an ultrafine nanocomposite.

As an example, the ultrafine nanocomposite is an ultrafine nanocomposite formed by the above-described manufacturing method, has a core-shell structure, the core is a metal nanoparticle, the shell contains a hydrogel, and the metal nanoparticle The average diameter of is 3 nm or less (more than 0). In addition, the number of atoms of the metal nanoparticles is 200 or less.

Another aspect of the present application provides an apparatus for manufacturing an ultrafine nanocomposite.

As an example, the manufacturing apparatus includes a chamber having an inlet and an outlet and generating a spark therein; A pair of metal electrodes positioned in the chamber and spaced apart at a predetermined interval to form a fluid passage; A unipolar ion supply unit that passes through the fluid passage and supplies unipolar ions that charge the generated metal nanoparticles to unipolar ions when a voltage is applied to the pair of metal electrodes, and is located in the chamber; A carrier gas supply unit that enters through the inlet and supplies a carrier gas to the unipolar ions; And a hydrogel tank in which metal nanoparticles supplied to the outside of the chamber are immersed through the outlet to form a hydrogel coating layer.

As an example, it further includes a plasma supply unit for supplying plasma to generate a spark in the chamber.

As an example, the carrier gas is nitrogen or an inert gas.

As an example, the concentration of the unipolar ions is 1 x 10 ⁶ ions/cm 3 to 1 x 10 ⁷ ions/cm 3.

As an example, the hydrogel contains at least one selected from the group consisting of proteins, peptides, lipids, biomolecules, and synthetic polymers.

According to the exemplary embodiment of the present application, by preventing the nanoparticles from agglomeration, a nanocomposite of 3 nm or less and the number of atoms of the metal nanoparticles may be 200 or less.

According to the exemplary embodiment of the present application, it is possible to provide a nanocomposite having a small variation and a constant size.

According to the exemplary embodiment of the present application, a nanocomposite controlled to be able to predict the size may be provided.

According to the exemplary embodiment of the present application, a nanocomposite may be manufactured through a continuous fluid process.

According to the exemplary embodiment of the present application, the toxicity of metal nanoparticles may be reduced by using a hydrogel.

According to an exemplary embodiment of the present application, by using a hydrogel, the adhesion of the prepared nanocomposite can be improved and applied to various applications.

According to the exemplary embodiment of the present application, it is possible to provide a nanocomposite having excellent antibacterial activity and capable of responding to a broad spectrum of bacteria.

1 is a flowchart of a method of manufacturing a nanocomposite according to an embodiment of the present application.
2 is a schematic diagram illustrating a method of manufacturing a nanocomposite according to an embodiment of the present application.
3 is a schematic diagram illustrating a method of manufacturing a nanocomposite according to an embodiment of the present application.
4 is a block diagram of an apparatus for manufacturing a nanocomposite according to an embodiment of the present application.
5 is a schematic diagram of an apparatus for manufacturing a nanocomposite according to an embodiment of the present application.
6 is a diagram illustrating an apparatus for manufacturing a nanocomposite according to an exemplary embodiment of the present application.
7 is a graph showing the results of measuring the aggregation ratio, the number of particles, and the number of atoms for Examples and Comparative Examples.
8 is a graph showing the results of measuring the dispersion degree of Cd and particle formation for Examples and Comparative Examples.
9 is a graph showing results of measuring voltage between positive electrodes versus time for Examples and Comparative Examples.
10 is a graph showing the results of measuring the time versus time, mass concentration, and number concentration diameter for Examples and Comparative Examples.
11 is a graph showing results of measuring the efficacy of MIC and antibacterial filters for Examples and Comparative Examples.
12 is a graph showing results of measuring MIC for multi-resistance bacteria for Examples and Comparative Examples.
13 is a graph showing the results of measuring antibacterial efficacy for Examples and Comparative Examples.
14 is a TEM image for Examples and Comparative Examples.
15 is a graph showing a result of measuring the degree of dispersion of particles for Examples and Comparative Examples.

The terms used in the present application are only used to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In the present application, terms such as "include" or "have" are intended to designate that features, elements, etc. described in the specification exist, but one or more other features or elements may not exist or be added. It doesn't mean none.

Unless otherwise defined, all terms used herein including technical or scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs. Terms such as those defined in a commonly used dictionary should be interpreted as having a meaning consistent with the meaning in the context of the related technology, and should not be interpreted as an ideal or excessively formal meaning unless explicitly defined in the present application. Does not.

In the present application, the term "nano" may mean a size in a nanometer (nm) unit, for example, it may mean a size of 1 to 1,000 nm, but is not limited thereto. In addition, in the present specification, the term "nanoparticle" may mean a particle having an average particle diameter in a nanometer (nm) unit, for example, may mean a particle having an average particle diameter of 1 to 1,000 nm, but It is not limited.

Hereinafter, a method of manufacturing an ultrafine nanocomposite according to an embodiment of the present application will be described in detail with reference to the accompanying drawings. However, the accompanying drawings are exemplary, and the scope of a method of manufacturing an ultrafine nanocomposite according to an embodiment of the present application is not limited by the accompanying drawings.

1 is a flowchart of a method of manufacturing an ultrafine nanocomposite according to an exemplary embodiment of the present application. 2 is a schematic diagram illustrating a method of manufacturing a nanocomposite according to an embodiment of the present application. In addition, FIG. 3 is a schematic diagram illustrating a method of manufacturing a nanocomposite according to an exemplary embodiment of the present application.

As shown in FIGS. 1 to 3, a method of manufacturing an ultrafine nanocomposite according to an embodiment of the present application includes the steps of preparing a carrier gas (S10); Supplying unipolar ions to the carrier gas to mount the unipolar ions on the carrier gas (S20); The carrier gas on which the unipolar ions are mounted is supplied into the chamber in which the spark is generated, is separated by a predetermined distance, and passed through a fluid passage between a pair of metal electrodes to which a voltage is applied, and between the pair of electrodes. , Step of forming metal nanoparticles (S30); And forming an ultrafine nanocomposite by being supplied to the outside of the chamber and combining the formed metal nanoparticles with a hydrogel material (S40).

Hereinafter, the present application will be described in more detail for each step.

First, a carrier gas is prepared (S10).

The carrier gas is not particularly limited, but can help to mount and move unipolar ions in the delivery of unipolar ions, such as a burr to be described later. In the present application, nitrogen or inert gas may be included as an example of such a carrier gas.

Then, unipolar ions are supplied to the carrier gas, and unipolar ions are mounted on the carrier gas (S20).

The unipolar ion refers to a group of ions composed of negative charges or a group of ions composed of positive charges. In particular, the concentration of unipolar ions may range from 1 x 10 ⁶ ions/cm 3 to 1 x 10 ⁷ ions/cm 3. However, the concentration of such ions is only an example of the concentration of unipolar ions, and this range does not limit the present application.

Then, the carrier gas loaded with unipolar ions is supplied into the chamber where the spark is generated, and is separated by a predetermined distance and passed through a fluid passage between a pair of metal electrodes to which a voltage is applied, and between the pair of electrodes. , Metal nanoparticles are formed (S30).

A carrier gas loaded with unipolar ions is supplied into the chamber. The size and shape of the chamber is not particularly limited, but includes an internal space, and may include an inlet through which gas is introduced and an outlet through which gas is discharged.

A pair of metal electrodes spaced apart from each other by a predetermined distance are disposed inside the chamber. A voltage is applied to the pair of metals, and as the ions move by the electric field, a conductive line is instantaneously formed and a spark is generated. At this time, the surfaces of the pair of electrodes are locally vaporized and condensed and agglomerated through the flow of air, thereby generating a low-temperature plasma phenomenon in which metal nanoparticles are generated.

At this time, the entire fluid passage between the pair of metal electrodes is charged by unipolar ions to the space itself and the metal nanoparticles generated in the pair of metal electrodes. That is, when the unipolar ion is an anion, the metal nanoparticles are charged as an anion, and when the unipolar ion is a cation, the metal nanoparticles are charged as a cation.

In this way, the metal nanoparticles charged with the same polarity exert a strong repulsive force with each other, thereby preventing the metal nanoparticles from agglomeration. The metal nanoparticles from which aggregation is prevented in this way have an average particle diameter of 3 nm or less (excluding 0), and preferably have a size of 2 nm to 3 nm. In addition, the number of atoms of the metal nanoparticles may be 200 or less, preferably 180 or less, 150 or less, 100 or less, or 50 or less. Through this, the variation in the number of atoms of the particles generated by ion implantation is remarkably reduced, making it easy to predict, and at the same time, it is possible to provide particles having strong antibacterial properties.

As shown in FIG. 3, when the ions are not implanted, the nanoparticles are thermally and electrostatically aggregated, and the size of the nanoparticles is randomly formed. On the other hand, when unipolar ions are implanted, due to electrostatic repulsion, as nanoparticles in which atomic-level metals are aggregated in a countable number, ultrafine nanoparticles of the size described above are formed. Through this, it is possible to provide ultrafine nanoparticles having a high surface area, and the metal ions released from the surface of the metal nanoparticles and the membrane protein of the bacteria interact to modify the cell membrane and DNA, thereby interfering with cell metabolism, and Acts to prevent its duplication. Through this, it is possible to provide an antibacterial effect against a broad spectrum of bacteria, and can be applied to various applications.

Then, the formed metal nanoparticles are supplied to the outside of the chamber, and are combined with the hydrogel material to form an ultrafine nanocomposite (S40).

The formed metal nanoparticles are provided to the outside of the chamber through the outlet, and at this time, they bind to the hydrogel material.

Here, the hydrogel material may generally be a three-dimensional structure consisting of a network of hydrophilic polymers, but it refers to a state in which particles are scattered in a liquid state. That is, proteins, peptides, lipids, biomolecules, and synthetic polymers refer to substances in which particles are scattered in a liquid state. As an example, it may be a polymer material having high bio-affinity, such as Albumin or Thiol material.

In the method of combining the hydrogel material with the metal nanoparticles, the metal nanoparticles are immersed in the hydrogel solution to form a hydrogel coating layer on the surface of the metal nanoparticles, and the hydrogel material is bonded thereto.

Another embodiment of the present application is an ultrafine nanocomposite. The nanocomposite prepared by the above method has a core-shell structure, the core is a metal nanoparticle, the shell contains a hydrogel, and the average diameter of the metal nanoparticles is 3 nm or less (more than 0). In addition, compared to the metal nanoparticles of the nanocomposite, the diameter may slightly increase. Thus, particles of about 3 nm or less may be coated to be 5 nm to 10 nm. Compared with the nanocomposite disclosed in the previously presented technique, this diameter is very small. Therefore, it still has many advantages. Here, it is preferable that the number of atoms of the metal nanoparticles is 200 or less.

Conventionally, attempts have been made to provide ultrafine nanoparticles, but since most of them provide nanoparticles with random or large deviations, it has been difficult to predict the effectiveness in the application field. However, as described above, by controlling the conditions of the manufacturing process, it is possible to manufacture an ultrafine nanocomposite that is uniform and has little variation. In particular, by controlling the conditions of the manufacturing process, it is possible to provide a nanocomposite having a predictable size. In addition, by using the hydrogel, the toxicity of the metal nanoparticles can be neutralized, and according to the properties of the hydrogel, the nanocomposite can be easily attached to the substrate in an application field. In addition, since ultrafine nanoparticles can be manufactured through a continuous fluid process, economical efficiency is also excellent.

Another embodiment of the present application is an apparatus for manufacturing an ultrafine nanocomposite.

4 is a block diagram of an apparatus for manufacturing a nanocomposite according to an embodiment of the present application.

Among the contents described in the above-described manufacturing method, descriptions of the same or similar contents with respect to the manufacturing apparatus are omitted, but the above-described contents may be applied to the manufacturing apparatus.

As shown in FIG. 4, the above-described manufacturing apparatus includes a chamber 10. The chamber has an inlet 11 and an outlet 13. The chamber 10 has a space therein, and sparks may be generated in this space. The size and shape of the inlet 11 and the outlet 13 of the chamber 10 are not particularly limited, and may be limited to allow the inflow and outflow of gas and nanocomposite.

Further, the manufacturing apparatus includes a pair of metal electrodes 20. The metal electrodes are located in the chamber 10 and are spaced apart at predetermined intervals, thereby forming the fluid passage 30 at predetermined intervals. The predetermined interval is not particularly limited, and is an interval controlled in advance to suit the intention of the present application.

Further, the manufacturing apparatus includes a unipolar ion supply unit 40 and a carrier gas supply unit 50. The unipolar ions (I) supplied through the unipolar ion supply unit 40 are mounted on the carrier gas supplied through the carrier gas supply unit 50 and pass through the fluid passage 30, in which case, a pair of metal electrodes When a voltage is applied to (20), metal nanoparticles are generated, and the metal nanoparticles are charged by unipolar ions (I). Here, the concentration of unipolar ions is 1 x 10 ⁶ ions/cm 3 to 1 x 10 ⁷ ions/cm 3.

In particular, the unipolar ion supply unit and the pair of electrodes are directly connected to increase the electrical repulsion between singlet (primary) metal particles, thereby forming metal nanoparticles of 3 nm or less. In addition, as will be described later, when the metal nanoparticles are manufactured without supplying unipolar ions, their size exceeds 10 nm.

In addition, the ion implantation increases the discharge coefficient of the gas passing between the fluid passages through the electrostatic choking phenomenon, thereby improving the stability of particle generation. In addition, by uniformly generating ultrafine metal nanoparticles, it is possible to provide stable results of minimum inhibitory concentration (MIC) and antimicrobial filter performance. By using such ultra-fine particles, it is possible to provide antibacterial properties twice or more than conventional ones.

Here, the unipolar ion supply unit may be a carbon brush ionizer, but the unipolar ion supply unit is not limited thereto. It is preferable that the ion supply unit is disposed immediately in front of the position where the electrode is located.

Here, the carrier gas is nitrogen or an inert gas.

For example, when the unipolar ion (I) is a cation, the metal nanoparticles are positively charged, and when the unipolar ion (I) is an anion, the metal nanoparticles are negatively charged. It is unipolarly charged, and repulsive force is generated with each other to prevent aggregation of the nanoparticles, thereby providing nanoparticles having a size of 2 to 3 nanometers.

Here, the unipolar ion supply unit 40 is located in the chamber 10, and is located at a position in direct contact with the electrode 20 or at a predetermined distance from the fluid passage between the electrodes, so that a large amount of ions are transferred to the fluid passage 30 Through, it is desirable to control to be moved. Through this, not only the generated metal nanoparticles, but also the fluid passage 30, and furthermore, the inside of the chamber is charged with positive or negative charges.

Through this, a large amount of ions may be provided, and the generated metal nanoparticles may be separated as far as possible by using a repulsive force due to the same electric charge, and aggregation may be prevented.

In addition, the manufacturing apparatus includes a hydrogel bath 60. As described above, ultrafine metal nanoparticles are supplied to the outside of the chamber 10 through the outlet 13 of the chamber 10, and the metal nanoparticles are brought into the hydrogel tank 60 located outside the chamber 10. After entering and being immersed, it is withdrawn again. Here, the hydrogel contains at least one selected from the group consisting of proteins, peptides, lipids, biomolecules, and synthetic polymers. In this process, the surface of the metal nanoparticles is provided with a hydrogel coating layer.

Using the above-described device, it is possible to manufacture a plug-in and provide an effective platform for antibacterial activity that is easy to change. In addition, using a compact small platform, it is possible to provide ultrafine antibacterial nanoparticles accurately enough to count the number of ions emitted from the antimicrobial nanoparticles. Particularly, FCC particles of 3.7 nm or less (consisting of 100 atoms or less) are quite suitable for active atoms, and their size affects the number of atoms of nanoparticles, including surface energy and chemical reactivity, for strong antibacterial activity. . In addition, the ultrafine size is suitable for renal excretion to minimize systemic toxicity from exposure to nanoparticles.

In addition, in the manufacturing apparatus of the present application, in addition to the above-described elements, additional elements may be added depending on the intention of the present application.

Hereinafter, the present application will be described in more detail through experimental examples.

[ Experimental example ]

The size of the manufacturing apparatus is not particularly limited, but as an example, it may be manufactured in the size of a business card. 5 is a schematic diagram of an apparatus for manufacturing a nanocomposite according to an embodiment of the present application. 5, the width x length x height of the polytetrafluoroethylene chamber was 32 x 32 x 32 (mm ³ ). The electrode was placed in the chamber described above, and a silver (AG-402651, Nilaco, Japan) or copper (CU-112651, Nilaco, Japan) rod was used as the electrode, and the electrodes were separated by 0.3 mm. A high voltage direct current (DC) voltage was applied to the electrode. Nitrogen gas was injected as a carrier gas, and unipolar ions were injected into the fluid passage using a carbon-brush type ion generator. The ion generator was installed to be separated by 10 mm of the fluid passage.

A carbon brush ion generator (SJ-1000, Sejin Electronics, Korea) containing 200 ± 20 carbon fibers (ion tip with a diameter of 5-10 μm) was used, and a resistance-controlled power pack was selected, Or an anion was formed. The concentration of ions was controlled by adjusting an adjustable resistor, and at this time, the number of ions was counted using an ion counter (AIC20M, AlphaLab, USA). Using an aerosol electrometer (Charme ^® , Palas, Germany), the polarity of the nanoparticles was monitored, which is shown in FIG. 6D.

6 is a view for explaining the driving of an apparatus for manufacturing an ultrafine metal nanocomposite according to an embodiment of the present application.

Specifically, Figs. 6A and 6B show a circuit diagram and an IGBT switch in a silver film or between a copper rod. 6A and 6B, an IGBT switch (IXBH12N300, IXYS, USA), a ceramic capacitor (1 nF, SV15JA102JAR, AVX, USA), and a high voltage DC power supply (UltraVolt, USA) are two silver bars or copper bars. Connected to.

The voltage waveform was monitored using a (digital oscilloscope (6050A, LeCroy, USA) equipped with two high voltage probes (1000:1, P6015A, Tektronix, USA), and a graph of the results is shown in Fig. 6c. As shown in Fig. 6c, square voltage signals W1 and W2 from two IGBT switches were transmitted as rhombic signals from the capacitor, and these were transmitted as silver rods or copper rods.

After the plug-in to her bladder Orientation system, the fluid passage is formed, and is a chance that some of the rods or copper rods, is (5 L min of steam or copper vapor is formed, (99.9999% purity) with a nitrogen gas of these room ^{temperature- 1} ) was condensed to form silver primary particles or copper primary particles.

As a comparative example, the experiment was performed in the same manner as the above experiment using a silver or copper rod as an electrode without implanting ions.

As described below, the silver nanoparticles and copper nanoparticles obtained in each experiment were tested for confirming the properties of the nanoparticles, and an antibacterial property test (minimum blocking concentration (MIC) and antibacterial filter efficacy) and multi-material resistance. Stability experiments were conducted on Escherichia coli (E. coli; gram-negative) and Staphylococcus epidermidis (S. epidermidis; gram-positive).

Additionally, experiments were conducted using the Examples and Comparative Examples shown in Table 1 below.

Metal electrode Presence or absence of ions Example 1 Silver (Ag) (+) 10 ⁶ ions/cm ³ Example 2 Silver (Ag) (+) 10 ⁷ ions/cm ³ Example 3 Silver (Ag) (-) 10 ⁶ ions/cm ³ Example 4 Silver (Ag) (-) 10 ⁷ ions/cm ³ Example 5 Copper (Cu) (+) 10 ⁶ ions/cm ³ Example 6 Copper (Cu) (+) 10 ⁷ ions/cm ³ Example 7 Copper (Cu) (-) 10 ⁶ ions/cm ³ Example 8 Copper (Cu) (-) 10 ⁷ ions/cm ³ Comparative Example 1 Silver (Ag) X Comparative Example 2 Copper (Cu) X

[ Experimental example One]

First, in order to confirm the effect of ion implantation during particle formation, the aggregation ratio (dN[t]/dt, particles cm ^-3 s ^-1 )) and morphology (transmission electron microscopy, TEM) of the nanoparticles were analyzed.

The aggregation rate was calculated according to Equation 1 below.

Here, N ₀ is the initial particle number concentration, K is the aggregation coefficient (), and t is the elapsed time (s).

In order to confirm the shape, the formed metal particles were directly deposited on a carbon-coated copper grid (Tedpella, USA) placed on a grid sampler (Ineris, France) through mechanical impulse.

Through Examples 1 to 8, the concentration of unipolar ions ^{was tested while increasing from 1 Х 10 6} to 1 Х 10 ⁷ ions cm ^{- 3} , and Comparative Examples 1 and 2 were experimented without ion implantation. The results are shown in FIGS. 7A and 7B, respectively. As shown in FIGS. 7A and 7B, as the concentration of ions increased, the aggregation coefficient decreased as an index, and the aggregation rate also decreased significantly. However, there was no significant difference between the case of providing a cation and the case of providing an anion, and the difference between silver particles or copper particles was not large. Through this, it was confirmed that placing the unipolar condition near the fluid passage is an important parameter for preventing the aggregation of nanoparticles.

In addition, TEM images measured using the TEMs (JEM-F200, JEOL, Japan) of Example 2 and Example 6 were inserted as insertion views of FIGS. 7A and 7B, respectively. As shown in the inset of FIGS. 7A and 7B, it was confirmed that aggregation of nanoparticles is prevented.

In addition, using ImageJ software ( N = 110), the degree of dispersion of the particle size of the silver particles and the copper particles was confirmed, and the results are shown in FIGS. 7C to 7F, respectively. In addition, the size dispersion and the number of atoms of the silver particles and the copper particles were measured and shown in Table 2.

[Table 2]

As shown in Table 2, a large difference in the number of atoms occurred due to the structural difference between the silver particles and the copper particles.

As shown in Figs. 7c to 7f, when ions were implanted, the size distribution of the generated particles decreased (7c-silver, 7e-copper), and accordingly, the number of atoms of the generated particles decreased (7d- Silver, 7f-copper). In particular, as shown in FIGS. 7C and 7F, it was confirmed that the variation in the number of atoms of the generated particles was significantly reduced by implanting ions. This means, for example, that one silver particle generated when no ions are implanted contains silver atoms in the range of 1 to 10000, and one silver particle generated when ions are implanted is silver in the range of 10 to 20 Since it can be predicted to contain atoms, as a result, the antimicrobial activity of silver particles in the absence of implantation of ions is too large to predict, whereas (e.g., in some cases, 1 (antibacterial activity is Very low), in other cases 10000 (antibacterial activity is very high)), and the antibacterial activity of silver particles in the case of ion implantation is very small, so it is easy to predict (it has similar antibacterial activity in any case). It could be confirmed that there is.

[ Experimental example 2]

Variables when ions are implanted or not are measured, and each numerical value is calculated through the following equation, and then shown in Figs. 8A and 8B.

8a and 8b were obtained through the following equation,

[equation]

C _d means the discharge coefficient. In the present application, the higher the factor, the higher the particle generation stability.

Q (flow rate), A (cross-sectional area of the flow path), and ρ (gas density) are constant, and eventually only ΔP changes with implantation of ions.

_{ΔP is ε 0} , d is a fixed value made of the above-mentioned equation _{, V s} and V _avg are measured voltages between two electrodes, and a measurement graph is shown in FIG. 9.

Specifically, FIG. 9 is a result of measuring a voltage between two electrodes when ions are implanted and when not implanted with an oscilloscope [oscilloscope]. As a result, it was found that the voltage between the two electrodes was more stable when ions were implanted. (It can be confirmed that the voltage between the two electrodes is jagged.) The voltage between the two electrodes is an important factor that determines the amount of particles generated in the spark discharge. However, when ions were implanted, the voltage was stably generated, so it could be predicted that the amount of particles generated would be stable.

Fig. 10 shows a graph of the results of measuring the time versus time, the mass concentration, and the number concentration diameter for Examples 1 to 8 and Comparative Examples 1 and 2 monitored in FIG. 10.

10 is a measurement of time versus time, mass concentration, water concentration, and diameter by a measuring instrument (Scanning Mibility Particle Sizer (SMPS)). It was confirmed that it was significantly reduced (the fluctuation of the graph was very reduced) than when was not injected, and it was possible to confirm whether the particles were stably generated for a long time.

[ Experimental example 3]

Antimicrobial properties experiments (minimum inhibitory concentration (MIC) and antibacterial filter efficacy) were performed on Escherichia coli (E. coli; gram-negative) and Staphylococcus epidermidis (S. epidermidis; gram-positive).

Specifically, the minimum inhibitory concentration is an experiment to find out from which concentration the growth of the target bacteria is inhibited when the target bacteria are treated with various concentrations of the substance (eg, silver nanoparticles 1 to 1000 μg/mL). For example, if the bacteria did not grow when treated with 30 μg/mL silver nanoparticles, and the bacteria grew when treated with 60 μg/mL, the MIC can be determined to be 30 μg/mL.

The antibacterial filter efficacy is an experiment in which the filter is coated with silver nanoparticles at 10 μg/cm ² , and then bacteria are attached to the coated filter in an aerosol state, and then re-desorbed to evaluate the survival rate of the bacteria.

These results are shown in FIG. 11. Referring to the results of FIG. 11, it was confirmed that the MIC decreased as ions were implanted (meaning improved antibacterial activity), the deviation was very reduced, and the antibacterial filter performance was also very reduced. It can be said that the performance of the application (antibacterial agent, antibacterial filter) derived from the particles produced when ions are implanted is stable.

[ Experimental example 4]

The experiment was carried out in the same manner as in Experimental Example 3 except for the type of bacteria.

In order to determine whether it shows an effect on resistant bacteria, extended-spectrum beta-lactamase [ESBL]-producing E. coli [gram-negative] and methicillin-resistant Staphylococcus aureus [MRSA, gram-positive] have multiple resistance properties. Antimicrobial properties experiments (minimum inhibitory concentration (MIC) and antibacterial filter efficacy) were conducted.

Results graphs are shown in FIGS. 12 and 13. As shown in FIGS. 12 and 13, as in FIG. 11, as ions are implanted, the MIC decreases (meaning that the antibacterial power is improved), the deviation is greatly reduced, and the antibacterial filter performance also decreases. It can be said that the performance of the application (antibacterial agent, antibacterial filter) derived from the particles produced when ions are implanted is stable. Therefore, it was found that it has an effective effect on resistant bacteria.

[ Experimental example 5]

Particles generated when ions were implanted and not implanted were collected in air on a TEM grid, and the results of transmission electron microscopy (TEM) analysis are shown in FIG. 14.

As a result of the analysis, it was confirmed that the same silver particles and copper particles were generated as intended in both the case of implanting and not implanting ions. 0.234 nm, Ag(111) means the intrinsic lattice distance of silver, and the observation of this lattice distance shows that silver particles are well formed. The same was true for copper (0.213 nm, Cu(111)).

[ Experimental example 6]

The size distribution of the generated particles in the case of implanting and not implanting ions was measured by a measuring instrument (Scanning Mibility Particle Sizer; SMPS), and is shown in Table 3 and FIG. 15.

[Table 3]

As shown in Table 3 and FIG. 15, it was confirmed that the result was that the particles were smaller when the ions were implanted than the particles when the ions were not implanted.

Although the above has been described with reference to the preferred embodiments of the present application, those skilled in the art will be able to variously modify and change the present application within the scope not departing from the spirit and scope of the present invention described in the following claims. You will understand that you can.

10: chamber
11: inlet
13: outlet
20: a pair of electrodes
30: fluid passage
40: unipolar ion supply
50: carrier gas supply
60: hydrogel tank
I: unipolar ion
G: carrier gas

Claims (13)

As a method for forming metal nanoparticles in a chamber and producing ultra-fine nanocomposites outside the chamber,
Preparing a carrier gas;
Supplying unipolar ions having a concentration of 1 x 10 ⁶ ions/cm 3 to 1 x 10 ⁷ ions/cm 3 to the carrier gas to mount the unipolar ions in the carrier gas;
The carrier gas on which the unipolar ions are mounted is supplied into the chamber in which the spark is generated, is separated by a predetermined distance, and passed through a fluid passage between a pair of metal electrodes to which a voltage is applied, and between the pair of electrodes. , Forming metal nanoparticles having an average diameter of 3 nm or less (excluding 0) and 200 or less atoms in which the gas and metal nanoparticles in the fluid passage are unipolarly charged; And
The formed metal nanoparticles are supplied to the outside of the chamber, and are combined with a hydrogel material to form an ultrafine nanocomposite, and a unipolar ion supply unit located in the chamber is a method of manufacturing an ultrafine nanocomposite. The method of claim 1,
The carrier gas is nitrogen or an inert gas, a method of manufacturing an ultrafine nanocomposite. delete delete delete The method of claim 1,
The hydrogel is a method of producing an ultrafine nanocomposite comprising at least one selected from the group consisting of proteins, peptides, lipids, biomolecules, and synthetic polymers. The method of claim 1,
The metal nanoparticles are immersed in a hydrogel solution to form a hydrogel coating layer on the surface of the metal nanoparticles to form an ultrafine nanocomposite that binds to the hydrogel material. As an ultrafine nanocomposite formed by the manufacturing method of claim 1, it has a core-shell structure,
The core is a metal nanoparticle, the shell contains a hydrogel, the average diameter of the metal nanoparticles is 3 nm or less (more than 0), the number of atoms of the metal nanoparticles is 200 or less ultrafine nanocomposite A chamber having an inlet and an outlet and generating sparks therein;
A pair of metal electrodes positioned in the chamber and spaced apart at a predetermined interval to form a fluid passage;
A stage having a concentration of ^{1 x 10 6} ions/cm 3 to 1 x 10 ⁷ ions/cm 3 that passes through the fluid passage and charges the generated metal nanoparticles with unipolar ions when a voltage is applied to the pair of metal electrodes A unipolar ion supply unit that supplies polar ions and is located in the chamber;
A carrier gas supply unit that enters through the inlet and supplies a carrier gas to the unipolar ions; And
It includes a hydrogel tank in which metal nanoparticles supplied to the outside of the chamber are immersed through the outlet to form a hydrogel coating layer,
The gas and metal nanoparticles in the fluid passage are unipolarly charged,
The average diameter of the metal nanoparticles is 3 nm or less (more than 0), and the number of atoms of the metal nanoparticles is 200 or less. The method of claim 9,
An apparatus for manufacturing an ultrafine nanocomposite further comprising a plasma supply unit for supplying plasma to generate a spark in the chamber. The method of claim 9,
The carrier gas is nitrogen or an inert gas, an apparatus for manufacturing an ultrafine nanocomposite. delete The method of claim 9,
The hydrogel is an apparatus for manufacturing an ultrafine nanocomposite comprising at least one selected from the group consisting of proteins, peptides, lipids, biomolecules, and synthetic polymers.

Images