KR20210121403A - HUMIDITY AND pH SENSITIVE SELF-HEALING ANTIMICROBIAL NANOCAUSULES AND MANUFACTURING METHOD THEREOF - Google Patents

Abstract

In an aspect of the present invention, provided is an antibacterial nano capsule which comprises a core; a ligand brush formed on at least a part of a surface of the core; and an antibacterial agent captured in the ligand brush, wherein the antibacterial agent is emitted in a condition of 40 to 100% of humidity and pH 5 to 7.

Description

Humidity and pH-sensitive antibacterial nanocapsules and manufacturing method thereof

The present invention relates to an antibacterial nanocapsule capable of self-healing because it has excellent antibacterial properties and is sensitive to humidity and pH, and a method for manufacturing the same.

Antibacterial agents are used for the purpose of inactivating microorganisms that cause not only bad odors but also infectious diseases. Numerous antibacterial agents have been developed for inactivation of these microorganisms, and the form of the antibacterial agent is variously used as a spray type, a patch type, and a film type. However, since this type of antibacterial agent has only a single or one-time effect, there is a problem in that the continuous antibacterial effect is not maintained.

In order to solve this problem, an antibacterial agent in the form of a nanocapsule carrying an antibacterial substance in a capsule has been proposed and applied to special textile products such as protective products and protective clothing, medical supplies, and special packaging materials. However, the existing nanocapsules are porous capsules It is a constant release system using a bead form, and the release period of the capsule cannot be controlled, so once the release starts, it is impossible to control. These existing nanocapsules have a problem in that the antibacterial material is easily wasted, and the lifespan thereof is consumed within a short period of about 6 months.

On the other hand, bacteria, Escherichia coli, and fungi can survive in conditions of pH 1 to 9, but they proliferate the most at pH 6 to 7, and the conventional nanocapsule system that is constantly released may miss an appropriate time and significantly reduce antibacterial properties. .

Accordingly, there is a need to develop a technology for nanocapsules capable of controlling the release of antibacterial substances by responding to specific conditions, in particular, in an environment in which the proliferation of bacteria, E. coli, etc. is active.

The present invention is to solve the problems of the prior art described above, and an object of the present invention is to control the release and suppression of the release of antibacterial substances under specific conditions, so that the lifespan characteristics are excellent, and the antibacterial nanocapsules having excellent antibacterial properties and a method for manufacturing the same is to provide

One aspect of the present invention is a core; a ligand brush formed on at least a portion of the surface of the core; and an antibacterial agent captured by the ligand brush, wherein the antibacterial agent provides an antibacterial nanocapsule that is released under conditions of 45-100% humidity and pH 5-7.

In an embodiment, the ligand brush may react the acrylic compound after bonding the silane compound to the core.

In one embodiment, the silane-based compound is 3-(trimethoxysilyl)propylmethacrylate (3-(Trimethoxysilyl)propylmethacrylate, MPS), 3-(glycidoxy)trimethoxysilane (3-(Glycidyloxypropyl) ) may be one selected from the group consisting of trimethoxysilane, GPS), 3-(mercaptopropyl) trimethoxysilane (3-(mercaptopropyl) trimethoxysilane, MCPS), and a mixture of two or more thereof.

In one embodiment, the acrylic compound is acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylic It may be one selected from the group consisting of rate, pentyl acrylate, pentyl methacrylate, polymethyl acrylate, polymethyl methacrylate, polyethyl acrylate, polyethyl methacrylate, and a mixture of two or more thereof.

In one embodiment, the antibacterial agent may be triclosan (Triclosan).

In one embodiment, the average particle diameter of the antibacterial nanocapsules may be 300 ~ 1,000㎚.

In addition, in order to achieve the above object, another aspect of the present invention, (a) preparing a silica core support by reacting an aqueous solution containing a _{silica (SiO 2 ) precursor;} (b) reacting by adding a silane-based compound to the silica core support; (c) adding an acrylic compound to the product of step (b) and reacting to form a ligand brush; And (d) capturing the antibacterial agent in the ligand brush; includes, wherein the antibacterial agent provides a method of manufacturing antibacterial nanocapsules that are released under the conditions of a humidity of 45-100% and a pH of 5-7.

In one embodiment, the process temperature of step (a) may be 40 ~ 60 ℃.

In one embodiment, the average particle diameter of the antibacterial nanocapsules may be 300 ~ 1,000㎚.

The self-healing antibacterial nanocapsule and its manufacturing method according to an aspect of the present invention include forming a ligand brush on a core and releasing the anionic antibacterial agent captured by the ligand brush under a specific range of humidity and pH conditions, If it is out of the range, the antibacterial life can be extended by self-healing to its original form, and the antibacterial substance can be selectively released in a specific range, that is, under environmental conditions where the proliferation of bacteria, E. coli, etc. is active, so that the antibacterial action can be accurately and effectively can be improved

It should be understood that the effects of the present invention are not limited to the above-described effects, and include all effects that can be inferred from the configuration of the invention described in the detailed description or claims of the present invention.

1 is a schematic view of the release mechanism according to the pH of the antibacterial nanocapsule according to an embodiment of the present invention.
Figure 2 is a schematic diagram of the release and suppression mechanism of the antibacterial nanocapsules according to the manufacturing method and humidity / pH conditions of the antibacterial nanocapsules according to an embodiment of the present invention.
3 is a SEM image of _{the NC@SiO 2} support according to the manufacturing temperature change.
4 is a SEM image of _{NC@SiO 2} support, NC@SiO ₂ -MPS intermediate, and NC@SiO ₂ -g-MAA nanocapsules according to an embodiment of the present invention.
5 is an XPS and XRD analysis graph of _{NC@SiO 2} -g-MAA nanocapsules according to an embodiment of the present invention.
6 is a TEM, SEM, EDS image and BET analysis graph _{of the NC@SiO 2} support according to an embodiment of the present invention, and is an SEM and EDS image of the _{NC@SiO 2 -g-MAA nanocapsule.}
Figure 7 shows the result of the antimicrobial agent that does not contain NC @ SiO ₂ -g-MAA and the antibacterial agent is trapped NC @ SiO ₂ -g-MAA antibacterial agent release before and after the release of the antimicrobial nanocapsules analysis FT-IR.
8 is a graph showing the UV-Vis measurement results _{of NC@SiO 2} -g-MAA antibacterial nanocapsules according to an embodiment of the present invention under pH 4 and pH 6 conditions.
9 is a result of evaluation of antibacterial properties _{of NC@SiO 2} -g-MAA antibacterial nanocapsules according to an embodiment of the present invention.

Hereinafter, the present invention will be described with reference to the accompanying drawings. However, the present invention may be embodied in several different forms, and thus is not limited to the embodiments described herein. And in order to clearly explain the present invention in the drawings, parts irrelevant to the description are omitted, and similar reference numerals are attached to similar parts throughout the specification.

Throughout the specification, when a part is "connected" with another part, this includes not only the case where it is "directly connected" but also the case where it is "indirectly connected" with another member interposed therebetween. . In addition, when a part "includes" a certain component, this means that other components may be further provided without excluding other components unless otherwise stated.

When a range of numerical values is recited herein, the values have the precision of the significant figures provided in accordance with the standard rules in chemistry for significant figures, unless the specific range is otherwise stated. For example, 10 includes the range of 5.0 to 14.9 and the number 10.0 includes the range of 9.50 to 10.49.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

One aspect of the present invention, the core; a ligand brush formed on at least a portion of the surface of the core; and an antibacterial agent captured by the ligand brush, wherein the antibacterial agent provides an antibacterial nanocapsule that is released under conditions of 45-100% humidity and pH 5-7.

Conventional antibacterial nanocapsules have a problem in that when the release of the antibacterial material starts, the release of the antibacterial material is continued until the end of the discharge, so that the release of the antibacterial material cannot be controlled, so that the lifespan characteristics and the antibacterial efficiency are lowered.

The antibacterial nanocapsule of the present invention may have a ligand brush formed on at least a portion of the surface of the core, and includes an antibacterial agent trapped in the ligand brush, and the antibacterial agent is a specific range of conditions, specifically, humidity 45-100%, and It can be released at pH 5-7 conditions, and when it is out of the above range, the release of the antibacterial agent is stopped, thereby preventing unnecessary release of the antibacterial agent.

The core may be silica (SiO ₂ ), and as the silica precursor, tetraethylorthosilicate (TEOS), tetramethylorthosilicate (TMOS), tetramethoxysilicate (TMS), and 2 of these It may be one selected from the group consisting of the above mixtures, but is not limited thereto.

Meanwhile, a ligand brush may be formed on the core, and the ligand brush may react with the acrylic compound after bonding the silane compound to the core. The core is made of silica and has low binding force with the acrylic compound forming the ligand brush, making it difficult to form the ligand brush uniformly. can form.

The silane compound is 3-(trimethoxysilyl)propylmethacrylate (3-(Trimethoxysilyl)propylmethacrylate, MPS), 3-(glycidoxy)trimethoxysilane (3-(Glycidyloxypropyl)trimethoxysilane, GPS), It may be one selected from the group consisting of 3-(mercaptopropyl)trimethoxysilane (3-(mercaptopropyl)trimethoxysilane, MCPS) and a mixture of two or more thereof, but is not limited thereto.

In addition, the acrylic compound is acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, pentyl acryl It may be one selected from the group consisting of rate, pentyl methacrylate, polymethyl acrylate, polymethyl methacrylate, polyethyl acrylate, polyethyl methacrylate, and a mixture of two or more thereof, but is not limited thereto.

An antibacterial agent may be captured in the ligand brush formed on the core, and the antimicrobial agent may be captured at a pH of 5-7. When the capture of the antimicrobial agent is out of the range of the above pH, the capture amount of the antimicrobial agent may be lowered and the release efficiency may be lowered. Meanwhile, the antibacterial agent may be triclosan. The triclosan has excellent sterilization and antibacterial effects against bacteria, bacteria and fungi, and is rapidly dispersed within a short time to have excellent deodorization, anti-inflammatory, cleaning, and antibacterial effects.

1 is a schematic view of the release mechanism according to the pH of the antibacterial nanocapsule according to an embodiment of the present invention.

Referring to FIG. 1(a), the silica support, which is the core _{, may be an NC@SiO 2} -MPS intermediate whose surface is modified by a silane-based compound, and the NC@SiO ₂ -MPS intermediate is the acrylic compound is bonded to NC@SiO ₂ -g-MAA nanocapsules can be prepared. On the surface of the NC@SiO ₂ -g-MAA nanocapsule, a ligand brush formed of a carboxyl group of MAA may be formed, and an antibacterial agent is trapped in the ligand brush.

1(b) and (c) show that the pH conditions satisfy pH 4 and pH 6, respectively. In FIG. 1(b), hydrogen bonds are formed between the carboxyl groups of MAA, that is, between the ligand brushes, and the ligand brush expands. (swelling) does not occur, and the release of the antimicrobial agent can be controlled due to the interaction between MAA and Si-O-Si group molecules, that is, electrostatic attraction and intermolecular hydrogen bonding on the surface of the nanocapsule. On the other hand, FIG. 1 (c) The carboxylic acid group of MAA -COO ^- may be anionic while generating a repulsive force to push each other, and this ligand brush is expanded along the lead to release of the antimicrobial agent.

On the other hand, the average particle diameter of the antibacterial nanocapsule may be 300 ~ 1,000㎚. In the antibacterial nanocapsule, the average particle diameter may increase when the antimicrobial agent is released, and the average particle diameter may decrease when the release is suppressed. If the average particle diameter of the antibacterial nanocapsule is less than 300 nm, the antibacterial effect may be reduced, and if it exceeds 1,000 nm, the uniformity of the nanocapsule particles may be reduced and the processability may be reduced due to enlargement.

In addition, in order to achieve the above object, another aspect of the present invention, (a) preparing a silica core support by reacting an aqueous solution containing a _{silica (SiO 2 ) precursor;} (b) reacting by adding a silane-based compound to the silica core support; (c) adding an acrylic compound to the product of step (b) and reacting to form a ligand brush; And (d) capturing the antibacterial agent in the ligand brush; includes, wherein the antibacterial agent provides a method of manufacturing antibacterial nanocapsules that are released under the conditions of a humidity of 45-100% and a pH of 5-7.

Figure 2 is a schematic diagram of the release and suppression mechanism of the antibacterial nanocapsules according to the manufacturing method and humidity / pH conditions of the antibacterial nanocapsules according to an embodiment of the present invention.

Referring to FIG. 2, referring to FIGS. 2(a) and (b), a silica core support (NC@SiO ₂ ) may be prepared by reacting an aqueous solution containing a silica precursor. The silica precursor may be one selected from the group consisting of tetraethylorthosilicate (TEOS), tetramethylorthosilicate (TMOS), tetramethoxysilicate (TMS), and mixtures of two or more thereof, but not limited

Referring to FIG. 2( c ), _{an intermediate (NC@SiO 2} -MPS) in which the surface of the silica core support is modified by adding and reacting a silane-based compound to _{the NC@SiO 2 support may be prepared. Referring to FIG. 2( d ), NC@SiO 2} -g-MAA nanocapsules having a ligand brush formed thereon can be prepared by adding and reacting an acrylic compound on the surface of the intermediate. Referring to FIG. 2(e), antibacterial nanocapsules can be prepared by loading an antibacterial agent into the ligand brush, and a specific range of environmental conditions, specifically, the antibacterial nanocapsules have a humidity of 45-100% and a pH of 5-7. conditions can release the antimicrobial agent. Figure 2 (f) shows the release inhibition of the antibacterial nanocapsule when pH 4, Figure 2 (g) shows the release of the antibacterial nanocapsule when the pH 6, Figure 2 (h) is the antibacterial nano When out of the conditions of 45-100% humidity and pH 5-7, which are the operating environment of the capsule, self-healing antibacterial nanocapsules can be identified in their original form.

On the other hand, the process temperature of step (a) may be 40 ~ 60 ℃. If the process temperature of the silica core support is less than 40 ℃, antibacterial properties may be reduced, and if it is more than 60 ℃, the silica core support particles are non-uniformly formed, so that it may be difficult to prepare the nanocapsules.

Hereinafter, an embodiment of the present invention will be described in more detail. However, the following experimental results describe only representative experimental results among the above examples, and the scope and content of the present invention cannot be construed as reduced or limited by the examples. Each effect of various embodiments of the present invention that is not explicitly presented below will be specifically described in the corresponding section. The experimental results below were performed at room temperature (25° C.) and atmospheric pressure (1 atm) unless otherwise specified.

sample

Tetraethyl orthosilicate (TEOS), ammonium hydroxide (28-30%, ammonium hydroxide), polyvinylpyrrolidone (Mw=40,000, Polyvinylpyrrolidone), 3-(trimethoxysilyl)propyl methacrylate (3 -(Trimethoxysilyl)propylmethacrylate, MPS), sodium dodecylbenzenseulfonate, poly (methalic acid, sodium salt) solution (MAA), N-N'-methylenebisacryl Amide (N,N'-methylenebisacrylamide, BIS), pentanol, sodium citrate, ammonium persulfate (APS), triclosan (anionic antibacterial substance), buffer (Buffer, pH 4, 6), absolute ethanol was used for the preparation of nanocapsules and the antibacterial agent loading process. All the samples were purchased from Korea-Sigma Aldrich, and deionized water was used in all processes.

Example 1: NC@SiO ₂ support manufacturing

2.5 g of PVP was dispersed in 25 ml of pentanol and stirred at 100 rpm for 30 minutes at 40 ° C, 50 ° C, 60 ° C, 65 ° C or 80 ° C, 40 ° C, 50 ° C, 60 ° C, 65 ° C or 80 ° C, 1 L of The mixture was prepared by transferring to a bath and sonicating for 1 hour. After sonication, the mixture was transferred to a centrifuge, and 2.5 g of water, sodium citrate solution (243.16 μl of water contains 0.016 g of sodium citrate), 1.8936 g of ethanol, and 250 μl of ammonium hydroxide were mixed, and then 2 at 2,000 rpm. Stir for minutes. At this time, the mixture was uniformly stirred, 1 mL of TEOS was added, stirred again at 2,000 rpm for 2 minutes, and then stirred at 2,000 rpm overnight. After centrifugation, after removing the supernatant, ethanol and a centrifuge were rinsed, and the sample dried overnight in a dryer was pulverized to prepare a _{nanocapsule NC@SiO 2 support.}

Example 2: NC@SiO ₂ -MPS intermediate preparation

After adding 100ml of ethanol and 0.5ml of MPS to 100mg of the prepared NC@SiO ₂ support and stirring at 250rpm for 24 hours at 25°C to coat the surface of the spherical nanocapsule, centrifuged at 8,000rpm for 10 minutes 20 _{NC@SiO 2} -MPS intermediate was prepared by washing with ethanol in weight %.

Example 3: NC@SiO ₂ Preparation of -g-MAA nanocapsules

The NC@SiO ₂ -MPS intermediate was dispersed in a solution in which 50 ml of water and 5 mg of sodium dodecylbenzenesulfonate were mixed, stirred at 250 rpm for 1 hour, and 200 mg of MMA and BIS were added and then bubbled in _{N 2 gas atmosphere for 30 minutes.} After bubbling and rapidly adding 10 mg of ammonium persulfate, the mixture was stirred at 250 rpm in an oil bath at 75° C. for 4 hours. Then, centrifuged at 8,000 rpm for 10 minutes, washed with deionized water, and dried at 40° C. for 24 hours to modify the surface of the _{NC@SiO 2 -MPS intermediate as shown in FIG. 2(b).}

MPS may induce a negative charge on the surface of _{the NC@SiO 2} -MPS intermediate due to the equilibrium action of the Si-O group. In addition, the ionized silanol group (Si-OH) can form a grafted ligand brush on the surface of the nanocapsule by crosslinking to the oxygen bridge of the MAA, which is shown in FIGS. 2(c) and (d) can be found in

50 mg of nanocapsules having the ligand brush formed thereon were dispersed in 10 ml of buffers of pH 4 and 6 to prepare a total of four samples, two for each pH. Of these, 10 mg of triclosan as an antibacterial substance was added to two samples with different pH, stirred in a water bath at 25° C., 100 rpm for 24 hours, and centrifuged at 2,000 rpm for 10 minutes, followed by centrifugation at 40° C. By drying for 24 hours, nanocapsules in which the antibacterial agent was captured were prepared, which can be seen in FIGS. 2(e) to (g).

Experimental Example 1: NC@SiO ₂ SEM analysis of scaffolds

3 is an SEM image of _{NC@SiO 2} supports prepared according to different process temperatures of 40° C., 50° C., 65° C. and 80° C. FIG. Referring to FIGS. 3(a) and (b), _{it can be confirmed that the NC@SiO 2} support is prepared at 40° C. and 50° C., respectively, and the surface of the NC@SiO ₂ is smooth and has a relatively uniform size, and in particular , FIG. 3(a) shows that the NC@SiO ₂ support was prepared at 40° C., and it was confirmed that the nanocapsules having a uniform size and a round spherical shape were prepared by inducing a reaction between Si-O-Si and C=O. have. On the other hand, Figures 3 (c) and (d) are produced at 65 ℃ and 80 ℃, respectively, NC@SiO ₂ The polymer chain of the polymer constituting the support is excessively tangled and agglomeration occurs, so the shape and size of the capsule is poorly manufactured became

Experimental Example 2: NC@SiO ₂ , NC@SiO ₂ -MPS, NC@SiO ₂ SEM analysis of -g-MAA

4 is a SEM image of _{NC@SiO 2} support, NC@SiO ₂ -MPS intermediate, and NC@SiO ₂ -g-MAA nanocapsules according to an embodiment of the present invention.

Figure 4 (a) is _{a surface shape image of the NC@SiO 2} support, formed by the Pickering method, due to the adsorption and reaction of polymer molecules on the surface due to the relatively mild form of the bumpy (bumpy) pattern It can be confirmed that this is formed. Figure 4(b) is _{an NC@SiO 2} -MPS intermediate prepared by modifying MPS on a _{NC@SiO 2} support, and the raspberry pattern is nano It can be confirmed that it is formed on the surface of the capsule. Figure 4(c) shows that the NC@SiO ₂ -MPS intermediate is chemically combined with MAA _{to form a ligand brush on the surface of the NC@SiO 2} -MPS intermediate, and in detail, the NC@SiO ₂ -MPS intermediate ( C = O) -OH bonding group reacts with the carboxyl group (-COOH) of MAA, MAA-grafted NC@SiO ₂ -g-MAA type nanocapsules can be prepared, the NC@SiO ₂ -g-MAA ^-COO- group exists on the surface where the ligand brush is formed, and can release the antibacterial agent under certain pH conditions.

Experimental Example 3: NC@SiO ₂ XPS and XRD analysis of -g-MAA

5 is an XPS and XRD analysis graph of _{NC@SiO 2} -g-MAA nanocapsules according to an embodiment of the present invention.

Figure 5 (a) Si group and a polymer having a crystal structure thus make the surface of the component to the XPS analysis of the NC @ SiO ₂ -g-MAA nanocapsules, the NC @ SiO ₂ -g-MAA nanocapsules, and It can be confirmed that there is a chemical bond of In detail, the valences of Si, N, O, and C components were shown as 21.25%, 4.07%, 42.27% and 31.71%, respectively. On the other hand, FIG. 5(b) is _{an XRD analysis of NC@SiO 2} -g-MAA nanocapsules, and it can be confirmed that a crystalline peak having an equivalent Bragg angle at 2θ=21.8° appeared. In general, by the sol-gel method, the Si-O-Si peak of crystalline SiO2 is shown in a wide range of 23°, and the 2θ value in FIG. 5(b) shows an extended XRD peak for crystalline silica, and the silanol group ( The pure Si peak appearing at 28.5° by the chemical interaction between Si-O) and the carboxyl group (-COOH) confirms that the Si-O-Si bond is observed at 23° as the Si element is shifted by polymerization with the oxygen element. can

Experimental Example 4: NC@SiO ₂ , NC@SiO ₂ BET, TEM, SEM and EDS analysis of -g-MAA

6 is a TEM, SEM, EDS image and BET analysis graph _{of the NC@SiO 2} support according to an embodiment of the present invention, and is an SEM and EDS image of the _{NC@SiO 2 -g-MAA nanocapsule.}

Figure 6 (a) and (d) is found to be, the NC @ SiO ₂ support is in the form of a smooth sphere that TEM and SEM analysis of the NC @ SiO ₂ support, respectively. Figure 6 (b) and (c) has confirmed that the Si and O being present in the EDS analysis result obtained after the SiO-Si bond, and C = O in the NC @ SiO ₂ SiO ₂ support, the support of the NC @ have. Figure 6 (e) is a graph of the BET results of measuring the surface area of _{the NC@SiO 2 support prepared at 40 ° C. The surface area of NC@SiO 2} was measured to be 347.03 cm / g, so that the surface area of the nanocapsules of 1 g is increased 3470 times. It can be verified that

On the other hand, Fig. 6 (f) is NC @ SiO ₂ as a SEM analysis of -g-MAA nanocapsules, the NC @ SiO ₂ pattern is formed on the surface of a raspberry -g-MAA MAA nanocapsules which ligand is grafted It can be confirmed that the brush is due to formation, and it can be confirmed that the particle size and its shape are uniform. 6(g) to (i) show the presence of Si, C and O atoms as a result of EDS analysis _{of NC@SiO 2 -g-MAA nanocapsules.}

Experimental Example 5: NC@SiO ₂ , NC@SiO ₂ -MPS, NC@SiO ₂ -G-MAA evaluation of physical properties

Zeta potential
[mV] Mobility
[cm2/Vs] Diameter
[nm] Std. Dev.
[nm] NC@SiO ₂ -37.43 -2.92E-04 676.3 119.6 NC@SiO ₂ -MPS -23.45 -1.86E-04 761.2 100.1 NC@SiO ₂ -g-MAA -36.41 -2.84E-04 887.8 141.2

_{Table 1 shows the surface energy of the NC@SiO 2} support, NC@SiO ₂ -MPS intermediate, and NC@SiO ₂ -g-MAA nanocapsules of each manufacturing step according to an embodiment of the present invention by measuring the surface zeta potential values. The change and anionization were confirmed to show the zeta potential value due to each chemical unit. The surface charge value changes due to the equilibrium of chemical potentials such as Si-O-Si and COO- on the surface of the nanocapsule. do. In the case of the NC@SiO ₂ support, it can be seen that the surface electron value is anionized (-37.43 mV) due to the Si-O group of TEOS, and the zeta value after MPS modification is reduced due to the C = O bond (-23.45 mV) In NC@SiO ₂ -g-MAA, MAA is graft-bonded, and accordingly, the electron density of negative charges on the surface of _{the NC@SiO 2 -g-MAA increases due to anionization of the carboxyl group, and the surface potential value rises again (} -36.41mV) can be confirmed.

In addition, in the case of the NC@SiO ₂ support in average diameter, it was 676.3 (±119.6) nm, and the NC@SiO ₂ -MPS intermediate had an average diameter of 761.2 (±100.1) nm, and NC@SiO ₂ -g-MAA It can be seen that the average diameter of the nanocapsules increased to 887.8 (± 141.2) nm. The average diameter of the nanocapsules increased as the surface modification progressed, and it can be seen that the size of the _{NC@SiO 2 -g-MAA nanocapsules on which the MAA was grafted and the ligand brush was formed increased the most.} Since the nanocapsule has excellent particle size and uniformity of shape, it can be predicted that excellent and uniform antibacterial and sterilization effects can be obtained when applied to a spray form, packaging material, or special fabric for protection.

Experimental Example 6: Evaluation of physical properties of antibacterial nanocapsules 1

Figure 7 is NC@SiO ₂ -g-MAA without antibacterial agent and NC@SiO ₂ -g-MAA antibacterial nanocapsules in which the antibacterial agent is captured FT-IR analysis to confirm the chemical composition change before and after the release of the antibacterial agent. As a result, FR-IR analysis of triclosan, an antibacterial agent, was also performed to confirm the presence or absence of an antimicrobial agent.

Referring to FIG. 7, the FT-IR spectrum of triclosan, an antibacterial agent, has a specific peak of 3,312 cm ^-1 due to a hydroxyl group (-OH), and a C-Cl absorption band was observed at ^{722-570 cm -1} _{, CH 2} A strong CH oscillation band for -Cl was observed at ^{1,300-1,150 cm -1 .} _{In the case of NC@SiO 2} -g-MAA without antibacterial agent, a peak of 1,115 cm ^{-1 caused by -COO -} was observed by the MAA-grafted ligand brush on the surface of the nanocapsule.

On the other hand, _{looking at the peak measured after NC@SiO 2} -g-MAA containing the antibacterial agent was subjected to an antimicrobial release experiment at pH 6, due to the buffer component under the pH 6 condition, at 3,400 cm ^-1 and 3,350 cm ^-1 - OH and -NH adsorption peaks were observed. _{In addition, in NC@SiO 2} -g-MAA containing antibacterial agents that were not subjected to antibacterial testing, the characteristic peak of C=O, the MAA absorption band, ^{was observed at 1,709 cm -1} , and the -COO ^- anion group by MAA-grafted was It was observed at 1,150 cm ^{-1 .}

Experimental Example 7: Evaluation of physical properties of antibacterial nanocapsules 2

_{Figure 8 is a graph of the UV-Vis measurement result of NC@SiO 2} -g-MAA antibacterial nanocapsules according to an embodiment of the present invention to evaluate the release behavior of the antibacterial agent at pH 4 and pH 6, respectively.

Referring to FIG. 8, NC@SiO _{2 -g-MAA nanocapsules at pH 6 are on the surface of the NC@SiO 2} -g-MAA nanocapsules due to electrostatic repulsion between negatively charged groups by ionization. It can be seen that the formed ligand brushes expand rapidly, and triclosan, an antibacterial agent, is released accordingly. On the other hand, _{it can be confirmed that the NC@SiO 2} -g-MAA nanocapsules under the pH 4 condition have a low pKa value, so that the antibacterial agent is partially released from the ligand brush, and a small amount of the antibacterial agent is released compared to pH 6. That is, in the NC@SiO ₂ -g-MAA nanocapsules, the selective antimicrobial agent is released by anionization of the carboxyl group present in the MAA according to a specific pH condition.

Specifically, NC@SiO ₂ -g-MAA nanocapsules at pH 4 formed a hydrogen bond between carboxyl groups of MAA on the surface and electrostatic attraction between Si-O-Si groups was Although the swelling phenomenon occurs weakly, under the pH 6 condition, the carboxyl group of MAA is ionized and electrically negatively charged, and electrostatic repulsion between the groups occurs so that the ligand brush expands rapidly, and the antibacterial agent trapped in the ligand brush is electrostatically charged. It can be confirmed that it is released by miraculous repulsion.

On the other hand, _{it can be seen that the NC@SiO 2} -g-MAA nanocapsules under the pH 4 condition have a low pKa negative charge value, but the ligand brush partially releases the antibacterial agent.

Experimental Example 8: Evaluation of physical properties of antibacterial nanocapsules 3

9 is an evaluation of the antibacterial properties of _{NC@SiO 2} -g-MAA antibacterial nanocapsules according to an embodiment of the present invention. For the antibacterial evaluation, (a) NC@SiO ₂ , (b) NC@SiO ₂ -g-MAA without antibacterial agent, (c) NC@ with antibacterial agent captured at pH 4 in medium pH 4 and pH 6, respectively SiO _{2 -g-MAA, (d) Samples of NC@SiO 2} -g-MAA captured with an antimicrobial agent at pH 6 were left at regular intervals at 45% humidity for 24 hours.

Referring to FIG. 8(A), in the medium of pH 4, no clear zone of E. coli was observed in all samples, and looking at FIG. 8(B), in (c) and (d), 13 mm and It can be seen that a clear zone of 15 to 20 mm was formed. This is because NC@SiO ₂ -g-MAA nanocapsules containing an antibacterial agent induce swelling of the ligand brush formed on the MAA under specific humidity and pH conditions. can be seen to indicate

_{In addition, in order to evaluate the antibacterial effect of NC@SiO 2} -g-MAA nanocapsules according to humidity 100% and pH 4, 6, 7 conditions, changes in E. coli density were observed in the initial and 24 hours. The results are shown in Table 2.

pH 4 pH 6 pH 7 Early
OD value after 24h
OD value Early
OD value after 24h
OD value Early
OD value after 24h
OD value NC@SiO ₂ -g-MAA
(including antibacterial x) 0.115 15.6 0.117 23.2 0.105 11.2 NC@SiO ₂ -g-MAA
(pH4, capture antibacterial) 0.115 0.9 0.117 0.7 0.105 0 NC@SiO ₂ -g-MAA
(pH6, antimicrobial capture) 0.115 3.5 0.117 0 0.105 0.3

Referring to Table 2, in _{the case of NC@SiO 2} -g-MAA without antibacterial agent, the OD value after 24 hours was increased from the initial OD value at all pH conditions, and in particular, the initial density of E. coli at pH 6 was 0.117 (OD ), but after culturing for 24 hours, it can be confirmed that E. coli was proliferated more than 20 times to 23.2 (OD). On the other hand, in the case of NC@SiO ₂ -g-MAA nanocapsules in which the antibacterial agent was captured at pH 4, the E. coli density after culturing at pH 6 for 24 hours was 0.7 (OD), so it can be confirmed that the proliferation was 4.5 times, and at pH 6 In the case of NC@SiO ₂ -g-MAA nanocapsules in which the antibacterial agent was captured, the density of E. coli after culturing for 24 hours was 0, confirming that all E. coli were killed, and thus NC@SiO ₂ -g captured at pH 6 - It can be confirmed that the antibacterial effect of the MAA nanocapsule is the best. The description of the present invention described above is for illustration, and those of ordinary skill in the art to which the present invention pertains can change the technical spirit or essential features of the present invention It will be understood that it can be easily transformed into another specific form without doing so. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive. For example, each component described as a single type may be implemented in a dispersed form, and likewise components described as distributed may be implemented in a combined form.

The scope of the present invention is indicated by the following claims, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included in the scope of the present invention.

Claims (9)

core;
a ligand brush formed on at least a portion of the surface of the core; and
and an antibacterial agent trapped in the ligand brush,
The antibacterial agent is an antibacterial nanocapsule that is released under the conditions of 45-100% humidity and pH 5-7. According to claim 1,
The ligand brush is an antibacterial nanocapsule in which an acrylic compound is reacted after binding a silane compound to the core. 3. The method of claim 2,
The silane compound is 3-(trimethoxysilyl)propylmethacrylate (3-(Trimethoxysilyl)propylmethacrylate, MPS), 3-(glycidoxy)trimethoxysilane (3-(Glycidyloxypropyl)trimethoxysilane, GPS), 3-(mercaptopropyl)trimethoxysilane (3-(mercaptopropyl)trimethoxysilane, MCPS) and an antibacterial nanocapsule which is one selected from the group consisting of mixtures of two or more thereof. 3. The method of claim 2,
The acrylic compound is acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, pentyl acrylate, Antibacterial nanocapsules which are one selected from the group consisting of pentyl methacrylate, polymethyl acrylate, polymethyl methacrylate, polyethyl acrylate, polyethyl methacrylate, and a mixture of two or more thereof. According to claim 1,
The antibacterial agent is triclosan (Triclosan) antibacterial nanocapsule. According to claim 1,
The average particle diameter of the antibacterial nanocapsule is 300 ~ 1,000nm antibacterial nanocapsule. (a) _{reacting an aqueous solution containing a silica (SiO 2} ) precursor to prepare a silica core support;
(b) reacting by adding a silane-based compound to the silica core support;
(c) adding an acrylic compound to the product of step (b) and reacting to form a ligand brush; and
(d) capturing the antimicrobial agent in the ligand brush;
The antibacterial agent is a method of producing an antibacterial nanocapsule that is released under the conditions of 45-100% humidity and pH 5-7. 8. The method of claim 7,
The process temperature of step (a) is a method of producing an antibacterial nanocapsule of 40 ~ 60 ℃. 8. The method of claim 7,
The average particle diameter of the antibacterial nanocapsule is a method of manufacturing an antibacterial nanocapsule of 300 ~ 1,000nm.

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