KR20220039906A - Triple-responsive nano motors, compositions of and manufacturing method thereof - Google Patents

Abstract

A triple-responsive nano motor of the present invention relates to a triple-responsive nano motor, a composition of the triple-responsive nano motor, and a motor manufacturing method. The triple-responsive nano motor is driven by thermophoretic, catalyst, and magnetic movement and is manufactured from a microfluidics system, thereby having a great yield amount and pickering efficiency.

Description

Triple-response nanomotor, composition used for its preparation, and method for manufacturing the same

The present invention relates to a triple response nanomotor, a composition used for the preparation thereof, and a method for preparing the same.

Micromotors or nanomotors have the advantage of being able to perform numerous tasks in a wide range of applications, so research on micromotors or nanomotors driven by a (bio)catalytic reaction or driven by a magnetic field, light or ultrasonic wave is active proceeded nicely.

The micro-motor or nano-motor exhibits movement by magnetism, which is caused by thermal or chemical reactions caused by geometrical and chemically asymmetric structures.

The micro-motor or nano-motor exhibits movement by magnetism, which is caused by thermal or chemical reactions caused by geometrical and chemically asymmetric structures.

On the other hand, the nanomotor was conventionally manufactured by physical coating, electroless coating, and Pickering emulsification through a large-scale batch system, and this batch process is complicated and requires a lot of time, and a homogeneous final product. It was difficult to manufacture.

An embodiment of the present invention is to provide a nano-motor composition.

An embodiment of the present invention is to provide a triple response nanomotor.

An embodiment of the present invention is to provide a method for manufacturing a triple response nanomotor.

In order to solve the above problems, the triple response nano-motor composition of the present invention is mesoporous (mesoporous) composite magnetic nanoparticles; Polydopamine solution; and a platinum (Pt) precursor.

As a preferred embodiment of the present invention, the platinum (Pt) precursor is one selected from potassium chloride (Potassium hexachloroplatinate), platinum hydrogen chloride (Hydrogen hexachloroplatinate), sodium platinum chloride (Sodium hexachloroplatinate), and platinum ammonium chloride (Ammonium hexachloroplatinate) It may include more than one species.

As a preferred embodiment of the present invention, the polydopamine solution may include a mixture of dopamine monomer, ammonia solution, purified water and ethanol.

As a preferred embodiment of the present invention, the composite magnetic nanoparticles include a core including silicon dioxide (SiO ₂ ); and a shell including iron oxide (Fe ₃ O ₄ ) magnetic nanoparticles.

As another object of the present invention, a method for manufacturing a triple response nanomotor includes the first step of preparing mesoporous composite magnetic nanoparticles; a second step of reacting a hydrophilic silane compound and a hydrophobic silane compound with the composite magnetic nanoparticles; Mixing and emulsifying a dispersed phase containing a photo resin and a photo initiator in the continuous phase containing the composite magnetic nanoparticles that performed the above steps to form a Pickering emulsion, and UV irradiation Step 3; 4 step of mixing a polydopamine solution with the Pickering emulsion; 5 step of mixing a solution containing a platinum (Pt) precursor to the Pickering emulsion that has been performed in step 4; and step 6 of ultrasonically treating the Pickering emulsion having performed step 5 to obtain a nanomotor.

As a preferred embodiment of the present invention, the hydrophilic silane compound and the hydrophobic silane compound may be added in a molar ratio of 1:0.032 to 1:0.10.

As a preferred embodiment of the present invention, the three-step Pickering emulsion is a dropletized optical resin; and the composite magnetic nanoparticles.

As a preferred embodiment of the present invention, the composite magnetic nanoparticles may be located at the interface between the dropletized optical resin and water.

As a preferred embodiment of the present invention, the continuous phase may contain the composite magnetic nanoparticles at a concentration of 20 to 90 mg/mL.

As a preferred embodiment of the present invention, steps 3 to 5 may be performed for 3.8 to 14.7 minutes.

As a preferred embodiment of the present invention, steps 3 to 5 may be continuously performed through a microfluidic system.

As a preferred embodiment of the present invention, the microfluidic system may include a hydrophilic glass tube, a primary surface modification unit, and a secondary surface modification unit.

As a preferred embodiment of the present invention, the first surface-modified portion and the second surface-modified portion may each include a hydrophobic polytetra fluorethylene (PTFE) tube.

As a preferred embodiment of the present invention, step 1 may be performed through a polytetra fluorethylene (PTFE) tube having a length of 3 to 200 cm.

As another object of the present invention, a triple response nanomotor is a composite magnetic nanoparticle; a polydopamine layer formed on a portion of the surface of the composite magnetic nanoparticles; and a platinum catalyst layer formed on the polydopamine layer.

Triple response nanomotor, triple response that is continuously manufactured through the microfluidics system of the present invention, not only has high process productivity, but also has excellent pickering efficiency, shows a triple response, and does not decrease its activity even after being reused several times. It is possible to provide a composition for a nanomotor and a method for manufacturing the same.

1 is a schematic diagram of a method for manufacturing a nanomotor according to an embodiment of the present invention.
2 a) is an optical image of a nanomotor according to an embodiment of the present invention, b) to c) are a field emission scanning microscope (FE) of the Pickering emulsion during the manufacturing process of the nanomotor according to an embodiment of the present invention. -SEM) is an image observed, d) is a high-resolution transmission electron microscope (HR-TEM) image and energy dispersive X-ray spectroscopy (EDX) of a nanomotor according to an embodiment of the present invention It is a color-mapped image, and is an image of silicon (Si), iron (Fe), oxygen (O), and platinum (Pt) elements in order.
FIG. 3 is a graph showing each of the nanomotors of Example 1 and Comparative Example 4 being manufactured 10 times, and each Pickering efficiency obtained.
4 is a graph showing the pickering efficiency according to the residence time (top) and the concentration of the composite magnetic nanoparticles in the continuous phase (bottom) in the microfluidic system when the nanomotor is manufactured according to an embodiment of the present invention.
5 is a graph showing a swimming trajectory of a nanomotor according to an embodiment of the present invention, respectively, hydrogen peroxide (H ₂ O ₂ ) 0% by weight, 2% by weight, 5% by weight, 10% by weight. It is a graph showing that one was carried out under near-infrared rays, and one carried out under near-infrared rays and 10% by weight of hydrogen peroxide (H ₂ O ₂ ) and those performed under near-infrared rays.
6 is a graph showing the mean square displacement (MSD) of the nanomotor according to an embodiment of the present invention, respectively, hydrogen peroxide (H ₂ O ₂ ) 0 wt%, 2 wt%, 5 wt%, 10 It is a graph showing what was carried out under wt%, what was carried out under near infrared rays, and what was carried out under 10 wt% of hydrogen peroxide (H ₂ O ₂ ) and near infrared rays.
7 is a graph showing the average speed of the nanomotor according to an embodiment of the present invention, respectively, hydrogen peroxide (H ₂ O ₂ ) 0% by weight, 2% by weight, 5% by weight, 10% by weight, and near infrared rays It is a graph showing that performed under, and hydrogen peroxide (H ₂ O ₂ ) 10% by weight and performed under near-infrared rays.
8 is a graph illustrating magnetic movement of a nanomotor according to an embodiment of the present invention.
9 is a graph (left) and experimental images (right) showing the rhodamine B (Rhodamine B) removal rate according to time of the nanomotors prepared in Example 1 and Comparative Example 1. FIG.
FIG. 10 a) is a transmission electron microscope (TEM) image of magnetic iron oxide nanoparticles prepared according to an embodiment of the present invention, and b) is a field emission scan of the composite magnetic nanoparticles prepared according to an embodiment of the present invention. It is a microscope (FE-SEM) image, and c) is a field emission scanning microscope (FE-SEM) image of the composite magnetic nanoparticles prepared according to an embodiment of the present invention.
11 is a schematic diagram of a method for manufacturing a composite magnetic nanoparticle according to an embodiment of the present invention.
12 is an image of the composite magnetic nanoparticles prepared in Comparative Examples 15 to 19 observed with a field emission scanning microscope (FE-SEM).
13 is a field emission scanning microscope (FE-SEM) image of the composite magnetic nanoparticles prepared in Comparative Example 18, Comparative Example 20, and Comparative Example 21.
The left image of FIG. 14 is an image in which the composite magnetic nanoparticles according to an embodiment of the present invention are dispersed in water, and the right image is an image obtained by obtaining the composite magnetic nanoparticles through an external magnet.
15 is a schematic diagram showing that hydrophilic and hydrophobic silane compounds are co-grafted on the composite magnetic nanoparticles according to an embodiment of the present invention.
16 is an image sampled before stirring the dispersed phase during Example 1, Example 5, Comparative Example 10 and Comparative Example 11. In FIG. 16, 1 means Comparative Example 11, and 2 is Example 5 means, 3 means Example 1, and 4 means Comparative Example 10.
17 is a schematic diagram (top) and an image (bottom) of a microfluidic reaction system according to an embodiment of the present invention.
18 a) is a graph showing the zeta potential of Comparative Example 2, Comparative Example 22, Comparative Example 18, Comparative Example 3 and Example 1, b1) to b2) are the synthesis times of Comparative Example 3 and Example 1, respectively It is a graph showing the zeta potential of the nanomotor according to
19 a) to 19 b) are images obtained by analyzing the nanoparticles prepared in Comparative Example 18, Comparative Example 2, Example 1, Comparative Example 3, and Comparative Example 22 by Fourier transform infrared spectroscopy. .
20 a) is a graph obtained by analyzing the particles prepared in Comparative Example 18 and Example 1 with a powder X-ray diffraction pattern (PXRD), b) is a graph prepared in Comparative Example 18 It is a graph performed by thermogravimetric analyzes (TGA) of particles.
21 a) is a graph of the nitrogen (N ₂ ) adsorption-desorption experiment of the particles prepared in Example 1 and Comparative Example 18, b) is the specific surface area (Brunauer) of the particles prepared in Example 1 and Comparative Example 18 -Emmett-Teller method, BET) analysis is performed.
22 a) is a schematic diagram of a batch system, FIG. 22 b) is a schematic diagram of a microfluidic system, and FIG. 22 c) is a nanomotor of Example 1 and Comparative Example 4, respectively, 10 times , the respective Pickering efficiencies were obtained and plotted as a graph.
23 is an image obtained by observing a Pickering emulsion generated as an intermediate product in the preparation of the nanomotors of Examples 7, 1 and 8 with a field emission scanning microscope (FE-SEM).
24 is a graph (above) showing the yield of particles prepared in Example 7, Example 1, Example 8 and Comparative Example 14, and Example 2, Example 3, Example 1 and Comparative Example 7 It is a graph (below) showing the yield of particles
25 is a graph showing the average velocity of the particles prepared in Examples 1 and 5, a) is a graph tracking the trajectory of the particles (left) and a schematic diagram of the interface of the Pickering emulsion (right), b) is the average speed measured and displayed as a graph.
26 a) to b) is a test for rhodamine B (Rh.B) adsorption performance of the nanomotors prepared in Comparative Example 1 and Example 1, respectively, and UV-visible light (UV-vis) according to the operating time ) is a graph showing the absorption spectrum.
27 is a graph showing the _Rh.B absorption performance of Example ₁ as a UV-visible light (UV-vis) absorption spectrum graph. , Figure 27 b) is hydrogen peroxide (H ₂ O ₂ ) It is carried out under 5 wt% aqueous solution, Figure 27 c) is hydrogen peroxide (H ₂ O ₂ ) It is carried out under 10 wt% aqueous solution, Figure 27 d) is hydrogen peroxide (H ₂ O ₂ ) 10% by weight aqueous solution and near infrared (NIR).
28 a) to b) show the rhodamine B adsorption performance when the nanomotor prepared in Example 1 was operated under 10 wt% of hydrogen peroxide (H ₂ O ₂ ) and near infrared (NIR) ultraviolet-visible light (UV- vis) absorption spectrum and rhodamine B concentration.

Hereinafter, with reference to the accompanying drawings, embodiments of the present invention will be described in detail so that those of ordinary skill in the art to which the present invention pertains can easily implement them. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. In order to clearly explain the present invention in the drawings, parts irrelevant to the description are omitted, and the same reference numerals are assigned to the same or similar components throughout the specification.

The composition of the triple response nanomotor according to an embodiment of the present invention includes: mesoporous composite magnetic nanoparticles; Polydopamine solution; and a platinum (Pt) precursor.

The composite magnetic nanoparticles may include a core including silicon dioxide (SiO ₂ ); and a shell including iron oxide (Fe ₃ O ₄ ) magnetic nanoparticles; may have a core-shell structure including.

In this case, the average particle diameter of the iron oxide (Fe ₃ O ₄ ) magnetic nanoparticles may be 10 to 20 nm, preferably 12 to 18 nm.

Meanwhile, the polydopamine solution may include a dopamine monomer, ethanol and ammonia solution.

In addition, the dopamine monomer may be preferably dopamine hydrochloride (dopamine hydrochloride).

On the other hand, the platinum (Pt) precursor may include one or more selected from potassium chloride (Potassium hexachloroplatinate), platinum hydrogen chloride (Hydrogen hexachloroplatinate), sodium platinum chloride (Sodium hexachloroplatinate), and platinum ammonium chloride (Ammonium hexachloroplatinate), , preferably platinum hydrogen chloride (Hydrogen hexachloroplatinate).

In addition, the platinum precursor may have an average particle diameter of 10 to 50 nm, preferably 10 to 20 nm.

Another object of the present invention is a method for manufacturing a triple-response nanomotor, including the first step of preparing mesoporous composite magnetic nanoparticles, as shown in FIG. 1 ; a second step of reacting a hydrophilic silane compound and a hydrophobic silane compound with the composite magnetic nanoparticles; Mixing and emulsifying a dispersed phase containing a photo resin and a photo initiator in the continuous phase containing the composite magnetic nanoparticles that performed the above steps to form a Pickering emulsion, and UV irradiation Step 3; 4 step of mixing a polydopamine solution with the Pickering emulsion; 5 step of mixing a solution containing a platinum (Pt) precursor to the Pickering emulsion that has been performed in step 4; and step 6 of ultrasonically treating the Pickering emulsion having performed step 5 to obtain a nanomotor.

Specifically, in step 1, a mixture of an aqueous ammonia solution containing 3 to 9% by weight, preferably 4 to 8% by weight of iron oxide (Fe ₃ O ₄ ) magnetic nanoparticles and a surfactant is mixed with microfluidics. After injecting into the reactor, separately injecting the surfactant into the microfluidic reactor and passing it through, the reaction product may be calcined at 500 to 800 ° C, preferably carried out at 550 to 750 ° C. .

If the iron oxide (Fe ₃ O ₄ ) magnetic nanoparticles are included in an amount of less than 3% by weight in the total weight of the aqueous ammonia solution, there may be a problem in that the yield is greatly reduced because the amount of the produced nanomotor is small, and 9% by weight If it is included in excess, there may be a problem in that dissolution occurs in the manufactured composite magnetic nanoparticles.

Meanwhile, the microfluidic reactor may include a polytetra fluorethylene (PTFE) capillary having a length of 3 to 200 cm, and preferably, a polytetra fluorethylene (PTFE) having a length of 5 to 150 cm. ) may contain capillaries.

In addition, each of the mixture and surfactant may be injected into the microfluidic reactor at an injection rate of 0.5 to 3 mL/min, preferably at an injection rate of 0.7 to 1.5 mL/min.

In this case, the surfactant may be at least one selected from tetraethyl orthosilicate (TEOS) and cetyl trimethyl ammonium bromide (CTAB), and preferably include both TEOS and CTAB. .

The composite magnetic nanoparticles prepared in step 1 may have an average size of 350 to 450 nm, preferably 370 to 430 nm.

In addition, the composite magnetic nanoparticles have mesoporous pores, and by having the mesoporous pores, a high surface area, good solvent absorption, and excellent nanomotor activity can be obtained.

In addition, the average pores of the composite magnetic nanoparticles may be about 2.5 ~ 3.1nm, preferably 2.6 ~ 3.0nm.

Next, step 2 may be performed by adding and mixing the hydrophilic silane compound and the hydrophobic silane compound to the composite magnetic nanoparticles in a molar ratio of 1: 0.032 to 0.10, preferably 1: adding and mixing in a molar ratio of 0.040 to 0.090. More preferably, it can be carried out by adding and mixing in a molar ratio of 1: 0.045 to 0.085, and still more preferably 1: adding and mixing in a molar ratio of 0.055 to 0.075 can be carried out. The hydrophilic silane compound and the hydrophobic silane compound impart amphiphilicity to the composite magnetic nanoparticles. As shown in FIG. 15 , the hydrophilic and hydrophobic silane compounds are co-grafted so that a hydrophobic optical resin is liquid. It becomes red and performs the role of colloidalizing in water. If the hydrophobic silane compound is included in a molar ratio of less than 0.032, the contact angle may be too low to cause a problem that the photoresin cannot be mixed with water. A problem in which the resin does not mix and separate may occur.

In this case, the hydrophilic silane compound and the hydrophobic silane compound may be co-grafted on the surface of the composite magnetic nanoparticles at a contact angle of 43 to 111°, preferably from 61 to 108°. It may have a contact angle, and more preferably, may have a contact angle of 71 to 105°. If the contact angle is out of the above range, the masking of the composite magnetic nanoparticles is not properly performed when the Pickering emulsion is formed, so that the Pickering efficiency may be lowered and the performance of the nanomotor may be deteriorated.

In addition, by performing the second step, a change in wettability may occur on the surface of the composite magnetic nanoparticles. The change in wettability refers to a property that the surface of a solid is wetted by contact with a liquid.

Hereinafter, steps 3 to 5 may be performed through a microfluidics system, and in other words, may be performed through a continuous flow process.

Conventionally, nanomotors have been manufactured through a batch system, but when the nanomotors are manufactured through a batch system, the dropletized photoresin is non-uniformly formed as in FIG. There may be a problem in that the pickering efficiency is low.

On the other hand, the microfluidics system not only increases the yield of the nanomotor by continuous flow as shown in FIG. There is this.

In addition, the microfluidics system may have a structure as shown in FIG. 17, and to be more specific, the microfluidic system includes a hydrophilic glass tube in which a Pickering emulsion is formed, a primary surface modification part, and a secondary surface. It may include a modified part.

In this case, the hydrophilic glass tube may have an inner diameter of 0.5 to 1.0 mm, preferably 0.6 to 0.9 mm.

In addition, the first surface-modified portion and the second surface-modified portion each include a hydrophobic polytetra fluorethylene (PTFE) capillary, and the PTFE capillary may have an inner diameter of 0.8 to 1.2 mm, preferably 0.9 It can be ~1.1 mm.

In addition, the outer diameter of the PTFE capillary may be 1.6 ~ 2.0mm, preferably 1.7 ~ 1.9mm.

In addition, the PTFE capillary may have a length of 50 to 150 cm, preferably, may have a length of 70 to 130 cm.

In addition, steps 3 to 5 may be performed for 3.8 to 14.3 minutes, preferably 5.0 to 12.5 minutes, which can be adjusted by adjusting the reaction time of each step. If the reaction is performed in less than 3.8 minutes, there may be a problem that the pickering efficiency is lowered, and if it is carried out for more than 14.3 minutes, there may be a problem in that the yield of the nanomotor is lowered and the productivity is poor.

Next, step 3 can be carried out in a hydrophilic glass tube of a microfluidic system, and as soon as the dispersed phase and the continuous phase are put into the glass tube, the reaction can be started immediately to form a Pickering emulsion, and the unstable Pickering emulsion can be liquid by UV irradiation It is possible to stabilize the Pickering emulsion by curing the applied photoresin.

In this case, the UV irradiation may be performed at an intensity of 3.0 to 4.0W, preferably at an intensity of 3.5 to 4.0W.

On the other hand, the continuous phase and the dispersed phase may be introduced at a flow rate ratio of 1:10 to 80, preferably at a flow rate ratio of 1:15 to 40, and the continuous phase and the dispersed phase are each independently added to the microfluidic system. can be put in If the dispersed phase is included at a flow rate ratio of less than 10, there may be a problem in that the Pickering efficiency is lowered, and if it is included in a flow rate ratio of 80, there may be a problem in that the Pickering emulsion is not formed by the pressure of the dispersed phase.

On the other hand, the three-step reaction (emulsification reaction) may be performed for 5.0 to 50.0 seconds, preferably 5.0 to 45.0 seconds. If it is carried out for less than 5.0 seconds, there may be a problem that the pickering efficiency is lowered due to insufficient reaction time, and if it is carried out for more than 50.0 seconds, the nanoparticles are generated as a multi-layer on the photoresin and pickering There may be a problem that the efficiency is further lowered.

Meanwhile, the continuous phase may include the composite magnetic nanoparticles at a concentration of 20 to 90 mg/mL, preferably 30 to 85 mg/mL, and more preferably 40 to 80 mg/mL. concentration may be included. If the composite magnetic nanoparticles are included in a concentration of less than 20 mg/mL in the continuous phase, the yield of the nano-motor is significantly lowered, which may cause a problem that the economic feasibility of the process is poor, and is included in excess of 90 mg/mL In this case, a problem in which the pickering efficiency is lowered may occur.

Separately, the dispersed phase may include a photoresin solution containing 0.5 to 1.5% by weight of the photoinitiator. In addition, the photoinitiator may be included in an amount of 0.7 to 1.3% by weight of the photoresin solution.

In this case, the photoinitiator is 2,2-dimethoxy-2-phenylacetophenone (2,2-Dimethoxy-2-phenylacetophenone, DMPA), 3-hydroxyacetophenone (3-Hydroxyacetophenone, HAP), diphenyl (2 ,4,6-trimethylbenzoyl)phosphine oxide (Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, TPO) and 2-hydroxy-2-methylpropiophenone (2-hydroxy-2-methylpropiophenone, HMPP ) may include one or more selected from, preferably 2-hydroxy-2-methylpropiophenone (2-hydroxy-2-methylpropiophenone, HMPP), 3-hydroxyacetophenone (3-Hydroxyacetophenone, HAP) ) and diphenyl (2,4,6-trimethylbenzoyl)phosphine oxide (Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, TPO).

In addition, the optical resin is polyethylene glycol dimethacrylate (Poly(ethylene glycol) diacrylate, PEGDA), polypropene glycol dimethacrylate (Poly(proplene glycol) dimethacrylate, PPGDMA), and trimethylolpropane ethoxylate triacryl. It may include at least one selected from among triethylolpropane ethoxylate triacrylate (ETPTA), but more preferably trimethylolpropane ethoxylate triacrylate (ETPTA), which rapidly and uniformly adsorbs the composite magnetic nanoparticles.

Pickering emulsion (Pickering emulsion) prepared by performing three steps is the droplet (droplet) the optical resin; and the composite magnetic nanoparticles; the composite magnetic nanoparticles may be positioned at the interface between the hydrophobic optical resin and water as amphiphilic is imparted, The area may be in a masked state.

Next, the mixing with the polydopamine solution in step 4 can be performed by passing through the first surface modification part, through which it is not masked by the optical resin cured in the composite magnetic nanoparticles of the Pickering emulsion (non-masking) ) portion may be coated with polydopamine (Pdop) to form a polydopamine layer, the polydopamine may not be coated on a masking portion, and the polydopamine layer is preferably on the surface of the composite magnetic nanoparticles. 45 to 55% may be coated, and more preferably, may be coated to 47 to 53%.

In addition, the polydopamine solution may be introduced into the microfluidic system at a flow rate of 3 to 7 μl/min, preferably at a flow rate of 4 to 6 μl/min.

On the other hand, the polydopamine layer is positioned between the platinum catalyst layer and the composite magnetism, and not only serves as a linker, but also has thermal properties, thereby increasing the activity of the nanomotor by heat.

In addition, one or more selected from carbon nanotube (CNT) and graphene oxide (GO) may be used in the polydopamine layer instead of the polydopamine solution, and when the CNT and/or GO are laminated, thermal properties are obtained. The same effect as the polydopamine layer can be achieved.

Next, the platinum (Pt) precursor of step 5 may be injected into the secondary surface modification unit of the microfluidic system, and thus a platinum (Pt) catalyst layer may be formed on the polydopamine layer.

In this case, the platinum (Pt) precursor may be introduced into the secondary surface modification unit at a flow rate of 3 to 7 μl/min, preferably at a flow rate of 4 to 6 μl/min.

Next, the nanomotor can be separated from the Pickering emulsion through 6-step sonication.

At this time, the sonication may be performed for 5 to 20 minutes, preferably for 5 to 10 minutes, may be performed at an intensity of 10 to 60 kHz, preferably at an intensity of 30 to 40 kHz can be done

The triple-resposive nanomotor according to an embodiment of the present invention manufactured by the above method includes mesoporous composite magnetic nanoparticles; a polydopamine layer formed on a portion of the surface of the composite magnetic nanoparticles; and a platinum catalyst layer formed on the polydopamine layer.

In addition, the nanomotor may have a Pickering efficiency of 66% or more, preferably 70-100%, and more preferably 72-95%, as measured by the following Relational Equation 1.

[Relational Expression 1]

In Relation 1, G _put means the weight of silica put in, and G _waste means the weight of silica that is not used.

In addition, in the process of manufacturing the nanomotor, the yield of the Pickering emulsion per minute (min) may be 3.0 to 20.0 mg, preferably 5.0 to 18.0 mg.

Meanwhile, the nanomotor may have an average pore size of 2.2 to 2.8 nm, preferably 2.3 to 2.6 nm.

Meanwhile, the 'triple response' means driving as a catalyst, driving by thermophoretic driving, and driving by magnetic movement.

Meanwhile, the nanomotor of the present invention can be used in various fields such as biological, sensor and environmental fields.

[Example]

Example 1: Triple Response Nanomotor (m-SiO ₂ /Fe ₃ O ₄ Preparation of -Pdop/Pt)

(1) Iron oxide (Fe ₃ O ₄ ) Preparation of magnetic nanoparticles

A solution in which 5.2 g of ferric chloride (FeCl ₃ ) powder and 2.0 g of ferrous chloride (FeCl ₂ ) powder were dissolved in a hydrogen chloride solution of 0.85 mL of hydrogen chloride (HCl) and 25 mL of water was prepared.

Then, the solution was reacted by dropping it dropwise into 250 mL of a 1.5M sodium hydroxide (NaOH) solution under strong stirring.

Then, using a magnetic field in the solution in which the reaction was performed, iron oxide (Fe ₃ O ₄ ) magnetic nanoparticles having an average particle diameter of 15 nm were obtained, which were rinsed with purified water several times.

(2) Preparation of mesoporous composite magnetic nanoparticles

The iron oxide (Fe ₃ O ₄ ) aqueous solution containing the magnetic nanoparticles in an amount of 5% by weight of 0.7M and cetyl trimethyl ammonium bromide (CTAB, surfactant) at a concentration of 13.7mM to prepare a mixture did.

After connecting the T-shaped capillary and the 100 cm polytetra fluorethylene (PTFE) capillary, the mixture and 0.3M concentration of tetraethyl orthosilicate were passed through the PHD 2000 syringe pump (Harvard Apparatus) to the two inlets, respectively. (Tetraethyl orthosilicate, TEOS) was injected to obtain a product that passed through the capillary for 23.5 seconds.

At this time, the polytetrafluoroethylene capillary had an inner diameter of 1,000 μm and an outer diameter of 1,800 μm, and the mixture and TEOS were each injected at a flow rate of 1 mL·min ⁻¹ .

Then, the product was calcined at 650° C. to obtain mesoporous composite magnetic nanoparticles.

In this case, the average particle diameter of the composite magnetic nanoparticles was 400 nm, and the average pores were 2.5 nm.

(3) imparting amphiphilicity to the composite magnetic nanoparticles

A dispersion solution in which 0.2 g of the composite magnetic nanoparticles were dispersed in 30 g of toluene was prepared.

Then, the hydrophobic silane compound 3-aminopropyl triethoxysilane (APTES) and the hydrophilic silane compound dimethyl dichloro silane (Dichlorodimethylsilane, DCMS) were added to the dispersion solution in a molar ratio of 1: 0.064, It was magnetically stirred for 2 hours.

Then, the product prepared through the above step was centrifuged and rinsed with ethanol several times.

Then, the product subjected to the above steps was dried under vacuum at room temperature for 24 hours to impart amphiphilicity to the composite magnetic nanoparticles.

(4) Fabrication of triple-response nanomotors

After passing the composite magnetic nanoparticles in step (3) through a microfluidic system for 7.4 minutes, ultrasonic treatment was performed to prepare a triple-response nanomotor.

The residence time in the microfluidic system was controlled through the reaction (flow) times of (4-1) to (4-4).

At this time, the microfluidic system has the structure as shown in FIG. 17, cross-connection part, hydrophilic glass tube 10 cm, first surface modification part (T-type connection part for polydopamine solution input, and hydrophobic polytetrafluorethylene (PTFE) tube 100 cm ), and the secondary surface modification part (T-type connection part for platinum precursor input and hydrophobic polytetra fluorethylene (PTFE) tube 100 cm) in that order.

Specifically,

(4-1) The continuous phase was each injected at a concentration of 100 μl/min into the two inlets of the cross-connection, and separately, the dispersed phase was injected into the remaining inlets at a concentration of 10 μl/min.

At this time, the continuous phase was prepared by mixing 0.7 g (70 mg/ml) of the composite magnetic nanoparticles prepared in Preparation Example 1 and 10 mL of a solution containing 2% by weight of polyvinyl alcohol (PVA),

Trimethylolpropane ethoxylate triacrylate (ETPTA) containing 1% by weight of 2-hydroxy-2-methylpropiophenone (photoinitiator) as the dispersed phase; photoresin) solution was prepared.

In addition, the continuous phase and the dispersed phase were mixed immediately after injection to form a Pickering emulsion.

(4-2) UV irradiation was performed on 10 cm of a hydrophilic glass tube, and the flow time through the glass tube was 11 seconds.

At this time, the UV irradiation was irradiated by dropping a UV lamp reactor (4W, 365nm) to the glass tube by 10 cm.

(4-3) The polydopamine solution was put into the T-type connection part of the first surface modification part at a flow rate of 5 μL·min ^-1 , and reacted while flowing through a PTTE tube 100 cm.

At this time, the polydopamine solution was prepared by dropping 1 ml of an aqueous solution of dopamine hydrochloride in a solution of 4 mL of ethanol, 9 mL of purified water, and 360 μl of aqueous ammonia (NH ₄ OH) at a rate of 50 mL min ^-1 dropwise.

(4-4) A solution containing a platinum precursor was put into the T-connection part of the secondary surface modification part at a flow rate of 5 μL min ^-1 , and it reacted while flowing through a PTTE tube 100 cm. The reaction product leaves the microfluidic system and contains purified water contained in a glass bottle.

At this time, the solution containing the platinum precursor was prepared including a mixture of platinum hydrogen chloride (Hydrogen hexachloroplatinate) 31.25X10 ^-6 M and methanol, and sodium borohydride (NaBH ₄ ) 0.066M.

(4-5) The reaction product in the glass bottle was washed three times with ethanol and then sonicated for 300 seconds to obtain a triple nanomotor in the form of an aqueous suspension.

Examples 2 to 8: Preparation of triple response nanomotors

A nanomotor was prepared in the same manner as in Example 1, but the concentration of the composite magnetic nanoparticles in the continuous phase, the microfluidic (MF) system residence time, or the molar ratio of the hydrophobic silane compound and the hydrophilic silane compound were shown in Tables 1 to 2 below. In the same way, Examples 2 to 8 were carried out.

Comparative Example 1: Preparation of non-mesoporous nanomotors

A nanomotor was prepared in the same manner as in steps (1), (3) and (4) of Example 1,

Step (2) was performed as follows to prepare a non-mesoporous nanomotor.

160.0 mL of ethanol and 26.4 g of aqueous ammonia were added to a four-neck flask and stirred to prepare a mixed solution.

In addition, 63.4 g of an iron oxide solution containing 5 wt% of iron oxide (Fe ₃ O ₄ ) magnetic nanoparticles and the remaining amount of ethanol in the flask, and separately from this, 17.4 g of tetraethyl orthosilicate (TEOS) were added to the flask for 24 hours, respectively. was added dropwise.

Then, the process of rinsing the product generated through the reaction and centrifuging at a rotation speed of 3,000 rpm for 10 minutes was repeated 3 times.

Then, the product subjected to the above step was dried under vacuum at room temperature for 24 hours to obtain non-mesoporous composite magnetic nanoparticles having an average particle diameter of 15 nm.

Comparative Example 2: iron oxide (Fe ₃ O ₄ ) Preparation of magnetic nanoparticles

A solution in which 5.2 g of ferric chloride (FeCl 3 ) powder and 2.0 g of ferrous chloride (FeCl ₂ ) powder were dissolved in a hydrogen chloride solution of 0.85 mL of hydrogen chloride (HCl) and 25 mL of water was prepared.

Then, the solution was reacted by dropping it dropwise into 250 mL of a 1.5M sodium hydroxide (NaOH) solution under strong stirring.

Then, using a magnetic field in the solution in which the reaction was performed, iron oxide (Fe ₃ O ₄ ) magnetic nanoparticles having an average particle diameter of 15 nm were obtained, which were rinsed with purified water several times.

Comparative Example 3: m-SiO ₂ /Fe ₃ O ₄ -Preparation of Pdop nanoparticles

Prepared in the same manner as (1) to (4-2) of Example 1,

The microfluidic system in which the reaction is performed uses a cross-connection part, a hydrophilic glass tube 10 cm, and a first surface modification part (a T-type connection part for polydopamine solution input and a hydrophobic polytetrafluorethylene (PTFE) tube 100 cm). did.

to the next,

(4-3) The polydopamine solution was put into the T-connection part of the first surface modification part at a flow rate of 50 mL·min ^-1 , and the reaction was performed while flowing 100 cm of the PTTE tube. contained in

At this time, the polydopamine solution was prepared by dropping 1 ml of an aqueous solution of dopamine hydrochloride in a solution of 4 mL of ethanol, 9 mL of purified water, and 360 μl of aqueous ammonia (NH ₄ OH).

(4-4) The reaction product in the glass bottle was washed with ethanol three times and then sonicated for 300 seconds to obtain m-SiO ₂ /Fe ₃ O ₄ -Pdop nanoparticles in the form of an aqueous suspension.

Comparative Example 4: Triple response nanomotor (m-SiO ₂ /Fe ₃ O ₄ Preparation of -Pdop/Pt)

It was carried out in the same way as (1) to (3) of Example 1,

A nanomotor was prepared in a batch (batch) system, and a homogenizer (16,000 rpm) of Yotec Instruments was used as the batch reactor,

Next, (4-1) polyvinyl alcohol (Polyvinyl alcohol, PVA) in a 2% by weight solution of the composite magnetic nanoparticles at a concentration of 70 mg / ml, 2-hydroxy-2-methylpropiophenone (2-hydroxy 0.5 mL of a trimethylolpropane ethoxylate triacrylate (ETPTA, optical resin) solution containing -2-methylpropiophenone, photoinitiator) in an amount of 1% by weight was added, and the mixture was stirred in the batch for 2 minutes to pickering. An emulsion was obtained.

(4-2) The Pickering emulsion was gently rinsed several times with ethanol, and then dried under vacuum at room temperature for 24 hours.

(4-3) After preparing a mixture by stirring 0.1 g of Pickering emulsion, 4 mL of ethanol, 9 mL of purified water, and 40 μl of aqueous ammonia (NHOH) at room temperature for 10 minutes, the polydopamine solution (Example 1) The same solution was used.) 1 mL was slowly added dropwise.

Then, the product produced through the reaction was washed several times with purified water, and then dried under vacuum at room temperature for 24 hours.

(4-4) The product obtained in the above step was supported in a solution containing a platinum precursor (the same solution as in Example 1 was used) and reacted, then gently stirred for 24 hours, rinsed 3 times in ethanol and vacuum Nanomotors were obtained by drying for 24 hours at room temperature under

Comparative Examples 5 to 14: Preparation of triple response nanomotors

A nanomotor was prepared in the same manner as in Example 1, but the concentration of the composite magnetic nanoparticles in the continuous phase, the microfluidic (MF) system residence time, or the molar ratio of the hydrophobic silane compound and the hydrophilic silane compound were shown in Tables 3 to 4 Comparative Examples 5 to 14 were carried out in the same manner.

Comparative Examples 15 to 19: Composite magnetic nanoparticles (m-SiO ₂ /Fe ₃ O ₄ ) manufacturing

The composite magnetic nanoparticles were prepared in the same manner as in Example 1 (1) to (2), but the length of the polytetra fluorethylene (PTFE) capillary was 3 cm, 7 cm, 30 cm, 100 cm and 200 cm, respectively. Comparative Examples 15 to 19 were carried out.

Comparative Example 20 ~ Comparative Example 21: Composite magnetic nanoparticles (m-SiO ₂ /Fe ₃ O ₄ ) manufacturing

(1) to (2) of Example 1 were performed in the same manner to prepare composite magnetic nanoparticles, but the iron oxide (Fe ₃ O ₄ ) magnetic nanoparticles of (2) were compared with 10 wt% and 20 wt%, respectively Examples 20 to 21 were implemented.

Comparative Example 22: Preparation of non-mesoporous composite magnetic nanoparticles

Step (1) of Example 1 was performed in the same manner,

160.0 mL of ethanol and 26.4 g of aqueous ammonia were added to a four-necked flask and stirred to prepare a mixed solution.

In addition, 63.4 g of an iron oxide solution containing 5 wt% of iron oxide (Fe ₃ O ₄ ) magnetic nanoparticles and the remaining amount of ethanol in the flask, and separately from this, 17.4 g of tetraethyl orthosilicate (TEOS) were added to the flask for 24 hours, respectively. was added dropwise.

Then, the process of rinsing the product generated through the reaction and centrifuging at a rotation speed of 3,000 rpm for 10 minutes was repeated 3 times.

Then, the product subjected to the above step was dried under vacuum at room temperature for 24 hours to obtain non-mesoporous composite magnetic nanoparticles having an average particle diameter of 15 nm.

Experimental Example 1: Performance evaluation of triple response nanomotors

The triple-response nanomotors prepared in Examples 1 to 8 and Comparative Examples 4 to 14 were evaluated in the following manner, and the result values are shown in Tables 1 to 4, FIGS. 3 to 4 and 22 c), as shown in FIGS. 24 and 25 a) to b).

(1) Measurement of contact angle

After sampling, the dried sample was dispersed in ethanol, drop-casted, and pressed flat on a silicon wafer with glass to form a film, and then measured using an optical contact angle meter (Pheonix series by SEO Co. Ltd). .

In addition, after repeating 5 times for accuracy, the average value was taken and recorded.

(2) Measurement of Pickering efficiency

In the process of manufacturing the nanomotor, the Pickering efficiency was calculated through the following relation 1.

[Relational Expression 1]

In Relation 1, G _put means the weight of silica put in, and G _waste means the weight of silica that is not used.

(3) Measurement of yield

In manufacturing the nanomotor, it was measured how many mg of Pickering emulsion was produced per minute.

Example 1 Example 2 Example 3 Example 4 Composite Magnetic Nanoparticles Molar ratio of hydrophilic silane compound to hydrophobic silane compound 1:0.064 1:0.064 1:0.064 1:0.064 Contact angle (°) 91 (±4) 91 (±4) 91 (±4) 91 (±4) microfluidic system Concentration of composite magnetic nanoparticles in continuous phase (mg/mL) 70 20 40 90 MF reactor residence time (min) 7.4 7.4 7.4 7.4 Pickering Efficiency (%) 86.7 91.3 89.4 81.6 Yield (mg/min) 12.1 3.7 7.2 14.2

Example 5 Example 6 Example 7 Example 8 Comparative Example 4 Composite Magnetic Nano
particle Molar ratio of hydrophilic silane compound to hydrophobic silane compound 1:0.032 1:0.10 1:0.064 1:0.064 1:0.64 Contact angle (°) 61 (±3) 99 (±3) 91 (±4) 91 (±4) 91 (±4) my
Crow fluid system Concentration of composite magnetic nanoparticles in continuous phase (mg/mL) 70 70 70 70 70 MF reactor residence time (min) 7.4 7.4 3.8 14.3 - Pickering Efficiency (%) 77.5 72.3 78.5 88.3 43.1 Yield (mg/min) 10.1 10.5 22.0 6.2 -

Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Composite Magnetic Nano
particle Molar ratio of hydrophilic silane compound to hydrophobic silane compound 1:0.064 1:0.064 1:0.064 1:0.020 1:0.120 Contact angle (°) 91 (±4) 91 (±4) 91 (±4) 42 (±8) 112 (±2) my
Crow fluid system Concentration of composite magnetic nanoparticles in continuous phase (mg/mL) 10 100 140 70 70 MF reactor residence time (min) 7.4 7.4 7.4 7.4 7.4 Pickering Efficiency (%) 92.5 75.5 59.2 61.2 65.8 Yield (mg/min) 1.8 14.2 16.6 9.3 8.5

Comparative Example 10 Comparative Example 11 Comparative Example 12 Comparative Example 13 Comparative Example 14 Composite Magnetic Nano
particle Molar ratio of hydrophilic silane compound to hydrophobic silane compound 1:0.191 1:0 1:0.064 1:0.064 1:0.064 Contact angle (°) 143 (±2) 0 91 (±4) 91 (±4) 91 (±4) my
Crow fluid system Concentration of composite magnetic nanoparticles in continuous phase (mg/mL) 70 70 70 70 70 MF reactor residence time (min) 7.4 7.4 3.0 16.0 30.7 Pickering Efficiency (%) 58.2 0 75.0 88.9 89.6 Yield (mg/min) 1.5 0 23.1 4.8 3.3

Looking at Tables 1 to 4, it was confirmed that Examples 1 to 8 had excellent Pickering efficiency and yield.

On the other hand, Comparative Example 1, which is a non-mesoporous nanomotor having few pores, has a very poor Pickering efficiency as the Pickering efficiency is less than 50% compared to Example 1, which is a mesoporous nanomotor. could

In addition, it can be seen that Comparative Example 4 using a batch system exhibits a very low efficiency with a Pickering efficiency of 43.1% compared to Example 1 prepared using a microfluidic system.

In addition, Comparative Examples 5 to 7 and Comparative Examples 12 to 14 in which the concentration of the composite magnetic nanoparticles in the continuous phase is out of 20 to 90 mg/ml or the residence time in the microfluidic system is out of 3.8 to 14.3 minutes It was found that the pickering efficiency and the yield of the nanomotor were significantly reduced, which was not suitable because the productivity was lowered.

In addition, Comparative Examples 8 to 11, in which the molar ratio of the hydrophilic silane compound and the hydrophobic silane compound deviates from the molar ratio of 1: 0.032 to 1: 0.10, had low Pickering efficiency and yield, which indicates that the contact angle of the surface of the composite magnetic nanoparticles is appropriate It is predicted that it is because the Pickering emulsion is not properly formed.

On the other hand, in FIGS. 3 and 22 c ) Example 1 and Comparative Example 4 were performed 10 times, respectively, and the Pickering efficiency was obtained and plotted as a graph. Example 1 shows a high Pickering efficiency of 86 (± 1)%, whereas Comparative Example 4 performed as a batch system has a very low Pickering efficiency of 43 (± 16)%. could

On the other hand, the graph above Fig. 4 relates to Example 7 (emulsification time 5.5 seconds), Example 1 (emulsion time 11.5 seconds), Example 8 (emulsion time 22 seconds), and Comparative Example 14 (emulsion time 44 seconds). , through this, the pickering efficiency increases as the emulsification time increases, but it was confirmed that there is a problem in that the degree of improvement in the pickering efficiency is insufficient when the emulsification time exceeds 25 seconds.

In addition, the graph below FIG. 4 shows Example 2 (composite magnetic nanoparticles concentration of 20 mg/mL), Example 3 (composite magnetic nanoparticles concentration of 40 mg/mL), Example 1 (composite magnetic nanoparticles concentration of 70 mg/mL) and Regarding Comparative Example 7 (composite magnetic nanoparticles concentration of 140 mg/mL), it was found that the Pickering efficiency decreased as the concentration of the composite magnetic nanoparticles in the continuous phase increased. Although the yield was shown to continuously increase, it was confirmed that the pickering efficiency decreased more rapidly.

On the other hand, the graph above Fig. 24 shows the number of nanomotors of Example 7 (residence time 3.8 minutes in the microfluidic system), Example 1 (7.4 minutes), Example 8 (14.3 minutes), and Comparative Example 14 (30.7 minutes) As a graph showing the yield, it could be seen that the productivity decreased as the total residence time increased, and when the residence time exceeded 16 minutes, the yield was less than 5 mg/mL, indicating that the process was not efficient.

In addition, the graph below FIG. 24 shows Example 2 (composite magnetic nanoparticles concentration of 20 mg/mL), Example 3 (composite magnetic nanoparticles concentration of 40 mg/mL), Example 1 (composite magnetic nanoparticles concentration of 70 mg/mL) and Regarding Comparative Example 7 (composite magnetic nanoparticles concentration of 140 mg/mL), it was confirmed that the yield of the nanomotors increased as the concentration of the composite magnetic nanoparticles in the continuous phase increased, and that of the composite magnetic nanoparticles When the concentration exceeded 90 mg/mL, it was confirmed that the degree of improvement in yield was insignificant.

On the other hand, looking at a) of FIG. 25 , Example 1 having a contact angle of 91° showed higher activity compared to Example 5 having a contact angle of 61°. It is considered that this is because about half of the applied photoresin surface can be masked.

Also, referring to b) of FIG. 25 , it was confirmed that Example 1 had an average speed of 14.2 μm/s, but Example 5 moved at a speed so slow that no average speed was observed.

On the other hand, looking at Tables 1 to 4, when the hydrophilic silane compound and the hydrophobic silane compound are out of the molar ratio of 0.032 to 0.010 (Comparative Examples 8 to 10), the Pickering efficiency is low as well as the yield of the Pickering emulsion is significantly higher. decrease could be observed.

In addition, when the concentration of the composite magnetic nanoparticles in the continuous phase was out of the range of 20 to 90 mg/mL (Comparative Examples 5 to 7), there was a problem that the Pickering efficiency was low or the yield of the Pickering emulsion was low.

In addition, when the residence time in the microfluidic system was out of 3.8 to 14.3 minutes (Comparative Example 12 to Comparative Example 14), there was a problem in that the Pickering efficiency was low or the yield of the Pickering emulsion was low.

Experimental Example 2: Observation of interface formation

In carrying out Example 1, Example 5, Comparative Example 10 and Comparative Example 11, after adding the dispersed phase in step (3), the sample was sampled and photographed before stirring, and images taken are shown in FIG. 16 . Through this, when the molar ratio of the hydrophilic silane compound and the hydrophobic silane compound is out of the range of the present invention, there is a problem in that the silane compound cannot form an interface. In particular, Comparative Example 11(1) without the hydrophilic silane compound is Example 1(3) It was confirmed that there was a problem that water and the silane compound did not mix when compared with .

Experimental Example 3: Zeta potential value measurement

The zeta potential of the particles or nanomotors prepared in Comparative Example 2, Comparative Example 22, Comparative Example 18, Comparative Example 3 and Example 1 was measured at room temperature through a Malvern nano particle size and a zeta potentiometer.

18 a) to b2), Comparative Example 22 showed a zeta potential of +33 mV through a) of FIG. 18, but Comparative Example 3 in which a polydopamine layer was formed on the surface of the composite magnetic particle had a zeta The potential was lowered to -36 mV, and it was confirmed that the zeta potential was very low to -48 mV by the additional formation of a platinum catalyst layer (Example 1).

Meanwhile, b1) to b2) of FIG. 18 are graphs showing the zeta potential according to the synthesis time of the nanomotors prepared in Comparative Examples 3 and 1, and in the case of the nanomotors prepared in Comparative Example 3, the zeta potential value during 0.92 This was significantly decreased to -29 mV, decreased to -36 mV for 3.65 minutes, and in the case of the nanomotor prepared in Example 1, it was decreased to -43 mV for 0.91 minutes, and it was confirmed that it decreased significantly to -48 mV for 3.57 minutes.

Experimental Example 4: Surface observation

The surfaces of Examples 1, 7, 8, and Comparative Examples 15 to 21 were observed in the following manner.

(1) Example 1 was observed with an optical microscope (DMIL LED microscope manufactured by Leica).

In detail, a) of FIG. 2 is an image of the nanomotor of Example 1 observed with an optical microscope, and it can be confirmed that the nanomotor of the present invention is a spherical particle.

(2) Example 1, Example 7, Example 8, and Comparative Examples 15 to 21 were observed with a field-emission scanning electron microscope (FE-SEM, JSM 7401F).

Specifically, b) to c) of FIG. 2 are images observed at a scale of 1 μm and 100 nm, respectively, of Pickering emulsion generated as an intermediate product during the manufacture of the nanomotor of Example 1, and dropletization It was found that the composite magnetic nanoparticles were evenly formed on the surface of the photo resin.

In addition, it was found that the polydopamine layer and the platinum catalyst layer were coated on about half of the surface of the composite magnetic nanoparticles through c) of FIG. 2 , and it was confirmed that the nanomotor of the present invention is a Janus type nanoparticle. .

In addition, in FIG. 10 b), the mesoporous composite magnetic nanoparticles prepared in Comparative Example 18 were observed, and it was confirmed that silicon dioxide was uniformly formed on the surface of the iron oxide magnetic nanoparticles.

In addition, FIG. 12 relates to the composite magnetic nanoparticles prepared in Comparative Examples 15 to 19. In Comparative Example 18, in which the hydrophilic glass tube has a length of 100 cm, the composite magnetic nanoparticles were formed not only in a uniform size but also evenly dispersed. On the other hand, in Comparative Examples 15 to 17, in which the length of the hydrophilic glass tube is 3 cm, 7 cm, and 30 cm, the size of the composite magnetic nanoparticles is not uniform and it can be confirmed that they are agglomerated without being dispersed, and the length of the hydrophilic glass tube is 200 cm In Comparative Example 19, it was confirmed that necking occurred in the composite magnetic nanoparticles.

In addition, FIG. 13 relates to the composite magnetic nanoparticles prepared in Comparative Examples 18, 20, and 21, and Comparative Example 18 prepared by including magnetic iron oxide nanoparticles in an amount of 5 wt% was uniformly spherical, but , in Comparative Examples 20 and 21 prepared by including 10 wt% and 20 wt%, it was confirmed that elution occurred in the composite magnetic nanoparticles.

In addition, FIG. 23 is an observation of Pickering emulsion generated as an intermediate product in manufacturing the nanomotors of Examples 7, 1 and 8. As the emulsification time increases, the composite magnetic properties on the surface of the photoresin dropletized. It was confirmed that the nanoparticles were evenly formed.

(3) Example 1 was observed with a high resolution transmission electron microscopy (TEM, JEOL JEM-2100F).

Specifically, d) of FIG. 2 is an image obtained by color mapping the nanomotor of Example 1 through a transmission electron microscope (TEM) energy dispersive X-ray spectrometer (EDS). , is a color mapping of silicon (Si), iron (Fe), oxygen (O), and platinum (Pt) elements, respectively, in that order. Through this, it was confirmed that silicon, iron, and oxygen elements are elements included in the composite magnetic nanoparticles and are evenly distributed throughout the nanomotor, and the platinum element included in the platinum catalyst layer is distributed over half the area of the nanomotor, covering It was found that the nanomotor was properly formed by the microfluidic Pickering emulsification method according to the masking method.

In addition, FIG. 10 a) is an observation of the magnetic iron oxide nanoparticles of Example 1.

Also, in FIG. 10 c), the composite magnetic nanoparticles of Example 1 were observed, and it was confirmed that the iron oxide nanoparticles were uniformly formed on the surface of the silicon dioxide.

Experimental Example 5: Fourier transform infrared spectroscopy (FT-IR) analysis

In order to check whether the surface modification (primary modification with polydopamine and secondary modification with platinum catalyst) of the particles prepared in Comparative Example 18, Comparative Example 2, Example 1 and Comparative Example 3, analysis was performed in the following manner. .

First, in FIGS. 19 a) and b), a range of 400 to 4,000 cm ^-1 was analyzed through Fourier transform infrared spectroscopy (FT-IR).

Specifically, referring to a) and b) of FIG. 19, the formation of the polydopamine layer is a hydroxyl group (-OH) peak at 3,350 cm ^-1 , an aromatic c=c peak at 1,490 cm ^-1 , 3,620 cm ^-1 and 1,620 cm ^-1 Bending (bending) amine group (-NH ₂ ) It was confirmed through the observation of the peak.

In addition, the formation of the platinum catalyst layer was confirmed through the amine group (-NH ₂ ) peak at 3,620 cm ^-1 and 1,620 cm ^-1 .

In addition, it was found through the CN peak at 1,399 cm ^-1 that a covalent bond was formed by Michael addition and Schiff base reaction between the surface amino group and the polydopamine layer.

Experimental Example 6: X-ray diffraction pattern analysis

In order to observe the surface of the particles prepared in Comparative Example 18 and Example 1, a powder X-ray diffraction pattern (PXRD) was analyzed through a HyPix 3000 detector, and Cu as a radiation source Using Kα, it was performed under the conditions of a wavelength of 1.5405*?* and a power of 30 mA at 30 kV, and recorded with a high resolution X-ray diffractometer (SmartLab, Rigaku Corporation).

Referring to FIG. 20 a), it was confirmed that magnetic iron oxide nanoparticles and a platinum catalyst layer were present in the nanomotor prepared in Example 1.

Experimental Example 6: X-ray diffraction pattern analysis

In order to observe the surface of the particles prepared in Comparative Example 18 and Example 1, a powder X-ray diffraction pattern (PXRD) was analyzed through a HyPix 3000 detector, and Cu as a radiation source Using Kα, it was carried out under the conditions of a wavelength of 1.5405 Å and a power of 30 mA at 30 kV, and recorded with a high resolution X-ray diffractometer (SmartLab, Rigaku Corporation).

Referring to FIG. 20 a), it was confirmed that magnetic iron oxide nanoparticles and a platinum catalyst layer were present in the nanomotor prepared in Example 1.

Experimental Example 7: Thermogravimetric Analysis

In order to observe the surface of the particles prepared in Comparative Example 18, thermogravimetric analysis (TGA) was performed using SDT Q600 as a thermogravimetric analysis equipment, and the condition of a heating rate of 10° C./min under 30 to 800° C. analysis was performed.

Looking at this through b) of FIG. 20 , it was confirmed that the thermal weight increased by 20% after firing as compared to before firing.

Experimental Example 8: Surface area and pore analysis

In order to analyze the surface area and pores of the particles prepared in Example 1 and Comparative Example 18, analysis was performed by the following experimental method.

First, looking at a) and b) of FIG. 21 , the specific surface area (Brunauer-Emmett-Teller method, BET) and nitrogen (N ₂ ) adsorption-desorption isotherm (77K) were analyzed through the ASAP 2020 instrument, and FIG. 21 a ) of nitrogen (N ₂ ) adsorption-desorption isotherm belongs to type IV with a hysteresis loop, and it was confirmed that it had mesoporous pores.

In addition, referring to FIG. 21 b), Example 1 has a specific surface area of 638 m ² /g and an average pore size of 2.5 nm, and Comparative Example 18 has a specific surface area of 1,020 m ² /g and an average pore size of 2.8 nm. It can be seen that, through this, it can be confirmed that the pores are not completely blocked even when the polydopamine layer and the platinum catalyst layer are formed on the surface of the composite magnetic nanoparticles.

Experimental Example 9: Evaluation of drivability by catalyst and heat

A sample (750 μg/mL) of the nanomotor prepared in Example 1 was extracted, and the behavior under hydrogen peroxide (H ₂ O ₂ ) and near-infrared (NIR) was observed.

Specifically, FIGS. 5 to 7 are the results of observing with an optical microscope (DMIL LED microscope of Leica), and analyzing the trajectories using the Tracker 5.1.3 program as a video analysis and modeling tool. As a graph of the swimming trajectory obtained as a result of the analysis, hydrogen peroxide (H ₂ O ₂ ) 0 wt%, 2 wt%, 5 wt%, 10 wt%, respectively, that performed under near infrared rays, It was shown that hydrogen peroxide (H ₂ O ₂ ) was carried out under 10 wt% and near infrared rays, and through this, it was found that the activity of the nanomotor was highest when hydrogen peroxide (H ₂ O ₂ ) was carried out under 10 wt% and near infrared rays. In addition, it showed relatively weak activity when there was little hydrogen peroxide or there was no near-infrared rays.

In addition, FIG. 6 shows a mean squared displacement (MSD) obtained by the analyzed trajectory, which was calculated through the following relational expression 2.

[Relational Expression 2]

In Relation 2, N denotes the number of particles, r _i (t)- r _i (t+Δt) denotes a vector distance traveled by the particles for a predetermined time (t), and t is 2 seconds or less.

As shown in FIG. 6, after operating for 2 seconds under 10% by weight of hydrogen peroxide (H ₂ O ₂ ), the mean square displacement was about 2,130 μm ² , showing the highest activity, but hydrogen peroxide (H ₂ O ₂ ) 0 weight After operating for 2 seconds under %, the mean square displacement was less than about 0.1 μm ² , which is thought to be due to the self-propelling force of the nanomotor under hydrogen peroxide (fuel).

In addition, Figure 7 is a graph showing the average velocity, each of hydrogen peroxide (H ₂ O ₂ ) 0% by weight, 2% by weight, 5% by weight, 10% by weight, that performed under near infrared rays, Hydrogen peroxide (H ₂ O ₂ ) Shows that it was carried out under 10 wt% and near infrared rays, and when hydrogen peroxide (H ₂ O ₂ ) was 0 wt% and 2 wt%, the speed was not observed, and when only near infrared rays were irradiated, 3 μm /s showed a low speed, hydrogen peroxide (H ₂ O ₂ ) 10% by weight and the one performed under near-infrared rays showed the highest activity at 16 μm/s.

Experimental Example 10: Evaluation of drivability by magnetism

In order to observe the magnetophoresis of the nanomotor prepared in Example 1, an external magnet (neodymium magnet) having a magnetic field of 500 mT was brought close to the nanomotor, and the movement of the nanomotor was shown as a graph in FIG. 8 . Through this, it was confirmed that the nanomotor of Example 1 moved in four directions.

On the other hand, as shown in FIG. 14 , after sampling the particles prepared in Comparative Example 18, an external magnet was applied to evaluate whether they had magnetism. As a result, it was confirmed that the particles prepared in Comparative Example 18 had magnetism through the movement of the composite magnetic nanoparticles toward the magnet, which is expected to be due to the magnetic iron oxide nanoparticles formed on the surface of the composite magnetic nanoparticles.

Experimental Example 11: Dye adsorption performance evaluation

In order to confirm the dye removal performance of the nanomotors prepared in Example 1 and Comparative Example 1, the adsorption performance of rhodamine B (RH.B), an organic dye, of the nanomotors was tested as follows.

At this time, the nanomotor was added so as to be 750 μg/mL in the total solution.

Specifically, the graph of Figure 9 (left) is hydrogen peroxide (H ₂ O ₂ ) 0 wt%, 2 wt%, 5 wt% and 10 wt% or hydrogen peroxide (H ₂ O ₂ ) 10 wt% Near-infrared (NIR) conditions The adsorption performance was tested in a graph and the results were shown in a graph, and through this, the adsorption performance was the best under 10 wt% near-infrared (NIR) conditions of hydrogen peroxide (H ₂ O ₂ ).

In addition, in the case of Example 1, the dye adsorption removal rate reached 99% after 20 minutes of operation of the nanomotor (refer to the image on the right of FIG. It was found that the adsorption rate was very poor at only about 17%, and it is predicted that the effect was not expressed because there were almost no pores.

Meanwhile, FIGS. 26 a) to b) and FIG. 27 are ultraviolet-visible ray (UV-vis) absorption spectra measured through an ultraviolet-visible spectrometer (UV-vis spectrometer manufactured by UV-vis spectrometer).

In detail, a) of FIG. 26 is a graph evaluating the adsorption performance when the nanomotor prepared in Comparative Example 1 was operated for 0 minutes, 1 minute, and 3 minutes, and the degree of adsorption of rhodamine B corresponding to a wavelength of 554 nm was I could see what was missing.

On the other hand, b) of FIG. 27 is a graph evaluating the adsorption performance when the nanomotor prepared in Example 1 was operated for 0 minutes, 5 minutes, 10 minutes, 15 minutes and 20 minutes, which corresponds to a wavelength of 554 nm. It was confirmed that the degree of adsorption of rhodamine B was very superior to that of Comparative Example 1.

In addition, FIG. 27 a) shows the absorbance when the nanomotor prepared in Example 1 was operated for 0 minutes, 5 minutes, 10 minutes and 15 minutes under 2% by weight of hydrogen peroxide (H ₂ O ₂ ).

In addition, FIG. 27 b) shows the absorbance when the nanomotor prepared in Example 1 was operated for 0 minutes, 1 minute, 5 minutes, 7 minutes and 10 minutes under 5 wt% of hydrogen peroxide (H ₂ O ₂ ) As a result, it was confirmed that hydrogen peroxide (H ₂ O ₂ ) exhibited excellent adsorption performance in a shorter time than when operated under 2% by weight.

In addition, FIG. 27 c) shows the absorbance when the nanomotor prepared in Example 1 was operated for 0 minutes, 1 minute, 5 minutes, and 7 minutes under 10% by weight of hydrogen peroxide (H ₂ O ₂ ), hydrogen peroxide (H ₂ O ₂ ) It was confirmed that excellent adsorption performance was exhibited in a shorter time than when operated under 5% by weight.

In addition, d) of FIG. 27 shows the absorbance when the nanomotor prepared in Example 1 was operated for 0 minutes and 1 minute under 10% by weight of hydrogen peroxide (H ₂ O ₂ ) and near infrared (NIR), 1 minute It was confirmed that the best performance was obtained by removing all of rhodamine B.

On the other hand, FIG. 28 a) shows the absorbance when the nanomotor prepared in Example 1 was operated for 0 minutes and 1 minute under 10% by weight of hydrogen peroxide (H ₂ O ₂ ) and near infrared (NIR), a total of 3 It was repeated several times. Through this, it was confirmed that the nanomotor of the present invention was excellent without deterioration in its activity even when reused.

In addition, FIG. 28 b) shows the degree of removal of rhodamine B when the nanomotor prepared in Example 1 was operated under 10% by weight of hydrogen peroxide (H ₂ O ₂ ) and near infrared (NIR), even if reused It had excellent performance and almost all dyes were removed in 1 minute, confirming that it was driven by self-propelled force without mechanical operation.

Although one embodiment of the present invention has been described above, the spirit of the present invention is not limited to the embodiments presented herein, and those skilled in the art who understand the spirit of the present invention can add components within the scope of the same spirit. , changes, deletions, additions, etc. may easily suggest other embodiments, but this will also fall within the scope of the present invention.

Claims (13)

mesoporous composite magnetic nanoparticles; Polydopamine solution; and a platinum (Pt) precursor; a triple response nanomotor composition comprising.
According to claim 1,
The platinum (Pt) precursor includes at least one selected from platinum potassium chloride (Potassium hexachloroplatinate), platinum hydrogen chloride (Hydrogen hexachloroplatinate), sodium platinum chloride (Sodium hexachloroplatinate), and platinum ammonium chloride (Ammonium hexachloroplatinate),
The polydopamine solution is a triple response nanomotor composition comprising a mixture of dopamine monomer, ammonia solution, purified water and ethanol.
According to claim 1,
The composite magnetic nanoparticles may include a core including silicon dioxide (SiO ₂ ); and a shell including iron oxide (Fe ₃ O ₄ ) magnetic nanoparticles.
Step 1 of preparing mesoporous composite magnetic nanoparticles;
a second step of reacting a hydrophilic silane compound and a hydrophobic silane compound with the composite magnetic nanoparticles;
Mixing and emulsifying a dispersed phase containing a photo resin and a photo initiator in the continuous phase containing the composite magnetic nanoparticles that performed the above steps to form a Pickering emulsion, and UV irradiation Step 3;
4 step of mixing a polydopamine solution with the Pickering emulsion;
5 step of mixing a solution containing a platinum (Pt) precursor to the Pickering emulsion that has been performed in step 4; and
A method of manufacturing a triple-response nanomotor comprising; a 6th step of obtaining a nanomotor by sonicating the Pickering emulsion having performed the 5th step.
5. The method of claim 4,
The hydrophilic silane compound and the hydrophobic silane compound are added in a molar ratio of 1:0.032 to 1:0.10.
5. The method of claim 4,
Pickering emulsion (Pickering emulsion) of the three steps is a droplet (droplet) of the optical resin; and the composite magnetic nanoparticles;
The method of manufacturing a triple response nanomotor, characterized in that the composite magnetic nanoparticles are located at the interface between the dropletized optical resin and water.
5. The method of claim 4,
The continuous phase is a method of manufacturing a triple-response nanomotor, characterized in that it contains the composite magnetic nanoparticles at a concentration of 20 to 90 mg/mL.
5. The method of claim 4,
Steps 3 to 5 are a method of manufacturing a triple response nanomotor, characterized in that it is performed for 3.8 to 14.3 minutes.
5. The method of claim 4,
The method of manufacturing a triple response nanomotor, characterized in that the steps 3 to 5 are continuously performed through a microfluidic system.
10. The method of claim 9,
The microfluidic system includes a hydrophilic glass tube, a primary surface modification unit and a secondary surface modification unit,
The method of manufacturing a triple-response nanomotor, characterized in that the first surface modification part and the secondary surface modification part each include a hydrophobic polytetra fluorethylene (PTFE) tube.
5. The method of claim 4,
The first step is a method of manufacturing a triple response nanomotor, characterized in that it is performed through a polytetra fluorethylene (PTFE) tube having a length of 3 ~ 200 cm.
5. The method of claim 4,
By performing step 2, the hydrophobic silane compound and the hydrophilic silane compound are co-grafted on the surface of the composite magnetic nanoparticles at a contact angle of 43° to 111°. Method of manufacturing a triple response nanomotor.
composite magnetic nanoparticles;
a polydopamine layer formed on a portion of the surface of the composite magnetic nanoparticles; and
A triple response nanomotor comprising a; a platinum catalyst layer formed on the polydopamine layer.

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