KR20140049196A - High sensibility surface plasmon resonance sensor containing gold nanoparticle pattern and preparing method thereof - Google Patents

Abstract

The present invention relates to a high sensitive surface Plasmon resonance sensor including a gold nanoparticle pattern and a manufacturing method thereof. The manufacturing method according to the embodiment of the present invention controls a localized surface Plasmon resonance coupling phenomenon by controlling the shape and arrangement of the gold nanoparticle pattern.

Description

HIGH SENSIBILITY SURFACE PLASMON RESONANCE SENSOR CONTAINING GOLD NANOPARTICLE PATTERN AND PREPARING METHOD THEREOF}

The present application relates to a high sensitivity surface plasmon resonance sensor comprising a gold nanoparticle pattern and a method of manufacturing the same.

Recently, self-assembly technology has been in the spotlight as a tool for manufacturing nano-sized devices such as medical, electronic / information, optics, and sensors. For example, two-dimensional or three-dimensional assemblies of monodisperse nanoparticles are widely used in functional coatings, dye-free paints, catalysts, luminescent materials, etc., templates for the growth of arranged micro or nanoporous materials, light splitting , Optical filters, photonic crystals, etc. have been utilized in optical materials and device applications.

The diblock copolymer tends to phase-separate each block into its respective domain due to the restriction of the covalent linkage point between the two blocks in a form in which two or more polymer chains are covalently linked through one end. Such a biblock copolymer can form a periodic nanostructure having a size of about 10 nm to 100 nm by spontaneous phase separation, the shape and size of the nanostructure is the molecular weight of the biblock copolymer, It is determined by the volume ratio, the Flory-Huggins interaction coefficient between blocks, and further, by dissolving in a solvent selective to one block, spontaneous or cylindrical micelles of spherical, cylindrical, or the like can be spontaneously formed.

Dissolving the diblock copolymer in a solvent selective to only one block can form micelles or reverse micelles in solution. At this time, the solvent is a non-polar solvent, the form of the hydrophilic block is located outside the micelle, the solvent is a polar solvent, the form of the hydrophilic block is located inside the reverse micelles. When the micelle or reverse micelle thin film coated on the solid substrate is immersed in a solvent selective to the inner block, the process of moving and exposing to the surface by rearrangement of the inner block polymer chain is defined as the reconstruction phenomenon of the micelle or reverse micelle. . Nanopores (nano ring shape) can be observed by reconstitution of spherical micelles or reverse micelles.

In addition, when the self-assembled biblock copolymer is used as a template, an array of various inorganic materials such as various semiconductor oxides or metal nanoparticles can be easily manufactured, and the size of the particles is within the nanostructure of the diblock copolymer. It can be limited to nanometer size without additional treatment, and the arrangement of the particles is also limited by the size and spacing of the nanostructures to control the size and arrangement of the particles.

Nanosized gold particles exhibit unusual localized surface plasmon resonance (LSPR) properties. This phenomenon is affected by the size of the gold nanoparticles, the distance between neighboring nanoparticles, and the surrounding environment of the gold nanoparticles, such that the movement of the characteristic peaks or the increase in absorbance are exhibited. The unusual optical properties of these gold nanoparticles are of increasing interest due to potential applications such as optical devices and optical sensors.

For example, regularly ordered gold nanoparticles can observe an increase in the field due to plasmon coupling between gold nanoparticles in addition to local surface plasmon resonance of individual gold nanoparticles, which is a protein It can be effectively applied to sensing DNA. Conversely, if the arrangement of gold nanoparticles is not regular and the nanoparticles form clusters with each other, the plasmon bonds between the gold nanoparticles are strongly induced, so that the wavelengths of characteristic peaks, such as one-dimensional nanomaterials, are strong. The change can be observed, which induces a change in the emission color, and thus is applicable to an optical display element.

Korean Patent Laid-Open Publication No. 10-2010-0069105 discloses a process of forming a micelle by self-assembly by mixing a nanoparticle including an organic ligand and a block copolymer including a block repeating unit having different solubility parameters in a solvent. A method for producing a nanoparticle / block copolymer is disclosed.

Accordingly, the present application is to provide a high-sensitivity surface plasmon resonance sensor comprising a gold nanoparticle pattern and a method of manufacturing the same.

However, the problems to be solved by the present invention are not limited to the above-mentioned problems, and other problems not mentioned can be clearly understood by those skilled in the art from the following description.

Method for producing a high sensitivity surface plasmon resonance sensor comprising a gold nanoparticle pattern according to the first aspect of the present application may include:

(a) dissolving the self-assembled diblock copolymer in a solvent to prepare a reverse micelle solution; (b) coating the reverse micelle solution on a substrate including a prism to prepare a self-assembled biblock copolymer reverse micelle thin film; (c) inducing a reconstruction of the reverse micelle thin film; And (d) adsorbing gold nanoparticles stabilized by citrate ligand on the reconstituted reverse micelles to form a gold nanoparticle pattern.

A method of manufacturing a high sensitivity surface plasmon resonance sensor comprising a gold nanoparticle pattern according to the second aspect of the present application may include:

(a) dissolving the self-assembled diblock copolymer in a solvent to prepare a reverse micelle solution; (b) coating the reverse micelle solution on a metal substrate including a prism to prepare a self-assembled biblock copolymer reverse micelle thin film; And (c ′) inducing reconstitution of the reverse micelle thin film and simultaneously adsorbing gold nanoparticles stabilized by citrate ligand to form a gold nanoparticle pattern.

A third aspect of the present application provides a high sensitivity surface plasmon resonance sensor prepared by the method according to the first aspect or the second aspect, and comprising a gold nanoparticle pattern exhibiting a unique local surface plasmon resonance binding phenomenon.

According to the present invention, the pattern of the gold nanoparticles can be prepared by reconstitution of the self-assembled biblock copolymer reverse micelle, and by controlling the molecular weight of the self-assembled copolymer, the size of the gold nanoparticles and the degree of deposition of the gold nanoparticles, etc. It is possible to control the shape and arrangement of the gold nanoparticle pattern, and to control local surface plasmon resonance coupling accordingly, which can be used for sensing various materials, and industries requiring nanostructures including such nanoparticle patterns. It can be usefully used in the field.

In addition, by integrating gold nanoparticle patterns on the surface of the gold substrate of the surface plasmon resonance sensor element based on the Kretschmann configuration, propagating propagating surface plasmon resonance (SPR) and localized surface plasmon resonance (SPR) ) Can induce a coupling effect, thereby improving the sensitivity of the sensing by about 10 to about 1000 times.

1 is a schematic diagram illustrating a process of preparing a gold nanoparticle pattern exhibiting a unique local surface plasmon resonance binding phenomenon according to an embodiment of the present application.
2 is an SEM image of a gold nanoparticle pattern according to an embodiment of the present disclosure.
3 is an SEM image of a gold nanoparticle pattern according to an embodiment of the present disclosure.
4 is an Image J particle analysis image according to the immersion time of gold nanoparticles in the Type II method according to an embodiment of the present disclosure.
5 is an Image J particle analysis image according to the immersion time of gold nanoparticles in the Type I method according to an embodiment of the present disclosure.
6a to 6d are AFM images according to a process of forming a gold nanoparticle pattern according to an embodiment of the present disclosure. (a): reverse micelle thin film, (b) reconstituted self-assembled biblock copolymer reverse micelle thin film, (c) gold nanoparticle pattern according to type I, and (d) gold nanoparticle pattern according to type II.
7 is a schematic diagram of SPR biosensing according to an experimental example of the present application: (a) Comparative Example, (b) Biosensing using Gold Nanoparticle Array according to Example 1, and (c) Example 2 Biosensing using Gold Nanoparticle Arrays.
8A to 8C show a time-reflectivity graph and an incident angle-reflectivity of SPR biosensing according to one experimental example of the present application: (a) comparative example, (b) implementation Biosensing using gold nanoparticle array according to Example 1, and (c) biosensing using gold nanoparticle array according to Example 2.
FIG. 9 shows an incidence angle-reflectivity graph of SPR biosensing comprising gold nanopatterns prepared by a type I method according to an experimental example of the present application.
FIG. 10 shows an incidence angle-reflectivity graph of SPR biosensing comprising gold nanopatterns prepared by a type II method according to an experimental example of the present disclosure.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention. It should be understood, however, that the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. In the drawings, the same reference numbers are used throughout the specification to refer to the same or like parts.

Throughout this specification, when a part is referred to as being "connected" to another part, it is not limited to a case where it is "directly connected" but also includes the case where it is "electrically connected" do.

Throughout this specification, when a member is located on another member, this includes not only when a member is in contact with another member but also when another member is present between the two members.

Throughout this specification, when an element is referred to as "including " an element, it is understood that the element may include other elements as well, without departing from the other elements unless specifically stated otherwise. The terms "about "," substantially ", etc. used to the extent that they are used throughout the specification are intended to be taken to mean the approximation of the manufacturing and material tolerances inherent in the stated sense, Accurate or absolute numbers are used to help prevent unauthorized exploitation by unauthorized intruders of the referenced disclosure. The word " step (or step) "or" step "used to the extent that it is used throughout the specification does not mean" step for.

Throughout this specification, the term combination (s) thereof in the expression of a machine form means a mixture or combination of one or more elements selected from the group consisting of the constituents described in the expression of the form of a marker, ≪ / RTI >< RTI ID = 0.0 > and / or < / RTI >

Hereinafter, exemplary embodiments will be described in detail with reference to the accompanying drawings. However, the present invention is not limited to these embodiments and examples.

Method for producing a highly sensitive surface plasmon resonance sensor comprising a gold nanoparticle pattern according to the first aspect of the present application (two-step method, hereinafter referred to as "Type I method"), (a) a self-assembled biblock copolymer in a solvent Dissolving to prepare a reverse micelle solution; (b) coating the reverse micelle solution on a metal substrate including a prism to prepare a self-assembled biblock copolymer reverse micelle thin film; (c) inducing reconstitution of the reverse micelle thin film; And (d) adsorbing gold nanoparticles stabilized by a citrate ligand to the reconstituted reverse micelle thin film to form a gold nanoparticle pattern.

The method for producing a gold nanoparticle pattern according to the second aspect of the present application (a one-step method, hereinafter referred to as “type II method”) is a method for preparing a reverse micelle solution by dissolving a self-assembled diblock copolymer in a solvent. step; (b) coating the reverse micelle solution on a metal substrate including a prism to prepare a self-assembled biblock copolymer reverse micelle thin film; (c ') inducing reconstitution of the reverse micelle thin film and simultaneously adsorbing gold nanoparticles stabilized by citrate ligand to form a gold nanoparticle pattern.

In one embodiment of the present application, the self-assembled diblock copolymer may include an amphiphilic diblock copolymer, but is not limited thereto.

In one embodiment of the invention, the amphiphilic diblock copolymer is polystyrene-block-poly (4-vinylpyridine) (PS-b-P4VP), polystyrene-block-poly (2-vinylpyridine) (PS-b -P2VP), polystyrene-block-poly (ethylene oxide) (PS-b-PEO), polystyrene-block-poly (acrylic acid) (PS-b-PAA), and combinations thereof It may be, but is not limited thereto.

In one embodiment of the present application, the solvent may be to selectively dissolve only one block of the self-assembled biblock copolymer, but is not limited thereto.

In one embodiment of the present application, the solvent may be one selected from the group consisting of chloroform, tetrahydrofuran (THF), toluene, and combinations thereof, but is not limited thereto.

In one embodiment of the present application, the reverse micelle solution may contain about 0.1 wt% to about 1.0 wt% of the self-assembled diblock copolymer, but is not limited thereto.

In one embodiment of the present application, the metal substrate may include a silicon wafer or a metal thin film, but is not limited thereto.

In one embodiment of the present application, the reconstitution of the reverse micelle thin film may be induced by immersing in a solvent for selectively dissolving only one block of the self-assembled biblock copolymer, but is not limited thereto.

In one embodiment of the present application, the solvent may be selected from the group consisting of alcohol, water, acidic solutions, and combinations thereof, but is not limited thereto.

In one embodiment of the present disclosure, the immersion time may be about 10 minutes to about 36 hours, for example, about 30 minutes to about 36 hours, about 1 hour to about 36 hours, about 5 hours to about 36 hours , About 10 hours to about 36 hours, or about 15 hours to about 36 hours, but is not limited thereto.

In one embodiment of the present application, the gold nanoparticles may include gold nanoparticles modified by a negatively charged molecule, but is not limited thereto.

In one embodiment of the present application, the metal substrate may include a gold thin film, but is not limited thereto. Plasmon resonance may be generated in the metal substrate by the light irradiated through the prism, but is not limited thereto.

In one embodiment of the present application, the metal substrate including the prism may be to further include a transparent substrate, but is not limited thereto.

A third aspect of the present application provides a high sensitivity surface plasmon resonance sensor prepared according to the method of the first side or the second side, and comprising a gold nanoparticle pattern exhibiting a unique local surface plasmon resonance binding phenomenon.

Hereinafter, a method of manufacturing a surface plasmon resonance sensor including a gold nanoparticle pattern according to an embodiment of the present disclosure will be described with reference to FIG. 1.

First, a method of manufacturing a gold nanoparticle pattern according to the type I method will be described.

(a) The self-assembled copolymer was dissolved in a solvent to prepare a reverse micelle solution.

The self-assembled copolymer is an amphiphilic diblock copolymer, which can form reverse micelles in a solution when dissolved in a solvent selective to only one block. As the diblock copolymer, for example, polystyrene-block-polyvinylpyridine can be used, for example, polystyrene-block-poly (4-vinylpyridine) (PS-b-P4VP), polystyrene-block-poly (2-vinylpyridine) (PS-b-P2VP), polystyrene-block-poly (ethylene oxide) (PS-b-PEO), polystyrene-block-poly (acrylic acid) (PS-b-PAA), and these It can be used selected from the group consisting of combinations, for example, polystyrene-block-poly (4-vinylpyridine) and polystyrene-block-poly (2-vinylpyridine) can be used, polystyrene-block-poly More preferred is (4-vinylpyridine), but is not limited thereto. As the solvent, a solvent having a selective affinity for the styrene block in the diblock copolymer may be used. For example, toluene, chloroform, tetrahydrofuran (THF), etc. may be used, and among them, toluene may be used. desirable.

The reverse micelle solution may contain, for example, about 0.1 wt% to about 1.0 wt% of the self-assembled copolymer, but is not limited thereto. If the self-assembled copolymer is less than about 0.1% by weight, there is a problem in that a uniform monomolecular film without defects is not produced, and when the self-assembled copolymer is more than about 1.0% by weight, a monomolecular film is not produced. The reverse micelle solution may comprise, for example, about 0.1 wt% to about 1.0 wt%, about 0.2 wt% to about 0.9 wt%, about 0.3 wt% to about 0.8 wt%, about 0.4 wt% of the self-assembled copolymer. To about 0.7 wt%, about 0.5 wt% to about 0.6 wt%, about 0.2 wt% to about 1.0 wt%, about 0.3 wt% to about 1.0 wt%, about 0.4 wt% to about 1.0 wt%, about 0.5 wt% To about 1.0 wt%, about 0.1 wt% to about 0.9 wt%, about 0.1 wt% to about 0.8 wt%, about 0.1 wt% to about 0.7 wt%, about 0.1 wt% to about 0.6 wt%, or about 0.1 wt% % To about 0.5% by weight, but is not limited thereto.

Subsequently, (b) coating the prepared reverse micelle solution to prepare a self-assembled biblock copolymer reverse micelle thin film.

The method of coating the reverse micelle solution may be performed by a method known in the art, for example, a coating method selected from the group consisting of spin coating, spray coating, dip coating, flow coating, and combinations thereof. It may be performed by, but is not limited thereto.

Subsequently, (c) induce reconstitution of the prepared reverse micelle thin film.

By immersing the prepared reverse micelle thin film in a solution having a selectivity to the P2VP block, rearrangement of P2VP block chains may induce the generation of pores through the opening of reverse micelles. As a solution for inducing reconstitution, for example, non-polar solvents such as alcohol and water and acidic solutions may be used, but are not limited thereto. For example, an acidic solution may be used among them, but is not limited thereto. The reverse micelle thin film may be immersed, for example, for about 20 minutes, but is not limited thereto.

Subsequently, (d) the gold nanoparticles stabilized by the citrate ligand are selectively adsorbed to the reconstituted reverse micelle thin film to form a gold nanoparticle pattern.

The reconstituted reverse micelle thin film is immersed in an aqueous solution containing gold nanoparticles stabilized by a citrate ligand, thereby allowing the gold nanoparticles to selectively bind to P2VP exposed on the surface. In this case, the aqueous solution of gold nanoparticles may have, for example, acidity 6, but is not limited thereto.

The reconstituted reverse micelle thin film can be immersed in an aqueous solution containing gold nanoparticles stabilized by citrate ligands, for example, from about 10 minutes to about 36 hours, and local surface plasmon resonance binding by controlling the degree of adsorption. You can control the phenomenon.

Next, a method for producing a gold nanoparticle pattern according to the type II method will be described.

(a) The self-assembled copolymer was dissolved in a solvent to prepare a reverse micelle solution.

The self-assembled copolymer is an amphiphilic diblock copolymer, which can form reverse micelles in a solution when dissolved in a solvent selective to only one block. As the diblock copolymer, polystyrene-block-polyvinylpyridine can be used, for example polystyrene-block-poly (4-vinylpyridine) and polystyrene-block-poly (2-vinylpyridine), and More preferably. As the solvent, a solvent having a selective affinity for the styrene block in the diblock copolymer may be used. For example, toluene, chloroform, tetrahydrofuran (THF), etc. may be used, and among them, toluene may be used. desirable.

The reverse micelle solution may contain, for example, about 0.1 wt% to about 1.0 wt% of the self-assembled copolymer, but is not limited thereto. If the self-assembled copolymer is less than about 0.1% by weight, there is a problem in that a uniform monomolecular film without defects is not produced, and when the self-assembled copolymer is more than about 1.0% by weight, a monomolecular film is not produced. The reverse micelle solution may comprise, for example, about 0.1 wt% to about 1.0 wt%, about 0.2 wt% to about 0.9 wt%, about 0.3 wt% to about 0.8 wt%, about 0.4 wt% of the self-assembled copolymer. To about 0.7 wt%, about 0.5 wt% to about 0.6 wt%, about 0.2 wt% to about 1.0 wt%, about 0.3 wt% to about 1.0 wt%, about 0.4 wt% to about 1.0 wt%, about 0.5 wt% To about 1.0 wt%, about 0.1 wt% to about 0.9 wt%, about 0.1 wt% to about 0.8 wt%, about 0.1 wt% to about 0.7 wt%, about 0.1 wt% to about 0.6 wt%, or about 0.1 wt% % To about 0.5% by weight, but is not limited thereto.

Subsequently, (b) coating the prepared reverse micelle solution to prepare a self-assembled biblock copolymer reverse micelle thin film.

The method of coating the reverse micelle solution may be performed by a method known in the art, for example, a coating method selected from the group consisting of spin coating, spray coating, dip coating, flow coating, and combinations thereof. It may be performed by, but is not limited thereto.

Subsequently, (c ′) induces reconstitution of the prepared reverse micelle thin film and simultaneously adsorbs gold nanoparticles stabilized by citrate ligand to form a gold nanoparticle pattern.

By immersing the prepared reverse micelle thin film in a solution having a selectivity to the P2VP block, rearrangement of P2VP block chains may induce the generation of pores through the opening of reverse micelles. As a solution for inducing reconstitution, for example, non-polar solvents such as alcohol and water and acidic solutions may be used, but are not limited thereto. For example, an acidic solution may be used among them, but is not limited thereto. The reverse micelle thin film may be immersed, for example, for about 20 minutes, but is not limited thereto.

The reconstituted reverse micelle thin film is immersed in an aqueous solution containing gold nanoparticles stabilized by a citrate ligand, thereby allowing the gold nanoparticles to selectively bind to P2VP exposed on the surface. At this time, the aqueous solution of the gold nanoparticles, for example, may have an acidity 6, but is not limited thereto.

The reconstituted reverse micelle thin film can be immersed in an aqueous solution containing gold nanoparticles stabilized by a citrate ligand, for example, from about 10 minutes to about 24 hours, and local surface plasmon resonance binding by controlling the degree of adsorption. You can control the phenomenon.

The present application provides a pattern of gold nanoparticles exhibiting a unique topical surface plasmon resonance binding phenomenon prepared according to the method.

The pattern of the gold nanoparticles prepared according to the present invention can easily control the shape and arrangement of the gold nanoparticle pattern by changing the molecular weight or the relative volume fraction between blocks of the diblock copolymer, and thus the local surface plasmon resonance coupling You can control the phenomenon.

In addition, the pattern of the gold nanoparticles prepared according to the present application can easily control the shape and arrangement of the gold nanoparticle pattern by changing the size of the gold nanoparticles, it is possible to control the local surface plasmon resonance coupling phenomenon.

In addition, the pattern of the gold nanoparticles prepared according to the present invention can be applied to the surface of the surface sensitized Raman scattering which can increase the intensity of Raman scattering of the molecules adsorbed on the gold nanoparticles.

Furthermore, the arrangement of regularly ordered gold nanoparticles can be applied to optical sensing.

Specifically, an example in which an array of gold nanoparticles prepared using a self-assembled copolymer as a template is applied to protein sensing (see Experimental Examples 2 and 3).

Therefore, the pattern of the gold nanoparticles of the present application can control the shape and arrangement of the pattern by using a diblock copolymer having a different molecular weight or by varying the size of the gold nanoparticles, thereby resulting in local surface plasmon resonance coupling The phenomenon can be confirmed, and the coupling with the surface plasmon resonance phenomena of the gold thin film of the surface plasmon resonance sensor can be induced to improve the sensing sensitivity.

Hereinafter, the present invention will be described in detail with reference to embodiments and drawings. However, the present invention is not limited to these embodiments and drawings.

[ Example ]

Example  1: Control and Preparation of Gold Nanoparticle Patterns by "Type I" Method

Step (a): containing self-assembled double block copolymer Reverse mice  Solution preparation

Polystyrene-block-poly (4-vinyl pyridine) (PS-b-P2VP), M _n ^ps = 172 kg / mol, M _n ^p2vp = 42 kg / mol, M _w / M _n = 1.07) was dissolved in toluene at a concentration of 0.5% by weight to prepare a reverse micelle solution.

Step (b): Self-Assembled Diblock Copolymer Reverse micelle  Manufacture of thin films

The self-assembled copolymer reverse micelle solution prepared in step (a) was spin coated on a metal thin film at 2000 rpm for 60 seconds to prepare a self-assembled copolymer reverse micelle thin film, and then dried overnight at room temperature.

Step (c): Reverse micelle  Reconstruction of thin film

The reverse micelle thin film prepared in step (b) was immersed in an aqueous solution containing 0.9 wt% hydrochloric acid for 20 minutes to induce reconstitution of reverse micelles.

Step (d): Citrate In the ligand  Adsorption of Stabilized Gold Nanoparticles

148.5 mL of deionized water and 1.5 mL of 25.4 mM HAuCl ₄ .3H ₂ O solution were added to a 250 mL Elenmeyer flask and the solution was heated on a hot plate with stirring to boil to a temperature of up to 130 ° C. Then 0.9 mL of sodium citrate aqueous solution (50 mg / ml) was added quickly and then the solution was further boiled for 20 minutes with stirring. When the color of the solution turned red, gold nanoparticles having a diameter in the range of 14 nm to 16 nm were obtained.

The reverse micelle thin film reconstructed in step (c) was immersed in an aqueous solution of acidity 6 containing the gold nanoparticles stabilized by citrate ligand for 10 minutes, 30 minutes, 1 hour and 24 hours by citrate ligand. The stabilized gold nanoparticles were adsorbed.

Example  2: Control and Preparation of Gold Nanoparticle Patterns by "Type II" Method

Step (a): containing self-assembled copolymer Reverse micelle  Solution preparation

Polystyrene-block-poly (4-vinyl pyridine) (PS-b-P2VP), M _n ^ps = 172 kg / mol, M _n ^p2vp = 42 kg / mol, M _w / M _n = 1.07) was dissolved in toluene at a concentration of 0.5% by weight to prepare a reverse micelle solution.

Step (b): Self-Assembly Copolymer Reverse micelle  Manufacture of thin films

The self-assembly copolymer reverse micelle solution prepared in step (a) was spin coated on the gold thin film at 2000 rpm for 60 seconds to prepare a self-assembled copolymer reverse micelle thin film.

Step ( c ' ): Reconstitution and Citrate of Reverse Micell Thin Film Adsorption of Gold Nanoparticles Stabilized by Ligands

The reverse micelle thin film prepared in step (b) was subjected to 1 hour, 3 hours, 10 hours and 24 hours in an aqueous solution of acidity 6 containing gold nanoparticles stabilized by citrate ligand prepared as in Example 1. Immersion of gold nanoparticles stabilized by the citrate ligand while simultaneously immersing induce reconstitution of reverse micelles.

<Result>

2 is an SEM image of the gold nanoparticle pattern according to Example 1. As can be seen in FIG. 2, when the block copolymer is primarily protonated and the negatively charged gold nanoparticles are adsorbed, electrostatic attraction acts to cause the gold nanoparticles to be generally disorderly placed on the substrate. have.

3 is an SEM image of the gold nanoparticle pattern according to Example 2. When the block copolymer reverse massel film is supported on the gold nanoparticle solution, the PVP in the core portion is protonated and interacts with the negatively charged gold nanoparticles through electrostatic attraction, thereby uniformly distributing the particles at specific positions. It can be seen that forms an array of.

FIG. 4 is an image J analysis result of immersion time of gold nanoparticles in the type II method of Example 2. As can be seen in Figure 4 and Table 1, it can be seen that the gold nanoparticle clusters are formed as the number of count (count) is reduced as the immersion time is longer.

Using Image J, the number of particles, size, area fraction occupied by the particles according to the immersion time of the gold nanoparticles were analyzed and the results are shown in FIG. 5 and Table 2 below. 5 is an image J analysis result according to the immersion time of gold nanoparticles, the image after counting the particles. As can be seen in Figure 5 and Table 2, as the immersion time is longer, the number of counts increases, it can be seen that the gold nanoparticles are dispersed and adsorbed in random disorder.

6A through 6D are AFM images according to the formation process of the gold nanoparticle patterns according to Examples 1 and 2 above. FIG. 6A shows a reverse micelle solution, FIG. 6B shows a self-assembled biblock copolymer reverse micelle thin film, FIG. 6C shows a gold nanoparticle pattern according to type I, and FIG. 6D shows an AFM image of a gold nanoparticle pattern according to type II. .

Experimental Example  : Protein Using Gold Nanoparticle Array Sensing

The following experiments were conducted to determine the sensing capability of using gold nanoparticle arrays prepared from self-assembled copolymer templates as sensors for detecting proteins.

An example in which an array of gold nanoparticles prepared from a self-assembled copolymer template can be used as a sensor for detecting a protein will be described as an example. In Fig. 7, a gold thin film SPR substrate (Comparative Example) (a) to which no gold nanoparticles are attached (a), a gold nanoparticle pattern (Type I) according to Example 1, and a gold nanoparticle pattern according to Example 2 ( After attaching the thiol-biotin (thiol-biotin) to the type II) (c), respectively, the schematic diagram showing the binding of the biotin and streptavidin (500 nM) is shown. The introduced biotin can detect streptavidin by selectively binding to streptavidin. The SPRs having the gold nanoparticle patterns according to Example 1 and Example 2 are those in which the gold nanoparticle pattern according to Example 1 was immersed in the gold nanoparticle solution for 30 minutes so that the area fraction is similar. The gold nanoparticle pattern was used as immersed in gold nanoparticle solution for 24 hours.

The sensing sensitivity of streptavidin of SPR without gold nanoparticles and SPR with gold nanoparticle pattern was shown in Table 3 and FIG. 8: (a) Comparative Example, (b) Gold according to Example 1 Biosensing using nanoparticle array, and (c) Biosensing using gold nanoparticle array according to Example 2.

As can be seen in Table 3 above, the surface to which the biotin, a probe material, can be attached is wider in the comparative example, while the SPR angle shift occurred most in the gold nanoparticle pattern according to type I.

Example 1 (Type I) formed by immersion in gold nanoparticle solution for 1 hour and 24 hours, respectively, to compare the increase in SPR sensing sensitivity due to the gold nanoparticle pattern introduced when immersed in gold nanoparticle solution for the same time. And measuring the streptavidin sensing of the gold nanoparticle pattern according to Example 2 (type II), and the results are shown in Table 4 and FIGS. 9 and 10, respectively.

As can be seen in Table 4, when immersed in the gold nanoparticle solution for 1 hour, the gold nanoparticle pattern according to the type II showed better sensitivity, and when immersed for 24 hours, the gold nanoparticle pattern according to the type I This was about 29% higher sensitivity.

It will be understood by those of ordinary skill in the art that the foregoing description of the embodiments is for illustrative purposes and that those skilled in the art can easily modify the invention without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.

The scope of the present invention is defined by the appended claims rather than the detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included within the scope of the present invention.

Claims (15)

(a) dissolving the self-assembled diblock copolymer in a solvent to prepare a reverse micelle solution;
(b) coating the reverse micelle solution on a metal substrate including a prism to prepare a self-assembled biblock copolymer reverse micelle thin film;
(c) inducing reconstruction of the reverse micelle thin film; And
(d) adsorbing gold nanoparticles stabilized by citrate ligand on the reconstituted reverse micelles to form a gold nanoparticle pattern
A method of manufacturing a high sensitivity surface plasmon resonance sensor comprising a gold nanoparticle pattern.
(a) dissolving the self-assembled diblock copolymer in a solvent to prepare a reverse micelle solution;
(b) coating the reverse micelle solution on a metal substrate including a prism to prepare a self-assembled biblock copolymer reverse micelle thin film; And
(c ') inducing reconstitution of the reverse micelle thin film and simultaneously adsorbing gold nanoparticles stabilized by citrate ligand to form a gold nanoparticle pattern
A method of manufacturing a high sensitivity surface plasmon resonance sensor comprising a gold nanoparticle pattern.
3. The method according to claim 1 or 2,
The self-assembling diblock copolymer comprises a amphiphilic diblock copolymer, a high sensitivity surface plasmon resonance sensor comprising a gold nanoparticle pattern.
The method of claim 3, wherein
The amphiphilic diblock copolymers are polystyrene-block-poly (4-vinylpyridine) (PS-b-P4VP), polystyrene-block-poly (2-vinylpyridine) (PS-b-P2VP), polystyrene-block- Gold nanoparticle pattern, including those selected from the group consisting of poly (ethylene oxide) (PS-b-PEO), polystyrene-block-poly (acrylic acid) (PS-b-PAA), and combinations thereof Method of manufacturing a high sensitivity surface plasmon resonance sensor comprising a.
3. The method according to claim 1 or 2,
The solvent is a method for producing a high sensitivity surface plasmon resonance sensor comprising a gold nanoparticle pattern, which will selectively dissolve only one block of the self-assembled biblock copolymer.
6. The method of claim 5,
Wherein said solvent comprises one selected from the group consisting of chloroform, tetrahydrofuran (THF), toluene, and combinations thereof, the method of producing a highly sensitive surface plasmon resonance sensor comprising gold nanoparticle patterns.
3. The method according to claim 1 or 2,
The reverse micelle solution containing 0.1 wt% to 1.0 wt% of the self-assembled biblock copolymer, a high sensitivity surface plasmon resonance sensor manufacturing method comprising a gold nanoparticle pattern.
3. The method according to claim 1 or 2,
The metal substrate comprises a silicon wafer, or a metal thin film, a high sensitivity surface plasmon resonance sensor comprising a gold nanoparticle pattern.
3. The method according to claim 1 or 2,
Reconstruction of the reverse micelle thin film is a method of manufacturing a high sensitivity surface plasmon resonance sensor comprising a gold nanoparticle pattern, which is induced by immersing in a solvent for selectively dissolving only one block of the self-assembled biblock copolymer.
The method of claim 9,
Wherein said solvent comprises one selected from the group consisting of alcohols, water, acidic solutions, and combinations thereof, a method for producing a highly sensitive surface plasmon resonance sensor comprising a gold nanoparticle pattern.
The method of claim 9,
The immersion time is 10 minutes to 36 hours, manufacturing method of high sensitivity surface plasmon resonance sensor comprising a gold nanoparticle pattern.
3. The method according to claim 1 or 2,
The gold nanoparticles comprising gold nanoparticles modified by a negatively charged molecule, the method of manufacturing a high sensitivity surface plasmon resonance sensor comprising a gold nanoparticle pattern.
3. The method according to claim 1 or 2,
The metal substrate comprises a gold thin film, a high sensitivity surface plasmon resonance sensor comprising a gold nanoparticle pattern.
3. The method according to claim 1 or 2,
The metal substrate including the prism further comprises a transparent substrate, a high sensitivity surface plasmon resonance sensor manufacturing method comprising a gold nanoparticle pattern.
A high sensitivity surface plasmon resonance sensor prepared according to the method of claim 1 or 2, comprising a gold nanoparticle pattern exhibiting a unique local surface plasmon resonance binding phenomenon.

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