KR20110138186A - Surface plasmon resonance sensor containing prism deposited metallic carbon nanostructure layer, and preparing method of the same - Google Patents

Abstract

PURPOSE: A surface plasmon resonance sensor including a prism with a metallic carbon nano-structure layer and a manufacturing method thereof are provided to secure the operation of a surface plasmon resonance sensor with a fixed wavelength because a metallic graphene layer is evenly deposited on one side of a prism. CONSTITUTION: A surface plasmon resonance sensor comprises a light source part(10), a sensing part(20), and a light receiving part(30). The sensing part comprises a prism(200) in which a metallic carbon nano-structure layer(300) is formed on one side and collects the light reflected off the prism. The metallic carbon nano-structure layer is selected from the group consiting of graphene, graphite, carbon nano-tube, and their combination.

Description

SURFACE PLASMON RESONANCE SENSOR CONTAINING PRISM DEPOSITED METALLIC CARBON NANOSTRUCTURE LAYER, AND PREPARING METHOD OF THE SAME}

The present application relates to a surface plasmon resonance sensor and a method of manufacturing the same. More specifically, the present invention relates to a surface plasmon resonance sensor comprising a prism having a metallic carbon nanostructure layer formed on one surface of a prism, and a manufacturing method thereof.

Recently, it is a key technology in the field of nano chemistry and biosensor, and it has a relatively high sensitivity (~ 1 pg / mm ² ) for the detection target, no labeling process such as fluorescent dye, and surface plasmon that can monitor the reaction degree in real time. Research on Surface Plasmon Resonance (SPR) sensors is ongoing.

Surface Plasmon is a Collective Charge Density Oscillation of electrons occurring on the surface of a metal thin film, and Surface Plasmon Wave caused by these vibrations travels along the interface between metal and dielectric. Surface electromagnetic waves. When an electric field is applied to two medium interfaces having different dielectric functions from outside, that is, the interface between metal and dielectric, surface charges are induced due to the discontinuity of the vertical component of the electric fields at the interface between the two mediums, and the vibrations of the surface charges appear as surface plasmon waves.

The incident wave of the light from the light source is reflected at the interface of the metal thin film and the evanescent wave is exponentially reduced into the metal thin film at the interface. At a specific incident angle and a specific thin film thickness, the resonance of the incident wave in the direction parallel to the interface coincides with the phase of the surface plasmon wave traveling along the interface between the metal thin film and the dielectric. At this time, the light energy of the incident wave is absorbed by the metal thin film, and the reflected wave disappears. This is called surface plasmon resonance (SPR). The angle at which the reflectance of incident light is minimized is called a surface plasmon resonance angle.

The resonance angle at which surface plasmon resonance occurs, that is, the angle at which the reflectance is minimized, changes the structure of the dielectric material in contact with the surface of the metal thin film and the environment, and as a result, the effective refractive index changes and the resonance angle changes. Using the surface plasmon resonance principle, which can measure the environmental change of a material in an optical way, it is possible to detect changes such as selective coupling or separation between various materials through appropriate chemical or physical changes in the surface layer of the metal thin film. Can be detected by the change of.

Surface plasmon resonance originated in the early 1900s when Wood observed anomalous diffraction due to surface plasma excitation on Fano's metal diffraction gratings. In 1968, two reticulated prisms were used by Kretschmann and Otto. Excitation of surface plasmon resonances with different structures has been attempted to demonstrate the general applicability of surface plasmon resonances. In the 1970s, the possibility of surface plasmon resonance for the characterization of thin films and the observation of changes at the metal interface was demonstrated. In 1982, Nylander and Liedberg used surface plasmon resonance sensors as gas detection and biosensors.

Accordingly, the present application, unlike the surface plasmon resonance sensor comprising a prism having a metal surface, to provide a surface plasmon resonance sensor comprising a prism formed with a metallic carbon nanostructure layer and a method of manufacturing the same. More specifically, the present invention provides a surface plasmon resonance sensor including a prism formed with a graphene layer having a multilayer or various thicknesses and a method of manufacturing the same.

However, the problem to be solved by the present application is not limited to the problem described above, another problem that is not described will be clearly understood by those skilled in the art from the following description.

One aspect of the present application, the light source unit for irradiating light; A sensing unit including a prism on which a metallic carbon nanostructure layer is deposited on one surface of the prism; It provides a surface plasmon resonance sensor, comprising: a light receiving unit for collecting light reflected from the prism.

Another aspect of the present application, to form a sensing unit by forming a metallic carbon nanostructure layer on one surface of the prism; It provides a method for producing a surface plasmon resonance sensor comprising: positioning the sensing unit including the prism between the light source and the light receiving unit.

The present disclosure provides a surface plasmon resonance sensor including a prism on which a metallic carbon nanostructure layer is deposited on one surface of a prism. The metallic carbon nanostructure layer has excellent metal properties, has excellent electrical conductivity, can be distributed over a large area, and has excellent mechanical strength. The present application utilizes the aforementioned properties of the metallic carbon nanostructure layer, and has excellent mechanical properties. It is an object to provide a surface plasmon resonance sensor that can be manufactured in large areas.

The surface plasmon resonance sensor according to the present invention can operate at a fixed wavelength and does not require a polarization regulator because the metallic graphene layer is deposited on one side of the prism on average.

1 is a schematic diagram of a surface plasmon resonance sensor according to an embodiment of the present disclosure.
2 is a conceptual diagram illustrating a surface plasmon resonance phenomenon of the surface plasmon resonance sensor according to an embodiment of the present application.
3 is a schematic configuration diagram of a surface plasmon resonance sensor capable of sensing a biomaterial according to an embodiment of the present disclosure.
4 is a flowchart illustrating a method of forming a prism including a metallic carbon nanostructure layer according to an embodiment of the present disclosure.
5 is a flowchart illustrating a method of forming a prism including a metallic carbon nanostructure layer according to an embodiment of the present disclosure.
6 is a schematic diagram of a surface plasmon resonance sensor according to an exemplary embodiment of the present disclosure.
7 is a view showing the experimental equipment of the surface plasmon resonance sensor according to an embodiment of the present application.
8 shows graphene coated prism SPR intensity reduction according to one embodiment of the present application (a) bilayer graphene, (b) buffer solution and DX biotin DNA nanostructure and (c) graphene, buffer and functionalized streptabi Comparison graph of DX biotin with Dean protein.

DETAILED DESCRIPTION Hereinafter, embodiments and examples of the present disclosure will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present disclosure.

It should be understood, however, that the present invention may be embodied in many different forms and is not limited to the embodiments and examples described herein. In the drawings, parts irrelevant to the description are omitted for simplicity of explanation, and like reference numerals designate like parts throughout the specification.

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.

Throughout this specification, when a layer or member is located "on" with another layer or member, it is not only when a layer or member is in contact with another layer or member, but also between two layers or another member between the two members. Or when another member is present. In addition, when a part is said to "include" a certain component, which means that it may further include other components, except to exclude other components unless specifically stated otherwise.

As used herein, the terms "about", "substantially", and the like, are used at, or in close proximity to, numerical values when manufacturing and material tolerances inherent in the stated meanings are set forth and are intended to be accurate to aid the understanding herein. Or absolute figures are used to prevent unfair use of unscrupulous infringers.

The present application is to provide a surface plasmon resonance sensor and a method for manufacturing the same, unlike a surface plasmon resonance sensor comprising a prism having a metal surface, and a prism formed with a metallic carbon nanostructure layer. It is to provide a surface plasmon resonance sensor having the above characteristics by using the metallic properties, high electrical conductivity, mechanical strength of the metallic carbon nanostructure layer.

In one aspect of the present application, the surface plasmon resonance sensor includes a light source unit for irradiating light; A sensing unit including a prism having a metallic carbon nanostructure layer formed on one surface of the prism; Light receiving unit for collecting light reflected from the prism: may include, but is not limited thereto.

In an exemplary embodiment, the metallic carbon nanostructure may include one selected from the group consisting of graphene, graphite, carbon nanotubes (CNT), and combinations thereof, but is not limited thereto.

In an exemplary embodiment, the prism may include one or more selected from the group consisting of glass, plastic, and polymer, but is not limited thereto. In one embodiment, the glass may be BK7 or SF11, but is not limited thereto. In one embodiment, the plastic is selected from the group consisting of Polymethyl methacrylate (PMMA), Polycarbonate (PC), Cyclic Olefin Copolymer (COC), and combinations thereof. It may include, but is not limited to. In one embodiment, the polymer is polydimethylsiloxane, polymethylmethacrylate, polycarbonate, polyethylene, polypropylene, polystyrene and their It may include one selected from the group consisting of a combination, but is not limited thereto.

In an exemplary embodiment, the prism can be used without limitation as long as the prism can be used in the art, for example, but may include a polygon or a semi-cylindrical shape, but is not limited thereto.

In an exemplary embodiment, the thickness of the metallic carbon nanostructure layer may be about 1 nm to about 200 nm, but is not limited thereto. For example, the thickness of the metallic carbon nanostructure layer is about 1 nm to about 200 nm, about 10 nm to about 200 nm, about 20 nm to about 200 nm, or about 1 nm to about 100 nm, about 10 nm to About 100 nm, about 20 nm to about 100 nm, or about 1 nm to about 50 nm, or about 10 nm to about 50 nm, or about 20 nm to about 50 nm, but is not limited thereto.

In an exemplary embodiment, the metallic carbon nanostructure layer may include a single layer or a plurality of layers, but is not limited thereto. In one embodiment, in order to form a multi-layered metallic carbon nanostructure layer, the forming of the metallic carbon nanostructure layer may be repeated a plurality of times to form a plurality of metallic carbon nanostructure layers. In another embodiment, as the metallic carbon nanostructure layer, the graphene layer formed by controlling the area and thickness by chemical vapor deposition may be used, but is not limited thereto.

In an exemplary embodiment, the metal layer may be formed on one surface of the prism in addition to the metallic carbon nanostructure layer, but is not limited thereto. For example, the metal layer may be a thin film of a metal such as gold, silver, copper, aluminum, but is not limited thereto. For example, the total thickness of the metallic carbon nanostructure layer and the additionally formed metal layer may be from about 1 nm to about 200 nm, from about 10 nm to about 200 nm, from about 20 nm to about 200 nm, or from about 1 nm to About 100 nm, about 10 nm to about 100 nm, about 20 nm to about 100 nm, or about 1 nm to about 50 nm, or about 10 nm to about 50 nm, or about 20 nm to about 50 nm, It is not limited to this.

In an exemplary embodiment, the light source of the light source unit may include any one of a TM or P-polarized monochromatic light source, a white light source, a laser and a light emitting diode (LED) to which light having a short wavelength or multiple wavelengths is irradiated. It is not limited to this.

In an exemplary embodiment, the light receiving unit may include any one of light receiving elements including a photodiode, an optical amplifier, a photosensitive paper, and an image sensor such as a CCD or a CMOS on the light receiving surface, but is not limited thereto.

In an exemplary embodiment, the surface plasmon resonance sensor may be to detect a chemical or biomaterial, but is not limited thereto. In one embodiment, when detecting the biomaterial may include an additional bio-molecule layer formed on the metallic carbon nanostructure layer formed on the prism, but is not limited thereto.

In another embodiment of the present invention, a method of manufacturing a surface plasmon resonance sensor may form a sensing unit by forming a metal carbon nanostructure layer on one surface of a prism; The sensing unit including the prism may be positioned between the light source unit and the light receiver, but is not limited thereto. In one embodiment, the forming of the sensing unit forms a metallic carbon nanostructure layer; Floating the metallic carbon nanostructure layer on the surface of distilled water; Contacting the suspended metallic carbon nanostructure layer with one surface of the prism may include transferring the metallic carbon nanostructure layer to one surface of the prism, but is not limited thereto.

In another embodiment, the forming of the sensing part may include forming a metallic carbon nanostructure layer; Transferring the metallic carbon nanostructure layer by contacting a stamper; Pressing the metallic carbon nanostructure layer transferred onto the stamper to one surface of the prism may include transferring the metallic carbon nanostructure layer to one surface of the prism, but is not limited thereto. In another embodiment, forming the sensing unit may include forming a metallic carbon nanostructure layer on one surface of the prism by a spray method.

Hereinafter, with reference to the drawings, the surface plasmon resonance sensor of the present application and its manufacturing method will be described in detail. However, the present application is not limited thereto.

1 is a schematic diagram of a surface plasmon resonance sensor including a prism on which a metallic carbon nanostructure layer of the present disclosure is deposited. As shown in FIG. 1, the surface plasmon resonance sensor of the present application includes a light source unit 10 for irradiating light and a prism including a metal carbon nanostructure layer on which surface plasmon resonance is generated. The unit 20 may include, but is not limited to, a light receiving unit 30 collecting light reflected from the prism.

The light source of the light source unit 10 serves to cause surface plasmon resonance in the metallic carbon nanostructure layer, and TM or P-polarized monochromatic light irradiated with light having a short wavelength or multiple wavelengths according to the operating principle of the sensor. It may be any one of a light source, a white light source, a laser, and a light emitting diode (LED), but is not limited thereto.

Light provided from the light source unit is incident through the prism 200 at a predetermined angle, and a wave vector component parallel to the metallic carbon nanostructure layer 300 is formed on the surface of the metallic carbon nanostructure layer and its surface. The energy of the incident light is mostly absorbed by the surface plasmon when it coincides with the electron density oscillating along the interface of the sample 400 positioned on the surface, that is, the wave vector of the surface plasmon (FIG. 2). At this time, the distribution of the plasmon field is exponentially reduced in both directions between the interface of the metallic carbon nanostructure layer and the sample. Therefore, the resonance absorption condition of the surface plasmon is sensitively changed according to the thickness, mass, refractive index, or liquid sample of the sample on the surface of the metallic carbon nanostructure layer, and the change is reflected by the reflectivity of light and Since the effective refractive index is changed, the change in refractive index, mass, thickness or concentration of the sample can be quantitatively determined by measuring the reflectance which is changed through the light receiving unit 30 or by measuring the resonance angle or the resonance wavelength at which the reflected light is minimized. have.

The surface plasmon resonance sensor has a high sensitivity because the sampling depth of the evanescent wave formed within the range of several hundred nm from the surface is much smaller than other conventional optical methods. Measurement is possible. That is, the area of action of the measurement material and the dissipation wave immobilized on the surface is very narrow compared to other optical methods, and the use of the dissipation wave makes it possible to easily measure the interaction between materials with only a very small amount of sample. The surface plasmon resonance sensor of the present application uses a method in which the effective refractive index changes when the sample mass on the surface of the metallic carbon nanostructure layer is increased or the structure is deformed so that the surface plasmon resonance occurs and the resonance angle or resonance wavelength at which the reflected light is minimized is changed. will be. The present application is intended to use the surface plasmon resonance principle using a metallic carbon nanostructure layer, unlike the conventional plasmon resonance principle using a metal thin film. The surface plasmon resonance sensor including the prism deposited with the metallic carbon nanostructure layer of the present invention can detect various samples by the change of the resonance angle or the resonance wavelength through appropriate chemical modification of the metallic carbon nanostructure layer. In various fields such as gas, aerosol, nanoparticles, such as control sensors, environmental pollution monitoring, chemical composition analysis, etc. can be widely applied.

3 is a schematic configuration diagram of a surface plasmon resonance sensor capable of sensing a biomaterial according to an embodiment of the present disclosure. By further forming a biomolecule layer on the metallic carbon nanostructure layer formed on the prism, it may be easier to sense the biomaterial. For example, the biolayer may include, but is not limited to, one selected from the group consisting of peptides, polypeptides, enzymes, antigens, antibodies, and combinations thereof.

4 and 5 are flowcharts and process diagrams of a manufacturing method for forming a prism in which a metallic carbon nanostructure layer is deposited on one surface, which forms a sensing unit of the surface plasmon resonance sensor of the present application.

First, the metallic carbon nanostructure layer 300 is formed (step S1). The metallic carbon nanostructure may include one selected from the group consisting of graphene, graphite, carbon nanotubes (CNT), and combinations thereof, but is not limited thereto. The metallic carbon nanostructure layer 300, for example, the graphene layer 140 may be used to derive high quality graphene synthesis conditions, and to produce a graphene layer having various thickness layers for a surface plasmon resonance sensor. . Graphene forming catalysts include Ni, Co, Fe, Pt, Au, Al, Cr, Cu, Mg, Mn, Rh, Si, Ta, Ti, W, U, V, Zr, Fe, brass, bronze ( It may include, but is not limited to, those selected from the group consisting of bronze, stainless steel, Ge, and combinations thereof. The graphene may be doped with a dopant including an organic dopant, an inorganic dopant, or a combination thereof, but is not limited thereto. For example, the dopant is NO ₂ BF ₄ , NOBF ₄ , NO ₂ SbF ₆ , HCl, H ₂ PO ₄ , H ₃ CCOOH, H ₂ SO ₄ , HNO ₃ , PVDF, Nafion, AuCl ₃ , HAuCl ₄ , SOCl ₂ , Br ₂ , dichloro dicyanoquinone, oxone, dimyristoyl phosphatidylinositol and trifluoromethanesulfonimide may include one or more selected from, but is not limited thereto.

The graphene forming catalyst may be deposited on the substrate 110 in a thin film form to form the metal catalyst layer 120. Here, the substrate 110 may include not only silicon oxide / silicon but also various foils / sheets such as nickel, stainless steel, and copper in the form of metal foils. In addition, the substrate and the metal catalyst layer may be in a pattern form. Then, the prepared substrate is inserted into a thermochemical vapor deposition chamber and heated to about 1000 ° C. in an argon atmosphere to heat the substrate. The deposited metal catalyst layer is put in a reactor and heated to flow hydrogen gas to remove the oxide layer and impurities of the metal catalyst layer, and the catalyst layer is reduced by using hydrogen gas so that a wide grain can be formed. Ensure catalyst bed conditions. Subsequently, the treated metal catalyst layer is heated to a high temperature to include a gas containing carbon together with argon (Ar) or helium (He) gas, for example, carbon monoxide, carbon dioxide, methane, ethane, ethylene, ethanol, acetylene, propane, Butane, butadiene, pentane, pentene, cyclopentadiene, hexane, cyclohexane, benzene, toluene and a combination thereof is injected into the reactor to form a carbon layer 130. The growth temperature can be lowered by using plasma-enhanced (PE) CVD, which increases the degree of vacuum and applies an electric field to form plasma. Finally, the graphene layer 140 may be completed by optimizing the cooling temperature using argon to secure cooling conditions to minimize defects and minimize amorphous carbon. While supplying the carbon source in the gas phase, for example, heat treatment at a temperature of about 300 ° C. to about 2000 ° C. causes the graphene layer to be formed while the carbon components present in the carbon source combine to form a hexagonal plate-like structure. . Here, the number of layers of the graphene film affects the values of transparency, gas, and humidity transmittance. In one embodiment, the graphene film grown on the Ni substrate has a transmittance value of about 80% to about 3 to about 8 layers. In addition, in one embodiment, a growth method using a Cu foil catalyst may grow a thin graphene film of about 1 layer to about 3 layers. The chemical vapor deposition may be performed at atmospheric pressure (AP CVD) or at low pressure (LP CVD).

The graphene layer may include a single layer or a plurality of layers, but is not limited thereto. For example, when a sufficient amount of carbon is absorbed into the metal thin film layer and rapidly cooled, carbon is separated from the metal catalyst layer such as a nickel (Ni) layer and crystallized as it comes out to the surface, and the number of layers varies depending on the amount. The graphene layer 140 may be formed.

The graphene layer may be controlled in area and thickness by chemical vapor deposition. For example, the thickness of the graphene layer may be adjusted by changing the reaction time, the thickness of the catalyst metal thin film, and the cooling rate. The shorter the reaction time, the thinner the metal thin film thickness, the thinner the graphene layer may be formed. . Alternatively, the formed graphene layer may be adjusted again by exposing UV having an intensity of about several tens of W at room temperature / atmospheric pressure.

The formed graphene layer 140 may be formed of the metal catalyst layer using various acid solutions 160, buffer oxidation etching solution (BOE), iron chloride (Iron (III) Chloride, FeCl ₃ ), Fe (NO ₃ ) _3, or the like. It is possible to separate from 120 and transfer to various substrates. More specifically, the graphene layer prepared as described above, and further, the graphene layer may be various acid solutions 160, buffered etch solutions (BOE), and Fe (NO ₃ ) ₃ serving as etch etching solutions. Alternatively, the metal catalyst layer 120 may be removed by placing it in a container containing a ferric chloride (FeCl ₃ ) solution. The redox process gradually etches the metal catalyst layer in the neutral pH region and does not generate a gaseous substance and thus does not require a dust collector to remove the gas. After a few minutes, the graphene layer floats on the acid solution and is ready for transfer to the prism. Thereafter, the graphene layer may be sufficiently washed four or more times with distilled water 170, and may be suspended in the distilled water (step S2).

Referring to FIG. 5F, the prism 200 is injected into a container in which the graphene layer is suspended, and the graphene layer 140 in the container is aligned with the prism, and the floating graphene is aligned with the prism. Lifting a layer may coat or transfer the graphene layer 140 on one surface of the prism. When the adhesion between the prism and the graphene layer is excellent, a method of stamping the prism on the floating graphene layer may be used, but is not limited thereto (steps S3 and S4).

In another embodiment in which the metallic carbon nanostructure layer 300 is formed on one surface of the prism 200, a stamper (not shown) is used to transfer the metallic carbon nanostructure layer 300 to the prism 200. The metallic carbon nanostructure layer may be, for example, a graphene layer. The method of forming the metallic carbon nanostructure layer on the prism using the stamper may include a dry transfer method in addition to the above-described wet transfer method, but is not limited thereto.

First, the wet transfer method transfers the graphene layer obtained in FIG. 5E onto a stamper (not shown) made of an elastomeric material such as PDMS, and warps and stretches the photonic lithography process on the graphene layer. This free and can form a protective film comprising a polymer (Elastomer) containing a porous nano-hole. After the alignment of the stamper (not shown) and the prism 200 using the stamper (not shown), the stamper (not shown) is pressed onto the prism and the stamper (not shown) and the prism are applied. By separating, the graphene layer may be transferred onto the prism 200 by coating or bonding. Thereafter, the graphene layer coated on one surface of the prism may be washed in distilled water and then dried. For example, the drying process may be performed at about 70 ° C. for about 30 minutes or more to improve the adhesion of the metallic carbon nanostructure layer. As a result, a prism in which a metallic carbon nanostructure layer is deposited on one surface of the prism may be manufactured. In the dry transfer method, the graphene layer formed on the metal catalyst layer may be transferred to a stamp together with the metal catalyst layer, and the metal catalyst layer may be contacted with the prism and then transferred to the prism layer.

In another embodiment of forming the metallic carbon nanostructure layer 300 on one surface of the prism 200, the method may include forming the metallic carbon nanostructure layer on one surface of the prism by a spray method. In one embodiment, the spray method may include a method of dispersing the metallic carbon nanostructure in a suitable solvent to the prism. The solvent may be used without limitation as long as the metallic carbon nanostructure is a solvent that can be dispersed in the solvent. For example, the solvent may include an organic solvent such as water or alcohol. It is not limited to this.

Furthermore, the surface plasmon resonance sensor can be completed by placing a prism on which the metallic carbon nanostructure layer manufactured by the method is deposited between the light source and the light receiver.

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

[ Example ]

Surface plasmon resonance (SPR) biosensors based on angular measurements rely on the excitation of surface plasmons by light. The propagation constant of the surface plasma wave (SPW) propagating at the interface between the metal or metallic material (double layer graphene in this embodiment) and the dielectric medium is measured. Surface plasmons were excited by beams of converging light, and the resonance angle was measured using a photo-detector. The change in resonance angle is correlated with the amount of analyte bound to the sensor surface. The light beam passes through the optical prism with the thin graphene layer and excites surface plasmons at the interface between the graphene layer and the analyte. A position-sensitive photo-detector was placed at a specific location near the prism.

The SPR sensor comprises a photodetector with a light source, a prism with a rotation table and a bilayer graphene deposited as a surface plasmon sensor head (FIG. 6 shows a schematic of the prism SPR, and FIG. 7 shows the actual Experimental equipment). The light from the light source (laser diode) is 660 nm. The sensor head comprises a high refractive index optical glass prism with bilayer graphene deposited as mentioned above, and the reflected light is directed to the photodetector through the optical fiber.

Substances :

Biotinylated DX (DX-biotin) lattice was designed based on the structure of fixed crossover branched junctions, and the DNA base sequence was found to contain errors due to undesirable complementary binding and sequence symmetry. It is designed to be minimal. Synthetic biotinylated DNA oligonucleotides purified by high performance liquid chromatography (HPLC) were obtained from Integrated DNA Technologies. Complex is a stoichiometric amount with physiologically first mixed in the × TAE / Mg ^{2 +} buffer [12.5 mM magnesium ahseteyiteugwa Tris-Acetate-EDTA (20 mM Tris (pH 7.6), 2 mM EDTA))] of the DNA strands (strand), respectively It was prepared by. For annealing the DX lattice, an equivalent molar mixture of the strands was placed at 95 ° C. by placing the test tube in 2 L of boiling water in a styrofoam box for at least 24 hours to facilitate hybridization and gradually to 25 ° C. (room temperature). )). After this, the samples were stored overnight at 4 ° C. for structural stabilization. The final concentration of the obtained DNA structure was 400 nM. Streptavidin was purchased from Rockland (PA, USA).

result:

Excitation of the surface plasmon was accompanied by the transition of light energy to the disappearance of the surface plasmon and the surface plasmon in the metallic graphene layer, which resulted in a narrow dip in the reflected light spectrum. The wavelength at which resonant excitation of the surface plasmon occurs depends on the refractive index of the analyte near the SPR surface. In SPR biosensors, the biomolecule's recognition element (DNA / protein) was immobilized on the sensor surface. The binding of target analyte molecules in the sample to the biomolecule recognition element resulted in a local refractive index change.

The experimental SPR curve is shown in FIGS. 8A-B for comparison between (a) bilayer graphene, (b) buffer and DX-biotin DNA and (c) DX-biotin buffer functionalized with graphene, buffer and streptavidin protein. Shown in 8c. Reflectance or reflected intensity reduction for bilayer graphene was observed at an angle of 50.2 degrees, as shown in FIG. 8A. The change in intensity reduction reflected after the placement of the buffer and 1 microliter drop of DX biotin DNA was observed at an angle of 49.8 degrees, as shown in FIG. 8B. On the other hand, when DX biotin was functionalized with streptavidin protein, the decrease in reflection intensity shifted further to 48.8 degrees, as shown in FIG. 8C.

Therefore, the change in the reflected intensity angle shows that the use of bilayer conductive graphene with prisms can be used as an SPR sensor to evaluate various chemicals and biochemical analytes. Furthermore, new methods are proposed to replace conventional metals used in various SPR technologies by nanomaterials such as graphene.

The above description of the present application is intended for illustration, and it will be understood by those skilled in the art that the present invention may be easily modified in other specific forms without changing the technical spirit or essential features of the present application. Therefore, it is to be understood that the embodiments described above are exemplary in all respects and not restrictive.

The scope of the present application is indicated by the following claims rather than the above description, and it should be construed that all changes or modifications derived from the meaning and scope of the claims and their equivalents are included in the scope of the present application.

10: light source
20: sensing unit
30: light receiver
110: substrate
120: metal catalyst layer
130: carbon layer
140: graphene layer
150: container
160: acid solution
170: distilled water
200: Prism
300: metallic carbon nanostructure layer
400: sample

Claims (20)

A light source unit for irradiating light;
A sensing unit including a prism having a metallic carbon nanostructure layer formed on one surface of the prism;
A light receiving unit collecting light reflected from the prism:
Surface plasmon resonance sensor comprising a.
The method of claim 1,
The metallic carbon nanostructure is graphene (graphene), graphite, carbon nanotubes (CNT) and the surface plasmon resonance sensor comprising a combination thereof.
The method of claim 1,
The prism comprises at least one selected from the group consisting of glass, plastic and polymer, surface plasmon resonance sensor.
The method of claim 1,
Wherein the prism comprises a polygon or a semi-cylindrical shape.
The method of claim 3, wherein
The glass is BK7 or SF11, surface plasmon resonance sensor.
The method of claim 3, wherein
The plastic is selected from the group consisting of polymethyl methacrylate (PMMA), polycarbonate (PC), cyclic olefin copolymer (Cyclic Olefin Copolymer, COC), and combinations thereof, surface plasmon Resonance sensor.
The method of claim 3, wherein
The polymer is selected from the group consisting of polydimethylsiloxane, polymethylmethacrylate, polycarbonate, polyethylene, polypropylene, polystyrene, and combinations thereof. Surface plasmon resonance sensor which is selected.
The method of claim 1,
The thickness of the metallic carbon nanostructure layer is 1 nm to 200 nm, surface plasmon resonance sensor.
The surface plasmon resonance sensor of claim 1, wherein the metallic carbon nanostructure layer comprises a single layer or a plurality of layers.
The method of claim 1,
The light source of the light source unit is a surface plasmon resonance sensor comprising any one of a TM or P-polarized monochromatic light source, a white light source, a laser and a light emitting diode (LED) to which light having a short wavelength or multiple wavelengths are irradiated.
The method of claim 1,
And the light receiving unit includes any one of a light receiving element including a photodiode, an optical amplifier, a photosensitive paper, and an image sensor such as a CCD or a CMOS on the light receiving surface.
The method of claim 1,
The surface plasmon resonance sensor is to detect a chemical or biomaterial, surface plasmon resonance sensor.
The method of claim 1,
Surface metal plasmon resonance sensor that is formed in addition to the metallic carbon nanostructure layer on one surface of the prism.
Forming a sensing unit by forming a metallic carbon nanostructure layer on one surface of the prism;
Positioning the sensing unit including the prism between the light source and the light receiving unit:
Comprising, surface plasmon resonance sensor manufacturing method.
The method of claim 14,
Forming the sensing unit,
Forming a metallic carbon nanostructure layer;
Floating the metallic carbon nanostructure layer on the surface of distilled water;
Contacting the suspended metallic carbon nanostructure layer with one surface of a prism to transfer the metallic carbon nanostructure layer to one surface of the prism:
To include, Method for producing a surface plasmon resonance sensor.
The method of claim 14,
Forming the sensing unit,
Forming a metallic carbon nanostructure layer;
Transferring the metallic carbon nanostructure layer by contacting a stamper;
And pressing the metallic carbon nanostructure layer transferred onto the stamper to one surface of the prism to transfer the metallic carbon nanostructure layer to one surface of the prism.
The method of claim 14,
Forming the sensing unit comprises forming a metallic carbon nanostructure layer on one surface of the prism by a spray method, the manufacturing method of the surface plasmon resonance sensor.
The method of claim 14,
Wherein the metallic carbon nanostructure is graphene (graphene), graphite, carbon nanotubes (CNT), and a combination comprising a combination of these, the manufacturing method of the surface plasmon resonance sensor.
The method of claim 14,
Method for producing a surface plasmon resonance sensor as the metallic carbon nanostructure layer using a graphene layer formed by controlling the area and thickness by chemical vapor deposition.
The method of claim 14,
Forming a plurality of metallic carbon nanostructure layers by repeating the forming of the metallic carbon nanostructure layers a plurality of times, the manufacturing method of the surface plasmon resonance sensor.

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