KR20150117198A - Sensor for spectroscopic analysis - Google Patents

Abstract

The present invention relates to a sensor for a spectroscopic analysis and a manufacturing method thereof. The sensor for the spectroscopic analysis according to one embodiment of the present invention includes a fiber layer which includes a plurality of flexible fibers and a surface Plasmon active layer which is formed on the surfaces of the fibers. The sensor for the spectroscopic analysis performs the spectroscopic analysis with high reliability by the surface Plasmon active layer with high precision. The flexible fiber layer easily secures a target material.

Description

[0001] The present invention relates to a sensor for spectroscopic analysis,

The present invention relates to a spectral analysis sensor, and more particularly, to a spectral analysis sensor for analyzing a biological or non-biological target using a surface plasmon phenomenon and a method of manufacturing the same.

A number of measurement techniques have been proposed and commercialized to sensitively and accurately detect samples, which are analytes included in samples in various fields. Among these measurement techniques, Raman spectroscopy and / or Surface Plasmon Resonance (SPR) are applied for chemical and biological molecular specificity analysis because they can precisely measure molecular samples.

The Raman spectroscopy method is a measurement method based on Raman scattering, which is an inelastic scattering phenomenon in which a frequency shift occurs in output light when incident light is transmitted through a medium of a type and excites specific light absorbing molecules in the medium and is scattered . The Raman spectroscopy method calculates the vibration energy level of the specific light absorbing molecule from the frequency deviation of the output light according to the Raman scattering, and the vibration energy of the specific light absorbing molecule depends on the structure of the molecule and the bonding strength The specific molecule is detected.

Although the Raman spectroscopy can accurately identify the molecule itself due to a frequency shift inherent to a specific molecule to be detected, the signal intensity of the Raman scattered output light is very weak, which limits practical applications. Surface-enhanced Raman spectroscopy (SERS) has been proposed in which the weak output of the Raman scattering is amplified to a practical level to improve detection efficiency and reproducibility. In the surface enhancement Raman analysis method, when a specific molecule exists in the periphery of the metal nanostructure, a Raman laser, which is incident light, generates surface plasmon on the surface of the metal nanostructure, and the surface plasmon interacts with the specific molecule (Hereinafter referred to as surface plasmon resonance) in which the Raman signal of the specific molecule is greatly amplified.

Various studies have been made on the shape and / or the type of the metal nanostructure in order to improve the accuracy of the surface enhanced Raman analysis method. Generally, metal nanoparticles are used as the metal nanostructures for the SERS. These nanoparticles are 10 to 10 ³ times larger in magnitude than the islands isolated from each other, . The structure of such agglomerated nanoparticles is preferable because the Raman signal can be amplified by a factor of more than 10 ⁴ times that of a metal thin film having a predetermined roughness.

Although nanopatterning techniques such as electron beam lithography, focused ion beam, or nanoimprint are possible as a method of producing the nanostructures, this technique has limitations in improving the yield in correspondence with the continuous process and various substrate sizes, Mechanical contact of the nanostructures can lead to defects or contamination of the nanostructures. Further, the above-described manufacturing method has a problem that it is difficult to cope with various materials and kinds of substrates for providing the surface on which the nanostructure is formed. For example, since the application of a technique such as electron beam lithography is limited to a substrate having a two-dimensional planar structure, it is difficult to form a nanoparticle structure on a substrate having a complicated three-dimensional structure.

Further, in order to obtain a Raman scattering signal with a high amplification ratio in the structure of the aggregated nanoparticles, it is required to uniformly form agglomerated nanoparticles on the surface of the substrate of the SER sensor. However, there is a problem that it is difficult to uniformly form the coagulated nanoparticles by the above-described production method. As another manufacturing method, a metal thin film having a continuous profile may be deposited and heat-treated. However, in this case, an isolated nano-island structure is liable to be formed rather than a structure of nanoparticles aggregated at a high density, and the material of the substrate is limited to a heat-resistant material such as glass.

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a high-resolution spectroscopic analyzer capable of performing high-reliability spectroscopic analysis based on surface plasmons, while having a complicated structure of a three- And a spectroscopic analysis sensor. It is another object of the present invention to provide a spectroscopic analysis sensor capable of diversifying the method of collecting a sample and expanding its application target.

Another object of the present invention is to provide a nanocomposite composite having a complex structure of a three-dimensional structure as described above or a nanocomposite composite having a high density And a method of manufacturing the spectral analysis sensor.

According to an aspect of the present invention, there is provided a spectroscopic analysis sensor including a fiber layer including a plurality of flexible fibers, and a surface plasmon active layer formed on a surface of the plurality of fibers.

The plurality of fibers may have a nonwoven fabric, a woven fabric, a bundle, or a combination thereof.

The surface plasmon active layer may include conductive nanoparticles and a polymeric binder that fixes the conductive nanoparticles on the surface of the plurality of fibers. The conductive nanoparticles may have an aggregated structure, or may have a shape of any one of spherical, nanotubes, nanocolumns, nano-rods, nanopores, and nanowires, or a combination thereof.

Wherein the conductive nanoparticles comprise particles of a conductive oxide of carbon, graphite, a metalloid, a metal, a metalloid, a metalloid or metalloid, or a conductive nitride of the metalloid or metal, Structure, or a combination thereof.

Wherein the metalloid includes any one of antimony (Sb), germanium (Ge), and arsenic (As) or an alloy thereof and the metal is a metal, a transition metal, Zn, Al, Al, Sc, Cr, Mn, Fe, Co, Ni, Cu, (Sn), yttrium (Y), zirconium (Zr), nebium (Nb), molybdenum (Mo), ruthenium (Ru), rhodium (Rh), palladium Wherein the conductive oxide includes at least one of indium (Ag), platinum (Pt), strontium (Sr), tungsten (W), cadmium (Cd), tantalum (Ta), titanium (Ti), titanium (ITO), indium zinc oxide (IZO), aluminum doped zinc oxide (AZO), gallium indium zinc oxide (GIZO), zinc oxide (ZnO), or mixtures thereof.

The thickness of the surface plasmon active layer may be in the range of 10 nm to 500 nm, and the plurality of fibers may include any one or both of natural fibers and synthetic fibers.

The surface of the fiber layer may include amorphous surface plasmon fiber protrusions provided with the plurality of fibers protruding, and the fiber layer may include pores between the plurality of fibers.

The polymeric binder may include a cationic polymer or an anionic polymer.

In addition, the surface plasmon active layer may further include a fixing substance capable of specifically binding to a target substance to be analyzed. The immobilizing material may include a small molecule compound, an antigen, an antibody, a protein, a peptide, Deoxyribonucleic Acid (DNA), Ribonucleic Acid (RNA), Peptide Nucleic Acid (PNA), an enzyme, an enzyme substrate, a hormone, a hormone receptor, Any of the synthetic reagents, a mimic thereof, or a combination thereof.

Wherein the target material is selected from the group consisting of amino acids, peptides, polypeptides, proteins, glycoproteins, lipoproteins, nucleosides, nucleotides, oligonucleotides, nucleic acids, sugars, carbohydrates, oligosaccharides, polysaccharides, fatty acids, lipids, hormones, metabolites, cytokines, Receptor, neurotransmitter, antigen, allergen, antibody, substrate, metabolite, cofactor, inhibitor, drug, drug, nutrient, plion, toxin, poison, explosive, insecticide, chemical agonist, biohazard agent, bacteria, virus , Radiation isotopes, vitamins, heterocyclic aromatic compounds, carcinogens, mutagen, drugs, amphetamines, barbiturates, hallucinogens, wastes, and contaminants.

The spectroscopic analysis sensor can be used for surface-enhanced Raman spectroscopy (SERS), surface plasmon resonance (SPR), local surface plasmon resonance (LSPR), absorption and / or fluorescence modes .

According to another aspect of the present invention, there is provided a method of manufacturing a spectroscopic analysis sensor, comprising: providing a mixed solution including an ionic polymer binder and conductive nanoparticles; And applying an electric field to the mixed solution in which the plurality of fibers are immersed so that the conductive nanoparticles are coated on the surface of the plurality of fibers.

A spectroscopic analysis sensor according to an embodiment of the present invention is a spectroscopic analysis sensor in which a surface plasmon active layer is formed on the surface of a plurality of fibers constituting a fiber layer and the flexibility of the fibers It is possible to collect a sample by rubbing or transmitting the fiber layer on the surface corresponding to various shapes and materials of the surface, thereby diversifying the object of the sample to be measured and simplifying the preparation process of the sample, And the product requirements such as required strength, transparency, porosity, heat resistance and chemical resistance can be easily satisfied according to the material of the fibers. Further, according to the embodiment of the present invention, the surface area capable of forming the surface plasmon active layer by the fibers is wider than the two-dimensional substrate, and the surface plasmon active layer is formed at high density, Can be performed.

According to the embodiment of the present invention, by injecting energy into the ionic polymer binder and the metal nanoparticles by an electric field, it is possible to produce a composite material having a three-dimensional structure and a flexible structure A surface plasmon active layer made of a high-density nano structure can be produced quickly and economically.

FIG. 1A is a perspective view of a spectroscopic analysis sensor according to an embodiment of the present invention, and FIG. 1B is a cross-sectional view of a plurality of fibers according to an embodiment of the present invention.
2 is a cross-sectional view illustrating a surface plasmon active layer formed on a fiber and a fiber of a spectroscopic analysis sensor according to an embodiment of the present invention.
3 is a cross-sectional view illustrating a surface plasmon active layer formed on a fiber and a fiber of a spectroscopic analysis sensor according to another embodiment of the present invention.
FIG. 4 is a flowchart for explaining a method of manufacturing a spectroscopic analysis sensor according to an embodiment of the present invention, and FIGS. 5A and 5B show the results of the manufacturing method.
6 shows an apparatus for manufacturing a spectroscopic analysis sensor according to an embodiment of the present invention.
7A and 7B are optical images of the spectroscopic analysis sensor obtained by the above Experimental Example and the spectroscopic analysis sensor according to the comparative example, respectively.
FIG. 8 is an optical photograph of a state of a wet state of a wet state of the spectroscopic analysis sensors manufactured according to an embodiment of the present invention.
FIG. 9A is an optical photographic image of a spectroscopic analysis sensor in which metal nanoparticles are coated on polycarbonate fibers, and FIG. 9B is a scanning electron microscope image of a spectroscopic analysis sensor.
FIG. 10A is a Raman spectrum of acetaminophen using a spectroscopic analysis sensor according to an embodiment of the present invention, and FIG. 9B is a Raman spectrum of acetaminophen on a fiber layer according to a comparative example.

Hereinafter, the present invention will be described in more detail with reference to examples.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are intended to provide further explanation of the invention as claimed and will become apparent to those skilled in the art. It is not limited to the embodiment. Rather, these embodiments are provided so that this disclosure will be more faithful and complete, and will fully convey the scope of the invention to those skilled in the art.

In the following drawings, thickness and size of each layer are exaggerated for convenience and clarity of description, and the same reference numerals denote the same elements in the drawings. As used herein, the term "and / or" includes any and all combinations of any of the listed items.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the singular forms "a," "an," and "the" include singular forms unless the context clearly dictates otherwise. Also, " comprise "and / or" comprising "when used herein should be interpreted as specifying the presence of stated shapes, numbers, steps, operations, elements, elements, and / And does not preclude the presence or addition of one or more other features, integers, operations, elements, elements, and / or groups.

Reference herein to a layer formed "on" on a fibrous layer or other layer refers to a layer formed directly on top of the fibrous layer or other layer, or to a layer formed on intermediate or intermediate layers formed on the fibrous or other layer Layer. ≪ / RTI > It will also be appreciated by those skilled in the art that structures or shapes that are "adjacent" to other features may have portions that overlap or are disposed below the adjacent features.

As used herein, the terms "below," "above," "upper," "lower," "horizontal," or " May be used to describe the relationship of one constituent member, layer or regions with other constituent members, layers or regions, as shown in the Figures. It is to be understood that these terms encompass not only the directions indicated in the Figures but also the other directions of the devices.

In the following, embodiments of the present invention will be described with reference to cross-sectional views schematically illustrating ideal embodiments (and intermediate structures) of the present invention. In these figures, for example, the size and shape of the members may be exaggerated for convenience and clarity of explanation, and in actual implementation, variations of the illustrated shape may be expected. Accordingly, embodiments of the present invention should not be construed as limited to any particular shape of the regions shown herein. In addition, reference numerals of members in the drawings refer to the same members throughout the drawings.

FIG. 1A is a perspective view of a spectroscopic analysis sensor 100 according to an embodiment of the present invention, and FIG. 1B is a cross-sectional view of a plurality of fibers 10F according to an embodiment of the present invention.

Referring to FIGS. 1A and 1B, the spectroscopic analysis sensor 100 includes a fiber layer 10 including a plurality of fibers 10F; And a surface plasmon active layer (SP) formed on the surface of the plurality of fibers 10F. The plurality of fibers 10F of the fibrous layer 10 may extend in at least two different directions and contact with each other to form a three-dimensional solid body having pores formed from the surface of the fibrous layer 10 to the inside thereof. The pores can provide a path of movement of the polymeric binder and the conductive nanoparticles to be coated on the surface of the plurality of fibers 10F from the surface to the inside of the fiber layer 10 as described later.

In some embodiments, the plurality of fibers 10F may comprise any one or both of natural and synthetic fibers. The natural fibers can be, for example, cotton, hemp, wool or silk. The synthetic fibers may be selected from, for example, rayon, nylon, cellulose, acrylic, polyester, polyethylene, polypropylene, polyethylene terephthalate, polypropylene terephthalate, polyacrylonitrile, polyethylene naphthalate, polyether sulfone, , Polyphenylene sulfide, polyvinylidene fluoride, or copolymers thereof. However, the above-mentioned materials are illustrative and the present invention is not limited thereto. For example, if a wiper method is required for sampling, a soft and flexible fiber material such as cellulose or polyester may be used as the material of the spectrometric sensor. If a filter method is required for sampling, A fiber material such as polycarbonate having high chemical property may be used.

According to another embodiment, the material of the plurality of fibers 10F may be selected from the group consisting of strength, elasticity, shrinkage, heat resistance, and / or heat resistance, depending on the object and place where the sample to be sampled by the spectroscopic analysis sensor exists, And chemical properties. The plurality of fibers 10F may be other polymeric materials, petroleum pitch, or coal tar.

In another embodiment, the plurality of fibers 10F may comprise an optical fiber capable of transmitting incident light or output light for spectroscopic analysis along the fibers. In this case, the fiber layer 10 may be composed of a plurality of optical fiber bundles or may have a woven or nonwoven structure in which the above-mentioned natural fibers and / or synthetic fibers and optical fibers are mixed. For example, a plurality of optical fibers may be exposed or blended irregularly so that the fiber layer 10 emits light out of the surface of the fiber layer 10 between the plurality of natural fibers and / or synthetic fibers.

The plurality of fibers 10F constituting the fibrous layer 10 may be segmented into uniform lengths or different lengths or may be a single continuous fiber. In some embodiments, the plurality of fibers 10F may have a nonwoven fabric, woven fabric, or a combination thereof. Figure la discloses a fiber layer 10 comprising a plurality of fibers 10F having a nonwoven structure. Such a fiber structure may increase the density of fibers in a unit volume through a compression process.

At least one amorphous fiber protrusion protruding from the upper surface of the fiber layer 10 may be provided. The amorphous fiber protrusions adjust the surface roughness of the fiber layer 10 or the fiber layer 10 facilitates the collection of the sample to be measured.

In terms of manufacturing, the fibrous layer 10 can be obtained by randomly scattering or blending a plurality of fibers 10F, optionally by performing an entanglement process to obtain a nonwoven structure, or by using a weaving process, Can be obtained. Such a preparation method is illustrative, and the present invention is not limited thereto. The surface plasmon active layer SP may be formed on the surface of the plurality of fibers 10F. A surface plasmon resonance (SPR) is generated by a light incident from the outside to amplify a signal for detecting a target material to be analyzed contained in the sample, thereby obtaining a reproducible and reliable spectral analysis .

For example, the surface plasmon active layer SP may have a plasmon resonance wavelength (hereinafter, referred to as " plasmon resonance wavelength ") having a maximum absorption rate or a scattering rate according to a change in the chemical and physical environment of the surface plasmon active layer And / or detecting a change in absorption rate, thereby identifying the target material in the sample or obtaining the concentration of the target material in the sample. In addition, the surface plasmon active layer SP generates surface plasmon on the surface of the surface plasmon active layer SP, and the surface plasmon interacts with a specific molecule of the sample, Surface-enhanced Raman spectroscopy (SERS) for the detection of specific molecules may also be performed.

The spectroscopic analysis sensor 100 according to the embodiment of the present invention can measure a variety of surfaces of an object or an organism in which a sample to be analyzed exists due to the flexibility of the fibers 10F serving as a base of the surface plasmon active layer SP It is possible to collect the sample by rubbing the fiber layer 10 on the surface corresponding to the shape and the material, thereby diversifying the objects to be measured and simplifying the sample preparation process. For example, in the case of an inelastic or plastic-like elastic body such as glass and metal, which has a lower flexibility than a fiber, a sample should be separately taken at the time of spectral analysis and coated on the spectral analysis sensor, The spectroscopic analysis sensor 100 of the present invention can sample and analyze the sample itself. According to the embodiment of the present invention, in the case of a liquid sample, the pores in the fiber layer 10 are quickly absorbed into the fiber layer 10 to quickly collect the sample, and the samples absorbed into the pore And can be safely kept in the fiber layer 10 for a long time.

2 is a sectional view showing a surface plasmon active layer SP formed on the fiber 10F and the fiber 10F of the spectroscopic analysis sensor according to an embodiment of the present invention.

Referring to Fig. 2, the fiber 10F is a single fiber constituting one of the plurality of segmented fiber filaments or the fiber layer 10 constituting the fiber layer 10 described above with reference to Fig. 1A. The surface plasmon active layer SP on the surface of the fiber 10F may include the conductive nanoparticles 20. These conductive nanoparticles 20 may include a polymeric binder 20 that fixes the conductive nanoparticles on the surface of the fiber 10F.

The polymeric binder 20 may be formed to a thickness larger than the diameter of the conductive nanoparticles 20 on the surface of the fiber 10F so as to contain the conductive nanoparticles 20. [ In some embodiments, the polymeric binder 20 may have a sufficient thickness so that the conductive nanoparticles 20 agglomerated into two or more layers may be contained in the polymeric binder 20.

The polymeric binder 20 may be formed to a thickness smaller than the diameter of the conductive nanoparticles 20. In this case, the surface of the conductive nanoparticles 20 may be exposed to the outside of the polymeric binder 20 Can be exposed. FIG. 2 illustrates that the surface of the conductive nanoparticles 20 is exposed to the outside of the polymeric binder 20. The thickness of the polymeric binder 20 and thus the number or the degree of exposure of the conductive nanoparticles 20 may vary depending on the mixing ratio of the polymeric binder 20 and the conductive nanoparticles of the mixed solvent and / Concentration or the temperature and time of the drying process.

The molecular weight of the polymeric binder 20 may be in the range of about 1,000 kDal to about 60,000 kDal. When the molecular weight is less than about 1,000 kDal, the bonding strength of the conductive nanoparticles fixed on the fibrous layer is not sufficient. When the molecular weight exceeds 60,000 kDal, the viscosity is excessively high in the liquid coating process, It is difficult to uniformly coat the conductive nanoparticles 20 on the fibers 10F because the transfer of the polymeric binder 20 and the conductive nanoparticles 20 is not easy.

The polymeric binder 20 may be an ionic polymer when dissolved in a suitable solvent. For example, the polymeric binder 20 may be a cationic polymer and may be selected from the group consisting of poly diallydimethylammonium chloride, poly allylamine hydrochloride, polyvinyl benzyl trimethyl ammonium chloride (poly 4 -vinylbenzyltrimethyl ammonium chloride, polyethyleneimine, or a mixture thereof. In another embodiment, the polymeric binder 20 may be an anionic polymer and may be selected from the group consisting of poly acrylic acid, poly sodium 4-styrene sulfonate, poly vinylsulfonic acid, Polysodium salt, poly amino acid, or a mixture thereof. The polymers are illustrative and may be polymers or copolymers having positive or negative ionic groups, polymers having positive or negative ionic groups attached to the polymer backbone, other synthetic resins, or natural resins.

The conductive nanoparticles 30 may have an average diameter of 10 nm to 200 nm and may have any of a spherical shape, a nanotube, a nanocolumn, a nanorod, a nanopore, and a nanowire, or a combination thereof. Depending on the shape, these particles may be in a buoyant form or may be porous or hollow. The conductive nanoparticles may be conductive particles of carbon, graphite, metalloid, metal, metalloid or metal, conductive metal oxide, metal nitride, or a conductive layer such as a metal thin film on a glass or polymer insulating bead Core shell structure. In one embodiment, the conductive nanoparticles 30 may be a noble metal such as gold or silver.

The metalloid may be any one of antimony (Sb), germanium (Ge) and arsenic (As) or an alloy thereof. The metal may be a metal, a transition metal or a transition metal, and may be at least one selected from the group consisting of Ti, Zn, Al, Sc, Cr, Mn, (Co), Ni, Cu, In, Sn, Y, Zr, Ne, Mo, Ru, Ru, (Pd), gold (Au), silver (Ag), platinum (Pt), strontium (Sr), tungsten (W) or cadmium (Cd), tantalum (Ta) Ti), titanium (Ti), or an alloy thereof.

As the conductive metal oxide, indium tin oxide (ITO), indium zinc oxide (IZO), aluminum doped zinc oxide (AZO), gallium indium zinc oxide (GIZO) or zinc oxide (ZnO) . As the conductive nitride, tungsten nitride (WN) can be exemplified without limitation.

In one embodiment, the thickness of the surface plasmon active layer (SP) may be in the range of 10 nm to 500 nm. When the thickness of the surface plasmon active layer (SP) is less than 10 nm, the amplification effect of the spectroscopic analysis signal by the surface plasmon active layer (SP) is insufficient, so that the intensity of the signal for analysis of the target material in the sample may not be within the analytical range. When the thickness of the surface plasmon active layer (SP) is more than 500 nm, the intensity of a signal for analysis of a target material is greatly amplified, and the error range also increases, so that the accuracy of the sample analysis may be lowered.

When the surface plasmon active layer SP is uniformly formed on the plurality of fibers 10F constituting the fiber layer 10 through the pores of the surface and the inner surface of the fiber layer 10, The measurement results can be reproducible. Further, the one-dimensional linear structure of the fibers 10F is spatially regularly or randomly arranged to form a three-dimensional structure, and the surface area is improved compared to other glass or plastic substrates such as a flat plate structure, The sensitivity can be improved by increasing the content of the active layer SP to increase the intensity of the analysis signal.

SPR by the conductive nanoparticles 30 enables spectroscopic analysis by localized surface plasmon resonance (LSPR) attributed to nanostructures as well as surface-enhanced Raman spectroscopy (SERS) do. The LSPR identifies a specific molecule by detecting a change in the plasmon resonance wavelength with a change in the chemical and physical environment of the surface of the nanoparticles or the nanostructure, for example, a maximum absorption rate or a scattering rate according to a change in the refractive index of a medium in contact with the surface Since the concentration of a specific molecule in a medium can be determined and the detection can be performed by a label-free method because of the high sensitivity to the change of the refractive index, a waveform due to a prism coupling It has many advantages over the bulk SPR sensor using plasmon.

In addition, since the spectral analysis sensor of the present invention has flexibility and surface roughness due to the structural characteristics of the fiber layer 10, it can correspond to various surface profiles on which the sample exists, It is possible to easily collect a small amount of the sample and improve the measurement sensitivity of the substrate by the surface plasmon.

3 is a cross-sectional view showing a surface plasmon active layer SP formed on the fiber 10F and the fiber 10F of the spectroscopic analysis sensor according to another embodiment of the present invention. As to the fiber and surface plasmon active layer (SP), the above description can be referred to.

Referring to FIG. 3, the surface plasmon active layer SP may include conductive nanoparticles and a polymeric binder that fixes the conductive nanoparticles on the surface of the fiber 10F. Fig. 3 shows a structure in which the conductive nanoparticles are aggregated with each other as a single layer, but this is illustrative and may have two or more layers as described above with reference to Fig. 2, or may have a discrete structure. In addition, the conductive nanoparticles may be embedded in or exposed out of the polymeric binder. Accordingly, the fixing material 40 can be formed on the surface of the polymer binder and / or the conductive nanoparticles 30 exposed to the outside.

The immobilizing material L may be any one selected from the group consisting of a low molecular compound capable of binding to the target substance, an antigen, an antibody, a protein, a peptide, DNA, RNA, PNA, enzyme, enzyme substrate, hormone, hormone receptor, Or a combination thereof, and a known technique may be referred to as a fixing method thereof. The target material may be selected from the group consisting of amino acids, peptides, polypeptides, proteins, glycoproteins, lipoproteins, nucleosides, nucleotides, oligonucleotides, nucleic acids, sugars, carbohydrates, oligosaccharides, polysaccharides, fatty acids, lipids, hormones, Chemokines, receptors, neurotransmitters, antigens, allergens, antibodies, substrates, metabolites, cofactors, inhibitors, drugs, drugs, nutrients, plion, toxins, poisons, explosives, pesticides, chemical agents, , Viruses, radioactive isotopes, vitamins, heterocyclic aromatic compounds, carcinogens, mutagen, drugs, amphetamines, barbiturates, hallucinogens, wastes and contaminants.

FIG. 4 is a flowchart for explaining a method of manufacturing a spectroscopic analysis sensor according to an embodiment of the present invention, and FIGS. 5A and 5B show the results of the manufacturing method.

Referring to FIG. 5A together with FIG. 4, a mixed solution SV including an ionic polymer binder 20S and conductive nanoparticles is prepared (S10). The mixed solution SV can prepare the mixed solution PL by dissolving the polymeric binder 20S in a suitable solvent SV and dispersing the conductive nanoparticles 30S in the solvent SV. In another embodiment, the polymeric binder 20S is dissolved in the solvent SV with a low molecular weight precursor such as a monomer and can be polymerized through a further crosslinking step at a subsequent step, e.g., S20, S30, or thereafter have. The polymeric binder 20S and the conductive nanoparticles 30S are entangled with each other in the mixed solution so that when a flux or a flux is generated in the polymeric binder 20S, The flux of the impurities 30S may occur.

The solvent SV may be any one of water such as distilled or deionized water, aliphatic alcohol, aliphatic ketone, aliphatic carboxylic acid ester, aliphatic carboxylic acid amide, aromatic hydrocarbon, aliphatic hydrocarbon, acetonitrile, aliphatic sulfoxide, Lt; / RTI > In addition, the solvent SV may be any known polarity solvent in which the ionic polymeric binder 20S can be easily dissolved.

The polymeric binder 20S is added to the mixed solution PL within the range of 0.01 to 10% by weight of the polymeric binder 20S based on the total weight of the mixed solution PL, and the conductive nanoparticles 30S have an A molar concentration of 0.01% to 10% Lt; / RTI > The remainder may be filled with solvent. Alternatively, a suitable dispersion stabilizer such as alginic acid, a monovalent acid derivative and mixtures thereof, or a pH adjusting agent such as boric acid, orthophosphoric acid, acetic acid, ascorbic acid, and citric acid may be added. Alternatively, in the case of a photosensitive polymer binder, a photoinitiator may be further added for the crosslinking reaction.

Referring to FIG. 5B together with FIG. 4, the fiber layer 10 is immersed in the mixed solution PL (S20). The fibrous layer 10 may be freely placed in the mixed solution PL or fixed by a mechanism such as a clamp. Further, two or more fibrous layers may be immersed. In another embodiment, the fiber layer 10 may be first dipped in the solvent SV to disperse and dissolve the polymeric binder 20S and the conductive nanoparticles 30S.

The fibrous layer 10 may be cleaned prior to the immersion step or may be surface treated to adhere the surface plasmon active layer. In one embodiment, the fibrous layer 10 may be coated with a photocatalyst. The photocatalyst can be produced by the same method as the sol-gel method and can be coated on the fibers 10F by spraying or coating. The photocatalyst may be titanium dioxide (TiO ₂ ), zinc oxide (ZnO), tungsten oxide (WO ₃ ), or the like. In another embodiment, the photocatalyst may be dispersed in the mixed solution PL.

The electric field E is applied in the state where the fiber layer 10 is immersed in the mixed solution SV (S30). The electric field E may have a DC, AC, or composite waveform thereof. The direction of the electric field E in the case of the direct current electric field can be applied in a direction perpendicular to the main surface of the fiber layer 10, for example, the upper surface, and the direction is determined according to the polarity of the ionic polymer binder 20S . For example, if the conductive nanoparticles 30S are to be transferred from the upper surface to the lower surface of the fibrous layer 10 as shown in FIG. 5B, if a cationic polymeric binder is used, an electric field can be formed vertically downward have. Conversely, when an anionic polymeric binder is used, an electric field may be formed vertically upward. In another embodiment, the direction of the electric field E may be any direction if the electric field E is an alternating electric field. In yet another embodiment, the electric field E may comprise a plurality of electric fields having electric fields of different directions or having different kinds of signals.

The electrophoresis of the polymeric binder 20S charged by the electric field E becomes possible. As a result, the flux of the polymeric binder 20S is generated and the flux of the polymeric binder 20S generates the flux of the conductive nanoparticles 30S. The flux is activated by the electric field E and is accelerated to have a larger kinetic energy so that the polymer binder 20S and the conductive nanoparticles 30S are injected into the surface of the fiber layer 10 and through the pores of the fiber layer 10 Lt; / RTI >

The kinetic energy of the polymeric conductive nanoparticles 30S and the polymeric binder 20S transferred onto the surface of the fibers 10F is such that the electric field is substantially random on the surface of the fibers 10F to be arranged three- And can be uniformly coated on the surface of the fibers 10F due to high kinetic energy. In addition, the conductive nanoparticles can be coated on the upper surface of the fibers 10F at a high density and uniformly.

In one embodiment, the fibrous layer 10 is in an electrically floating state, and the electric field E is formed outside the mixed solution SV and can penetrate into the mixed solution SV. The electric field E may have an electrostatic field, an alternating electric field or other waveform as described above, and the present invention is not limited thereto. The electric field E can be generated by a plasma discharge in the chamber, which will be described later with reference to Fig.

Thereafter, when the conductive nanoparticles 30S are sufficiently coated and fixed on the fibrous layer 10, the fibrous layer 10 is recovered from the mixed solution 50. Then, The time required for step S30 is extremely short, from 10 seconds to 5 minutes, as compared with coating with a conventional stirring process. Thereafter, the recovered fiber layer 10 may be dried, or ultraviolet rays or heat may be irradiated for crosslinking reaction of the polymeric binder. In some embodiments, cleaning of the fibrous layer 10 can be accomplished. The cleaning may remove unfixed conductive nanoparticles or the polymeric binder, and then shrinkage of the polymeric binder may be caused by the drying process. In this case, as described above with reference to FIG. 2, the polymer binder 20 coated on the fibers 10F shrinks and some surfaces of the conductive nanoparticles 30 can be exposed.

In the above-described embodiment, the fibrous layer of the nonwoven fabric structure is prepared in advance and the coating process of the metal nanoparticles is performed. However, the present invention is not limited thereto. For example, a coating process of metal nanoparticles on the strands of a plurality of fibers may be performed first, followed by recovery of the metal nanoparticles, and then a woven or nonwoven fabric process may be performed to produce a fiber layer-type spectroscopic analysis sensor.

FIG. 6 illustrates an apparatus 1000 for manufacturing a spectroscopic analysis sensor according to an embodiment of the present invention.

Referring to FIG. 6, the manufacturing apparatus 1000 is an apparatus for generating an electric field E. FIG. The manufacturing apparatus 1000 may have two electrodes for generating an electric field, that is, an anode (AE) and a cathode (CE). There may be a plurality of the anode (SE) and the cathode (CE), and may be spatially arranged so as to have electric fields in different directions.

In one embodiment, the manufacturing apparatus 1000 may further comprise suitable gas supply means capable of generating an electric field by gas discharge. The gas P is introduced into the space defined by the anode (AE) and the cathode (CE) as indicated by the arrow A, and the gas P is continuously discharged as indicated by the arrow B. A pump system (not shown) may be provided for the release of the gas P or for the depressurization of the space between the anode AE and the cathode CE.

The gas P may be provided from either or both of the anode AE and the cathode CE and for this purpose the anode AE and the cathode CE may have through holes similar in shape to the showerhead have. The gas may include any one or a mixed gas of helryu (He), neon (Ne), argon (Ar), nitrogen (N _2), and air. However, this is illustrative and the gas P may be another reactive gas.

The cathode CE may be electrically coupled to an RF generator for generating a gas discharge of the gas P, that is, for generating a plasma, and the anode AE may be grounded. Alternatively, a positive voltage may be applied to the anode (AE) and a negative voltage may be applied to the cathode (CE) for direct current discharge other than the above AC discharge. After the container 60 in which the fiber layer 10 is immersed in the mixed solution 50 is placed between the cathode CE and the anode AE and the power is supplied to the anode AE and / And the fixing process of the nanoparticles is carried out for several seconds to several minutes while being supplied. The distance between the anode (AE) and the vessel (60) can be maintained between 0.5 cm and 40 cm.

In the manufacturing apparatus 1000 of FIG. 5, when power is applied to the AC generator of the cathode CE, the cathode CE has a negative potential by a self-bias, whereby the grounded anode AE ) And the cathode (CE). Thereby, the flow of the conductive nanoparticles (30) and the polymeric binder (20) in the mixed solution is generated, and the conductive nanoparticles can be fixed on the fiber layer (10) by maintaining this for several seconds to several minutes.

The positions of the anode (AE) and the cathode (CE) shown may be opposite to each other. In addition, the anode (AE) is not limited to being flat, and may have a side wall such as a lid to define a gas discharge space or may be the body of the chamber. In some embodiments, the pressure of the space for the gas discharge may be atmospheric pressure or a vacuum condition below atmospheric pressure, and a vacuum pump may be provided to the manufacturing apparatus 1000 for this purpose. The plasma apparatus described above is a capacitively coupled plasma chamber, but may also include other inductively coupled plasma or other plasma sources.

Experimental Example

0.01 wt% ethlyleneglycolamine was added as a polymer binder, and 0.05 wt% gold nanoparticles having an average diameter of 50 nm as conductive nanoparticles were added to distilled water as a solvent and stirred to prepare a mixed solution. As the fiber layer to be coated with the gold nanoparticles, the polyester fabric was washed and treated with distilled water, and then immersed in the mixed solution.

Then, the gold nanoparticles bonded to the polymer binder were placed in the electric field generator in the polyester fabric, and an electric field was applied to the mixed solution to perform the coating reaction. The mixed solution and the container containing the polyester fabric were placed in a plasma chamber in a plasma chamber, and the electric field was applied by discharging the plasma. Plasma discharge was performed for 30 seconds, and the fibrous layer was recovered and dried to prepare a spectral analysis sensor according to an embodiment of the present invention. As a comparative experiment to the present experimental example, the polyester fabric in the mixed solution was stirred for 4 hours without applying an electric field, and recovered and dried to prepare a spectral analysis sensor according to a comparative example.

7A and 7B are optical images of the spectroscopic analysis sensor 200a obtained by the above experimental example and the spectroscopic analysis sensor 200b of the comparative example, respectively. Referring to FIG. 7A, the spectroscopic analysis sensor 200a according to the experimental example is darker in color than the spectroscopic analysis sensor 200b according to the comparative example, and has uniform color over the entire area. Thus, according to the embodiment of the present invention, the surface plasmon active layer can be more uniformly and densely coated on the fibrous layer.

FIG. 8 is a graph showing optical photographs of the dry state (Dry; 1a, 1b, 1c, and 1d) and wet states (Wet; 1b, 2b, 3b, and 4b) of the spectral analysis sensors manufactured according to an embodiment of the present invention; to be. Each of the samples was manufactured in accordance with an embodiment of the present invention. The images 1a, 1b, 2a, 2b, 3a, 3b and 4a, The nanoparticles were prepared by performing a coating process under an electric field for 30 seconds at different concentrations of 1, 2, and 3 times. It can be confirmed that the color of the substrate for analyzing the sample in a wet state is thicker than the substrate for the analysis of the sample in the dry state.

The reason why the surface enhancement Raman spectroscopy has superior analytical sensitivity is due to the amplification of the surface Raman signal due to the local surface plasmon resonance of the conductive nanoparticles. Therefore, the conductive nanoparticles can be fixed to the surface of the substrate and the local surface plasmon resonance phenomenon can be expressed, which can be used as a sensor substrate capable of expressing the surface enhanced Raman phenomenon. This expression of local surface plasmon resonance can be confirmed by measuring the degree of change in absorbance, that is, the degree of darkness, by artificially changing the refractive index around the substrate coated with the conductive nanoparticles.

FIG. 8 is a graph showing the results of exposure (1b, 2b, 3b, 4b) of water having a refractive index of 1.333 after exposing the coated lipid coated with conductive nanoparticles to air having a refractive index of 1 This is the result of measuring the color change. Referring to FIG. 8, in the case where the conductive nanoparticles are not coated (1a), there is no change in color even when the refractive index of the surroundings is increased to 1.333 (water) with the lipid not coated with the conductive nanoparticles (1b). However, when the conductive nanoparticles are coated (2a, 3a, 4a), the ambient refractive index increases from 1 (air) to 1.333 (water) (2a, 3a, 4a) , Respectively. This increase in absorbance indicates that the degree of coating of the conductive nanoparticles increases more remarkably as the degree of coating increases. Therefore, in the case of the spectral analysis sensor in which the conductive nanoparticles are coated at high density, the local surface plasmon resonance phenomenon is clearly manifested and the surface enhancement Raman phenomenon can be further amplified, so that a small amount of the sample can be analyzed accurately.

9A is an optical photographic image of the spectroscopic analysis sensor 300 on which the metal nanoparticles are coated on the polycarbonate fibers, and FIG. 9B is a scanning electron microscope image of the spectroscopic analysis sensor 300. FIG.

Referring to FIG. 9A, the non-woven structure spectral analysis sensor 300 based on polycarbonate fibers exhibits a darker color as compared with a spectral analysis sensor based on the above-described polyester fibers after coating gold nanoparticles. Since the spectroscopic analysis sensor 300 having a non-woven structure based on polycarbonate fibers has high strength and chemical resistance, it is possible to collect samples by a filter method as well as a wiper. Referring to FIG. 9B, gold nanoparticles are coated on the binder layer of the spectroscopic analysis sensor 300 at a high density.

FIG. 10A is a Raman spectrum of acetaminophen using a spectroscopic analysis sensor according to an embodiment of the present invention, and FIG. 9B is a Raman spectrum of acetaminophen on a fiber layer according to a comparative example.

Referring to FIG. 10A, a Raman shift signal based on the bonding structure of acetaminophen appears on a polycarbonate fiber-based spectrometric sensor coated with gold nanoparticles, and the peak size thereof is large enough to be detectable and reproducible Raman spectrum . 10B, in the polycarbonate fiber substrate in which gold nanoparticles are not coated, both the Raman shift signal and the noise are amplified during signal amplification in order to detect a signal, so that the Raman shift signal is more difficult to detect than the Raman shift signal in FIG. 10A , There is no reproducibility.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention as defined in the appended claims. It will be clear to those who have knowledge.

Claims (15)

A fibrous layer containing a plurality of flexible fibers, forming a three-dimensional solid body having pores from the surface to the inside thereof; And
And a polymer binder formed on the surface of the plurality of fibers from the surface to the inside of the fiber layer through the pores and fixing the conductive nanoparticles and the conductive nanoparticles on the surface of the plurality of fibers, A spectral analysis sensor comprising an active layer. The method according to claim 1,
Wherein the plurality of fibers have a nonwoven fabric, a woven fabric, a bundle, or a combination thereof. The method according to claim 1,
Wherein the conductive nanoparticles have an aggregated structure. The method according to claim 1,
Wherein the conductive nanoparticles have a shape selected from the group consisting of a spherical shape, a nanotube, a nanocolumn, a nanorod, a nanopore, and a nanowire, or a combination thereof. The method according to claim 1,
Wherein the conductive nanoparticles comprise particles of a conductive oxide of carbon, graphite, a metalloid, a metal, a metalloid, a metalloid or metalloid, or a conductive nitride of the metalloid or metal, ≪ / RTI > or a combination thereof. 6. The method of claim 5,
The metalloid includes any one of antimony (Sb), germanium (Ge) and arsenic (As) or an alloy thereof,
The metal may be a metal, a transition metal or a transition metal, and may be at least one selected from the group consisting of Ti, Zn, Al, Sc, Cr, Mn, (Co), Ni, Cu, In, Sn, Y, Zr, Ne, Mo, Ru, Ru, (Pd), gold (Au), silver (Ag), platinum (Pt), strontium (Sr), tungsten (W) or cadmium (Cd), tantalum (Ta) Ti), titanium (Ti), or alloys thereof,
Wherein the conductive oxide is selected from the group consisting of indium tin oxide (ITO), indium zinc oxide (IZO), aluminum doped zinc oxide (AZO), gallium indium zinc oxide (GIZO), zinc oxide (ZnO) . The method according to claim 1,
Wherein the thickness of the surface plasmon active layer is in the range of 10 nm to 500 nm. The method according to claim 1,
Wherein the plurality of fibers comprise either or both of natural fibers and synthetic fibers. The method according to claim 1,
Wherein the surface of the fiber layer comprises amorphous surface plasmon fiber protrusions provided with the plurality of fibers protruding. The method according to claim 1,
Wherein the fiber layer comprises pores between the plurality of fibers. The method according to claim 1,
Wherein the polymeric binder comprises a cationic polymer or an anionic polymer. The method according to claim 1,
And a fixing substance capable of specifically binding with a target substance to be analyzed on the surface plasmon active layer. 13. The method of claim 12,
The immobilizing material may include a small molecule compound, an antigen, an antibody, a protein, a peptide, Deoxyribonucleic Acid (DNA), Ribonucleic Acid (RNA), Peptide Nucleic Acid (PNA), an enzyme, an enzyme substrate, a hormone, a hormone receptor, A synthetic reagent, a compound thereof, or a combination thereof. 13. The method of claim 12,
Wherein the target material is selected from the group consisting of amino acids, peptides, polypeptides, proteins, glycoproteins, lipoproteins, nucleosides, nucleotides, oligonucleotides, nucleic acids, sugars, carbohydrates, oligosaccharides, polysaccharides, fatty acids, lipids, hormones, metabolites, cytokines, Receptor, neurotransmitter, antigen, allergen, antibody, substrate, metabolite, cofactor, inhibitor, drug, drug, nutrient, plion, toxin, poison, explosive, insecticide, chemical agonist, biohazard agent, bacteria, virus A radioactive isotope, a vitamin, a heterocyclic aromatic compound, a carcinogen, a mutagen, a drug, an amphetamine, a barbiturate, a hallucinogen, a waste and a pollutant. The method according to claim 1,
The spectroscopic analysis sensor can be used for surface-enhanced Raman spectroscopy (SERS), surface plasmon resonance (SPR), local surface plasmon resonance (LSPR), absorption and / or fluorescence modes Spectral analysis sensor.

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