CN110763659B - Optical fiber SPR biosensor and preparation method thereof - Google Patents
Optical fiber SPR biosensor and preparation method thereof Download PDFInfo
- Publication number
- CN110763659B CN110763659B CN201911213723.9A CN201911213723A CN110763659B CN 110763659 B CN110763659 B CN 110763659B CN 201911213723 A CN201911213723 A CN 201911213723A CN 110763659 B CN110763659 B CN 110763659B
- Authority
- CN
- China
- Prior art keywords
- optical fiber
- molybdenum disulfide
- gold film
- spr biosensor
- sensing area
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000013307 optical fiber Substances 0.000 title claims abstract description 128
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000010931 gold Substances 0.000 claims abstract description 55
- 229910052737 gold Inorganic materials 0.000 claims abstract description 55
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 52
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 50
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 48
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000011248 coating agent Substances 0.000 claims abstract description 25
- 238000000576 coating method Methods 0.000 claims abstract description 25
- SVFBTCPDFFIYMW-UHFFFAOYSA-N [Au].[Mo](=S)=S Chemical compound [Au].[Mo](=S)=S SVFBTCPDFFIYMW-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011229 interlayer Substances 0.000 claims abstract description 22
- 229960003638 dopamine Drugs 0.000 claims abstract description 13
- 238000005452 bending Methods 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- GFLJTEHFZZNCTR-UHFFFAOYSA-N 3-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OCCCOC(=O)C=C GFLJTEHFZZNCTR-UHFFFAOYSA-N 0.000 claims description 9
- 239000002135 nanosheet Substances 0.000 claims description 9
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 9
- 239000000835 fiber Substances 0.000 claims description 7
- 239000010410 layer Substances 0.000 claims description 7
- 238000000151 deposition Methods 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 6
- 229920001690 polydopamine Polymers 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000000707 layer-by-layer assembly Methods 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 241000252506 Characiformes Species 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000011247 coating layer Substances 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 230000035945 sensitivity Effects 0.000 abstract description 22
- 238000001514 detection method Methods 0.000 abstract description 19
- 239000000427 antigen Substances 0.000 abstract description 13
- 102000036639 antigens Human genes 0.000 abstract description 13
- 108091007433 antigens Proteins 0.000 abstract description 13
- 230000003287 optical effect Effects 0.000 abstract description 13
- 230000031700 light absorption Effects 0.000 abstract description 6
- 230000005684 electric field Effects 0.000 abstract description 5
- 238000005259 measurement Methods 0.000 abstract description 5
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 5
- 239000011733 molybdenum Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract 1
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 55
- 108060003951 Immunoglobulin Proteins 0.000 description 10
- 102000018358 immunoglobulin Human genes 0.000 description 10
- 238000005253 cladding Methods 0.000 description 7
- 230000008859 change Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000012491 analyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 241000283707 Capra Species 0.000 description 1
- 208000033830 Hot Flashes Diseases 0.000 description 1
- 206010060800 Hot flush Diseases 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000011076 safety test Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000009870 specific binding Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- -1 transition Metal Disulfides Chemical class 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000000411 transmission spectrum Methods 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/55—Specular reflectivity
- G01N21/552—Attenuated total reflection
- G01N21/553—Attenuated total reflection and using surface plasmons
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
- G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
- G01N33/53—Immunoassay; Biospecific binding assay; Materials therefor
- G01N33/543—Immunoassay; Biospecific binding assay; Materials therefor with an insoluble carrier for immobilising immunochemicals
- G01N33/551—Immunoassay; Biospecific binding assay; Materials therefor with an insoluble carrier for immobilising immunochemicals the carrier being inorganic
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
- G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
- G01N33/53—Immunoassay; Biospecific binding assay; Materials therefor
- G01N33/543—Immunoassay; Biospecific binding assay; Materials therefor with an insoluble carrier for immobilising immunochemicals
- G01N33/551—Immunoassay; Biospecific binding assay; Materials therefor with an insoluble carrier for immobilising immunochemicals the carrier being inorganic
- G01N33/553—Metal or metal coated
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
- G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
- G01N33/68—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing involving proteins, peptides or amino acids
- G01N33/6854—Immunoglobulins
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Immunology (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biomedical Technology (AREA)
- Physics & Mathematics (AREA)
- Hematology (AREA)
- Molecular Biology (AREA)
- Urology & Nephrology (AREA)
- General Health & Medical Sciences (AREA)
- Pathology (AREA)
- General Physics & Mathematics (AREA)
- Biochemistry (AREA)
- Analytical Chemistry (AREA)
- Microbiology (AREA)
- Cell Biology (AREA)
- Biotechnology (AREA)
- Food Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Plasma & Fusion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Proteomics, Peptides & Aminoacids (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
Abstract
The invention provides an optical fiber SPR biosensor and a preparation method thereof, wherein the sensor adopts a sensing structure based on a U-shaped optical fiber molybdenum disulfide-gold film interlayer, the middle bending part of the U-shaped optical fiber is a sensing area, the surface of the optical fiber in the sensing area is coated with a molybdenum disulfide coating, the surface of the molybdenum disulfide coating is plated with a gold film, and the surface of the gold film is fixed with an antibody through dopamine. The SPR biosensor provided by the invention adopts an optical fiber-molybdenum disulfide-gold film sandwich structure, molybdenum disulfide has a larger band gap and higher light absorption efficiency, can excite a stronger SPR effect and strengthen the surface electric field of the sensor, can effectively improve the sensitivity of the sensor, and uses a dopamine immobilized antibody on the surface of the sensor to realize the measurement of high sensitivity and low detection limit of antigens, so that the sensor has wider application in the aspect of biological detection.
Description
Technical Field
The invention relates to the technical field of biosensors, in particular to an optical fiber SPR biosensor and a preparation method thereof.
Background
In recent years, the application of Surface Plasmon Resonance (SPR) technology in various fields has raised a double study on hot flashes, such as food safety tests, environmental monitoring, medical diagnostics, bioengineering, and the like. Particularly, the application of SPR in the biosensing technology is particularly attracting extensive attention and research, and various high-performance biosensors are sequentially developed, wherein the optical fiber biosensor is favored by people because of the advantages of small volume, no labeling, high detection speed and the like. Surface plasmon resonance (surface plasma resonance, SPR) biosensors are one of the more rapidly and more comprehensively developed sensors among optical sensors, but SPR biosensors use a metal having a negative dielectric constant as an excitation element, which increases the internal loss of the sensor, thereby affecting the sensitivity and detection limit of the sensor.
After 21 st century, material science has entered a brand new rapid development stage, and many new materials have been found and have attracted great interest, some advanced and practical two-dimensional materials such as graphene, transition metal compounds (TMDCs), black phosphorus, etc. are used for improving the performance of the biosensor, so as to compensate the limitation problems of low sensitivity and high detection limit in the SPR biosensor, and accordingly, the invention provides a U-shaped optical fiber-based molybdenum disulfide-gold film interlayer optical fiber SPR biosensor and a preparation method thereof.
Disclosure of Invention
In order to solve the problems of low sensitivity and high detection limit of the existing optical fiber SPR biosensor, the invention provides an optical fiber SPR biosensor and a preparation method thereof.
The invention provides an optical fiber SPR biosensor, which adopts a sensing structure based on a molybdenum disulfide-gold film interlayer of a U-shaped optical fiber, wherein the middle bending part of the U-shaped optical fiber is a sensing area, the surface of the optical fiber in the sensing area is coated with a molybdenum disulfide coating, the surface of the molybdenum disulfide coating is plated with a gold film, and the surface of the gold film is fixed with an antibody through dopamine.
Further, the molybdenum disulfide coating is coated on the surface of the optical fiber by an electrostatic self-assembly method.
Further, the length of the sensor optical fiber is 30-40 cm, and the length of the sensing area is 20-30 mm.
Further, the thickness of the molybdenum disulfide coating is 0.65-13 nm.
Further, the thickness of the gold film layer is 40-55 nm.
Preferably, the total thickness of the molybdenum disulfide-gold film interlayer is 60nm.
Further preferably, the molybdenum disulfide coating is 10nm, and the thickness of the gold film layer is 50nm.
In another aspect, the present invention provides a method for preparing the optical fiber SPR biosensor, which comprises the following steps:
(a) Pretreatment of optical fibers: taking a multimode optical fiber with a length of 30 cm-40 cm, taking down a coating layer with a length of 20-30 mm in the middle of the optical fiber, removing impurities attached to the surface of the optical fiber in a sensing area to form the sensing area, bending the optical fiber to form a U shape, and heating the bending part by using an alcohol lamp outer flame to fix the shape;
(b) Preparing a molybdenum disulfide coating: soaking the U-shaped optical fiber bent part in a piranha solution for 0.5-1.5 hours, taking out, soaking in a PDDA aqueous solution of 10mg/ml-1g/ml for 0.5-1.5 hours, and then soaking in a molybdenum disulfide nanosheet water or ethanol dispersion of 0.1 mg/ml-200 mg/ml for 3-12 hours; the PDDA solution is used as a connecting medium between the optical fiber and the molybdenum disulfide, the PDDA is positively charged, the molybdenum disulfide nanosheets are negatively charged, and the molybdenum disulfide is fixed on the surface of the optical fiber by an electrostatic adsorption method;
(c) Deposition of a gold film layer: depositing a gold film by using a magnetron sputtering instrument, wherein the discharge time is 1.5-5 min, the current is 0-10 mA, and controlling the thickness of the gold film by adjusting the discharge time and the current;
(d) Immobilization of antibodies: immersing the U-shaped optical fiber bending part in 1 mg/ml-100 mg/ml dopamine solution for half an hour, carrying out polymerization reaction on dopamine in water to form polydopamine on the gold film surface of a sensing area, taking out, drying in a constant temperature oven at 60 ℃ for half an hour, and immersing the sensing area of the sensor in 0.01 mg/ml-1 mg/ml antibody solution for 12 hours; the polydopamine is used as a connecting medium for the gold membrane and the immobilized antibody, and the antibody is immobilized on the surface of the gold membrane.
The principle of the invention is as follows:
transition Metal Disulfides (TMDC), like graphene, belong to two-dimensional nanomaterials, molybdenum disulfide and tungsten disulfide belong to TMDC, molybdenum disulfide has a larger band gap and higher light absorption efficiency than graphene, and they also have a high specific surface area and good biocompatibility, which makes it possible to introduce transition metal dichalcogenides into SPR sensors, which can better improve the sensitivity of the sensors.
The molybdenum disulfide-gold film interlayer optical fiber SPR biosensor based on the U-shaped optical fiber has higher sensitivity, and the molybdenum disulfide has a large band gap and higher light absorption efficiency, so that the surface electric field can be further enhanced to improve the sensitivity; the specific combination between the antibody and the antigen causes resonance wavelength drift, the high-sensitivity measurement of the antigen is realized according to the ratio of the concentration of the biological analyte to the movement of the resonance wavelength, and the measurement of the minimum detection limit is realized by calculating the limit detection efficacy index LOD, so that the sensor has better application in the field of biological detection.
The sensor coated with the molybdenum disulfide nanosheets between the gold film and the optical fiber has better sensitivity performance than the sensor coated with the molybdenum disulfide nanosheets on the surface of the gold film, and most of light in a cladding mode disappears in surrounding media because light conducted in the cladding does not meet the condition of total reflection due to the fact that the optical fiber is bent and light conducted in the fiber core leaks into the cladding. In a U-shaped fiber SPR sensing system, a portion of the light energy generated by the disappearance of cladding modes is used to excite the SPR phenomenon, while the remaining losses are in the surrounding medium. When only a gold film exists on the surface of the optical fiber, the light energy absorbed by the gold film is insufficient to support the strong excitation of SPR phenomenon. When molybdenum disulfide nanosheets are added between the fibers and the gold film, moS is due to the high light absorption (5%) of molybdenum disulfide 2 The presence of (2) may effectively increase the absorption of light energy, thereby facilitating stronger excitation of SPR phenomena. At the same time due to single-layer MoS 2 Is a direct band gap semiconductor, the absorbed energy is used for electron transfer, and the energy loss in the transfer process is small. More electrons are transferred from the molybdenum disulfide to the gold film, thereby increasing the surface electric field strength of the sensor. The coating of a layer of molybdenum disulfide on the surface of the gold film of the sensor only increasesThe utilization of the light energy absorbed by the sensor system is added. However, on the basis of the molybdenum disulfide coating between the gold film and the optical fiber, the utilization rate of the absorbed optical energy is improved, and the absorptivity of the optical energy is improved.
Compared with the prior art, the invention has the beneficial effects that:
1. the molybdenum disulfide-gold film interlayer optical fiber SPR biosensor based on the U-shaped optical fiber has higher sensitivity through the molybdenum disulfide-gold film interlayer structure;
2. the functional sensor for detecting human IgG by using the dopamine immobilized antibody on the surface of the sensor has excellent biological sensing characteristics, and can better reduce the detection limit; different kinds of antigens can be fixed by using dopamine, so that detection of different antibodies is realized;
3. the interlayer mechanism is adopted, so that the molybdenum disulfide in the sensor structure can not fall off while the sensitivity is enhanced, and the stability of the sensor structure is enhanced;
in summary, the invention solves the problems of lower sensitivity and higher detection limit of the existing optical fiber SPR biosensor, and provides a new solution for detecting low-concentration biological analytes.
Drawings
FIG. 1 is a schematic diagram of a structure of a molybdenum disulfide-gold film interlayer optical fiber SPR biosensor based on a U-shaped optical fiber in embodiment 1 of the present invention;
FIG. 2 is a schematic diagram of a structure of a molybdenum disulfide-gold film interlayer optical fiber SPR biosensor system based on a U-shaped optical fiber in embodiment 1 of the present invention;
FIG. 3 is a schematic diagram of a U-shaped optical fiber-based gold film optical fiber SPR biosensor in example 1 of the present invention;
FIG. 4 is a schematic diagram of the structure of an optical fiber SPR biosensor based on gold film molybdenum disulfide of U-shaped optical fiber in example 1 of the present invention;
FIG. 5 is a transmission spectrum diagram of a molybdenum disulfide-gold film interlayer optical fiber SPR biosensor based on a U-shaped optical fiber in the embodiment 1 of the invention in ethanol solutions with different refractive indexes;
FIG. 6 is a graph showing a fitted refractive index sensitivity curve of a U-shaped optical fiber-based molybdenum disulfide-gold film interlayer optical fiber SPR biosensor in example 1 of the present invention;
FIG. 7 shows the change of resonance wavelength with time in different concentrations of igG solutions of the U-shaped optical fiber-based molybdenum disulfide-gold film interlayer optical fiber SPR biosensor in example 1 of the present invention;
FIG. 8 shows the change of the shift amount of resonance wavelength of the U-shaped optical fiber-based molybdenum disulfide-gold film interlayer optical fiber SPR biosensor according to the embodiment 1 of the present invention with the concentration of igG solution;
FIG. 9 is a linear fitting curve of the shift amount of resonance wavelength of the U-shaped optical fiber-based molybdenum disulfide-gold film interlayer optical fiber SPR biosensor in the embodiment 1 of the present invention in the range of igG concentration of 5-20 μg/ml;
reference numerals:
1. a multimode optical fiber core; 2. an optical fiber cladding; 3. a molybdenum disulfide coating; 4. gold film; 5. antibody-sheep anti-human immunoglobulin;
A. molybdenum disulfide-gold film interlayer optical fiber SPR biosensor of U-shaped optical fiber; B. a broadband light source; C. a spectrometer; D. a multimode optical fiber path; E. a computer; F. a beaker;
Detailed Description
It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other. The invention will be described in detail below with reference to the drawings in connection with embodiments.
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. The following description of at least one exemplary embodiment is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present invention. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
The relative arrangement of the components and steps, numerical expressions and numerical values set forth in these embodiments do not limit the scope of the present invention unless it is specifically stated otherwise. Meanwhile, it should be clear that the dimensions of the respective parts shown in the drawings are not drawn in actual scale for convenience of description. Techniques, methods, and apparatus known to those of ordinary skill in the relevant art may not be discussed in detail, but are intended to be part of the specification where appropriate. In all examples shown and discussed herein, any specific values should be construed as merely illustrative, and not a limitation. Thus, other examples of the exemplary embodiments may have different values. It should be noted that: like reference numerals and letters denote like items in the following figures, and thus once an item is defined in one figure, no further discussion thereof is necessary in subsequent figures.
In the description of the present invention, it should be understood that the azimuth or positional relationships indicated by the azimuth terms such as "front, rear, upper, lower, left, right", "lateral, vertical, horizontal", and "top, bottom", etc., are generally based on the azimuth or positional relationships shown in the drawings, merely to facilitate description of the present invention and simplify the description, and these azimuth terms do not indicate and imply that the apparatus or elements referred to must have a specific azimuth or be constructed and operated in a specific azimuth, and thus should not be construed as limiting the scope of protection of the present invention: the orientation word "inner and outer" refers to inner and outer relative to the contour of the respective component itself.
Spatially relative terms, such as "above … …," "above … …," "upper surface at … …," "above," and the like, may be used herein for ease of description to describe one device or feature's spatial location relative to another device or feature as illustrated in the figures. It will be understood that the spatially relative terms are intended to encompass different orientations in use or operation in addition to the orientation depicted in the figures. For example, if the device in the figures is turned over, elements described as "above" or "over" other devices or structures would then be oriented "below" or "beneath" the other devices or structures. Thus, the exemplary term "above … …" may include both orientations of "above … …" and "below … …". The device may also be positioned in other different ways (rotated 90 degrees or at other orientations) and the spatially relative descriptors used herein interpreted accordingly.
In addition, the terms "first", "second", etc. are used to define the components, and are only for convenience of distinguishing the corresponding components, and the terms have no special meaning unless otherwise stated, and therefore should not be construed as limiting the scope of the present invention.
Example 1
In this embodiment, a U-shaped optical fiber-based molybdenum disulfide-gold film interlayer optical fiber SPR biosensor for detecting human immunoglobulin IgG is prepared, i.e., the antigen to be detected is human immunoglobulin IgG, and the detected antibody is goat anti-human immunoglobulin.
As shown in figure 1, the optical fiber SPR biosensor adopts a sensing structure based on a U-shaped optical fiber molybdenum disulfide-gold film interlayer, the optical fiber SPR biosensor comprises a U-shaped multimode optical fiber with the length of 30-40 cm, the middle bending part of the U-shaped multimode optical fiber is a sensing area, the length of the sensing area is 20-30 mm, a molybdenum disulfide coating 3 is fixed on the optical fiber surface of the sensing area through electrostatic self-assembly, the thickness of the molybdenum disulfide coating is 0.65-13 nm, a gold film 4 is fixed on the surface of the molybdenum disulfide coating, the thickness of the gold film is 40-55 nm, an antibody-goat anti-human immunoglobulin 5 film is solidified on the gold film surface through dopamine, an antigen to be detected is human immunoglobulin, and the antibody-goat anti-human immunoglobulin is combined with the antigen-human immunoglobulin 6 in the detection process, so that the antigen-human immunoglobulin is fixed on the antibody-goat anti-human immunoglobulin film.
The sensing system formed by the molybdenum disulfide-gold film interlayer optical fiber SPR biosensor based on the U-shaped optical fiber is shown in fig. 2, and comprises an optical fiber SPR biosensor A, wherein the system takes multimode optical fibers as optical paths, namely multimode optical fibers as optical paths D, the input end of the optical fiber SPR biosensor A is connected with a broadband light source B with a spectrum of visible light wave band, the output end of the optical fiber SPR biosensor A is connected with a broadband spectrometer C, the broadband spectrometer C is connected with a computer E through a data interface, the optical fiber SPR biosensor A is arranged in a container to be detected, the container to be detected is a beaker F in the embodiment, and the optical fiber SPR biosensor A is arranged in a solution to be detected.
The preparation method of the optical fiber SPR biosensor comprises the following steps:
(a) Pretreatment of optical fibers: taking a 35cm multimode optical fiber, taking down a coating layer 25mm long in the middle of the optical fiber, removing impurities attached to the surface of the optical fiber in a sensing area to form a sensing area, bending the optical fiber to form a U shape, heating a bending part by using an alcohol lamp flame to fix the shape, and checking the curvature radius of the U-shaped optical fiber by controlling the curvature;
(b) Preparing a molybdenum disulfide coating: soaking the U-shaped optical fiber bent part in a piranha solution (mixed solution of concentrated sulfuric acid with the mass fraction of 95-98% and hydrogen peroxide with the mass fraction of 30% in a volume ratio of 7:3) for 1 hour, taking out, soaking in 100mg/ml PDDA aqueous solution for 1 hour, and then soaking in 0.1mg/ml molybdenum disulfide nanosheet absolute ethyl alcohol dispersion for 3 hours; the PDDA solution is used as a connecting medium between the optical fiber and the molybdenum disulfide, the PDDA is positively charged, the molybdenum disulfide nanosheets are negatively charged, the molybdenum disulfide is fixed on the surface of the optical fiber by an electrostatic adsorption method, and the thickness of a molybdenum disulfide coating is 10nm;
(c) Deposition of a gold film layer: depositing a gold film by using a magnetron sputtering instrument, and controlling the thickness of the gold film to be 50nm by adjusting the discharge time to be 3 minutes and the current to be 7 mA;
(d) Immobilization of antibodies: immersing the U-shaped optical fiber bending part in 5mg/ml dopamine solution (tris buffer solution with 2% of solvent) for half an hour, carrying out polymerization reaction on dopamine in water to form polydopamine on the gold film surface of a sensing area, taking out, drying in a constant temperature oven at 60 ℃ for half an hour, and immersing the sensing area of the sensor in 0.1mg/ml antibody solution for 12 hours; the polydopamine is used as a connecting medium of the gold membrane and the immobilized antibody, and the antibody is immobilized on the surface of the gold membrane;
(f) Detection of antigens
At the temperature of 25 ℃, immersing the SPR biosensor with the U-shaped optical fiber-molybdenum disulfide-gold film sandwich structure in an IgG solution, and realizing detection of the antigen according to resonance wavelength shift caused by specific binding between the antibody and the antigen, and simultaneously obtaining wavelength shift caused by specific adsorption between the actual antigen and the antibody according to the wavelength shift.
The refractive index sensing characteristic test of the SPR biosensor based on the U-shaped optical fiber-molybdenum disulfide-gold film sandwich structure, the gold film optical fiber SPR biosensor based on the U-shaped optical fiber and the gold film molybdenum disulfide optical fiber SPR biosensor based on the U-shaped optical fiber is carried out:
the gold film optical fiber SPR biosensor of the U-shaped optical fiber is shown in figure 3, multimode optical fiber is adopted, and the surface of the outer cladding 2 of the U-shaped multimode optical fiber core 1 is plated with a gold film 4 with the thickness of 50nm; as shown in figure 4, the optical fiber SPR biosensor of U-shaped optical fiber-gold film-molybdenum disulfide adopts multimode optical fiber, and the surface of the outer cladding 2 of the U-shaped multimode optical fiber core 1 is sequentially coated with a gold film 4 and a molybdenum disulfide coating 3 from inside to outside.
In order to study the refractive index sensing performance of the sensor after the molybdenum disulfide coating and the gold-plated film are sequentially fixed on the surface of the multimode optical fiber from inside to outside, the sensor is connected into a sensing system taking the multimode optical fiber as a light path, a deuterium-halogen lamp with the wavelength range of 215nm to 2500nm is used as a light source at the input end, a marine optical spectrometer is used for detecting resonance spectrum, then the sensor is respectively immersed into ethanol solution with the refractive index ranging from 1.3314 to 1.3623, the resonance spectrum is shown in figure 5, and the resonance wavelength shifts rightwards along with the increase of the refractive index. The sensitivity of the sensor can be expressed as the shift Δλ of the resonance peak p Change delta n of refractive index from sample to be measured a Ratio of (2), namely:
the refractive index sensitivity of the gold film optical fiber SPR biosensor of the U-shaped optical fiber is 3887.6nm/RIU through detection; the refractive index sensitivity of the optical fiber SPR biosensor of the U-shaped optical fiber-gold film-molybdenum disulfide is 4946.8nm/RIU; the optical fiber SPR biosensor is based on a U-shaped optical fiber-molybdenum disulfide-gold film sandwich structure, a refractive index sensitivity fitting curve of the optical fiber SPR biosensor is shown in figure 6, and the refractive index sensitivity of the optical fiber SPR biosensor is 6184.4nm/RIU according to the slope of the fitting curve.
The optical fiber SPR biosensor is based on a U-shaped optical fiber-molybdenum disulfide-gold film sandwich structure, wherein the change of resonance wavelength in IgG solutions with different concentrations with time is shown in figure 7, the change of resonance wavelength shift quantity with the concentration of the IgG solution is shown in figure 8, and a linear fitting curve of the resonance wavelength shift quantity within the range of 5-20 mug/ml of the IgG concentration is shown in figure 9.
Obviously, the sensitivity of the molybdenum disulfide-gold film interlayer optical fiber SPR biosensor based on the U-shaped optical fiber is higher than that of a general sensor.
The invention mainly utilizes the molybdenum disulfide-gold film sandwich structure to enhance the surface electric field intensity so as to improve the detection sensitivity of the sensor. The method is characterized in that a molybdenum disulfide coating is fixed on the surface of a multimode optical fiber through an electrostatic self-assembly method, the absorption of light energy is promoted by utilizing molybdenum disulfide, the surface electric field is enhanced to improve the sensitivity, the detection limit can be better reduced by using a dopamine-fixed antibody to detect an antigen, the specific combination between the antibody and the antigen causes resonance wavelength drift, the measurement of high sensitivity of the antigen is realized according to the ratio of the concentration of a biological analyte to the movement of the resonance wavelength, and the measurement of the minimum detection limit is realized through the calculation of a limit inspection efficacy index LOD.
The technical scheme of the invention is explained in the technical scheme, the protection scope of the invention cannot be limited by the technical scheme, and any changes and modifications to the technical scheme according to the technical substance of the invention belong to the protection scope of the technical scheme of the invention.
Claims (7)
1. The optical fiber SPR biosensor is characterized in that the sensor adopts a sensing structure based on a molybdenum disulfide-gold film interlayer of a U-shaped optical fiber, the middle bending part of the U-shaped optical fiber is a sensing area, the surface of the optical fiber in the sensing area is coated with a molybdenum disulfide coating, the surface of the molybdenum disulfide coating is plated with a gold film, and the surface of the gold film is fixed with an antibody through dopamine;
the preparation method comprises the following steps:
(a) Pretreatment of optical fibers: taking a multimode fiber with a length of 30 cm-40 cm, taking down a coating layer with a length of 20-30 mm in the middle of the fiber, removing impurities attached to the surface of the fiber in a sensing area to form the sensing area, bending the fiber to form a U shape, and heating the bent part by using an alcohol lamp outer flame to fix the shape;
(b) Preparing a molybdenum disulfide coating: soaking the U-shaped optical fiber bent part in a piranha solution for 0.5-1.5 hours, taking out, soaking in a PDDA aqueous solution of 10mg/ml-1g/ml for 0.5-1.5 hours, and then soaking in a molybdenum disulfide nanosheet water or ethanol dispersion of 0.1 mg/ml-200 mg/ml for 3-12 hours; the PDDA solution is used as a connecting medium between the optical fiber and the molybdenum disulfide, the PDDA is positively charged, the molybdenum disulfide nanosheets are negatively charged, and the molybdenum disulfide is fixed on the surface of the optical fiber by an electrostatic adsorption method;
(c) Deposition of a gold film layer: depositing a gold film by using a magnetron sputtering instrument, wherein the discharge time is 1.5-5 min, the current is 0-10 mA, and controlling the thickness of the gold film by adjusting the discharge time and the current;
(d) Immobilization of antibodies: immersing the U-shaped optical fiber bending part in 1 mg/ml-100 mg/ml dopamine solution for half an hour, carrying out polymerization reaction on dopamine in water to form polydopamine on the surface of a gold film of a sensing area, taking out, drying in a constant temperature box at 60 ℃ for half an hour, and immersing the sensing area of the sensor in 0.01 mg/ml-1 mg/ml antibody solution for 12 hours; the polydopamine is used as a connecting medium for the gold membrane and the immobilized antibody, and the antibody is immobilized on the surface of the gold membrane.
2. The optical fiber SPR biosensor as claimed in claim 1, wherein the molybdenum disulfide coating is coated on the surface of the optical fiber by an electrostatic self-assembly method.
3. The optical fiber SPR biosensor according to claim 1, wherein the length of the sensor optical fiber is 30-40 cm, and the length of the sensing area is 20-30 mm.
4. The optical fiber SPR biosensor according to claim 1, wherein the molybdenum disulfide coating has a thickness of 0.65-13 nm.
5. The optical fiber SPR biosensor according to claim 1, wherein the gold film layer has a thickness of 40-55 nm.
6. The optical fiber SPR biosensor as claimed in claim 1, wherein the total thickness of the molybdenum disulfide-gold film interlayer is 60nm.
7. The optical fiber SPR biosensor as claimed in claim 1, wherein the molybdenum disulfide coating is 10nm and the gold film is 50nm thick.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911213723.9A CN110763659B (en) | 2019-12-02 | 2019-12-02 | Optical fiber SPR biosensor and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911213723.9A CN110763659B (en) | 2019-12-02 | 2019-12-02 | Optical fiber SPR biosensor and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110763659A CN110763659A (en) | 2020-02-07 |
| CN110763659B true CN110763659B (en) | 2024-04-09 |
Family
ID=69340769
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911213723.9A Active CN110763659B (en) | 2019-12-02 | 2019-12-02 | Optical fiber SPR biosensor and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110763659B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111744566A (en) * | 2020-06-30 | 2020-10-09 | 吉林大学 | Biochip, preparation method, application and kit thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105067824A (en) * | 2015-07-21 | 2015-11-18 | 天津大学 | Polydopamine-modification-based method for binding anti-bodies to surface of optical fiber SPR sensor |
| CN106680243A (en) * | 2016-12-07 | 2017-05-17 | 山东师范大学 | Large-area molybdenum disulfide-based fiber sensing probe and preparation method thereof |
| CN106896087A (en) * | 2017-03-31 | 2017-06-27 | 丁利 | The preparation method of the surface plasma resonance instrument chip based on hyperbranched amphion polymethyl base cysteine modified |
| CN106896066A (en) * | 2017-02-28 | 2017-06-27 | 武汉理工大学 | Optical fiber surface plasmon resonance body immune sensing probe and preparation method thereof |
| CN107356561A (en) * | 2017-06-29 | 2017-11-17 | 暨南大学 | Surface plasma resonance sensor of tungsten disulfide enhanced sensitivity and preparation method thereof |
| CN107402187A (en) * | 2017-07-27 | 2017-11-28 | 山东师范大学 | A kind of optical evanescent wave sensor device and preparation method thereof |
| CN109085140A (en) * | 2018-08-22 | 2018-12-25 | 东北大学 | A kind of high sensitivity optical fiber surface plasmon resonance biosensor |
| CN109596574A (en) * | 2018-12-26 | 2019-04-09 | 暨南大学 | A kind of surface plasma resonance sensor and preparation method thereof of molybdenum disulfide enhanced sensitivity |
| CN109655515A (en) * | 2018-11-13 | 2019-04-19 | 天津大学 | A kind of optical fiber surface plasmon resonance sensor of nano composite structure modification |
| CN110132322A (en) * | 2019-04-08 | 2019-08-16 | 东莞理工学院 | A kind of ultraviolet irradiation enhanced fiber sensor and preparation method thereof |
| CN211478067U (en) * | 2019-12-02 | 2020-09-11 | 东北大学 | Optical fiber SPR biosensor |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8476007B2 (en) * | 2010-02-19 | 2013-07-02 | Indian Institute Of Technology Bombay | Optical fiber probe |
| WO2012125693A2 (en) * | 2011-03-15 | 2012-09-20 | Northwestern University | Multifunctional metal nanoparticles having a polydopamine-based surface and methods of making and using the same |
-
2019
- 2019-12-02 CN CN201911213723.9A patent/CN110763659B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105067824A (en) * | 2015-07-21 | 2015-11-18 | 天津大学 | Polydopamine-modification-based method for binding anti-bodies to surface of optical fiber SPR sensor |
| CN106680243A (en) * | 2016-12-07 | 2017-05-17 | 山东师范大学 | Large-area molybdenum disulfide-based fiber sensing probe and preparation method thereof |
| CN106896066A (en) * | 2017-02-28 | 2017-06-27 | 武汉理工大学 | Optical fiber surface plasmon resonance body immune sensing probe and preparation method thereof |
| CN106896087A (en) * | 2017-03-31 | 2017-06-27 | 丁利 | The preparation method of the surface plasma resonance instrument chip based on hyperbranched amphion polymethyl base cysteine modified |
| CN107356561A (en) * | 2017-06-29 | 2017-11-17 | 暨南大学 | Surface plasma resonance sensor of tungsten disulfide enhanced sensitivity and preparation method thereof |
| CN107402187A (en) * | 2017-07-27 | 2017-11-28 | 山东师范大学 | A kind of optical evanescent wave sensor device and preparation method thereof |
| CN109085140A (en) * | 2018-08-22 | 2018-12-25 | 东北大学 | A kind of high sensitivity optical fiber surface plasmon resonance biosensor |
| CN109655515A (en) * | 2018-11-13 | 2019-04-19 | 天津大学 | A kind of optical fiber surface plasmon resonance sensor of nano composite structure modification |
| CN109596574A (en) * | 2018-12-26 | 2019-04-09 | 暨南大学 | A kind of surface plasma resonance sensor and preparation method thereof of molybdenum disulfide enhanced sensitivity |
| CN110132322A (en) * | 2019-04-08 | 2019-08-16 | 东莞理工学院 | A kind of ultraviolet irradiation enhanced fiber sensor and preparation method thereof |
| CN211478067U (en) * | 2019-12-02 | 2020-09-11 | 东北大学 | Optical fiber SPR biosensor |
Non-Patent Citations (1)
| Title |
|---|
| Rapid detection of Escherichia coli using fiber optic surface plasmon resonance immunosensor based on biofunctionalized Molybdenum disulfide (MoS2) nanosheets;Siddharth Kaushik等;OPTICS, PHOTONICS AND LASERS;第126卷;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110763659A (en) | 2020-02-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Niu et al. | Sensitivity enhanced D-type large-core fiber SPR sensor based on Gold nanoparticle/Au film co-modification | |
| Chauhan et al. | Review on recent experimental SPR/LSPR based fiber optic analyte sensors | |
| Wang et al. | Research advances on surface plasmon resonance biosensors | |
| Liu et al. | Plasmonic sensor based on offset-splicing and waist-expanded taper using multicore fiber for detection of Aflatoxins B1 in critical sectors | |
| Kaushik et al. | Two-dimensional transition metal dichalcogenides assisted biofunctionalized optical fiber SPR biosensor for efficient and rapid detection of bovine serum albumin | |
| Yang et al. | Development of glucose sensor using gold nanoparticles and glucose-oxidase functionalized tapered fiber structure | |
| CN208752007U (en) | A kind of high sensitivity optical fiber surface plasmon resonance biosensor | |
| US8703505B2 (en) | Optical fiber probe | |
| Sai et al. | Label-free fiber optic biosensor based on evanescent wave absorbance at 280 nm | |
| Xia et al. | Ultra-high sensitivity SPR fiber sensor based on multilayer nanoparticle and Au film coupling enhancement | |
| CN208705231U (en) | Optical fiber SPR sensor based on graphene oxide and gold nanorods enhanced sensitivity | |
| Jang et al. | Optical fiber SPR biosensor with sandwich assay for the detection of prostate specific antigen | |
| Liu et al. | Specialty optical fibers and 2D materials for sensitivity enhancement of fiber optic SPR sensors: A review | |
| CN109060727B (en) | Dual-channel optical fiber SPR biosensor | |
| Shrivastav et al. | Ion-imprinted nanoparticles for the concurrent estimation of Pb (II) and Cu (II) ions over a two channel surface plasmon resonance-based fiber optic platform | |
| Srivastava et al. | Surface plasmon resonance based fiber optic glucose biosensor | |
| Chen et al. | Self-referencing SPR biosensing with an ultralow limit-of-detection using long-wavelength excitation | |
| CN110763659B (en) | Optical fiber SPR biosensor and preparation method thereof | |
| Jamil et al. | Urea biosensor utilizing graphene-MoS 2 and Kretschmann-based SPR | |
| CN103472237A (en) | Bio-sensitive chip as well as preparation method and use thereof | |
| CN211478067U (en) | Optical fiber SPR biosensor | |
| Fu et al. | Signal-enhanced multi-core fiber-based WaveFlex biosensor for ultra-sensitive xanthine detection | |
| Wang et al. | 3D fiber-probe surface plasmon resonance microsensor towards small volume sensing | |
| Gupta et al. | Recent advances in molecular imprinting technique based fiber optic biosensors | |
| Phuong et al. | Application of hybrid Au@ Ag nanostructures in fiber optic biosensor for rapid detection of C-reactive protein |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |