CN110823843A - Broadband interference type optode biomolecule sensor of graphene oxide fiber grating - Google Patents
Broadband interference type optode biomolecule sensor of graphene oxide fiber grating Download PDFInfo
- Publication number
- CN110823843A CN110823843A CN201911007889.5A CN201911007889A CN110823843A CN 110823843 A CN110823843 A CN 110823843A CN 201911007889 A CN201911007889 A CN 201911007889A CN 110823843 A CN110823843 A CN 110823843A
- Authority
- CN
- China
- Prior art keywords
- fiber
- grating
- graphene oxide
- fiber grating
- angle inclined
- 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.)
- Pending
Links
Images
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
- G01N21/59—Transmissivity
-
- 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
- G01N21/21—Polarisation-affecting properties
- G01N21/23—Bi-refringence
-
- 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
- G01N21/59—Transmissivity
- G01N2021/5903—Transmissivity using surface plasmon resonance [SPR], e.g. extraordinary optical transmission [EOT]
Abstract
The invention relates to a photoelectrode biomolecule sensor, in particular to a broadband interference type photoelectrode biomolecule sensor of a graphene oxide fiber grating and a method thereof, wherein the broadband interference type photoelectrode biomolecule sensor comprises a fiber core, a fiber cladding and a fiber coating layer, wherein the middle section of the fiber core is provided with a large-angle inclined fiber grating, the coating layers of the middle section and the rear section of the fiber are completely removed, the end surface of the tail end of the fiber rear section is plated with a silver reflecting film, and the distance from the rear end of the large-angle inclined fiber grating to the silver reflecting film at the tail end of the fiber is 30-60 mm to form a fiber micro Michelson interference cavity; inclining the starting end of the fiber bragg grating at a large angle until the surface of a cladding layer at the tail end of the optical fiber is provided with a silane layer, a nanogold shell particle layer, a graphene oxide layer and a biomolecule sensitive layer; the structure of the optode biomolecule sensor adopting the scheme of the invention can increase the action distance between LSPR excited by a light wave evanescent field and biomolecules, is convenient for integration and application, has very high robustness, and can be applied to the fields of biomedicine, life science, environmental monitoring and the like.
Description
Technical Field
The invention relates to an optode biomolecule sensor, in particular to a broadband interference optode biomolecule sensor and a broadband interference optode biomolecule sensor method of a graphene oxide fiber grating.
Background
Graphene has the excellent characteristics of large specific surface area, high electron mobility, high conductivity, biomolecule affinity and the like, and an oxide of graphene oxide contains rich oxygen-containing functional groups such as carboxyl, hydroxyl and the like, so that covalent or non-covalent connection with biomolecules is facilitated. Therefore, two-dimensional materials such as graphene and graphene oxide are combined with conventional electrochemical, piezoelectric and optical sensors, such as: the surface plasma resonance sensor, various types of optical fiber sensors, and the biochemical sensing technology formed by combining the sensors are widely researched.
In the field of biochemical detection, a Surface Plasmon Resonance (SPR) sensor is an optical sensor that is very sensitive to Refractive Index (RI) of an external medium. Various nano gold particles (such as gold nanospheres, star-shaped gold nanoparticles, gold nanorods, gold nanocages, gold nanoshells and the like) are used for replacing gold films to form Local SPR effect (LSPR for short), and due to the Local field enhancement effect of the LSPR, the sensitivity in the aspect of biochemical detection can be further enhanced. At present, most of the commercially available LSPR sensors are based on a Kretschmann prism coupling structure for angle detection, as shown in fig. 1, but such LSPR sensors have large volume, long scanning time and high price. Because the optical fiber has the advantages of corrosion resistance, electromagnetic interference resistance, small volume, remote sensing and the like, various optical fiber materials and devices can be used as an excitation platform to realize the miniaturization of the LSPR sensor, such as: LSPR sensors based on multimode silica (or polymer material) fibers, heterocore structured fibers or photonic crystal fibers, etc., all of which are of the type of pure fiber type LSPR sensors, but most of them have a major problem: the resonance bandwidth of the LSPR peak is typically between a few tens of nanometers to a hundred nanometers, and thus the quality factor (i.e., Q value) of the sensor is low.
Therefore, to overcome the problem of low quality factor (i.e., Q value) of the pure fiber LSPR sensor, in recent years, fiber grating-based LSPR sensors have been proposed, which mainly include three types: sensors based on Long Period Fiber Gratings (LPFG), optical Fiber Bragg Gratings (FBG) with the cladding removed, small angle (<11 °) Tilted Fiber Bragg Gratings (TFBG). The LPFG is a transmission type grating, has too high cross sensitivity of temperature and strain, and is not strong in practicability; the mechanical property of removed cladding FBG is reduced, small-angle TFBG has a plurality of dense cladding modes with narrow line width in near infrared band (1200 nm-1700 nm), so that LSPR effect can be easily excited by fixing nano gold particles on the surface of TFBG without complex design, but RI sensitivity of small-angle TFBG-LSPR sensor is far lower than that of traditional multimode fiber SPR sensor, and the narrow-line-width cladding modes in loss spectrum are too dense and numerous as shown in figure 2, so that accurate positioning of LSPR peak is inconvenient in practical application.
Currently, with the development of the above subjects including graphene materials, fiber grating sensing technology, LSPR sensing technology, etc., the integration of the respective advantages of graphene (graphene oxide), fiber grating sensing technology, and LSPR sensing technology is one of the important technical trends for manufacturing fiber grating LSPR biomolecular sensors with high performance, strong practicability, and strong stability.
However, a common problem in combining the above existing fiber LSPR techniques is: 1) most of the devices adopt a mode of detecting transmission spectrum, and a light source and a spectrum analyzer are respectively arranged at two ends of a sensor, so that the device is inconvenient to integrate and use; 2) the binding ability of the gold nanoparticles to biomolecules is relatively weak (about 1 pg/mm)2) The detection range of the biochemical sensor is smaller; 3) the traditional optical fiber SPR/LSPR sensor detects the quantity of target biomolecules based on the resonance wavelength shift or the change principle of resonance absorption power of SPR/LSPR, and real-time monitoring of the reaction (combination) kinetic process of a biomolecule sensitive layer on the surface of an optical fiber and the biomolecules is difficult. This is because the biomolecule reaction (binding) process is a slow variable, the resonance wavelength shift or the change of the resonance absorption power caused in a short period of time is very weak, while the resolution (1pm) of the existing spectrometer cannot achieve such a fine resonance wavelength change or a weak fluctuation of the light source intensityThe signal noise will overwhelm the change in the resonant absorbed power of the LSPR. Other personality issues are: 1) the LSPR spectrum excited by the LSPR sensor based on the pure fiber type is in a certain wavelength range of 500 nm-900 nm, and the bandwidth is general>50nm, as shown in fig. 3, the pure fiber type LSPR sensor is a schematic diagram of the increase of the molecular concentration of the substance to be measured, so the Q value of the sensor is very low, and most of the sensors need to corrode or grind the fiber cladding to excite the LSPR, thereby reducing the mechanical strength and robustness of the sensor; 2) the cladding modes of the small-angle TFBG-LSPR sensor in the resonance spectrum envelope of a communication waveband (1500 nm-1600 nm) are too dense and numerous, and the accurate positioning of the LSPR peak is inconvenient in practical application.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a broadband interference type optode biomolecule sensor of a graphene oxide fiber grating and a method thereof, so as to solve the problems of the existing fiber SPR/LSPR biosensor.
The broadband interference type optode biomolecule sensor of the graphene oxide fiber grating comprises a fiber core, a fiber cladding and a fiber coating layer, wherein the middle section of the fiber core is provided with a large-angle inclined fiber grating, the coating layers of the middle section and the rear section of the fiber are completely removed, the end face of the tail end of the fiber rear section is plated with a silver reflecting film, the distance from the rear end of the large-angle inclined fiber grating to the silver reflecting film at the tail end of the fiber is 30-60 mm, and a fiber micro Michelson interference cavity is formed; a silane layer is arranged on the surface of a cladding layer from the starting end of the large-angle inclined fiber bragg grating to the tail end of the optical fiber, nano-gold shell particles are fixed on the surface of the silane layer, a graphene oxide layer is adsorbed on the surface of the nano-gold shell particle layer, and a biomolecule sensitive layer is fixed on the surface of the graphene oxide layer; the inclination angle of the large-angle inclined fiber grating is between 60 and 85 degrees, and the grating period is between 25 and 40 mu m; the size of the outer diameter of the shell of the nano gold shell particle is 155 nm-200 nm so as to ensure that the LSPR absorption spectrum covers 500 nm-1600 nm.
The invention further aims to provide a sensing method of nano gold shell LSPR optode biomolecules of a graphene oxide fiber grating, which utilizes the drift of the resonance center wavelength of a cladding mode of a large-angle inclined fiber grating or the change of the intensity to determine the final content of target biomolecules, and simultaneously utilizes the change of interference fringes in the resonance band of the cladding mode to monitor the biomolecule reaction (binding) dynamic process on the surface of an optical fiber in real time.
Preferably, the length of the large-angle inclined fiber grating is 20-30 mm, the coupling of the light energy from the fiber core mold to the cladding mold is more than 20dB, the reflectivity of the silver reflecting film is more than 90%, and the number of graphene oxide layers is 5-15.
The invention discloses a broadband interference type optode biomolecule sensor of a graphene oxide fiber grating and a method thereof, and the principle and the advantages are as follows:
1) according to the invention, nano gold shell particles are used as a carrier for exciting the LSPR, the size of the outer diameter of the shell is designed to be 150-200 nm, and the resonance absorption spectrum of the LSPR effect can be ensured to cover 500-1600 nm, as shown in FIG. 4. The silane layer on the surface of the optical fiber is used for fixing the nano gold shell particles in an electrostatic mode or a covalent bond mode.
2) The invention uses a large-angle inclined fiber grating as a platform for exciting the surface nano gold shell particles LSPR. The inclination angle of the large-angle inclined fiber grating is between 60 and 85 degrees, the grating period is between 25 and 40 microns, and simultaneously, due to the fiber birefringence effect caused by large-angle inclined stripes, the spectrum of the large-angle inclined fiber grating has strong polarization correlation, a fiber core fundamental mode can be coupled to a TM/TE mode of a forward-propagating high-order cladding mode, and a transmission spectrum of the large-angle inclined fiber grating in 1250 to 1650nm has a series of polarization-dependent resonance peaks with the distance of dozens of nm, as shown in FIG. 5, the full spectrum of a certain large-angle inclined fiber grating; only the TM mode and the TE mode of each polarization-dependent resonance peak can be excited by adjusting the polarization direction of incident linearly polarized light, or the TM mode and the TE mode can be excited at the same time in equal intensity, and as shown in FIG. 6, the polarization-dependent characteristic spectrums of the TM mode and the TE mode of a certain large-angle inclined fiber grating in a communication waveband (namely, a C/L waveband) are shown. Therefore, any one TM mode or TE mode of a high-order cladding mode resonant peak of the large-angle inclined fiber grating in a transmission spectrum of 1250 nm-1650 nm can cause the resonant absorption of the LSPR by taking nano-gold shell particles as a carrier on the surface of the optical fiber. In addition, the spectral bandwidth of the TM mode or the TE mode of the large-angle inclined fiber grating is 2 nm-4 nm, so that the sensor has a very high Q value compared with a pure fiber type LSPR sensor.
3) A silver reflecting film is plated at the tail end of an optical fiber which is 30-60 mm away from the rear end of the large-angle inclined optical fiber grating to form an optical fiber micro Michelson interference cavity, the optical fiber micro Michelson interference cavity is used for reflecting TM modes (or TE modes) of high-order cladding modes of the large-angle inclined optical fiber grating and light energy which is not coupled into a cladding in a fiber core, the light energy of the reflected TM modes (or TE modes) of the high-order cladding modes is transmitted to the large-angle inclined optical fiber grating, one part of the light energy is re-coupled back into the fiber core of the optical fiber for transmission, and the part of the light interferes with the light energy which is reflected by the silver film in the fiber core and has the same wave band in a gate area. Therefore, the structure is in a form of a broadband interference type optical pole biomolecule sensor of the graphene oxide fiber grating, is convenient to integrate and use in practical application, and has high robustness. In addition, the structure can increase the action length of the LSPR wave excited by the light wave evanescent field and external biomolecules, thereby increasing the sensitivity of the sensor.
4) The graphene oxide layer is attached to the nanogold shell particle layer, the biomolecule sensitive layer sensitive to the specificity of the object to be detected is attached to the graphene oxide layer, the graphene oxide layer has a large specific surface area, effective adsorption sites for sensitive layer biomolecules in a unit volume can be greatly increased, and therefore the detection range of the sensor to the concentration of the object to be detected can be greatly enlarged. When the target biological molecules are combined with the biological molecule sensitive layer, the change of the LSPR resonance wavelength absorption spectrum intensity is caused, the effective refractive index of a cladding mode is changed, the change of the reflected resonance wavelength is caused, the change of the LSPR absorption spectrum intensity and the resonance wavelength is in a direct proportion relation with the concentration of the target biological molecules in a certain detection range, and the information such as the concentration of the target biological molecules can be calculated by detecting the change of the LSPR absorption spectrum intensity and the resonance wavelength through a spectrum analyzer at a reflection end. More importantly, the optical interference type sensor is based on the principle of optical phase modulation/demodulation and has extremely high sensitivity and weak signal detection capability, so that the phase difference of the interference spectrum in the resonance band of the broadband interference type optode biomolecular sensor is also sensitive to the molecular microscopic adsorption process on the surface of an interference arm (namely, from the rear end of a large-angle inclined fiber grating to a silver reflecting film at the tail end of an optical fiber), and the reaction dynamic process of the molecules on the surface of the optical fiber can be monitored by using the change of the interference fringes of the interference spectrum in the resonance band.
5) On the other hand, the graphene oxide has certain enhancement on the LSPR effect of the nano-gold shell particles.
6) As the temperature sensitivity of any high-order cladding mode of the large-angle inclined fiber grating in the transmission spectrum of 1250 nm-1650 nm is 3.0 pm/DEG C-7.0 pm/DEG C and is lower than the temperature coefficient of the traditional FBG sensor, the LSPR effect of exciting nano gold shell particles by taking the large-angle inclined fiber grating as a platform has very good temperature stability.
The invention has the advantages of the general optical fiber LSPR sensor, small and light sensor size, high refractive index sensitivity and the like. In addition, the present invention has many unique advantages over conventional pure fiber LSPR sensors and fiber grating LSPR sensors, including: the sensor has compact, unique and ingenious structure, the nano gold shell particles are fixed on the surface of the large-angle inclined fiber grating, and the silver reflecting film is plated at the tail end of the optical fiber at a certain distance (30-60 mm) from the rear end of the large-angle inclined fiber grating to form an optical fiber micro Michelson interference cavity, so that the sensor of the wide-band interference type optopolar biomolecular sensor of the large-angle inclined fiber grating is formed. The most key point of the sensor is that the outer diameter of the shell of the nano gold shell particles is designed to be 150-200 nm, the resonance absorption spectrum of the LSPR effect can be ensured to cover 500-1600 nm, and the TM mode or TE mode of any high-order cladding mode resonance peak of the large-angle inclined fiber grating in the transmission spectrum of 1250-1650 nm can cause the resonance absorption of the LSPR by taking the nano gold shell particles as carriers on the surface of the optical fiber. Furthermore, the graphene oxide layer is fixed on the nano-gold shell particle layer, so that effective adsorption sites for sensitive layer biomolecules in unit volume are greatly increased, the defect that the dynamic range of the conventional optical fiber LSPR sensor for biomolecule detection is low is overcome, meanwhile, the sensor has a certain enhancement effect on the LSPR effect of the nano-gold shell particles, and the sensitivity of the sensor is further increased. In a word, the broadband interference type optode biomolecule sensor of the graphene oxide fiber grating integrates the advantages of all the conventional fiber LSPR sensors, avoids the defects of the various fiber LSPR sensors, and can be widely applied to ultra-trace detection of biochemical substance molecules and biomolecule reaction (combination) dynamic processes on the surface of optical fibers in the fields of biology, medicine, environmental monitoring, food safety, life science and the like, such as DNA/RNA/miRNA, antibodies/antigens, bacteria, viruses and the like.
Drawings
FIG. 1 prism LSPR sensor structure;
FIG. 2 is a schematic diagram of the transmission spectrum of a small angle TFBG-LSPR sensor;
FIG. 3 is a schematic diagram of the spectrum of a pure fiber LSPR sensor varying with the refractive index
FIG. 4 is a schematic diagram of the LSPR resonance absorption spectrum of the nano-gold shell particles obtained by the experiment;
FIG. 5 shows the transmission spectrum characteristics of a large-angle tilted fiber grating (a) at 1250-1650 nm;
FIG. 6 shows the polarization-dependent characteristic spectra of TM and TE modes in the C/L band of a large-angle tilted fiber grating (C);
FIG. 7 is a schematic structural diagram of a broadband interferometric optode biomolecular sensor with graphene oxide fiber gratings according to the present invention;
FIG. 8 is a schematic diagram of optical path transmission of a broadband interferometric optode biomolecular sensor according to the graphene oxide fiber grating of the present invention;
FIG. 9 is a schematic diagram of a sensing system of a broadband interferometric optode biomolecular sensor according to graphene oxide fiber grating of the present invention;
FIG. 10 is a schematic diagram of the change of the spectrum signal of the broadband interferometric optode biomolecular sensor with graphene oxide fiber grating according to the present invention.
Detailed Description
The following is further detailed by the specific embodiments:
description of reference numerals: the optical fiber grating comprises an optical fiber core 1, an optical fiber cladding 2, an optical fiber coating layer 3, a large-angle inclined optical fiber grating 4, a silane layer 5, a nanogold shell particle layer 6, a graphene oxide layer 7, a biomolecule sensitive layer 8, a silver reflecting film 9, a bandwidth light source 10, an optical fiber polarizer 11, an optical fiber polarization controller 12, a 3dB coupler 13, a graphene oxide optical fiber grating broadband interference type optode biomolecule sensor 14, a spectrum analyzer 15 and a computer 16.
Referring to fig. 7, the broadband interferometric optode biomolecular sensor of graphene oxide fiber grating includes: the optical fiber micro Michelson interference cavity comprises an optical fiber core 1, an optical fiber cladding 2 and an optical fiber coating layer 3, wherein a large-angle inclined optical fiber grating 4 is arranged at the middle section of the optical fiber core 1, the coating layers of the middle section and the rear section of the optical fiber are completely removed, a silver reflecting film 9 is plated on the end face of the tail end of the optical fiber rear section, and the distance from the rear end of the large-angle inclined optical fiber grating to the silver reflecting film at the tail end of the optical fiber is 30-60 mm, so that an optical fiber micro; the method comprises the following steps that a silane layer 5 is arranged on the surface of a cladding layer from the starting end of the large-angle inclined fiber bragg grating to the tail end of an optical fiber, nanogold shell particles 6 are fixed on the surface of the silane layer, a graphene oxide layer 7 is adsorbed on the surface of the nanogold shell particle layer, and a biomolecule sensitive layer 8 is fixed on the surface of the graphene oxide layer; the inclination angle of the large-angle inclined fiber grating is between 60 and 85 degrees, and the grating period is between 25 and 40 mu m; the size of the outer diameter of the shell of the nano gold shell particle is 155 nm-200 nm so as to ensure that the LSPR absorption spectrum covers 500 nm-1600 nm.
Specifically, the method for manufacturing the broadband interference type photoelectrode biomolecule sensor of the graphene oxide fiber grating mainly comprises the following steps:
1) the manufacture of the large-angle inclined fiber grating, adopting a frequency doubling Ar + laser with the wavelength of 244nm and a scanning amplitude mask plate technology to write the large-angle inclined fiber grating into the single-mode fiber subjected to hydrogen loading treatment, wherein the inclination angle of the grating is designed to be between 60 and 85 degrees, and the grating period is designed to be between 25 and 40 mu m; after the grating is manufactured, the grating is placed in a natural convection oven at 80 ℃ for annealing treatment to obtain the stable spectral characteristics of the grating.
2) Preparing a reflecting film, accurately cutting an optical fiber at the end of the optical fiber at a certain distance (30-60 mm) from the rear end of the large-angle inclined optical fiber grating by using an optical fiber cutter, ensuring the cut end face to be vertical to an axial plane, then immersing the cut end face of the optical fiber into a prepared Torontal reagent for about 30 minutes, taking out the Torontal reagent and drying the Torontal reagent in the air, wherein the Torontal reagent is prepared by mixing a silver nitrate solution (AgNO30.1M, 640uL) and a potassium hydroxide solution (KOH 0.8M, 440uL), adding ammonia water (NH 330% w/w, 2 drops) and stirring to precipitate and dissolve, and then adding a glucose (dextrose) solution (0.25M, 64 uL).
3) Hydroxylating the surface of the optical fiber, namely immersing the large-angle inclined optical fiber grating until the part of the cut end face of the optical fiber is immersed in 8mg/mL NaOH solution for 3.5h (40 ℃), then immersing for 30min at normal temperature, finally repeatedly washing the surface of the grating for about 10min by deionized water to remove redundant impurities, and then drying for 10min at 50 ℃.
4) Silanization, soaking the grating in MPTMS solution (1% volume concentration, glacial acetic acid configuration) for 8-12 min in a 80-degree convection oven to generate sulfhydryl groups ('-SH') on the surface of the optical fiber.
5) Fixing the nano gold shell particles, inclining the fiber bragg grating by a large angle until the part of the cut fiber end surface is immersed in the centrifuged nano gold shell solution for about 12 hours, and covalently bonding the nano gold shell particles with MPTMS molecules on the surface of the grating through gold-sulfur bonds.
6) Amination of the nano gold shell, soaking the grating modified by the gold nano shell in ethanolamine (MEA) solution with the concentration of 10M for 1h (room temperature), and then washing with deionized water for two to three times.
7) Fixing graphene oxide layer, immersing the part of the large-angle inclined fiber grating until the cut fiber end surface into the centrifuged graphene oxide dispersion liquid, and allowing the surface of the nano-gold shell to have amino (-NH) because the MEA can aminate the nano-gold shell2) And thus can be bonded with the carboxyl group (-COOH) dehydration condensation of graphene oxide in the form of peptide bond.
8) Fixing a biomolecule sensitive layer, and immersing the part of the fiber grating inclined at a large angle until the cut fiber end surface into biomolecule sensitive liquid (such as: monoclonal antibodies, oligonucleotide aptamers, etc.), the biomolecules will chemically bond with functional groups on the graphene oxide (e.g.: carboxyl, hydroxyl or amino).
Referring to fig. 8, the optical path transmission principle of the broadband interferometric optode biomolecular sensor of the graphene oxide fiber grating is as follows: adjusting incident linearly polarized light lambda by an external polarization controllercoOf polarization direction of (1), when λcoWhen the fiber grating is inclined by a large angle, the fiber grating can completely excite the resonance wavelength lambda of the TM mode or the TE mode of the cladding mode of the fiber grating inclined by the large anglecl。λclThe evanescent field acts with the nano-gold shell particles on the surface of the fiber in the process of transiting the fiber cladding, and the LSPR resonance absorption of the nano-gold shell particles covers the C/L wave band, so that the lambdaclWill cause resonant absorption of the LSPR wave of the nanogold shell particles; when lambda isclλ is transmitted to the end of the optical fiber and reflected by the high-reflectivity silver film at the end face to be transmitted in the reverse directionclAnd the LSPR wave of the nano gold shell particles is subjected to resonant absorption, and is gradually coupled into the fiber core by the large-angle inclined fiber grating for propagation, and the part of light interferes with the light energy which is reflected by the silver film in the fiber core and has the same wave band in the grating region.
In practical application, a nano gold shell LSPR optode biomolecular sensor of a graphene oxide fiber grating can form a system, as shown in fig. 9 and 10, random polarized broadband light (1250nm to 1650nm) emitted by a bandwidth light source 10 is transmitted to an optical fiber polarizer 11 through a single mode fiber, the polarization direction of the linearly polarized light is changed through an optical fiber polarization controller 12, and then the linearly polarized broadband light is transmitted to a nano gold shell LSPR optode biomolecular sensor 14 of the graphene oxide fiber grating through a 3dB coupler 13, a high-order cladding mode of a large-angle inclined fiber grating in a C/L wave band can be completely operated in a TM mode or a TE mode state by adjusting the optical fiber polarization controller 11, so that resonant absorption of the nano gold shell LSPR is efficiently caused, the TM mode or the TE mode of the high-order cladding mode is reflected by a silver film at the end of the fiber and reversely transmitted to cause resonant absorption of LSPR waves of nano gold shell particles again, meanwhile, the part of light is coupled to the fiber core by the large-angle inclined fiber grating step by step and is transmitted, the interference occurs between the part of light and the light energy which is reflected by the silver film in the fiber core and has the same wave band in the grating region, the reflected wave is transmitted to the 3dB coupler and is coupled to the other port for output, the part of light is transmitted to the optical spectrum analyzer 15, the change of the resonant wavelength and the intensity of the demodulated reflected spectrum reflects the change of the measured target biomolecule, the change of the interference fringe in the cladding mode resonant band monitors the biomolecule reaction (combination) power process of the fiber surface in real time, and the change is finally transmitted to the computer 16 for analysis and calculation.
The foregoing is merely an example of the present invention, and common general knowledge in the field of known specific structures and characteristics is not described herein in any greater extent than that known in the art at the filing date or prior to the priority date of the application, so that those skilled in the art can now appreciate that all of the above-described techniques in this field and have the ability to apply routine experimentation before this date can be combined with one or more of the present teachings to complete and implement the present invention, and that certain typical known structures or known methods do not pose any impediments to the implementation of the present invention by those skilled in the art. It should be noted that, for those skilled in the art, without departing from the structure of the present invention, several changes and modifications can be made, which should also be regarded as the protection scope of the present invention, and these will not affect the effect of the implementation of the present invention and the practicability of the patent. The scope of the claims of the present application shall be determined by the contents of the claims, and the description of the embodiments and the like in the specification shall be used to explain the contents of the claims.
Claims (8)
1. The broadband interference type photoelectrode biomolecule sensor of the graphene oxide fiber grating is characterized in that: the large-angle inclined fiber grating interference cavity comprises a fiber core, a fiber cladding and a fiber coating layer, wherein the middle section of the fiber core is provided with a large-angle inclined fiber grating, the coating layers of the middle section and the rear section of the fiber are completely removed, the end face of the tail end of the fiber rear section is plated with a silver reflecting film, and the distance from the rear end of the large-angle inclined fiber grating to the silver reflecting film at the tail end of the fiber is 30-60 mm, so that a fiber micro Michelson interference cavity is formed; the surface of a cladding layer from the starting end of the large-angle inclined fiber bragg grating to the tail end of the optical fiber is provided with a silane layer, nanogold shell particles are fixed on the surface of the silane layer, a graphene oxide layer is adsorbed on the surface of the nanogold shell particle layer, and a biomolecule sensitive layer is fixed on the surface of the graphene oxide layer.
2. The graphene oxide fiber grating broadband interferometric optode biomolecular sensor of claim 1, wherein: the inclination angle of the inclined stripes of the large-angle inclined fiber grating is 60-85 degrees.
3. The graphene oxide fiber grating broadband interferometric optode biomolecular sensor of claim 1, wherein: the grating period is 25-40 μm.
4. The graphene oxide fiber grating broadband interferometric optode biomolecular sensor of claim 1, wherein: the outer diameter of the shell of the nano gold shell particle is 155 nm-200 nm.
5. The graphene oxide fiber grating broadband interferometric optode biomolecular sensor of claim 1, wherein: the length of the large-angle inclined fiber grating is between 20mm and 30 mm.
6. The graphene oxide fiber grating broadband interferometric optode biomolecular sensor of claim 1, wherein: the core mode to cladding mode light energy coupling is >20 dB.
7. The graphene oxide fiber grating broadband interferometric optode biomolecular sensor of claim 2, wherein: the reflectivity of the silver reflecting film is greater than 90%, and the number of layers of graphene oxide is 5-15.
8. A method for manufacturing a broadband interferometric optode biomolecular sensor with a graphene oxide fiber grating according to claim 1, comprising the following steps:
1) the manufacturing of the large-angle inclined fiber grating, the large-angle inclined fiber grating with the length of 20 mm-30 mm is written in the single-mode fiber subjected to hydrogen loading treatment by adopting a frequency doubling Ar + laser with the wavelength of 244nm and a scanning amplitude mask plate technology, the inclination angle of the grating is designed to be 60-85 degrees, the period of the grating is designed to be 25-40 mu m, and after the grating is manufactured, the grating is placed in a natural convection oven at 80 ℃ for annealing treatment;
2) preparing a reflecting film, namely cutting an optical fiber at the end of the optical fiber with the rear end of 30-60 mm of the large-angle inclined fiber grating by using an optical fiber cutter, ensuring the cut end surface to be vertical to an axial surface, then immersing the cut end surface of the optical fiber into the prepared Toronto reagent for 25-35 minutes, taking out and air-drying in the air;
3) hydroxylating the surface of an optical fiber, immersing a large-angle inclined optical fiber grating at 40 ℃ until the part of the cut end face of the optical fiber is immersed in 8mg/mL NaOH solution for 3.5h, then immersing at normal temperature for 30min, washing the surface of the grating with deionized water to remove redundant impurities, and finally drying at 50 ℃ for 10 min;
4) silanization, soaking the grating in 1% MPTMS solution with volume concentration prepared by glacial acetic acid in a 80-degree convection oven for 8-12 min to generate a mercapto group on the surface of the optical fiber;
5) fixing nano gold shell particles, inclining the fiber bragg grating by a large angle until the part of the cut fiber end surface is immersed in the centrifuged nano gold shell solution for about 12 hours, and covalently bonding the nano gold shell particles with MPTMS molecules on the surface of the grating through gold-sulfur bonds;
6) amination of a nano gold shell, soaking the grating modified by the gold nanoshell in ethanolamine solution with the concentration of 10M for 1h at room temperature, and then cleaning the grating by using deionized water;
7) fixing a graphene oxide layer, immersing a part of the large-angle inclined fiber grating, which is up to the cut fiber end face, into the centrifuged graphene oxide dispersion liquid, so that amino groups on the surface of the nano-gold shell and carboxyl groups of the graphene oxide are subjected to dehydration condensation and are combined in a peptide bond form;
8) fixing a biomolecule sensitive layer, and immersing the part of the large-angle inclined fiber grating fixed with the graphene oxide layer until the cut fiber end surface into biomolecule sensitive liquid with specific identification on a target object to be detected, so that the biomolecule is combined with a functional group on the graphene oxide in a chemical bond mode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911007889.5A CN110823843A (en) | 2019-10-22 | 2019-10-22 | Broadband interference type optode biomolecule sensor of graphene oxide fiber grating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911007889.5A CN110823843A (en) | 2019-10-22 | 2019-10-22 | Broadband interference type optode biomolecule sensor of graphene oxide fiber grating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110823843A true CN110823843A (en) | 2020-02-21 |
Family
ID=69550106
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911007889.5A Pending CN110823843A (en) | 2019-10-22 | 2019-10-22 | Broadband interference type optode biomolecule sensor of graphene oxide fiber grating |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110823843A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111337446A (en) * | 2020-05-08 | 2020-06-26 | 宁波大学 | Biosensor based on chalcogenide glass optical fiber and preparation method thereof |
| CN112051237A (en) * | 2020-09-10 | 2020-12-08 | 重庆理工大学 | Biosensor for detecting avian influenza virus and preparation method thereof |
| CN112304906A (en) * | 2020-10-23 | 2021-02-02 | 重庆理工大学 | Dual-channel probe type 81-degree inclined fiber bragg grating sensor system and preparation method and application thereof |
| CN112730325A (en) * | 2020-12-23 | 2021-04-30 | 汕头大学 | Preparation method of coated optical fiber, coated optical fiber and refractive index detection device |
| CN113125384A (en) * | 2021-03-03 | 2021-07-16 | 汕头大学医学院 | Probe, circulating tumor cell detection equipment and preparation method |
| CN113155748A (en) * | 2021-03-24 | 2021-07-23 | 汕头大学 | Detection device for virus detection and sensing probe |
| CN113205899A (en) * | 2021-04-25 | 2021-08-03 | 中国工程物理研究院激光聚变研究中心 | X-ray refraction blazed grating and preparation method thereof |
| CN113280843A (en) * | 2021-05-20 | 2021-08-20 | 山东大学 | Graphene sensitive tilt-increasing grating optical fiber SPR sensor and analysis method and application |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1712931A (en) * | 2005-07-01 | 2005-12-28 | 曾祥楷 | Interference SPR chemical and biological sensor and system with fibre-optical microstructure Michelson |
| CN101009520A (en) * | 2006-12-29 | 2007-08-01 | 北京交通大学 | A novel optical fiber grating temperature compensation encapsulation method |
| CN201885824U (en) * | 2010-11-09 | 2011-06-29 | 成都智源电气有限责任公司 | Online distributing cable temperature monitoring device |
| CN104407117A (en) * | 2014-11-12 | 2015-03-11 | 浙江大学 | Preparation method of graphene oxide optical biosensor for TNT detection |
| CN105387923A (en) * | 2015-10-22 | 2016-03-09 | 重庆理工大学 | Great-angle tilted fiber bragg grating mechanical vibration sensing array and system |
| CN106199820A (en) * | 2016-06-24 | 2016-12-07 | 深圳市畅格光电有限公司 | A kind of manufacture method of weak reflectance fiber grating |
| CN109085140A (en) * | 2018-08-22 | 2018-12-25 | 东北大学 | A kind of high sensitivity optical fiber surface plasmon resonance biosensor |
| CN109266641A (en) * | 2018-09-27 | 2019-01-25 | 福建海峡石墨烯产业技术研究院有限公司 | A kind of method and detecting electrode that enzyme is fixed on graphene based on glutaraldehyde |
| CN110028062A (en) * | 2019-04-29 | 2019-07-19 | 苏州大学 | A kind of preparation method of surface modification oil solubility graphene oxide |
-
2019
- 2019-10-22 CN CN201911007889.5A patent/CN110823843A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1712931A (en) * | 2005-07-01 | 2005-12-28 | 曾祥楷 | Interference SPR chemical and biological sensor and system with fibre-optical microstructure Michelson |
| CN101009520A (en) * | 2006-12-29 | 2007-08-01 | 北京交通大学 | A novel optical fiber grating temperature compensation encapsulation method |
| CN201885824U (en) * | 2010-11-09 | 2011-06-29 | 成都智源电气有限责任公司 | Online distributing cable temperature monitoring device |
| CN104407117A (en) * | 2014-11-12 | 2015-03-11 | 浙江大学 | Preparation method of graphene oxide optical biosensor for TNT detection |
| CN105387923A (en) * | 2015-10-22 | 2016-03-09 | 重庆理工大学 | Great-angle tilted fiber bragg grating mechanical vibration sensing array and system |
| CN106199820A (en) * | 2016-06-24 | 2016-12-07 | 深圳市畅格光电有限公司 | A kind of manufacture method of weak reflectance fiber grating |
| CN109085140A (en) * | 2018-08-22 | 2018-12-25 | 东北大学 | A kind of high sensitivity optical fiber surface plasmon resonance biosensor |
| CN109266641A (en) * | 2018-09-27 | 2019-01-25 | 福建海峡石墨烯产业技术研究院有限公司 | A kind of method and detecting electrode that enzyme is fixed on graphene based on glutaraldehyde |
| CN110028062A (en) * | 2019-04-29 | 2019-07-19 | 苏州大学 | A kind of preparation method of surface modification oil solubility graphene oxide |
Non-Patent Citations (5)
| Title |
|---|
| BINBIN LUO ET AL: "Label-free and specific detection of soluble programmed death ligand-1 using a localized surface plasmon resonance biosensor based on excessively tilted fiber gratings", 《BIOMEDICAL OPTICS EXPRESS》 * |
| QI WANG ET AL: "Highly Sensitive SPR Biosensor Based on Graphene Oxide and Staphylococcal Protein A Co-Modified TFBG for Human IgG Detection", 《IEEE TRANSACTIONS ON INSTRUMENTATION AND MEASUREMENT》 * |
| 张婳: "纳米材料的合成及其在表面等离子体共振生物传感器中的应用", 《中国博士学位论文全文数据库 工程科技I辑》 * |
| 童利民 等: "《纳米光子学研究前沿》", 31 December 2014, 上海交通大学出版社 * |
| 赵明富 等: "修饰不同金纳米颗粒的极大角倾斜光纤光栅折射率传感特性研究", 《半导体光电》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111337446A (en) * | 2020-05-08 | 2020-06-26 | 宁波大学 | Biosensor based on chalcogenide glass optical fiber and preparation method thereof |
| CN112051237A (en) * | 2020-09-10 | 2020-12-08 | 重庆理工大学 | Biosensor for detecting avian influenza virus and preparation method thereof |
| CN112304906A (en) * | 2020-10-23 | 2021-02-02 | 重庆理工大学 | Dual-channel probe type 81-degree inclined fiber bragg grating sensor system and preparation method and application thereof |
| CN112304906B (en) * | 2020-10-23 | 2024-01-23 | 重庆理工大学 | Dual-channel probe type 81-degree inclined fiber bragg grating sensor system and preparation method and application thereof |
| CN112730325A (en) * | 2020-12-23 | 2021-04-30 | 汕头大学 | Preparation method of coated optical fiber, coated optical fiber and refractive index detection device |
| CN113125384A (en) * | 2021-03-03 | 2021-07-16 | 汕头大学医学院 | Probe, circulating tumor cell detection equipment and preparation method |
| CN113155748A (en) * | 2021-03-24 | 2021-07-23 | 汕头大学 | Detection device for virus detection and sensing probe |
| CN113205899A (en) * | 2021-04-25 | 2021-08-03 | 中国工程物理研究院激光聚变研究中心 | X-ray refraction blazed grating and preparation method thereof |
| CN113205899B (en) * | 2021-04-25 | 2023-02-28 | 中国工程物理研究院激光聚变研究中心 | X-ray refraction blazed grating and preparation method thereof |
| CN113280843A (en) * | 2021-05-20 | 2021-08-20 | 山东大学 | Graphene sensitive tilt-increasing grating optical fiber SPR sensor and analysis method and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110823843A (en) | Broadband interference type optode biomolecule sensor of graphene oxide fiber grating | |
| Liu et al. | Fiber-optic surface plasmon resonance sensors and biochemical applications: a review | |
| CN110672564A (en) | Nano-gold shell LSPR (localized surface plasmon resonance) optode biosensor of graphene oxide fiber bragg grating | |
| Ahmadivand et al. | Photonic and plasmonic metasensors | |
| Yuan et al. | Investigation for terminal reflection optical fiber SPR glucose sensor and glucose sensitive membrane with immobilized GODs | |
| Jing et al. | Refractive index sensing characteristics of carbon nanotube-deposited photonic crystal fiber SPR sensor | |
| Chen et al. | Review of surface plasmon resonance and localized surface plasmon resonance sensor | |
| US8920729B2 (en) | Porous membrane waveguide sensors and sensing systems therefrom for detecting biological or chemical targets | |
| Xiong et al. | Fiber-tip polymer microcantilever for fast and highly sensitive hydrogen measurement | |
| Jiang et al. | Refractive index sensitivity enhancement of optical fiber SPR sensor utilizing layer of MWCNT/PtNPs composite | |
| Memon et al. | A review of optical fibre ethanol sensors: Current state and future prospects | |
| Divagar et al. | Graphene oxide coated U-bent plastic optical fiber based chemical sensor for organic solvents | |
| Srivastava et al. | Fiber optic plasmonic sensors: past, present and future | |
| Wang et al. | Barium titanate film based fiber optic surface plasmon sensor with high sensitivity | |
| Liu et al. | One-dimensional plasmonic sensors | |
| Wang et al. | 2-D nanomaterials assisted LSPR MPM optical fiber sensor probe for cardiac troponin I detection | |
| Vikas et al. | Urea detection using bio-synthesized gold nanoparticles: an SPR/LSPR based sensing approach realized on optical fiber | |
| CN104596992A (en) | Maximally tilted fiber bragg grating SPR (Surface Plasmon Resonance) biochemical sensor and manufacture method thereof | |
| Zhu et al. | Metal-organic framework materials coupled to optical fibers for chemical sensing: A review | |
| Tou et al. | Fiber optic refractometer based on cladding excitation of localized surface plasmon resonance | |
| Zhang et al. | Advances in tapered optical fiber sensor structures: From conventional to novel and emerging | |
| Kumari et al. | Hybrid plasmonic SOI ring resonator for bulk and affinity bio-sensing applications | |
| Sun et al. | A quasi-3D Fano resonance cavity on optical fiber end-facet for high signal-to-noise ratio dip-and-read surface plasmon sensing | |
| Li et al. | Plasmonic-photonic hybrid configuration on optical fiber tip: Toward low-cost and miniaturized biosensing probe | |
| Liu et al. | Fiber microsphere SPR sensor and its detection of low concentration Hg2+ |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200221 |
|
| RJ01 | Rejection of invention patent application after publication |