CN208705231U - Optical fiber SPR sensor based on graphene oxide and gold nanorods enhanced sensitivity - Google Patents

Optical fiber SPR sensor based on graphene oxide and gold nanorods enhanced sensitivity Download PDF

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Publication number
CN208705231U
CN208705231U CN201821483588.0U CN201821483588U CN208705231U CN 208705231 U CN208705231 U CN 208705231U CN 201821483588 U CN201821483588 U CN 201821483588U CN 208705231 U CN208705231 U CN 208705231U
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graphene oxide
optical fiber
gold nanorods
spr sensor
sensitivity
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王�琦
王雪州
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Northeastern University China
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Northeastern University China
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/55Specular reflectivity
    • G01N21/552Attenuated total reflection
    • G01N21/553Attenuated total reflection and using surface plasmons

Abstract

Sensitivity in order to solve the problems, such as existing fiber surface plasmon resonance biosensor is lower, the utility model proposes a kind of optical fiber SPR sensor based on graphene oxide and gold nanorods enhanced sensitivity.The utility model enhances electric field strength using the phasmon coupling effect between the plasma wave on golden film surface and the local surface plasma wave on gold nanorods surface, simultaneous oxidation graphene can promote the electric charge transfer between golden film and gold nanorods, and then enhance the interaction of surface plasma wave and test substance, improve detection sensitivity;In addition, graphene oxide has excellent bio-sensing characteristic, there is biocompatibility and bigger serface, the measurement of biomass and chemical quantity can be better achieved.The utility model compared to common optical fiber SPR sensor have higher sensing sensitivity and chemical stability, can real-time monitoring, it is compact-sized, the fields such as physics, chemistry, biology, medical treatment, food safety can be widely applied.

Description

Optical fiber SPR sensor based on graphene oxide and gold nanorods enhanced sensitivity
Technical field
The utility model relates to biosensor technology fields, and in particular to surface plasmon resonance biosensor more particularly to a kind of base In the optical fiber SPR sensor of graphene oxide and gold nanorods enhanced sensitivity.
Background technique
Optical fiber surface plasmon resonance (Surface Plasmon Resonance) be present in optical fiber surface metal film and On the interface of external agency, when light is incident on optically thinner medium from optically denser medium, it may occur that total reflection, but still some light Through optically thinner medium, evanescent wave is formed, simultaneously as the electron density distribution of metal inside can become when metal is by electromagnetic interference The collective's concussion that unevenly thus will cause electronics is obtained, and is showed in the form of wave, referred to as plasma wave.When evanescent wave and table When face plasma wave resonates, energy is transferred to surface plasma from photon, most of energy of incident light by surface etc. from Wavelet absorbs, and reduces the energy of reflected light sharply, reflective light intensity response curve can generate a trough, at this time corresponding incidence The a length of resonant wavelength of light wave.Optical fiber SPR sensor has many advantages, such as simple, at low cost, the easy miniaturization of production and electromagnetism interference, It is widely applied in biological and chemical detection field.
Surface plasma body resonant vibration (SPR) biosensor in biology and is changed due to its highly sensitive and biocompatibility It learns in detection and causes great concern.According to the interaction between surface plasma wave and surrounding biologic molecule, can lead The drift for causing resonance angle or resonant wavelength, thus can realize the detection of external biomolecule.With traditional SPR biology based on prism Sensor is compared, and optical fiber biosensor has production simply, at low cost, sensing arrangement miniaturization and electromagnetism interference Characteristic.However, traditional SPR bio-sensing relies primarily on golden film to realize detection, lack sufficiently high sensitivity to detect more The biomolecule of low relative molecular mass facilitates to expand in this way therefore, there is still a need for further increasing the sensitivity of sensor The application range of sensor.
Utility model content
Sensitivity in order to solve the problems, such as existing fiber surface plasmon resonance biosensor is lower, and the utility model proposes one kind Optical fiber SPR sensor based on graphene oxide and gold nanorods enhanced sensitivity, the utility model utilize the plasma on golden film surface Phasmon coupling effect between wave and the local surface plasma wave on gold nanorods surface enhances electric field strength, meanwhile, Graphene oxide can promote the electric charge transfer between golden film and gold nanorods, and then enhance surface plasma wave and test substance Interaction improves detection sensitivity.
To achieve the above object, the utility model uses following technical scheme:
Optical fiber SPR sensor based on graphene oxide and gold nanorods enhanced sensitivity, including single mode side-polished fiber, in list On the rubbing down face of mode fiber Side polishing fiber, it is followed successively by the golden film of 40~60nm thickness, the graphite oxide of 0.1~1nm thickness from inside to outside Alkene film and gold nanorods layer.
Further, graphene oxide membrane is fixed by Covalent bonding together method in the golden film surface.
Further, the gold nanorods are fixed on the surface of graphene oxide membrane by electrostatic self-assembled method.
Further, the single mode side-polished fiber, rubbing down face length are 0.5~2cm.
Further, when the golden film is with a thickness of 50nm, transducer sensitivity highest.
Further, the graphene oxide membrane with a thickness of 0.5nm when, transducer sensitivity highest.
Further, the diameter of the gold nanorods is 20~40nm, and draw ratio is 2.5~10.
The sensor-based system formed by above-mentioned high sensitivity optical fiber surface plasmon resonance biosensor, which is characterized in that including with multimode light Fibre is the optical fiber SPR sensor based on graphene oxide and gold nanorods enhanced sensitivity of optical path, and it is visible that input terminal, which connects spectrum, The wideband light source of optical band, output end connect broadband light spectrometer, and broadband light spectrometer is connected to external calculating by data-interface Machine, the optical fiber SPR sensor based on graphene oxide and gold nanorods enhanced sensitivity are placed in biomolecule solution to be detected.
The preparation method of the above-mentioned optical fiber SPR sensor based on graphene oxide and gold nanorods enhanced sensitivity, steps are as follows:
(1) single mode side-polished fiber is prepared
Single mode optical fiber Side polishing fiber, rubbing down face length are 0.5~2cm, are turned using motor and computer control polish-grinding grinding wheel Dynamic and propulsion, gradually polishes off the covering of optical fiber side, and microscope is utilized to carry out the rubbing down depth of observation optical fiber in real time;
Further, described to prepare single mode side-polished fiber, when single mode optical fiber Side polishing fiber, optical fiber both ends respectively at Light source is connected with spectrometer, and the loss situation of optical power in output spectrum can be monitored in real time, needed for microscopic obtains It can stop when the polishing thickness wanted.
(2) gold-plated film
Single mode side-polished fiber is put into vacuum ionic beam sputtering instrument, to the rubbing down face table of single mode optical fiber Side polishing fiber Face sputters golden film, and the electric current of vacuum ionic beam sputtering instrument is 5~7mA, and the time is 2~4 minutes, and golden film is with a thickness of 40~60nm;
(3) fixed graphene oxide film
The single mode side-polished fiber of gold-plated film is immersed 6 in the 4- aminothiophenol ethanol solution of 0.5~2mmol/L~ 24 hours, to carry out golden film surface amination, 4- aminothiophenol molecule can be connect by Au-S covalent bond with golden film, and Golden film outer surface forms amido (- NH2);After distilled water flushing, single mode side-polished fiber is immersed 0.05~1mg/mL's In graphene oxide water solution, putting the graphene oxide water solution into temperature is in 30~60 DEG C of insulating box, 20~ After sixty minutes, graphene oxide dispersion is evaporated, and is realized by physical evaporation method thin in the fixed graphene oxide in golden film surface Film, graphene oxide film is with a thickness of 0.1~1nm;
(4) fixed gold nanorods
Negatively charged kayexalate (PSS) solution of 0.5~5mg/mL is impregnated and is coated with graphene oxide The single mode side-polished fiber of film 10~30 minutes, then by draw ratio is 2.5~10, concentration is 0.05~0.1mg/mL gold Nanometer rods solution impregnates optical fiber 12~24 hours, realizes gold nanorods in graphene oxide membrane table by the method for electrostatic self-assembled The fixation in face.
The beneficial effect of the utility model compared with prior art is:
1, enhance local electric field intensity using the coupling effect between golden film, graphene oxide membrane, gold nanorods, so that The utility model sensor has the advantages that highly sensitive and low detection limit;The plasma wave and gold nanorods table on golden film surface Phasmon coupling effect between the local surface plasma wave in face enhances electric field strength, meanwhile, graphene oxide can promote Into the electric charge transfer between golden film and gold nanorods, and then enhance the interaction of surface plasma wave and test substance, improves Detection sensitivity;
2, graphene oxide has excellent bio-sensing characteristic, has biocompatibility and bigger serface, Ke Yigeng The measurement of biomass and chemical quantity is realized well;
Optical fiber SPR sensor structure of the utility model based on graphene oxide and gold nanorods enhanced sensitivity is compared to common Optical fiber SPR sensor have higher sensing sensitivity and chemical stability, can real-time monitoring, compact-sized, Neng Gouguang The fields such as general Applied Physics, chemistry, biology, medical treatment, food safety.
Detailed description of the invention
In order to illustrate the technical solutions in the embodiments of the present application or in the prior art more clearly, to embodiment or will show below There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this The some embodiments recorded in application, for those of ordinary skill in the art, without creative efforts, It is also possible to obtain other drawings based on these drawings.
Fig. 1 is the optical fiber SPR sensor based on graphene oxide and gold nanorods enhanced sensitivity in the utility model embodiment 1 Structural schematic diagram;
Fig. 2 is the sensing that the utility model is formed based on the optical fiber SPR sensor of graphene oxide and gold nanorods enhanced sensitivity System structure diagram;
Fig. 3 is the transmitted light spectrogram that the utility model is used to measure solution refractive index in the utility model embodiment 1;
Fig. 4 is the linear fit curve of the utility model measurement result in the utility model embodiment 1;
In figure: 1, fiber core, 2, fibre cladding, 3, golden film, 4, graphene oxide membrane, 5, gold nanorods, 1 ', broadband light Source, 2 ', multimode fibre, 3 ', the optical fiber SPR sensor based on graphene oxide and gold nanorods enhanced sensitivity, 4 ', spectrometer.
Specific embodiment
It should be noted that in the absence of conflict, the feature in the embodiments of the present invention and embodiment can To be combined with each other.The utility model will be described in detail below with reference to the accompanying drawings and embodiments.
It is practical new below in conjunction with this to keep the objectives, technical solutions, and advantages of the embodiments of the present invention clearer Attached drawing in type embodiment, the technical scheme in the utility model embodiment is clearly and completely described, it is clear that is retouched The embodiment stated is only the utility model a part of the embodiment, instead of all the embodiments.Below at least one example The description only actually of property embodiment be it is illustrative, never as to the utility model and its application or any limit used System.Based on the embodiments of the present invention, those of ordinary skill in the art are obtained without making creative work The every other embodiment obtained, fall within the protection scope of the utility model.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root According to the illustrative embodiments of the utility model.As used herein, unless the context clearly indicates otherwise, otherwise singular Form be also intended to include plural form, additionally, it should be understood that, when in the present specification use term "comprising" and/or When " comprising ", existing characteristics, step, operation, device, component and/or their combination are indicated.
Unless specifically stated otherwise, positioned opposite, the digital table of the component and step that otherwise illustrate in these embodiments Up to the unlimited the scope of the utility model processed of formula and numerical value.Simultaneously, it should be clear that for ease of description, each shown in attached drawing The size of a part is not to draw according to actual proportionate relationship.Skill known for person of ordinary skill in the relevant Art, method and apparatus may be not discussed in detail, but in the appropriate case, and the technology, method and apparatus should be considered as awarding Weigh part of specification.In shown here and discussion all examples, example should be construed as merely by appointing to occurrence Property, not as limitation.Therefore, the other examples of exemplary embodiment can have different values.It should also be noted that similar Label and letter similar terms are indicated in following attached drawing, therefore, once be defined in a certain Xiang Yi attached drawing, then with In attached drawing afterwards do not need that it is further discussed.
In the description of the present invention, it should be understood that the noun of locality such as " front, rear, top, and bottom, left and right ", " laterally, Vertically, vertically, it is horizontal " and " pushing up, bottom " etc. indicated by orientation or positional relationship be normally based on orientation or position shown in the drawings Relationship is set, is merely for convenience of describing the present invention and simplifying the description, in the absence of explanation to the contrary, these nouns of locality Do not indicate that and imply that signified device or element must have a particular orientation or be constructed and operated in a specific orientation, because This should not be understood as the limitation to scope of protection of the utility model: the noun of locality " inside and outside " refers to the wheel relative to each component itself Wide is inside and outside.
For ease of description, spatially relative term can be used herein, as " ... on ", " ... top ", " ... upper surface ", " above " etc., for describing such as a device shown in the figure or feature and other devices or spy The spatial relation of sign.It should be understood that spatially relative term is intended to comprising the orientation in addition to device described in figure Except different direction in use or operation.For example, being described as if the device in attached drawing is squeezed " in other devices It will be positioned as " under other devices or construction after part or construction top " or the device of " on other devices or construction " Side " or " under its device or construction ".Thus, exemplary term " ... top " may include " ... top " and " in ... lower section " two kinds of orientation.The device can also be positioned with other different modes and (is rotated by 90 ° or in other orientation), and And respective explanations are made to the opposite description in space used herein above.
In addition, it should be noted that, limiting components using the words such as " first ", " second ", it is only for be convenient for Corresponding components are distinguished, do not have Stated otherwise such as, there is no particular meanings for above-mentioned word, therefore should not be understood as to this The limitation of utility model protection range.
Embodiment 1
As shown in Figure 1, the optical fiber SPR sensor based on graphene oxide and gold nanorods enhanced sensitivity, including single mode side are thrown The fibre cladding 2 that polishing fibre, i.e. rubbing down fall single mode optical fiber side, but rubbing down depth does not reach fiber core 1, and rubbing down face length is 0.5~2cm;On single mode optical fiber side-polished fiber rubbing down face, be followed successively by from inside to outside the golden film 3,0.1 of 40~60nm thickness~ The graphene oxide membrane 4 of 1nm thickness and 4 layers of gold nanorods, graphene oxide is fixed by Covalent bonding together method in 3 surface of golden film Film 4, gold nanorods 5 are fixed on 4 surface of graphene oxide membrane by electrostatic self-assembled method, and the diameter of gold nanorods 5 is 20~ 40nm, draw ratio be 2.5~10, golden film 3 with a thickness of 50nm, graphene oxide membrane 4 with a thickness of 0.5nm when, sensor is sensitive Spend highest.
As shown in Fig. 2, the sensor-based system formed by above-mentioned high sensitivity optical fiber surface plasmon resonance biosensor, which is characterized in that packet Include the optical fiber SPR sensor 3 ' based on graphene oxide and gold nanorods enhanced sensitivity with multimode fibre 2 ' for optical path, input terminal The wideband light source 1 ' that spectrum is visible light wave range is connected, output end connects broadband light spectrometer 4 ', and broadband light spectrometer 1 ' passes through number It is connected to outer computer according to interface, the optical fiber SPR sensor 3 ' based on graphene oxide and gold nanorods enhanced sensitivity is placed in be checked In the biomolecule solution of survey.
The preparation method of the above-mentioned optical fiber SPR sensor based on graphene oxide and gold nanorods enhanced sensitivity, steps are as follows:
(1) single mode side-polished fiber is prepared;
The outer diameter of single mode optical fiber is 125 μm, and 8.2 μm of core diameter, rubbing down length is 0.5~2cm, and rubbing down depth is 58.4nm.Using the wheeled rubbing down method in side, the pre- rubbing down area coat of single mode optical fiber is peeled off and cleaned, it will using fiber support frame To the optical fiber of rubbing down, its pre- rubbing down area is suspended vacantly and is tightly attached to the side of grinding wheel, controls grinding wheel using motor and computer Rotation and propulsion, so that the covering of optical fiber side can be polished off gradually.The rubbing down for carrying out observation optical fiber in real time using microscope is deep Degree.Meanwhile optical fiber both ends are connected respectively at light source with spectrometer, and the loss feelings of optical power in output spectrum can be monitored in real time Condition can stop when polishing thickness required for microscopic obtains.
(2) golden film is sputtered
Single mode side-polished fiber is put into vacuum ionic beam sputtering instrument, to sensor surface sputter golden film, vacuum from The electric current when sputtering of beamlet sputter is 7mA, the time be 3 points 30 seconds, golden film is with a thickness of 40~60nm;
(3) fixed graphene oxide film
Single mode side-polished fiber is immersed to the ethanol solution for filling the 4- aminothiophenol that 20mL concentration is 2mmol/L In culture dish, after 24 hours, distilled water flushing is used;4- aminothiophenol molecule can be connect by Au-S covalent bond with golden film, And amido (- NH2) is formed in golden film outer surface;Single mode side-polished fiber sensor is fixed on glass slide, concentration is taken For the graphene oxide dispersion 0.5mL of 0.5mg/mL, single mode side-polished fiber sensor is submerged, and is put into 40 DEG C of constant temperature In case, after forty minutes, graphene oxide dispersion evaporation is realized by physical evaporation method in the fixed graphite oxide in golden film surface Alkene film, graphene oxide film is with a thickness of 0.1~1nm;
(4) fixed gold nanorods:
Negatively charged kayexalate (PSS) solution of 5mg/mL is impregnated to the list for being coated with graphene oxide membrane It is mould side-polished fiber 10 minutes, then that diameter is 20nm, draw ratio 2.5, concentration are 0.05mg/mL gold nanorods are molten Liquid impregnates optical fiber 12 hours, realizes gold nanorods in the fixation of graphene oxide film surface by the method for electrostatic self-assembled.
Using the above-mentioned refractive index examination based on the optical fiber SPR sensor of graphene oxide and gold nanorods enhanced sensitivity measurement liquid It tests:
The utility model is successively immersed into refractive index based on the optical fiber SPR sensor of graphene oxide and gold nanorods enhanced sensitivity In the solution for being 1.3323,1.3337,1.3342,1.3352,1.3361, it is as shown in Figure 3 to obtain transmission spectrum curve.
Above-mentioned measurement result is subjected to linear fit, as shown in figure 4, the sensitivity of available sensor is 22248nm/ RIU, the linearity 0.9907 are improved compared to existing based on the optical fiber SPR sensor sensitivity of golden film/graphene oxide membrane About 400%.
D-type optical fiber has extremely strong evanescent wave, and evanescent wave can generate interaction with its ambient substance.Noble metal film has Good SPR effect, between the plasma wave on golden film surface and the local surface plasma wave on gold nanorods surface etc. Enhance electric field strength from excimer coupling effect, meanwhile, graphene oxide can promote the electric charge transfer between golden film and gold nanorods, And then enhance the interaction of surface plasma wave and test substance, improve detection sensitivity.
Optical fiber SPR sensor structure of the utility model based on graphene oxide and gold nanorods enhanced sensitivity is compared to common Optical fiber SPR sensor have higher sensing sensitivity and chemical stability, can real-time monitoring, it is compact-sized, answer extensively With fields such as physics, chemistry, biology, medical treatment, food safeties.
Finally, it should be noted that the above various embodiments is only to illustrate the technical solution of the utility model, rather than it is limited System;Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should Understand: it is still possible to modify the technical solutions described in the foregoing embodiments, or to some or all of Technical characteristic is equivalently replaced;And these are modified or replaceed, it does not separate the essence of the corresponding technical solution, and this is practical new The range of each embodiment technical solution of type.

Claims (8)

1. the optical fiber SPR sensor based on graphene oxide and gold nanorods enhanced sensitivity, which is characterized in that including single mode Side polishing fiber It is thick to be followed successively by the golden film of 40~60nm thickness, 0.1~1nm on the rubbing down face of single mode optical fiber Side polishing fiber from inside to outside for optical fiber Graphene oxide membrane and gold nanorods layer.
2. the optical fiber SPR sensor according to claim 1 based on graphene oxide and gold nanorods enhanced sensitivity, feature exist In graphene oxide membrane is fixed by Covalent bonding together method in the golden film surface.
3. the optical fiber SPR sensor according to claim 1 based on graphene oxide and gold nanorods enhanced sensitivity, feature exist In the gold nanorods are fixed on the surface of graphene oxide membrane by electrostatic self-assembled method.
4. the optical fiber SPR sensor according to claim 1 based on graphene oxide and gold nanorods enhanced sensitivity, feature exist In the single mode side-polished fiber, rubbing down face length is 0.5~2cm.
5. the optical fiber SPR sensor according to claim 1 based on graphene oxide and gold nanorods enhanced sensitivity, feature exist In, when the golden film is with a thickness of 50nm, transducer sensitivity highest.
6. the optical fiber SPR sensor according to claim 1 based on graphene oxide and gold nanorods enhanced sensitivity, feature exist When, the graphene oxide membrane is with a thickness of 0.5nm, transducer sensitivity highest.
7. the optical fiber SPR sensor according to claim 1 based on graphene oxide and gold nanorods enhanced sensitivity, feature exist In the diameter of the gold nanorods is 20~40nm, and draw ratio is 2.5~10.
8. the biography that high sensitivity optical fiber surface plasmon resonance biosensor is formed as described in any one of claim 1 to 7 claim Sensing system, which is characterized in that including using multimode fibre as the optical fiber based on graphene oxide and gold nanorods enhanced sensitivity of optical path Sensor, input terminal connect the wideband light source that spectrum is visible light wave range, and output end connects broadband light spectrometer, broadband spectral Instrument is connected to outer computer by data-interface, and the optical fiber SPR sensor based on graphene oxide and gold nanorods enhanced sensitivity is set In biomolecule solution to be detected.
CN201821483588.0U 2018-08-22 2018-09-11 Optical fiber SPR sensor based on graphene oxide and gold nanorods enhanced sensitivity Expired - Fee Related CN208705231U (en)

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