CN105445242A - Special optical fiber biochemical sensor based on evanescent wave technique - Google Patents
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- CN105445242A CN105445242A CN201510779036.9A CN201510779036A CN105445242A CN 105445242 A CN105445242 A CN 105445242A CN 201510779036 A CN201510779036 A CN 201510779036A CN 105445242 A CN105445242 A CN 105445242A
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- 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
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/645—Specially adapted constructive features of fluorimeters
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- 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
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/645—Specially adapted constructive features of fluorimeters
- G01N2021/6463—Optics
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Abstract
The invention relates to a special optical fiber biochemical sensor based on an evanescent wave technique and belongs to the field of biological optical fiber sensing in biomedicine photonics. A special porous microstructure optical fiber with fiber core diameter being 1+/-0.2 microns serves as a detecting probe; Schott N-BK7 series glass is taken as the material of the fiber core; a cavity of the optical fiber is divided into two independent parts by the film for supporting the fiber core; the two ends of the film for supporting the fiber core are respectively connected with the optical fiber; the D263T series glass is taken as the material and the glass film is equivalent to the boundary between two holes of the optical fiber. The laser enters into the fiber core of the optical fiber through space optical coupling, the core diameter of the optical fiber is approximate to the optical wavelength size, the exterior of the fiber core of the optical fiber is full of air and the refractive index difference between air and fiber core is large, so that the ultra-strong evanescent wave can be generated on the exterior of the fiber core and the evanescent wave brings great convenience to the biochemical sensing.
Description
Technical field
The present invention relates to the extraordinary sub-nanostructured optical fiber of application to reach biochemical material by combining with laser and detect object, belong to the biological sensory field of optic fibre in Biomedical Photonics.
Background technology
Along with the fast development of China's economic, environmental problem (comprising the quality problems of air and water), food security, drug safety and health care all become the problem improving people's living standard and preecedence requirement solution.Miniaturization, can carry, low cost, high-sensitive be realize monitoring in real time for chemistry and the biochemical sensor part of biological field, and the necessary supplementary means addressed these problems technically quickly and accurately.
For the optical sensor of chemical detection, multiple fields in biomedical research, health care, medicine, environmental monitoring, Homeland Security and battlefield can be widely used in.Be characterized in that there is powerful determination and analysis function, not by electromagnetic interference (EMI), can remote sensing be carried out, and Multiple detection can be provided in individual equipment.Compare with other optical waveguide sensors, optical fiber has the low advantage of cost in low transmission loss, long light path, unit length, and the sensor of fiber form can dock with common low-loss telecommunication optical fiber easily, thus realize the object of remote monitor.So optical fiber is obviously very good be used for realizing low cost, Miniaturizable and portability and have the form of medium of highly sensitive detection chemical substance.
So far nearly 20 years at the bottom of last century, porous microstructure optical fibre (being often called as microstructured optical fibers or photonic crystal fiber again) (as shown in Figure 1), as a kind of novel structured optical fiber, obtains and payes attention to greatly and development.
Porous microstructure optical fibre is except being used in the traditional field such as high power laser, long-distance optical communication, because the hollow-core construction in its covering makes the fibre core of optical fiber and covering have great refringence, make the core diameter of optical fiber can be very little, to the yardstick close to optical wavelength, thus the intensity of the unit area of the light propagated in fibre core is made to reach very big; Meanwhile, the light of the evanescent wave (evanescentfield) outside core and the registration of environment also quite large.Meanwhile, the covering of porous structure, for accommodation gas and liquid provide the passage of a macro structural scale.When the host material using non-quartz glass (as fluoride glass, heavy metal oxide glass, chalcogenide glass) as porous microstructure optical fibre, optical fiber can extend to middle-infrared band (2-20 micron) from visible ray (400-700 nanometer) and near infrared (700-1700 nanometer) wave band through wave band, thus can directly detect the fundamental vibration of the organic and inorganic molecule that many kinds exist with gas or liquid form by evanescent wave absorption spectroscopy and quantize its content.Above four basic characteristics, the porous microstructure optical fibre determining little core diameter is desirable, Miniaturizable, portable and have the platform of highly sensitive evanescent wave chemical sensor.
Summary of the invention
The object of the invention is to create with extraordinary porous microstructure optical fibre as probe material is to carry out the biochemical sensor of biochemical material detection.
The present invention only has the extraordinary porous microstructure optical fibre of 1 ± 0.2 micron with core diameter, as exploratory probe, structure is as shown in Fig. 2 (Electronic Speculum figure), and the core material of this optical fiber is commercial SchottN-BK7 P series glass; The cavity of optical fiber is divided into independently two parts by the film supporting fibre core, wherein supports the two ends of the film of fibre core respectively together with Fiber connection; The thickness supporting the film of fibre core is generally 160nm, and material belongs to D263T P series glass, and this glass film is equivalent to the boundary between optical fiber holes; Mentioned this two kinds of glass all belong to borosilicate glass above, are the difference that the thermodynamic behaviour of two kinds of glass has some tiny.Next, laser enters in the fibre core of this optical fiber by space optical coupling, because the core diameter of this optical fiber is close to optical wavelength size, and the outside of fiber core is air, differ larger with the refractive index (about 1.5) of fibre core, will can produce extremely strong evanescent wave in the outside of fibre core like this, this evanescent wave (evanescentfield) provides a great convenience for biological chemistry sensing.
The present invention is based on the special optical fiber biochemical sensor of evanescent wave technology, it is characterized in that, the extraordinary porous microstructure optical fibre of 1 ± 0.2 micron is only had with core diameter, as exploratory probe, the cavity of optical fiber is divided into independently two parts by the film supporting fibre core, wherein supports the two ends of the film of fibre core respectively together with Fiber connection; Concrete structure: the upper fixing extraordinary porous microstructure optical fibre probe (2) of three-dimensional adjustment platform (1), the front end of extraordinary porous microstructure optical fibre probe (2) is provided with the first fiber coupling lens (3), the front end of fiber coupling lens is provided with 45 ° of tilted-putted dichroic mirrors (4), the front end of dichroic mirror (4) is provided with a pair catoptron, for catoptron A and catoptron B, the front end of catoptron B is provided with the second fiber coupling lens (5), and the front end of the second fiber coupling lens (5) is provided with large core diameter multimode optical fiber (6); Also be provided with laser instrument laser to be irradiated on dichroic mirror (4).
During test, extraordinary porous microstructure optical fibre probe (2) is due to micron-sized core bore, determinand is filled into extraordinary porous microstructure optical fibre probe (2) core bore from the tail end of extraordinary porous microstructure optical fibre probe (2) by the capillary action of extraordinary porous microstructure optical fibre probe (2) core bore fast, extraordinary porous microstructure optical fibre probe (2) core bore part is filled with determinand, namely the end section of extraordinary porous microstructure optical fibre probe (2) is filled with, and the initiating terminal of extraordinary porous microstructure optical fibre probe (2) is not filled with, still retain air, laser is irradiated on dichroic mirror (4) by laser instrument, the laser of the upper reflection of dichroic mirror (4) is coupled in extraordinary porous microstructure optical fibre probe (2) by the first fiber coupling lens (3), when laser transmits in the fibre core of extraordinary porous microstructure optical fibre probe (2), due to the singularity that the core diameter of this optical fiber is little especially, so will produce extremely strong evanescent wave in the airport outside fibre core, evanescent wave can excite the determinand be filled with in optic fibre hole, determinand can be excited generation fluorescence by evanescent wave, fluorescence to turn back to the initiating terminal of special optical fiber through special optical fiber by launching effect, again successively by the first coupled lens, dichroic mirror, catoptron A, catoptron B enters into the multimode optical fiber of the large core diameter accepting fluorescence, and then enter into spectrometer or monochromator, photoluminescence spectrum intensity is measured by fluorescent probe, and then quantize the concentration of determinand.
Because the diameter of this extraordinary porous microstructure optical fibre is smaller, the biological or chemical material be detected can be filled in optical fiber by capillary action by we, because the diameter of this porous structure optical fiber only has micron dimension, so test substance can be very fast be charged in optical fiber, this feature makes Fibre Optical Sensor fast become possibility, when solution to be measured is filled into a part (as 2/3 place) for fiber lengths, another part or air, under the effect of strong evanescent wave, measured matter can with evanescent wave generation effect, so just can produce fluorescent spectrometry by evanescent wave absorption spectroscopy or evanescent wave fluorescence excitation carry out the existence of detecting material and quantize.
For sensor performance, the volume of required measured matter, detection time, the sensitivity of instrument and the detection limit of instrument are the parameters of several important assessment sensor performance.
The present invention, by adhering to nm of gold or Argent grain in extraordinary porous microstructure optical fibre fibre core, increases the sensitivity of detection.
Compared with prior art, the present invention has following advantage:
1. measured matter volume is little.When we carry out detection experiment, consider the factor such as fibre loss or material absorbing coefficient, we generally can use the special optical fiber of 0.3m-0.5m length, add the diameter in our this special optical fiber hole in micron dimension, be detected the volume of material through calculating needed for us in nL magnitude, this is also a large advantage in sensing circle.
2. detection time is short.If when laser coupled has been entered in the fibre core of special optical fiber by we, its fiber core can produce evanescent wave at once, so when measured matter is charged among optical fiber, evanescent wave can with measured matter immediate response, the change of such spectrum can detect, immediately so the detection time of this special optical fiber sensor is very short on spectrum display instrument.
3. detection limit is low.Sensor detection limit DL (or lower limit) is another important parameter being used for characterizing sensor performance.The noise level σ (Minimum Discernible Signal) that this parameter exists when the change of amalyzing substances can be converted to signal by sensor releases: DL=σ/S (S is instrumental sensitivity).Improve DL to be realized by the noise level increasing sensitivity or reduction.So when noise of instrument is certain, core diameter is less, and evanescent wave is larger, and sensitivity is higher.So, also be favourable based on the chemical sensor of the porous microstructure optical fibre of little core diameter to improving detection limit inevitable.
As a whole, the possible optical fiber structure design by means of only optimizing optical fiber structure, the performance of fibre optic chemical sensor (particularly sensitivity) being improved all has been taken into account with theoretical modeling by experiment.The sensitivity of fibre optic chemical sensor to being improved again further, considering from the aspect beyond optical fiber structure with regard to needing.
Because sensitivity can be improved by the interaction increased between light and material, in most of the cases, this is equivalent to the mark of the light added near sensitive surface.This can be realized by the various functional nano structural material of compound on the surface of fiber core.Utilize the surface enhanced effect brought by nano structural material, surface plasma body resonant vibration (the Surfaceplasmonresonance realized as utilized metal nanoparticle, and Surface enhanced raman spectroscopy (surface-enhancedRamanspectra SPR), SERS), the detection limit of individual molecule can be reached in Molecular Detection.What this invented finally will continue to improve the detection limit of sensor by the improvement of optical fiber structure with new material (particularly the functional material of nanostructured), SPR and SERS etc. add conventional absorption spectrum and detect and fluorescence spectrum detection, combine with as the optical wavelength of evanescent wave sensor medium or the microstructured optical fibers of sub-optical wavelength size naked core, transducer sensitivity can be improved further, improve detection limit.
Accompanying drawing illustrates:
Fig. 1 is used as the structural scheme of mechanism of the photonic crystal fiber of Fibre Optical Sensor.
The extraordinary porous microstructure optical fibre scanning electron microscope (SEM) photograph that Fig. 2 the present invention is used.
The utilizing emitted light spectrogram of rhodamine B under Fig. 3 variable concentrations under 532nm laser excitation.
Fig. 4 detects rhodamine B concentration experiment apparatus structure schematic diagram
The fluorescence spectrum of 1 μm of oL rhodamine B solution that Fig. 5 embodiment 1 records.
1 three-dimensional adjustment platform, 2 extraordinary porous microstructure optical fibre probes, 3 first fiber coupling lens, 4 dichroic mirrors, 5 second fiber coupling lens, 6 large core diameter multimode optical fibers, 7 laser instruments, 8 liquid to be measured.
Embodiment
Below in conjunction with embodiment, the present invention will be further described, but the present invention is not limited to following examples.
Embodiment 1
Accompanying drawing 2 is experimental provision schematic diagram, and this tests the continuous wave laser that LASER Light Source used is 532nm or its all band, and detecting material is bioluminescence element, protein, amino acid, biology enzyme, cancer cell etc.One of such as detecting material wherein rhodamine B: 532nm wavelength be rhodamine B better excite wave band, its maximum emission wavelength is at about 580nm, so selected by us the parameter of dichroic mirror be high reverse--bias wave band 525-556nm, high wave transparent section 580-650nm.Fig. 5 is under the effect of 532nm exciting light, the emission spectrum spectrum of variable concentrations rhodamine B.Can find out, under too high concentration, the emission spectrum of rhodamine B is poor all the better, this is because too high concentration produces fluorescent quenching under the effect of laser, thus causes photoluminescence spectrum intensity to be deteriorated.
First, rhodamine B is filled in the airport of special optical fiber by capillary action by we, because the diameter of airport only has micron dimension, so the speed be filled with is very fast.Following 532nm laser is by space optical coupling technology, laser is coupled in the fibre core of the optical fiber of extraordinary porous microstructure by condenser lens, when laser transmits in fiber core, due to the singularity that the core diameter of this optical fiber is little especially, so will produce extremely strong evanescent wave in the airport outside fibre core, evanescent wave can excite the rhodamine B solution be filled with in airport, rhodamine B solution can be excited generation fluorescence by evanescent wave, fluorescence to turn back to the initiating terminal of special optical fiber through special optical fiber by launching effect, the multimode optical fiber of the large core diameter accepting fluorescence is entered into again by coupled lens and dichroic mirror, and then enter into spectrometer or monochromator, we just can see fluorescence spectrum by spectrometer like this, the concentration of rhodamine B solution is quantized by photoluminescence spectrum intensity.The device that we detect fluorescence spectrum must be spectrometer or the monochromator of high s/n ratio, and this also has vital effect to the raising of the detection limit of sensor.
Last result we will draw the spectrum of variable concentrations rhodamine B from spectrometer, by the intensity difference between spectrum, we just can quantize the concentration of rhodamine B, thus reach detection and the object quantized, finally we can obtain the detection limit concentration of a rhodamine B, the concentration of rhodamine B that we can detect at present is 1 μm of oL, the fluorescence spectrum detected is Fig. 5, follow-up we also can detect the rhodamine B of lower concentration, and the rhodamine B concentration that can be detected by analog simulation and this optical fiber of literature survey can reach pmoL magnitude.This is a kind of very large propelling to fiber-optic biosensor.
Case study on implementation two.
We in conjunction with utilizing SPR and SERS technology, by adhering to nm of gold or Argent grain in extraordinary porous microstructure optical fibre fibre core, increase the sensitivity of detection, thus improving the detection limit of sensor and the performance of Fibre Optical Sensor further.
Claims (4)
1. based on the special optical fiber biochemical sensor of evanescent wave technology, it is characterized in that, the extraordinary porous microstructure optical fibre of 1 ± 0.2 micron is only had with core diameter, as exploratory probe, the cavity of optical fiber is divided into independently two parts by the film supporting fibre core, wherein supports the two ends of the film of fibre core respectively together with Fiber connection; Concrete structure: the upper fixing extraordinary porous microstructure optical fibre probe (2) of three-dimensional adjustment platform (1), the front end of extraordinary porous microstructure optical fibre probe (2) is provided with the first fiber coupling lens (3), the front end of fiber coupling lens is provided with 45 ° of tilted-putted dichroic mirrors (4), the front end of dichroic mirror (4) is provided with a pair catoptron, for catoptron A and catoptron B, the front end of catoptron B is provided with the second fiber coupling lens (5), and the front end of the second fiber coupling lens (5) is provided with large core diameter multimode optical fiber (6); Also be provided with laser instrument laser to be irradiated on dichroic mirror (4).
2. according to the special optical fiber biochemical sensor based on evanescent wave technology of claim 1, it is characterized in that, in extraordinary porous microstructure optical fibre fibre core, adhere to nm of gold or Argent grain, increase the sensitivity of detection.
3. according to the special optical fiber biochemical sensor based on evanescent wave technology of claim 1, it is characterized in that, the thickness supporting the film of fibre core is 160nm, and material belongs to D263T P series glass.
4. adopt the special optical fiber biochemical sensor based on evanescent wave technology described in any one of claim 1-3 to carry out the method for biochemical test, it is characterized in that, during test, extraordinary porous microstructure optical fibre probe (2) is due to micron-sized core bore, determinand is filled into extraordinary porous microstructure optical fibre probe (2) core bore from the tail end of extraordinary porous microstructure optical fibre probe (2) by the capillary action of extraordinary porous microstructure optical fibre probe (2) core bore fast, extraordinary porous microstructure optical fibre probe (2) core bore part is filled with determinand, namely the end section of extraordinary porous microstructure optical fibre probe (2) is filled with, and the initiating terminal of extraordinary porous microstructure optical fibre probe (2) is not filled with, still retain air, laser is irradiated on dichroic mirror (4) by laser instrument, the laser of the upper reflection of dichroic mirror (4) is coupled in extraordinary porous microstructure optical fibre probe (2) by the first fiber coupling lens (3), when laser transmits in the fibre core of extraordinary porous microstructure optical fibre probe (2), due to the singularity that the core diameter of this optical fiber is little especially, so will produce extremely strong evanescent wave in the airport outside fibre core, evanescent wave can excite the determinand be filled with in optic fibre hole, determinand can be excited generation fluorescence by evanescent wave, fluorescence to turn back to the initiating terminal of special optical fiber through special optical fiber by launching effect, again successively by the first coupled lens, dichroic mirror, catoptron A, catoptron B enters into the multimode optical fiber of the large core diameter accepting fluorescence, and then enter into spectrometer or monochromator, photoluminescence spectrum intensity is measured by fluorescent probe, and then quantize the concentration of determinand.
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CN110174380A (en) * | 2019-05-10 | 2019-08-27 | 北京工业大学 | Biochemical sensor based on hollow antiresonance optical fiber |
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CN110174380A (en) * | 2019-05-10 | 2019-08-27 | 北京工业大学 | Biochemical sensor based on hollow antiresonance optical fiber |
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