CN104155280B - Raman optics Fibre Optical Sensor self-reference quantified detection method - Google Patents
Raman optics Fibre Optical Sensor self-reference quantified detection method Download PDFInfo
- Publication number
- CN104155280B CN104155280B CN201410036536.9A CN201410036536A CN104155280B CN 104155280 B CN104155280 B CN 104155280B CN 201410036536 A CN201410036536 A CN 201410036536A CN 104155280 B CN104155280 B CN 104155280B
- Authority
- CN
- China
- Prior art keywords
- raman
- optical sensor
- fibre optical
- detection method
- optics fibre
- 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.)
- Expired - Fee Related
Links
Abstract
Raman optics Fibre Optical Sensor self-reference quantified detection method, belongs to technical field of optical signal detection.The trace analysis detection quantization solving existing organic molecule and biomolecule need to separately set derived reference signal and standard sample mutability, causes quantified precision low, the problem that the most affected by environment and testing cost is high.It is 100 550cm that the quantified detection method of the present invention mixes raman frequency in the optical fiber preparing Raman optics Fibre Optical Sensor‑1Semiconductor-quantum-point, using the Raman light scattering spectral signal intensity of semiconductor-quantum-point as standard reference signal intensity.The method quantified precision of the present invention is high and not by environmental disturbances, and detected value is stable, it is not necessary to analysis system separately sets reference source, it is adaptable to organic molecule, biochemical bacterial warfare agent, the trace detection of biomolecule and biomedical detection.
Description
Technical field
The invention belongs to technical field of optical signal detection, be specifically related to a kind of Raman optics Fibre Optical Sensor certainly
Reference quantization detection method.
Background technology
Raman optics Fibre Optical Sensor is to be applied to multi-field organic molecule and the biography of the low trace measurement of biomolecule
One of sense detection method, in prior art, including surface-enhanced Raman light scattering and Raman light scattering
Raman optics Fibre Optical Sensor research existing many reports.But, most of Raman optics Fibre Optical Sensors
Analyze testing result and be qualitative or semi-quantitative analysis detection.And draw for carrying out quantitative analysis detection application
Graceful optical fibers sensor, needs to use the Raman light scattering spectral intensity of the standard sample of known quantity (or concentration)
It is analyzed detection as quantifying reference standard, carries out the quantitative analysis of signal intensity by drawing standard curve.
But, strengthen Raman light scattering or Raman light scattering spectrum analysis for each organic molecular species and biomolecule table
The standard reference sample of detection mostly is organic standard sample or biological sample, and the optical property of this kind of sample is easily subject to
Time and environmental effect and change, thus affect and quantify detection and stability, precision and the accuracy of inspection；
It addition, for the instrument system of Raman optics Fibre Optical Sensor, instrument and equipment is required to peripheral hardware standard signal
Reference path or reference source, this adds increased analytical tool design and the complexity of structure and cost.
Semiconductor-quantum-point, such as CdTe, CdSe and CdS etc., has low Raman light scattering frequency, CdTe
LO phonon light scattering be located approximately at 167cm-1Place, the LO phonon light scattering of CdSe are located approximately at 208cm-1Place and
The LO phonon light scattering of CdS is located approximately at 306cm-1Place.In prior art, utilize CdTe, CdSe and CdS
Deng the report of semiconductor-quantum-point doped-glass, but the glass material of these doped semiconductor quantum dots is mainly
For optical Quality Research, and do not have any about the arrowband low frequency Raman of quantum dot in optical fiber will be doped in
Light scattering signal is for testing molecule surface enhanced raman spectroscopy or the reference signal strength of Raman light scattering detection
Report.
Summary of the invention
The trace analysis detection that it is an object of the invention to solve existing organic molecule and biomolecule quantifies to need separately
If derived reference signal and standard sample are variable, cause quantified precision low, the most affected by environment and testing cost is high
Technical problem, it is provided that a kind of Raman optics Fibre Optical Sensor self-reference quantified detection method.
The Raman optics Fibre Optical Sensor self-reference quantified detection method of the present invention, is to pass at Raman optical fibers
The raman frequency that adulterates in the optical fiber of sensor is 100-550cm-1Semiconductor-quantum-point, and with this semiconductor quantum
The Raman light scattering spectral signal intensity of point is joined as the standard of the Raman light scattering spectral signal intensity of determinand
Examine signal intensity.
Further, also include, with Raman light scattering spectral signal intensity and the semiconductor-quantum-point of determinand
Raman light scattering spectral signal intensity ratio/difference be quantitative analysis detected value, by draw standard curve, enter
And complete the quantization detection of determinand.
Further, described semiconductor-quantum-point is CdTe, CdSe or CdS.
Further, described optical fiber is glass optical fiber or plastic optical fiber.
Further, described semiconductor-quantum-point is entrained in being all-trans in layer of fiber core or optical fiber.
Further, described determinand is organic molecule, biomolecule, nanoparticle or biochemical bacterial warfare agent
Molecule.
The method have the benefit that
(1) present invention use semiconductor-quantum-point CdTe, CdSe and CdS have arrowband low frequency Raman light dissipate
Penetrate, and the Raman light scattering of organic molecule and biomolecule frequency is higher, the most all at 700cm-1Above, therefore
Join using semiconductor-quantum-point Raman light scattering signal intensity as the standard of determinand Raman light scattering signal intensity
Examine signal intensity, do not disturb the detection of determinand；
(2) self-reference of the present invention quantifies Raman optics Fibre Optical Sensor for instrument system, it is not necessary to separately design
Standard signal reference source, simplifies the structure of instrument system, reduces testing cost, and improves to be measured
Thing quantifies degree of accuracy and the accuracy of detection, and detected value is stable, not by environmental disturbances；
(3) the doped semiconductor quantum dot of the present invention is applicable to the Raman optics Fibre Optical Sensor of various diameter and shape
Device, and in the range of being suitably applied in whole Raman spectrum, including being applied to surface-enhanced Raman light scattering spectrum
Detection or the optical fibers sensor of Raman light scattering spectral detection.
Accompanying drawing explanation
Fig. 1 is Raman spectrum and the Raman spectrum of CdSe quantum dot of 4-MBA molecule in embodiment 1；
Fig. 2 is (I in embodiment 1203-IDeterminand)/I203Standard curve with testing concentration；
Fig. 3 is the Raman spectrum of 4-MBA molecule in comparative example 1；
Fig. 4 is the standard curve in comparative example 1.
Detailed description of the invention
In order to further appreciate that the present invention, below in conjunction with detailed description of the invention to the preferred embodiments of the invention
It is described, but it is to be understood that these describe simply for further illustrating the features and advantages of the present invention
It it not limiting to the claimed invention.
Raman optics Fibre Optical Sensor self-reference quantified detection method, comprises the following steps:
(1) raman frequency that adulterates in the optical fiber preparing Raman optics Fibre Optical Sensor is 100-550cm-1Half
Conductor quantum dot, prepares Raman optics Fibre Optical Sensor the most again, other in Raman optics Fibre Optical Sensor
Parts are not changed in, and semiconductor-quantum-point is preferably CdTe, CdSe or CdS, and optical fiber can be glass optical fiber
Or plastic optical fiber, doping position can being all-trans in layer at fiber core or optical fiber, doping method is existing skill
Art；
(2) by the laser input of the Raman optics Fibre Optical Sensor of step (1) and signal output part and Raman spectrum
Analyser carries out coupling and couples, in order to makes excitation source can be coupled into Raman optics Fibre Optical Sensor, will treat
The Raman signal surveying thing can feed back to be analyzed in analyser；
(3) sensor ends of Raman optics Fibre Optical Sensor is inserted aqueous solution or the buffer of determinand of determinand
In carry out collection and the detection of Raman signal, then will be simultaneously at 100-550cm-1Spectral region is interior and is more than
800cm-1Spectral region in the Raman light scattering spectral signal intensity of semiconductor-quantum-point detected respectively and treat
Survey the Raman light scattering spectral signal intensity of thing, with semiconductor-quantum-point at 100-550cm-1In spectral region
Raman light scattering spectral signal intensity as determinand more than 800cm-1Spectral region in Raman light dissipate
Penetrate the standard reference signal intensity of spectral signal intensity；
Noble metal nano particles also can be fixed on Raman optics Fibre Optical Sensor sensor ends surface, by determinand
The mode of covalency or absorption of carrying out with the noble metal nano particles of optical fiber surface is combined and carries out resonating surface and strengthen and draw
Graceful spectrum analysis detects；
(4) Raman light scattering spectral signal and the semiconductor-quantum-point Raman light scattering spectral signal to determinand
Relative intensity is analyzed, and then completes the detection of determinand；Generally use the Raman light scattering of determinand
Spectral signal intensity and the ratio of semiconductor-quantum-point Raman light scattering spectral signal intensity or difference are as quantization
Raman analysis detected value, as with semiconductor-quantum-point Raman light scattering spectral signal intensity IQuantum dotWith determinand
Raman light scattering spectral signal intensity IDeterminandDifference and IQuantum dotRatio, i.e. (IQuantum dot-IDeterminand)/IQuantum dotFor quantifying
Raman analysis detected value, and draw standard curve, mark with the functional relationship of this detected value with testing concentration x
Directrix curve is: (IQuantum dot-IDeterminand)/IQuantum dot=a+bx, a, b are constant, then (I detection obtainedQuantum dot-IDeterminand)/
IQuantum dotSubstitute into standard curve, and then obtain testing concentration x.
Present embodiment indication determinand is all with Raman optics Fibre Optical Sensor analysis be applicable to prior art
The material of detection, common for organic molecule, biomolecule, nanoparticle or biochemical bacterial warfare agent molecule,
Aqueous solution or the buffer buffer of determinand is generally used during analysis；Nanoparticle (such as gold or Nano silver grain)
Can detect with arbitrary shape, such as spherical, rod, triangle and elliposoidal etc..
Embodiment 1
In conjunction with Fig. 1 and Fig. 2, embodiment 1 is described
(1) doping CdSe quantum dot in the optical fiber that Raman optics Fibre Optical Sensor uses, optical fiber is glass light
Fibre, doping position is at fiber core；
(2) by laser input and the signal of the Raman optics Fibre Optical Sensor of step (1) CdSe quantum dot doping
Outfan couples with system of fluorescence analysis；
(3) sensor ends of Raman optics Fibre Optical Sensor CdSe quantum dot adulterated is inserted directly into volume respectively
Be the concentration of 50 μ L be respectively 5 and 40ng/mL the 4-MBA molecule with Nano silver grain surface recombination molten
In liquid, detection 4-MBA molecule is at 1100cm-1Surface enhanced raman spectroscopy and CdSe quantum dot 203
cm-1Raman spectrum, obtain CdSe quantum dot at 203cm-1Raman spectrum strength I203Divide with 4-MBA
Son is at 1100cm-1Raman spectrum strength IDeterminandDifference and I203Ratio, i.e. (I203-IDeterminand)/I203, and
Draw standard curve with the functional relationship of this value with testing concentration x, obtain (I203-IDeterminand)/I203=0.2+0.41x；
(4), after obtaining standard curve, the sensor ends of the Raman optics Fibre Optical Sensor of step (2) is the most directly inserted
Enter the concentration of 50 μ L be respectively 5,10,20, the 4-MBA with Nano silver grain surface recombination of 30ng/mL
In molecular solution, detection 4-MBA molecule is at 1100cm-1Surface enhanced raman spectroscopy and CdSe quantum dot
At 203cm-1Raman spectrum, obtain CdSe quantum dot at 203cm-1Raman spectrum strength I203With
4-MBA is at 1100cm-1Raman spectrum strength IDeterminandDifference and I203Ratio, i.e. (I203-IDeterminand)/I203,
Substitute into standard curve, obtain concentration x of determinand, calculate concentration value be close to 5 respectively, 10,20,
30ng/mL, illustrates that the present invention can be used in Raman optics Fibre Optical Sensor self-reference and quantifies detection；To obtain again
(I203-IDeterminand)/I203With respective concentration 5,10,20,30ng/mL be respectively coordinate the most in length and breadth, this transverse and longitudinal is sat
The point that mark determines is filled in detection curve, and the point obtained is denoted as shown in a, b, c, d, in fig. 2 from figure
2, it can be seen that the match value of standard curve of embodiment 1 is R=0.999, illustrate that the method for the present invention has
Higher accuracy and precision.
Fig. 1 is that the surface enhanced raman spectroscopy of 4-MBA molecule and CdSe quantum dot are at 203cm-1Raman
Spectrum, Fig. 2 is (I in embodiment 1203-IDeterminand)/I203Standard curve with testing concentration.
Comparative example 1
In conjunction with Fig. 3 and Fig. 4, comparative example 1 is described
(1) laser input and the signal of the Raman optics Fibre Optical Sensor adulterated without CdSe quantum dot are exported
End couples with system of fluorescence analysis；
(2) concentration that the Raman fiber sensor adulterated without CdSe quantum dot inserts 50 μ L respectively is respectively
5, in the 4-MBA molecular solution with Nano silver grain surface recombination of 40ng/mL, with directly gather
4-MBA molecule is at 1100cm-1Raman spectrum, exist with the 4-MBA molecule that the two concentration directly gathers
1100cm-1The functional relationship of raman spectrum strength and 4-MBA molecular concentration draw standard curve, standard is bent
Line is as shown in Figure 4；
(3) concentration that Raman fiber sensor is inserted directly into 50 μ L respectively is respectively 5,10,20,30 and
In the 4-MBA molecular solution with Nano silver grain surface recombination of 40ng/mL, directly gather respective concentration
4-MBA molecule is at 1100cm-1Surface enhanced raman spectroscopy；With directly gather 4-MBA molecule 1100
cm-1Raman spectrum strength tie up to the pass of corresponding 4-MBA molecular concentration on Fig. 4, draw its corresponding point
Value, respectively a0、b0、c0、d0、e0、f0, from fig. 4, it can be seen that standard curve and the match value of detected value
R=0.969, illustrates that the degree of accuracy of detection method and accuracy are higher.
Fig. 3 is the Raman spectrum in comparative example 1 with the 4-MBA molecule of Nano silver grain surface recombination；Fig. 4
For the standard curve in comparative example 1.
Obviously, the explanation of above example is only intended to help to understand method and the core concept thereof of the present invention.
It should be pointed out that, for the those of ordinary skill of described technical field, before without departing from the principle of the invention
Putting, it is also possible to the present invention is carried out some improvement and modification, these improve and modification also falls into present invention power
In the protection domain that profit requires.
Claims (7)
1. Raman optics Fibre Optical Sensor self-reference quantified detection method, it is characterised in that at Raman optics light
The raman frequency that adulterates in the optical fiber of fiber sensor is 100-550cm-1Semiconductor-quantum-point, and with quasiconductor amount
The Raman light scattering spectral signal intensity of son point is as the standard of the Raman light scattering spectral signal intensity of determinand
Reference signal strength.
Raman optics Fibre Optical Sensor self-reference quantified detection method the most according to claim 1, it is special
Levy and be, also include, with Raman light scattering spectral signal intensity and the Raman of semiconductor-quantum-point of determinand
The ratio of light scattering spectrum signal intensity/difference, as quantifying Raman analysis detected value, by drawing standard curve, is entered
And complete the quantization detection of determinand.
Raman optics Fibre Optical Sensor self-reference quantified detection method the most according to claim 1 and 2,
It is characterized in that, described semiconductor-quantum-point is CdTe, CdSe or CdS.
Raman optics Fibre Optical Sensor self-reference quantified detection method the most according to claim 1 and 2,
It is characterized in that, described optical fiber is glass optical fiber or plastic optical fiber.
Raman optics Fibre Optical Sensor self-reference quantified detection method the most according to claim 1 and 2,
It is characterized in that, described semiconductor-quantum-point is entrained in being all-trans in layer of fiber core or optical fiber.
Raman optics Fibre Optical Sensor self-reference quantified detection method the most according to claim 1 and 2,
It is characterized in that, described determinand is organic molecule, biomolecule or nanoparticle.
Raman optics Fibre Optical Sensor self-reference quantified detection method the most according to claim 6, it is special
Levying and be, described biomolecule is biochemical bacterial warfare agent molecule.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410036536.9A CN104155280B (en) | 2014-01-26 | 2014-01-26 | Raman optics Fibre Optical Sensor self-reference quantified detection method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410036536.9A CN104155280B (en) | 2014-01-26 | 2014-01-26 | Raman optics Fibre Optical Sensor self-reference quantified detection method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104155280A CN104155280A (en) | 2014-11-19 |
| CN104155280B true CN104155280B (en) | 2016-08-17 |
Family
ID=51880840
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410036536.9A Expired - Fee Related CN104155280B (en) | 2014-01-26 | 2014-01-26 | Raman optics Fibre Optical Sensor self-reference quantified detection method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104155280B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101059439A (en) * | 2006-04-19 | 2007-10-24 | 中国科学院半导体研究所 | Combined test system of micro-Raman spectroscopy and near infrared spectrometer |
| CN101393202A (en) * | 2008-11-06 | 2009-03-25 | 中国科学院长春光学精密机械与物理研究所 | Evanescent wave optical fiber biosensor and use thereof |
| CN101487046A (en) * | 2008-12-19 | 2009-07-22 | 天津工业大学 | DNA fluorescent probe and preparation thereof |
| CN102095719A (en) * | 2010-12-30 | 2011-06-15 | 浙江工业大学 | Optical fiber type sensor system based on surface plasma resonance and stimulated Raman scattering |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080166706A1 (en) * | 2005-03-30 | 2008-07-10 | Jin Zhang | Novel gold nanoparticle aggregates and their applications |
| US8456630B2 (en) * | 2011-05-06 | 2013-06-04 | Polaronyx, Inc. | Fiber based SERS sensor |
-
2014
- 2014-01-26 CN CN201410036536.9A patent/CN104155280B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101059439A (en) * | 2006-04-19 | 2007-10-24 | 中国科学院半导体研究所 | Combined test system of micro-Raman spectroscopy and near infrared spectrometer |
| CN101393202A (en) * | 2008-11-06 | 2009-03-25 | 中国科学院长春光学精密机械与物理研究所 | Evanescent wave optical fiber biosensor and use thereof |
| CN101487046A (en) * | 2008-12-19 | 2009-07-22 | 天津工业大学 | DNA fluorescent probe and preparation thereof |
| CN102095719A (en) * | 2010-12-30 | 2011-06-15 | 浙江工业大学 | Optical fiber type sensor system based on surface plasma resonance and stimulated Raman scattering |
Non-Patent Citations (4)
| Title |
|---|
| A Shape-Engineered Surface-Enhanced Raman Scattering Optical Fiber Sensor Working from the Visible to the Near-Infrared;Antonino Foti et al.;《Plasmonics》;20120624;第8卷;第13-23页 * |
| Quantum Dot-Based Biosensor for Detection of Human Cardiac Troponin I Using a Liquid-Core Waveguide;R. Cody Stringer et al.;《IEEE SENSORS JOURNAL》;20080331;第8卷(第3期);第295-300页 * |
| 较高掺杂浓度下CdSe /ZnS 量子点光纤光致荧光光谱;程成 等;《光学学报》;20091031;第29卷(第10期);第2698-2704页 * |
| 采用Simplex 编码光外调制的拉曼散射分布式光纤传感器;宋牟平等;《中国激光》;20100630;第37卷(第6期);第1462-1466页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104155280A (en) | 2014-11-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zuber et al. | Detection of gold nanoparticles with different sizes using absorption and fluorescence based method | |
| Cennamo et al. | Monitoring of low levels of furfural in power transformer oil with a sensor system based on a POF-MIP platform | |
| Virkler et al. | Blood species identification for forensic purposes using Raman spectroscopy combined with advanced statistical analysis | |
| De Luca et al. | Modulated Raman spectroscopy for enhanced cancer diagnosis at the cellular level | |
| CN103785492B (en) | Based on the SERS microfluidic system of PDMS three-D micro-nano antenna | |
| Wang et al. | Application of near-infrared spectroscopy to agriculture and food analysis | |
| CN101666750A (en) | Surface-enhanced raman scattering torquemaster based on optical fiber fuse-tapered coupler | |
| Galievsky et al. | Improvement of LOD in fluorescence detection with spectrally nonuniform background by optimization of emission filtering | |
| Sandfort et al. | Monitoring the wobbe index of natural gas using fiber-enhanced Raman spectroscopy | |
| Chen et al. | Determination of nicotinyl pesticide residues in vegetables by micellar electrokinetic capillary chromatography with quantum dot indirect laser‐induced fluorescence | |
| EP2151679A3 (en) | Method and apparatus for the analysis of materials | |
| DE50012985D1 (en) | PROCESS FOR INFRARED-OPTIC DETERMINATION OF THE CONCENTRATION OF AT LEAST ONE ANALYTE IN A LIQUID SAMPLE | |
| CN106596499A (en) | Real-time Raman spectrum calibration method | |
| CN104155280B (en) | Raman optics Fibre Optical Sensor self-reference quantified detection method | |
| Ishibashi et al. | Precise determination of Mg/Fe ratios applicable to terrestrial olivine samples using Raman spectroscopy | |
| Nachtmann et al. | Molecule sensitive optical imaging and monitoring techniques—A review of applications in micro-process engineering | |
| Mello et al. | Analysis of the DNA Fourier transform-infrared microspectroscopic signature using an all-reflecting objective | |
| WO2017011877A1 (en) | Detection of gold nanoparticles | |
| Zhao et al. | Method for extracting Raman spectra characteristic variables of biological sample based on Hilbert–Huang transform | |
| CN104165852A (en) | Resonance Rayleigh scattering energy transfer spectroscopy method for determining fluorinion simply and rapidly | |
| CN106880338A (en) | Neoplasm in situ on-line detecting system based on SERS technology | |
| RU2556285C1 (en) | Measuring method of geometrical parameters of non-spherical particles in liquid as per depolarised dynamic light scattering and device for its implementation | |
| Li et al. | A high‐sensitivity LIF detector with silver mirror coating detection window and small‐angle optical deflection from collinear system for CE | |
| CN103868897A (en) | Fluorescent biomarker multi-micropore plate self-reference quantitative detection method | |
| Fernandez de la Ossa et al. | Analysis and differentiation of paper samples by capillary electrophoresis and multivariate analysis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160817 Termination date: 20180126 |