CN102012368A - System and method for detecting multi-parameter of up-conversion luminescent particles - Google Patents

System and method for detecting multi-parameter of up-conversion luminescent particles Download PDF

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CN102012368A
CN102012368A CN 201010501521 CN201010501521A CN102012368A CN 102012368 A CN102012368 A CN 102012368A CN 201010501521 CN201010501521 CN 201010501521 CN 201010501521 A CN201010501521 A CN 201010501521A CN 102012368 A CN102012368 A CN 102012368A
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detecting unit
conversion luminescence
cuvette
data
ucp
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CN102012368B (en
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冯春霞
王剑波
黄立华
屈建峰
黄惠杰
周蕾
杨瑞馥
郑岩
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Shanghai Institute of Optics and Fine Mechanics of CAS
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Abstract

The invention relates to system and method for detecting multi-parameter of up-conversion luminescent particles. The system comprises an illumination unit, a sample cell, a power detection unit, a transmitted light detection unit, a scattered light detection unit, an up-conversion luminescent detection unit, a power detection unit pre-amplification circuit, a transparent light detection unit pre-amplification circuit, a scattered light detection unit pre-amplification circuit, a control and data acquisition unit and a data processing unit. The bigger measured offset caused by slight fluctuation of a light source is compensated through detecting the power of the light source; and the turbidity and the concentration of a UCP suspension are detected through simultaneously collecting the up-conversion luminescence, the transmitted light and the scattered light of the particles. The ratio of the scattered light to the transmitted light of the UCP suspension to be detected and an up-conversion luminescent signal are compared with a standard work curve to obtain the turbidity value and the concentration value of the UCP suspension sample to be detected. The invention has the advantages of high sensitivity and reliability, favorable stability, simple structure, lower cost and low requirement on an operator, is easy for assembling and correcting, and the like.

Description

Up-conversion luminescence particle multiparameter detection system and method
Technical field
The present invention relates to up-conversion luminescence, particularly a kind of up-conversion luminescence particle multiparameter detection system and method.The present invention determines the turbidity and the concentration of up-conversion luminescence suspension by transmitted light, scattered light and the up-conversion luminescence that receives the up-conversion luminescence particle simultaneously, with realize to the optical characteristics of up-conversion luminescence particle quick, objective, quasi real time even in real time detect.
Background technology
Infrared up-conversion luminous material (Up-Converting Phosphor, be designated hereinafter simply as UCP) be the nano-scale particle that in the lattice of crystal, constitutes by rare earth doped, so be called up-conversion luminescence particle (abbreviating the UCP particle as) again, (wavelength＞780nm) excites visible emitting (wavelength is 475-670nm) down, and it is with a wide range of applications in 3 D stereo demonstration, infrared acquisition, bioluminescence spike, all many-sides such as false proof at infrared light for it.After the UCP particle being carried out a series of finishinges and activating, it can be combined with multiple bioactive molecule as biomarker, with high responsive specific identification between its unique up-conversion luminescence characteristic indicator organism bioactive molecule.When UCP particle during,, can obtain the concentration of the biological substance that combines with it by detecting its up-conversion luminescence intensity as biomarker.Therefore, in order accurately to obtain the concentration of biological substance, must hold and the up-conversion luminescence strength characteristics of control UCP particle under specific concentrations and turbidity.The UCP particle detection system realizes by scattered light, transmitted light and the up-conversion luminescence intensity that detects the UCP suspension.
Technology 1 " laser turbidimeter " (application number: 200920099825.8) formerly, the scattered light of detection by quantitative suspension and/or transmitted intensity, realization is to the detection of its turbidity, this detection method can only obtain the turbidity value of suspension, can not directly detect the up-conversion luminescence characteristic and the concentration of UCP particle; Adopt high-brightness laser as optical transmitting set, the signal to noise ratio (S/N ratio) of turbidimeter is improved greatly, improved the stability of instrument comprehensively, but can't handle the fluctuation of the caused signal of fluctuation of light source, and this turbidimeter adopts optical signal transmissive as detection signal, and the linearity is relatively poor, and sensitivity is lower.
Technology 2 " doubly scattered light turbidimeter " (application number: 01253067.0) formerly, adopt the differential output of doubly scattered light passage as measured value, make and disturb electrical signal noise to cancel out each other, improved signal to noise ratio (S/N ratio), but it adopts lamp as light source, because the light that lamp sends is many in visible-range, is influenced by colourity easily, can not detect band tinctorial pattern product when detecting coloured sample.
Summary of the invention
Deficiency at above-mentioned prior art existence, the objective of the invention is to propose a kind of up-conversion luminescence particle multiparameter detection system and method, this detection system should have susceptibility height, reliability height, good stability, simple in structure, be easy to adorn the school and cost is lower, operating personnel are required advantages such as low.
The present invention is based on up-conversion luminescence theory, Lambert-Beer theorem and light scattering theory, and the turbidity of UCP suspension and concentration are detected.The detection principle is:
The up-conversion luminescence intensity of UCP suspension is relevant with following factor:
1. excitating light strength I 0
2.UCP the UCP amounts of particles N in the suspension unit volume, i.e. UCP suspension concentration;
3.UCP particle up-conversion luminescence efficiency eta.
When the excitating light strength of incident satisfies excitation threshold condition and excitating light strength I 0With one timing of up-conversion luminescence efficiency eta, the up-conversion luminescence intensity of the suspension that UCP suspension concentration is certain is tending towards a definite value; The concentration that is the UCP suspension is high more, and its up-conversion luminescence intensity is big more.
There are proportionate relationship in the total content M of UCP particle and the capacity V and the UCP suspension concentration N of measurement zone in the measurement zone, promptly
M∝V×N， (1)
Satisfying I 0After the constant condition of η, the up-conversion luminescence intensity I -90 °Satisfy following relation:
I -90°∝M∝V×N. (2)
By the Lambert-Beer theorem as can be known, a beam intensity is I 0, wavelength is that the monochromatic collimated beam of λ incides when containing unordered and equally distributed tested particle swarm medium, because particle is to scattering of light and absorption, the transmission light intensity will be decayed, its attenuation degree is relevant with the size and the concentration of particle, and this just provides a yardstick for particle detection.The intensity I of transmitted light 0 °For:
I 0°＝K 0I 0e -Kτ， (3)
Total scattering light intensity I along 90 ° of directions 90 °For:
I 90°＝K 1I 0τe -Kτ， (4)
When low turbidity, be along the scattered light intensity of 90 ° of directions:
I 90°＝K 1I 0τe -Kτ∝K 1I 0τ (5)
During high turbidity, scattered light intensity and transmitted intensity than (turbidimetry, abbreviate as loose thoroughly than) are:
Figure BSA00000296135900021
Wherein: I 0Be incident intensity;
τ is a turbidity, is proportional to the content of suspension in the unit volume;
K is the coefficient relevant with measured zone;
K 0, K 1, K 2Be the coefficient relevant with the photoelectric transformation efficiency of photodetector.
By formula (5) and formula (6) as can be known, when hanging down turbidity, the better linearity relation is arranged between scattered light intensity signal and the turbidity, loose during high turbidity saturating than and turbidity between have better linearity to concern, therefore, when low turbidity and high turbidity, adopt (5) formula and formula (6) respectively, can access the range of linearity of broad, as shown in Figure 1, draw 0～τ tMatched curve in the turbidity scope, as shown in Figure 1, this curve is with turbidity τ QAs the separatrix, when being lower than this turbidity, carry out match with formula (5), carry out match with formula (6) when being higher than this turbidity.
Technical solution of the present invention is as follows:
A kind of up-conversion luminescence particle multiparameter detection system, characteristics are that its formation comprises lighting unit, sample cell, power detecting unit, transmitted light detecting unit, scattered light detecting unit, up-conversion luminescence detecting unit, power detecting unit pre-amplification circuit, transmitted light detecting unit pre-amplification circuit, scattered light detecting unit pre-amplification circuit, control and data acquisition unit and data processing unit:
Described lighting unit is made up of laser instrument, collimating mirror, dichronic mirror, cylindrical mirror, the laser that described laser instrument sends becomes parallel beam through described collimating mirror, this parallel beam is divided into folded light beam and transmitted light beam through described dichronic mirror, and described folded light beam is shone described sample cell through the excitation beam that cylindrical mirror forms certain size, shape; In described transmitted light beam direction described power detecting unit is set;
Described power detecting unit is made up of first optical filter, first focus lamp, first aperture and first photodetector successively along the transmitted light beam direction;
Described sample cell is made up of cuvette and cuvette groove; Described cuvette is transparent, is used to install up-conversion luminescence suspension to be measured, abbreviates the UCP suspension as; This cuvette is arranged in the light path of described excitation beam, and described excitation beam forms transmitted light, scattered light and up-conversion luminescence after shining the UCP suspension to be measured of described cuvette;
Transmitted light direction at described cuvette is provided with described transmitted light detecting unit, and this transmitted light detecting unit is made up of second optical filter, second focus lamp, attenuator, second aperture and second photodetector successively along the transmitted light direction;
Described scattered light detecting unit is set above described cuvette, and this scattered light detecting unit is made up of the 3rd focus lamp, the 3rd optical filter, the 4th focus lamp, the 3rd aperture and the 3rd photodetector successively;
Described up-conversion luminescence detecting unit is set below described cuvette, and this up-conversion luminescence detecting unit is made up of the 4th focus lamp, the 5th focus lamp, the 4th aperture and photomultiplier successively along described up-conversion luminescence direction;
The electric signal that the electric signal of first photodetector output is exported behind described power detecting unit pre-amplification circuit, the electric signal that the electric signal of second photodetector output is exported behind described transmitted light detecting unit pre-amplification circuit, the electric signal of voltage signal that the electric signal of described the 3rd photodetector output is exported behind described scattered light detecting unit pre-amplification circuit and the output of described photomultiplier is together through described control and data acquisition unit collection, realize that sending into described data processing unit after A/D changes carries out data processing, with the parameter demonstration of tested UCP suspension, storage or output;
Described detection system should be carried out necessary adjustment and demarcation before measurement.
Described transmitted light detecting unit, scattered light detecting unit and up-conversion luminescence detecting unit are integrated in the same cavity.
The light path position of described scattered light detecting unit and up-conversion luminescence detecting unit can exchange, and unique requirement is that the light path of described scattered light detecting unit and up-conversion luminescence detecting unit is not disturbed and mutually perpendicular to described excitation beam and by in the plane of described cuvette.
Described first optical filter, second optical filter, the 3rd optical filter are the long-pass type optical filter, only see through the infrared light of described laser instrument emission, are used for the filtering veiling glare.
Described first aperture, second aperture, the 3rd aperture, the 4th aperture are used to limit the aperture and the solid angle of collecting light beam, and the receiving area that limits detector is less than or equal to the photosensitive area of detector with the aperture that guarantees light beam.
The method of described adjustment and demarcation comprises the steps:
(1) determining of circuit parameter:
1. be after the standard UCP suspension sample concussion of 2.0mg/ml shakes up with concentration, get a certain amount of standard UCP suspension sample with pipettor and put into cuvette, open described laser instrument, described excitation beam shines described cuvette, regulate the resistance of power detecting unit and scattered light detecting unit pre-amplification circuit respectively: this pre-amplification circuit changes voltage by electric current and signal amplification two-stage circuit is formed, adjust the adjustable resistance of one-level amplifying circuit, make a step voltage be output as 0.5～1V; Adjust the adjustable resistance of second amplifying circuit, make the one-level output voltage after secondary amplifies, be output as 9.5V (being slightly less than output saturation value 10V), fixing each resistance value at this moment; Regulate the up-conversion luminescence added bias voltage of light path photomultiplier (0～5V is adjustable), the enlargement factor when working with definite photomultiplier makes output voltage 9.5V (being slightly less than output saturation value 10V), the bias voltage value of fixing this moment;
2. get a certain amount of zero turbidity water and inject cuvette, open described laser instrument, described excitation beam shines described cuvette, adjusts the resistance of transmitted light detecting unit pre-amplification circuit: adjust the adjustable resistance of one-level amplifying circuit, make a step voltage be output as 0.5～1V; Adjust the adjustable resistance of second amplifying circuit, make the one-level output voltage after secondary amplifies, be output as 9.5V, fixing each resistance value at this moment;
The calibration measurements of (two) scattering light path and transmitted light path:
1. prepare a series of known turbidity value τ 1, τ 2..., τ i..., τ tThe standard solution of formal hydrazine;
2. be τ with turbidity 1Standard solution concussion shake up the back and get a certain amount of with pipettor and put into cuvette, open described laser instrument, described excitation beam shines described cuvette, to each acquisition channel continuous acquisition 30 seconds, each passage has M data, and the power of the first photodetector detection light source, second photodetector are collected forward direction transmitted light I 0 °, the 3rd photodetector collects the side scattered light I of measurement zone 90 °Each road signal amplifies after described control and data acquisition unit collection realize obtaining having turbidity value τ after A/D changes through power detecting unit pre-amplification circuit, transmitted light detecting unit pre-amplification circuit, scattered light detecting unit pre-amplification circuit respectively 1The raw data P that gathers of the pairing power detecting unit of standard suspension 0 τ 1The raw data S that [j], scattered light detecting unit are gathered 0 τ 1The raw data T that [j] and transmitted light detecting unit are gathered 0 τ 1[j] sends into described data processing unit and carries out data processing, j=1 wherein, and 2,3 ..., M, j are the ordinal number of institute's image data in 30 second sampling time, M is the total degree of each detecting unit institute image data in 30 second sampling time;
3. the turbidity value that changes formal hydrazine standard solution in the described cuvette is followed successively by τ 2..., τ i... τ t, 2. repeat set by step to measure, obtain the raw data P that gathers with the corresponding power detecting unit of the UCP suspension of each standard turbidity 0 τ iThe raw data S that [j], scattered light detecting unit are gathered 0 τ iThe raw data T that [j] and transmitted light detecting unit are gathered 0 τ i[j], i=1 wherein, 2 ..., t;
(4) measure comparing sample zero turbidity water:
The standard model that changes in the described cuvette is comparative sample zero a turbidity water, open described laser instrument, described excitation beam shines described cuvette, to each acquisition channel continuous acquisition 30 seconds, each passage has M data, and the power of the first photodetector detection light source, second photodetector are collected forward direction transmitted light I 0 °, the 3rd photodetector collects the side scattered light I of measurement zone 90 °, collect the up-conversion luminescence intensity I with photomultiplier -90 °, obtain the raw data ZP that the power detecting unit of zero turbidity water is gathered 0The raw data ZS that [j], scattered light detecting unit are gathered 0The raw data ZT that [j], transmitted light detecting unit are gathered 0The raw data ZF that [j] and up-conversion luminescence detecting unit are gathered 0[j], j=1 wherein, 2,3 ..., M;
(5) data processing:
1. for fear of the caused measured bigger skew of the minor fluctuations of light source, be τ with turbidity iThe raw data T that gathers of the pairing transmitted light detecting unit of standard solution 0 τ iThe raw data S that [j] and scattered light detecting unit are gathered 0 τ i[j] corresponding respectively raw data P divided by the power detecting unit collection τ i[j], the data T after the light source that the is eliminated influence 1 τ i[j]=T 0 τ i[j]/P 0 τ i[j] and S 1 τ i[j]=S 0 τ i[j]/P 0 τ i[j];
2. data smoothing filtering: to eliminating the data T after light source influences 1 τ i[j] and S 1 τ i[j] carries out filtering with the Fast Fourier Transform (FFT) method, obtains filtered data T 2 τ i[j] and S 2 τ i[j];
3. in order to guarantee the stability of testing result, respectively above-mentioned filtered data are asked in detection time on average, obtaining turbidity is τ iStandard solution pairing:
Transmission mean value T 3 τ i={ T 2 τ i[1]+T 2 τ i[2]+...+T 2 τ i[j] ...+T 2 τ i[M] }/M,
Scattering mean value S 3 τ i={ S 2 τ i[1]]+S 2 τ i[2]+...+S 2 τ i[j] ...+S 2 τ i[M] }/M;
4. the repeatedly measured value that compares sample zero turbidity water is asked on average, obtained pairing transmission mean value ZT 0With scattering mean value ZS 0, in order to eliminate the influence of cuvette and comparative sample, with the transmission mean value T of standard model 3 τ iWith scattering mean value S 3 τ iWith the corresponding mean value ZT of comparative sample 0, ZS 0Between difference T τ i=T 3 τ i-ZT 0With
S τ i=S 3 τ i-ZS 0As measured value;
(6) make the turbidity standard working curve:
According to the concrete measured value of standard turbidity value and scattering, the saturating ratio that looses, make the scattered light intensity of suspension or loose thoroughly than with the calibration curve of its turbidity.
Described a certain amount of volume on described cuvette is decided, and is 5～30ml.
Utilize above-mentioned up-conversion luminescence particle multiparameter detection system to carry out the method for up-conversion luminescence particle measuring multiple parameters, comprise following measuring process:
(1) opens laser instrument, preheating 30 minutes;
(2) calibration measurements of up-conversion luminescence:
1. UCP particle formulation to be measured is become to have a series of concentration value N 1, N 2..., N i... N kStandard UCP suspension;
2. be N with described concentration earlier 1Standard UCP suspension fully shake and shake up the back and get a certain amount of and place described cuvette with pipettor, open described laser instrument, described excitation beam shines described cuvette, collects up-conversion luminescence intensity I in 30 seconds with photomultiplier -90 °, first photodetector detects corresponding light source power, by after follow-up amplification and the A/D conversion, obtains having concentration value N respectively 1The raw data F that gathers of the up-conversion luminescence detecting unit of standard UCP suspension in 30s 0N1The raw data P that [j] and power detecting unit are gathered 0N1[j], j=1 wherein, 2,3 ..., M, j are the ordinal number of institute's image data in the 30s sampling time, M is the total degree of each detecting unit institute image data in the 30s sampling time;
3. the concentration value that changes standard UCP particle suspension in the described cuvette is followed successively by N 2..., N i... N k, 2. repeat set by step to measure, obtain the raw data F that gathers with the corresponding up-conversion luminescence detecting unit of the UCP particle suspension of each normal concentration 0NiThe raw data P that [j] and power detecting unit are gathered 0Ni[j], i=2 wherein, 3 ..., k, j=1,2,3 ..., M;
4. for fear of the caused measured bigger skew of the minor fluctuations of light source, be N with concentration iThe raw data F that gathers of the pairing up-conversion luminescence of standard UCP suspension unit 0NiThe raw data P that [j] gathers divided by power detecting unit Ni[j], the data F after the light source that the is eliminated influence 1Ni[j]=F 0Ni[j]/P 0Ni[j];
5. data smoothing filtering: to eliminating the data F after light source influences 1Ni[j] carries out filtering with the Fast Fourier Transform (FFT) method, obtains filtered data F 2Ni[j];
6. in order to guarantee the stability of testing result, above-mentioned filtered data are asked in detection time on average, obtaining concentration is N iThe pairing up-conversion luminescence mean value of standard UCP particle suspension:
F 3Ni＝{F 2Ni[1]+F 2Ni[2]]+...+F 2Ni[j]...+F 2Ni[M]}/M；
7. change that standard model is a corresponding solvent in the described cuvette, sample according to 3. 4. 5. 6. duplicate measurements of above-mentioned steps, obtains the pairing up-conversion luminescence mean value of the up-conversion luminescence intensity ZF of this comparative sample as a comparison 3, in order to eliminate the influence of cuvette and comparative sample, with the up-conversion luminescence mean value F of standard model 3NiWith the corresponding mean value ZF of comparative sample 3Between difference F Ni=F 3Ni-ZF 3As measured value;
8. with the measured value of normal concentration value and up-conversion luminescence intensity, set up 0～N kUp-conversion luminescence intensity F in the concentration range NiAnd the concentration standard working curve that concerns between the UCP suspension normal concentration value N;
(3) UCP suspension to be measured is measured:
1. required UCP suspension to be measured concussion being shaken up the back gets a certain amount of with pipettor and the injection cuvette, open described laser instrument, described excitation beam shines described cuvette, continuous acquisition 30 seconds, each passage collects M data, obtains the raw data P of power detecting unit 0The raw data T of [j], transmitted light detecting unit 0The raw data S of [j], scattered light detecting unit 0The raw data F of [j] and up-conversion luminescence unit 0[j], j=1 wherein, 2,3 ..., M, j are the ordinal number of institute's image data in 30 second sampling time, M is the total degree of each detecting unit institute image data in 30 second sampling time;
2. eliminate the light source influence:
T 1[j]＝T 0[j]/P 0[j]，
S 1[j]＝S 0[j]/P 0[j]，
F 1[j]＝F 0[j]/P 0[j].
3. data smoothing filtering: to T 1[j], S 1[j], F 1[j] carries out filtering with the Fast Fourier Transform (FFT) method, obtains filtered data T 2[j], S 2[j], F 2[j];
4. to T 2[j], S 2[j], F 2[j] asks respectively on average, obtains:
Transmission mean value T 3={ T 2[1]+T 2[2]+...+T 2[j] ...+T 2[M] }/M,
Scattering mean value S 3={ S 2[1]+S 2[2]+...+S 2[j] ...+S 2[M] }/M,
With up-conversion luminescence mean value F 3={ F 2[1]+F 2[2]+...+F 2[j] ...+F 2[M] }/M;
5. change that standard model is a corresponding solvent in the described cuvette, sample according to 3. 4. 5. 6. duplicate measurements of above-mentioned steps, obtains the pairing transmission mean value of the transmitted intensity ZT of this comparative sample as a comparison 3, the pairing scattering mean value of scattered light intensity ZS 3With the pairing up-conversion luminescence mean value of up-conversion luminescence intensity ZF 3,
6. with T=T 3-ZT 3, S=S 3-ZS 3, F=F 3-ZF 3Measured value as testing sample;
7. obtain the turbidity of testing sample by the measured value S of described testing sample or S/T and the contrast of turbidity standard working curve, the measured value F and the concentration standard working curve of testing sample contrasted, obtain the concentration value of testing sample.
Describedly a certain amount ofly deciding on described cuvette, is 5～30ml.
The present invention compares with technology formerly has following technique effect:
1. UCP particle multiparameter detection system of the present invention is transmitted light, scattered light and the up-conversion luminescence of test sample simultaneously, can obtain the turbidity of sample and the information of concentration simultaneously.
2. UCP particle multiparameter detection system of the present invention adopts infrared laser as light source, has not only improved signal to noise ratio (S/N ratio) greatly, and is not subject to colourity influence in the suspension, can be used for detecting the sample of band colourity.
3. UCP particle multiparameter detection system of the present invention adopts the minor fluctuations of light source power detecting unit compensatory light to cause measured bigger skew, thereby avoids producing bigger measuring error.
4. UCP particle multiparameter detection system of the present invention detects its unique up-conversion luminescence characteristic, detects susceptibility, dirigibility and stability with height.
5. UCP particle multiparameter detection system of the present invention adopts different angles to receive scattering and transmission signal, when the suspension turbidity is low, adopt the scattered light detection method, adopt than turbid method during high turbidity, thereby improved the linearity that detects between dynamic range and whole measurement zone; Light path was identical when turbidimetry made transmitted light with scattered light measuring, and it is identical that light source changes the influence that turbidity is detected, and can eliminate part and disturb, and improved sensitivity.
6. UCP particle multiparameter detection system of the present invention gathers together excitation light path and the triple receiving light paths of transmitted light, scattered light and up-conversion luminescence, simple in structure, not only reduce cost, and effectively reduce the apparatus structure size, lowering apparatus is installed, the difficulty of debugging, has improved the functional reliability of system.
Description of drawings
Fig. 1 be the scattered light intensity of suspension or loose thoroughly than with the calibration curve synoptic diagram of its turbidity;
Fig. 2 is the calibration curve synoptic diagram of up-conversion luminescence intensity and its concentration of UCP suspension;
Fig. 3 is a UCP particle multiparameter detection system structured flowchart of the present invention;
Fig. 4 is a UCP particle multiparameter detection system index path of the present invention;
Fig. 5 is the flow chart of data processing figure of UCP particle multiparameter while detection system of the present invention;
Fig. 6 is the spectral transmittance curve map of the 980nm optical filter that adopts in the embodiment of the invention.
Embodiment
The present invention is further illustrated below in conjunction with drawings and Examples, but should not limit protection scope of the present invention with this.
See also Fig. 3 and Fig. 4, Fig. 3 is a UCP particle multiparameter detection system structured flowchart of the present invention, and Fig. 4 is a UCP particle multiparameter detection system index path of the present invention.As seen from the figure, the formation of up-conversion luminescence particle multiparameter detection system of the present invention comprises lighting unit 1, sample cell 2, power detecting unit 3, transmitted light detecting unit 4, scattered light detecting unit 5, up-conversion luminescence detecting unit 6, power detecting unit pre-amplification circuit 7, transmitted light detecting unit pre-amplification circuit 8, scattered light detecting unit pre-amplification circuit 9, control and data acquisition unit 10 and data processing unit 11:
Described lighting unit 1 is made up of laser instrument 101, collimating mirror 102, dichronic mirror 104, cylindrical mirror 106, the laser that described laser instrument 101 sends becomes parallel beam 103 through described collimating mirror 102, this parallel beam 103 is divided into folded light beam 105 and transmitted light beam 301 through described dichronic mirror 104, and described folded light beam 105 forms the described sample cell 2 of excitation beam 201 irradiations of certain size, shape behind cylindrical mirror 106; In described transmitted light beam 301 directions described power detecting unit 3 is set;
Described power detecting unit 3 is made up of first optical filter 302, first focus lamp 303, first aperture 304 and first photodetector 305 successively along transmitted light beam 301 directions;
Described sample cell 2 is made up of cuvette 203 and cuvette groove 202; Described cuvette 203 is transparent, is used to install up-conversion luminescence suspension to be measured, abbreviates the UCP suspension as; This cuvette 203 is arranged in the light path of described excitation beam 201, forms transmitted light 401, scattered light 501 and up-conversion luminescence 601 behind the UCP suspension to be measured of the described cuvette 203 of described excitation beam 201 irradiations;
Transmitted light 401 directions at described cuvette 203 are provided with described transmitted light detecting unit 4, and this transmitted light detecting unit 4 is made up of second optical filter 402, second focus lamp 403, attenuator 404, second aperture 405 and second photodetector 406 successively along transmitted light 401 directions;
Described scattered light detecting unit 5 is set above described cuvette 203, and this scattered light detecting unit 5 is made up of the 3rd focus lamp 502, the 3rd optical filter 503, the 4th focus lamp 504, the 3rd aperture 505 and the 3rd photodetector 506 successively;
Described up-conversion luminescence detecting unit 6 is set below described cuvette 203, and this up-conversion luminescence detecting unit 6 is made up of the 4th focus lamp 602, the 5th focus lamp 603, the 4th aperture 604 and photomultiplier 605 successively along described up-conversion luminescence 601 directions;
The electric signal of first photodetector, 305 outputs is through the electric signal of described power detecting unit pre-amplification circuit 7 outputs, the electric signal of second photodetector, 406 outputs is through the electric signal of described transmitted light detecting unit pre-amplification circuit 8 outputs, the electric signal of the electric signal of described the 3rd photodetector 406 output output voltage signal and 605 outputs of described photomultiplier through described scattered light detecting unit pre-amplification circuit 9 after is together through described control and data acquisition unit 10 collections, realize that sending into described data processing unit 11 after A/D changes carries out data processing, with the parameter demonstration of tested UCP suspension, storage or output;
Described detection system has also been carried out necessary adjustment and demarcation.
Transmitted light detecting unit 4 described in the present embodiment, scattered light detecting unit 5 and up-conversion luminescence detecting unit 6 are integrated in the same cavity.
The light path position of described scattered light detecting unit 5 and up-conversion luminescence detecting unit 6 can exchange, and unique requirement is that the light path of described scattered light detecting unit 5 and up-conversion luminescence detecting unit 6 is not disturbed and mutually perpendicular to described excitation beam 201 and by in the plane of described cuvette 203.
Described first optical filter, second optical filter, the 3rd optical filter are the long-pass type optical filter, only see through the infrared light of described laser instrument 101 emissions, are used for the filtering veiling glare.The 980nm optical filter that adopts in the present embodiment, its spectrum transmitting rate curve as shown in Figure 6.
Described first aperture, second aperture, the 3rd aperture, the 4th aperture are used to limit the aperture and the solid angle of collecting light beam, and the receiving area that limits detector is less than or equal to the photosensitive area of detector with the aperture that guarantees light beam.
In the present embodiment:
Described laser instrument 101 is the LD infrared laser of wavelength 980nm, collimates the oval-shaped beam that is focused to bore 4mm * 2mm through collimating mirror 102, and power is about 70mW, excites up-conversion luminescent material can launch the visible light of 541.5nm.
Described cuvette 203 is a four-way light cuvette, and physical dimension is 12.4mm (L) * 12.4mm (W) * 45mm (H), and inside dimension is 10mm (L) * 10mm (W), and the high volume of every 10mm was 10ml when promptly liquid was adorned in inside.
Described dichronic mirror 104 is coated with deielectric-coating, is about 1% to the transmitance (45 ° of incident angles) of 980nm light, and reflectivity is about 99%, is 45 with the laser instrument output light path and places.
Described transmitted light 401 and side scattered light 501 are the infrared light of 980nm, adopt photodiode (PD) to survey, and its model can be the S1223-01 type that the loose company in Japanese shore produces; The up-conversion luminescence 601 that the UCP particle sends is the last convert light of wavelength 541.5nm, receives in side direction, avoids the influence of transmitted light, can adopt MPA224 or MPA224U type photomultiplier assembly to survey.
Described optical filter 302,402 and 503 sees through the 980nm infrared light, and the strong absorption visible light is used for the veiling glare of filtering wavelength below 980nm.
Described capture card is realized needing at least 4 road A/D input channels (single-ended or both-end) and at least 1 road D/A output channel by the transformation of simulating signal to digital signal, can be USB7360 series multifunctional data acquisition module.
Described prime amplifier can be LF353 or LF412.Filter capacitor that strengthens at the positive and negative power end of integrated transporting discharging and the high-frequency bypass capacitor of 0.01～0.1 μ F in parallel.
The adjustment of up-conversion luminescence particle multiparameter detection system of the present invention and the method for demarcation comprise the steps:
(1) determining of circuit parameter:
1. be after the standard UCP suspension sample concussion of 2.0mg/ml shakes up with concentration, get a certain amount of standard UCP suspension sample with pipettor and put into cuvette, open described laser instrument, the described cuvette of described excitation beam 201 irradiations, regulate the resistance of power detecting unit and scattered light detecting unit pre-amplification circuit respectively: this pre-amplification circuit changes voltage by electric current and signal amplification two-stage circuit is formed, adjust the adjustable resistance of one-level amplifying circuit, make a step voltage be output as 0.5～1V; Adjust the adjustable resistance of second amplifying circuit, make the one-level output voltage after secondary amplifies, be output as 9.5V (being slightly less than output saturation value 10V), fixing each resistance value at this moment; Regulate the up-conversion luminescence added bias voltage of light path photomultiplier (0～5V is adjustable), the enlargement factor when working with definite photomultiplier makes output voltage 9.5V (being slightly less than output saturation value 10V), the bias voltage value of fixing this moment;
2. get a certain amount of zero turbidity water and inject cuvette, open described laser instrument, the described cuvette of described excitation beam 201 irradiations, the resistance of adjustment transmitted light detecting unit pre-amplification circuit: adjust the adjustable resistance of one-level amplifying circuit, make a step voltage be output as 0.5～1V; Adjust the adjustable resistance of second amplifying circuit, make the one-level output voltage after secondary amplifies, be output as 9.5V, fixing each resistance value at this moment;
The calibration measurements of (two) scattering light path and transmitted light path:
1. prepare a series of known turbidity value τ 1, τ 2..., τ i..., τ tThe standard solution of formal hydrazine;
2. be τ with turbidity 1Standard solution concussion shake up the back and get respectively with pipettor and a certain amount ofly put into cuvette as 10ml, open described laser instrument, the described cuvette of described excitation beam 201 irradiations, to each acquisition channel continuous acquisition 30 seconds, each passage has M data, and the power of first photodetector, 305 detection light source, second photodetector 401 are collected forward direction transmitted light I 0 °, the 3rd photodetector 506 collects the side scattered light I of measurement zones 90 °Each road signal amplifies after described control and data acquisition unit 10 are gathered through power detecting unit pre-amplification circuit 7, transmitted light detecting unit pre-amplification circuit 8, scattered light detecting unit pre-amplification circuit 9 respectively, realizes obtaining having turbidity value τ after the A/D conversion 1The raw data P that gathers of the pairing power detecting unit of standard suspension 0 τ 1The raw data S that [j], scattered light detecting unit are gathered 0 τ 1The raw data T that [j] and transmitted light detecting unit are gathered 0 τ 1[j] sends into described data processing unit 11 and carries out data processing, j=1 wherein, and 2,3 ..., M, j are the ordinal number of institute's image data in 30 second sampling time, M is the total degree of each detecting unit institute image data in 30 second sampling time;
3. the turbidity value that changes formal hydrazine standard solution in the described cuvette 203 is followed successively by τ 2..., τ i... τ t, 2. repeat set by step to measure, obtain the raw data P that gathers with the corresponding power detecting unit of the UCP suspension of each standard turbidity 0 τ iThe raw data S that [j], scattered light detecting unit are gathered 0 τ iThe raw data T that [j] and transmitted light detecting unit are gathered 0 τ i[j], i=1 wherein, 2 ..., t;
(4) measure comparing sample zero turbidity water:
The standard model that changes in the described cuvette is comparative sample zero a turbidity water, open described laser instrument, the described cuvette of described excitation beam 201 irradiations, to each acquisition channel continuous acquisition 30 seconds, each passage has M data, and the power of first photodetector, 305 detection light source, second photodetector 401 are collected forward direction transmitted light I 0 °, the 3rd photodetector 506 collects the side scattered light I of measurement zones 90 °, collect the up-conversion luminescence intensity I with photomultiplier 605 -90 °, obtain the raw data ZP that the power detecting unit of zero turbidity water is gathered 0The raw data ZS that [j], scattered light detecting unit are gathered 0The raw data ZT that [j], transmitted light detecting unit are gathered 0The raw data ZF that [j] and up-conversion luminescence detecting unit are gathered 0[j], j=1 wherein, 2,3 ..., M;
(5) data processing, its flow process are referring to Fig. 5:
1. for fear of the caused measured bigger skew of the minor fluctuations of light source, should be τ with turbidity iThe raw data T that gathers of the pairing transmitted light detecting unit of standard solution 0 τ iThe raw data S that [j] and scattered light detecting unit are gathered 0 τ i[j] corresponding respectively raw data P divided by the power detecting unit collection τ i[j], the data T after the light source that the is eliminated influence 1 τ i[j]=T 0 τ i[j]/P 0 τ i[j] and S 1 τ i[j]=S 0 τ i[j]/P 0 τ i[j];
2. data smoothing filtering: to eliminating the data T after light source influences 1 τ i[j] and S 1 τ i[j] carries out filtering with the Fast Fourier Transform (FFT) method, obtains filtered data T 2 τ i[j] and S 2 τ i[j];
3. in order to guarantee the stability of testing result, respectively above-mentioned filtered data are asked in detection time on average, obtaining turbidity is τ iStandard solution pairing:
Transmission mean value T 3 τ i={ T 2 τ i[1]+T 2 τ i[2]+...+T 2 τ i[j] ...+T 2 τ i[M] }/M,
Scattering mean value S 3 τ i={ S 2 τ i[1]]+S 2 τ i[2]+...+S 2 τ i[j] ...+S 2 τ i[M] }/M;
4. the repeatedly measured value that compares sample zero turbidity water is asked on average, obtained pairing transmission mean value ZT 0With scattering mean value ZS 0i, in order to eliminate the influence of cuvette and comparative sample, with the transmission mean value T of standard model 3 τ iWith scattering mean value S 3 τ iWith the corresponding mean value ZT of comparative sample 0, ZS 0Between difference T τ i=T 3 τ i-ZT 0And S τ i=S 3 τ i-ZS 0As measured value;
(6) make the turbidity standard working curve:
According to the concrete measured value of standard turbidity value and scattering, the saturating ratio that looses, make the scattered light intensity of suspension or loose thoroughly than with the calibration curve of its turbidity, as shown in Figure 1.
Utilize up-conversion luminescence particle multiparameter detection system of the present invention to carry out the method for up-conversion luminescence particle measuring multiple parameters, comprise following measuring process:
(1) opens laser instrument, preheating 30 minutes;
(2) calibration measurements of up-conversion luminescence:
1. UCP particle configuration to be measured had a series of concentration value N 1, N 2..., N i... N kStandard UCP suspension;
2. be N with described concentration earlier 1Standard UCP suspension fully shake shake up the back get a certain amount of described cuvette 203 that places with pipettor, open described laser instrument, the described cuvette of described excitation beam 201 irradiations, the up-conversion luminescence intensity I of using photomultiplier 605 to collect in 30 seconds -90 °, first photodetector 305 detects corresponding light source power, by after follow-up amplification and the A/D conversion, obtains having concentration value N respectively 1The raw data F that gathers of the up-conversion luminescence detecting unit of standard UCP suspension in 30s 0N1The raw data P that [j] and power detecting unit are gathered 0N1[j], j=1 wherein, 2,3 ..., M, j are the ordinal number of institute's image data in the 30s sampling time, M is the total degree of each detecting unit institute image data in the 30s sampling time;
3. the concentration value that changes standard UCP particle suspension in the described cuvette 203 is followed successively by N 2..., N i... N k, 2. repeat set by step to measure, obtain the raw data F that gathers with the corresponding up-conversion luminescence detecting unit of the UCP particle suspension of each normal concentration 0NiThe raw data P that [j] and power detecting unit are gathered 0Ni[j], i=2 wherein, 3 ..., i ... k, j=1,2,3 ..., M;
4. for fear of the caused measured bigger skew of the minor fluctuations of light source, should be the raw data F of the pairing up-conversion luminescence of the standard UCP suspension unit collection of Ni with concentration 0NiThe raw data P that [j] gathers divided by power detecting unit Ni[j], the data F after the light source that the is eliminated influence 1Ni[j]=F 0Ni[j]/P 0Ni[j];
5. data smoothing filtering: to eliminating the data F after light source influences 1Ni[j] carries out filtering with the Fast Fourier Transform (FFT) method, obtains filtered data F 2Ni[j];
6. in order to guarantee the stability of testing result, above-mentioned filtered data are asked in detection time on average, obtaining concentration is N iThe pairing up-conversion luminescence mean value of standard UCP particle suspension:
F 3Ni＝{F 2Ni[1]+F 2Ni[2]]+...+F 2Ni[j]...+F 2Ni[M]}/M；
7. change that standard model is a corresponding solvent in the described cuvette, sample according to 3. 4. 5. 6. duplicate measurements of above-mentioned steps, obtains the pairing up-conversion luminescence mean value of the up-conversion luminescence intensity ZF of this comparative sample as a comparison 3, in order to eliminate the influence of cuvette and comparative sample, with the up-conversion luminescence mean value F of standard model 3NiWith the corresponding mean value ZF of comparative sample 3Between difference F Ni=F 3Ni-ZF 3As measured value;
8. normal concentration value and each concrete measured value of up-conversion luminescence intensity are carried out match, set up the up-conversion luminescence intensity of UCP suspension and the calibration curve of its concentration, as shown in Figure 2.
(3) UCP suspension to be measured is measured:
1. required UCP suspension to be measured concussion is shaken up the back and get a certain amount of injection cuvette with pipettor, open described laser instrument, the described cuvette of described excitation beam 201 irradiations, continuous acquisition 30 seconds, each passage collects M data, obtains the raw data P of power detecting unit 0The raw data T of [j], transmitted light detecting unit 0The raw data S of [j], scattered light detecting unit 0The raw data F of [j] and up-conversion luminescence unit 0[j], j=1 wherein, 2,3 ..., M, j are the ordinal number of institute's image data in 30 second sampling time, M is the total degree of each detecting unit institute image data in 30 second sampling time;
2. eliminate the light source influence:
T 1[j]＝T 0[j]/P 0[j]，
S 1[j]＝S 0[j]/P 0[j]，
F 1[j]＝F 0[j]/P 0[j].
3. data smoothing filtering: to T 1[j], S 1[j], F 1[j] carries out filtering with the Fast Fourier Transform (FFT) method, obtains filtered data T 2[j], S 2[j], F 2[j];
4. to T 2[j], S 2[j], F 2[j] asks respectively on average, obtains:
Transmission mean value T 3={ T 2[1]+T 2[2]+...+T 2[j] ...+T 2[M] }/M,
Scattering mean value S 3={ S 2[1]+S 2[2]+...+S 2[j] ...+S 2[M] }/M,
With up-conversion luminescence mean value F 3={ F 2[1]+F 2[2]+...+F 2[j] ...+F 2[M] }/M;
5. change that standard model is a corresponding solvent in the described cuvette, sample according to 3. 4. 5. 6. duplicate measurements of above-mentioned steps, obtains the pairing transmission mean value of the transmitted intensity ZT of this comparative sample as a comparison 3, the pairing scattering mean value of scattered light intensity ZS 3With the pairing up-conversion luminescence mean value of up-conversion luminescence intensity ZF 3,
6. with T=T 3-ZT 3, S=S 3-ZS 3, F=F 3-ZF 3Measured value as testing sample;
7. obtain the turbidity of testing sample by the measured value S of described testing sample or S/T and the contrast of turbidity standard working curve, the measured value F and the concentration standard working curve of testing sample contrasted, obtain the concentration value of testing sample.
Experiment shows that characteristics of the present invention are:
UCP particle multi-parameter of the present invention is transmitted light, scattered light and the up-conversion luminescence of detection system while test sample simultaneously, can obtain simultaneously turbidity and the concentration information of testing sample;
Adopt infrared laser as light source, not only greatly improved signal to noise ratio, and be not subject to colourity impact in the suspension, can be used for detecting the sample with colourity;
Adopt the minor fluctuations of light source power detecting unit compensatory light to cause measured bigger skew, thereby avoid producing bigger measure error;
Detect the Upconversion luminescence of UCP particle uniqueness, detect sensitiveness, flexibility and stability with height;
Adopt different angles receiving scattered light signal and optical signal transmissive, when the suspension turbidity is low, adopt the scattered light detection method, adopt than turbid method when turbidity is higher, thereby improved the linearity that detects dynamic range and whole surveying range;
Turbidimetry so that transmitted light during with scattered light measuring light path identical, it is identical that light source changes the impact that turbidity is detected, and can eliminate part and disturb, and improves sensitivity.
Excitation light path and the triple receiving light paths of transmitted light, scattered light and up-conversion luminescence are integrated into same cavity, simple in structure, not only reduce cost, and effectively reduce the apparatus structure size, lowering apparatus is installed, the difficulty of debugging, has improved the functional reliability of system.
In a word, the present invention have sensitiveness height, reliability height, good stability, simple in structure, be easy to fill the school and cost is lower, operating personnel are required the advantages such as low.

Claims (9)

1. up-conversion luminescence particle multiparameter detection system is characterised in that its formation comprises lighting unit (1), sample cell (2), power detecting unit (3), transmitted light detecting unit (4), scattered light detecting unit (5), up-conversion luminescence detecting unit (6), power detecting unit pre-amplification circuit (7), transmitted light detecting unit pre-amplification circuit (8), scattered light detecting unit pre-amplification circuit (9), control and data acquisition unit (10) and data processing unit (11):
Described lighting unit (1) is made up of laser instrument (101), collimating mirror (102), dichronic mirror (104), cylindrical mirror (106), the laser that described laser instrument (101) sends becomes parallel beam (103) behind described collimating mirror (102), this parallel beam (103) is divided into folded light beam (105) and transmitted light beam (301) through described dichronic mirror (104), and described folded light beam (105) forms certain size, shape behind cylindrical mirror (106) excitation beam (201) shines described sample cell (2); In described transmitted light beam (301) direction described power detecting unit (3) is set;
Described power detecting unit (3) is made up of first optical filter (302), first focus lamp (303), first aperture (304) and first photodetector (305) successively along transmitted light beam (301) direction;
Described sample cell (2) is made up of cuvette (203) and cuvette groove (202); Described cuvette (203) is transparent, is used to install sample to be measured; This cuvette (203) is arranged in the light path of described excitation beam (201), and described excitation beam (201) forms transmitted light (401), scattered light (501) and up-conversion luminescence (601) after shining the sample to be measured of described cuvette (203);
Transmitted light (401) direction in described cuvette (203) is provided with described transmitted light detecting unit (4), and this transmitted light detecting unit (4) is made up of second optical filter (402), second focus lamp (403), attenuator (404), second aperture (405) and second photodetector (406) successively along transmitted light (401) direction;
Side at described cuvette (203) is provided with described scattered light detecting unit (5), and this scattered light detecting unit (5) is made up of the 3rd focus lamp (502), the 3rd optical filter (503), the 4th focus lamp (504), the 3rd aperture (505) and the 3rd photodetector (506) successively;
The opposing party at described cuvette (203) is provided with described up-conversion luminescence detecting unit (6), and this up-conversion luminescence detecting unit (6) is made up of the 4th focus lamp (602), the 5th focus lamp (603), the 4th aperture (604) and photomultiplier (605) successively along described up-conversion luminescence (601) direction;
The electric signal of first photodetector (305) output is through the electric signal of described power detecting unit pre-amplification circuit (7) output, the electric signal of second photodetector (406) output is through the electric signal of described transmitted light detecting unit pre-amplification circuit (8) output, the electric signal of the electric signal of described the 3rd photodetector (406) output output voltage signal and described photomultiplier (605) output through described scattered light detecting unit pre-amplification circuit (9) after is together through described control and data acquisition unit (10) collection, realize that sending into described data processing unit (11) after A/D changes carries out data processing, with the parameter demonstration of tested UCP suspension, storage or output;
Described detection system has also been carried out necessary adjustment and demarcation.
2. up-conversion luminescence particle multiparameter detection system according to claim 1 is characterized in that described transmitted light detecting unit (4), scattered light detecting unit (5) and up-conversion luminescence detecting unit (6) are integrated in the same cavity.
3. up-conversion luminescence particle multiparameter detection system according to claim 1, the light path position that it is characterized in that described scattered light detecting unit (5) and up-conversion luminescence detecting unit (6) can exchange, and unique requirement is that the light path of described scattered light detecting unit (5) and up-conversion luminescence detecting unit (6) is not disturbed and mutually perpendicular to described excitation beam (201) and by in the plane of described cuvette (203).
4. up-conversion luminescence particle multiparameter detection system according to claim 1, it is characterized in that described first optical filter, second optical filter, the 3rd optical filter are the long-pass type optical filter, only see through the infrared light of described laser instrument (101) emission, be used for the filtering veiling glare.
5. up-conversion luminescence particle multiparameter detection system according to claim 1, it is characterized in that described first aperture, second aperture, the 3rd aperture, the 4th aperture are used to limit the aperture and the solid angle of collecting light beam, the receiving area that limits detector is less than or equal to the photosensitive area of detector with the aperture that guarantees light beam.
6. up-conversion luminescence particle multiparameter detection system according to claim 1 is characterized in that comprising the steps: the method for described adjustment and demarcation
(1) determining of circuit parameter:
1. be after the standard UCP suspension sample concussion of 2.0mg/ml shakes up with concentration, get a certain amount of standard UCP suspension sample with pipettor and put into cuvette, open described laser instrument, described excitation beam (201) shines described cuvette, regulate the resistance of power detecting unit and scattered light detecting unit pre-amplification circuit respectively: this pre-amplification circuit changes voltage by electric current and signal amplification two-stage circuit is formed, adjust the adjustable resistance of one-level amplifying circuit, make a step voltage be output as 0.5～1V; Adjust the adjustable resistance of second amplifying circuit, make the one-level output voltage after secondary amplifies, be output as 9.5V, fixing each resistance value at this moment; Regulate the added bias voltage of up-conversion luminescence light path photomultiplier, the enlargement factor when working with definite photomultiplier makes output voltage 9.5V, the bias voltage value of fixing this moment;
2. get a certain amount of zero turbidity water and inject cuvette, open described laser instrument, described excitation beam (201) shines described cuvette, adjusts the resistance of transmitted light detecting unit pre-amplification circuit: adjust the adjustable resistance of one-level amplifying circuit, make a step voltage be output as 0.5～1V; Adjust the adjustable resistance of second amplifying circuit, make the one-level output voltage after secondary amplifies, be output as 9.5V, fixing each resistance value at this moment;
The calibration measurements of (two) scattering light path and transmitted light path:
1. prepare a series of known turbidity value τ 1, τ 2..., τ i..., τ tThe standard solution of formal hydrazine;
2. be τ with turbidity 1Standard solution concussion shake up the back and get a certain amount of cuvette of putting into pipettor, open described laser instrument, described excitation beam (201) shines described cuvette, to each acquisition channel continuous acquisition 30 seconds, each passage has M data, and the power of first photodetector (305) detection light source, second photodetector (401) are collected forward direction transmitted light I 0 °, the 3rd photodetector (506) collects the side scattered light I of measurement zone 90 °Each road signal amplifies after described control and data acquisition unit (10) are gathered through power detecting unit pre-amplification circuit (7), transmitted light detecting unit pre-amplification circuit (8), scattered light detecting unit pre-amplification circuit (9) respectively, realizes obtaining having turbidity value τ after the A/D conversion 1The raw data P that gathers of the pairing power detecting unit of standard suspension 0 τ 1The raw data S that [j], scattered light detecting unit are gathered 0 τ 1The raw data T that [j] and transmitted light detecting unit are gathered 0 τ 1[j] sends into described data processing unit (11) and carries out data processing, j=1 wherein, and 2,3 ..., M, j are the ordinal number of institute's image data in 30 second sampling time, M is the total degree of each detecting unit institute image data in 30 second sampling time;
3. change the middle formal hydrazine standard solution turbidity value of described cuvette (203) and be followed successively by τ 2..., τ i... τ t, 2. repeat set by step to measure, obtain the raw data P that gathers with the corresponding power detecting unit of the UCP suspension of each standard turbidity 0 τ iThe raw data S that [j], scattered light detecting unit are gathered 0 τ iThe raw data T that [j] and transmitted light detecting unit are gathered 0 τ i[j], i=1 wherein, 2 ..., t;
(4) measure comparing sample zero turbidity water:
The standard model that changes in the described cuvette is comparative sample zero a turbidity water, open described laser instrument, described excitation beam (201) shines described cuvette, to each acquisition channel continuous acquisition 30 seconds, each passage has M data, and the power of first photodetector (305) detection light source, second photodetector (401) are collected forward direction transmitted light I 0 °, the 3rd photodetector (506) collects the side scattered light I of measurement zone 90 °, collect the up-conversion luminescence intensity I with photomultiplier (605) -90 °, obtain the raw data ZP that the power detecting unit of zero turbidity water is gathered 0The raw data ZS that [j], scattered light detecting unit are gathered 0The raw data ZT that [j], transmitted light detecting unit are gathered 0The raw data ZF that [j] and up-conversion luminescence detecting unit are gathered 0[j], j=1 wherein, 2,3 ..., M;
(5) data processing:
1. for fear of the caused measured bigger skew of the minor fluctuations of light source, should be τ with turbidity iThe raw data T that gathers of the pairing transmitted light detecting unit of standard solution 0 τ iThe raw data S that [j] and scattered light detecting unit are gathered 0 τ i[j] corresponding respectively raw data P divided by the power detecting unit collection τ i[j], the data T after the light source that the is eliminated influence 1 τ i[j]=T 0 τ i[j]/P 0 τ i[j] and S 1 τ i[j]=S 0 τ i[j]/P 0 τ i[j];
2. data smoothing filtering: to eliminating the data T after light source influences 1 τ i[j] and S 1 τ i[j] carries out filtering with the Fast Fourier Transform (FFT) method, obtains filtered data T 2 τ i[j] and S 2 τ i[j];
3. in order to guarantee the stability of testing result, respectively above-mentioned filtered data are asked in detection time on average, obtaining turbidity is τ iStandard solution pairing:
Transmission mean value T 3 τ i={ T 2 τ i[1]+T 2 τ i[2]+...+T 2 τ i[j] ...+T 2 τ i[M] }/M,
Scattering mean value S 3 τ i={ S 2 τ i[1]]+S 2 τ i[2]+...+S 2 τ i[j] ...+S 2 τ i[M] }/M;
4. the repeatedly measured value that compares sample zero turbidity water is asked on average, obtained pairing transmission mean value ZT 0With scattering mean value ZS 0i, in order to eliminate the influence of cuvette and comparative sample, with the transmission mean value T of standard model 3 τ iWith scattering mean value S 3 τ iWith the corresponding mean value ZT of comparative sample 0, ZS 0Between difference T τ i=T 3 τ i-ZT 0With
S τ i=S 3 τ i-ZS 0As measured value;
(6) make the turbidity standard working curve:
According to the concrete measured value of standard turbidity value and scattering, the saturating ratio that looses, make the scattered light intensity of suspension or loose thoroughly than with the calibration curve of its turbidity.
7. up-conversion luminescence particle multiparameter detection system according to claim 6 is characterized in that the described a certain amount of 5～30ml of being.
8. utilize the described up-conversion luminescence particle of claim 1 multiparameter detection system to carry out the method for up-conversion luminescence particle measuring multiple parameters, it is characterized in that comprising following measuring process:
(1) opens laser instrument, preheating 30 minutes;
(2) calibration measurements of up-conversion luminescence:
1. UCP particle formulation to be measured is become to have a series of concentration value N 1, N 2..., N i... N kStandard UCP suspension;
2. be N with described concentration earlier 1Standard UCP suspension fully shake shake up the back get a certain amount of described cuvette (203) that places with pipettor, open described laser instrument, described excitation beam (201) shines described cuvette, and usefulness photomultiplier (605) is collected the up-conversion luminescence intensity I in 30 seconds -90 °, first photodetector (305) detects corresponding light source power, by after follow-up amplification and the A/D conversion, obtains having concentration value N respectively 1The raw data F that gathers of the up-conversion luminescence detecting unit of standard UCP suspension in 30s 0N1The raw data P that [j] and power detecting unit are gathered 0N1[j], j=1 wherein, 2,3 ..., M, j are the ordinal number of institute's image data in the 30s sampling time, M is the total degree of each detecting unit institute image data in the 30s sampling time;
3. the concentration value that changes standard UCP particle suspension in the described cuvette (203) is followed successively by N 2..., N i... N k, 2. repeat set by step to measure, obtain the raw data F that gathers with the corresponding up-conversion luminescence detecting unit of the UCP particle suspension of each normal concentration 0NiThe raw data P that [j] and power detecting unit are gathered 0Ni[j], i=2 wherein, 3 ..., i ... k, j=1,2,3 ..., M;
4. for fear of the caused measured bigger skew of the minor fluctuations of light source, should be N with concentration iThe raw data F that gathers of the pairing up-conversion luminescence of standard UCP suspension unit 0NiThe raw data P that [j] gathers divided by power detecting unit Ni[j], the data F after the light source that the is eliminated influence 1Ni[j]=F 0Ni[j]/P 0Ni[j];
5. data smoothing filtering: to eliminating the data F after light source influences 1Ni[j] carries out filtering with the Fast Fourier Transform (FFT) method, obtains filtered data F 2Ni[j];
6. in order to guarantee the stability of testing result, above-mentioned filtered data are asked in detection time on average, obtaining concentration is N iThe pairing up-conversion luminescence mean value of standard UCP particle suspension:
F 3Ni＝{F 2Ni[1]+F 2Ni[2]]+...+F 2Ni[j]...+F 2Ni[M]}/M；
7. change that standard model is a corresponding solvent in the described cuvette, sample according to 3. 4. 5. 6. duplicate measurements of above-mentioned steps, obtains the pairing up-conversion luminescence mean value of the up-conversion luminescence intensity ZF of this comparative sample as a comparison 3, in order to eliminate the influence of cuvette and comparative sample, with the up-conversion luminescence mean value F of standard model 3NiWith the corresponding mean value ZF of comparative sample 3Between difference F Ni=F 3Ni-ZF 3As measured value;
8. normal concentration value and each concrete measured value of up-conversion luminescence intensity are carried out match, set up the calibration curve of UCP suspension up-conversion luminescence intensity and concentration relationship;
(3) UCP suspension to be measured is measured:
1. required UCP suspension to be measured concussion is shaken up the back and get a certain amount of injection cuvette with pipettor, open described laser instrument, described excitation beam (201) shines described cuvette, continuous acquisition 30 seconds, each passage collects M data, obtains the raw data P of power detecting unit 0The raw data T of [j], transmitted light detecting unit 0The raw data S of [j], scattered light detecting unit 0The raw data F of [j] and up-conversion luminescence unit 0[j], j=1 wherein, 2,3 ..., M, j are the ordinal number of institute's image data in 30 second sampling time, M is the total degree of each detecting unit institute image data in 30 second sampling time;
2. eliminate the light source influence:
T 1[j]＝T 0[j]/P 0[j]，
S 1[j]＝S 0[j]/P 0[j]，
F 1[j]＝F 0[j]/P 0[j].
3. data smoothing filtering: to T 1[j], S 1[j], F 1[j] carries out filtering with the Fast Fourier Transform (FFT) method, obtains filtered data T 2[j], S 2[j], F 2[j];
4. to T 2[j], S 2[j], F 2[j] asks respectively on average, obtains:
Transmission mean value T 3={ T 2[1]+T 2[2]+...+T 2[j] ...+T 2[M] }/M,
Scattering mean value S 3={ S 2[1]+S 2[2]+...+S 2[j] ...+T 2[M] }/M,
With up-conversion luminescence mean value F 3={ F 2[1]+F 2[2]+...+F 2[j] ...+T 2[M] }/M;
5. change that standard model is a corresponding solvent in the described cuvette, sample according to 3. 4. 5. 6. duplicate measurements of above-mentioned steps, obtains the pairing transmission mean value of the transmitted intensity ZT of this comparative sample as a comparison 3, the pairing scattering mean value of scattered light intensity ZS 3With the pairing up-conversion luminescence mean value of up-conversion luminescence intensity ZF 3,
6. with T=T 3-ZT 3, S=S 3-ZS 3, F=F 3-ZF 3Measured value as testing sample;
7. obtain the turbidity of testing sample by the measured value S of described testing sample or S/T and the contrast of turbidity standard working curve, the measured value F and the concentration standard working curve of testing sample contrasted, obtain the concentration value of testing sample.
9. the method for up-conversion luminescence particle measuring multiple parameters according to claim 8 is characterized in that the described a certain amount of 5～30ml of being.
CN 201010501521 2010-10-09 2010-10-09 System and method for detecting multi-parameter of up-conversion luminescent particles Expired - Fee Related CN102012368B (en)

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CN104614071A (en) * 2014-12-09 2015-05-13 浙江福立分析仪器有限公司 Miniature optical path structure of spectrophotometer and application method thereof
CN104807798A (en) * 2015-05-18 2015-07-29 合肥工业大学 Method and device for detecting up-conversion luminescence by utilizing mobile phone
CN104833620A (en) * 2015-04-20 2015-08-12 江苏苏净集团有限公司 Atmospheric particulate matter concentration monitoring device
CN105353115A (en) * 2015-10-21 2016-02-24 中国科学院上海光学精密机械研究所 Measuring device and method of spatial distribution of scattering light field of immunochromatographic test strip
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CN106483102A (en) * 2016-12-09 2017-03-08 长春市金佳光电科技有限公司 Analyser for the analyser degree on-line checking of free water in aerial kerosene and minute impurities concentration on-line checking
WO2017088214A1 (en) * 2015-11-24 2017-06-01 江南大学 Fluorescence-based biological detection system
CN108051344A (en) * 2017-11-23 2018-05-18 浙江工业大学 The realtime on-line monitoring method of polishing fluid bulky grain in a kind of polishing process
CN108776103A (en) * 2018-05-15 2018-11-09 三诺生物传感股份有限公司 A kind of detector optical system
CN111504869A (en) * 2020-05-15 2020-08-07 中国计量科学研究院 Flow type aggregate impurity analyzer
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CN113552049A (en) * 2021-07-26 2021-10-26 苏州苏信环境科技有限公司 Working method of particle counter
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CN113552044B (en) * 2021-07-26 2024-06-21 苏州苏信环境科技有限公司 Particle counter metering method

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CN103018209B (en) * 2011-09-20 2016-09-28 深圳迈瑞生物医疗电子股份有限公司 A kind of concentration detection apparatus and method
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CN104614071A (en) * 2014-12-09 2015-05-13 浙江福立分析仪器有限公司 Miniature optical path structure of spectrophotometer and application method thereof
CN104833620A (en) * 2015-04-20 2015-08-12 江苏苏净集团有限公司 Atmospheric particulate matter concentration monitoring device
CN104833620B (en) * 2015-04-20 2018-03-13 江苏苏净集团有限公司 A kind of monitoring device of atmosphere particle concentration
CN104807798A (en) * 2015-05-18 2015-07-29 合肥工业大学 Method and device for detecting up-conversion luminescence by utilizing mobile phone
CN104807798B (en) * 2015-05-18 2018-07-13 合肥工业大学 A kind of method and device detecting up-conversion luminescence using mobile phone
CN105353115A (en) * 2015-10-21 2016-02-24 中国科学院上海光学精密机械研究所 Measuring device and method of spatial distribution of scattering light field of immunochromatographic test strip
WO2017088214A1 (en) * 2015-11-24 2017-06-01 江南大学 Fluorescence-based biological detection system
CN106483102A (en) * 2016-12-09 2017-03-08 长春市金佳光电科技有限公司 Analyser for the analyser degree on-line checking of free water in aerial kerosene and minute impurities concentration on-line checking
CN108051344A (en) * 2017-11-23 2018-05-18 浙江工业大学 The realtime on-line monitoring method of polishing fluid bulky grain in a kind of polishing process
CN108776103A (en) * 2018-05-15 2018-11-09 三诺生物传感股份有限公司 A kind of detector optical system
WO2019218735A1 (en) * 2018-05-15 2019-11-21 三诺生物传感股份有限公司 Optical system of detector
CN111650097B (en) * 2020-04-30 2022-12-02 张家港谱析传感科技有限公司 High-speed sampling data processing method of aerodynamic particle size and concentration detector
CN111650097A (en) * 2020-04-30 2020-09-11 张家港谱析传感科技有限公司 High-speed sampling data processing method of aerodynamic particle size and concentration detector
CN111504869A (en) * 2020-05-15 2020-08-07 中国计量科学研究院 Flow type aggregate impurity analyzer
CN113552048A (en) * 2021-07-26 2021-10-26 苏州苏信环境科技有限公司 Particle counting method
CN113552050A (en) * 2021-07-26 2021-10-26 苏州苏信环境科技有限公司 Working method of particle counter
CN113552046A (en) * 2021-07-26 2021-10-26 苏州苏信环境科技有限公司 Calibration method and working method of particle counter
CN113552049A (en) * 2021-07-26 2021-10-26 苏州苏信环境科技有限公司 Working method of particle counter
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