CN102012368B - 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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CN102012368B
CN102012368B CN 201010501521 CN201010501521A CN102012368B CN 102012368 B CN102012368 B CN 102012368B CN 201010501521 CN201010501521 CN 201010501521 CN 201010501521 A CN201010501521 A CN 201010501521A CN 102012368 B CN102012368 B CN 102012368B
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detecting unit
ucp
suspension
data
cuvette
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CN102012368A (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

Multi-parameter of up-conversion luminescent particles detection system and method
Technical field
The present invention relates to up-conversion luminescence, particularly a kind of multi-parameter of up-conversion luminescent particles detection system and method.The present invention determines turbidity and the concentration of up-conversion luminescence suspension by transmitted light, scattered light and the up-conversion luminescence that receives simultaneously the up-conversion luminescence particle, to realize quick, objective, the quasi real time detection even in real time to the optical characteristics of up-conversion luminescence particle.
Background technology
Infrared up-conversion luminous material (Up-Converting Phosphor, be designated hereinafter simply as UCP) be the nano-scale particle that is consisted of in the lattice of crystal by rare earth doped, therefore be called again up-conversion luminescence particle (referred to as the UCP particle), (wavelength＞780nm) excites lower emission visible light (wavelength is 475-670nm), 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 Upconversion luminescence indicator organism bioactive molecule.During as biomarker, by detecting its Up-conversion Intensity, can obtain the concentration of biological substance combined with it when the UCP particle.Therefore, in order accurately to obtain the concentration of biological substance, must hold and control the Up-conversion Intensity characteristic of UCP particle under specific concentrations and turbidity.The UCP particle detection system realizes by the scattered light, transmitted light and the Up-conversion Intensity that detect the UCP suspension.
Technology 1 " laser turbidity meter " (application number: 200920099825.8) formerly, quantitatively detect scattered light and/or the transmitted intensity of suspension, the detection of realization to its turbidity, this detection method can only obtain the turbidity value of suspension, Upconversion luminescence and concentration that can not direct-detection UCP particle; Adopt the laser of high brightness 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 process 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 " Double scattered light turbimeter " (application number: 01253067.0) formerly, adopt doubly scattered light passage differential output 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, the light that sends due to lamp is many in visible-range, is easily affected by colourity when detecting coloured sample, can not detect band tinctorial pattern product.
Summary of the invention
Deficiency for above-mentioned prior art existence, the object of the invention is to propose a kind of multi-parameter of up-conversion luminescent particles detection system and method, this detection system should have that susceptibility is high, reliability is high, good stability, simple in structure, be easy to fill the school and cost is lower, operating personnel are required the 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 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 Intensity of the suspension that UCP suspension concentration is certain is tending towards a definite value; The concentration that is the UCP suspension is higher, and its Up-conversion Intensity is larger.
In measurement zone, there are proportionate relationship in the total content M of UCP particle and capacity V and the UCP suspension concentration N of measurement zone, namely
M∝V×N， (1)
Satisfying I 0After the constant condition of η, Up-conversion 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, due to particle to scattering of light and absorption, the transmission light intensity will be decayed, its attenuation degree is relevant to 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, along the scattered light intensity of 90 ° of directions be:
I 90°＝K 1I 0τe -Kτ∝K 1I 0τ (5)
During high turbidity, scattered light intensity and transmitted intensity than (turbidimetry, referred to as loose thoroughly than) be:
Figure GSB00000636630000021
Wherein: I 0Be incident intensity;
τ is turbidity, is proportional to the content of suspension in 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 low turbidity, linear relationship is preferably arranged between scattered light intensity signal and turbidity, during high turbidity loose thoroughly than and turbidity between linear relationship is preferably arranged, therefore, adopt respectively (5) formula and formula (6) when low turbidity and high turbidity, can access the wider range of linearity, 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, carry out match with formula (5) lower than this turbidity the time, carry out match with formula (6) during higher than this turbidity.
Technical solution of the present invention is as follows:
A kind of multi-parameter of up-conversion luminescent particles 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 comprised 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 forms the described sample cell of excitation beam irradiation of certain size, shape through cylindrical mirror; In described transmitted light beam direction, described power detecting unit is set;
Described power detecting unit is comprised of the first optical filter, the first focus lamp, the first aperture and the first photodetector successively along the transmitted light beam direction;
Described sample cell is comprised of cuvette and cuvette groove; Described cuvette is transparent, is used for installing up-conversion luminescence suspension to be measured, referred to as the UCP suspension; This cuvette is arranged in the light path of described excitation beam, forms transmitted light, scattered light and up-conversion luminescence after the UCP suspension to be measured of the described cuvette of described excitation beam irradiation;
Transmitted light direction at described cuvette arranges described transmitted light detecting unit, and this transmitted light detecting unit is comprised of the second optical filter, the second focus lamp, attenuator, second orifice diaphragm and the 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 comprised 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 comprised of the 5th focus lamp, the 6th focus lamp, the 4th aperture and photomultiplier successively along described up-conversion luminescence direction;
the electric signal that the electric signal of the first photodetector output is exported after described power detecting unit pre-amplification circuit, the electric signal that the electric signal of the second photodetector output is exported after described transmitted light detecting unit pre-amplification circuit, the electric signal of the voltage signal that the electric signal of described the 3rd photodetector output is exported after 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 sending into after A/D changes described data processing unit and carry out the data processing, parameter display with 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 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 does not interfere with each other and perpendicular to described excitation beam and by in the plane of described cuvette.
Described the first optical filter, the 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 the first aperture, second orifice diaphragm, the 3rd aperture, the 4th aperture are used for limiting 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, the described cuvette of described excitation beam irradiation, the resistance of difference regulating power detecting unit and scattered light detecting unit pre-amplification circuit: this pre-amplification circuit turns voltage by electric current and signal amplification two-stage circuit forms, 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 be output as 9.5V (being slightly less than output saturation value 10V) after secondary amplifies, 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 during with definite photomultiplier work 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 irradiation, 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 be output as 9.5V after secondary amplifies, 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 and get a certain amount of and put into cuvette with pipettor afterwards, open described laser instrument, the described cuvette of described excitation beam irradiation, to each acquisition channel continuous acquisition 30 seconds, each passage has M data, and the power of the first photodetector detection light source, the 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 by described control and data acquisition unit collection through power detecting unit pre-amplification circuit, transmitted light detecting unit pre-amplification circuit, scattered light detecting unit pre-amplification circuit respectively, realizes obtaining having turbidity value τ after the A/D conversion 1The raw data P that gathers of the corresponding power detecting unit of standard suspension 0 τ 1The raw data S that [j], scattered light detecting unit gather 0 τ 1The raw data T that [j] and transmitted light detecting unit gather 0 τ 1[j] sends into described data processing unit and carries out data and process, 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 described cuvette is followed successively by τ 2..., τ i... τ t, 2. repeat to measure by step, obtain the raw data P that the power detecting unit corresponding with the UCP suspension of each standard turbidity gathers 0 τ iThe raw data S that [j], scattered light detecting unit gather 0 τ iThe raw data T that [j] and transmitted light detecting unit gather 0 τ i[j], i=1 wherein, 2 ..., t;
(4) measure comparing sample zero Turbidity Water:
The standard model that changes in described cuvette is comparative sample zero Turbidity Water, open described laser instrument, the described cuvette of described excitation beam irradiation, to each acquisition channel continuous acquisition 30 seconds, each passage has M data, and the power of the first photodetector detection light source, the second photodetector are collected forward direction transmitted light I 0 °, the 3rd photodetector collects the side scattered light I of measurement zone 90 °, collect Up-conversion Intensity I with photomultiplier -90 °, obtain the raw data ZP that the power detecting unit of zero Turbidity Water gathers 0The raw data ZS that [j], scattered light detecting unit gather 0The raw data ZT that [j], transmitted light detecting unit gather 0The raw data ZF that [j] and up-conversion luminescence detecting unit gather 0[j], j=1 wherein, 2,3 ..., M;
(5) data are processed:
1. for fear of the caused measured larger skew of the minor fluctuations of light source, be τ with turbidity iThe raw data T that gathers of the corresponding transmitted light detecting unit of standard solution 0 τ iThe raw data S that [j] and scattered light detecting unit gather 0 τ i[j] be corresponding raw data P divided by the power detecting unit collection respectively τ i[j], the data T after the light source that is eliminated impact 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: on eliminating the data T after light source affects 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 were averaging within detection time, obtaining turbidity is τ iStandard solution corresponding:
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 averaging, obtains corresponding transmission mean value ZT 0With scattering mean value ZS 0, in order to eliminate the impact 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, loose saturating ratio, make suspension scattered light intensity or loose thoroughly than with the calibration curve of its turbidity.
The volume of described a certain amount of depending on described cuvette is 5～30ml.
Utilize above-mentioned multi-parameter of up-conversion luminescent particles detection system to carry out the method that multi-parameter of up-conversion luminescent particles is measured, comprise following measuring process:
(1) open 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 first N with described concentration 1Standard UCP suspension fully shake to shake up and get a certain amount of and be placed in described cuvette with pipettor afterwards, open described laser instrument, the described cuvette of described excitation beam irradiation is collected Up-conversion Intensity I in 30 seconds with photomultiplier -90 °, the first photodetector detects corresponding light source power, by after follow-up amplification and 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 gather 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 described cuvette Plays UCP particle suspension is followed successively by N 2..., N i... N k, 2. repeat to measure by step, obtain the raw data F that the up-conversion luminescence detecting unit corresponding with the UCP particle suspension of each normal concentration gathers 0NiThe raw data P that [j] and power detecting unit gather 0Ni[j], i=2 wherein, 3 ..., k, j=1,2,3 ..., M;
4. for fear of the caused measured larger skew of the minor fluctuations of light source, be N with concentration iThe raw data F that gathers of the corresponding 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 is eliminated impact 1Ni[j]=F 0Ni[j]/P 0Ni[j];
5. data smoothing filtering: on eliminating the data F after light source affects 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 were averaging within detection time, obtaining concentration is N iThe corresponding 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. changing described cuvette Plays sample is corresponding solvent, and sample, according to 3. 4. 5. 6. duplicate measurements of above-mentioned steps, obtain the corresponding up-conversion luminescence mean value of the Up-conversion Intensity ZF of this comparative sample as a comparison 3, in order to eliminate the impact 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 Intensity, set up 0～N kUp-conversion Intensity F in concentration range NiConcentration standard working curve with UCP suspension normal concentration value N Relations Among;
(3) UCP suspension to be measured is measured:
1. the concussion of required UCP suspension to be measured is shaken up and get a certain amount of and inject cuvette with pipettor afterwards, open described laser instrument, the described cuvette of described excitation beam irradiation, 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 impact:
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] is averaging respectively, 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. changing described cuvette Plays sample is corresponding solvent, and sample, according to 3. 4. 5. 6. duplicate measurements of above-mentioned steps, obtain the corresponding transmission mean value of the transmitted intensity ZT of this comparative sample as a comparison 3, the corresponding scattering mean value of scattered light intensity ZS 3With the corresponding up-conversion luminescence mean value of Up-conversion 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. obtained 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, measured value F and the concentration standard working curve of testing sample contrasted, obtain the concentration value of testing sample.
Described a certain amount of depending 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 transmitted light, scattered light and the up-conversion luminescence of test sample simultaneously can be obtained 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 greatly improved signal to noise ratio (S/N ratio), and is not subject to colourity impact in suspension, can be used for detecting the sample with 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 larger skew, thereby avoids producing larger measuring error.
4. UCP particle multiparameter detection system of the present invention detects its unique Upconversion luminescence, 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, adopt the scattered light detection method when the suspension turbidity is low, adopt than turbid method during high turbidity, thereby improved the linearity that detects dynamic range and whole surveying range; When turbidimetry makes transmitted light with scattered light measuring, light path is identical, and it is identical that light source changes the impact that turbidity is detected, and can eliminate part and disturb, and improves 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 costs, 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 suspension scattered light intensity or loose thoroughly than with the calibration curve schematic diagram of its turbidity;
Fig. 2 is the Up-conversion Intensity of UCP suspension and the calibration curve schematic diagram of its concentration;
Fig. 3 is UCP particle multiparameter detection system structured flowchart of the present invention;
Fig. 4 is UCP particle multiparameter detection system index path of the present invention;
Fig. 5 is the UCP particle multiparameter of the present invention flow chart of data processing figure of detection system simultaneously;
Fig. 6 is the spectral transmittance curve map of the 980nm optical filter that adopts in the embodiment of the present 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 UCP particle multiparameter detection system structured flowchart of the present invention, and Fig. 4 is UCP particle multiparameter detection system index path of the present invention.As seen from the figure, the formation of multi-parameter of up-conversion luminescent particles 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 comprised 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 excitation beam 201 described sample cells 2 of irradiation of certain size, shape after cylindrical mirror 106; In described transmitted light beam 301 directions, described power detecting unit 3 is set;
Described power detecting unit 3 is comprised of the first optical filter 302, the first focus lamp 303, the first aperture 304 and the first photodetector 305 successively along transmitted light beam 301 directions;
Described sample cell 2 is comprised of cuvette 203 and cuvette groove 202; Described cuvette 203 is transparent, is used for installing up-conversion luminescence suspension to be measured, referred to as the UCP suspension; 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 after the UCP suspension to be measured of the described excitation beam 201 described cuvettes 203 of irradiation;
Transmitted light 401 directions at described cuvette 203 arrange described transmitted light detecting unit 4, and this transmitted light detecting unit 4 is comprised of the second optical filter 402, the second focus lamp 403, attenuator 404, second orifice diaphragm 405 and the 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 comprised 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 comprised of the 5th focus lamp 602, the 6th focus lamp 603, the 4th aperture 604 and photomultiplier 605 successively along described up-conversion luminescence 601 directions;
the electric signal of the first photodetector 305 outputs is through the electric signal of described power detecting unit pre-amplification circuit 7 outputs, the electric signal of the 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 after described scattered light detecting unit pre-amplification circuit 9 is together through described control and data acquisition unit 10 collections, realize sending into after A/D changes described data processing unit 11 and carry out the data processing, parameter display with 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 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 does not interfere with each other and perpendicular to described excitation beam 201 and by in the plane of described cuvette 203.
Described the first optical filter, the 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 spectral transmittance curve as shown in Figure 6.
Described the first aperture, second orifice diaphragm, the 3rd aperture, the 4th aperture are used for limiting 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, is the oval-shaped beam of bore 4mm * 2mm through collimating mirror 102 collimation focusings, and power is the 70mW left and right, excites up-conversion luminescent material can launch the visible light of 541.5nm.
Described cuvette 203 is 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 when namely inside fills liquid, the high volume of every 10mm is 10ml.
Described dichronic mirror 104 is coated with deielectric-coating, is 1% left and right to the transmitance (45 ° of incident angles) of 980nm light, and reflectivity is 99% left and right, is 45° angle 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 at Side direction receiving, is avoided the impact of transmitted light for the upper conversion light of wavelength 541.5nm, 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 by the transformation of simulating signal to digital signal, needs at least 4 road A/D input channels (single-ended or both-end) and at least 1 road D/A output channel, can be USB7360 series multifunctional data acquisition module.
Described prime amplifier can be LF353 or LF412.The 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 multi-parameter of up-conversion luminescent particles 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 excitation beam 201 described cuvettes of irradiation, the resistance of difference regulating power detecting unit and scattered light detecting unit pre-amplification circuit: this pre-amplification circuit turns voltage by electric current and signal amplification two-stage circuit forms, 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 be output as 9.5V (being slightly less than output saturation value 10V) after secondary amplifies, 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 during with definite photomultiplier work 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 excitation beam 201 described cuvettes of irradiation, 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 be output as 9.5V after secondary amplifies, 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 rear getting respectively with pipettor and a certain amount ofly put into cuvette as 10ml, open described laser instrument, the described excitation beam 201 described cuvettes of irradiation, to each acquisition channel continuous acquisition 30 seconds, each passage has M data, and the power of the first photodetector 305 detection light source, the 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 by described control and data acquisition unit 10 collections 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 corresponding power detecting unit of standard suspension 0 τ 1The raw data S that [j], scattered light detecting unit gather 0 τ 1The raw data T that [j] and transmitted light detecting unit gather 0 τ 1[j] sends into described data processing unit 11 and carries out data and process, 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 described cuvette 203 is followed successively by τ 2..., τ i... τ t, 2. repeat to measure by step, obtain the raw data P that the power detecting unit corresponding with the UCP suspension of each standard turbidity gathers 0 τ iThe raw data S that [j], scattered light detecting unit gather 0 τ iThe raw data T that [j] and transmitted light detecting unit gather 0 τ i[j], i=1 wherein, 2 ..., t;
(4) measure comparing sample zero Turbidity Water:
The standard model that changes in described cuvette is comparative sample zero Turbidity Water, open described laser instrument, the described excitation beam 201 described cuvettes of irradiation, to each acquisition channel continuous acquisition 30 seconds, each passage has M data, and the power of the first photodetector 305 detection light source, the 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 Up-conversion Intensity I with photomultiplier 605 -90 °, obtain the raw data ZP that the power detecting unit of zero Turbidity Water gathers 0The raw data ZS that [j], scattered light detecting unit gather 0The raw data ZT that [j], transmitted light detecting unit gather 0The raw data ZF that [j] and up-conversion luminescence detecting unit gather 0[j], j=1 wherein, 2,3 ..., M;
(5) data are processed, and its flow process is referring to Fig. 5:
1. for fear of the caused measured larger skew of the minor fluctuations of light source, should be τ with turbidity iThe raw data T that gathers of the corresponding transmitted light detecting unit of standard solution 0 τ iThe raw data S that [j] and scattered light detecting unit gather 0 τ i[j] be corresponding raw data P divided by the power detecting unit collection respectively τ i[j], the data T after the light source that is eliminated impact 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: on eliminating the data T after light source affects 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 were averaging within detection time, obtaining turbidity is τ iStandard solution corresponding:
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 averaging, obtains corresponding transmission mean value ZT 0With scattering mean value ZS 0i, in order to eliminate the impact 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, loose saturating ratio, make suspension scattered light intensity or loose thoroughly than with the calibration curve of its turbidity, as shown in Figure 1.
Utilize multi-parameter of up-conversion luminescent particles detection system of the present invention to carry out the method that multi-parameter of up-conversion luminescent particles is measured, comprise following measuring process:
(1) open 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 first N with described concentration 1Standard UCP suspension fully shake to shake up and get a certain amount of described cuvette 203 that is placed in pipettor afterwards, open described laser instrument, the described excitation beam 201 described cuvettes of irradiation, the Up-conversion Intensity I that uses photomultiplier 605 to collect in 30 seconds -90 °, the first photodetector 305 detects corresponding light source power, by after follow-up amplification and 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 gather 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 described cuvette 203 Plays UCP particle suspensions is followed successively by N 2..., N i... N k, 2. repeat to measure by step, obtain the raw data F that the up-conversion luminescence detecting unit corresponding with the UCP particle suspension of each normal concentration gathers 0NiThe raw data P that [j] and power detecting unit gather 0Ni[j], i=2 wherein, 3 ..., i ... k, j=1,2,3 ..., M;
4. for fear of the caused measured larger skew of the minor fluctuations of light source, should be the raw data F of the corresponding 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 is eliminated impact 1Ni[j]=F 0Ni[j]/P 0Ni[j];
5. data smoothing filtering: on eliminating the data F after light source affects 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 were averaging within detection time, obtaining concentration is N iThe corresponding 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. changing described cuvette Plays sample is corresponding solvent, and sample, according to 3. 4. 5. 6. duplicate measurements of above-mentioned steps, obtain the corresponding up-conversion luminescence mean value of the Up-conversion Intensity ZF of this comparative sample as a comparison 3, in order to eliminate the impact 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 Intensity are carried out match, set up the Up-conversion 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. the concussion of required UCP suspension to be measured is shaken up and get a certain amount of injection cuvette with pipettor afterwards, open described laser instrument, the described excitation beam 201 described cuvettes of irradiation, 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 impact:
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] is averaging respectively, 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. changing described cuvette Plays sample is corresponding solvent, and sample, according to 3. 4. 5. 6. duplicate measurements of above-mentioned steps, obtain the corresponding transmission mean value of the transmitted intensity ZT of this comparative sample as a comparison 3, the corresponding scattering mean value of scattered light intensity ZS 3With the corresponding up-conversion luminescence mean value of Up-conversion 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. obtained 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, measured value F and the concentration standard working curve of testing sample contrasted, obtain the concentration value of testing sample.
Experiment shows, characteristics of the present invention are:
UCP particle multiparameter 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 (S/N ratio), and be not subject to colourity impact in 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 larger skew, thereby avoid producing larger measuring error;
Detect the Upconversion luminescence of UCP particle uniqueness, detect susceptibility, dirigibility and stability with height;
Adopt different angles receiving scattered light signal and optical signal transmissive, adopt the scattered light detection method when the suspension turbidity is low, adopt than turbid method when turbidity is higher, thereby improved the linearity that detects dynamic range and whole surveying range;
When turbidimetry makes transmitted light with scattered light measuring, light path is identical, and 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 costs, 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 that susceptibility is high, reliability is high, 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 (8)

1. multi-parameter of up-conversion luminescent particles 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 by laser instrument (101), collimating mirror (102), dichronic mirror (104), cylindrical mirror (106) forms, the laser that described laser instrument (101) sends becomes parallel beam (103) after 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), described folded light beam (105) forms certain size after cylindrical mirror (106), the excitation beam of shape (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 comprised of the first optical filter (302), the first focus lamp (303), the first aperture (304) and the first photodetector (305) successively along transmitted light beam (301) direction;
Described sample cell (2) is comprised of cuvette (203) and cuvette groove (202); Described cuvette (203) is transparent, is used for installing UCP suspension 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 UCP suspension to be measured of described cuvette (203);
Transmitted light (401) direction in described cuvette (203) arranges described transmitted light detecting unit (4), and this transmitted light detecting unit (4) is comprised of the second optical filter (402), the second focus lamp (403), attenuator (404), second orifice diaphragm (405) and the second photodetector (406) successively along transmitted light (401) direction;
A side at described cuvette (203) arranges described scattered light detecting unit (5), and this scattered light detecting unit (5) is comprised 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) arranges described up-conversion luminescence detecting unit (6), and this up-conversion luminescence detecting unit (6) is comprised of the 5th focus lamp (602), the 6th focus lamp (603), the 4th aperture (604) and photomultiplier (605) successively along described up-conversion luminescence (601) direction;
the electric signal of the first photodetector (305) output is through the electric signal of described power detecting unit pre-amplification circuit (7) output, the electric signal of the 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 (506) 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 sending into after A/D changes described data processing unit (11) and carry out the data processing, parameter display with UCP suspension to be measured, storage or output,
Described detection system also will be adjusted and be demarcated, and 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 (201) shines described cuvette, the resistance of difference regulating power detecting unit and scattered light detecting unit pre-amplification circuit: this pre-amplification circuit turns voltage by electric current and signal amplification two-stage circuit forms, 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 be output as 9.5V after secondary amplifies, fixing each resistance value at this moment; Regulate the added bias voltage of up-conversion luminescence light path photomultiplier, the enlargement factor during with definite photomultiplier work 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, adjust 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 be output as 9.5V after secondary amplifies, 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 tFormal hydrazine standard solution;
2. be τ with turbidity 1Formal hydrazine standard solution concussion shake up and get a certain amount of cuvette of putting into pipettor afterwards, 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 the first photodetector (305) detection light source, the second photodetector (406) 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 by described control and data acquisition unit (10) collection 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 corresponding power detecting unit of formal hydrazine standard solution 0 τ 1The raw data S that [j], scattered light detecting unit gather 0 τ 1The raw data T that [j] and transmitted light detecting unit gather 0 τ 1[j] sends into described data processing unit (11) and carries out data and process, 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 described cuvette (203) is followed successively by τ 2..., τ i... τ t, 2. repeat to measure by step, obtain the raw data P that the power detecting unit corresponding with the formal hydrazine standard solution of each standard turbidity gathers 0 τ iThe raw data S that [j], scattered light detecting unit gather 0 τ iThe raw data T that [j] and transmitted light detecting unit gather 0 τ i[j], i=1 wherein, 2 ..., t;
(3) measure comparing sample zero Turbidity Water:
The formal hydrazine standard solution that changes in described cuvette is comparative sample zero 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 the first photodetector (305) detection light source, the second photodetector (406) are collected forward direction transmitted light I 0 °, the 3rd photodetector (506) collects the side scattered light I of measurement zone 90 °, collect Up-conversion Intensity I with photomultiplier (605) -90 °, obtain the raw data ZP that the power detecting unit of zero Turbidity Water gathers 0The raw data ZS that [j], scattered light detecting unit gather 0The raw data ZT that [j], transmitted light detecting unit gather 0The raw data ZF that [j] and up-conversion luminescence detecting unit gather 0[j], j=1 wherein, 2,3 ..., M;
(4) data are processed:
1. for fear of the caused measured larger skew of the minor fluctuations of light source, should be τ with turbidity iThe raw data T that gathers of the corresponding transmitted light detecting unit of formal hydrazine standard solution 0 τ iThe raw data S that [j] and scattered light detecting unit gather 0 τ i[j] be corresponding raw data P divided by the power detecting unit collection respectively 0 τ i[j], the data T after the light source that is eliminated impact 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: on eliminating the data T after light source affects 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 were averaging within detection time, obtaining turbidity is τ iFormal hydrazine standard solution corresponding:
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 averaging, obtains corresponding transmission mean value ZT 0With scattering mean value ZS 0, in order to eliminate the impact of cuvette and comparative sample, with the transmission mean value T of formal hydrazine standard solution 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;
(5) make the turbidity calibration curve:
According to the concrete measured value of the turbidity value of formal hydrazine standard solution and scattered light intensity, loose saturating ratio, make suspension scattered light intensity or loose thoroughly than with the turbidity calibration curve of its turbidity.
2. multi-parameter of up-conversion luminescent particles 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 same cavity.
3. multi-parameter of up-conversion luminescent particles 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) does not interfere with each other and perpendicular to described excitation beam (201) and by in the plane of described cuvette (203).
4. multi-parameter of up-conversion luminescent particles detection system according to claim 1, it is characterized in that described the first optical filter, the 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. multi-parameter of up-conversion luminescent particles detection system according to claim 1, it is characterized in that described the first aperture, second orifice diaphragm, the 3rd aperture, the 4th aperture are used for limiting 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. multi-parameter of up-conversion luminescent particles detection system according to claim 1, is characterized in that the described a certain amount of 5～30ml of being.
7. utilize multi-parameter of up-conversion luminescent particles detection system claimed in claim 1 to carry out the method that multi-parameter of up-conversion luminescent particles is measured, it is characterized in that comprising following measuring process:
(1) open 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 first N with described concentration 1Standard UCP suspension fully shake to shake up and get a certain amount of described cuvette (203) that is placed in pipettor afterwards, open described laser instrument, described excitation beam (201) shines described cuvette, and use photomultiplier (605) is collected the Up-conversion Intensity I in 30 seconds -90 °, the first photodetector (305) detects corresponding light source power, by after follow-up amplification and 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 gather 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 described cuvette (203) Plays UCP suspension is followed successively by N 2..., N i... N k, 2. repeat to measure by step, obtain the raw data F that the up-conversion luminescence detecting unit corresponding with the standard UCP suspension of each normal concentration gathers 0NiThe raw data P that [j] and power detecting unit gather 0Ni[j], i=2 wherein, 3 ..., i ... k, j=1,2,3 ..., M;
4. for fear of the caused measured larger skew of the minor fluctuations of light source, should be N with concentration iThe raw data F that gathers of the corresponding up-conversion luminescence of standard UCP suspension unit 0NiThe raw data P that [j] gathers divided by power detecting unit 0 τ i[j], the data F after the light source that is eliminated impact 1Ni[j]=F 0Ni[j]/P ONi[j];
5. data smoothing filtering: on eliminating the data F after light source affects 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 were averaging within detection time, obtaining concentration is N iThe corresponding up-conversion luminescence mean value of standard UCP suspension:
F 3Ni＝{F 2Ni[1]+F 2Ni[2]+…+F 2Ni[j]…+F 2Ni[M]}/M；
7. changing described cuvette Plays UCP suspension is corresponding solvent, and sample, according to 3. 4. 5. 6. duplicate measurements of above-mentioned steps, obtain the corresponding up-conversion luminescence mean value of the Up-conversion Intensity ZF of this comparative sample as a comparison 3, in order to eliminate the impact of cuvette and comparative sample, with the up-conversion luminescence mean value F of standard UCP suspension 3NiWith the corresponding mean value ZF of comparative sample 3Between difference F Ni=F 3Ni-ZF 3As measured value;
8. concentration value and each the concrete measured value of Up-conversion Intensity with standard UCP suspension carries out match, the concentration calibration curve of Criterion UCP suspension Up-conversion Intensity and concentration relationship;
(3) UCP suspension to be measured is measured:
1. required UCP suspension to be measured concussion is shaken up and get a certain amount of injection cuvette with pipettor afterwards, 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 impact:
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] is averaging respectively, 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 in described cuvette, UCP suspension to be measured is corresponding solvent, sample, according to 1. 2. 3. 4. duplicate measurements of above-mentioned steps, obtain the corresponding transmission mean value of the transmitted intensity ZT of this comparative sample as a comparison 3, the corresponding scattering mean value of scattered light intensity ZS 3With the corresponding up-conversion luminescence mean value of Up-conversion Intensity ZF 3,
6. with T=T 3-ZT 3, S=S 3-ZS 3, F=F 3-ZF 3Measured value as UCP suspension to be measured;
7. obtained the turbidity of UCP suspension to be measured by the measured value S of described UCP suspension to be measured or S/T and the contrast of turbidity calibration curve, measured value F and the concentration calibration curve of UCP suspension to be measured contrasted, obtain the concentration value of UCP suspension to be measured.
8. the method for multi-parameter of up-conversion luminescent particles measurement according to claim 7, 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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