CN1591006A - Chemical luminous detecting system for liquid chromatography - Google Patents
Chemical luminous detecting system for liquid chromatography Download PDFInfo
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- CN1591006A CN1591006A CN 03156107 CN03156107A CN1591006A CN 1591006 A CN1591006 A CN 1591006A CN 03156107 CN03156107 CN 03156107 CN 03156107 A CN03156107 A CN 03156107A CN 1591006 A CN1591006 A CN 1591006A
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Abstract
The present invention relates to a chemical luminescence detection equipment for liquid chromatography. Said equipment includes flow-through cell, photosensor, modem, operation amplifier, signal processor, A/D converter and computer. The flow-through cell is set on the photosensitive window of photosensor, and the produced optical signal can be undergone the processes of converting it into electric signal, modulation, demodulation, separating high frequency signal, filtering, converting electric signal into digital signal, using computer to make digital signal collection, recording and processing so as to implement its detection process. Said invention has the advantages of high sensitivity, stable performance and low production cost, etc.
Description
Technical field
The present invention is a kind of chemiluminescence detection system, particularly a kind of phase chromatography-use chemiluminescence detection system.
Background technology
Luminesceence analysis is the abbreviation of mulecular luminescence spectral analysis.Mulecular luminescence is divided into three kinds of fluorescence, phosphorescence and chemiluminescences, and wherein fluorescence and phosphorescence belong to photoluminescence.The energy jump that discharges in the ground state molecule absorption chemical reaction is to excited state, and the molecule that is in excited state returns ground state with the form of optical radiation and then produces chemiluminescence.Based on concerning between mulecular luminescence intensity and the measured object content that the analytical approach of setting up is luminescence analysis.Because luminescence analysis is the method for directly carrying out photon metering, its sensitivity and selectivity generally all are better than absorption photometry, thereby provide a kind of highly sensitive research means for inorganics and organic trace and extreme trace analysis.Application in fields such as environment, medical science, life science, industry is developed rapidly.High performance liquid chromatography has become the most frequently used high efficient separation technology of Pharmaceutical Analysis, environmental analysis, biochemical analysis and technical analysis, high performance liquid chromatography and the coupling of chemiluminescence detection provide a kind of analysis means that accurately separates with super sensitivity detection, the continuous development of chemiluminescence detection has promoted popularizing of high performance liquid chromatography, makes extreme trace analysis become possibility.The liquid chromatography chemiluminescence analysis system possesses the general advantage of chemiluminescence and high performance liquid chromatography simultaneously: pick-up unit is simple, and is easy to operate; Method is highly sensitive, generally at ng/g-pg/g (ng/g-pik/gram) order of magnitude; The range of linearity is wide, and the luminous intensity of reactant and the concentration of determinand can be linear in 4-5 number order magnitude range; The separation efficiency height, the post of liquid chromatography packed column is imitated can reach 2 * 10
3～5 * 10
4Piece/rice theoretical cam curve.Chemiluminescence detector generally comprises three parts, reaction tank, signal receiving processing system and computer-processing software.At present, the application of chemiluminescence in high performance liquid chromatography has some reports, the fluorescence spectrophotometer of most uses oneself repacking or ultraviolet-visible pectrophotometer are as chemiluminescence detector, not only waste one's talent on a petty job, cause the wasting of resources, and may cause the reduction of instrument performance, even can't use because of reasons such as renovation technique, methods.External existing high performance liquid chromatography comes out with chemiluminescence detector, and used reaction tank is traditional helix tube type or through type, and domestic do not have pertinent instruments to come out as yet.
(1) the straight channel formula flow cell of making such as straight channel formula flow cell: Scott etc., reagent enters from the flow cell bottom, flow out (S.Stieg from the flow cell top, T.A.Nieman, Experimental and TheoreticalConsiderations of Flow Cell Design in Analytical Chemiluminescence, Anal.Chem., 1978,50,401-404).The shortcoming of this flow cell is that detection sensitivity is lower.
(2) the screw type flow cell sensitivity that greatly improved chemiluminescence detection of screw type flow cell: J.L.Burguera and A.Townshend design, be present flow cell (the J.L.Burguera and Alan Townshend.Flow In jection Analysis For MonitoringChemiluminescence Reactions.Anal.Chim.Acta commonly used of portable injection chemiluminescence system, 1980,114,209-214).The shortcoming of this flow cell is a complex manufacturing technology, and the manufacturing cost height can't be realized producing in batches.
(3) Soma S-3400 chemiluminescence detector (Japan) uses the luminous pond of spiral pipe, and shortcoming is a flow cell manufacturing cost height, can't low-costly produce in batches; Main circuit is direct amplifying circuit (high resistant operational amplification circuit), high-pass filtering circuit; For domestic, import instrument is costly, and a lot of R﹠D institutions can't bear, and maintenance difficult, and accessory is bought inconvenience.
(4) Tianjin, island CLD-10A chemiluminescence detector (Japan), the luminous pond of use and main circuit system class seemingly exist same or similarly not enough with Soma S-3400 chemiluminescence detector.The domestic chromatographic grade chemiluminescence detector that presses for the function admirable of the relative low price of oneself producing.
Summary of the invention
The purpose of this invention is to provide a kind of phase chromatography-use chemiluminescence detection system, this system makes the chip circulation pond with standard photolithography techniques and Micrometer-Nanometer Processing Technology, adopt high-quality photoelectricity multiplier tube as sensor, adopt high frequency modulated detuner, operational amplifier filtering slicing, number converter, computer-processing software, its automaticity height, good stability, easy to use, diverse in function, and cheap, be fit to China's national situation.
Technical scheme of the present invention is as follows:
Phase chromatography-use chemiluminescence detecting provided by the invention comprises chip type flow cell, optical sensor, modulator-demodular unit, operational amplifier, signal processor, analog to digital converter and computing machine;
Described chip type flow cell places on the photosensitive window of optical sensor, and the light signal that the chemiluminescence reaction that the chip type flow cell takes place produces is sent into optical sensor by the photosensitive window of optical sensor, is converted into electric signal;
Modulator-demodular unit is made up of the modulator, oscillator and detuner three parts that link to each other, and the output terminal of optical sensor is electrically connected with modulator, and the electric signal of optical sensor output enters modulator and modulates the influence of other homogenous frequency signal in the erasure signal transmission course; Oscillator produces the required high frequency of modulation, and gives detuner with high-frequency signal transmission, and detuner is separated required electric signal under the control of this high-frequency signal from high frequency;
The output terminal of described modulator is electrically connected with operational amplifier, and the signal after the modulation enters operational amplifier and amplifies, and amplifying signal is separated from modulation signal through the detuner that is electrically connected with operational amplifier again; Isolated signal enters the signal processor that is electrically connected with detuner carry out slicing, Filtering Processing after, enter the analog to digital converter that is electrically connected with signal processor, with analog signal conversion is digital signal, this digital signal enters the computing machine that is electrically connected with analog to digital converter, by computing machine to digital signal gather, record and computing.
The structure of described chip type flow cell is made up of the last substrate 11 that is stacked together, subtegulum 22 and cover plate 33, on subtegulum 22, be carved with flow cell conduit 44, C place near the conduit 44 the initiating terminal A of distance conduit 44 is provided with a conduit BC who communicates with conduit 44, position relative with B with the port A of conduit 44 on last substrate is provided with through hole A ' and B ', also is carved with the feed liquor conduit 55 and 56 that is connected with this through hole A ' and B ' respectively on last substrate 11; Described cover plate 33 is incumbent on the substrate to form chip type flow cell integral body; Described flow cell conduit 44 is screw type conduit or bent tube type conduit; Described optical sensor is the photomultiplier of wavelength in the 350-700 nanometer range.
Phase chromatography-use chemiluminescence detection system provided by the invention, make the chip circulation pond with standard photolithography techniques and Micrometer-Nanometer Processing Technology, adopt high-quality photoelectricity multiplier tube as sensor, adopt high frequency modulated detuner, operational amplifier, filtering peak clipper, analog to digital converter, computer-processing software, simplified the technology of chemiluminescence detection, saved raw material, improved yield rate, its automaticity height, good stability, easy to use, diverse in function, and cheap, be fit to China's national situation.
Description of drawings
Fig. 1 is the structured flowchart of phase chromatography-use chemiluminescence detection system of the present invention;
Fig. 2 is a kind of structural representation of the chip circulation pond with the screw type conduit;
Fig. 3 is a kind of structural representation of the chip circulation pond with the bent tube type conduit;
Fig. 4 is the structure of a subtegulum synoptic diagram of the present invention;
Fig. 5 is the structural representation of last substrate;
Fig. 6 is the structure of cover plate synoptic diagram;
Wherein: go up substrate 11, subtegulum 22 cover plates 33
The both port of origination A of conduit 44 props up the both port of origination B through hole A ' and the B ' of conduit
Embodiment
Fig. 1 is the block diagram of phase chromatography-use chemiluminescence detector of the present invention, as shown in Figure 1, phase chromatography-use chemiluminescence detecting provided by the invention comprises chip type flow cell, optical sensor, modulator-demodular unit, operational amplifier, signal processor, analog to digital converter and computing machine;
Described chip type flow cell places on the photosensitive window of optical sensor, and the light signal that the chemiluminescence reaction that the chip type flow cell takes place produces is sent into optical sensor by the photosensitive window of optical sensor, is converted into electric signal;
Modulator-demodular unit is made up of the modulator, oscillator and detuner three parts that link to each other, and the output terminal of optical sensor is electrically connected with modulator, and the electric signal of optical sensor output enters modulator, the influence of other homogenous frequency signal in the erasure signal transmission course; Oscillator produces the required high frequency of modulation signal is modulated, and gives detuner with high-frequency signal transmission, and detuner is separated required electric signal under the control of this high-frequency signal from high frequency;
The output terminal of described modulator is electrically connected with operational amplifier, and the signal after the modulation enters operational amplifier and amplifies, and amplifying signal is separated from modulation signal through the detuner that is electrically connected with operational amplifier again; Isolated signal enters the signal processor that is electrically connected with detuner carry out slicing, Filtering Processing after, enter the analog to digital converter that is electrically connected with signal processor, with analog signal conversion is digital signal, this digital signal enters the computing machine that is electrically connected with analog to digital converter, by computing machine to digital signal gather, record and computing.
By Fig. 2-Fig. 6 as can be known, the structure of described chip type flow cell is made up of the last substrate 11 that is stacked together, subtegulum 22 and cover plate 33, on subtegulum 22, be carved with flow cell conduit 44, C place near the conduit 44 the initiating terminal A of distance conduit 44 is provided with a conduit BC who communicates with conduit 44, position relative with B with the port A of conduit 44 on last substrate is provided with through hole A ' and B ', also is carved with the feed liquor conduit 55 and 56 that is connected with this through hole A ' and B ' respectively on last substrate 11; Described cover plate 33 is incumbent on the substrate to form chip type flow cell integral body; As Fig. 2, Fig. 4, Fig. 5 and shown in Figure 6, described flow cell conduit 44 can be the screw type conduit; Described flow cell conduit 44 also can be the bent tube type conduit, as shown in Figure 3; Described optical sensor is the photomultiplier of wavelength in the 350-700 nanometer range. Feed liquor conduit 55 and 56 inflow point are separately installed with feed tube 1,2, and the not end of flow cell conduit 44 is equipped with drain pipe 3.
During use, sample and luminescence reagent are respectively from feed tube 1, the 2 pond conduit 44 that circulates, enter screw type conduit or bent tube type conduit at A, B place, converge, in whole conduit, react then and luminous at C, its light signal enters photomultiplier, and reacted waste liquid is discharged by drain pipe 3;
Because chip type flow cell of the present invention is positioned on the photosensitive window of optical sensor, the light signal that the chemiluminescence reaction that takes place at flow cell produces enters photomultiplier by photosensitive window, be converted into electric signal, enter modulator-demodular unit from photomultiplier output electric signal, with other homogenous frequency signals in the erasure signal transmission course (as power frequency, low-frequency noise of directly putting and dc shift etc.) interference, signal after the modulation enters operational amplifier, from modulation signal, separate through detuner through amplifying signal, the signal entering signal processor of separating carries out filtering, after slicing is handled, enter analog to digital converter, is digital signal with signal by analog signal conversion, in this digital signal input computing machine, digital signal is gathered by computing machine, record, detect and handle and calculate.The oscillator of modulator-demodular unit not only produce modulation signal thin high-frequency signal, but also provide reference signal for detuner.
Its method for making:
(1) on quartz substrate, carve passage-sandblast, use sandblast special paper, directly be attached on the piezoid, paper is set level clothes after, slight pressurization is promptly pasted closely and is bonded on the piezoid surface, carves out pattern on paper, and hollow out; Be placed on then under the sand-blasting machine, use smooth electro-corundum finer abrasive woodcarving by sand blast;
The high temperature bonding with being carved with the quartz substrate and the cover plate wash clean of passage, closes up high temperature sintering in certain sequence;
(2) outlet and inlet duct welding are truncated into the tubule of 0.5-1.0 centimeter length, wash clean, high temperature sintering then with quartz glass tube;
(3) chemical polishing, the preparation chemical brightening solution, fluohydric acid content 40～50%, sulfuric acid 90%～96%, filling a prescription is H
2O: HF: H
2SO
4=1: 2: 3 (V: V: V), the polishing fluid circulation is fed in the flow cell passage, bright and clean up to channel surface.
The optical sensor that the present invention uses is the photomultiplier of wavelength in the 350-700 nanometer range, flow cell and photomultiplier can be made an integral sealing and get up to prevent the interference of parasitic light, and original signal enters computing machine through high frequency modulated detuner, high resistance operating amplifier, signal processor (filtering, slicing etc.), sixteen bit analog to digital converter.The signal that chemiluminescence produces has lower frequency spectrum, when signal is more weak, in the signal transport process, being subject to other homogenous frequency signals disturbs, as be subject to that power frequency is disturbed and influences such as the low-frequency noise of directly putting and dc shift, native system adopts the method for modulation-demodulation, with respect to abroad for quasi-instrument, has improved antijamming capability, the transmittability of circuit and has improved signal to noise ratio (S/N ratio) effectively.Modulation be with the low frequency analog information of original input and time thereof change, load on the characteristic parameter of the carrier wave of high frequency, demodulation is exactly from the high frequency modulated wave after amplifying, and recovers the process of original input signal.Signal processing circuit is by technology such as filtering, slicings, eliminate the false and retain the true, accurately and the sensitive Useful Information that obtains, native system is with respect to external like product, amplitude limit clipping circuit in signal processor, having added, effectively strangulation and eliminated the influence of ground noise and high frequency interference.The use of sixteen bit analog to digital conversion circuit has guaranteed the accurate transformation of simulating signal to digital signal.The voltage resolution of determining Circuits System after tested is 0.05 millivolt, is better than external like product.
The LUM chromatogram software that the present invention uses in computing machine has two parts function: spectrogram collection and chromatographic data are handled, the basic function that integrated chromatographic data is handled, and focus on the intellectuality that spectral data is handled, make spectral data handle by numerous and diverse obscure become clear and easy to understand, the spectral data that the user need be possessed is handled knowledge and is reduced to minimum, but it still possesses professional processing capacity, when needs reach certain particular processing effect, regulating measure is easily arranged still.
The present invention adopts multithreading, realizes signals collecting, data processing collaborative work simultaneously.Simple and clear compactness is made every effort at the interface, adopt the window cutting techniques, file management hurdle, spectrogram, the form relevant with spectrogram are presented in the same interface, it is very convenient to operate, spectrogram original sampling data and relative information, be kept in the file as disposal route, correlation parameter etc. are all concentrated, follow the GLP standard.Whole procedure is weaved into VC++, has incomparable advantage at aspects such as dirigibility, stability and execution efficient.Take into full account the requirement of good laboratory standard (GLP) in the design, guarantee desired data tracing ability of GLP and data integrity.
Data acquisition and spectrogram show: simulating signal shows by the workstation software record and with the form of spectrogram through A/D conversion back, and with corresponding form preservation, in the spectrogram gatherer process, sampling time and range all over the screen can arbitrarily be adjusted, and also can adjust automatically simultaneously.
Data processing: have that baseline correction, overlap peak are cut apart, increased the peak, delete the peak, the basic function of general chromatographic work stations such as the peak merges, acromion cutting, the assorted peak of degradation, background correction baseline, can calculate liquid chromatograph indexs such as baseline noise and drift, chromatographic column column plate number, peak degree of separation, tailing factor, capacity factor measure.
Qualitative and quantitative: as to adopt peak start-stop scope cover peak mode, with mouse or keyboard setting or adjustment each component cover peak time.Can calculate the average correction factor and mean concentration.Can realize various quantitative algorithms, as index method, minusing etc.Result output: spectrogram not only can directly copy to files such as Word, and its data can also directly output to electrical form such as Excel and calculate and handle.
Claims (4)
1, a kind of phase chromatography-use chemiluminescence detecting comprises chip type flow cell, optical sensor, modulator-demodular unit, operational amplifier, signal processor, analog to digital converter and computing machine;
Described chip type flow cell places on the photosensitive window of optical sensor, and the light signal that the chemiluminescence reaction that the chip type flow cell takes place produces is sent into optical sensor by the photosensitive window of optical sensor, is converted into electric signal;
Modulator-demodular unit is made up of the modulator, oscillator and detuner three parts that link to each other, and the output terminal of optical sensor is electrically connected with modulator, and the electric signal of optical sensor output enters modulator and modulates the influence of other homogenous frequency signal in the erasure signal transmission course; Oscillator produces the required high frequency of modulation, and gives detuner with high-frequency signal transmission, and detuner is separated required electric signal under the control of this high-frequency signal from high frequency;
The output terminal of described modulator is electrically connected with operational amplifier, and the signal after the modulation enters operational amplifier and amplifies, and amplifying signal is separated from modulation signal through the detuner that is electrically connected with operational amplifier again; Isolated signal enters the signal processor that is electrically connected with detuner carry out slicing, Filtering Processing after, enter the analog to digital converter that is electrically connected with signal processor, with analog signal conversion is digital signal, this digital signal enters the computing machine that is electrically connected with analog to digital converter, by computing machine to digital signal gather, record and computing.
2, by the described phase chromatography-use chemiluminescence detecting of claim 1, it is characterized in that, the structure of described chip type flow cell is by the last substrate (11) that is stacked together, subtegulum (22) and cover plate (33) are formed, on subtegulum (22), be carved with flow cell conduit (44), (C) near the conduit (44) the initiating terminal (A) of distance conduit (44) locates to be provided with a conduit (BC) that communicates with conduit (44), on last substrate with the port (A) of conduit (44) and (B) relative position be provided with through hole (A ') and (B '), on last substrate, also be carved with respectively and this through hole (A ') and the feed liquor conduit (55) and (56) that (B) are connected; Described cover plate (33) is incumbent on substrate (11) upward to form chip type flow cell integral body.
3, by the described phase chromatography-use chemiluminescence detecting of claim 2, it is characterized in that described flow cell conduit (44) is screw type conduit or bent tube type conduit.
4, by the described phase chromatography-use chemiluminescence detecting of claim 1, it is characterized in that described optical sensor is the photomultiplier of wavelength in the 350-700 nanometer range.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03156107 CN1254680C (en) | 2003-08-29 | 2003-08-29 | Chemical luminous detecting system for liquid chromatography |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 03156107 CN1254680C (en) | 2003-08-29 | 2003-08-29 | Chemical luminous detecting system for liquid chromatography |
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| Publication Number | Publication Date |
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| CN1591006A true CN1591006A (en) | 2005-03-09 |
| CN1254680C CN1254680C (en) | 2006-05-03 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03156107 Expired - Fee Related CN1254680C (en) | 2003-08-29 | 2003-08-29 | Chemical luminous detecting system for liquid chromatography |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102854275A (en) * | 2012-07-29 | 2013-01-02 | 安徽皖仪科技股份有限公司 | Ion chromatography digital conductance detecting device based on digital signal processor (DSP) |
| CN103217216A (en) * | 2013-03-27 | 2013-07-24 | 启东文鑫电子有限公司 | Photoelectric detector circuit |
-
2003
- 2003-08-29 CN CN 03156107 patent/CN1254680C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102854275A (en) * | 2012-07-29 | 2013-01-02 | 安徽皖仪科技股份有限公司 | Ion chromatography digital conductance detecting device based on digital signal processor (DSP) |
| CN102854275B (en) * | 2012-07-29 | 2014-11-12 | 安徽皖仪科技股份有限公司 | Ion chromatography digital conductance detecting device based on digital signal processor (DSP) |
| CN103217216A (en) * | 2013-03-27 | 2013-07-24 | 启东文鑫电子有限公司 | Photoelectric detector circuit |
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| Publication number | Publication date |
|---|---|
| CN1254680C (en) | 2006-05-03 |
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Granted publication date: 20060503 Termination date: 20120829 |