CN202126403U - Antibiotics analysis device based on resolution of excitation time characteristics of fluorescence spectrum - Google Patents

Antibiotics analysis device based on resolution of excitation time characteristics of fluorescence spectrum Download PDF

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CN202126403U
CN202126403U CN2011201868776U CN201120186877U CN202126403U CN 202126403 U CN202126403 U CN 202126403U CN 2011201868776 U CN2011201868776 U CN 2011201868776U CN 201120186877 U CN201120186877 U CN 201120186877U CN 202126403 U CN202126403 U CN 202126403U
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photomultiplier
fluorescence
convex lens
led
fluorescence spectrum
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陈国颖
李岱明
刘明端
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Abstract

An antibiotics analysis device based on resolution of excitation time characteristics of fluorescence spectrum comprises a light-emitting diode pulse excitation stable light source unit, a time resolved fluorescence spectrum test unit and a control and display unit. The control and display unit is connected with the time resolved fluorescence spectrum test unit which is connected with the light-emitting diode pulse excitation stable light source unit. Therefore, the antibiotics analysis device based on the resolution of the excitation time characteristics of the fluorescence spectrum is simple in structure, small in volume, convenient to take and suitable for on-site tests.

Description

Based on the microbiotic analytical equipment of differentiating fluorescence spectrum firing time characteristic
One, technical field
The utility model is the microbiotic analytical equipment that is applied to fields such as Food Inspection, environmental monitoring, medical science and study of pharmacy, relates to a kind of chemical analysis instrument, and is a kind of especially based on the microbiotic analytical equipment of differentiating fluorescence spectrum firing time characteristic.
Two, background technology
In people's live and work; In order to satisfy the requirement of certain aspect; The content that needs detection of antibiotics particularly in order to guarantee the safety of food vegetables, needs to detect the antibiotic content in the food vegetables; Therefore the microbiotic analytical equipment is an important chemical analysis apparatus; Mainly be to use the spectrum of fluorescence is analyzed in existing microbiotic analytical equipment, its principle of work reaches qualitative and purpose detection by quantitative based on the wavelength and the intensity of check and analysis thing institute's emitting fluorescence under optical excitation.Has the advantage highly sensitive, that selectivity is strong.
The ion of some microbiotic meeting and REE forms the huge legendary turtle compound.If the atomic energy level of antibiotic molecular entergy level and rare earth ion is close, the luminous energy that then microbiotic absorbed can shift to rare earth atom effectively.The atomic fluorescence that the latter accepts to be launched behind the energy has the characteristic that bands of a spectrum are narrow, intensity is high, and lifetime of excited state significantly increases.According to this, can introduce time delay, abandon early signal, the fluorescence signal that an integration special time is interval.Because through delay, the fluorescence and the scattering of light source parasitic light and most chaff interferences decay totally all, so the fluorescence signal interference free performance greatly improves, reach high sensitivity.
At present, the most employing of commodity fluorescence spectrophotometer spectrometer xenon flash lamp is an excitation source.Because xenon flash lamp belongs to the wide spectrum white light source, the spectral background noise is higher; Residual light emission after the xenon lamp flash of light has than long streaking, does time resolution and measures, and its background noise is also high; In addition, xenon flash lamp leans on moment heavy current discharge, certainly will produce moment electromagnetic interference (EMI) noise at the high-gain testing circuit.These noises are superimposed, and must reduce signal to noise ratio (S/N ratio), influence the sensitivity for analysis of instrument.The most employing of commodity fluorescence spectrophotometer spectrometer photomultiplier is a photodetector.Supply power with Constant Direct Current as the one of which, so the fluorescence of light source parasitic light and interfering material will cause background noise.Minority fluorescence spectrophotometer spectrometer adopts light detecter for semiconductor, and like photodiode or charge transfer device (CCD), its response is slower, influence time resolution.
Most commodity fluorescence spectrophotometer spectrometer weight and volumes are all big, can only be placed on indoorly, are not suitable for on-site measurement, and analysis precision is not high.
Three, summary of the invention
In order to overcome above-mentioned technical disadvantages, the purpose of the utility model provides a kind of based on the microbiotic analytical equipment of differentiating fluorescence spectrum firing time characteristic, and therefore simple in structure, volume is little, and is easy to carry.
For achieving the above object; The technical scheme that the utility model is taked is: based on the microbiotic analytical equipment of differentiating fluorescence spectrum firing time characteristic; Include light emitting diode pulse excitation stabilized light source unit, time resolution fluorescence spectral detecting unit and control display unit; The control display unit is set to be connected with the time resolution fluorescence spectral detecting unit, and the time resolution fluorescence spectral detecting unit is set to be connected with diode pulse excitation stabilized light source unit.
The utility model has designed, and also includes light emitting diode excitation pulse intensity monitoring unit, and light emitting diode excitation pulse intensity monitoring unit is set to be connected with the control display unit with the time resolution fluorescence spectral detecting unit.
The utility model has designed, and also includes the protected location of photomultiplier, and the protected location of photomultiplier is set to be connected with the time resolution fluorescence spectral detecting unit.
The utility model has designed; Light emitting diode pulse excitation stabilized light source unit is set to include UV LED, exciting light convex lens, exciting light optical filter, sample cell, fluorescence convex lens and fluorescent optical filter; Exciting light convex lens and sample cell are successively set on the radiation direction of UV LED; Between exciting light convex lens and sample cell, be provided with the exciting light optical filter; Fluorescence convex lens and photomultiplier are successively set on the radiation direction of fluorescence of sample cell; Between fluorescence convex lens and photomultiplier, be provided with fluorescent optical filter, the angle between the longitudinal center line of the longitudinal center line of exciting light convex lens and fluorescence convex lens is set to 90 °.
The utility model has designed, and UV LED is set to the UV LED of 285 or 327 nanometers.When TCs was analyzed, UV LED was set to the UV LED of 285 nanometers, and when quinoline was analyzed as if ketone antibiotic, UV LED 1 was set to the UV LED of 285 or 327 nanometers.
The utility model has designed, and the xsect of sample cell is set to quadrilateral or triangle or is set to base plate; When sample was muddy sample or high concentration liquid, the xsect of sample cell was set to triangle; When sample was solid or the SPE sheet that contains the fluid sample composition, sample cell replaced with base plate, was placed into solid sample and SPE sheet on the base plate.
Designed at the utility model, the time resolution fluorescence spectral detecting unit is set to include photomultiplier, gate socket, computing machine sum, direct supply, digital to analog converter, photomultiplier power supply, timer, voltage follower, UV LED driver, current-to-voltage convertor, low-pass filter and digital to analog converter 0; Photomultiplier is arranged in the darkroom; The darkroom is provided with opening; And opening be set in the dead ahead of fluorescence convex lens to, photomultiplier is set to be connected with the gate socket, the gate socket is provided with power input mouth a, control gate input port c and signal output port b; The input port of digital to analog converter be set to computer bus in a control line be connected; The output port of digital to analog converter is set to be connected with the input port of photomultiplier power supply, and the output port of photomultiplier power supply is set to be connected with the power input mouth a of gate socket; The input port of timer be set to the computing machine sum in a control line be connected; The output port of timer is set to respectively be connected with voltage follower, digital to analog converter 0 input port, and the output port one tunnel of voltage follower is set to be connected with the control gate input port c of gate socket, another road is set to be connected with the input port of UV LED through LED drive; The output port b of gate socket is set to be connected with low-pass filter through current-to-voltage convertor successively; The output port of low-pass filter is connected with the input port of analog to digital converter 0, and the output port of analog to digital converter 0 is connected with a data lines in the computer bus.
Designed at the utility model; The control display unit is set to computing machine or includes embedded microprocessor and touch display screen; Touch display screen is set to be connected with embedded microprocessor; Embedded microprocessor is provided with printer interface and USB interface, and the control display unit is set to be connected with computer bus.
Designed at the utility model; Light emitting diode excitation pulse intensity monitoring unit is set to include prism, photodiode, timer, electric weight amplifier and analog to digital converter 1; Be provided with prism with the parallel direction of the longitudinal center line of exciting light convex lens; The catoptrical radiation direction of prism is provided with photodiode, and the photodiode output mouth is set to be connected with analog to digital converter 1 through the electric weight amplifier.
Designed at the utility model; The protected location of photomultiplier is set to include interlock switch I, interlock switch II and relay; Interlock switch I, interlock switch II are arranged on the door of unlatching of the cavity of placing sample cell; Be set to be connected with relay after interlock switch I, the series connection of interlock switch II, direct supply is set to be connected with the photomultiplier power supply through relay.
Owing to designed use ultraviolet pulse fluorescence excitation signal, thereby fluorescence signal carried out time-resolved fluorescence integrated intensity I TRLCalculating, to judge antibiotic content, designed optical system and carried out fluorescence signal and excite, designed integrated electricity system and carried out fluorescence signal and handle, therefore simple in structure, volume is little, and is easy to carry.
Four, description of drawings
Fig. 1 is the synoptic diagram of the utility model.
Fig. 2 is the synoptic diagram of the light emitting diode pulse excitation stabilized light source unit among first embodiment.
Fig. 3 is the synoptic diagram of second light emitting diode pulse excitation stabilized light source unit among the embodiment.
Fig. 4 is the synoptic diagram of the 3rd the light emitting diode pulse excitation stabilized light source unit among the embodiment.
Fig. 5 is the synoptic diagram of second use embedded system among the embodiment as centralized control unit.
Fig. 6 is a sequential chart.Wherein a representes integral time, and b representes the total data acquisition time, and c representes 600ms; D representes-40V, 6 oscillograms from top to bottom, and first oscillogram is represented digital I/O line 1; Second oscillogram represented the timer signal output waveform, and the 3rd oscillogram represented the light emitting diode pulse waveform, and the 4th oscillogram represented photomultiplier gating pulse waveform; The 5th oscillogram represented the photomultiplier signal output waveform, and the 6th oscillogram represented the photodiode signal waveform.
Five, embodiment
Fig. 1 in the accompanying drawing is first embodiment of the utility model, specifies present embodiment in conjunction with accompanying drawing.
First embodiment includes UV LED 1; Exciting light convex lens 3; Exciting light optical filter 4; Sample cell 5; Prism 7; Photodiode 9; Fluorescence convex lens 10; Fluorescent optical filter 12; Photomultiplier 13; Gate socket 14; Interlock switch I 18; Interlock switch II 19; Computing machine 20; Computing machine sum 21; Direct supply 22; Relay 23; Digital to analog converter 24; Photomultiplier power supply 25; Timer 26; Voltage follower 27; UV LED driver 28; Current-to-voltage convertor 29; Low-pass filter 30; Analog to digital converter 031; Electric weight amplifier 32 and analog to digital converter 133; Exciting light convex lens 3 are successively set on the radiation direction of UV LED 1 with sample cell 5; Between exciting light convex lens 3 and sample cell 5, be provided with exciting light optical filter 4; Fluorescence convex lens 10 and photomultiplier 13 are successively set on the radiation direction of fluorescence of sample cell 5; Between fluorescence convex lens 10 and photomultiplier 13, be provided with fluorescent optical filter 12; Angle between the longitudinal center line of the longitudinal center line of exciting light convex lens 3 and fluorescence convex lens 10 is set to 90 °; Be provided with prism 7 with the parallel direction of the longitudinal center line of exciting light convex lens 3; The catoptrical radiation direction of prism 7 is provided with photodiode 9, and photomultiplier 13 is arranged in the darkroom, the darkroom be provided with opening and opening be set in the dead ahead of fluorescence convex lens 10 to; Photomultiplier 13 is set to be connected with gate socket 14; Gate socket 14 is provided with power input mouth a, control gate input port c and signal output port b, and interlock switch I 18 and interlock switch II 19 are arranged on the door of unlatching of the cavity of placing sample cell 5, interlock switch I 18 be set to be connected after interlock switch II 19 is connected with relay 23; Direct supply 22 is set to be connected with photomultiplier power supply 25 through relay 23; A control line in the computer bus 21 is connected to the input end of digital to analog converter 24, and the output terminal of digital to analog converter 24 is connected with the control port of photomultiplier power supply 25, and the output port of photomultiplier power supply 25 is set to be connected with the power input mouth a of gate socket 14; Data lines in the computer bus 21 is connected to the input port of timer 26, and the output port of timer 26 is set to respectively be connected with voltage follower 27, analog to digital converter 031 and the input port of analog to digital converter 133; The output port one tunnel of voltage follower 27 is set to be connected with the control gate input port c of gate socket 14, and another road is set to be connected through the input port of LED drive 28 with UV LED 1; The signal output port b of gate socket 14 is set to be connected to successively current-to-voltage convertor 29, low-pass filter 30 and the input port of analog to digital converter 031 and is connected, and the output port of analog to digital converter 031 is connected to computer bus 21; The output port of photodiode 9 is connected to electric weight amplifier 32, analog to digital converter 133 successively) input end, the output port of analog to digital converter 133 is connected to computer bus 21.
In first embodiment, UV LED 1, exciting light convex lens 3, photodiode 9, electric weight amplifier 32, analog to digital converter 133 and control display unit are set to form light emitting diode pulse excitation stabilized light source unit.
UV LED 1 is set to the UV LED of 285 or 327 nanometers; When TCs is analyzed; UV LED 1 is set to the UV LED of 285 nanometers; When quinoline was analyzed as if ketone antibiotic, UV LED 1 was set to the UV LED of 285 or 327 nanometers.UV LED is a light source, and specific analyte is carried out selective excitation.Light emitting diode is narrow spectrum light source, and photoelectric transformation efficiency is high, does not need heavy current, and background noise significantly reduces, and has improved sensitivity for analysis.
The xsect of sample cell 5 is set to quadrilateral.Be applicable to general sample, fluorescence signal need be angled from the liquid layer collection sensitive surface and the excitation beam of the transmission of liquid sensitive surface light institute.
When sample is liquid; In sample, be added with the salt of a small amount of certain REE; As fluorescence-enhancing agent, in sample, contain TCs, with europium nitrate or hydrochloric acid europium as fluorescence-enhancing agent; In sample, contain quinoline if ketone antibiotic, with terbium nitrate or hydrochloric acid terbium as fluorescence-enhancing agent.When sample is liquid, in sample, add damping fluid, regulate the potential of hydrogen of sample.Under desirable potential of hydrogen, REE and analyte to be determined form the huge legendary turtle compound.
When sample is liquid, also can the SPE sheet be immersed in fluid sample such as milk, or certain hour in the sample homogenization, then residual antibiotic can be adsorbed onto on carbon 18 thin layers of SPE sheet.After purifying, adding reagent, drying, again the SPE sheet is placed on the base plate 17, directly at the antibiotic fluorescence signal of carbon 18 thin layer surface measurements.
In first embodiment, prism 7, photodiode 9, timer 26, electric weight amplifier 32 and digital to analog converter I 33 are set to form light emitting diode excitation pulse intensity monitoring unit.In the periphery of excitation beam, with 45 ° prism 7 of one side, intercepting fraction light beam wherein light beam 8 as a reference from excitation beam; Irradiates light electric diode 9; Produce photocurrent,, it is carried out the intensity that integration gained signal has reflected excitation light pulse through electric weight amplifier 32 and digital to analog converter 133; Driver is the intensity fluctuation of compensating excitation light pulse according to this; Improve the reappearance of analytic signal, the fluctuating of the excitation light pulse intensity of UV LED 1 can influence fluorescence signal 11 and rise and fall.For improving signal reproducibility, can keep watch on the variation of the light intensity of individual pulse.
In first embodiment, photomultiplier 13, gate socket 14, computer bus 21, direct supply 22, digital to analog converter 24, photomultiplier power supply 25, timer 26, voltage follower 27, UV LED driver 28, current-to-voltage convertor 29, low-pass filter 30 and digital to analog converter 031 are set to form the time resolution fluorescence spectral detecting unit.
In first embodiment, interlock switch I 18, interlock switch II 19 and relay 23 are set to the protected location of photomultiplier 13.When the user need open annular seal space; Send to or when taking out sample,, can damage because of exposure immediately if photomultiplier 13 has been supplied power; In order to prevent this situation; Driver is just supplied power to photomultiplier after the user begins to detect, and also is provided with interlock switch I 18 and interlock switch II 19 on the exterior and interior cover at annular seal space in outage immediately after the image data, places the photomultiplier in the light tight annular seal space protected by this interlock switch I 18 and interlock switch II 19 and relay 23; When the user opens that annular seal space is sent to or when taking out sample; Interlock switch I 18 and interlock switch II 19 trigger relays 23 on the annular seal space exterior and interior cover are cut off power supply, damage to ensure annular seal space when opening, to make public under the unlikely state that adding high pressure of photomultiplier.
In first embodiment, computing machine 20 is set to control display unit.
Programmed control through the control display unit; Timer in the time resolution fluorescence spectral detecting unit 26 is produced the high level pulse of 10-20 microsecond; Thereby the UV LED in the stimulated luminescence diode pulse excitation stabilized light source unit 1 produces ultraviolet pulse 2; Excited sample 6 produces fluorescence signal 11, and fluorescence signal 11 converts voltage signal to through the time resolution fluorescence spectral detecting unit, carries out time-resolved fluorescence integrated intensity I by the control display unit TRLCalculating; According to time-resolved fluorescence integrated intensity I TRLValue size, thereby judge the antibiotic content that contains in the sample.
In second embodiment of the utility model; When sample is muddy sample or high concentration liquid; The xsect of sample cell 5 is set to triangle; Sample cell 5 is triangular sample pond 15 during for triangle when xsect in the present embodiment, fluorescence signal need from the liquid layer of liquid sensitive surface light institute transmission collect sensitive surface and excitation beam angled.The control display unit is set to include embedded microprocessor 47 and touch display screen 46; Use embedded system as shown in Figure 5 includes embedded microprocessor 47 and touch display screen 46 as the embodiment of centralized control unit; Touch display screen 46 is set to be connected with embedded microprocessor 47, and embedded microprocessor 47 is provided with printer interface 48 and USB interface 49.Wherein 45 expressions are provided with part by the whole optics that Fig. 2 or Fig. 3 or Fig. 4 formed, 46 expression touch display screens, 47 expression embedded systems, 48 expression printer interfaces, 49 expression USB interfaces.The model of embedded microprocessor is the S3C44B0 chip of the ARM7 of Samsung kernel or the AT89C51 chip of atmel corp's 8051 kernels, operation system and driver on this chip, and wherein embedded OS can adopt μ CLinux.Printer, USB interface, touch-screen driver can adopt the C language, and the driver of embedded microprocessor can adopt the LabVIEW language.
In the 3rd embodiment of the utility model, when sample is solid sample or the SPE sheet that contains the fluid sample composition, sample cell 5 usefulness base plates 17 replace, and are placed into solid sample and SPE sheet 16 on the base plate 17 and test.
Centralized control unit in the control display unit has two kinds of models, is selected for use according to use habit by the user.Shown in Figure 1 for example notebook computer is as the embodiment of centralized control unit in order to use a computer, and shown in Figure 5 is to use the embodiment of embedded system as centralized control unit.
The method of application step of the utility model is:
1, UV LED 1 is set; UV LED 1 is set to the UV LED of 285 or 327 nanometers; When TCs is analyzed; UV LED 1 is set to the UV LED of 285 nanometers, and when quinoline was analyzed as if ketone antibiotic, UV LED 1 was set to the UV LED of 285 or 327 nanometers.UV LED is a light source, and specific analyte is carried out selective excitation.Light emitting diode is narrow spectrum light source, and photoelectric transformation efficiency is high, does not need heavy current, and background noise significantly reduces, and has improved sensitivity for analysis.
Sample cell 5 is set, and sample cell is set to the square pond; For muddy sample or high concentration liquid sample, sample cell is set to the tri-prismoid sample cell, and fluorescence signal need be angled from the liquid layer collection sensitive surface and the excitation beam of the transmission of liquid sensitive surface light institute; Need not sample cell for solid sample, be placed into solid sample on the base plate 17 and detect; Also can the SPE sheet be immersed in fluid sample (like milk), or certain hour in the sample homogenization, after purifying, adding reagent, drying, again the SPE sheet is placed on the base plate 17, directly at the antibiotic fluorescence signal of carbon 18 thin layer surface measurements.
Fluorescence-enhancing agent is set; When sample is liquid, in sample, be added with the salt of a small amount of certain REE, as fluorescence-enhancing agent; In sample, contain TCs; As fluorescence-enhancing agent, in sample, contain quinoline if ketone antibiotic with europium nitrate or hydrochloric acid europium, with terbium nitrate or hydrochloric acid terbium as fluorescence-enhancing agent.When sample is liquid, in sample, add damping fluid, regulate the potential of hydrogen of sample.Under desirable potential of hydrogen, REE and analyte to be determined form the huge legendary turtle compound.
Setting to the protected location of photomultiplier 13; Annexation through two interlock switchs 18,19 and relay 23; Two interlock switchs 18,19 are arranged on the door of unlatching of the cavity of placing sample cell 5; Two interlock switchs 18,19 are set to be connected with relay 23, and direct supply 22 is set to be connected with photomultiplier power supply 25 through relay 23.When the user need open annular seal space, send to or when taking out sample, if photomultiplier 13 has been supplied power; Can damage because of exposure immediately; So that prevent this situation, driver after the user begins to detect to the photomultiplier power supply, and outage immediately after image data; Also on the exterior and interior cover of annular seal space, be provided with two interlock switchs 18,19; Place the photomultiplier in the light tight annular seal space to receive these two interlock switchs 18,19 and relay 23 protections; When the user opens that annular seal space is sent to or when taking out sample; Two interlock switchs, 18,19 trigger relays 23 on the annular seal space exterior and interior cover cut off power supply, damage to ensure annular seal space when opening, to make public under the unlikely state that adding high pressure of photomultiplier.
2, put into the detection position to sample cell 5, close the door of the unlatching of the cavity of placing sample cell 5, two interlock switchs 18,19 drive relays 23 work, photomultiplier power supply 25 are communicated with, for photomultiplier 13 provides working power with direct supply 22.
3, set photomultiplier 13 operating voltages through the control display unit; Calculate through driver; Draw corresponding DC input voitage; The control display unit is added to the control end of photomultiplier power supply 25 with this voltage through digital to analog converter 24, to photomultiplier 13 operating voltage is provided by the output terminal of photomultiplier power supply 25.Be the 400-800 millisecond preheating time that the control display unit is set photomultiplier 13.
When detecting; The control display unit sends instruction, and digital I/O line 1 uprises level by low level, through a control line in the computer bus 21; Send the high level pulse of a 10-20 microsecond to timer 26, its pulse waveform is shown in timer signal output waveform 40.
The high level pulse of this 10-20 microsecond also sends to LED drive 28 through voltage follower 27; UV LED 1 sends a ultraviolet light pulse with identical duration under it triggers; Its pulse waveform is shown in light emitting diode pulse waveform 41, and the sample in the excited sample pond 5 produces fluorescence signal.
The fluorescence signal of from sample cell 5, launching is transferred on the photocathode of photomultiplier 13, in photomultiplier 13, produces photocurrent, and its waveform is shown in photomultiplier signal output waveform 43.The current-to-voltage convertor 29 that photocurrent constitutes through the low noise operational amplifier amplifies and converts voltage to; High frequency noise in this signal is after low-pass filter 30 filters; Be transferred to analog to digital converter 0 (31); To the pulse signal acquisition time-resolved fluorescence signal data of photomultiplier output, the analog-to-digital time interval is 4 microseconds in analog to digital converter 0 (31), and amplitude resolution is 12.The control display unit is accomplished time-resolved fluorescence integrated intensity I in user's designated time intervals TRLCalculating, according to time-resolved fluorescence integrated intensity I TRLValue size, thereby judge the antibiotic content that contains in the sample.
When sending to LED drive 28; The high level pulse of this 10-20 microsecond sends to gate socket 14 control gate input end c through voltage follower 27; In gate socket 14, producing a negative pulse is photomultiplier gating pulse waveform 42; Take electrode for second dozen that is added to photomultiplier 13, interrupt the photomultiplier transit process, it is zero that its gain is fallen sharply; Thereby the background noise that lets the light source parasitic light that occurs during this, interference fluorescence and scattered light that the sample substrate sends caused, receive very big containment; And after this negative voltage pulse, photomultiplier 13 recovers its high-gain immediately, continues to detect fluorescence signal.
4, in the ultraviolet light pulse that UV LED 1 sends,, be transferred to photodiode 9 through a branch of reference beam of prism 7 interceptings; The signal waveform that photodiode 9 sends is shown in photodiode signal waveform 44; This signal process capacitor interchange is coupled to electric weight amplifier 32 and carries out integration, obtains the total charge dosage of this light pulse, after amplifying; By analog to digital converter 1 (33) digitizing, the energy (E of its maximal value and optical exciting pulse LED) be directly proportional, therefore be used for standard time-resolved fluorescence signal by driver, correct excitation pulse-interpulse energy hunting, to improve the reappearance of analytic signal.Ratio (the I of the energy of itself and optical exciting pulse TRL/ E LED) and sample concentration be directly proportional, but the strength fluctuation of the pulse that is not stimulated influences.Be presented on the screen with " standard fluorescence signal integration " digital form.The analog-to-digital time interval is 4 microseconds, and amplitude resolution is 12.
5, adopt multiple-pulse to excite to UV LED 1, multiple signal is averaged, be generally 3-5 time, but consider the bleaching effect of uv excitation light to sample, selected excitation pulse number should suitably be controlled.For further improving the reappearance of low concentration signal, can the baseline of fluorescence decay curve be calibrated with driver.
The utlity model has following characteristics:
1, owing to designed use ultraviolet pulse fluorescence excitation signal, thereby fluorescence signal is carried out time-resolved fluorescence integrated intensity I TRLCalculating, thereby judge antibiotic content, designed optical system and carried out fluorescence signal and excite, designed integrated electronic system and carried out fluorescence signal and handle, therefore simple in structure, volume is little, and is easy to carry.
2, the utility model is to the existing technology limitation of above-mentioned commodity XRF; Excitation source and photodetector are carried out technological innovation; Improve sensitivity and selectivity, satisfied the requirement of trace detection, reduced the deadweight and the volume of instrument; Reach and be convenient for carrying, can carry out on-site measurement; The utility model adopts the SPE sheet, has simplified the specimen preparation process, has shortened detection time, and testing result can be taken in the user scene.
3, the UV LED of the utility model employing specific emission wavelength is a light source, and specific analyte is carried out selective excitation.Light emitting diode is narrow spectrum light source, and photoelectric transformation efficiency is high, does not need heavy current, and background noise significantly reduces, and has improved sensitivity for analysis.TCs can excite with the UV LED of 385 nanometers, and quinoline is if ketone antibiotic then excites with the UV LED of 285 or 327 nanometers.
4, the utility model makes light emitting diode work in pulse mode.Utilize electronic drive circuit to produce the square light pulse of pulsewidth, specific analyte is carried out moment excite for the microsecond level.When carrying out time resolution mensuration,, reduced background noise, improved sensitivity for analysis because the light pulse that is produced does not have hangover.
5, the utility model is measured the background noise angle from time resolution, and photomultiplier is carried out gate control.Its principle of work is: with excitation light pulse simultaneously, with a negative potential pulse-break photomultiplier transit process, it is zero making its gain fall sharply, and the disturbing pulse during this is suppressed.Treat that the photomultiplier transit process is recovered immediately after light pulse and the negative potential pulse, photomultiplier recovers its high-gain, to detect long fluorescence signal of life-span.Gating technology has been got rid of the interference of short life fluorescence signal effectively, has improved the detection sensitivity to the long-life fluorescence signal.
In based on the microbiotic analytical equipment technical field of differentiating fluorescence spectrum firing time characteristic; The foregoing description is a kind of way of realization based on the microbiotic analytical equipment of differentiating fluorescence spectrum firing time characteristic that the utility model provides; Other distortion according to the scheme that the utility model provided; Increase or minimizing step wherein, perhaps the utility model is used for other the technical field approaching, all belong to the protection domain of the utility model with the utility model.

Claims (10)

1. one kind based on the microbiotic analytical equipment of differentiating fluorescence spectrum firing time characteristic; It is characterized in that: include light emitting diode pulse excitation stabilized light source unit, time resolution fluorescence spectral detecting unit and control display unit; The control display unit is set to be connected with the time resolution fluorescence spectral detecting unit, and the time resolution fluorescence spectral detecting unit is set to be connected with diode pulse excitation stabilized light source unit.
2. according to claim 1 based on the microbiotic analytical equipment of differentiating fluorescence spectrum firing time characteristic; It is characterized in that: also include light emitting diode excitation pulse intensity monitoring unit, light emitting diode excitation pulse intensity monitoring unit is set to be connected with the control display unit with the time resolution fluorescence spectral detecting unit.
3. according to claim 1 based on the microbiotic analytical equipment of differentiating fluorescence spectrum firing time characteristic; It is characterized in that: also include the protected location of photomultiplier (13), the protected location of photomultiplier (13) is set to be connected with the time resolution fluorescence spectral detecting unit.
4. according to claim 1,2 or 3 described microbiotic analytical equipments based on resolution fluorescence spectrum firing time characteristic; It is characterized in that: light emitting diode pulse excitation stabilized light source unit is set to include UV LED (1), exciting light convex lens (3), exciting light optical filter (4), sample cell (5), fluorescence convex lens (10) and fluorescent optical filter (12); Exciting light convex lens (3) and sample cell (5) are successively set on the radiation direction of UV LED (1); Between exciting light convex lens (3) and sample cell (5), be provided with exciting light optical filter (4); Fluorescence convex lens (10) and photomultiplier (13) are successively set on the radiation direction of fluorescence of sample cell (5); Between fluorescence convex lens (10) and photomultiplier (13), be provided with fluorescent optical filter (12), the angle between the longitudinal center line of the longitudinal center line of exciting light convex lens (3) and fluorescence convex lens (10) is set to 90 °.
5. according to claim 4 based on the microbiotic analytical equipment of differentiating fluorescence spectrum firing time characteristic; It is characterized in that: UV LED (1) is set to the UV LED of 285 or 327 nanometers.
6. according to claim 4 based on the microbiotic analytical equipment of differentiating fluorescence spectrum firing time characteristic; It is characterized in that: the xsect of fluid sample pond (5) is set to square or triangle or is set to base plate (17).
7. according to claim 1,2 or 3 described microbiotic analytical equipments based on resolution fluorescence spectrum firing time characteristic; It is characterized in that: the time resolution fluorescence spectral detecting unit is set to include photomultiplier (13), gate socket (14), computing machine sum (21), direct supply (22), digital to analog converter (24), photomultiplier power supply (25), timer (26), voltage follower (27), UV LED driver (28), current-to-voltage convertor (29), low-pass filter (30) and digital to analog converter 0 (31); Photomultiplier (13) is arranged in the darkroom; The darkroom is provided with opening; And opening be set in the dead ahead of fluorescence convex lens (10) to; Photomultiplier (13) is set to be connected with gate socket (14), and gate socket (14) is provided with power input mouth a, control gate input port c and signal output port b; The input port of digital to analog converter (24) be set to computer bus (21) in a control line be connected; The output port of digital to analog converter (24) is set to be connected with the input port of photomultiplier power supply (25), and the output port of photomultiplier power supply (25) is set to be connected with the power input mouth a of gate socket (14); The input port of timer (26) be set to computing machine sum (21) in a control line be connected; The output port of timer (26) is set to respectively be connected with voltage follower (27), digital to analog converter 0 (31) input port, and the output port one tunnel of voltage follower (27) is set to be connected with the control gate input port c of gate socket (14), another road is set to be connected through the input port of LED drive (28) with UV LED (1); The output port b of gate socket (14) is set to be connected with low-pass filter (30) through current-to-voltage convertor (29) successively; The output port of low-pass filter (30) is connected with the input port of analog to digital converter 0 (31), and the output port of analog to digital converter 0 (31) is connected with a data lines in the computer bus (21).
8. according to claim 1,2 or 3 described microbiotic analytical equipments based on resolution fluorescence spectrum firing time characteristic; It is characterized in that: the control display unit is set to computing machine (20) or includes embedded microprocessor (47) and touch display screen (46); Touch display screen (46) is set to be connected with embedded microprocessor (47); Embedded microprocessor (47) is provided with printer interface (48) and USB interface (49), and the control display unit is set to be connected with computing machine sum (21).
9. according to claim 1,2 or 3 described microbiotic analytical equipments based on resolution fluorescence spectrum firing time characteristic; It is characterized in that: light emitting diode excitation pulse intensity monitoring unit is set to include prism (7), photodiode (9), timer (26), electric weight amplifier (32) and analog to digital converter 1 (33); Be provided with prism (7) with the parallel direction of the longitudinal center line of exciting light convex lens (3); The catoptrical radiation direction of prism (7) is provided with photodiode (9), and the output port of photodiode (9) is set to be connected with analog to digital converter 1 (33) through electric weight amplifier (32).
10. according to claim 1,2 or 3 described microbiotic analytical equipments based on resolution fluorescence spectrum firing time characteristic; It is characterized in that: the protected location of photomultiplier (13) is set to include interlock switch I (18), interlock switch II (19) and relay (23); Interlock switch I (18), interlock switch II (19) are arranged on the door of unlatching of the cavity of placing sample cell (5); Be set to be connected with relay (23) after interlock switch I (18), interlock switch II (19) series connection, direct supply (22) is set to be connected with photomultiplier power supply (25) through relay (23).
CN2011201868776U 2011-06-05 2011-06-05 Antibiotics analysis device based on resolution of excitation time characteristics of fluorescence spectrum Expired - Fee Related CN202126403U (en)

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