CN103257128B - serial double light path laser induced fluorescence spectrometer - Google Patents

serial double light path laser induced fluorescence spectrometer Download PDF

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Publication number
CN103257128B
CN103257128B CN201310175950.3A CN201310175950A CN103257128B CN 103257128 B CN103257128 B CN 103257128B CN 201310175950 A CN201310175950 A CN 201310175950A CN 103257128 B CN103257128 B CN 103257128B
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photomultiplier
plane mirror
signal
laser
mirror
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CN103257128A (en
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阎超
姚凡
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Shanghai Tong Micro Analysis Technology Co ltd
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Shanghai Tong Micro Analysis Technology Co ltd
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Priority to PCT/CN2014/000472 priority patent/WO2014183468A1/en
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64Fluorescence; Phosphorescence
    • G01N21/645Specially adapted constructive features of fluorimeters
    • G01N21/6456Spatial resolved fluorescence measurements; Imaging
    • G01N21/6458Fluorescence microscopy

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  • Health & Medical Sciences (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)

Abstract

A kind of serial double light path laser induced fluorescence spectrometer, comprises LASER Light Source, the first plane mirror, detects groove, capillary column, confocal optics measurement module, half-reflecting half mirror, the second plane mirror, gradual filter, stepper motor, the 3rd plane mirror, modulation panel, synchronous motor, light beam distinguishing sensor, photomultiplier, control panel and chromatographic signal sampling processor; Laser beam excited sample from LASER Light Source sends fluorescence beam, then fluorescence beam and laser beam input to photomultiplier respectively by sample arm and reference path, control panel processes from the reference path signal of photomultiplier, sample arm signal and overall background signal, finally inputs chromatographic signal sampling processor.This invention removes the impact of LASER Light Source Strength Changes, the change of photomultiplier dark current and system veiling glare, light leak, improve measuring accuracy.

Description

Serial double light path laser induced fluorescence spectrometer
Technical field
The present invention relates to a kind of laser-induced fluorescence spectroscopy measurement mechanism, be specifically related to a kind of serial double light path laser induced fluorescence spectrometer, belong to laser spectrum tech field.
Background technology
Laser spectrum becomes the Major research field of laser technology with its high resolution, sensitivity, degree of accuracy and the advantage such as harmless, safe, quick.Along with carrying out in a deep going way of laser spectrum tech research, it is widely applied in the technical field such as biology, medical science, and wherein more concerned is the autofluorescence studying fabric texture.
When ultraviolet light or the shorter radiation of visible light of wavelength are to Cucumber, these materials can launch the visible ray of shades of colour and varying strength, and when light source stops irradiating, this light disappears thereupon.This light produced under exciting light induction is called fluorescence, and the material that can send fluorescence is called fluorescent material.Nearly all material molecule has absorption spectrum, but not all material all can fluoresce, and namely not all substances are all fluorescent materials.Material produces fluorescence must possess following condition: 1. this material molecule must have the frequency identical with irradiated light, and the structure of this and molecule is closely related.2. absorb the material molecule after the energy identical with characteristic frequency own, high fluorescence efficiency must be had.From the principle of luminosity of fluorescence, the wavelength of molecular fluorescence spectroscopy and excitation source has nothing to do, only relevant with the level structure of fluorescent material itself, so, qualitative analysis discriminating can be carried out according to fluorescent line to fluorescent material.
Laser-induced fluorescence spectroscopy instrument is exactly the device that the above-mentioned principle of application detects material.Refer to Fig. 1, existing laser-induced fluorescence spectroscopy instrument generally comprises LASER Light Source 02, plane mirror 01, capillary column 03, detect groove 04, confocal optics measurement module 05, photomultiplier 06 and chromatographic signal sampling processor 07, wherein, the capillary column 03 injecting measured matter sample is arranged at and detects in groove 04, the laser that LASER Light Source 02 sends imports confocal optics measurement module 05 after plane mirror 01 reflects, and the sample in directive capillary column 03, sample is sent the fluorescence with Strength Changes and is inputted photomultiplier 06 by confocal optics measurement module 05 after laser excitation, this photomultiplier 06 is by the optical signal amplification of Strength Changes and transfer electric signal to and input chromatographic signal sampling processor 07.
Above-mentioned laser-induced fluorescence spectroscopy instrument is monochromatic light line structure, its advantage is that structure is simple, but also have larger defect: the Strength Changes of the sample signal exported by photomultiplier 06, not only include the change of LASER Light Source 02 Emission Lasers intensity, and containing factors such as the change of photomultiplier 06 dark current and system veiling glares (comprising light leak), the error that sample is measured therefore can be caused.
Summary of the invention
The technical problem to be solved in the present invention is the deficiency overcoming existing laser-induced fluorescence spectroscopy instrument, a kind of serial double light path laser induced fluorescence spectrometer is provided, it can get rid of the impact of LASER Light Source Strength Changes, the change of photomultiplier dark current and system veiling glare, light leak, has the advantage that accuracy of detection is high.
It is as follows that the present invention solves the technical scheme that its technical matters takes:
A kind of serial double light path laser induced fluorescence spectrometer, comprise LASER Light Source, detect groove, capillary column, confocal optics measurement module and chromatographic signal sampling processor, it also includes the first plane mirror, half-reflecting half mirror, the second plane mirror, gradual filter, stepper motor, the 3rd plane mirror, modulation panel, synchronous motor, light beam distinguishing sensor, photomultiplier and control panel, described first plane mirror is placed in the front of described LASER Light Source, and the half-reflecting half mirror laser beam direction from LASER Light Source is placed within described confocal optics measurement module, capillary column in order to the sample injecting measured matter is arranged in the detection groove on rear side of confocal optics measurement module, described second plane mirror is relative with the first plane mirror by described half-reflecting half mirror, described 3rd plane mirror is placed in the front of the second plane mirror, the gradual filter rotated by driving stepper motor is placed between this second plane mirror and the 3rd plane mirror, described photomultiplier is placed in the front of confocal optics measurement module, the modulation panel rotated by synchronous machine drives comprises echo area, transmission area and hypersorption district, and be arranged between described confocal optics measurement module and photomultiplier, described laser beam reflexes to described capillary column through described half-reflecting half mirror and excites described sample to send the fluorescence beam of Strength Changes, and the transmission area then through half-reflecting half mirror and described modulation panel inputs to described photomultiplier and forms sample arm, described laser beam passes this half-reflecting half mirror after described second plane mirror reflection simultaneously, to be led described modulation panel by described 3rd plane mirror through the gradual filter for balancing double light path energy, then the reflection through this modulation panel echo area inputs to described photomultiplier and forms the reference path with described sample arm serial, described modulation panel is by being realized in turn successively inputting the laser beam of photomultiplier by the rotation of synchronous machine drives, fluorescence beam input and without input, described light beam distinguishing sensor to be arranged in the light path between this modulation panel and photomultiplier and to respond to the rotation of this modulation panel, this light beam distinguishing sensor is connected with described control panel and to this control panel input light path distinguishing signal, described control panel is connected with photomultiplier and stepper motor simultaneously, and to the reference path signal from photomultiplier, sample arm signal and overall background signal process, then the chromatographic signal sampling processor be connected with this control panel is inputted.
Described gradual filter is one can to rotate with its central shaft, and makes the optical element that the absorbance through the incident light of its effective workspace changes with its anglec of rotation.
Described gradual filter refers to for balancing double light path energy, when being full of damping fluid in described capillary column, the signal intensity of comparative sample optical path signal and reference path signal, when reference path signal intensity is greater than more than sample arm signal intensity order of magnitude, the direction that described step motor control gradual filter increases to absorbance rotates, until the intensity ratio of sample arm signal and reference path signal is less than an order of magnitude.
With existing Technical comparing, present invention employs the structure of double light path, the basis of original sample arm adds reference path, realize in turn successively inputting the laser beam of the reference path of photomultiplier by modulation panel, sample arm fluorescence beam input and without input, and to this reference path signal in control panel, sample arm signal and overall background signal process, deduct the light source change of reference path signal, the change of photomultiplier dark current and veiling glare, the factor of light leak, thus reach eliminating LASER Light Source Strength Changes, the change of photomultiplier dark current and system veiling glare, the object of the impact of light leak, achieve the effect improving measuring accuracy.
Accompanying drawing explanation
Fig. 1 is the structural representation of existing laser-induced fluorescence spectroscopy instrument.
Fig. 2 is structural representation of the present invention.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is elaborated, but protection scope of the present invention is not limited to following embodiment.
As shown in Figure 2, described serial double light path laser induced fluorescence spectrometer includes LASER Light Source 2, first plane mirror 1, detects groove 4, capillary column 3, confocal optics measurement module 5, half-reflecting half mirror, the second plane mirror 6, gradual filter 7, stepper motor 8, the 3rd plane mirror 9, modulation panel 13, synchronous motor 15, light beam distinguishing sensor 14, photomultiplier 10, control panel 11 and chromatographic signal sampling processor 12.
Described LASER Light Source 2 is for Emission Lasers bundle, described first plane mirror 1 is placed in the front of described LASER Light Source 2, described capillary column 3 is in order to inject the sample of measured matter, and be arranged in described detection groove 4, described detection groove 4 is placed in the rear side of described confocal optics measurement module 5, described half-reflecting half mirror is placed within this confocal optics measurement module 5, described second plane mirror 6 is relative with the first plane mirror 1 by described half-reflecting half mirror, described 3rd plane mirror 9 is placed in the front of the second plane mirror 6, the gradual filter 7 of rotation is driven to be arranged between this second plane mirror 6 and the 3rd plane mirror 9 by stepper motor 8, described photomultiplier 10 is placed in the front of confocal optics measurement module 5, described modulation panel 13 comprises echo area, transmission area and hypersorption district, and drive rotation by synchronous motor 15, it is arranged between described confocal optics measurement module 5 and photomultiplier 10, described light beam distinguishing sensor 14 is arranged at the three kinds of optical path signals being connected to distinguish this control panel 11 in the light path between this modulation panel 13 with photomultiplier 10 and with described control panel 11 and obtaining, described control panel 11 is connected with photomultiplier 10 and stepper motor 8 simultaneously, described chromatographic signal sampling processor 12 is connected with this control panel 11.
Described first plane mirror 1 is by the half-reflecting half mirror in confocal optics measurement module 5 described in the laser beam direction from LASER Light Source 2, this laser beam reflexes to through half-reflecting half mirror the fluorescence beam that described capillary column 3 excited sample send Strength Changes, this fluorescence beam inputs to described photomultiplier 10 through the transmission area of half-reflecting half mirror and described modulation panel 13, forms sample arm; Described laser beam passes half-reflecting half mirror after described second plane mirror 6 reflects simultaneously, to be led described modulation panel 13 by described 3rd plane mirror 9 through the gradual filter 7 for balancing double light path energy, reflection again through this modulation panel 13 echo area inputs to described photomultiplier 10, forms the reference path with described sample arm serial; Described modulation panel 13 is by the rotation in the echo area that driven by synchronous motor 15, transmission area and hypersorption district, realize in turn successively inputting the laser beam of the reference path of photomultiplier 10, the fluorescence beam input of sample arm and without input, described light beam distinguishing sensor 14 respond to this modulation panel 13 rotation and to control panel 11 input light path distinguishing signal, described control panel 11 processes from the reference path signal of photomultiplier 10, sample arm signal and overall background signal, then inputs chromatographic signal sampling processor 12.
Described stepper motor 8 and gradual filter 7 can balance the principle of work of double light path energy:
Because reference path is by directly to be formed after half-reflecting half mirror in laser light confocal optics measurement module 5, therefore reference path signal intensity is the multiple of several orders of magnitude of sample arm signal intensity, work, so arrange stepper motor 8 and gradual filter 7 under the state of energy intensity (signal intensity of reference path is not more than sample arm signal intensity order of magnitude) in a basic balance to make double light path.Gradual filter 7 is one can to rotate with its central shaft, and makes the optical element that the absorbance of the incident light through its effective workspace (dimming capability) changes with itself anglec of rotation.When being full of damping fluid in capillary column 3, the signal intensity of comparative sample optical path signal and reference path signal, when the signal intensity of reference path is greater than more than sample arm signal intensity order of magnitude, the direction that control step motor 8 makes gradual filter 7 increase to absorbance rotates, until two optical path signal intensity ratios are less than an order of magnitude.
The principle of work of described modulation panel 13 and light beam distinguishing sensor 14 is as follows:
After instrument start, the modulation panel 13 be arranged on synchronous motor 15 axle just starts continuous rotation, and when the echo area incision light path of modulation panel 13, the laser beam of reference path is reflected input photomultiplier 10, and what now control panel 11 obtained is reference path signal; When the transmission area incision light path of modulation panel 13, the fluorescence beam input photomultiplier 10 of sample arm, what now control panel 11 obtained is sample arm signal; When the hypersorption district incision light path of modulation panel 13, photomultiplier 10 is without input, and what now control panel 11 obtained is the overall background signal comprising photomultiplier dark current, veiling glare and light leak.With the rotation of modulation panel 13, reference path signal, overall background signal and sample arm signal enter control panel 11 in turn successively.Whenever the forward position incision light beam distinguishing sensor 14 of modulation panel 13 echo area, light beam distinguishing sensor 14 is to control panel 11 input light path distinguishing signal.

Claims (3)

1. a serial double light path laser induced fluorescence spectrometer, comprise LASER Light Source, detect groove, capillary column, confocal optics measurement module and chromatographic signal sampling processor, it is characterized in that: described laser-induced fluorescence spectroscopy instrument also includes the first plane mirror, half-reflecting half mirror, the second plane mirror, gradual filter, stepper motor, the 3rd plane mirror, modulation panel, synchronous motor, light beam distinguishing sensor, photomultiplier and control panel, described first plane mirror is placed in the front of described LASER Light Source, and the half-reflecting half mirror laser beam direction from LASER Light Source is placed within described confocal optics measurement module, capillary column in order to the sample injecting measured matter is arranged in the detection groove on rear side of confocal optics measurement module, described second plane mirror is relative with the first plane mirror by described half-reflecting half mirror, described 3rd plane mirror is placed in the front of the second plane mirror, the gradual filter rotated by driving stepper motor is placed between this second plane mirror and the 3rd plane mirror, described photomultiplier is placed in the front of confocal optics measurement module, the modulation panel rotated by synchronous machine drives comprises echo area, transmission area and hypersorption district, and be arranged between described confocal optics measurement module and photomultiplier, described laser beam reflexes to described capillary column through described half-reflecting half mirror and excites described sample to send the fluorescence beam of Strength Changes, and the transmission area then through half-reflecting half mirror and described modulation panel inputs to described photomultiplier and forms sample arm, described laser beam passes this half-reflecting half mirror after described second plane mirror reflection simultaneously, to be led described modulation panel by described 3rd plane mirror through the gradual filter for balancing double light path energy, then the reflection through this modulation panel echo area inputs to described photomultiplier and forms the reference path with described sample arm serial, described modulation panel is by being realized in turn successively inputting the laser beam of photomultiplier by the rotation of synchronous machine drives, fluorescence beam input and without input, described light beam distinguishing sensor to be arranged in the light path between this modulation panel and photomultiplier and to respond to the rotation of this modulation panel, this light beam distinguishing sensor is connected with described control panel and to this control panel input light path distinguishing signal, described control panel is connected with photomultiplier and stepper motor simultaneously, and to the reference path signal from photomultiplier, sample arm signal and overall background signal process, then the chromatographic signal sampling processor be connected with this control panel is inputted.
2. serial double light path laser induced fluorescence spectrometer according to claim 1, it is characterized in that: described gradual filter is one can to rotate with its central shaft, and makes the optical element that the absorbance through the incident light of its effective workspace changes with its anglec of rotation.
3. serial double light path laser induced fluorescence spectrometer according to claim 2, it is characterized in that: described gradual filter refers to for balancing double light path energy, when being full of damping fluid in described capillary column, the signal intensity of comparative sample optical path signal and reference path signal, when reference path signal intensity is greater than more than sample arm signal intensity order of magnitude, the direction that described step motor control gradual filter increases to absorbance rotates, until the intensity ratio of sample arm signal and reference path signal is less than an order of magnitude.
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PCT/CN2014/000472 WO2014183468A1 (en) 2013-05-13 2014-05-08 Serial dual-optical path laser-induced fluorescence spectrometer

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CN107560713A (en) * 2017-10-27 2018-01-09 罗沛棋 Vibration signal extraction element based on gradual change transmitance filter
CN108593554B (en) * 2018-05-24 2020-10-30 大连民族大学 Laser-induced fluorescence collection and photoelectric conversion device capable of being adjusted in multiple dimensions
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