WO2014183468A1 - Serial dual-optical path laser-induced fluorescence spectrometer - Google Patents

Serial dual-optical path laser-induced fluorescence spectrometer Download PDF

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Publication number
WO2014183468A1
WO2014183468A1 PCT/CN2014/000472 CN2014000472W WO2014183468A1 WO 2014183468 A1 WO2014183468 A1 WO 2014183468A1 CN 2014000472 W CN2014000472 W CN 2014000472W WO 2014183468 A1 WO2014183468 A1 WO 2014183468A1
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Prior art keywords
optical path
sample
signal
laser
photomultiplier tube
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PCT/CN2014/000472
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French (fr)
Chinese (zh)
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阎超
姚凡
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Yan Chao
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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

Definitions

  • the invention relates to a laser induced fluorescence spectrum measuring device, in particular to a serial double optical path laser induced fluorescence spectrometer, belonging to the technical field of laser spectroscopy.
  • Laser spectroscopy has become the main research area of laser technology due to its high resolution, sensitivity, accuracy and non-destructive, safe and fast. With the in-depth development of laser spectroscopy, it has been widely used in the fields of biology and medicine. Among them, the autofluorescence of the tissue is studied.
  • the molecular fluorescence spectrum is independent of the wavelength of the excitation source, and is only related to the energy level structure of the fluorescent substance itself. Therefore, the fluorescent substance can be qualitatively analyzed and identified according to the fluorescence line.
  • Laser-induced fluorescence spectrometers are devices that use the above principles to detect substances.
  • a conventional laser-induced fluorescence spectrometer generally includes a laser light source 02, a plane mirror 01, a capillary column 03, a detection tank 04, a confocal optical measurement module 05, a photomultiplier tube 06, and a chromatographic data acquisition processor 07, wherein The capillary column 03 for injecting the sample of the test substance is disposed in the detecting tank 04.
  • the laser light emitted by the laser light source 02 is reflected by the plane mirror 01 and then introduced into the confocal optical measuring module 05, and is directed to the sample in the capillary column 03, and the sample is
  • the laser is excited to emit fluorescence having a change in intensity and is input to the photomultiplier tube 06 through the confocal optical measurement module 05.
  • the photomultiplier tube 06 amplifies and converts the optical signal of varying intensity into an electrical signal and inputs it to the chromatographic data acquisition processor 07.
  • the laser induced fluorescence spectrometer described above has a single optical path structure, and has the advantages of simple structure, but there are also large defects: the intensity change of the sample signal outputted by the photomultiplier tube 06 includes not only the change of the laser intensity of the laser light source 02, Moreover, it contains changes in the dark current of the photomultiplier tube 06 and system stray light (including light leakage), which may cause errors in the measurement of the sample.
  • the technical problem to be solved by the present invention is to overcome the deficiencies of the existing laser-induced fluorescence spectrometer, and provide a serial dual-path laser-induced fluorescence spectrometer capable of eliminating the intensity variation of the laser source, the change of the dark current of the photomultiplier tube, and the system stray light, The effect of light leakage has the advantage of high detection accuracy.
  • the technical solution adopted by the present invention to solve the technical problems thereof is as follows:
  • a serial dual-path laser induced fluorescence spectrometer includes a laser light source, a detection tank, a capillary column, a confocal optical measurement module, and a chromatographic data acquisition processor, and further includes a first planar mirror, a half mirror, and a second a plane mirror, a gradation filter, a stepping motor, a third plane mirror, a modulating plate, a synchronous motor, a beam distinguishing sensor, a photomultiplier tube, and a control board;
  • the first plane mirror is disposed on the laser light source Front, and directing the laser beam from the laser source to the semi-reverse half lens disposed inside the confocal optical measurement module, and the capillary column for injecting the sample of the test substance is disposed on the back side of the confocal optical measurement module
  • the second planar mirror is opposite to the first planar mirror by the half mirror
  • the third planar mirror is placed in front of the second planar mirror, and the gradient is driven by the stepping motor
  • a filter is disposed between the second planar mirror and the third planar mirror, the photomultiplier tube is disposed in front of the confocal optical measurement module, a modulation plate driven by a synchronous motor includes a reflection area, a transmission area, and a total absorption area, and is disposed between the confocal optical measurement module and the photomultiplier tube;
  • the laser beam is reflected by the semi-reflex lens a capillary column and exciting a fluorescent beam of a change in intensity of the sample, and then passing through a transflective lens and a transmissive region of the modulation plate to the photomultiplier tube to form a sample optical path; and the laser beam passes through the half After being reflected by the second planar mirror, the reverse half lens passes through a gradation filter for balancing the energy of the two optical paths and is guided by the third planar mirror to the modulating plate, and then passes through the reflective region of the modulating plate.
  • Reflecting is input to the photomultiplier tube to form a reference optical path serially connected to the optical path of the sample; the modulation plate realizes laser beam input, fluorescent beam input, and no input to the photomultiplier tube by rotating in turn by a synchronous motor.
  • the beam distinguishing sensor is disposed in an optical path between the modulating plate and the photomultiplier tube and senses rotation of the modulating plate, the beam distinguishing between the sensor and the
  • the control board is connected and inputs an optical path distinguishing signal to the control board, the control board is simultaneously connected with the photomultiplier tube and the stepping motor, and processes the reference optical path signal, the sample optical path signal and the overall background signal from the photomultiplier tube, and then Enter the chromatographic data acquisition processor connected to the control board.
  • the control board processes the reference optical path signal, the sample optical path signal and the overall background signal from the photomultiplier tube, and the control board performs the following specific operations on the reference optical path signal, the sample optical path signal and the overall background signal:
  • the gradation filter is an optical element that is rotatable about its central axis and that changes the absorbance of incident light passing through its active working area as a function of its angle of rotation.
  • the gradient filter is used to balance the energy of the dual optical path.
  • the buffer column is filled with the buffer, the signal intensity of the sample optical path signal and the reference optical path signal is compared.
  • the reference optical path signal strength is greater than the sample optical path signal strength,
  • the stepper motor controls the gradual filter to rotate in the direction of increasing absorbance until the ratio of the intensity of the sample path signal to the reference path signal is less than an order of magnitude.
  • the invention adopts the structure of the double optical path, adds a reference optical path to the original sample optical path, and realizes the laser beam input to the reference optical path of the photomultiplier tube and the fluorescence of the sample optical path through the modulation plate in turn.
  • Beam input and no input and processing the reference optical path signal, sample optical path signal and overall background signal in the control board, deducting the change of the light source of the reference optical path signal, the change of the dark current of the photomultiplier tube, and the factors of stray light and light leakage
  • the purpose of eliminating the influence of the intensity variation of the laser light source, the change of the dark current of the photomultiplier tube, and the effects of stray light and light leakage of the system is achieved, and the effect of improving the measurement accuracy is obtained.
  • Figure 1 is a schematic view showing the structure of a conventional laser induced fluorescence spectrometer.
  • Figure 2 is a schematic view of the structure of the present invention.
  • the serial dual optical path laser induced fluorescence spectrometer comprises a laser light source 2, a first plane mirror 1, a detecting tank 4, a capillary column 3, a confocal optical measuring module 5, a half mirror half lens 16, Second plane mirror 6, gradient filter 7, stepper motor 8, third plane mirror 9, modulation plate 13, synchronous motor 15, beam discrimination sensor 14, photomultiplier tube 10, control board 11, and chromatographic data acquisition Processor 12.
  • the laser light source 2 is for emitting a laser beam
  • the first plane mirror 1 is placed in front of the laser light source 2
  • the capillary column 3 is used for injecting a sample of the substance to be tested, and is disposed in the detection tank.
  • the detection slot 4 is placed on the rear side of the confocal optical measurement module 5
  • the semi-reverse half lens 16 is placed in the confocal optical measurement module 5
  • the second planar mirror 6 passes
  • the half mirror half 16 is opposite to the first plane mirror 1
  • the third plane mirror 9 is placed in front of the second plane mirror 6, and the gradient filter 7 driven by the stepping motor 8 is disposed on
  • the photomultiplier tube 10 is placed in front of the confocal optical measuring module 5, and the modulating plate 13 includes a reflective area, a transmissive area and a total absorption area.
  • the optical path between the modulating plate 13 and the photomultiplier tube 10 is connected to the control board 11 to distinguish three kinds of optical path signals obtained by the control board 11, and the control board 11 is simultaneously connected with the photomultiplier tube 10 and the stepping motor. 8 is connected, and the chromatographic data acquisition processor 12 is connected to the control board 11.
  • the first planar mirror 1 directs a laser beam from the laser source 2 to a half mirror half 16 in the confocal optical measurement module 5, the laser beam being reflected by the half mirror half 16 to the capillary column 3 and Exciting the sample to emit a fluorescent beam having a change in intensity, the fluorescent beam is input to the photomultiplier tube 10 through the transflective lens 16 and the transmissive region of the modulation plate 13 to form a sample optical path; and the laser beam passes through the semi-reverse half lens
  • the gradation filter 7 for balancing the energy of the two optical paths is transmitted to the modulation plate 13 by the third planar mirror 9, and then passed through the modulating plate 13
  • the reflection of the reflection region is input to the photomultiplier tube 10 to form a reference optical path serially connected to the sample optical path; the modulation plate 13 is sequentially rotated by the reflection region, the transmission region, and the total absorption region driven by the synchronous motor 15.
  • the laser beam input to the reference optical path of the photomultiplier tube 10, the fluorescent beam input of the sample optical path, and the no input are alternately performed, and the beam discrimination sensor 14 senses the rotation of the modulation plate 13 and is directed to the control panel.
  • the input path discrimination signal is input to the control board 11 for processing the reference optical path signal, the sample optical path signal, and the overall background signal from the photomultiplier tube 10, and then input to the chromatographic data acquisition processor 12.
  • the control board 11 performs the following specific operations on the reference optical path signal, the sample optical path signal, and the overall background signal:
  • I sample (I S -I B ) /(I R - )*K
  • the sample signal I obtained eliminates the variation of the intensity of the laser light source, the change of the dark current of the photomultiplier tube, and the effects of system stray light and light leakage.
  • the stepper motor 8 and the gradation filter 7 are capable of balancing the working principle of the dual optical path energy:
  • the reference optical path signal strength is a multiple of several orders of magnitude of the sample optical path signal strength, in order to make the dual optical path substantially balanced in energy intensity.
  • the reference signal path is not more than an order of magnitude greater than the sample path signal strength
  • the stepping motor 8 and the gradation filter 7 are provided.
  • the gradation filter 7 is an optical element capable of rotating with its central axis and changing the absorbance (light reducing ability) of incident light passing through its effective working area with its own rotation angle.
  • the stepping motor 8 is controlled to cause the gradient filter 7 to The direction in which the absorbance increases increases until the ratio of the signal strengths of the two optical paths is less than an order of magnitude.
  • the working principle of the modulation board 13 and the beam distinguishing sensor 14 is as follows:
  • the modulating plate 13 mounted on the 15th axis of the same motor starts to continuously rotate.
  • the laser beam of the reference optical path is reflected and input to the photomultiplier tube 10, and the control board 11 is at this time.
  • the reference optical path signal is obtained; when the transmission region of the modulation plate 13 is cut into the optical path, the fluorescent beam of the sample optical path is input to the photomultiplier tube 10, and the control panel 11 obtains the sample optical path signal; when the full absorption region of the modulation plate 13 is cut In the optical path, the photomultiplier tube 10 has no input.
  • the control board 11 obtains an overall background signal including the photomultiplier tube dark current, stray light, and light leakage.
  • the reference optical path signal, the overall background signal, and the sample optical path signal are sequentially inputted into the control board 11.
  • the beam discrimination sensor 14 inputs an optical path discrimination signal to the control board 11.

Abstract

A serial dual-optical path laser-induced fluorescence spectrometer, comprising a laser light source (2), a first plane mirror (1), a detection tank (4), a capillary column (3), a confocal optical measurement module (5), a semi-transparent mirror (16), a second plane mirror (6), a gradient filter (7), a stepping motor (8), a third plane mirror (9), a modulation board (13), a synchronous motor (15), a light beam distinguishing sensor (14), a photomultiplier (10), a control board (11) and a chromatographic data acquisition processor (12), wherein a laser beam from the laser light source (2) stimulates a sample to emit a fluorescent beam; then, the fluorescent beam and the laser beam are respectively input into the photomultiplier (10) through a sample optical path and a reference optical path; the control board (11) is used for processing a reference optical path signal, a sample optical path signal and an integral background signal from the photomultiplier (10),and finally, inputting same into the chromatographic data acquisition processor (12). The present invention eliminates the change in intensity of the laser light source (2), the change in the dark current of the photomultiplier (10) and the influences of parasitic light and light leakage on a system, and improves the measurement accuracy.

Description

串行双光路激光诱导荧光光谱仪 技术领域  Serial dual optical path laser induced fluorescence spectrometer
本发明涉及一种激光诱导荧光光谱测量装置,具体涉及一种串行双光路激光诱导荧光 光谱仪, 属于激光光谱技术领域。  The invention relates to a laser induced fluorescence spectrum measuring device, in particular to a serial double optical path laser induced fluorescence spectrometer, belonging to the technical field of laser spectroscopy.
背景技术 Background technique
激光光谱以其极高的分辨率、 灵敏度、 精确度以及无损、 安全、 快速等优点而成为激 光技术的主要研究领域。 随着激光光谱技术研宄的深入开展, 其在生物学、 医学等技术领 域中得到了广泛应用, 其中比较受关注的是研宄物组织的自体荧光。  Laser spectroscopy has become the main research area of laser technology due to its high resolution, sensitivity, accuracy and non-destructive, safe and fast. With the in-depth development of laser spectroscopy, it has been widely used in the fields of biology and medicine. Among them, the autofluorescence of the tissue is studied.
当紫外光或波长较短的可见光照射到某些物质时,这些物质会发射出各种颜色和不同 强度的可见光, 而当光源停止照射时, 这种光线随之消失。这种在激发光诱导下产生的光 称为荧光, 能发出荧光的物质称为荧光物质。 几乎所有物质分子都有吸收光谱, 但不是所 有物质都会发荧光, 即并非所有物质都是荧光物质。物质产生荧光必须具备以下条件: ① 该物质分子必须具有与所照射的光线相同的频率, 这与分子的结构密切相关。②吸收了与 本身特征频率相同的能量之后的物质分子, 必须具有高的荧光效率。 由荧光的发光原理可 知, 分子荧光光谱与激发光源的波长无关, 只与荧光物质本身的能级结构有关, 所以, 可 以根据荧光谱线对荧光物质进行定性分析鉴别。  When ultraviolet light or short-wavelength visible light is irradiated to certain substances, these substances emit visible light of various colors and different intensities, and when the light source stops emitting, the light disappears. This kind of light generated by excitation light is called fluorescence, and a substance that emits fluorescence is called a fluorescent substance. Almost all matter molecules have an absorption spectrum, but not all substances fluoresce, that is, not all substances are fluorescent substances. The substance must produce the following conditions: 1 The molecule of the substance must have the same frequency as the light to be irradiated, which is closely related to the structure of the molecule. 2 A substance molecule that absorbs the same energy as its own characteristic frequency must have high fluorescence efficiency. It is known from the principle of fluorescence emission that the molecular fluorescence spectrum is independent of the wavelength of the excitation source, and is only related to the energy level structure of the fluorescent substance itself. Therefore, the fluorescent substance can be qualitatively analyzed and identified according to the fluorescence line.
激光诱导荧光光谱仪就是应用上述原理对物质进行检测的装置。 请参阅图 1, 现有激 光诱导荧光光谱仪一般包括激光光源 02、 平面反射镜 01、 毛细管柱 03、 检测槽 04、 共焦 光学测量模块 05、 光电倍增管 06和色谱数据采集处理器 07, 其中, 注入被测物质样品的 毛细管柱 03设置于检测槽 04内,激光光源 02发出的激光经平面反射镜 01反射后导入共 焦光学测量模块 05, 并且射向毛细管柱 03中的样品, 样品被激光激发后发出具有强度变 化的荧光并通过共焦光学测量模块 05输入光电倍增管 06, 该光电倍增管 06将强度变化 的光信号放大并转为电信号且输入色谱数据采集处理器 07。  Laser-induced fluorescence spectrometers are devices that use the above principles to detect substances. Referring to FIG. 1, a conventional laser-induced fluorescence spectrometer generally includes a laser light source 02, a plane mirror 01, a capillary column 03, a detection tank 04, a confocal optical measurement module 05, a photomultiplier tube 06, and a chromatographic data acquisition processor 07, wherein The capillary column 03 for injecting the sample of the test substance is disposed in the detecting tank 04. The laser light emitted by the laser light source 02 is reflected by the plane mirror 01 and then introduced into the confocal optical measuring module 05, and is directed to the sample in the capillary column 03, and the sample is The laser is excited to emit fluorescence having a change in intensity and is input to the photomultiplier tube 06 through the confocal optical measurement module 05. The photomultiplier tube 06 amplifies and converts the optical signal of varying intensity into an electrical signal and inputs it to the chromatographic data acquisition processor 07.
上述激光诱导荧光光谱仪为单光路结构, 其优点是结构简单, 然而也存在有较大的缺 陷: 由光电倍增管 06输出的样品信号的强度变化, 不仅包含有激光光源 02发射激光强度 的变化, 而且含有光电倍增管 06暗电流的变化以及系统杂光(包括漏光)等因素, 因此 会导致对样品测量的误差。  The laser induced fluorescence spectrometer described above has a single optical path structure, and has the advantages of simple structure, but there are also large defects: the intensity change of the sample signal outputted by the photomultiplier tube 06 includes not only the change of the laser intensity of the laser light source 02, Moreover, it contains changes in the dark current of the photomultiplier tube 06 and system stray light (including light leakage), which may cause errors in the measurement of the sample.
发明内容 Summary of the invention
本发明要解决的技术问题是克服现有激光诱导荧光光谱仪的不足,提供一种串行双光 路激光诱导荧光光谱仪,其能够排除激光光源强度变化、光电倍增管暗电流的变化以及系 统杂光、 漏光的影响, 具有检测精度高的优点。 本发明解决其技术问题采取的技术方案如下: The technical problem to be solved by the present invention is to overcome the deficiencies of the existing laser-induced fluorescence spectrometer, and provide a serial dual-path laser-induced fluorescence spectrometer capable of eliminating the intensity variation of the laser source, the change of the dark current of the photomultiplier tube, and the system stray light, The effect of light leakage has the advantage of high detection accuracy. The technical solution adopted by the present invention to solve the technical problems thereof is as follows:
一种串行双光路激光诱导荧光光谱仪, 包括激光光源、 检测槽、 毛细管柱、 共焦光学 测量模块和色谱数据采集处理器, 其还包括有第一平面反射镜、 半反半透镜、第二平面反 射镜、 渐变滤光片、 步进电机、 第三平面反射镜、 调制板、 同步电机、 光束区分传感器、 光电倍增管和控制板; 所述第一平面反射镜置于所述激光光源的前方, 并且将来自激光光 源的激光束导向置于所述共焦光学测量模块之内的半反半透镜,用以注入被测物质的样品 的毛细管柱设置于共焦光学测量模块后侧的检测槽内,所述第二平面反射镜通过所述半反 半透镜与第一平面反射镜相对, 所述第三平面反射镜置于第二平面反射镜的前方, 由步进 电机驱动旋转的渐变滤光片置于该第二平面反射镜与第三平面反射镜之间,所述光电倍增 管置于共焦光学测量模块的前方, 由同步电机驱动旋转的调制板包括反射区、透射区和全 吸收区, 并且设置于所述共焦光学测量模块与光电倍增管之间; 所述激光束经所述半反半 透镜反射至所述毛细管柱并激发所述样品发出强度变化的荧光束,然后穿过半反半透镜和 所述调制板的透射区输入至所述光电倍增管而形成样品光路;同时所述激光束穿过该半反 半透镜经所述第二平面反射镜反射后,透过用于平衡双光路能量的渐变滤光片并被所述第 三平面反射镜导向所述调制板,再经该调制板反射区的反射输入至所述光电倍增管而形成 与所述样品光路串行的参考光路;所述调制板通过由同步电机驱动的旋转依次轮流实现对 光电倍增管的激光束输入、荧光束输入和无输入, 所述光束区分传感器设置于该调制板与 光电倍增管之间的光路中且感应该调制板的旋转,该光束区分传感器与所述控制板连接并 向该控制板输入光路区别信号, 所述控制板同时与光电倍增管和步进电机连接, 并且对来 自光电倍增管的参考光路信号、样品光路信号和整体背景信号进行处理, 然后输入与该控 制板连接的色谱数据采集处理器。  A serial dual-path laser induced fluorescence spectrometer includes a laser light source, a detection tank, a capillary column, a confocal optical measurement module, and a chromatographic data acquisition processor, and further includes a first planar mirror, a half mirror, and a second a plane mirror, a gradation filter, a stepping motor, a third plane mirror, a modulating plate, a synchronous motor, a beam distinguishing sensor, a photomultiplier tube, and a control board; the first plane mirror is disposed on the laser light source Front, and directing the laser beam from the laser source to the semi-reverse half lens disposed inside the confocal optical measurement module, and the capillary column for injecting the sample of the test substance is disposed on the back side of the confocal optical measurement module In the slot, the second planar mirror is opposite to the first planar mirror by the half mirror, the third planar mirror is placed in front of the second planar mirror, and the gradient is driven by the stepping motor. a filter is disposed between the second planar mirror and the third planar mirror, the photomultiplier tube is disposed in front of the confocal optical measurement module, a modulation plate driven by a synchronous motor includes a reflection area, a transmission area, and a total absorption area, and is disposed between the confocal optical measurement module and the photomultiplier tube; the laser beam is reflected by the semi-reflex lens a capillary column and exciting a fluorescent beam of a change in intensity of the sample, and then passing through a transflective lens and a transmissive region of the modulation plate to the photomultiplier tube to form a sample optical path; and the laser beam passes through the half After being reflected by the second planar mirror, the reverse half lens passes through a gradation filter for balancing the energy of the two optical paths and is guided by the third planar mirror to the modulating plate, and then passes through the reflective region of the modulating plate. Reflecting is input to the photomultiplier tube to form a reference optical path serially connected to the optical path of the sample; the modulation plate realizes laser beam input, fluorescent beam input, and no input to the photomultiplier tube by rotating in turn by a synchronous motor. The beam distinguishing sensor is disposed in an optical path between the modulating plate and the photomultiplier tube and senses rotation of the modulating plate, the beam distinguishing between the sensor and the The control board is connected and inputs an optical path distinguishing signal to the control board, the control board is simultaneously connected with the photomultiplier tube and the stepping motor, and processes the reference optical path signal, the sample optical path signal and the overall background signal from the photomultiplier tube, and then Enter the chromatographic data acquisition processor connected to the control board.
所述的控制板对来自光电倍增管的参考光路信号、样品光路信号和整体背景信号进行 处理是指, 所述控制板对参考光路信号、样品光路信号和整体背景信号进行如下具体运算 处理:  The control board processes the reference optical path signal, the sample optical path signal and the overall background signal from the photomultiplier tube, and the control board performs the following specific operations on the reference optical path signal, the sample optical path signal and the overall background signal:
1 ) 当毛细管柱 3中充满缓冲液时, 测得仪器归一因子  1) When the capillary column 3 is filled with buffer, the instrument normalization factor is measured.
K=(IR-IB)/ (IS-IB)  K=(IR-IB)/ (IS-IB)
2)在毛细管柱 3中注入被测物质的样品后, 测得  2) After injecting a sample of the test substance into the capillary column 3, it is measured
I样 = (IS-IB) /(IR-IB)*K I sample = (IS-IB) / (IR-IB) * K
式中,  In the formula,
IR—参考光路信号, I R — reference optical path signal,
18_样品光路信号, 1 8 _ sample light path signal,
IB—整体背景信号, K_双光路归一系数, I B - the overall background signal, K_double optical path normalization coefficient,
I样一消除影响后的样品信号。  I sample to eliminate the affected sample signal.
所述的渐变滤光片为一能够以其中心轴旋转,且使穿过其有效工作区的入射光的吸光 度随其旋转角度而改变的光学元件。  The gradation filter is an optical element that is rotatable about its central axis and that changes the absorbance of incident light passing through its active working area as a function of its angle of rotation.
所述的渐变滤光片用于平衡双光路能量是指, 在所述毛细管柱中充满缓冲液时, 比较 样品光路信号与参考光路信号的信号强度,当参考光路信号强度大于样品光路信号强度一 个数量级以上时, 所述步进电机控制渐变滤光片向吸光度增加的方向旋转, 直至样品光路 信号与参考光路信号的强度之比小于一个数量级。  The gradient filter is used to balance the energy of the dual optical path. When the buffer column is filled with the buffer, the signal intensity of the sample optical path signal and the reference optical path signal is compared. When the reference optical path signal strength is greater than the sample optical path signal strength, Above the order of magnitude, the stepper motor controls the gradual filter to rotate in the direction of increasing absorbance until the ratio of the intensity of the sample path signal to the reference path signal is less than an order of magnitude.
与现有的技术比较, 本发明采用了双光路的结构, 在原有样品光路的基础上增加了参 考光路, 通过调制板依次轮流实现对光电倍增管的参考光路的激光束输入、样品光路的荧 光束输入和无输入, 并在控制板中对该参考光路信号、样品光路信号与整体背景信号进行 处理, 扣除了参考光路信号的光源变化、 光电倍增管暗电流的变化和杂光、 漏光的因素, 从而达到了排除激光光源强度变化、光电倍增管暗电流的变化以及系统杂光、漏光的影响 的目的, 取得了提高测量精度的效果。  Compared with the prior art, the invention adopts the structure of the double optical path, adds a reference optical path to the original sample optical path, and realizes the laser beam input to the reference optical path of the photomultiplier tube and the fluorescence of the sample optical path through the modulation plate in turn. Beam input and no input, and processing the reference optical path signal, sample optical path signal and overall background signal in the control board, deducting the change of the light source of the reference optical path signal, the change of the dark current of the photomultiplier tube, and the factors of stray light and light leakage Thus, the purpose of eliminating the influence of the intensity variation of the laser light source, the change of the dark current of the photomultiplier tube, and the effects of stray light and light leakage of the system is achieved, and the effect of improving the measurement accuracy is obtained.
附图说明 DRAWINGS
图 1为现有激光诱导荧光光谱仪的结构示意图。  Figure 1 is a schematic view showing the structure of a conventional laser induced fluorescence spectrometer.
图 2为本发明的结构示意图。  Figure 2 is a schematic view of the structure of the present invention.
具体实施方式 detailed description
下面结合实施例和附图对本发明作详细说明,但本发明的保护范围不限于下述的实施 例。  The present invention will be described in detail below with reference to the embodiments and drawings, but the scope of the invention is not limited to the embodiments described below.
如图 2所示, 所述串行双光路激光诱导荧光光谱仪包括有激光光源 2、 第一平面反射 镜 1、 检测槽 4、 毛细管柱 3、 共焦光学测量模块 5、 半反半透镜 16、 第二平面反射镜 6、 渐变滤光片 7、 步进电机 8、 第三平面反射镜 9、 调制板 13、 同步电机 15、 光束区分传感 器 14、 光电倍增管 10、 控制板 11和色谱数据采集处理器 12。  As shown in FIG. 2, the serial dual optical path laser induced fluorescence spectrometer comprises a laser light source 2, a first plane mirror 1, a detecting tank 4, a capillary column 3, a confocal optical measuring module 5, a half mirror half lens 16, Second plane mirror 6, gradient filter 7, stepper motor 8, third plane mirror 9, modulation plate 13, synchronous motor 15, beam discrimination sensor 14, photomultiplier tube 10, control board 11, and chromatographic data acquisition Processor 12.
所述激光光源 2用于发射激光束,所述第一平面反射镜 1置于所述激光光源 2的前方, 所述毛细管柱 3用以注入被测物质的样品, 并且设置于所述检测槽 4内, 所述检测槽 4置 于所述共焦光学测量模块 5的后侧,所述半反半透镜 16置于该共焦光学测量模块 5之内, 所述第二平面反射镜 6通过所述半反半透镜 16与第一平面反射镜 1相对, 所述第三平面 反射镜 9置于第二平面反射镜 6的前方,由步进电机 8驱动旋转的渐变滤光片 7设置于该 第二平面反射镜 6与第三平面反射镜 9之间, 所述光电倍增管 10置于共焦光学测量模块 5的前方,所述调制板 13包括反射区、透射区和全吸收区, 并且由同步电机 15驱动旋转, 其设置于所述共焦光学测量模块 5与光电倍增管 10之间,所述光束区分传感器 14设置于 该调制板 13与光电倍增管 10之间的光路中且与所述控制板 11连接以区分该控制板 11得 到的三种光路信号, 所述控制板 11同时与光电倍增管 10和步进电机 8连接, 所述色谱数 据采集处理器 12与该控制板 11连接。 The laser light source 2 is for emitting a laser beam, and the first plane mirror 1 is placed in front of the laser light source 2, and the capillary column 3 is used for injecting a sample of the substance to be tested, and is disposed in the detection tank. 4, the detection slot 4 is placed on the rear side of the confocal optical measurement module 5, the semi-reverse half lens 16 is placed in the confocal optical measurement module 5, and the second planar mirror 6 passes The half mirror half 16 is opposite to the first plane mirror 1, the third plane mirror 9 is placed in front of the second plane mirror 6, and the gradient filter 7 driven by the stepping motor 8 is disposed on Between the second planar mirror 6 and the third planar mirror 9, the photomultiplier tube 10 is placed in front of the confocal optical measuring module 5, and the modulating plate 13 includes a reflective area, a transmissive area and a total absorption area. And being rotated by the synchronous motor 15, which is disposed between the confocal optical measuring module 5 and the photomultiplier tube 10, and the beam distinguishing sensor 14 is disposed at The optical path between the modulating plate 13 and the photomultiplier tube 10 is connected to the control board 11 to distinguish three kinds of optical path signals obtained by the control board 11, and the control board 11 is simultaneously connected with the photomultiplier tube 10 and the stepping motor. 8 is connected, and the chromatographic data acquisition processor 12 is connected to the control board 11.
所述第一平面反射镜 1将来自激光光源 2的激光束导向所述共焦光学测量模块 5中的 半反半透镜 16, 该激光束经半反半透镜 16反射至所述毛细管柱 3并激发样品发出强度变 化的荧光束,该荧光束穿过半反半透镜 16和所述调制板 13的透射区输入至所述光电倍增 管 10, 形成样品光路; 同时所述激光束穿过半反半透镜 16经所述第二平面反射镜 6反射 后,透过用于平衡双光路能量的渐变滤光片 7并被所述第三平面反射镜 9导向所述调制板 13 , 再经该调制板 13反射区的反射输入至所述光电倍增管 10, 形成与所述样品光路串行 的参考光路;所述调制板 13通过由同步电机 15驱动的反射区、透射区和全吸收区的旋转, 依次轮流实现对光电倍增管 10的参考光路的激光束输入、 样品光路的荧光束输入和无输 入, 所述光束区分传感器 14感应该调制板 13的旋转并向控制板 11输入光路区别信号, 所述控制板 11对来自光电倍增管 10的参考光路信号、样品光路信号和整体背景信号进行 处理, 然后输入色谱数据采集处理器 12。  The first planar mirror 1 directs a laser beam from the laser source 2 to a half mirror half 16 in the confocal optical measurement module 5, the laser beam being reflected by the half mirror half 16 to the capillary column 3 and Exciting the sample to emit a fluorescent beam having a change in intensity, the fluorescent beam is input to the photomultiplier tube 10 through the transflective lens 16 and the transmissive region of the modulation plate 13 to form a sample optical path; and the laser beam passes through the semi-reverse half lens After being reflected by the second planar mirror 6, the gradation filter 7 for balancing the energy of the two optical paths is transmitted to the modulation plate 13 by the third planar mirror 9, and then passed through the modulating plate 13 The reflection of the reflection region is input to the photomultiplier tube 10 to form a reference optical path serially connected to the sample optical path; the modulation plate 13 is sequentially rotated by the reflection region, the transmission region, and the total absorption region driven by the synchronous motor 15. The laser beam input to the reference optical path of the photomultiplier tube 10, the fluorescent beam input of the sample optical path, and the no input are alternately performed, and the beam discrimination sensor 14 senses the rotation of the modulation plate 13 and is directed to the control panel. The input path discrimination signal is input to the control board 11 for processing the reference optical path signal, the sample optical path signal, and the overall background signal from the photomultiplier tube 10, and then input to the chromatographic data acquisition processor 12.
所述控制板 11对参考光路信号、 样品光路信号和整体背景信号进行如下具体运算处 理:  The control board 11 performs the following specific operations on the reference optical path signal, the sample optical path signal, and the overall background signal:
1 ) 当毛细管柱 3中充满缓冲液时, 测得仪器归一因子 1) When the capillary column 3 is filled with buffer, the instrument normalization factor is measured.
Figure imgf000006_0001
Figure imgf000006_0001
2)在毛细管柱 3中注入被测物质的样品后, 测得  2) After injecting a sample of the test substance into the capillary column 3, it is measured
I样 = (IS-IB) /(IR- )*K I sample = (I S -I B ) /(I R - )*K
式中,  In the formula,
Ir_参考光路信号, Ir _ reference optical path signal,
IS—样品光路信号, I S — sample path signal,
一整体背景信号,  a whole background signal,
K一双光路归一系数,  K a pair of optical path normalization coefficients,
I样一消除影响后的样品信号。  I sample to eliminate the affected sample signal.
这时得到的样品信号 I样 就消除了激光光源强度变化、光电倍增管暗电流的变化以及 系统杂光、 漏光的影响。  At this time, the sample signal I obtained eliminates the variation of the intensity of the laser light source, the change of the dark current of the photomultiplier tube, and the effects of system stray light and light leakage.
所述步进电机 8和渐变滤光片 7能够平衡双光路能量的工作原理:  The stepper motor 8 and the gradation filter 7 are capable of balancing the working principle of the dual optical path energy:
因为参考光路由激光透过共焦光学测量模块 5中半反半透镜 16后直接形成的, 因此 参考光路信号强度为样品光路信号强度的数个数量级的倍数,为了使双光路在能量强度基 本平衡(参考光路的信号强度不大于样品光路信号强度一个数量级)的状态下工作, 所以 设置步进电机 8和渐变滤光片 7。 渐变滤光片 7为一能够以其中心轴旋转, 并且使穿过其 有效工作区的入射光的吸光度(减光能力)随其本身旋转角度而改变的光学元件。 在毛细 管柱 3中充满缓冲液时, 比较样品光路信号与参考光路信号的信号强度, 当参考光路的信 号强度大于样品光路信号强度一个数量级以上时,控制步进电机 8使渐变滤光片 7向吸光 度增加的方向旋转, 直至两个光路信号强度之比小于一个数量级。 Since the reference light routing laser is directly formed after passing through the semi-reverse half lens 16 in the confocal optical measuring module 5, the reference optical path signal strength is a multiple of several orders of magnitude of the sample optical path signal strength, in order to make the dual optical path substantially balanced in energy intensity. (The reference signal path is not more than an order of magnitude greater than the sample path signal strength), so The stepping motor 8 and the gradation filter 7 are provided. The gradation filter 7 is an optical element capable of rotating with its central axis and changing the absorbance (light reducing ability) of incident light passing through its effective working area with its own rotation angle. When the capillary column 3 is filled with the buffer, the signal intensity of the sample optical path signal and the reference optical path signal is compared. When the signal intensity of the reference optical path is greater than one order of magnitude of the sample optical path signal strength, the stepping motor 8 is controlled to cause the gradient filter 7 to The direction in which the absorbance increases increases until the ratio of the signal strengths of the two optical paths is less than an order of magnitude.
所述调制板 13和光束区分传感器 14的工作原理如下:  The working principle of the modulation board 13 and the beam distinguishing sensor 14 is as follows:
仪器开机后, 安装在同歩电机 15轴上的调制板 13就开始连续旋转, 当调制板 13的 反射区切入光路时, 参考光路的激光束被反射输入光电倍增管 10, 此时控制板 11得到的 是参考光路信号; 当调制板 13的透射区切入光路时, 样品光路的荧光束输入光电倍增管 10, 此时控制板 11得到的是样品光路信号; 当调制板 13的全吸收区切入光路时, 光电倍 增管 10无输入, 此时控制板 11得到的是包括光电倍增管暗电流、杂光和漏光在内的整体 背景信号。 随调制板 13的旋转, 参考光路信号、 整体背景信号和样品光路信号是依次轮 流进入控制板 11。每当调制板 13反射区的前沿切入光束区分传感器 14时,光束区分传感 器 14向控制板 11输入光路区别信号。  After the instrument is turned on, the modulating plate 13 mounted on the 15th axis of the same motor starts to continuously rotate. When the reflecting area of the modulating plate 13 is cut into the optical path, the laser beam of the reference optical path is reflected and input to the photomultiplier tube 10, and the control board 11 is at this time. The reference optical path signal is obtained; when the transmission region of the modulation plate 13 is cut into the optical path, the fluorescent beam of the sample optical path is input to the photomultiplier tube 10, and the control panel 11 obtains the sample optical path signal; when the full absorption region of the modulation plate 13 is cut In the optical path, the photomultiplier tube 10 has no input. At this time, the control board 11 obtains an overall background signal including the photomultiplier tube dark current, stray light, and light leakage. With reference to the rotation of the modulating plate 13, the reference optical path signal, the overall background signal, and the sample optical path signal are sequentially inputted into the control board 11. Whenever the leading edge of the reflection area of the modulation plate 13 cuts into the beam discrimination sensor 14, the beam discrimination sensor 14 inputs an optical path discrimination signal to the control board 11.

Claims

权利 要求 Rights request
1、 一种串行双光路激光诱导荧光光谱仪, 包括激光光源、 检测槽、 毛细管柱、 共焦 光学测量模块和色谱数据采集处理器, 其特征在于: 所述激光诱导荧光光谱仪还包括有第 一平面反射镜、半反半透镜、第二平面反射镜、渐变滤光片、步进电机、第三平面反射镜、 调制板、 同步电机、 光束区分传感器、 光电倍增管和控制板; 所述第一平面反射镜置于所 述激光光源的前方,并且将来自激光光源的激光束导向置于所述共焦光学测量模块之内的 半反半透镜,用以注入被测物质的样品的毛细管柱设置于共焦光学测量模块后侧的检测槽 内, 所述第二平面反射镜通过所述半反半透镜与第一平面反射镜相对, 所述第三平面反射 镜置于第二平面反射镜的前方, 由步进电机驱动旋转的渐变滤光片置于该第二平面反射镜 与第三平面反射镜之间, 所述光电倍增管置于共焦光学测量模块的前方, 由同步电机驱动 旋转的调制板包括反射区、透射区和全吸收区, 并且设置于所述共焦光学测量模块与光电 倍增管之间;所述激光束经所述半反半透镜反射至所述毛细管柱并激发所述样品发出强度 变化的荧光束,然后穿过半反半透镜和所述调制板的透射区输入至所述光电倍增管而形成 样品光路; 同时所述激光束穿过该半反半透镜经所述第二平面反射镜反射后, 透过用于平 衡双光路能量的渐变滤光片并被所述第三平面反射镜导向所述调制板,再经该调制板反射 区的反射输入至所述光电倍增管而形成与所述样品光路串行的参考光路;所述调制板通过 由同步电机驱动的旋转依次轮流实现对光电倍增管的激光束输入、 荧光束输入和无输入, 所述光束区分传感器设置于该调制板与光电倍增管之间的光路中且感应该调制板的旋转, 该光束区分传感器与所述控制板连接并向该控制板输入光路区别信号,所述控制板同时与 光电倍增管和步进电机连接, 并且对来自光电倍增管的参考光路信号、样品光路信号和整 体背景信号进行处理, 然后输入与该控制板连接的色谱数据采集处理器。 1. A serial dual-optical path laser-induced fluorescence spectrometer, including a laser light source, a detection tank, a capillary column, a confocal optical measurement module and a chromatographic data acquisition processor, characterized in that: the laser-induced fluorescence spectrometer also includes a first Plane mirror, half-reflecting half-mirror, second plane mirror, gradient filter, stepper motor, third plane mirror, modulation board, synchronous motor, beam differentiation sensor, photomultiplier tube and control board; described in Chapter 1 A plane mirror is placed in front of the laser light source, and guides the laser beam from the laser light source to a semi-reflective semi-transparent mirror placed within the confocal optical measurement module to inject the capillary column of the sample of the measured substance. It is arranged in the detection slot on the back side of the confocal optical measurement module. The second plane mirror is opposite to the first plane mirror through the half-reflective half mirror. The third plane mirror is placed on the second plane mirror. In front of the confocal optical measurement module, a gradient filter driven by a stepper motor is placed between the second plane mirror and the third plane mirror. The photomultiplier tube is placed in front of the confocal optical measurement module and is driven by a synchronous motor. The rotating modulation plate includes a reflection area, a transmission area and a total absorption area, and is arranged between the confocal optical measurement module and the photomultiplier tube; the laser beam is reflected to the capillary column through the half-reflective half-mirror and The sample is excited to emit a fluorescent beam with varying intensity, and then passes through the semi-reflective half mirror and the transmission area of the modulation plate and is input to the photomultiplier tube to form a sample optical path; at the same time, the laser beam passes through the semi-reflective semi-reflective mirror. After reflection by the second plane reflector, it passes through the gradient filter used to balance the energy of the two optical paths and is guided to the modulation plate by the third plane reflector, and then is input to the modulation plate through reflection in the reflection area of the modulation plate. The photomultiplier tube forms a reference optical path in series with the sample optical path; the modulation plate sequentially realizes laser beam input, fluorescence beam input and no input to the photomultiplier tube through rotation driven by a synchronous motor, and the beam The discrimination sensor is arranged in the optical path between the modulation plate and the photomultiplier tube and senses the rotation of the modulation plate. The beam discrimination sensor is connected to the control board and inputs the optical path discrimination signal to the control board. The control board simultaneously communicates with The photomultiplier tube is connected to the stepper motor, and the reference optical path signal, sample optical path signal and overall background signal from the photomultiplier tube are processed, and then input to the chromatographic data acquisition processor connected to the control board.
2、 根据权利要求 1所述的串行双光路激光诱导荧光光谱仪, 其特征在于: 所述的控 制板对来自光电倍增管的参考光路信号、样品光路信号和整体背景信号进行处理是指, 所 述控制板对参考光路信号、 样品光路信号和整体背景信号进行如下具体运算处理: 2. The serial dual-optical path laser-induced fluorescence spectrometer according to claim 1, characterized in that: the control panel processes the reference optical path signal, the sample optical path signal and the overall background signal from the photomultiplier tube. The above control panel performs the following specific operations on the reference optical path signal, sample optical path signal and overall background signal:
1 ) 当毛细管柱 3中充满缓冲液时, 测得仪器归一因子 1) When capillary column 3 is filled with buffer, measure the instrument normalization factor
Figure imgf000008_0001
Figure imgf000008_0001
2)在毛细管柱 3中注入被测物质的样品后, 测得 2) After injecting the sample of the substance to be measured into the capillary column 3, measure
I样 = (IS-IB) /(IR-IB)*K I = (I S -I B ) /(I R -I B )*K
式中, In the formula,
IR—参考光路信号, Is—样品光路信号, I R —reference optical path signal, Is—sample optical path signal,
IB一整体背景信号, I B - overall background signal,
K一双光路归一系数, K double optical path normalization coefficient,
I ^- 除影响后的样品信号。 I^- sample signal after removing the influence.
3、 根据权利要求 1所述的串行双光路激光诱导荧光光谱仪, 其特征在于: 所述的渐 变滤光片为一能够以其中心轴旋转,且使穿过其有效工作区的入射光的吸光度随其旋转角 度而改变的光学元件。 3. The serial dual-optical path laser-induced fluorescence spectrometer according to claim 1, characterized in that: the gradient filter is one that can rotate about its central axis and make the incident light passing through its effective working area An optical element whose absorbance changes with its angle of rotation.
4、 根据权利要求 3所述的串行双光路激光诱导荧光光谱仪, 其特征在于: 所述的渐 变滤光片用于平衡双光路能量是指, 在所述毛细管柱中充满缓冲液时, 比较样品光路信号 与参考光路信号的信号强度,当参考光路信号强度大于样品光路信号强度一个数量级以上 时, 所述步进电机控制渐变滤光片向吸光度增加的方向旋转, 直至样品光路信号与参考光 路信号的强度之比小于一个数量级。 4. The serial dual-optical path laser-induced fluorescence spectrometer according to claim 3, characterized in that: the gradient filter is used to balance the dual-optical path energy when the capillary column is filled with buffer. The signal intensity of the sample optical path signal and the reference optical path signal. When the reference optical path signal intensity is greater than the sample optical path signal intensity by more than one order of magnitude, the stepper motor controls the gradient filter to rotate in the direction of increasing absorbance until the sample optical path signal is in contact with the reference optical path signal. The ratio of signal strengths is less than an order of magnitude.
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