SU1278614A1

SU1278614A1 - Pulsing laser fluorescent spectrometer

Info

Publication number: SU1278614A1
Application number: SU853944469A
Authority: SU
Inventors: Максим Леонидович Александров; Александр Львович Мельцин; Лев Васильевич Новиков
Original assignee: Институт Аналитического Приборостроения Научно-Технического Объединения Ан Ссср
Priority date: 1985-08-20
Filing date: 1985-08-20
Publication date: 1986-12-23

Abstract

Изобретение относитс к спектральному приборостроению. Цель изобретени заключаетс в повышении достоверности измерений аналитических параметров быстропротекающих процессов. Лазерный флуоресцентный спектрометр, содержащий лазер на красител х, дополн етс устройством сравнени интенсивности флуоресценции на выбранной длине волны с опорным напр жением. Рассогласование формирует сигнал в блоке синхронизации на повторный импульс лазерного излучени . Устройство стробировани запирающего напр жени на фотокатоде телевизионной трубки обеспечивает отсутствие темновых , токов трубки в интервале между импульсами генерации лазера. Устройство управлени напр жени на модул сл торе телевизионной трубки обеспечивает выбор световой характеристики в соответствии с интенсивностью падающего излучени . Интегратором проводитс суммирование сигнала с трубки при считывании интенсивности каждой спектральной компоненты зарегистрированного спектра. 1 ил. N5 00This invention relates to spectral instrumentation. The purpose of the invention is to increase the reliability of measurements of the analytical parameters of fast processes. A laser fluorescence spectrometer containing a dye laser is complemented by a device for comparing fluorescence intensity at a selected wavelength with a reference voltage. The error generates a signal in the synchronization unit for a repeated pulse of laser radiation. A gating device for blocking voltage on the photocathode of a television tube ensures that there are no dark tube currents in the interval between laser generation pulses. A voltage control unit on a television tube module provides a selection of the light characteristic according to the intensity of the incident radiation. The integrator conducts the summation of the signal from the tube while reading the intensity of each spectral component of the recorded spectrum. 1 il. N5 00

Description

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Изобретение относитс к спектральному приборостроению.This invention relates to spectral instrumentation.

Цель изобретени -- повышение достоверности измерени аналитических параметров быстропротекающих процессов .The purpose of the invention is to increase the reliability of measurement of the analytical parameters of fast processes.

На чертеже представлена блок-схема предлагаемого устройства.,The drawing shows a block diagram of the proposed device.,

Устройство содержит лазер 1 накачки , лазер 2 на красител х с перестраиваемой частотой излучени , кюветный блок 3, канал измерени спектра флуо ресцендии, содержащий спектрограф 4, передающую телевизионную трубку 5, телевизионный регистратор 6, пол риметрический канал, содержащий моно- хроматор 7, пол ризатор 8, фотоприем ники 9. и 10, измерители падающего и прошедшего через кюветный блок излучени : светоделитель 11, фотоприемники 12 и 13, многоканальный фотометр 14; блоки синхронизации 15 и управлени 16, магистраль ЭВМ 17, Устройства 6, 14, 15 и 16 св заны с магистралью ЭВМ. Канал измерени спектра флуоресценции дополнительно содержит устройство 18 сравнени , устройство 19 стробировани фотокатода , устройство 20 управлени напр жением модул тора трубки и интегратор 21 строки.The device contains a pumping laser 1, a dye-frequency laser 2 with a tunable radiation frequency, a cuvette unit 3, a fluorescence spectrum measurement channel containing a spectrograph 4, a transmitting television tube 5, a television recorder 6, a polarimetric channel containing a monochromator 7, a field Surveyor 8, photodetectors 9. and 10, meters of radiation incident on and passing through a cuvette unit: a beam splitter 11, photodetectors 12 and 13, a multichannel photometer 14; synchronization units 15 and control 16, computer mainline 17, Devices 6, 14, 15 and 16 are connected to computer mainline. The fluorescence spectrum measurement channel further comprises a comparison device 18, a photocathode gating device 19, a tube modulator voltage control device 20, and a line integrator 21.

Принцип работы устройства состоит в следующем.The principle of operation of the device is as follows.

В режиме начальной установки в перестраиваемом лазере 2 и монохрома торе 7 через блок управлени устанавливаютс требуемые длины волн,энерги генерации лазера 2. В режиме измерений по сигналу блока 15 синхронизации лазер 1 накачки генерирует импульс , накачивающий лазер 2 на красител х . Излучение лазера на красител х на выбранной длине волны возбуждает в кюветном блоке 3 луоресцен- цию исследуемой средыо При этом фотоприемники 12 и 13, регистриру интенсивность падающего и прошедшего среду лазерного излучени соответственно , обеспечивают с помощью фотометра 14 вычислени коэффициента поглощени . Одновременно импульс флуоресценции пропускаетс через спектрометрический и пол риметрический каналы. В спектрометрическом канале излучение флуоресценции разлагаетс в спектрографе 4 в пространственный спектр, который проецируетс в фокальной плоскости на фотокатод пере14 2In the initial setup mode, in the tunable laser 2 and the monochrome torus 7, the required wavelengths and the laser generation energy 2 are set through the control unit. In the measurement mode, the pump laser 1 generates a pulse that pumps the dye laser 2. The dye laser radiation at a selected wavelength excites in the cuvette unit 3 the luorescence of the medium under investigation. At the same time, the photoreceivers 12 and 13, recording the intensity of the incident and transmitted laser radiation, respectively, are provided with a photometer 14 to calculate the absorption coefficient. At the same time, a fluorescence pulse is transmitted through the spectrometric and polarimetric channels. In the spectrometric channel, the fluorescence emission in the spectrograph 4 is decomposed into a spatial spectrum that is projected in the focal plane onto a photocathode re-2

дающей телевизионной трубки 5. Импульсом лазера 2 в устройстве 19 ст- робирований формируетс строб, который отпирает фотокатод и переноситof a television tube 5. A laser pulse 2 forms a strobe in the strobe device 19, which unlocks the photocathode and transfers

изобрлже ше спектра флуоресценции на патенциальный рельеф мишени телевизионной трубки 5. Спектр считываетс электронньсм лучом трубки вдоль спектральных линий и по каждой строке суммируетс в интеграторе 21 строки,запоминаетс в телевизионнон регистраторе 6. В результате в последнем образуетс массив данных, определ емый числом строк развертки, отражающийimage of the fluorescence spectrum to the target topography of the television tube 5. The spectrum is read by an electron beam of the tube along the spectral lines and is summed up in an integrator 21 lines on each line, stored in the television recorder 6. As a result, the latter produces an array of data defined by the number of scan lines, reflecting

спектр флуоресценции исследуемого вещества.fluorescence spectrum of the test substance.

Интенсивность флуоресценции в полосе пропускани монохроматора 7 определ етс суммой токов с фотоприемников 9 и 10. Величина этого сигнала через устройство 20 управлени напр жением на модул торе трубки определ ет уровень напр жени на модул торе , обеспечива регистрацию спек-The fluorescence intensity in the passband of the monochromator 7 is determined by the sum of the currents from the photodetectors 9 and 10. The magnitude of this signal through the voltage control device 20 on the tube modulator determines the voltage level on the modulator, providing a recording of the spectra

тра флуоресценции данной интенсивности на линейном участке световой характеристики телевизионной трубки.Tra fluorescence of a given intensity on a linear portion of the light characteristics of a television tube.

Пол риметрический канал обеспечи- вает измерение степени пол ризации флуоресценции в полосе пропускани монохроматора 7 путем регистрации интенсивностей световых потоков Р и S компонент пол ризации, выдел емых пол ризатором 8 и фиксируемых фотоприемниками 9 и 10 соответственно,Степень пол ризации определ етс в фотометре 14, как (I, - I,Q )/(Ig + 1,0), где 1 и I,Q - интенсивности световых потоков, зарегистрированных фотоприемниками 9 и 10. Одновременна регистраци энергии падающего и прошедшего кюветный блок световых потоков фотоприемниками 12 и 13 и энергии флуоресценции на выбранной длине волны фотоприемниками 9 и 10 с последующей обработкой этих сигналов в многоканальном фотометре 14 обеспечивает измерени энергетического и кванто-вого выходов флуоресценции. С выходов The polarimetric channel provides a measure of the degree of polarization of the fluorescence in the passband of the monochromator 7 by recording the intensities of the light fluxes of the P and S components of polarization allocated by the polarizer 8 and fixed by the photoreceivers 9 and 10, respectively. The degree of polarization is determined in the photometer 14, as (I, - I, Q) / (Ig + 1.0), where 1 and I, Q are the intensities of the luminous fluxes recorded by the photoreceivers 9 and 10. Simultaneous recording of the energy of the incident and past the cuvette of the luminous fluxes by the photodetectors 12 and 13 and the fluorescence energy at a selected wavelength by photoreceivers 9 and 10, followed by processing these signals in a multi-channel photometer 14, provides measurements of the energy and quantum yields of fluorescence. From the outputs

телевизионного регистратора и многоканального фотометра 14 информаци поступает через магистраль 17 в ЭВМ дл последующей обработки.the television recorder and the multichannel photometer 14, the information enters via computer 17 into a computer for further processing.

Дл регистрации флуоресцентных ха- рактеристик сред, обладающих низким квантовым выходом флуоресценции,предусмотрен режим М1 огократного повторени зондирующих лазерных импульсов.For detecting the fluorescent characteristics of media with a low fluorescence quantum yield, the M1 mode of repeating probe laser pulses is provided.

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При этом в устройстве 18 сравнени происходит накопление сигналов 21In this case, the comparison device 18 accumulates signals 21

(Ifj + I,Q ) (i - число импульсов флуоресценции ) с фотоприемников 9 и 10 до уровн , соответствующего необходимому отношению сигнал - шум на потенциальном рельефе мишени телевизионной Tpv6- ки 5. После достижени необходимого уровн накоплени сигнала устройство 18 сравнени выдает сигнал в блок хронизации на прекращение генерации и считывание электронным пучком с мишени трубки накопленного суммарного спектра флуоресценции.(Ifj + I, Q) (i is the number of fluorescence pulses) from photodetectors 9 and 10 to a level corresponding to the required signal-to-noise ratio on the potential relief of a Tpv6-k TV target 5. After the required accumulation level of the signal is reached, the comparator 18 outputs a signal block of chronization on termination of generation and electron beam reading from the target of the tube of the accumulated total fluorescence spectrum.

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Изобретение позвол ет повысить достоверность результатов измерений благодар более интенсивному, чем вThe invention allows to increase the reliability of measurement results due to more intensive than in

известном устройстве, подавлению шумаknown device noise suppression

с учетом данных, поступающих по всем каналам измерени , а также расширить область применени спектрометрических приборов на анализ веш;еств с низким квантовым.выходом и малым временем 25 жизни флуореценции за счет системы многократного повторени зондировани с накоплением.taking into account data from all measurement channels, as well as expanding the field of application of spectrometric instruments for analyzing substances with a low quantum output and a short fluorescence lifetime of 25 due to the system of repeated repetition of sounding with accumulation.

Claims

f The invention relates to spectral instrumentation. The purpose of the invention is to increase the reliability of measurement of the analytical parameters of fast processes. The drawing shows block diagrams of the device. The device contains a laser 1 pump, a laser 2 on dyes with a tunable radiation frequency, a cuvette unit 3, a fluorescence spectrum measuring channel containing a spectrograph 4, a transmitting television tube 5, a television recorder 6 , a polarimetric channel containing a monochromator 7, a polarizer 8, photodetectors 9. and 10, measures of the radiation incident and transmitted through the cuvette unit: a beam splitter 11, photodetectors 12 and 13, a multichannel photometer 14; synchronization units 15 and control 16, computer mainline 17, Devices 6, 14, 15 and 16 are connected to computer mainline. The fluorescence spectrum measurement channel further comprises a comparison device 18, a photocathode gating device 19, a tube modulator voltage control device 20, and a line integrator 21. The principle of operation of the device is as follows. In the initial setup mode, in the tunable laser 2 and the monochrome torus 7, the required wavelengths are set through the control unit, the laser generation energy

2. In the measurement mode, according to the signal of the synchronization unit 15, the pump 1 laser generates a pulse pumping the dye laser 2. The radiation of the dye laser xx at the selected wavelength excites in the cuvette unit 3 the luorescence of the medium under investigation. In this case, the photodetectors 12 and 13, registering the intensity of the incident and transmitted laser radiation, respectively, are provided with a photometer 14 to calculate the absorption coefficient. At the same time, a fluorescence pulse is transmitted through the spectrometric and polarimetric channels. In the spectrometry channel, the fluorescence emission is decomposed in the spectrograph 4 into a spatial spectrum projected in the focal plane onto the photocathode of the transceiver 14 2 television tube 5. A laser pulse 2 in the gating device 19 produces a strobe that unlocks the photocathode and transfers fluorescence to the pathogen in a plasma wave that transforms the pathogen to the pathogen, which unlocks the photocathode and transfers fluorescence to the pathogen in the spectrometer, which transmits the strobe to the pathogen, and then transmits the pathogen fluorescence to a pattener. The targets of the television tube 5. The spectrum is read by the electron beam of the tube along the spectral lines and is summed up by 21 lines in each integrator, memorized in the television recorder 6. As a result, in the latter, an array of data is formed, determined by the number of scanning lines, reflecting the fluorescence spectrum of the analyte. The fluorescence intensity in the passband of the monochromator 7 is determined by the sum of the currents from the photodetectors 9 and 10. The magnitude of this signal through the voltage control device 20 on the tube modulator determines the voltage level on the modulator, ensuring registration of the fluorescence spectrum of this intensity on a linear segment light characteristics of the television tube. The polarimetric channel provides a measure of the degree of polarization of the fluorescence in the passband of the monochromator 7 by recording the intensities of the light fluxes P and S of the polarization components allocated by the polarizer 8 and fixed by the photoreceivers 9 and 10, respectively. The degree of polarization is determined in (14) I, - I, Q) / (Ig + 1.0), where 1 and I, Q are the intensities of the luminous fluxes recorded by the photoreceivers 9 and 10. Simultaneous recording of the energy of the incident and past the ditch unit of the luminous fluxes by the photoreceivers 12 and 13 and the fluorescence energy at a selected wavelength by photoreceivers 9 and 10, followed by processing these signals in a multi-channel photometer 14, provides measurements of the energy and quantum yields of fluorescence. From the outputs of the television recorder and the multichannel photometer 14, information flows through the main line 17 to a computer for further processing. To register the fluorescence characteristics of media with a low fluorescence quantum yield, the M1 mode of repeating probe laser pulses is provided. 312 At the same time, in the comparison device 18, signals 21 (Ifj + I, Q) accumulate (i is the number of fluorescence pulses) from the photoreceivers 9 and 10 to a level corresponding to the required signal-to-noise ratio on the potential topography of the television Tpv6ki target 5. After reaching the required signal accumulation level, the comparator device 18 generates a signal in the sync block to stop the generation and read the electron beam from the target of the tube of the accumulated total fluorescence spectrum. The invention makes it possible to increase the reliability of measurement results due to more intense noise suppression than in the known device, taking into account data from all measurement channels, as well as expand the field of application of spectrometric instruments for analyzing items with low quantum yield and short fluorescence. due to the system of multiple repetition sounding with accumulation. The invention includes a pulsed laser fluorescence spectrometer containing a radiation source consisting of a dye laser with a pump laser and synchronization and control units, the outputs of the synchronization unit being connected to the pump laser and a control device, and the output of which is connected to a laser dyes, a beam splitter, a cuvette and a reference photodetector connected to the first input of a multichannel photometer, a spectrometric channel5. including a spectrograph directed at a cuvette and connected to a television transmitting tube whose output is connected to a television recorder; a polarimetric channel including a monochromator directed to a cuvette, a control input of which is connected to the output of the control unit, a polarizer and two recording photo detectors P and the S component of the fluorescence polarization, located at the output of the polarized radiation components, the outputs of which are connected to the second and third inputs of the multichannel photometer, the measurement channel -absorption, including a photodetector connected to the fourth input of a multi-channel photometer, the synchronization and control units, a television recorder and a multi-channel photometer connected to a computer highway, which is equipped with an integrator to increase the accuracy of measurement of the analytical parameters of fast processes. which is connected to the output of the television tube, and the output to the input of the television recorder, an additional voltage gating device on the photocathode, the input of which is connected to the output of the reference photodetector, and the output to the first input of the television tube, the modulator voltage control device, the output of which is connected to the second input of the television tube, and two control inputs to the outputs of the photometric receivers of the polarimetric channel, the comparator, the inputs of which are connected to the outputs of the photodetectors of the polarimetric channel, and the outputs - with the synchronization unit and the third input of the television tube.