CN111443074A - Automatic on-line pretreatment and Raman detection device and method thereof - Google Patents
Automatic on-line pretreatment and Raman detection device and method thereof Download PDFInfo
- Publication number
- CN111443074A CN111443074A CN202010391711.1A CN202010391711A CN111443074A CN 111443074 A CN111443074 A CN 111443074A CN 202010391711 A CN202010391711 A CN 202010391711A CN 111443074 A CN111443074 A CN 111443074A
- Authority
- CN
- China
- Prior art keywords
- injection pump
- phase extraction
- liquid
- pipeline
- detection
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
Landscapes
- Health & Medical Sciences (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)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention discloses an automatic on-line pretreatment and Raman detection device and a method thereof, relating to the field of biochemical automatic detection, wherein the device comprises: the sample pretreatment device is used for quantitatively extracting a sample to be detected: performing solid phase extraction on a sample to be detected to obtain a liquid to be detected; the spectrum detection device is used for quantitatively measuring the pretreated liquid to be detected and the Raman enhancing reagent to the detection pool, analyzing whether the liquid to be detected in the detection pool contains target components or not through Raman spectrum detection, and forming detection data; and the control system is used for controlling the sample pretreatment device and the spectrum detection device to circularly execute the following processes, and comprises: the automatic quantitative sample introduction, the automatic solid-phase extraction, the automatic spectrum detection and the data processing of the sample to be detected, thereby realizing the automatic on-line detection of the target component in the complex liquid matrix sample.
Description
Technical Field
The invention relates to the field of biochemical detection, in particular to an automatic online pretreatment and Raman detection device and method for target components in a complex liquid matrix sample.
Background
In recent years, with the development of worldwide economy and globalization, drug abuse is spreading increasingly, and the drug abuse poses serious threats to physical and mental health, social and public safety and the like of the masses. Abuse of illegal drugs has become a global problem, and has attracted high attention from governments of various countries. The Raman spectrum has the fingerprint characteristic of substances, has high sensitivity, can detect trace drug components, is widely applied to the detection of various drugs, and provides great help for drug enforcement and other works.
With the increasing awareness and capability of anti-reconnaissance of virus-involved personnel, the traditional information collection method is difficult to meet the requirement of virus banning work, the domestic sewage drug detection technology is gradually applied to the collection of information, but the detection means also mainly depends on a large-scale analytical instrument. The general method is that after sewage is sampled on site, the sewage is refrigerated at low temperature and sent to a professional laboratory as soon as possible for off-line ex-situ detection, which brings great influence on the collection range, real-time performance and accuracy of information.
In recent years, with the development of science and technology, such as the rapid development of the surface enhanced raman technology, the field rapid detection can be realized through portable raman, but due to the complex components of the sewage and the extremely low drug content, the sewage to be detected needs to be subjected to complex pretreatment by professionals, such as Solid Phase Extraction (SPE), purification and concentration of the sewage, and the like, so that the detection can be further performed. The pretreatment and detection of sewage are mainly completed by manual operation of professionals at present, and no automatic online detection device is provided.
Disclosure of Invention
One of the objectives of the present invention is to provide an automatic on-line pretreatment and raman detection apparatus for target components in a complex liquid matrix sample, which can automatically perform the whole processes of sample sampling, solid-phase extraction and surface enhanced raman detection, so as to realize the automatic on-line detection of target components such as drugs in the complex liquid matrix sample such as sewage.
In order to achieve the above object, the present invention provides an automatic on-line pretreatment and raman detection apparatus, comprising:
sample pretreatment device includes: pretreatment ration advances kind pipeline and device and solid-phase extraction device for the sample that awaits measuring is drawed to the ration: performing solid phase extraction on a sample to be detected to obtain a liquid to be detected;
the spectrum detection device is used for quantitatively measuring the pretreated liquid to be detected and the Raman enhancing reagent to the detection pool, analyzing whether the liquid to be detected in the detection pool contains target components or not through Raman spectrum detection, and forming detection data;
and the control system is used for controlling the sample pretreatment device and the spectrum detection device to circularly execute the following processes, and comprises: automatic quantitative sample introduction, automatic solid phase extraction, automatic spectrum detection and data processing of a sample to be detected.
Further, the pretreatment quantitative sample feeding pipeline and the device comprise a first injection pump, a first multi-position valve, a plurality of reversing valves, at least one electromagnetic valve and a connecting pipeline,
the injection pump is used for providing a power source and quantitative control for input and output of various liquids or air in the flow path;
the multi-position valve and the reversing valve are used for controlling the direction of the flow path;
the electromagnetic valve is used for controlling the on-off of the flow path;
the first injection pump is connected with the public end of the first multi-position valve or connected with the sample introduction end of the solid phase extraction device through a reversing valve and an electromagnetic valve, or connected with air or a cleaning solution storage device through the reversing valve, and the gating end of the first multi-position valve is connected with a sample introduction pipeline of a sample to be detected, a plurality of solvent storage devices, a waste liquid collection device and air.
Further, the plurality of reversing valves comprise a three-way valve A, a three-way valve B and a three-way valve C;
the three-way valve A is communicated with the air and cleaning liquid storage device and the three-way valve B;
the three-way valve B is communicated with the three-way valve A, the first injection pump and the three-way valve C;
the electromagnetic valve is arranged between the three-way valve B and the three-way valve C or between the three-way valve C and the sample introduction end of the solid phase extraction device.
Further, the solid phase extraction device comprises: an automatic replacing device of the solid phase extraction column, a positive pressure applying device, a position switching device, a collecting tank and a waste liquid tank,
the automatic solid-phase extraction column replacing device is used for automatically replacing the solid-phase extraction column below the positive pressure applying device when the detection of each sample is started;
the positive pressure applying device acts on an inlet of the solid phase extraction column to seal or open the inlet of the solid phase extraction column, a sample injection pipeline of the solid phase extraction device is arranged in the center of the positive pressure applying device, the inlet of the solid phase extraction column is in a sealed state or an open state, and the sample injection pipeline is communicated with the inlet of the solid phase extraction column;
the position switching device is used for switching a flow path of the outlet of the solid-phase extraction column, so that liquid at the outlet of the solid-phase extraction column is classified and collected to obtain liquid to be detected after pretreatment or waste liquid generated in the solid-phase extraction process.
The collecting tank is used for collecting the liquid subjected to primary treatment at the outlet of the solid-phase extraction column, a new reagent is added through a pipeline directly communicated with the collecting tank through the first multi-position valve, the liquid in the collecting tank is uniformly mixed through rapid vibration, and the liquid in the collecting tank is kept stand for layering to form liquid to be detected;
and the waste liquid pool is used for collecting waste liquid generated in the solid-phase extraction process and discharging the waste liquid into the waste liquid bin.
Further, the positive pressure applying device includes: linear guide, backup pad, hollow tube, spring unit and sealing washer, linear guide is vertical to be fixed in the backup pad, the outside of hollow tube with linear guide's slider is connected, the upper end of hollow tube is the introduction of the appearance end of solid phase extraction device, spring unit cup joints on the hollow tube, its up end with the slider is connected, and the lower terminal surface is provided with the sealing washer, linear guide drives the hollow tube up-and-down motion to the realization is sealed or is opened the import of solid phase extraction post.
Further, the spectrum detection device comprises a second injection pump, a second multi-position valve, a detection pool automatic replacement device, a detection reagent sampling device, a Raman enhanced reagent storage device and a spectrum detection sensor,
the second syringe pump is connected to a common port of a second multi-position valve,
the gating end of the second multi-position valve is at least connected with the liquid storage device to be detected, the detection reagent sampling device, the cleaning liquid storage device and the air,
the detection reagent sampling device is used for quantitatively sampling from the liquid storage device to be detected and sampling from various Raman enhancement reagent storage devices,
the spectrum detection sensor is used for performing spectrum detection on the mixed liquid of the liquid to be detected and the enhanced reagent stored in the detection pool;
the automatic detection pool replacing device is used for automatically replacing a new detection pool when each detection is started;
and the control system is used for carrying out data processing and analysis on the result of the spectrum detection.
Further, the Raman spectrum detection device also comprises a three-way valve D, a three-way valve E and a connecting pipeline thereof,
the three-way valve D is communicated with the collecting tank, the waste liquid collecting device and the three-way valve E;
the three-way valve E is communicated with the three-way valve D, the second multi-position valve and the detection reagent sampling device;
the detection reagent sampling device comprises a first sampling needle and a plurality of second sampling needles, wherein the first sampling needle is communicated with a three-way valve E and is used for quantitatively injecting liquid to be detected into a detection pool, and the second sampling needles are respectively communicated with different pipelines of a second multi-position valve and are used for quantitatively detecting a detection reagent into the detection pool from a corresponding enhanced reagent storage device.
Further, the detection reagent sampling device specifically includes:
a multi-dimensional transmission mechanism with lifting and rotating functions;
the fan-shaped turntable is fixedly arranged on a vertical Z axis of the multi-dimensional transmission mechanism and can rotate around the Z axis of the multi-dimensional transmission mechanism or move along the Z axis under the driving of the multi-dimensional transmission mechanism;
the sampling needles are fixed on the fan-shaped rotary table, needle heads of the sampling needles face downwards, and pipelines are connected above the sampling needles;
the plurality of enhanced reagent placing tables are used for placing various enhanced reagent storage devices respectively, the plurality of enhanced reagent placing tables are all positioned below the corresponding movement path of the sampling needle, and the sampling needle samples from various enhanced reagent storage devices through rotation and lifting;
and the plurality of needle head cleaning tanks are arranged below the movement path of the sampling needle, and the needle head of the sampling needle can be put into the cleaning liquid of the corresponding needle head cleaning tank to be soaked through rotation and lifting.
The technical effects are as follows:
the device for the automatic online pretreatment and Raman detection of the target components of the complex liquid matrix sample can automatically and circularly execute the whole processes of sampling, solid-phase extraction, Raman detection and detection data processing of the complex liquid matrix sample, thereby realizing the automatic online detection of the target components of the complex liquid matrix sample.
The invention also aims to provide an automatic on-line pretreatment and Raman detection method for target components in a complex liquid matrix sample, which comprises at least one of the following process control methods:
a quantitative sample introduction method;
sample and reagent mixing methods;
a pipeline cleaning and drying method;
a solid phase extraction column pressurizing and column passing method;
a method for drying a filter layer of a solid phase extraction column;
and (3) uniformly mixing liquid in a collecting pool.
Further, the quantitative sample injection method comprises the following steps: a pipeline communicated with the injection pump and led to the sample storage device through the multiway valve; controlling the injection pump to quantitatively suck the sample to the injection pump; a pipeline communicated with the injection pump and led to air through the multiway valve; controlling the injection pump to suck air and suck the liquid metered in the pipeline into the injection pump as much as possible; a conduit communicating the syringe pump to the target device; controlling the syringe pump to push a quantitative sample to the target device;
the sample and reagent mixing method comprises the following steps: a pipeline which is communicated with the injection pump to the sample storage device through the multiway valve and enables the outlet of the injection pump to be arranged downwards; controlling the injection pump to quantitatively suck the sample to the injection pump; a pipeline which is communicated with the multi-way valve and leads to the reagent storage device, and a pipeline which is communicated with the multi-way valve and leads to the injection pump; controlling the injection pump to quantitatively suck the reagent into the injection pump; a pipeline which is communicated with the multiway valve and leads to air, and a pipeline which is communicated with the multiway valve and leads to the injection pump; controlling the injection pump to suck air, sucking the liquid metered in the pipeline into the injection pump as much as possible, and mixing the sample and the reagent by air bubbles generated by the sucked air; a conduit communicating the syringe pump to the target device; controlling an injection pump to push a mixed solution of a sample and a reagent to a target device;
the pipeline cleaning and drying method comprises the following steps: a pipeline which is communicated with the multi-way valve and leads to the cleaning liquid storage device, and a pipeline which is communicated with the multi-way valve and leads to the injection pump; a pipeline for communicating the injection pump to the cleaning solution storage device and controlling the injection pump to suck a proper amount of cleaning solution; a pipeline for communicating the injection pump to the waste liquid storage device through the multi-way valve; controlling the injection pump to discharge the cleaning liquid in the pump into a waste liquid storage device for cleaning a pipeline between the injection pump and the multi-way valve; a pipeline communicated with the injection pump and communicated with air controls the injection pump to suck air; a pipeline for communicating the injection pump to the waste liquid storage device through the multi-way valve; controlling the injection pump to enable air in the pump to form rapid airflow to discharge liquid in the pipeline into a waste liquid storage device, and drying the pipeline between the injection pump and the multi-way valve;
the method for pressurizing and passing the solid phase extraction column comprises the following steps: mixing a sample to be detected and a reagent in an injection pump to form a mixed solution; injecting a mixed solution into the solid phase extraction column: opening an inlet of the solid-phase extraction column, communicating a pipeline for controlling a first injection pump to the inlet of the solid-phase extraction column, and slowly injecting the mixed solution in the first injection pump into the solid-phase extraction column; pressurizing a solid phase extraction column: sealing an inlet of the solid phase extraction column, closing a pipeline from a first injection pump to the inlet of the solid phase extraction column, and sucking air by the first injection pump; the pipeline is communicated with the injection pump to the solid-phase extraction column, and air in the first injection pump is slowly pressurized to the inlet of the solid-phase extraction column, so that the mixed liquid in the solid-phase extraction column slowly flows through the filtering filler layer in the middle of the solid-phase extraction column and flows out from the outlet of the solid-phase extraction column;
the drying method of the solid phase extraction column filter layer comprises the following steps: a pipeline for communicating the injection pump with air and controlling the injection pump to suck air; closing an input and output pipeline of the injection pump, and controlling the injection pump to pressurize air in the pump to a specified pressure; a pipeline communicated with the injection pump and communicated with the solid phase extraction column controls the injection pump to enable pressurized air in the injection pump to form pressurized airflow to flow through a filter layer of the solid phase extraction column at a high speed;
the liquid mixing method for the collecting pool comprises the following steps: storing liquid obtained by solid phase extraction into a collecting tank; adding a new reagent into the collection pool through a pipeline directly communicated with the collection pool through a first multi-position valve, uniformly mixing the liquid in the collection pool through rapid vibration, or uniformly mixing the liquid in the collection pool through air injected from the bottom of the collection pool and bubbles generated by the injected air; and standing and layering the liquid in the collecting tank, wherein the lower layer liquid is the liquid to be detected.
The automatic on-line pretreatment and Raman detection method is suitable for the automatic on-line pretreatment and Raman detection device, can provide quantitative sampling, sample and reagent mixing, prevents the pipeline cleaning and blow-drying of mixed pollution of different reagents in the pipeline, and controls the processes of pressurizing, column passing, blow-drying, liquid collection and the like of the solid phase extraction column, thereby accurately and quantitatively extracting the liquid to be detected in the whole pretreatment process and ensuring the detection precision.
Drawings
FIG. 1 is a schematic diagram of the functional modules of the automatic on-line pretreatment and Raman detection apparatus of the present invention;
FIG. 2 is a schematic structural view of an SPE column automatic exchange device of the present invention;
FIG. 3 is a schematic view of the structure of the positive pressure applying apparatus of the present invention;
FIG. 4 is a schematic view of the structure of the sampling device for detecting reagent of the present invention.
Detailed Description
To further illustrate the various embodiments, the invention provides the accompanying drawings. The accompanying drawings, which are incorporated in and constitute a part of this disclosure, illustrate embodiments of the invention and, together with the description, serve to explain the principles of the embodiments. Those skilled in the art will appreciate still other possible embodiments and advantages of the present invention with reference to these figures. Elements in the figures are not drawn to scale and like reference numerals are generally used to indicate like elements.
The invention will now be further described with reference to the accompanying drawings and detailed description.
As shown in fig. 1, the invention discloses an automatic on-line pretreatment and raman detection device, which comprises a control system, a sample pretreatment device and a spectrum detection device. The device comprises a sample pretreatment device, a sample pretreatment device and a sample pretreatment device, wherein the sample pretreatment device comprises a multi-position valve A, a three-way valve B, a three-way valve C, an electromagnetic valve, an injection pump A, a positive pressure applying device, an SPE column automatic replacing device, a position switching device, a collecting pool, a waste liquid pool, a three-way valve D and the like; the spectrum detection device, in particular to an enhanced Raman spectrum detection device, comprises a multi-position valve B, a three-way valve E, a detection pool, an automatic detection pool replacement device, a Raman detector, a detection reagent sampling device and the like.
The control system controls the sample pretreatment device and the enhanced Raman spectrum detection device to complete the full-automatic processing process from sample sampling, solid phase extraction to enhanced Raman spectrum detection.
The multi-position valve A, B is used to automatically switch between the various reagents used to satisfy the needs of different assay procedures and methods. For example, in this embodiment, a plurality of reagents such as a PH solution, a eluent, an eluent, and an extract are applied in the sample sampling process, and a plurality of reagents such as a raman enhancement reagent are applied in the raman detection process.
In this embodiment, air is introduced into the sample pre-treatment device and the enhanced raman spectroscopy detection device from different locations for generating a rapid air flow to evacuate the liquid in the line.
In this embodiment, use the pure water as the washing liquid, the pure water inserts sample pretreatment device and reinforcing raman spectrum detection device from different positions for wash the pipeline.
In the sample pretreatment process of the embodiment, a sample to be tested, various solvents and reagents can share one section of the same pipeline, and the pipeline is cleaned and emptied, so that cross contamination of the solvents and the reagents in the shared pipeline can be reduced, and the test precision is influenced.
The three-way valve A, the three-way valve B, the three-way valve C, the three-way valve D and the three-way valve E are used for controlling the flow direction of the flow path, the electromagnetic valve is used for controlling the on-off of the flow path, and the injection pump A and the injection pump B are used for providing power sources and quantitative control for the input and output of various liquids or air in the flow path.
In this embodiment, the pipeline connection relationship of the sample pre-treatment device is as follows:
the multi-position valve A comprises a central pipeline and a plurality of gating pipelines, the central pipeline is communicated with the three-way valve C, and the gating pipelines are respectively communicated with a sample to be detected, a PH solution, an eluent, an extraction liquid, other reagents, air A, a waste liquid bin and a collecting pool;
the three-way valve A is communicated with air B, purified water and the three-way valve B;
the three-way valve B is communicated with the three-way valve A, the injection pump A and the electromagnetic valve;
the electromagnetic valve is communicated with the three-way valve B and the three-way valve C;
the three-way valve C is communicated with the electromagnetic valve, the central pipeline of the multi-position valve A and the positive pressure applying device of the solid phase extraction device.
The solenoid valve can also be arranged between the three-way valve C and the positive pressure applying device, the three-way valve C is directly connected with the three-way valve B, and the pipeline on-off of the injection pump A, the solid phase extraction device and the multi-position valve A can be controlled by controlling the three-way valve B, the three-way valve C and the solenoid valve.
The control system controls a multi-position valve A, a three-way valve B, a three-way valve C, an electromagnetic valve, an injection pump A and the like, so that the effects of: quantitatively extracting a sample to be tested, and mixing the sample with a quantitative reagent (such as a PH solution or a specific reagent) to form a mixed solution.
Air a, air B and air C behind are all air, which is used to identify the different locations of the air access lines.
In this embodiment, the waste liquid bin is provided with a negative pressure device for collecting all waste liquids generated by the sampling device, the solid phase extraction device and the raman detection device in the working process.
As shown in fig. 2 and fig. 3, in this embodiment, the SPE column automatic replacement device includes an SPE column tray and an SPE column feeding mechanism, and the SPE column feeding mechanism takes the SPE column (solid phase extraction column) from the SPE column tray and recovers the used SPE column.
SPE post feed mechanism is mainly by electric putter 13, separation blade 12, carousel 14 and linear guide 11 are constituteed, the draw-in groove that SPE post 15 was sent the carousel to linear guide with electric putter's mode has been adopted according to SPE post 15 characteristics, electric putter 13 moves SPE post 15 directly over under linear guide 11's the drive, then electric putter stretches into SPE post 15 with the axle, linear guide 11 drives SPE post 15 and moves together and send SPE post 15 to the draw-in groove of carousel 14. Separation blade 12's effect is limiting displacement, and separation blade 12 cooperation is installed the photoelectric switch on linear guide 11 and is played spacing effect to deliver SPE post 15 to appointed station, SPE post 15 on the original station simultaneously falls in the storehouse of collecting at carousel pivoted in-process.
When liquid passes through the SPE column, if the liquid cannot pass through a packing (a filter layer) in the SPE column by the gravity of the liquid, a pressure needs to be applied to the outside to promote the liquid to pass through the SPE column, so a positive pressure application device of the SPE column is needed. The positive pressure applying device is arranged above the inlet of the SPE column, and the inlet of the SPE column can be sealed and separated through a conventional lifting machine. The pipeline is installed at the center of positive pressure applying device, and positive pressure applying device can also make liquid enter into SPE post when exerting positive pressure.
As shown in fig. 3, the positive pressure applying apparatus is mainly composed of a linear guide 30, a support plate 31, a baffle 32, a hollow tube 33, a spring assembly 34, a seal ring 35, and the like. The pipeline of the flow path system is connected on a hollow pipe 33, various reagents can pass through the SPE column 15 in sequence through the hollow pipe 33, the linear guide rail 30 can drive the hollow pipe 33 to move up and down, the position determination is realized by matching the blocking piece 32 with the photoelectric switch, when the SPE column 15 needs to be replaced or the inlet at the upper end of the SPE column 15 needs to be opened, the hollow pipe 33 moves up, when liquid needs to pass through the column, the hollow pipe 33 moves down, the upper end (inlet) of the SPE column 15 and the hollow pipe 33 are in a tightly-jointed airtight state through the compression of the spring assembly 34 and the sealing of the sealing ring 35, and the liquid can smoothly pass through the SPE column 15 without liquid leakage.
The liquid flowing out of the SPE column 15 needs to be classified and collected to obtain the liquid to be detected. A position switching mechanism is arranged at the outlet at the lower end of the SPE column 15, the position switching mechanism mainly comprises a buffer pool 36 and a linear guide rail 37, and two chambers are arranged on the buffer pool 36: collecting pit and waste liquid pond, under the condition that the liquid that flows from SPE post 15 lower extreme is the waste liquid, linear guide 37 can take buffer pool 36 motion to aim at SPE post 15 lower extreme with the waste liquid pond and during the waste liquid can flow into the waste liquid storehouse like this, waste liquid in the waste liquid pond finally can be inhaled in the waste liquid storehouse, linear guide 37 just takes buffer pool 36 motion to aim at the collecting pit the lower extreme of SPE post 15 when needing to collect the liquid of waiting to survey, the location of collecting pit is realized by separation blade and photoelectric switch on the linear guide. The miniature vibrating motor is installed to the bottom of collecting pit, can drive the collecting pit and vibrate, improves mixing efficiency and cleaning efficiency between the liquid in the collecting pit.
In this embodiment, the detection reagent sampling device includes a multi-dimensional movement device capable of lifting and rotating, the multi-dimensional movement device is provided with a plurality of sampling needles, and different sampling needles are used for extracting different reagents and injecting the reagents into the detection cell. The reagent comprises a Raman enhancement reagent, a liquid to be detected and the like.
As shown in fig. 4, the detection reagent sampling device adopts a turntable structure to realize the absorption of reagents, and in order to prevent mutual contamination among reagents such as a raman enhancement reagent 1, a raman enhancement reagent 2, a liquid to be detected and the like, three different sampling needles are adopted to respectively complete the sampling of the reagents, and the reagents are added into a detection pool. When the reagent is added, the position of the detection pool is fixed, so that the rotating mechanism needs to be controlled to respectively add the liquid sucked by different sampling needles into the detection pool, the space utilization rate can be improved by adopting a turntable structure, and the volume of the device is reduced.
As shown in fig. 4, in the present embodiment, the detection reagent sampling device mainly comprises a reagent bottle supporting plate 38, a reagent bottle mounting plate 39, a first raman-enhanced reagent bottle mounting table 40, a sampling needle 41, a sector turntable 42, a Z-axis linear sliding table 43, a gear 44, a gear motor 45, a waste liquid tank 46, a purified water mounting table 47, a second raman-enhanced reagent bottle mounting table 48, and the like. The working principle is that the first Raman-enhanced reagent bottle mounting platform 40, the second Raman-enhanced reagent bottle mounting platform 48 and the purified water mounting platform 47 are all mounted on the reagent bottle mounting plate 39. Auxiliary agent and pure water are respectively placed on the corresponding mounting tables, three sampling needles 41 are mounted on the fan-shaped turntable, and the end parts of the sampling needles 41 are connected with pipelines. The gear motor drives the gear to rotate the sector rotary disk so as to rotate the sampling needle 41 to the corresponding reagent bottle. The Z-axis linear sliding table 43 drives the sampling needle 41 to move up and down, the needle head of the sampling needle 41 is inserted into a corresponding reagent bottle, and quantitative reagent can be sucked into the detection pool through the mutual matching of the injection pump and the valve. The excess reagent and the final waste solution after washing drawn by the sampling needle 41 can be discharged to a waste solution tank 46, and a liquid outlet is provided in the waste solution tank 46 to discharge the waste solution to a final waste solution bin.
The detection pool is usually a quartz glass tube which has the characteristics of stable physical and chemical properties, high transparency and the like, and is convenient for the Raman detector to acquire Raman signals of liquid in the tube.
The automatic detection replacing device comprises a multi-shaft motion mechanism and a detection pool tray, wherein the multi-shaft motion mechanism automatically replaces a detection pool in the detection pool tray to a designated position to wait for adding a liquid to be detected and a detection reagent.
The device can continuously obtain the sample to be detected from the complex liquid matrix sample, and detect the target component of the sample to be detected, thereby realizing the on-line automatic monitoring of the target component of the complex liquid matrix sample.
In order to obtain the detection data of the target components of the complex liquid matrix sample in real time and the operation condition of the monitoring device, the device is also provided with a wireless communication module, and the control system can upload the detection data and the operation data to the server through the wireless communication module.
The invention discloses an automatic on-line pretreatment and Raman detection method for target components in a complex liquid matrix sample, which comprises the following steps:
sample pretreatment: quantitatively extracting a sample to be detected; performing solid phase extraction on a sample to be detected to obtain a liquid to be detected;
and (3) a spectrum detection process: injecting an enhanced reagent into the liquid to be detected, analyzing target components in the liquid to be detected through spectrum detection, and outputting detection data;
and (3) data processing: and the detection data is locally stored and analyzed and/or uploaded to a server for storage and analysis.
In this embodiment, on-line automatic detection is performed by using sewage as a complex liquid matrix sample and using drug components such as heroin and methamphetamine in the sewage as target components.
(1) The system controls the injection pump A, the three-way valve B, the electromagnetic valve, the three-way valve C and the multi-position valve A to be switched to ① ports, and quantitatively takes the sewage to be measured into the injection pump A.
(2) And the system controls the injection pump A, the three-way valve B, the electromagnetic valve, the three-way valve C and the multi-position valve A to be switched to ② ports, and a fixed amount of PH solution is taken into the injection pump A.
(3) In order to ensure that liquid in a pipeline between the multi-position valve A and the injection pump is sucked into the injection pump A as much as possible and reduce the residual liquid on the pipeline, the injection pump A, the three-way valve B, the electromagnetic valve, the three-way valve C and the multi-position valve A are controlled to be switched to ⑦ ports, so that a proper amount of air is sucked rapidly and high-speed airflow is formed in the passing pipeline, and the residual liquid on the pipeline is taken away as much as possible.
In order to await measuring sewage and PH solution misce bene, can be installed the syringe pump export down, when quick inhaled air, the bubble is inhaled from the bottom of mixing liquid, can be with mixed liquid misce bene.
(4) The new SPE column was automatically replaced. And the control system controls the SPE column automatic replacement device to automatically replace a new SPE column after the old SPE column is unloaded.
(5) The mixture was injected into the SPE column. The system control position switching device places the waste liquid pool under the SPE column, separates the positive pressure applying device from the upper end of the SPE column, and then controls the injection pump A, the three-way valve B, the electromagnetic valve and the three-way valve C to slowly inject the mixed liquid in the injection pump A into the SPE column through a pipeline arranged at the center of the positive pressure applying device.
(6) The SPE column was pressurized. The device is applyed to system control malleation is sealed SPE post upper end, then control syringe pump A, three-way valve B, solenoid valve, three-way valve C, slowly pressurize the air in the syringe pump A to the SPE post on for mixed liquid in the SPE post slowly flows through the filtration packing layer in the middle of the SPE post, and falls into the waste liquid pond from the export of SPE post, is collected by the waste liquid storehouse at last. The filter layer may have a substance to be measured concentrated thereon.
(7) And introducing a quick airflow to discharge the residual liquid in the pipeline. Because more liquid is remained on the pipeline and the SPE column filter layer, after air can be sucked in by controlling the injection pump A, the three-way valve B and the three-way valve A, the injection pump A, the three-way valve B, the electromagnetic valve and the three-way valve C are controlled again, the air in the injection pump is quickly injected into the SPE column to form high-speed airflow, and therefore residual liquid can be taken away as far as possible.
(8) And introducing pressurized airflow to blow dry the residual liquid in the filter layer. Because the liquid that remains on the SPE post filter layer easily produces the influence to the detection effect, control three-way valve B and solenoid valve intercommunication after through control syringe pump A, three-way valve B, inhaled air B earlier to close the solenoid valve. Then, air in the injection pump is pressurized through the injection pump A, after air pressure with certain pressure is formed, the electromagnetic valve is opened instantly, so that pressurized air flow flows through the filtering layer of the SPE column at high speed, and residual liquid in the filtering layer can be blown dry as much as possible after the step is circulated for many times.
(9) The purified water in the injection pump can be discharged into a waste liquid bin at a high speed by controlling the injection pump A, the three-way valve B and the three-way valve A to quickly suck the purified water into the injection pump A, then controlling the injection pump A, the three-way valve B, the electromagnetic valve, the three-way valve C and the multi-position valve A to switch to ⑧ ports, and cleaning the pipeline by utilizing high-speed water flow.
(10) The pipeline after cleaning may have more liquid remaining, can be through controlling syringe pump A, three-way valve B, three-way valve A after the air of inhaling, and then control syringe pump A, three-way valve B, solenoid valve, three-way valve C, the multiposition valve switches over to ⑧ mouths, discharges the ⑧ mouths of the multiposition valve to the waste liquid storehouse with the air in the syringe pump fast to can take away the raffinate as far as possible.
(11) In order to ensure that the quantitative leacheate in a flow path from the multi-position valve A to the injection pump A is effectively sucked into the injection pump A, the multi-position valve A can be switched to ⑦ ports after the quantitative leacheate is taken, so that the proper amount of air can be quickly sucked, and the quantitative leacheate can be guaranteed to be sucked into the injection pump A as far as possible.
(12) The SPE cartridge was injected with the eluent. And (5) slowly injecting the eluent into the SPE column.
(13) The eluate is passed through the column under pressure. And (4) slowly pressurizing the leacheate by adopting the method in the step (6), so that the leacheate slowly passes through the column and is finally collected by a waste liquid bin.
(14) And (4) draining residual liquid on the pipeline and the SPE column filter layer as far as possible by adopting the methods similar to the steps (7) and (8).
(15) Cleaning the pipeline by adopting the similar method of the steps (9) and (10) and discharging the residual liquid in the pipeline as much as possible.
(16) A similar method to that of step (11) can be used to take a fixed amount of eluent from port ④ of the multi-position valve to syringe pump A.
(17) Eluent was injected into the SPE column. And (3) controlling the position switching device to switch the collection pool to be right below the SPE column, and then slowly injecting the eluent into the SPE by adopting a method similar to the step (5).
(18) The eluent is pressurized and passed through the column. The eluent can be slowly pressurized by the method in the step 6, and then falls into a collection pool from the lower part of the SPE column after the eluent slowly passes through the column.
(19) And (4) draining residual liquid on the pipeline and the SPE column filter layer as far as possible by adopting the methods similar to the steps (7) and (8).
(20) Cleaning the pipeline by adopting the similar method of the steps (9) and (10) and discharging the residual liquid in the pipeline as much as possible.
(21) A similar method as in step (11) can be used to withdraw a fixed amount of extract from port ⑤ of the multi-position valve into syringe pump A.
(22) And (3) injecting the extraction liquid into the collection pool, and slowly injecting the quantitative extraction liquid in the injection pump A into the collection pool by controlling the injection pump A, the three-way valve B, the electromagnetic valve, the three-way valve C and the multi-position valve A to switch to ⑨ ports.
(23) And (4) draining the residual liquid in the pipeline to a collecting tank as far as possible by adopting a method similar to the step (7).
(24) In order to ensure that the eluent and the extract liquid in the collecting pool are effectively mixed uniformly, the liquid in the collecting pool can be quickly and uniformly mixed by vibration through a vibration device, or the injection pump B can be controlled to be switched to ① ports of a multi-position valve B to suck proper amount of air firstly, then the injection pump B is controlled to be switched to ③ ports of the multi-position valve B, the air in the injection pump is quickly injected from the bottom of the collecting pool through a three-way valve E and a three-way valve D, and the liquid in the collecting pool is uniformly mixed through bubbles.
(25) Standing for layering. And standing the collecting tank for a period of time, and layering the liquid in the uniformly mixed collecting tank to obtain the lower layer liquid as the liquid to be detected.
(26) The detection pool is automatically replaced. And controlling the automatic detection pool replacing device to unload the old detection pool and automatically load the old detection pool into the new detection pool.
(27) And controlling the injection pump B, the three-way valve E and the three-way valve D, cutting the injection pump B to ③ ports, taking a proper amount of lower-layer liquid from the bottom of the collection pool to a pipeline between the three-way valve E and the multi-position valve B, and then controlling the three-way valve E and the detection reagent sampling device to quantitatively inject the liquid to be detected in the middle section of the pipeline into the detection pool from the No. ① needle point port, and discharging the redundant liquid to be detected as waste liquid.
(28) And controlling a detection reagent sampling device to sequentially take quantitative Raman enhancement reagent 1 and Raman enhancement reagent 2 to the detection pool through ② and ③ needle tips.
(29) And (4) uniformly mixing the liquid in the detection cell. In order to ensure that the liquid to be detected and the Raman enhancing reagent which are sequentially added into the detection pool are effectively mixed, the detection pool can be rapidly vibrated by the vibration device, so that the liquid in the pool is uniformly mixed.
(30) And (4) detecting by using a Raman spectrum. And controlling the Raman spectrometer to automatically acquire and identify Raman spectrum signals of the liquid to be detected in the detection pool, and uploading the detection result to the cloud server for recording and analyzing, thereby completing an automatic online in-situ detection process.
(31) In order to prevent the liquid to be detected, nano particles, auxiliary agents and the like remained on the detection reagent sampling device from influencing the next detection result, the pipeline and the needle point can be cleaned by adopting a method similar to the steps (9) and (10), and the lifting and rotating mechanism can be controlled to soak the needle point in the cleaning tank.
(32) The above steps are automatically repeated when a new detection process is required.
The automatic on-line pretreatment and Raman detection device can automatically and circularly execute the whole processes of quantitative sampling, solid-phase extraction, enhanced Raman detection and data processing of the complex liquid matrix sample, thereby realizing the automatic on-line detection of the target component in the complex liquid matrix sample.
The method of the automatic on-line pretreatment and Raman detection device is applied to the automatic on-line pretreatment and Raman detection device, can provide quantitative sampling, sample and reagent mixing, prevents the mixed pollution of different reagents in pipelines, such as pipeline cleaning and blow-drying, and controls the processes of pressurization column passing, blow-drying, liquid collection and the like of the SPE column, thereby accurately and quantitatively extracting the liquid to be detected in the whole pretreatment process and ensuring the detection precision.
While the invention has been particularly shown and described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. An automatic on-line pretreatment and Raman detection device, comprising:
sample pretreatment device includes: the pretreatment quantitative sample introduction pipeline and device and the solid phase extraction device are used for quantitatively extracting a sample to be detected; performing solid phase extraction on a sample to be detected to obtain a liquid to be detected;
the spectrum detection device is used for quantitatively measuring the pretreated liquid to be detected and the enhanced reagent to the detection pool, analyzing whether the liquid to be detected in the detection pool contains target components or not through Raman spectrum detection, and forming detection data;
and the control system is used for controlling the sample pretreatment device and the spectrum detection device to circularly execute the following processes, and comprises: automatic quantitative sample introduction, automatic solid phase extraction, automatic spectrum detection and data processing of a sample to be detected.
2. The automated on-line pre-processing and raman detection apparatus of claim 1, wherein:
the pretreatment quantitative sample feeding pipeline and the device comprise a first injection pump, a first multi-position valve, a plurality of reversing valves, at least one electromagnetic valve and a connecting pipeline,
the injection pump is used for providing a power source and quantitative control for input and output of various liquids or air in the flow path;
the multi-position valve and the reversing valve are used for controlling the direction of the flow path;
the electromagnetic valve is used for controlling the on-off of the flow path;
the first injection pump is connected with the public end of the first multi-position valve or connected with the sample introduction end of the solid phase extraction device through a reversing valve and an electromagnetic valve, or connected with air or a cleaning solution storage device through the reversing valve, and the gating end of the first multi-position valve is connected with a sample introduction pipeline of a sample to be detected, a plurality of solvent storage devices, a waste liquid collection device and air.
3. The automatic on-line preprocessing and raman detection apparatus of claim 2, wherein: the plurality of reversing valves comprise a three-way valve A, a three-way valve B and a three-way valve C;
the three-way valve A is communicated with the air and cleaning liquid storage device and the three-way valve B;
the three-way valve B is communicated with the three-way valve A, the first injection pump and the three-way valve C;
the electromagnetic valve is arranged between the three-way valve B and the three-way valve C or between the three-way valve C and the sample introduction end of the solid phase extraction device.
4. The automated on-line pre-processing and raman detection apparatus of claim 3, wherein:
the solid phase extraction device comprises: an automatic replacing device of the solid phase extraction column, a positive pressure applying device, a position switching device, a collecting tank and a waste liquid tank,
the automatic solid-phase extraction column replacing device is used for automatically replacing the solid-phase extraction column below the positive pressure applying device when the detection of each sample is started;
the positive pressure applying device acts on an inlet of the solid phase extraction column, the inlet of the solid phase extraction column is sealed or opened, a sample injection pipeline of the solid phase extraction device is arranged in the center of the positive pressure applying device, and the sample injection pipeline is communicated with the inlet of the solid phase extraction column; when the inlet of the solid phase extraction column is opened, liquid flows into the solid phase extraction column through a sample introduction pipeline; when the inlet of the solid phase extraction column is sealed, pressurized air pushes the liquid to flow through the solid phase extraction column;
the position switching device is used for switching a flow path of an outlet of the solid-phase extraction column so as to classify and collect liquid from the outlet of the solid-phase extraction column to obtain pretreated liquid to be detected or waste liquid generated in the solid-phase extraction process;
the collecting tank is used for collecting the liquid subjected to primary treatment at the outlet of the solid-phase extraction column, a new reagent is added through a pipeline directly communicated with the collecting tank through the first multi-position valve, the liquid in the collecting tank is uniformly mixed through rapid vibration, and the liquid in the collecting tank is kept stand for layering to form liquid to be detected;
and the waste liquid pool is used for collecting waste liquid generated in the solid-phase extraction process and discharging the waste liquid into the waste liquid bin.
5. The automated on-line pre-processing and raman detection apparatus of claim 4, wherein: the positive pressure applying device includes: linear guide, backup pad, hollow tube, spring unit and sealing washer, linear guide is vertical to be fixed in the backup pad, the outside of hollow tube with linear guide's slider is connected, the upper end of hollow tube is the introduction of the appearance end of solid phase extraction device, spring unit cup joints on the hollow tube, its up end with the slider is connected, and the lower terminal surface is provided with the sealing washer, linear guide drives the hollow tube up-and-down motion to the realization is sealed or is opened the import of solid phase extraction post.
6. The automatic on-line preprocessing and raman detection apparatus of claim 2, wherein: the spectrum detection device comprises a second injection pump, a second multi-position valve, a detection pool automatic replacement device, a detection reagent sampling device, an enhanced reagent storage device and a spectrum detection sensor,
the second syringe pump is connected to a common port of a second multi-position valve,
the gating end of the second multi-position valve is at least connected with the liquid storage device to be detected, the detection reagent sampling device, the cleaning liquid storage device and the air,
the detection reagent sampling device is used for quantitatively sampling from the liquid storage device to be detected and sampling from various enhanced reagent storage devices,
the spectrum detection sensor is used for performing spectrum detection on the mixed liquid of the liquid to be detected and the enhanced reagent stored in the detection pool;
the automatic detection pool replacing device is used for automatically replacing a new detection pool when each detection is started;
and the control system is used for carrying out data processing and analysis on the result of the spectrum detection.
7. The automated on-line pre-processing and raman detection apparatus of claim 6, wherein: the spectrum detection device also comprises a three-way valve D, a three-way valve E and a connecting pipeline thereof,
the three-way valve D is communicated with the collecting tank, the waste liquid collecting device and the three-way valve E;
the three-way valve E is communicated with the three-way valve D, the second multi-position valve and the detection reagent sampling device;
the detection reagent sampling device comprises a first sampling needle and a plurality of second sampling needles, wherein the first sampling needle is communicated with a three-way valve E and is used for quantitatively injecting liquid to be detected into a detection pool, and the second sampling needles are respectively communicated with different pipelines of a second multi-position valve and are used for quantitatively detecting a detection reagent into the detection pool from a corresponding enhanced reagent storage device.
8. The automated on-line pre-processing and raman detection apparatus of claim 7, wherein: the detection reagent sampling device specifically comprises:
a multi-dimensional transmission mechanism with lifting and rotating functions;
the fan-shaped turntable is fixedly arranged on a vertical Z axis of the multi-dimensional transmission mechanism and can rotate around the Z axis of the multi-dimensional transmission mechanism or move along the Z axis under the driving of the multi-dimensional transmission mechanism;
the sampling needles are fixed on the fan-shaped rotary table, needle heads of the sampling needles face downwards, and pipelines are connected above the sampling needles;
the plurality of enhanced reagent placing tables are used for placing various enhanced reagent storage devices respectively, the plurality of enhanced reagent placing tables are all positioned below the corresponding movement path of the sampling needle, and the sampling needle samples from various enhanced reagent storage devices through rotation and lifting;
and the plurality of needle head cleaning tanks are arranged below the movement path of the sampling needle, and the needle head of the sampling needle can be put into the cleaning liquid of the corresponding needle head cleaning tank to be soaked through rotation and lifting.
9. An automatic on-line pretreatment and Raman detection method is characterized in that: the automatic on-line pretreatment and Raman detection device applied to any one of claims 4-5, wherein the method comprises at least one of the following process control methods:
a quantitative sample introduction method;
sample and reagent mixing methods;
a pipeline cleaning and drying method;
a solid phase extraction column pressurizing and column passing method;
a method for drying a filter layer of a solid phase extraction column;
and (3) uniformly mixing liquid in a collecting pool.
10. The automated on-line pre-processing and raman detection method of claim 9, wherein:
the quantitative sample injection method comprises the following steps: a pipeline communicated with the injection pump and led to the sample storage device through the multiway valve; controlling the injection pump to quantitatively suck the sample to the injection pump; a pipeline communicated with the injection pump and led to air through the multiway valve; controlling the injection pump to suck air and suck the liquid metered in the pipeline into the injection pump as much as possible; a conduit communicating the syringe pump to the target device; controlling the syringe pump to push a quantitative sample to the target device;
the sample and reagent mixing method comprises the following steps: a pipeline which is communicated with the injection pump to the sample storage device through the multiway valve and enables the outlet of the injection pump to be arranged downwards; controlling the injection pump to quantitatively suck the sample to the injection pump; a pipeline which is communicated with the multi-way valve and leads to the reagent storage device, and a pipeline which is communicated with the multi-way valve and leads to the injection pump; controlling the injection pump to quantitatively suck the reagent into the injection pump; a pipeline which is communicated with the multiway valve and leads to air, and a pipeline which is communicated with the multiway valve and leads to the injection pump; controlling the injection pump to suck air, sucking the liquid metered in the pipeline into the injection pump as much as possible, and mixing the sample and the reagent by air bubbles generated by the sucked air; a conduit communicating the syringe pump to the target device; controlling an injection pump to push a mixed solution of a sample and a reagent to a target device;
the pipeline cleaning and drying method comprises the following steps: a pipeline which is communicated with the multi-way valve and leads to the cleaning liquid storage device, and a pipeline which is communicated with the multi-way valve and leads to the injection pump; a pipeline for communicating the injection pump to the cleaning solution storage device and controlling the injection pump to suck a proper amount of cleaning solution; a pipeline for communicating the injection pump to the waste liquid storage device through the multi-way valve; controlling the injection pump to discharge the cleaning liquid in the pump into a waste liquid storage device for cleaning a pipeline between the injection pump and the multi-way valve; a pipeline communicated with the injection pump and communicated with air controls the injection pump to suck air; a pipeline for communicating the injection pump to the waste liquid storage device through the multi-way valve; controlling the injection pump to enable air in the pump to form rapid airflow to discharge liquid in the pipeline into a waste liquid storage device, and drying the pipeline between the injection pump and the multi-way valve;
the method for pressurizing and passing the solid phase extraction column comprises the following steps: mixing a sample to be detected and a reagent in an injection pump to form a mixed solution; injecting a mixed solution into the solid phase extraction column: opening an inlet of the solid-phase extraction column, communicating a pipeline for controlling a first injection pump to the inlet of the solid-phase extraction column, and slowly injecting the mixed solution in the first injection pump into the solid-phase extraction column; pressurizing a solid phase extraction column: sealing an inlet of the solid phase extraction column, closing a pipeline from a first injection pump to the inlet of the solid phase extraction column, and sucking air by the first injection pump; the pipeline is communicated with the injection pump to the solid-phase extraction column, and air in the first injection pump is slowly pressurized to the inlet of the solid-phase extraction column, so that the mixed liquid in the solid-phase extraction column slowly flows through the filtering filler layer in the middle of the solid-phase extraction column and flows out from the outlet of the solid-phase extraction column;
the drying method of the solid phase extraction column filter layer comprises the following steps: a pipeline for communicating the injection pump with air and controlling the injection pump to suck air; closing an input and output pipeline of the injection pump, and controlling the injection pump to pressurize air in the pump to a specified pressure; a pipeline communicated with the injection pump and communicated with the solid phase extraction column controls the injection pump to enable pressurized air in the injection pump to form pressurized airflow to flow through a filter layer of the solid phase extraction column at a high speed;
the liquid mixing method for the collecting pool comprises the following steps: storing liquid obtained by solid phase extraction into a collecting tank; adding a new reagent into the collection pool through a pipeline directly communicated with the collection pool through a first multi-position valve, uniformly mixing the liquid in the collection pool through rapid vibration, or uniformly mixing the liquid in the collection pool through air injected from the bottom of the collection pool and bubbles generated by the injected air; and standing and layering the liquid in the collecting tank, wherein the lower layer liquid is the liquid to be detected.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010391711.1A CN111443074B (en) | 2020-05-11 | 2020-05-11 | Automatic on-line pretreatment and Raman detection device and method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010391711.1A CN111443074B (en) | 2020-05-11 | 2020-05-11 | Automatic on-line pretreatment and Raman detection device and method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111443074A true CN111443074A (en) | 2020-07-24 |
| CN111443074B CN111443074B (en) | 2021-08-31 |
Family
ID=71656778
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010391711.1A Active CN111443074B (en) | 2020-05-11 | 2020-05-11 | Automatic on-line pretreatment and Raman detection device and method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111443074B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112683887A (en) * | 2021-03-19 | 2021-04-20 | 苏州长光华医生物医学工程有限公司 | Device and method for discharging and drying waste liquid of chemiluminescence instrument |
| CN113156146A (en) * | 2021-04-12 | 2021-07-23 | 上海禹视科技有限公司 | Full-automatic high-throughput cell analysis equipment and detection method thereof |
| CN113238009A (en) * | 2021-05-13 | 2021-08-10 | 新疆农垦科学院 | A solid-phase extraction device for food detects |
| CN113238065A (en) * | 2021-04-19 | 2021-08-10 | 吴志洪 | Full-automatic detection device and detection method for trace drugs in sewage |
| CN113375980A (en) * | 2021-05-08 | 2021-09-10 | 上海环境卫生工程设计院有限公司 | Online sampling system and sampling method for wet garbage anaerobic digestion material |
| CN113617057A (en) * | 2021-08-11 | 2021-11-09 | 成都理工大学 | Series column solid phase extraction system and operation method thereof |
| CN114034652A (en) * | 2021-11-11 | 2022-02-11 | 浙江大学 | Automatic on-line extraction and determination device for active ingredients in sediment or soil |
| CN115574871A (en) * | 2022-12-09 | 2023-01-06 | 津海威视技术(天津)有限公司 | Quick screening system for solid waste of port |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101590333A (en) * | 2009-06-23 | 2009-12-02 | 东南大学 | Array solid-phase extraction device based on nanofiber absorption |
| CN101601938A (en) * | 2009-07-20 | 2009-12-16 | 中国检验检疫科学研究院 | A kind of solid phase chromatography pressurizes and liquid-adding device with independent |
| CN102166433A (en) * | 2011-01-21 | 2011-08-31 | 北京莱伯泰科仪器有限公司 | Multichannel parallel automatic solid phase extraction device |
| CN201983963U (en) * | 2011-01-26 | 2011-09-21 | 南京工业大学 | Pretreatment device and system of online Raman spectrometer |
| CN103920306A (en) * | 2014-04-15 | 2014-07-16 | 东南大学 | Pressurization device of nanofiber solid phase extraction column |
| CN103933754A (en) * | 2014-04-01 | 2014-07-23 | 北京润东仪器厂 | Automatic solid phase extraction equipment |
| CN104225958A (en) * | 2014-08-29 | 2014-12-24 | 康国华 | Pressurization solid phase extraction device |
| CN204269554U (en) * | 2014-12-04 | 2015-04-15 | 华东理工大学 | For the micro-fluidic array load sample device that In-situ SERS detects |
| CN205139018U (en) * | 2015-10-27 | 2016-04-06 | 厦门市普识纳米科技有限公司 | Surface reinforcing raman of integrated solid -phase extraction post detects chip |
| CN107469406A (en) * | 2017-09-08 | 2017-12-15 | 中国热带农业科学院分析测试中心 | One kind pressurization solid-phase extraction device |
| CN208171864U (en) * | 2018-03-30 | 2018-11-30 | 赛默科技便携式分析仪器有限公司 | Semiautomatic plant and detection device based on Solid Phase Extraction |
| CN208568601U (en) * | 2018-07-28 | 2019-03-01 | 厦门谱识科仪有限公司 | A kind of Raman spectrum pretreating device |
| CN109916700A (en) * | 2019-03-26 | 2019-06-21 | 华东理工大学 | A kind of small-sized Solid Phase Extraction and solid phase spectra detect aggregate device |
| CN111089856A (en) * | 2019-12-26 | 2020-05-01 | 厦门大学 | Post-processing method for extracting Raman spectrum weak signal |
-
2020
- 2020-05-11 CN CN202010391711.1A patent/CN111443074B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101590333A (en) * | 2009-06-23 | 2009-12-02 | 东南大学 | Array solid-phase extraction device based on nanofiber absorption |
| CN101601938A (en) * | 2009-07-20 | 2009-12-16 | 中国检验检疫科学研究院 | A kind of solid phase chromatography pressurizes and liquid-adding device with independent |
| CN102166433A (en) * | 2011-01-21 | 2011-08-31 | 北京莱伯泰科仪器有限公司 | Multichannel parallel automatic solid phase extraction device |
| CN201983963U (en) * | 2011-01-26 | 2011-09-21 | 南京工业大学 | Pretreatment device and system of online Raman spectrometer |
| CN103933754A (en) * | 2014-04-01 | 2014-07-23 | 北京润东仪器厂 | Automatic solid phase extraction equipment |
| CN103920306A (en) * | 2014-04-15 | 2014-07-16 | 东南大学 | Pressurization device of nanofiber solid phase extraction column |
| CN104225958A (en) * | 2014-08-29 | 2014-12-24 | 康国华 | Pressurization solid phase extraction device |
| CN204269554U (en) * | 2014-12-04 | 2015-04-15 | 华东理工大学 | For the micro-fluidic array load sample device that In-situ SERS detects |
| CN205139018U (en) * | 2015-10-27 | 2016-04-06 | 厦门市普识纳米科技有限公司 | Surface reinforcing raman of integrated solid -phase extraction post detects chip |
| CN107469406A (en) * | 2017-09-08 | 2017-12-15 | 中国热带农业科学院分析测试中心 | One kind pressurization solid-phase extraction device |
| CN208171864U (en) * | 2018-03-30 | 2018-11-30 | 赛默科技便携式分析仪器有限公司 | Semiautomatic plant and detection device based on Solid Phase Extraction |
| CN208568601U (en) * | 2018-07-28 | 2019-03-01 | 厦门谱识科仪有限公司 | A kind of Raman spectrum pretreating device |
| CN109916700A (en) * | 2019-03-26 | 2019-06-21 | 华东理工大学 | A kind of small-sized Solid Phase Extraction and solid phase spectra detect aggregate device |
| CN111089856A (en) * | 2019-12-26 | 2020-05-01 | 厦门大学 | Post-processing method for extracting Raman spectrum weak signal |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112683887A (en) * | 2021-03-19 | 2021-04-20 | 苏州长光华医生物医学工程有限公司 | Device and method for discharging and drying waste liquid of chemiluminescence instrument |
| CN112683887B (en) * | 2021-03-19 | 2021-06-04 | 苏州长光华医生物医学工程有限公司 | Device and method for discharging and drying waste liquid of chemiluminescence instrument |
| CN113156146A (en) * | 2021-04-12 | 2021-07-23 | 上海禹视科技有限公司 | Full-automatic high-throughput cell analysis equipment and detection method thereof |
| CN113156146B (en) * | 2021-04-12 | 2024-06-07 | 上海禹视科技有限公司 | Full-automatic high-flux cell analysis equipment and detection method thereof |
| CN113238065A (en) * | 2021-04-19 | 2021-08-10 | 吴志洪 | Full-automatic detection device and detection method for trace drugs in sewage |
| CN113375980A (en) * | 2021-05-08 | 2021-09-10 | 上海环境卫生工程设计院有限公司 | Online sampling system and sampling method for wet garbage anaerobic digestion material |
| CN113238009A (en) * | 2021-05-13 | 2021-08-10 | 新疆农垦科学院 | A solid-phase extraction device for food detects |
| CN113617057A (en) * | 2021-08-11 | 2021-11-09 | 成都理工大学 | Series column solid phase extraction system and operation method thereof |
| CN113617057B (en) * | 2021-08-11 | 2022-05-17 | 成都理工大学 | Series column solid phase extraction system and operation method thereof |
| CN114034652A (en) * | 2021-11-11 | 2022-02-11 | 浙江大学 | Automatic on-line extraction and determination device for active ingredients in sediment or soil |
| CN114034652B (en) * | 2021-11-11 | 2023-03-21 | 浙江大学 | Automatic on-line extraction and determination device for active ingredients in sediment or soil |
| CN115574871A (en) * | 2022-12-09 | 2023-01-06 | 津海威视技术(天津)有限公司 | Quick screening system for solid waste of port |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111443074B (en) | 2021-08-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111443074B (en) | Automatic on-line pretreatment and Raman detection device and method thereof | |
| WO2018233324A1 (en) | Water quality analyzer and water quality analysis method | |
| CN105891391A (en) | Automatic sampling device | |
| CN109444070A (en) | Oil content all automatic measurement instrument in water | |
| CN108732135A (en) | A kind of blood cell and analysis of protein device | |
| CN205352808U (en) | Online enrichment and separation device of trace silver in sea water | |
| CN111624277A (en) | Full-automatic comprehensive sample pretreatment instrument | |
| KR101448911B1 (en) | Apparatus for Pretreating Analytes Using Magnetic Particles, Apparatus and Method for Detecting Analytes Using the Same | |
| CN106404965B (en) | A kind of automatic pretreating device for polyaromatic hydrocarbon samples in PM2.5 | |
| CN101592568B (en) | Sailing multi-channel membrane filtration suspended particle sampling system | |
| CN201444157U (en) | Full-automatic infrared oil tester | |
| CN104422780B (en) | A kind of protein express-analysis pick-up unit based on the totally-enclosed system of micro-fluidic chip | |
| JP2006119136A (en) | Solid phase extracting apparatus and method therefor | |
| CN106771293B (en) | Automatic clinical chemistry analyzer with allocation unit | |
| CN109294890A (en) | Microbial fermentation multi-component online analysis device and use method thereof | |
| CN108548879B (en) | Automatic change rapid detection equipment | |
| CN203216848U (en) | Sample injection device of atomic fluorescence spectrometer | |
| CN110794157A (en) | Tester for anionic surfactant in water | |
| CN207366412U (en) | A kind of separate type sample pre-treatment device with discharging to connection function | |
| CN109916817A (en) | A kind of liquid relief and analytical equipment | |
| CN207366410U (en) | A kind of integrated form sample pre-treatment device with discharging to connection function | |
| CN206594116U (en) | It is a kind of to be used for the automatic pretreating device of polyaromatic hydrocarbon samples in PM2.5 | |
| CN211235899U (en) | Tester for anionic surfactant in water | |
| CN106442026B (en) | Seven-station sampling rotary table type heavy metal enrichment sampling and pretreatment system based on nano functional material | |
| CN110715882B (en) | Proportioning device for determining dilution ratio of ferrographic experiment based on oil granularity |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Xue Wendong Inventor after: Guo Hongxu Inventor after: Shi Jian Inventor after: Zeng Yongming Inventor before: Xue Wendong Inventor before: Shi Jian Inventor before: Guo Hongxu Inventor before: Zeng Yongming |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |