CN208766081U - High throughput micro-scale automatic sample handling system - Google Patents

High throughput micro-scale automatic sample handling system Download PDF

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CN208766081U
CN208766081U CN201821486969.4U CN201821486969U CN208766081U CN 208766081 U CN208766081 U CN 208766081U CN 201821486969 U CN201821486969 U CN 201821486969U CN 208766081 U CN208766081 U CN 208766081U
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way valve
micro
sample
handling system
quantitative loop
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胡立刚
孙玉贞
刘念
王丁
王丁一
刘丽红
何滨
江桂斌
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Research Center for Eco Environmental Sciences of CAS
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Abstract

A kind of high throughput micro-scale automatic sample handling system, the automatic sample handling system include sample cell, syringe pump, six-way valve, quantitative loop, four-way valve etc., so that sample is inhaled into quantitative loop from sample cell by the switching of six-way valve and are transferred in sp-ICPMS again.The utility model with sp-ICPMS method by being combined, it can not only realize and quickly big flux detection is carried out to the size distribution and number concentration of nano particle in sample and the concentration of metal ions of dissolution, efficiency of transmission is improved simultaneously, and reducing reagent consumption improves the quality of data;The system operatio is simple, quickly, and sample throughput is big, efficiency of transmission is high, amount of samples is few, stability and reproducible, reduces sample loss, reduces cross contamination;Nano particle and concentration of metal ions in on-line checking micro-example are realized with sp-ICPMS combination.

Description

High throughput micro-scale automatic sample handling system
Technical field
The utility model belongs to nano particle technical field of analytical instruments, and in particular to a kind of high throughput micro-scale automatic sampling System.
Background technique
With being constantly progressive for production technology, requirement of the people to analysis test is quasi- in sample size, analytical cycle, data True property, reduction job costs and raising working efficiency etc. are proposed higher standard and the request.Individual particle inductive coupling Plasma-Mass Spectroscopy (sp-ICPMS) is analytical technology fast-developing in recent years, mainly for detection of the number of nano particle in sample Amount and size distribution.Sp-ICPMS by acquiring data under TRA mode, can size distribution to nano particle in solution and Nano particle number concentration is analyzed.After metal nanoparticle enters ICPMS, single metal nanoparticle is in the extremely short time It is interior to generate extremely strong pulse strength signal.Nano particle generate pulse signal quantity and sample in nano particle number concentration at than Example, it is proportional to nanoparticle mass/granularity that nano particle generates pulse signal strength.Due to this method have it is highly sensitive and The advantages such as low detection limits have been widely used in the ionic state of multiple element and the measurement of particle, while sp-ICPMS at present As a kind of method of emerging stabilization Accurate Determining molecule, it is applied not only to nano particle in water sample and detects, be also applied to Nano particle detection in animal tissue.
However, sp-ICPMS method is all made of peristaltic pump sample introduction at present, take considerable time and manpower, simultaneously because wriggling The limitation for pumping sample introduction, causes to be difficult to detect the lower micro-example of concentration, greatly limits it in environment and biology neck The application in domain.Therefore, there is an urgent need to develop a kind of high efficiency and time conservation while can be used for detecting nanoparticles partial size in micro-example With the automatic sample handling system of concentration.
Utility model content
In view of this, the main purpose of the utility model is to provide a kind of high throughput micro-scale automatic sample handling system, to It at least is partially solved at least one of above-mentioned technical problem.
To achieve the goals above, as the one aspect of the utility model, provide a kind of high throughput micro-scale automatically into Sample system, including sample cell, sample injection unit, switch unit and automatic control unit, it is characterised in that:
Sample injection unit includes the feed unit of sample introduction needle and control sample introduction needle movement;
Switch unit include six-way valve, quantitative loop, the first micro-injection pump, the second micro-injection pump, the first four-way valve and Second four-way valve;Wherein, the six-way valve includes six feeder connections, including " load " position and the gear of " injection " position two, is determined Amount ring both ends are connected on two opposite feeder connections of the six-way valve;When six-way valve is in " load position ", with into The connected feeder connection of sample needle be connected with the feeder connection of connection quantitative loop one end, the feeder connection of the connection quantitative loop other end and Connect the feeder connection conducting of the first four-way valve, the feeder connection connecting with ICPMS and the feeder connection for connecting the second four-way valve Conducting, the first four-way valve for being separately connected the first micro-injection pump and waste collection container at this time switch to and the first micro-injection The second four-way valve for pumping the gear of conducting, and being separately connected the second micro-injection pump and pure water container then switches to and pure water The gear of container conducting;When six-way valve is in " injection position ", the feeder connection that is connected with sample introduction needle with connect the first four-way valve Feeder connection conducting, connect quantitative loop one end feeder connection with connection ICPMS feeder connection be connected, connect quantitative loop it is another The feeder connection of one end is connected with the feeder connection of the second four-way valve of connection, and the first four-way valve is switched at this time holds with wastewater collection The gear of device conducting, and the second four-way valve then switches to the gear be connected with the second micro-injection pump;
Automatic control unit is automatically brought into operation for realizing whole device.
As the other side of the utility model, a kind of individual particle inductive coupling plasma mass spectrometry detection system is additionally provided System, which is characterized in that the individual particle inductive coupling plasma mass spectrometry detection system uses high throughput micro-scale as described above certainly Dynamic sampling system carrys out sample introduction.
Based on the above-mentioned technical proposal it is found that under the automatic sample handling system of the utility model at least has compared with the existing technology State one of beneficial effect:
(1) easy to operate, controllability and stability are good, and amount of samples is few, and analysis time is short, and sample absorption is few;
(2) efficiency of transmission, sensitivity can be improved in system at low flow rates, quick and precisely to detect the samples such as environment and biology The partial size and concentration of middle metal nanoparticle provide technological means;
(3) can by the combination of software realization and sp-ICP MS and the size distribution to nano particle in micro-example and Number concentration carries out online high-throughput detection.
Detailed description of the invention
When Figure 1A and 1B is that the six-way valve in the automatic sample handling system of the utility model is in load position and injection position respectively Flow path schematic diagram;
Fig. 2 is the movement decomposition and ICPMS analysis method decomposition diagram of the automatic sample handling system of the utility model;
Fig. 3 is the original signal map of the ultrapure water between the sample of ICPMS detection;
Fig. 4 be the utility model automatic sample handling system using sample introduction different in flow rate (5 μ L/min (A), 10 μ L/min (B), 15 μ L/min (C), 20 μ L/min (D), 50 μ L/min (E) and 300 μ L/min (F)), ICPMS measures Au+Ion (0.2 μ g/L) Original signal map;
Fig. 5 is the automatic sample handling system of the utility model using sample introduction different in flow rate, the 30nm AuNPs of ICPMS measurement The number concentration of (0.048 μ g/L) and the efficiency of transmission scatter plot for calculating acquisition;
Fig. 6 A and 6B are sp-ICPMS measurement Au respectively+The original of (0.2 μ g/L) and 30nm AuNPs (0.048 μ g/L) solution Beginning signal graph;
Fig. 7 A~7C is 30nm (0.048 μ g/L), 50nm (0.100 μ g/L), the different grains of 100nm (0.530 μ g/L) respectively The grain size distribution of diameter AuNPs.
Specific embodiment
Technical term used in the utility model is technical term well known in the art, such as " high throughput " and " micro- Amount ", uses the definition that technical field of analytical instruments is general, use will not influence the protection scope of the utility model.
The utility model discloses a kind of high throughput micro-scale automatic sample handling systems, realize height for being combined with sp-ICPMS Flux quickly detects the concentration and size distribution and concentration of metal ions of the nano particle in micro-example, the automatic sampling system System is analyzed using continuous automatic sampling, quickly and accurately, improves working efficiency and reduce operating cost as essential characteristic, with sp- ICPMS combination may be implemented quick and precisely to detect the quantity of nano particle in micro low concentration sample and partial size, realize The efficiency of sp-ICPMS maximizes.
Specifically, the automatic sample handling system of the utility model includes sample cell, sample injection unit, switch unit and automatic control Unit processed, in which:
Sample injection unit includes the feed unit of sample introduction needle and control sample introduction needle movement, and the cleaning list of cleaning sample introduction pipeline Member;
Switch unit include six-way valve, quantitative loop, the first micro-injection pump, the second micro-injection pump, the first four-way valve and Second four-way valve;Wherein, which includes six feeder connections, including " load " position and the gear of " injection " position two, quantitative Ring both ends are connect respectively in two opposite feeder connections of six-way valve, such as on the 1st and the 4th feeder connection (midfeather 2);When When six-way valve is in " load position ", the feeder connection being connected with sample introduction needle is connected with the feeder connection of connection quantitative loop one end, even The feeder connection for connecing the quantitative loop other end is connected with the feeder connection of the first four-way valve of connection, the feeder connection connecting with ICPMS It is connected with the feeder connection of the second four-way valve of connection, is separately connected the first of the first micro-injection pump and waste collection container at this time Four-way valve switches to the gear be connected with the first micro-injection pump, and is separately connected the second micro-injection pump and pure water container Second four-way valve then switches to the gear be connected with pure water container;When six-way valve is in " injection position ", it is connected with sample introduction needle Feeder connection with connection the first four-way valve feeder connection be connected, connection quantitative loop one end feeder connection with connect ICPMS Feeder connection conducting, connect the quantitative loop other end feeder connection with connect the second four-way valve feeder connection be connected, at this time First four-way valve switches to the gear be connected with waste collection container, and the second four-way valve then switches to and the second micro-injection pump The gear of conducting;
Automatic control unit is automatically brought into operation for realizing whole device.
Wherein, cleaning unit is used to clean sample introduction pipeline after sample introduction, when cleaning unit works, by the compacted of ICPMS Cleaning solution is injected into service sink by dynamic pump, and six-way valve is in " injection position ", and quantitative loop is connected with the second micro-injection pump, sample introduction Needle is moved in service sink, and eluent is drawn into the pipeline including quantitative loop by the first micro-injection pump, by the flushing of pipeline Completely, it re-injects into waste liquid pool.
Wherein, sample cell includes the PFA bottle, 24 orifice plates and/or 64 orifice plates of 10mL.
Wherein, micro-injection pump is high precision micro syringe pump, and material is quartz and PFA, accurately controls flow velocity in 1- Between 1000 μ L/min, especially can accurately coutroi velocity it change by 1 μ L/min.
Wherein, six-way valve is the six-way valve of PFA material.
Wherein, it is 0.5mm that quantitative loop, which includes internal diameter, and 50,100,150,250 μ L of capacity and internal diameter are 1.0mm, and capacity is The capillary of 1mL.
Wherein, the control software used in automatic control unit, can be automatic by this by ESI software for ESI SC software Sampling system is linked up with ICPMS instrument, realizes on-line checking.
Wherein, sample introduction needle, all pipelines and quantitative loop are PFA material.
A kind of individual particle inductive coupling plasma mass spectrometry detection system is also disclosed in the utility model, the individual particle inductance Coupled Plasma-Mass Spectroscopy detection system is using high throughput micro-scale automatic sample handling system as described above come sample introduction.
In one embodiment, the automatic sample handling system of the utility model includes following analysis step when work:
Step 1: six-way valve is in " load position ", and quantitative loop is connected with the first micro-injection pump, and sample introduction needle is moved on sample Side, sample is drawn into quantitative loop by the first micro-injection pump, while the second micro-injection pump injects carrier fluid with constant speed Into ICPMS;
Step 2: six-way valve is " injection position ", and quantitative loop is connected with the second micro-injection pump, and the first micro-injection pump will manage Into waste liquid pool, the sample in quantitative loop is injected into extra sample injection in road by the second micro-injection pump with constant speed In ICPMS;
Step 3: six-way valve is " injection position ", and quantitative loop is connected with the second micro-injection pump, and sample introduction needle is moved to service sink In, eluent is drawn into the pipeline including quantitative loop by the first micro-injection pump, is re-injected into waste liquid pool, by flushing of pipeline Completely;
Step 4: six-way valve is " injection position ", and quantitative loop is connected with the second micro-injection pump, and the second micro-injection pump is by sample After product at the uniform velocity shift ICPMS onto, continues for carrier fluid to be pushed into ICPMS, signal is eluted.
In yet another embodiment, the automatic sample handling system of the utility model operation comprising the following steps:
Step 1:ICPMS apparatus selection automatic sampling mode, analysis method start, and ESI software obtains ICPMS software instruction Control autosampler starts to sample;
Step 2: autosampler six-way valve is " load position ", and quantitative loop is connected with the first micro-injection pump, and sample introduction needle is moved Move above sample, sample is drawn into quantitative loop by the first micro-injection pump, while the second micro-injection pump by carrier fluid with perseverance Constant speed degree is injected into ICPMS;
Step 3: autosampler six-way valve is " injection position ", and quantitative loop is connected with the second micro-injection pump, and first is micro Syringe pump is by the extra sample injection in pipeline into waste liquid pool, and the second micro-injection pump is by the sample in quantitative loop with constant Speed injection is into ICPMS;
Step 4: autosampler six-way valve is " injection position ", and quantitative loop is connected with the second micro-injection pump, and sample introduction needle is moved It moves into service sink, eluent is drawn into pipeline by the first micro-injection pump, is re-injected into waste liquid pool, and flushing of pipeline is done Only;
Step 5: autosampler six-way valve is " injection position ", and quantitative loop is connected with the second micro-injection pump, and second is micro Syringe pump continues after sample injection to ICPMS for carrier fluid to be pushed into ICPMS, signal is eluted.
ICPMS is obtained by optimization sample extraction time, signal stabilization time, signal acquisition time, elution time simultaneously Obtain optimal on-line checking analysis method.
To keep the purpose of this utility model, technical solution and advantage apparent clear, below in conjunction with specific embodiment, and join According to attached drawing, the utility model is described in further detail.
In order to reduce sample absorption, sample introduction needle, transfer conduit and quantitative loop are PFA material.The system can control The load and conveying of sample, sample introduction flow velocity can be adjusted in 1~1000 μ L/min, be especially suitable for micro and submicrosample biography It is defeated, while efficiency of transmission can achieve 90% or more at low flow rates.The system operatio simple and stable, is easily assembled to, while can To greatly improve sample throughput, the sample analysis work that can not be completed originally in the short time is rapidly completed.
As shown in Figure 1A and 1B, automatic sample handling system is mainly by a six-way valve, two syringe pumps (syringe pumps 1, injection Pump 2, i.e. two micro-injection pumps) connect the composition such as two four-way valves, sample cell and quantitative loop.When six-way valve is " load position ", Quantitative loop is connected with syringe pump 1, and sample introduction needle is inserted into sample, and sample is injected pump 1 and is drawn into quantitative loop, while syringe pump 2 are injected into carrier fluid in ICPMS with constant speed;After sample is inhaled into quantitative loop, six-way valve is switched to " injection position ", fixed Amount ring is connected with syringe pump 2, and for syringe pump 1 by the extra sample injection in pipeline into waste liquid pool, syringe pump 2 will be in quantitative loop Sample be injected into ICPMS with constant speed;After extra sample is discharged syringe pump 1, sample introduction needle is moved in service sink, Eluent is drawn into pipeline and is re-injected into waste liquid pool, syringe pump 2 continues after sample injection to ICPMS in quantitative loop Carrier fluid is pushed into ICPMS, sample signal elutes.
As shown in Fig. 2, autosampler by sample extraction, sample transfer, sample acquisition, elute sample from sample cell In be loaded into ICPMS with constant flow rate;And ICPMS then establishes the analysis method of autosampler, is mentioned by setting sample It takes the time, stablize time, analysis time and elution time, acquisition signal completes analysis.
As shown in figure 3, a pure water sample is measured after analyzing each sample, it is noiseless between sample to ensure.
As shown in figure 4,5 μ L/min, 10 μ L/min, 15 μ L/min, 20 μ L/min, 50 μ L/min and 300 μ L/ are respectively adopted The Au of the measurement of rate of flow same concentrations of min+Standard solution, it can be seen from the figure that under different sample introduction flow velocitys, ICPMS signal Intensity is consistent, shows that autosampler under different in flow rate, can keep stable flow velocity sample introduction.
As shown in figure 5, using the gold nano grain in (NIST8012, the U.S.) 30nm, sample introduction at different flow rates, according to reason By granule density and detection particle number concentration calculate it is different in flow rate under efficiency of transmission, from figure 5 it can be seen that in 5 μ L/ Under the low flow velocity of min, efficiency of transmission can achieve 92.9% efficiency of transmission, show automatic sample handling system under micro-sampling, Can with high efficiency of transmission by sample input into ICPMS, sample loss is few;The flow velocity of 20 μ L/min or more again, transmission effect Rate is 23.7%, and with the increase of flow velocity, efficiency of transmission is gradually decreased.
As shown in Figure 6 A and 6B, Au is measured using automatic sample handling system combination sp-ICPMS+(0.2 μ g/L) and 30nm The original signal figure of AuNPs (0.048 μ g/L) solution, as can be seen from the figure gold ion due to its be uniformly distributed in the solution because This produces stable signal strength, and the signal of gold nano grain then forms high-intensitive pulse signal.
As figs. 7 a to 7 c, after nano particle enters plasma, the bigger nanoparticle of grain diameter is generated Signal response is also bigger, and signal strength relationship proportional to corresponding nano particle diameter, using automatic sample handling system It is combined sp-ICPMS measurement 30nm (0.048 μ g/L), 50nm (0.100 μ g/L) and 100nm (0.530 μ g/L) different-grain diameter AuNPs particle, grain size distribution is as figs. 7 a to 7 c.
Explanation is further elaborated to the utility model below with reference to embodiment.
Embodiment 1
Reagent: AuNPs solution (50mg/L, the U.S. of 30nm (NIST8012, the U.S., 48mg/L), 50nm, 100nm NanoComposix);Solubilised state gold ion standard solution be Au (I) standard solution (1000mg/L, 1.5mol/L HCl medium, National non-ferrous metal and electronic material Institute of Analysis);ICP-MS tunes liquid (1 μ g/L:Li, Co, Y, Tl, Ce and Ba, An Jie Human relations, 2%HNO3Medium), ultrapure water (18.2M Ω/cm, U.S. Millpore)
Instrument: 8800ICP-MS (Agilent company of the U.S.);ICPMS instrument parameter: acquisition mode TRA;Residence time For 3ms;Acquisition time is 60s;RF power is 1550W;RF matching is 1.8W;Sampling depth is 10mm;Flow rate of carrier gas is 1L/ min;Being atomized room temperature is 2 DEG C;Compensation current amount is 1L/min.Liquid argon (purity > 99.99%), ultrapure water (DDW, 18M Ω .cm) Milli-Q Advantage A10 system (Millipore company, the U.S.) is come from;Ultrasound Instrument (city of Kunshan's Ultrasound Instrument Device Co., Ltd).
The dilution of gold ion standard solution is diluted to the nanometer of 0.1,0.2,0.5,1.0,2.0 μ g/L, AuNPs solution respectively Amounts of particles concentration is diluted to 1.7 × 105/mL (30nm), 8.3 × 105/mL (50nm), 5.7 × 104/mL respectively (100nm).Ultrasound 15min after the sample dilution constant volume of nano particle, guarantees that it is uniformly dispersed, and the same day prepares, same day measurement.
Using tuning liquid tuning instrument before measurement, make instrumental sensitivity highest.When measuring sample, increase between each sample One ultrapure water sample guarantees noiseless between sample.Under TRA mode, ultrapure water, the Au of 0.1 μ g/L are measured+Solution and The AuNPs solution of 30nm (1.7 × 105/mL)197Au time signal scanning figure can be seen that AuNPs letter from Fig. 6 A and 6B It number is pulse signal, and the signal strength of Au+ solution is small and uniform.It can be received using autosampler combination sp-ICPMS The analysis detection of rice solution.
Under TRA mode, solubilised state Au+Ion and high purity water generate stable197Au signal value, and individual particle AuNPs is then It generates197Au particle pulse signal.The standard of entire data is calculated using the iterative method of the propositions such as Mitrano and Turoiniemi Deviation, using 5 times of standard deviations and average value as the signal distinguishing boundary value of nano particle and ion, obtain nano particle signal and Ion signal.Measure the Au of various concentration+Ion standard solution obtains the standard curve of solion, according to standard curve and The particle diameter distribution (as figs. 7 a to 7 c) of the transmission efficiency calculation nano particle of measurement, measurement nano particles distribution with TEM is measured consistent.
Particular embodiments described above has carried out into one the purpose of this utility model, technical scheme and beneficial effects Step is described in detail, it should be understood that the foregoing is merely specific embodiment of the utility model, are not limited to this reality With novel, within the spirit and principle of the utility model, any modification, equivalent substitution, improvement and etc. done should all include It is within the protection scope of the utility model.

Claims (10)

1. a kind of high throughput micro-scale automatic sample handling system, including sample cell, sample injection unit, switch unit and automatic control unit, It is characterized by:
Sample injection unit includes the feed unit of sample introduction needle and control sample introduction needle movement;
Switch unit includes six-way valve, quantitative loop, the first micro-injection pump, the second micro-injection pump, the first four-way valve and second Four-way valve;Wherein, the six-way valve includes six feeder connections, including " load " position and the gear of " injection " position two, quantitative loop Both ends are connected on two opposite feeder connections of the six-way valve;When six-way valve is in " load position ", with sample introduction needle Connected feeder connection is connected with the feeder connection of connection quantitative loop one end, connects feeder connection and the connection of the quantitative loop other end The feeder connection of first four-way valve is connected, and is connected with the feeder connection of ICPMS connection with the feeder connection of the second four-way valve of connection, The first four-way valve for being separately connected the first micro-injection pump and waste collection container at this time is switched to leads with the first micro-injection pump Logical gear, and the second four-way valve for being separately connected the second micro-injection pump and pure water container then switches to and pure water container The gear of conducting;When six-way valve is in " injection position ", the feeder connection that is connected with sample introduction needle with connect leading to for the first four-way valve The conducting of road entrance, the feeder connection for connecting quantitative loop one end are connected with the feeder connection of connection ICPMS, connect the quantitative loop other end Feeder connection with connection the second four-way valve feeder connection be connected, the first four-way valve is switched at this time leads with waste collection container Logical gear, and the second four-way valve then switches to the gear be connected with the second micro-injection pump;
Automatic control unit is automatically brought into operation for realizing whole device.
2. high throughput micro-scale automatic sample handling system according to claim 1, which is characterized in that the sample cell includes 10mL PFA bottle, 24 orifice plates and/or 64 orifice plates.
3. high throughput micro-scale automatic sample handling system according to claim 1, which is characterized in that the syringe pump is high-precision Micro-injection pump, material are quartz and PFA, can accurate coutroi velocity between 1-1000 μ L/min, flow velocity can be controlled accurately System is changed by 1 μ L/min.
4. high throughput micro-scale automatic sample handling system according to claim 1, which is characterized in that the six-way valve is PFA material The six-way valve of matter.
5. high throughput micro-scale automatic sample handling system according to claim 1, which is characterized in that the quantitative loop includes internal diameter For 0.5mm, the capillary of capacity 50,100,150 or 250 μ L or the capillary that internal diameter is 1.0mm, capacity is 1mL.
6. high throughput micro-scale automatic sample handling system according to claim 1, which is characterized in that the switch unit further includes One cleaning unit, the cleaning unit after sample introduction for cleaning the sample introduction pipeline.
7. high throughput micro-scale automatic sample handling system according to claim 6, which is characterized in that the cleaning unit work When, cleaning solution is injected into service sink by the peristaltic pump of ICPMS, six-way valve is in " injection position ", and quantitative loop is micro with second Syringe pump is connected, and sample introduction needle is moved in service sink, and eluent is drawn into the pipeline including quantitative loop by the first micro-injection pump In, the flushing of pipeline is clean, it re-injects into waste liquid pool.
8. high throughput micro-scale automatic sample handling system according to claim 1, which is characterized in that in the automatic control unit The control software used can have been coupled the automatic sample handling system with ICPMS instrument by ESI software for ESI SC software Come, realizes on-line checking.
9. high throughput micro-scale automatic sample handling system according to claim 1, which is characterized in that the sample introduction needle, Suo Youguan Road and quantitative loop are PFA material.
10. a kind of individual particle inductive coupling plasma mass spectrometry detection system, which is characterized in that described individual particle inductive coupling etc. from Sub- Mass Spectrometer Method system is using high throughput micro-scale automatic sample handling system as described in any one of claim 1 to 9 come sample introduction.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110057968A (en) * 2019-05-28 2019-07-26 上海安杰环保科技股份有限公司 A kind of full-automatic permanganate index analyzer of modularization
CN113495164A (en) * 2020-04-02 2021-10-12 中国科学院深圳先进技术研究院 Continuous liquid sampling system and control method thereof
CN113495095A (en) * 2020-04-03 2021-10-12 重庆超硅半导体有限公司 Silicon wafer metal impurity detection sample protection device and silicon wafer metal impurity detection method
CN114018678A (en) * 2021-11-26 2022-02-08 中国科学院地理科学与资源研究所 Device and method for purifying and separating copper isotopes in soil
WO2022127928A1 (en) * 2020-12-19 2022-06-23 北京大学 Automatic sample feeding system

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110057968A (en) * 2019-05-28 2019-07-26 上海安杰环保科技股份有限公司 A kind of full-automatic permanganate index analyzer of modularization
CN113495164A (en) * 2020-04-02 2021-10-12 中国科学院深圳先进技术研究院 Continuous liquid sampling system and control method thereof
CN113495164B (en) * 2020-04-02 2023-11-21 中国科学院深圳先进技术研究院 Continuous liquid sample injection system and control method thereof
CN113495095A (en) * 2020-04-03 2021-10-12 重庆超硅半导体有限公司 Silicon wafer metal impurity detection sample protection device and silicon wafer metal impurity detection method
WO2022127928A1 (en) * 2020-12-19 2022-06-23 北京大学 Automatic sample feeding system
CN114018678A (en) * 2021-11-26 2022-02-08 中国科学院地理科学与资源研究所 Device and method for purifying and separating copper isotopes in soil

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