CN109270192A - Pretreating device, method and purposes for the detection of aquatic products sulfa antibiotics - Google Patents

Pretreating device, method and purposes for the detection of aquatic products sulfa antibiotics Download PDF

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CN109270192A
CN109270192A CN201811461724.0A CN201811461724A CN109270192A CN 109270192 A CN109270192 A CN 109270192A CN 201811461724 A CN201811461724 A CN 201811461724A CN 109270192 A CN109270192 A CN 109270192A
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mobile phase
valves
interfaces
valve
aquatic products
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CN109270192B (en
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李涛
石亚东
徐枫
徐兆安
虞霖
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Hydrology And Water Resources Monitoring Center Of Taihu River Basin (water Environment Monitoring Center Of Taihu River Basin)
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Hydrology And Water Resources Monitoring Center Of Taihu River Basin (water Environment Monitoring Center Of Taihu River Basin)
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G01N30/08—Preparation using an enricher
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G01N30/14—Preparation by elimination of some components
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/24—Automatic injection systems
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/26—Conditioning of the fluid carrier; Flow patterns
    • G01N30/28—Control of physical parameters of the fluid carrier
    • G01N30/32—Control of physical parameters of the fluid carrier of pressure or speed
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/26—Conditioning of the fluid carrier; Flow patterns
    • G01N30/28—Control of physical parameters of the fluid carrier
    • G01N30/34—Control of physical parameters of the fluid carrier of fluid composition, e.g. gradient
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/62—Detectors specially adapted therefor
    • G01N30/72—Mass spectrometers
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G01N2030/062—Preparation extracting sample from raw material
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G01N2030/067—Preparation by reaction, e.g. derivatising the sample
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/26—Conditioning of the fluid carrier; Flow patterns
    • G01N30/28—Control of physical parameters of the fluid carrier
    • G01N30/32—Control of physical parameters of the fluid carrier of pressure or speed
    • G01N2030/324—Control of physical parameters of the fluid carrier of pressure or speed speed, flow rate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/80—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in fisheries management
    • Y02A40/81—Aquaculture, e.g. of fish

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Abstract

The present invention relates to aquatic product qualities to monitor field, more particularly to the monitoring field of antibiotic in aquatic products, more particularly relate to pretreating device, method and the purposes detected for aquatic products sulfa antibiotics.Sulfa antibiotics on-line preconcentration is used for by foundation, the on-line solid phase extraction of purification elutes pretreating device and the on-line preconcentration based on the device, purification preprocess method, the low loss of sulfa antibiotics in pretreated high automation and pretreatment process may be implemented.This method can realize the automatic on-line purification of complex matrices sample, have the characteristics that analysis efficiency is high, acetonitrile solvent consumption is few, purification and impurity removal effect is good, measurement result accurate recreation is good, provides more succinct, convenient, sensitive reliable analysis foundation and analysis method for sulfamido measurement in aquatic products.

Description

Pretreating device, method and purposes for the detection of aquatic products sulfa antibiotics
Technical field
The present invention relates to aquatic product qualities to monitor field, more particularly to the monitoring field of antibiotic in aquatic products, more Particularly relate to pretreating device, method and the purposes detected for aquatic products sulfa antibiotics.
Background technique
Aquatic products are the aquatic products animals and plants product of ocean and fresh water fishery production and its general name of converted products.In aquatic products Breeding process in, in order to which prevention and control aquaculture disease is needed using the prevention and control drug such as antibiotics.Sulfamido is common anti- Control antibiotics fishing medicine.Currently, the abuse phenomenon of antibiotic occurs repeatedly, sulfa antibiotics drug can be accumulated and be stored In aquatic products, threaten to aquatic ecosystem.
The abuse of antibiotic in order to prevent, especially sulfa antibiotics, national correlation department has formulated inspection at present Mark is quasi-.It mainly include the detections such as extraction, purification, concentration, upper machine testing step in the detection method of existing sulfa antibiotics Suddenly.Wherein extracting, purify, being concentrated is the pre-treatment step detected, and accuracy and the pre-treatment step of testing result are closely related, Therefore, the validity for improving pre-treatment is an important factor for improving testing result accuracy.
Purification is the technological difficulties of sample pre-treatments as the ring in pretreatment process, while being also place before improving The key link of validity is managed, the quality of clean-up effect is to influence the key factor of final detection result accuracy.
The interfering substances such as the nonpolar lipid in leaching liquor are removed using n-hexane in currently available technology, to reduce base Matter annoyance level.The shortcomings that being purified using this method be, the main function of n-hexane be ungrease treatment is carried out to sample, but It is that in the sample, also containing the substances such as segment polarity phosphatide and/or glycoprotein, these substances can not take off under the action of n-hexane again It removes, and the polar phospho and/or glycoprotein that remain in the sample can equally generate matrix effect, influence the accurate of testing result Property.Also, for n-hexane as degreasing agent, degreasing clean-up effect is also unsatisfactory, after the degreasing operation of n-hexane, leaching Still contain small part nonpolarity lipid in extract, these lipids not removed can equally generate matrix effect, influence detection knot The accuracy of fruit.
Meanwhile these remain the substances such as protein and lipid in the sample, not only will affect the accurate of testing result Property, while also will increase the detection difficulty of aquatic products antibiotic, and due to containing protein and lipid material in sample, also hold Easily cause chromatographic column column pressure to increase, the blocking of mass spectrometric ion source nozzle needle and taper hole and the pollution of pre- level four bars etc. it is unfavorable as a result, And then it highly shortened the service life of detection device.
In order to reduce the residual of the substances such as protein and lipid, clean-up effect is improved, existing purification run not only walks It is rapid cumbersome, and need using a large amount of acetonitriles and other toxic reagents, and the Solid Phase Extraction consumptive material consumption in purification process Greatly, nitrogen blows concentration time-consuming, and artificial to manipulate difficulty big.It is not only time-consuming and laborious, while being limited in pretreatment process should not be excessively Drying, leads to the loss of target compound, therefore clean-up effect is poor, the poor repeatability of sample between batch, quantitative result accuracy It is unstable.
So for those skilled in the art, new purification techniques method is established, so that clean-up effect is improved, The matrix effect during sample detection is reduced, improving sample detection accuracy is to improve aquatic products sulfa antibiotics detection effect The research emphasis in the emphasis of rate and the field.
Summary of the invention
The first technical problem to be solved by the present invention be to provide it is a kind of for aquatic products sulfa antibiotics detection before Processing unit simplifies sample pre-treatments process so as to realize the in-line purification of complex matrices sample, shortens sample pre-treatments Time improves sample pre-treatments efficiency, realizes quick, the efficient completion of aquatic products sulfa antibiotics detection pre-treatment process.
Meanwhile the second technical problem to be solved by the present invention is to provide one kind and is based on being previously described for aquatic products sulfamido The pre-treating method of the pretreating device of antibiotic detection has simultaneously so as to reduce the consumption of the organic reagents such as acetonitrile Effect improves the clean-up effect of pre-treatment.
Finally, the present invention used the technical issues of solving third is that further providing for being used for aquatic products sulfamido based on this anti- The detection method of sulfa antibiotics in the pretreating device of raw element detection and the aquatic products of method.
In order to solve the above-mentioned technical problem, the present invention discloses the pre-treatment dress for the detection of aquatic products sulfa antibiotics It sets, including four six-way valves, respectively No.1 valve, No. two valves, No. three valves, No. four valves, wherein there are six each six-way valve tools Interface passes through the connection status of adjacent interface in the rotation regulating valve of six-way valve internal rotor.No. five interfaces of No.1 valve and No. two By piping connection between the No.1 interface of valve, connected between No. four interfaces of No.1 valve and No. two interfaces of No. four valves by pipeline It connects, passes through piping connection between No. three interfaces of No. three valves and No. three interfaces of No. four valves；It further include having mixer, the mixing There are two import and one outlets for utensil, pass through piping connection between the No.1 import of mixer and No. three interfaces of No. two valves, Pass through piping connection, the outlet and the No.1 of No. three valves of mixer between No. two imports of mixer and No. six interfaces of No. four valves Pass through piping connection between interface；Wherein it is provided with quantitative loop between No. three interfaces and No. six interfaces of No.1 valve, No. two valves It is provided with solid-phase extraction column between No. two interfaces and No. six interfaces, is also equipped between No. two interfaces and No. six interfaces of No. three valves Solid-phase extraction column；The No.1 interface of the No.1 valve is injection port, and No. five interfaces of No. two valves are with No. five interfaces of No. three valves No. four interfaces of waste discharge mouth, No. two valves are blocked using solid plug, and the No.1 interface of No. four valves is on-line solid phase extraction mobile phase Inlet, No. five interfaces of No. four valves are liquid phase pump mobile phase inlet, and No. four interfaces of No. four valves are outlet.
Preferably, on-line solid phase extraction column includes that mixed type cation exchange on-line solid phase extraction column and hydrophilelipophile are online Solid-phase extraction column.
It is exchanged online it is further preferred that being provided with mixed type cation between No. two interfaces of No. two valves and No. six interfaces Solid-phase extraction column (SPE1) is also equipped with hydrophilelipophile on-line solid phase extraction column between No. two interfaces and No. six interfaces of No. three valves (SPE2)。
The processes such as activation, sample introduction, Solid Phase Extraction may be implemented by switching the valve of different six-way valves using the device Iterative cycles operation, while passing through the conversion seamless switching of six-way valve between these processes, not only high degree of automation, effectively real Showing the automatic on-line pretreatment of complex matrices sample, and sample loses small in pretreatment process, purification and impurity removal effect is good, Basis is provided for subsequent efficient, accurate detection.
For example, six kinds of different connection status are further disclosed in the present invention, to form six kinds of different pipelines Connection structure:
State one: No.1 valve is according to 1-6, and 2-3,4-5 mode is logical, and-No. four valves of No. two valves are according to 1-2, the mode of 3-4,5-6 Connection；
State two: No.1 Vavle switching is 1-2, the mode of communicating of 3-4,5-6, No. two valves-No. four valves maintenances 1-2,3-4,5-6 Mode of communicating；
State three: No.1 valve is according to 1-6, and 2-3,4-5 mode is logical, and-No. four valves of No. two valves are according to 1-2, the mode of 3-4,5-6 Connection；
State four: No.1 valve and No. four valve states are switched to 1-2, the mode of communicating of 3-4,5-6, No. two valves and No. three valve dimensions Hold the mode of communicating of 1-2,3-4,5-6；
State five: No.1 valve and No. two valve states are switched to 1-6, the mode of communicating of 2-3,4-5, No. three valves and No. four valve dimensions Hold the mode of communicating of 1-2,3-4,5-6；
State six: No.1 valve and No. three valve states are switched to 1-6, the mode of communicating of 2-3,4-5, No. two valves and No. four valve dimensions Hold the mode of communicating of 1-2,3-4,5-6；
Wherein " 1 ", " 2 ", " 3 ", " 4 ", " 5 ", " 6 " respectively indicate No.1 interface, No. two interfaces, No. three interfaces, No. four connect Mouth, No. five interfaces, No. six interfaces.
Meanwhile the invention also discloses the pre-treatments based on the pretreating device detected for aquatic products sulfa antibiotics Method, comprising the following steps:
S1: pretreated sample to be tested is extracted into system injection port by online solid phase and is transferred to quantitative loop, then with mobile phase Sulfa antibiotics are enriched in mixed type cation exchange on-line solid phase extraction pillar (SPE1), by eluting waste discharge, are gone Except the albumen and the impurity such as phosphatide in on-line solid phase extraction column；
S2: switching six-way valve, alkalinity flowing exchange on-line solid phase extraction pillar to elution mixed type cation on the contrary (SPE1), sample to be tested imports mixer with alkaline eluant；
S3: while reversely elution SPE1, in addition the low organic phase mobile phase of acidity imports mixer all the way；Pass through acid After alkali neutralization, determinand flows on hydrophilelipophile on-line solid phase extraction column (SPE2) with the low organic phase mobile phase after mixing；
S4: liquid phase gradient reversely elutes SPE2, the sample to be tested after being purified.
In conjunction with the different conditions for the pretreating device for being previously used for the detection of aquatic products sulfa antibiotics, the pre-treating method Specifically includes the following steps:
1. No.1 valve is according to 1-6,2-3,4-5 mode is logical, and-No. four valves of No. two valves are connected to according to 1-2, the mode of 3-4,5-6； And mobile phase one and mobile phase one ' are successively passed through by on-line solid phase extraction mobile phase inlet；Then it is infused by injection port Enter sample solution to be processed；
2. No.1 Vavle switching is 1-2, the mode of communicating of 3-4,5-6 ,-No. four valves maintenance 1-2 of No. two valves, the company of 3-4,5-6 Logical mode；By mobile phase two from injection port injection device；
3. No.1 valve is according to 1-6,2-3,4-5 mode is logical, and-No. four valves of No. two valves are connected to according to 1-2, the mode of 3-4,5-6； And mobile phase three is passed through by on-line solid phase extraction mobile phase inlet；
4. No.1 valve and No. four valve states are switched to 1-2, the mode of communicating of 3-4,5-6, No. two valves and No. three valves maintain 1- The mode of communicating of 2,3-4,5-6；And mobile phase four and stream are successively each led by on-line solid phase extraction mobile phase inlet Dynamic phase four '；
5. No.1 valve and No. two valve states are switched to 1-6, the mode of communicating of 2-3,4-5, No. three valves and No. four valves maintain 1- The mode of communicating of 2,3-4,5-6；And mobile phase five is passed through by on-line solid phase extraction mobile phase inlet, is passed through a period of time Afterwards, mobile phase five ' is passed through by liquid phase pump mobile phase inlet, and is proportionally mixing mobile phase five and mobile phase five ' Device mixing；
6. No.1 valve and No. three valve states are switched to 1-6, the mode of communicating of 2-3,4-5, No. two valves and No. four valves maintain 1- The mode of communicating of 2,3-4,5-6；Mobile phase six is passed through by liquid phase pump mobile phase inlet；
Wherein " 1 ", " 2 ", " 3 ", " 4 ", " 5 ", " 6 " respectively indicate No.1 interface, No. two interfaces, No. three interfaces, No. four connect Mouth, No. five interfaces, No. six interfaces.
Preferably, the mobile phase one is methanol, and mobile phase one ' is pure water.And it is further preferred that one He of mobile phase The flow velocity of mobile phase one ' is 1mL/min.It is further preferred that the mobile phase one is methanol 1.5mL, mobile phase one ' is pure water 1.0mL。
Preferably, the mobile phase two is pure water.And it is further preferred that the flow velocity of mobile phase two is 1.0mL/min.
Preferably, the mobile phase three is methanol-water mixed solution, and wherein the volume ratio of methanol and water is 5:95.And The flow velocity of further preferred mobile phase three is 1.0mL/min.
Preferably, the mobile phase four is methanol, and mobile phase four ' is pure water, and it is further preferred that four He of mobile phase The flow velocity of mobile phase four ' is 1.0mL/min.It is further preferred that the mobile phase four is methanol 1.5mL, mobile phase four ' is pure Water 1.0mL.
Preferably, the mobile phase five is methanol-acetonitrile-ammonium hydroxide-water mixed solution, wherein methanol: acetonitrile: ammonium hydroxide: water Volume ratio be 10:10:1:79；The mobile phase five ' is formic acid-aqueous solution, and wherein the volume ratio of formic acid and water is 1:1000. It is further preferred that the flow velocity of the mobile phase five is 0.15ml/min, the flow velocity of mobile phase five ' is 0.45ml/min.
It may further be preferable that the mixed proportion of the mobile phase five and mobile phase five ' is 1:3 (volume ratio).
Preferably, the mobile phase six is formic acid-aqueous solution, and wherein the volume ratio of formic acid and water is that 1:1000. gradient is washed De- program is as follows: wherein the volume ratio of formic acid and water is 1:1000；Gradient elution program is as follows: with 0.1% (volume fraction) first Acid/aqueous solution (A): acetonitrile (B)=95:5, the reversed elution SPE2 of 0.4mL/min starting keep 0.5min, and when 1.0min rises to 25% (B), and then rises to 95% (B) in 3.5min, keep to 6.1min, and when 6.5min is reduced to 5% (B), and when 8.0min ties Beam.
It is further preferred that further including that 7. system regeneration cycles through setting reasonable online transfer time and adjusting is online Flow path composition, so that completing to switch reset condition after line transfer, and enter regeneration activating state, guarantee next period Sample introduction and Solid Phase Extraction, circulation carry out.
Finally, the invention also discloses the aquatic products for including the pretreating device based on the detection of aquatic products sulfa antibiotics The detection device of middle sulfa antibiotics, including the pretreating device detected based on aquatic products sulfa antibiotics, wherein sample out Mouth passes through piping connection to liquid chromatography mass instrument.
Meanwhile the invention also discloses the pre-treating methods of the pretreating device detected based on aquatic products sulfa antibiotics Aquatic products in sulfa antibiotics detection method, liquid phase color is entered by pipeline with mobile phase six by purified sample It composes mass spectrograph and carries out analysis detection.
The present invention provides the on-line solid phase extraction elution pre-treatment dresses for sulfa antibiotics on-line preconcentration, purification Set, and further establish on-line preconcentration based on the device, purification preprocess method, and further by the device with High performance liquid chromatography mass spectrometry can be used for measuring sulfa antibiotics in aquatic products simultaneously.Method disclosed by the invention is certainly Dynamicization degree is high, and the loss of sulfa antibiotics is few in pretreatment process.This method can realize complex matrices sample it is automatic Line purification, has analysis efficiency is high, acetonitrile solvent consumption is few, purification and impurity removal effect is good, measurement result accurate recreation is good etc. Feature provides more succinct, convenient, sensitive reliable analysis foundation and analysis method for sulfamido measurement in aquatic products.
Detailed description of the invention
Fig. 1 different conditions flow diagram.
Fig. 2 is the liquid chromatography mass figure of conventional method (n-hexane liquid-liquid extraction purification).
Fig. 3 is this method liquid chromatography mass figure.
Fig. 4-21 is 18 kinds of sulfamido mass spectrograms.
Figure 22 is 18 kinds of sulfamido standard curve schematic diagrames of this method detection, and wherein abscissa is 18 kinds of sulfamido concentration (ng/L), ordinate is 18 kinds of sulfamido peak areas.
Specific embodiment
In order to better understand the present invention, we in conjunction with specific embodiments carry out the present invention with attached drawing further below Elaboration, it should be noted that implementation of the invention is not limited only to this.
Embodiment 1
Firstly, the pretreating device that assembling is detected for aquatic products sulfa antibiotics in the following way, including four Six-way valve, respectively 33, No. four valves 44 of the valve 22, three of No.1 valve 11, two valve, wherein there are six connect each six-way valve tool Mouthful, pass through piping connection, No.1 valve 11 between No. five interfaces 11 (5) of No.1 valve 11 and the No.1 interface 22 (1) of No. two valves 22 No. four interfaces 11 (4) and No. four valves 44 No. two interfaces 44 (2) between by piping connection, No. three interfaces 33 of No. three valves 33 (3) pass through piping connection between No. three interfaces 44 (3) of No. four valves 44；It further include having mixer 55, the mixer 55 has There are two import and one outlets, pass through between the No.1 import 55 (1) of mixer 55 and No. three interfaces 22 (3) of No. two valves 22 Piping connection passes through piping connection, mixer between No. two import 55-2 of mixer and No. six interfaces 44 (6) of No. four valves 44 Pass through piping connection between 55 outlet 55 (3) and the No.1 interface 33 (1) of No. three valves 33；Wherein No. three interfaces of No.1 valve 11 Be provided with quantitative loop between 11 (3) and No. six interfaces 11 (6), No. two interfaces 22 (2) of No. two valves 22 and No. six interfaces 22 (6) it Between be provided with solid-phase extraction column 66, be also equipped between No. two interfaces 33 (2) and No. six interfaces 33 (6) of No. three valves 33 solid phase extraction Take column 77；The No.1 interface 11 (1) of the No.1 valve 11 is injection port, No. five interfaces 22 (5) of No. two valves 22 and No. three valves 33 No. five interfaces 33 (5) be waste discharge mouth, the No.1 interfaces 44 (1) of No. four valves 44 is on-line solid phase extraction mobile phase inlet, four No. five interfaces 44 (5) of number valve 44 are liquid phase pump mobile phase inlet, and No. four interfaces 44 (4) of No. four valves 44 are outlet.
Preferably, solid-phase extraction column includes mixed type cation exchange on-line solid phase extraction column and the online solid phase of hydrophilelipophile Extraction column.
It is further preferred that be provided between No. two interface 22-1 and No. six interface 22-6 of No. two valves 22 mixed type sun from Son exchange on-line solid phase extraction column (SPE1), it is online to be also equipped with hydrophilelipophile between No. two interfaces and No. six interfaces of No. three valves Solid-phase extraction column (SPE2).
Then, the pre-treatment of sample is followed the steps below:
1. No.1 valve is according to 1-6,2-3,4-5 mode is logical, and-No. four valves of No. two valves are connected to according to 1-2, the mode of 3-4,5-6； And mobile phase one and mobile phase one ' are successively passed through by on-line solid phase extraction mobile phase inlet；Then it is infused by injection port Enter sample solution to be processed, as shown in Figure 1；
2. No.1 Vavle switching is 1-2, the mode of communicating of 3-4,5-6 ,-No. four valves maintenance 1-2 of No. two valves, the company of 3-4,5-6 Logical mode；By mobile phase two from injection port injection device, as shown in Figure 1；
3. No.1 valve is according to 1-6,2-3,4-5 mode is logical, and-No. four valves of No. two valves are connected to according to 1-2, the mode of 3-4,5-6； And mobile phase three is passed through by on-line solid phase extraction mobile phase inlet, as shown in Figure 3；
4. No.1 valve and No. four valve states are switched to 1-2, the mode of communicating of 3-4,5-6, No. two valves and No. three valves maintain 1- The mode of communicating of 2,3-4,5-6；And mobile phase four and stream are successively each led by on-line solid phase extraction mobile phase inlet Dynamic phase four ', as shown in Figure 1；
5. No.1 valve and No. two valve states are switched to 1-6, the mode of communicating of 2-3,4-5, No. three valves and No. four valves maintain 1- The mode of communicating of 2,3-4,5-6；And mobile phase five is passed through by on-line solid phase extraction mobile phase inlet, is passed through a period of time Afterwards, mobile phase five ' is passed through by liquid phase pump mobile phase inlet, and is proportionally mixing mobile phase five and mobile phase five ' Device mixing, as shown in Figure 1；
6. No.1 valve and No. three valve states are switched to 1-6, the mode of communicating of 2-3,4-5, No. two valves and No. four valves maintain 1- The mode of communicating of 2,3-4,5-6；Mobile phase six is passed through by liquid phase pump mobile phase inlet；
Wherein " 1 ", " 2 ", " 3 ", " 4 ", " 5 ", " 6 " respectively indicate No.1 interface, No. two interfaces, No. three interfaces, No. four connect Mouth, No. five interfaces, No. six interfaces, as shown in Figure 1；
Preferably, the mobile phase one is methanol, and mobile phase one ' is pure water.And it is further preferred that one He of mobile phase The flow velocity of mobile phase one ' is 1mL/min.It is further preferred that the mobile phase one is methanol 1.5mL, mobile phase one ' is pure water 1mL。
Preferably, the mobile phase two is pure water.And it is further preferred that the flow velocity of mobile phase two is 1mL/min.
Preferably, the mobile phase three is methanol-water mixed solution, and wherein the volume ratio of methanol and water is 5:95.And The flow velocity of further preferred mobile phase three is 1mL/min.
Preferably, the mobile phase four is methanol, and mobile phase four ' is pure water, and it is further preferred that four He of mobile phase The flow velocity of mobile phase four ' is 1mL/min.It is further preferred that the mobile phase four is methanol 1.5mL, mobile phase four ' is pure water 1mL。
Preferably, the mobile phase five is methanol-acetonitrile-ammonium hydroxide-water mixed solution, wherein methanol: acetonitrile: ammonium hydroxide: water Volume ratio be 10:10:1:79；The mobile phase five ' is formic acid-aqueous solution, and wherein the volume ratio of formic acid and water is 1:1000. It is further preferred that the flow velocity of the mobile phase five is 0.15ml/min, the flow velocity of mobile phase five ' is 0.45ml/min.
It may further be preferable that the mixed proportion of the mobile phase five and mobile phase five ' is 1:3 (volume ratio).
Preferably, the mobile phase six is formic acid-aqueous solution, and wherein the volume ratio gradient of formic acid and water is 1:1000, liquid Phase mobile phase, with 0.1% (volume fraction) formic acid/aqueous solution (A): acetonitrile (B)=95:5, the reversed elution of 0.4mL/min starting 25% (B) is risen to when SPE2, holding 0.5min, 1.0min, 95% (B) is and then risen in 3.5min, is kept to 6.1min, It is reduced to 5% (B) when 6.5min, when 8.0min terminates.
It is further preferred that further including that 7. system regeneration cycles through setting reasonable online transfer time and adjusting is online Flow path composition, so that completing to switch reset condition after line transfer, and enter regeneration activating state, guarantee next period Sample introduction and Solid Phase Extraction, circulation carry out.
Further, in the following manner as optimal technical solution:
1. No. 1 valve is according to 1-6,2-3,4-5 mode is logical, and 2-4 valve is connected to according to 1-2, the mode of 3-4,5-6.It is online solid Mutually extraction flow path flow rate of mobile phase sets 1mL/min, successively with 1.5mL methanol and 1mL pure water activation balance SPE1.At this point, from Dynamic sample injector pipettes 1mL prepare liquid injection No. 1 position of No. 1 valve, stores prepare liquid in the 1mL quantitative loop of the position 6-3.See Fig. 1.
2. No. 1 Vavle switching is 1-2, the mode of communicating of 3-4,5-6,2-4 valve maintenance 1-2, the mode of communicating of 3-4,5-6. On-line solid phase extraction flow path sets 1mL/min flow velocity, and the prepare liquid in No. 1 valve in quantitative loop is pushed into SPE1 by pure water.See Fig. 1.
3. 1-4 valve state is the same as 1. SPE1 activation balance.On-line solid phase extraction flow path sets 1mL/min flow velocity, injection 2.0mL methanol aqueous solution (methanol: water=5:95), is shown in Fig. 1.
4. No. 1 valve and No. 4 valve states are switched to 1-2, the mode of communicating of 3-4,5-6, No. 2 valves and No. 3 valves maintain 1-2,3- The mode of communicating of 4,5-6.On-line solid phase extraction flow path sets 1mL/min flow velocity, successively injects 1.5mL methanol and 1mL pure water, living Change balance SPE2.See Fig. 1.
5. No. 1 valve and No. 2 valve states are switched to 1-6, the mode of communicating of 2-3,4-5, No. 3 valves and No. 4 valves maintain 1-2,3- The mode of communicating of 4,5-6.On-line solid phase extraction flow path sets 0.15mL/min flow velocity, and mobile phase is that the mixing of methanol acetonitrile ammonium hydroxide is molten Liquid (methanol: acetonitrile: ammonium hydroxide: water=10:10:1:79) reversely elutes SPE16min (No. 2 positions valve 6-2)；Liquid phase pump flow path is set Determine 0.45mL/min flow velocity, mobile phase is aqueous formic acid (formic acid: water=1:1000).On-line solid phase extraction flow path and liquid phase pump Flow path converges according to the ratio of 1:3 and mixer so that be loaded with organic Phase Proportion in the mobile phase of determinand be reduced to 5% with Under.Mobile phase is mixed into No. 1 position of No. 3 valves, and the position 2-6 is through SPE2HLB solid-phase extraction column on-line preconcentration.See Fig. 1.
6. No. 1 valve and No. 3 valve states are switched to 1-6, the mode of communicating of 2-3,4-5, No. 2 valves and No. 4 valves maintain 1-2,3- The mode of communicating of 4,5-6.
The elution of liquid phase pump eluent gradient, on-line solid phase extraction flow path deactivate.Liquid phase pump startup, gradient reversely elute SPE2HLB on-line solid phase extraction column mutually enters liquid chromatography mass instrument with liquid phase pump flow path and tests and analyzes.See Fig. 1.
Comparative example 1
(1) instrument and reagent
UPLC-5500Trap high performance liquid chromatography QQ-TOF mass spectrometry instrument (AB, the U.S.), ACE C18-PFP chromatographic column (100mm3.0mm, 2.1 μm, ACE, Britain), Q-700DE type supersonic wave cleaning machine (new sesame, Ningbo), 5810R centrifuge (Eppendorf Centrifuge, Germany), 24 nitrogen evaporators (Chinese promise, Shanghai), 2 vortex vortex mixer of Vortex Cenie (Scientifie Industries, the U.S.).
(2) chromatography and Mass Spectrometry Conditions
Mobile phase is 0.1% (V:V, similarly hereinafter) formic acid/aqueous solution (A), acetonitrile (B)；Flow velocity is 0.4mL/min；Initial flow Dynamic Phase Proportion is 5% (B), keeps 1min, 1.1min to rise to 15% (B), 9.5min rises to 75% (B), and 9.6min rises to 95% (B), 11.5min is remained to, 11.6min is reduced to 5% (B), and 13.5min terminates.10 μ L of sample volume, 40 DEG C of column temperature, electron spray is electric From source (ESI), nebulizer pressure 60psi, capillary voltage 4000V, dry temperature degree is 400 DEG C, flow velocity 9L/min, Detection mode is multiple-reaction monitoring (MRM) positive ion mode.
(3) sample pretreatment
After aquatic products are blended, 2g is taken, 10mL acetonitrile is added, leaching liquor is transferred to nitrogen after centrifugation by ultrasound extraction 15min In blowpipe, soft nitrogen is blown to close dry.The aqueous hydrochloric acid solution of 0.1moL/L is added, is vortexed and redissolves, add n-hexane liquid-liquid extraction, whirlpool Rotation discards, and repeats 2-3 times, until leaching liquor is limpid.
Embodiment 2
The detection of sulfa antibiotics drug is carried out with embodiment 1 and comparative example 1 treated sample respectively.
In the present embodiment, we detect 18 kinds of common sulfa antibiotics drugs altogether, are specifically shown in Table 1:
Table 1:
Standard solution is prepared
With the aqueous hydrochloric acid solution of 0.1moL/L, 1.0ng/L, 5.0ng/L, 10.0ng/L, 20.0ng/L, 50.0ng/L are prepared Standard solution, each concentration sample introduction 1mL, using peak area as abscissa, concentration be ordinate draw standard curve, with 3 times believe It makes an uproar and calculates detection limit (LOD) (being shown in Table 2) than (S/N).Linearly dependent coefficient is not less than 0.998.
Linearity curve is as shown in figure 22, wherein
Experimental result is shown in Fig. 2 and Fig. 3.We can significantly find out with the comparison of Fig. 3 according to fig. 2, obtain through the invention The liquid chromatography mass figure miscellaneous peak obtained is few, and noise is few, and peak shape is good, and sample purity is high, testing result clear data.
Embodiment 3
The measurement of the sample recovery rate of method disclosed by the invention
Prepare a water sample, measures 7 parts, every part of 10mL.Label, 0-6.No. 0 sample is set as blank, No. 1-3 each sample Add 5.0ng/L standard items；No. 3-6, each sample adds 50.0ng/L standard items.The sample for carrying out low, high two kinds of concentration returns It is dense to deduct testing concentration and the determinand of addition in blank sample by testing concentration in standard addition sample for yield experiment Ratio calculation sample recovery rate is spent, the results are shown in Table 2.
The measurement of the sample precision of method disclosed by the invention
Prepare a water sample, measures 8 parts, every part of 10mL.Label 0-7, No. 0 sample are set as blank, the addition of 1-7 sample 10.0ng/L standard items；The densimeter in sample in testing concentration deduction blank sample after testing concentration is added by standard Sample relative standard deviation is calculated, the results are shown in Table 2.
Table 2:
The foregoing is a specific embodiment of the present invention.It should be pointed out that for those skilled in the art For, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also considered as Protection scope of the present invention.

Claims (10)

1. the pretreating device for the detection of aquatic products sulfa antibiotics, it is characterised in that: including four six-way valves, respectively No.1 valve, No. two valves, No. three valves and No. four valves pass through six-way valve internal rotor wherein there are six interfaces for each six-way valve tool The connection status for rotating adjacent interface in regulating valve, passes through liquid phase between No. five interfaces of No.1 valve and the No.1 interface of No. two valves Piping connection is connected between No. four interfaces of No.1 valve and No. two interfaces of No. four valves by liquid phase pipeline, No. three of No. three valves Pass through piping connection between interface and No. three interfaces of No. four valves；It further include having mixer, there are two imports for the hybrid instrument And one outlet, by piping connection between the No.1 import of mixer and No. three interfaces of No. two valves, No. two of mixer into By piping connection between mouth and No. six interfaces of No. four valves, pass through pipe between the outlet and the No.1 interface of No. three valves of mixer Road connection；Wherein it is provided with quantitative loop between No. three interfaces and No. six interfaces of No.1 valve, No. two interfaces of No. two valves and No. six It is provided with on-line solid phase extraction column between interface, online solid phase extraction is also equipped between No. two interfaces and No. six interfaces of No. three valves Take column；The No.1 interface of the No.1 valve is injection port, and No. five interfaces of No. two valves and No. five interfaces of No. three valves are waste discharge mouth, No. four interfaces of No. two valves are blocked using solid plug, and the No.1 interface of No. four valves is on-line solid phase extraction mobile phase inlet, No. five interfaces of No. four valves are liquid phase pump mobile phase inlet, and No. four interfaces of No. four valves are outlet.
2. the pretreating device according to claim 1 for the detection of aquatic products sulfa antibiotics, it is characterised in that: Line solid-phase extraction column includes mixed type cation exchange on-line solid phase extraction column and hydrophilelipophile on-line solid phase extraction column；It is more excellent Choosing, is provided with mixed type cation between No. two interfaces and No. six interfaces of No. two valves and exchanges on-line solid phase extraction column (SPE1), hydrophilelipophile on-line solid phase extraction column (SPE2) is also equipped between No. two interfaces and six number of connecing interfaces of No. three valves.
3. it is a kind of based on described in claims 1 or 2 be used for aquatic products sulfa antibiotics detection pretreating device before Processing method, it is characterised in that: the following steps are included:
1. No.1 valve is according to 1-6,2-3,4-5 mode is logical, and-No. four valves of No. two valves are connected to according to 1-2, the mode of 3-4,5-6；And Mobile phase one and mobile phase one ' are successively passed through by on-line solid phase extraction mobile phase inlet；Then by injection port inject to Handle sample solution；
2. No.1 Vavle switching is 1-2, the mode of communicating of 3-4,5-6 ,-No. four valves of No. two valves maintain 1-2,3-4, the connection side of 5-6 Formula；By mobile phase two from injection port injection device；
3. No.1 valve is according to 1-6,2-3,4-5 mode is logical, and-No. four valves of No. two valves are connected to according to 1-2, the mode of 3-4,5-6；And Mobile phase three is passed through by on-line solid phase extraction mobile phase inlet；
4. No.1 valve and No. four valve states are switched to 1-2, the mode of communicating of 3-4,5-6, No. two valves and No. three valves maintain 1-2,3- The mode of communicating of 4,5-6；And mobile phase four and mobile phase are successively each led by on-line solid phase extraction mobile phase inlet Four '；
5. No.1 valve and No. two valve states are switched to 1-6, the mode of communicating of 2-3,4-5, No. three valves and No. four valves maintain 1-2,3- The mode of communicating of 4,5-6；And mobile phase five is passed through by on-line solid phase extraction mobile phase inlet, after being passed through a period of time, It is passed through mobile phase five ' by liquid phase pump mobile phase inlet, and proportionally that mobile phase five and mobile phase five ' is mixed in mixer It closes；
6. No.1 valve and No. three valve states are switched to 1-6, the mode of communicating of 2-3,4-5, No. two valves and No. four valves maintain 1-2,3- The mode of communicating of 4,5-6；Mobile phase six is passed through by liquid phase pump mobile phase inlet；
Wherein " 1 ", " 2 ", " 3 ", " 4 ", " 5 ", " 6 " respectively indicate No.1 interface, No. two interfaces, No. three interfaces, No. four interfaces, five Number interface, No. six interfaces.
4. it is according to claim 3 based on described in claims 1 or 2 be used for aquatic products sulfa antibiotics detection The pre-treating method of pretreating device, it is characterised in that: the mobile phase one is methanol, and mobile phase one ' is pure water；And into one Step is preferred, and the flow velocity of mobile phase one and mobile phase one ' is 1.0mL/min；It is further preferred that the mobile phase one is methanol 1.5mL, mobile phase one ' are pure water 1.0mL.
5. it is according to claim 3 based on described in claims 1 or 2 be used for aquatic products sulfa antibiotics detection The pre-treating method of pretreating device, it is characterised in that: the mobile phase two is pure water；And it is further preferred that mobile phase Two flow velocity is 1.0mL/min.
6. it is according to claim 3 based on described in claims 1 or 2 be used for aquatic products sulfa antibiotics detection The pre-treating method of pretreating device, it is characterised in that: the mobile phase three is methanol-water mixed solution, wherein methanol and water Volume ratio be 5:95；And the flow velocity of further preferred mobile phase three is 1.0mL/min.
7. it is according to claim 3 based on described in claims 1 or 2 be used for aquatic products sulfa antibiotics detection The pre-treating method of pretreating device, it is characterised in that: the mobile phase four is methanol, and mobile phase four ' is pure water, and into one Step is preferred, and the flow velocity of mobile phase four and mobile phase four ' is 1mL/min；It is further preferred that the mobile phase four is methanol 1.5mL, mobile phase four ' are pure water 1mL.
8. it is according to claim 3 based on described in claims 1 or 2 be used for aquatic products sulfa antibiotics detection The pre-treating method of pretreating device, it is characterised in that: the mobile phase five is methanol-acetonitrile-ammonium hydroxide-water mixed solution, Middle methanol: acetonitrile: ammonium hydroxide: the volume ratio of water is 10:10:1:79；The mobile phase five ' be formic acid-aqueous solution, wherein formic acid with The volume ratio of water is 1:1000；It is further preferred that the flow velocity of the mobile phase five is 0.15ml/min, the stream of mobile phase five ' Speed is 0.45ml/min；It may further be preferable that the mixed proportion of the mobile phase five and mobile phase five ' is 1:3 (volume ratio).
9. it is according to claim 3 based on described in claims 1 or 2 be used for aquatic products sulfa antibiotics detection The pre-treating method of pretreating device, it is characterised in that: on-line solid phase extraction mobile phase six is formic acid-aqueous solution, wherein formic acid Volume ratio with water is 1:1000；Gradient elution program is as follows: with 0.1% (volume fraction) formic acid/aqueous solution (A): acetonitrile (B) 25% (B) is risen to when=95:5,0.4mL/min starting reversed elution SPE2, holding 0.5min, 1.0min, and then 3.5min It inside rises to 95% (B), keeps to 6.1min, when 6.5min is reduced to 5% (B), and when 8.0min terminates.
It is further preferred that further include 7. system regeneration cycle through setting reasonable online transfer time and adjust online flow path Composition, so that completing to switch reset condition after line transfer, and enter regeneration activating state, guarantee the sample introduction in next period And Solid Phase Extraction, circulation carry out.
10. pretreating device and method comprising being used for the detection of aquatic products sulfa antibiotics described in claims 1 or 2 Aquatic products sulfa antibiotics detection device and method.
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