CN1890562A - Method of analyzing organic chemical substance and apparatus for analysis - Google Patents

Method of analyzing organic chemical substance and apparatus for analysis Download PDF

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Publication number
CN1890562A
CN1890562A CN 200480036198 CN200480036198A CN1890562A CN 1890562 A CN1890562 A CN 1890562A CN 200480036198 CN200480036198 CN 200480036198 CN 200480036198 A CN200480036198 A CN 200480036198A CN 1890562 A CN1890562 A CN 1890562A
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CN
China
Prior art keywords
solid
analytic target
phase extraction
extraction column
gas chromatography
Prior art date
Application number
CN 200480036198
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Chinese (zh)
Inventor
佐佐野僚一
中西丰
Original Assignee
财团法人杂贺技术研究所
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Priority to JP2003407067 priority Critical
Priority to JP407067/2003 priority
Priority to JP161061/2004 priority
Application filed by 财团法人杂贺技术研究所 filed Critical 财团法人杂贺技术研究所
Publication of CN1890562A publication Critical patent/CN1890562A/en

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Abstract

A combination of a liquid chromatograph and a gas chromatograph was a possible measure for improving precision in analyzing organic chemical substances. However, because elutes from liquid chromatographs contain water and a highly polar solvent, injection thereof into a gas chromatograph has been impossible. Consequently, to develop an analytical method which realizes that combination and an apparatus therefor has been a subject. The method of quantitative analysis comprises subjecting a sample for analysis prepared beforehand by extracting organic chemical substances from an assay sample to fractionation by a liquid chromatograph, continuously adsorbing a fractionated elute containing a substance to be determined onto a solid-phase cartridge while conducting the fractionation, eluting this substance, which has been adsorbed on the solid-phase cartridge, with an eluent, and transferring the elute to a storage chamber of a gas chromatograph.

Description

The analytical approach of organic chemicals and analytical equipment
Technical field
The present invention relates in the analysis of organic chemicals, lateral dominance with liquid chromatography to from the analytic target sample, extract in advance organic chemicals and the preparation analytical approach and analytical equipment that assay sample separates, lateral dominance carries out the organic chemicals of quantitative test to the analytic target material that is separated with gas chromatography.
Background technology
To the analysis of organic chemicals, particularly agricultural chemicals, adopt analytical approach (for example, with reference to patent documentation 1) based on liquid chromatography always.In addition, to the analysis of the agricultural chemicals that uses in the golf course, also use liquid phase chromatography (for example, with reference to patent documentation 2) always.After this, the security of the remains of pesticide that adheres on crops becomes problem, not only because of utilizing liquid phase chromatography to cause but also because utilizing gas chromatography to cause.In addition, proposed the method for gas chromatography and infrared absorption spectrum and usefulness or used the method (for example, with reference to patent documentation 3 and patent documentation 4) of little drip catcher (micro-trap) as the pre-treatment of gas chromatography.On the other hand, along with environmental problem receives publicity, also studied the analytical approach (for example, with reference to patent documentation 5) of bioxin etc.
Patent documentation 1: the spy opens flat 6-331618 communique
Patent documentation 2: the spy opens flat 5-306998 communique
Patent documentation 3: the spy opens flat 8-170941 communique
Patent documentation 4: the spy opens the 2002-328121 communique
Patent documentation 5: the spy opens the 2002-48688 communique
Summary of the invention
When organic chemicalss such as remains of pesticide, environmental hormone were analyzed, in order to improve its precision, the present invention considered the combination of liquid chromatography and gas chromatography, but, because contain moisture in the eluate from liquid chromatography, so, can not be with in the direct injection gas chromatography of this eluate.Therefore, thereby the objective of the invention is to realize that the combination of liquid chromatography and gas chromatography analyzes organic chemicals rapidly and critically, problem of the present invention is its analytical approach of exploitation and analytical equipment.
In order to solve above-mentioned problem, the inventor furthers investigate, and the result proposes the present invention.Promptly, it is a kind of analytical approach of organic chemicals, it is characterized in that: in the analysis of organic chemicals, lateral dominance separates the assay sample that extracts organic chemicals and preparation from the analytic target sample in advance with liquid chromatography, the limit adds different solution in this isolated eluate that contains the analytic target material, this analytic target material is adsorbed on the solid-phase extraction column (solid phase cartridge) continuously from liquid chromatography, utilize eluent will be attracted to upright the connecing in the storeroom (storagechamber) that is eluted to gas chromatography of material for testing on this solid-phase extraction column, utilize gas chromatography analysis.Preferably: utilize eluent will be attracted to analytic target material wash-out on the above-mentioned solid phase extraction column, when directly being eluted in the storeroom of gas chromatography, derivatization reagent is dissolved in this eluent, is injected in the storeroom of gas chromatography with the analytic target material, in storeroom, with after the analytic target material derivantization, utilize this derivant of gas chromatographic analysis.Preferably: utilize eluent will be attracted to analytic target material wash-out on the above-mentioned solid phase extraction column, then, this eluent by another solid-phase extraction column, is injected into the effluent of removing behind the snotter in the storeroom of gas chromatography, utilizes gas chromatography analysis.Preferably: utilize eluent will be attracted to analytic target material wash-out on the above-mentioned solid phase extraction column, then, this eluent is passed through another solid-phase extraction column, when the effluent after will removing snotter is injected in the storeroom of gas chromatography, derivatization reagent is dissolved in this effluent, is injected in the storeroom of gas chromatography with the analytic target material, in storeroom, with after the analytic target material derivantization, utilize this derivant of gas chromatographic analysis.Preferred especially above-mentioned analytic target material is a kind~20 kinds.
A second aspect of the present invention is a kind of analytical approach of organic chemicals, it is characterized in that: in the analysis of organic chemicals, lateral dominance separates the assay sample that extracts organic chemicals and preparation from the analytic target sample in advance with liquid chromatography, solid-phase extraction column is passed through with this isolated eluate that contains the analytic target material in the limit, this analytic target material is adsorbed on this solid-phase extraction column continuously, utilize eluent will be attracted to upright the connecing in the storeroom that is eluted to gas chromatography of material for testing on this solid-phase extraction column, utilize gas chromatography analysis.Preferably: utilize eluent will be attracted to analytic target material wash-out on the above-mentioned solid phase extraction column, when directly being eluted in the storeroom of gas chromatography, derivatization reagent is dissolved in this eluent, is injected in the storeroom of gas chromatography with the analytic target material, in storeroom, with after the analytic target material derivantization, utilize this derivant of gas chromatographic analysis.Preferably: utilize eluent will be attracted to analytic target material wash-out on the above-mentioned solid phase extraction column, then, this eluent by another solid-phase extraction column, is injected into the effluent of removing behind the snotter in the storeroom of gas chromatography, utilizes gas chromatography analysis.Preferably: utilize eluent will be attracted to analytic target material wash-out on the above-mentioned solid phase extraction column, then, this eluent is passed through another solid-phase extraction column, when the effluent after will removing snotter is injected in the storeroom of gas chromatography, derivatization reagent is dissolved in this effluent, is injected in the storeroom of gas chromatography with the analytic target material, in storeroom, with after the analytic target material derivantization, utilize this derivant of gas chromatographic analysis.Preferred especially above-mentioned analytic target material is a kind~20 kinds.
A third aspect of the present invention is a kind of analytical equipment of organic chemicals, it is characterized in that, comprising: the liquid chromatography that is used for importing and separating organic chemicals extraction that the analytic target sample is contained and the assay sample of preparing; Be used for according to this analytic target material by the isolated time that washes out of containing the eluate of analytic target material of this liquid chromatography, supply with first feed mechanism of first solution different automatically with this eluate; Be used to adsorb the solid-phase extraction column of the analytic target material that utilizes described first solution and shift by the mixed liquor of the isolated eluate of liquid chromatography; Be used for supplying with automatically second feed mechanism of the eluent that is used to make the analytic target material wash-out that is attracted on this solid-phase extraction column; With the entry needle that is used for described eluted analytic target material is imported gas chromatography, is connected with the flow export of described solid-phase extraction column.Preferably: utilize described first solution and be adsorbed onto first path on the described solid-phase extraction column by the analytic target material that the mixed liquor of the isolated eluate of liquid chromatography shifts except being used to make, be provided with in addition being attracted to the analytic target material wash-out on the described solid-phase extraction column and importing second path of described gas chromatography, described solid-phase extraction column constituted 2 paths can freely mount and dismount separately.Preferably: be provided with transfer valve, be used for supply condition is switched to second supply condition that will utilize described first solution and be supplied with described solid-phase extraction column and made it be adsorbed on first supply condition on this solid-phase extraction column and described eluent is supplied with described solid-phase extraction column, will be attracted to the analytic target material wash-out on this solid-phase extraction column and import described gas chromatography by the analytic target material that the mixed liquor of the isolated eluate of liquid chromatography shifts.Preferred especially: above-mentioned gas chromatography is provided with the storeroom that does not contain the trapping agent that can store the analytic target material that imports from described entry needle for the time being in vaporizer.
A fourth aspect of the present invention is a kind of analytical equipment of organic chemicals, it is characterized in that, comprising: the liquid chromatography that is used for importing and separating organic chemicals extraction that the analytic target sample is contained and the assay sample of preparing; Be used to detect testing agency by the analytic target material of this liquid chromatography separation and transfer; Be used for surveying signal, will discharging the destination switches to predominating path one side from discharge path one side discharge destination transfer valve according to material for testing quality inspection from this testing agency; Be used to adsorb utilize described discharge destination transfer valve switch to predominating path one side, with the analytic target material that eluate shifts, be arranged on the solid-phase extraction column on this predominating path; Be used to supply with the feed mechanism that the analytic target material that will be attracted on this solid-phase extraction column imports the eluent of gas chromatography; Be used for import with the analytic target material of described eluent wash-out gas chromatography, be connected with the flow export of described solid-phase extraction column can knee-action entry needle.Preferably: be adsorbed onto first path on the described solid-phase extraction column except being used to make the analytic target material that shifts with described eluate, the eluent be used to from described feed mechanism is set in addition, will be attracted to the analytic target material wash-out on the described solid-phase extraction column and imports second path of described gas chromatography, described solid-phase extraction column is constituted 2 paths can freely mount and dismount separately.Preferably: be provided with the supply condition transfer valve, be used for supply condition is switched to second supply condition that the analytic target material that shifts with described eluate is supplied with described solid-phase extraction column and made it be adsorbed on first supply condition on this solid-phase extraction column and supply with described eluent, will be attracted to the analytic target material wash-out on this solid-phase extraction column and import described gas chromatography to described solid-phase extraction column.Preferred especially: described gas chromatography is provided with the storeroom that does not contain the trapping agent that can store the analytic target material that imports from described entry needle for the time being in vaporizer.
Analytical approach of the present invention, excellence aspect the organic chemicals that contains snotter is analyzed accurately, especially, when organic chemicals is a kind~20 kinds, bring into play most its effect, can be accurately, rapidly the analytic target material is analyzed.
According to the present invention, lateral dominance separates assay sample with reversed-phase liquid chromatography, the limit with this eluate by solid-phase extraction column, with adsorption analysis object material, thus, can not follow water and high polarity solvent, the analytic target material is supplied with gas chromatography (GC) from liquid chromatography (LC), so can analyze multiple organic chemicals accurately.
According to the present invention because entry needle that can knee-action is connected with the flow export of solid-phase extraction column, so, can have no to lose ground, simply will be from the analytic target material injection gas chromatography of solid-phase extraction column.In addition, as gas chromatography, by using the storeroom in vaporizer, be provided with, can store the analytic target material that imports from entry needle for the time being, can be with whole elution amount injection gas chromatographies from solid-phase extraction column.In addition, because the liquid chromatography (LC) in the analytical approach that is made of liquid chromatography (LC)-gas chromatography (GC) has purification function, so, can analyze and omit the pre-treatment that purifies.
According to the present invention, utilize analytic target material wash-out that eluent will adsorb by solid-phase extraction column, directly in the storeroom of injection gas chromatography the time, with derivatization reagent be dissolved in the eluent, with the storeroom of analytic target material injection gas chromatography, after generating the derivant of analytic target material, can utilize gas chromatography analysis, so, can increase the kind of analytic target material and improve its analysis precision.
According to the present invention, supply with first supply condition of first eluate and supply with the transfer valve of second supply condition of eluent to solid-phase extraction column by being provided for switching to solid-phase extraction column, do not need solid-phase extraction column is pulled down and be installed in operation in second path from first path, can more promptly carry out analysis operation.
Description of drawings
Fig. 1 is the skeleton diagram of analytical equipment.
Fig. 2 is the chromatogram of expression by the detected result of detecting device.
Fig. 3 is the chromatogram that the result of recovery test is added in expression.
Fig. 4 is the result's of another interpolation recovery test of expression a chromatogram.
Fig. 5 is can be by the skeleton diagram of transfer valve change to another analytical equipment of the supply stream of solid-phase extraction column.
Fig. 6 represents the enlarged drawing of the major part of analytical equipment shown in Figure 5, (a) expression makes the analytic target material be adsorbed on first supply condition on the solid-phase extraction column, and (b) expression makes the analytic target material wash-out that is adsorbed and supplies with second supply condition of chromatogram.
Fig. 7 is the skeleton diagram with the second pump abridged analytical equipment.
Fig. 8 is equipped with the skeleton diagram that purifies with other analytical equipment of solid-phase extraction column.
Fig. 9 is other the skeleton diagram of analytical equipment that a plurality of solid-phase extraction columns are installed.
Figure 10 can make material for testing matter flow out to the skeleton diagram of other analytical equipment of 2 formations in the storeroom respectively.
Figure 11 is the skeleton diagram that keeps other analytical equipment of 3 solid-phase extraction columns in cylinder anchor clamps (cartridge holder).
Chromatogram when Figure 12 is to use derivatization reagent.
Symbol description
1 liquid chromatography
2 gas chromatographies
3 interfaces
4 inlets
5 pumps
6 pre-columns
7 LC posts
8 detecting devices
9 discharge paths
10 first paths
11 valves
12 pumps
13 mixers
14 solid-phase extraction columns
15 escape holes
16,16A second path
17,17A second pump
18,18A entry needle
19,19A storeroom
20,20A vaporizer
The peak of 21A ethoprop
The peak of 21B chlopyrifos
22 transfer valves
22A, 22B, 22C stream
23~27 solid-phase extraction columns
28 cylinder anchor clamps
Embodiment
Organic chemicals among the present invention is the organic chemicals that contains remains of pesticide, environmental hormone, spices etc., and there is no particular limitation.As remains of pesticide, can enumerate the spirit of sulphur grass (asulam), copper 8-hydroxyquinolinate, 2-methyl-4-chlorophenoxy acetic acid propionic acid (mecoprop), thiuram (thiuram), Tupersan (siduron), iprodione (iprodione), Bravo (chlorothalonil), Pencycuron (pencycuron), bensulide (bensulide), chlopyrifos (chlorpyrifos), ethoprop (ethoprophos) etc.In addition,, can enumerate phenols such as nonylphenol, bisphenol-A, phthalic ester, PCB , dioxin etc., organo-tin compounds such as tributyl tin, triphenyltin, synthetic estrogens such as ethyl estradiol, estriol etc. as environmental hormone.As spices, can enumerate citrene, cinene, terpinolene, alloocimene, ocimenum, linalool, geraniol, nerol, citronellol, laurine dimethyl acetal etc.
Analytic target sample among the present invention limits especially, but comprises organic chemicals that the food composition as vegetalitas and animality contains and object sample that the organic chemicals that adheres at food surface etc. should be analyzed.For example, for the remains of pesticide of the surface attachment of greengrocery or environmental hormone etc. are analyzed, greengrocery etc. are suitable as the analytic target sample.
At this, in the analytic target sample,, regulate its concentration with the organic chemicals that solvent extraction should be analyzed, the assay sample of liquid chromatography is supplied with in preparation.For example, vegetables, fruit class are chopped up, after after cereal, beans are pulverized, adding water, it fully being expanded, add acetonitrile, acetone, methyl alcohol, ether, ethyl acetate, water etc. as solvent, carry out homogenizing after, filter, extract organic chemicals.This organic chemicals extract is called assay sample.
So-called analytic target material is the organic chemicals that contains in the analytic target sample among the present invention, is the object material that will analyze its content.In the present invention, for the kind of analytic target material, there is no particular limitation, but consider from the rapid property aspect of analysis precision and analysis, is preferably a kind~20 kinds.
So-called derived reagent among the present invention, be when utilizing gas chromatography directly the analytic target material to be analyzed, under the inadequate situation of its analysis precision, utilize derivatization reagent to obtain the derivant of analytic target material, thereby improve the reagent of its analysis precision, can enumerate N, two (trimethyl silyl) trifluoroacetamides (BSTFA) of O-, trimethyl silyl-diazomethane (TMS-diazomethane) etc.
In addition, before utilizing liquid chromatography that assay sample is separated, can place solid-phase extraction column, remove snotter.At this moment, can change the kind of the filling agent of solid-phase extraction column according to the kind of snotter.
Fig. 1 represents the structure of the analytical equipment that liquid chromatography 1 and gas chromatography 2 are connected by interface 3.
Above-mentioned liquid chromatography 1 has: be used for to the pump 5 that is used for assay sample is imported the inlet 4 supply solution of LC post one side; The snotter pre-column of removing 6 and the LC post 7 that is used to snotter is separated with the analytic target material that are used for assay sample is contained, the LC post is worsened; With the detecting device 8 that is used for the analytic target material that contains by LC post 7 isolated eluates is detected.
Above-mentioned interface 3 has: when above-mentioned detecting device 8 detects the analytic target material of expectation, will contain to come the discharge destination of eluate of the analytic target material of self-detector 8 to switch to the valve 11 of first path, 10 1 sides from discharge path 9 one sides; Be used for according to above-mentioned analytic target material the time that washes out, promptly according to the switching signal of above-mentioned valve 11, in the eluate that contains above-mentioned analytic target material that is directed to first path, 10 1 sides, supply with first pump 12 of conduct first feed mechanism of first solution different automatically with the solution that contains in this eluate; Be used to mix from first solution of said pump 12 with from the mixer 13 of the eluate of above-mentioned valve 11; With the solid-phase extraction column 14 that is used for adsorbing from the analytic target material of the effluent of above-mentioned mixer 13, do not discharged by escape hole 15 from the below by the moisture of above-mentioned solid phase extraction column 14 absorption etc.In addition, above-mentioned interface 3 also has: will be used for wash-out is supplied to conduct second feed mechanism in second path 16 different with above-mentioned first path 10 automatically by the eluent of the analytic target material of above-mentioned solid phase extraction column 14 absorption second pump 17.
Above-mentioned solid phase extraction column 14 is constituted as: with respect to first path 10, installation and removal freedom, terminal, the installation and removal with respect to above-mentioned second path 16 are free simultaneously.Therefore, the solid-phase extraction column 14 that is adsorbed with the analytic target material can be pulled down and be installed on the terminal in second path 16 from first path 10.Constitute: according to detect by detecting devices such as sensors with the solid-phase extraction column 14 that is adsorbed with the analytic target material pull down from above-mentioned first path 10, and detection signal when being installed in this solid-phase extraction column 14 on above-mentioned second path 16, make 17 actions of above-mentioned second pump, make the analytic target material wash-out that is attracted on the solid-phase extraction column 14 and import in the gas chromatography 2 and analyze.In addition, as the filling agent of solid-phase extraction column, can enumerate C18, C8, CN, dibasic alcohol, NH2, aluminium oxide, florisil (florisil), silicon dioxide, activated charcoal etc.
Entry needle 18 is connected with the flow export of the below of above-mentioned solid phase extraction column 14, by solid-phase extraction column 14 being installed on second path 16, from the analytic target material that solid-phase extraction column 14 flows out, can have no loss ground, be injected into by entry needle 18 simply.At this moment, will contain the solution of derivatization reagent and the analytic target material that flows out from solid-phase extraction column 14 injects storeroom 19 together, can be with analytic target material derivantization in storeroom 19.
Gas chromatography 2 is constituted as: be provided with the storeroom 19 that can store for the time being from the analytic target material of above-mentioned entry needle 18 importings in vaporizer 20.
Fig. 2 represents from the chromatogram of the state of solution wash-out along with effluxion of the assay sample of above-mentioned inlet 4 injections, origin self-pumping 5,2 times that local expression analytic target material flows out of Fig. 2, detect by above-mentioned detecting device 8 its outflows during (or the analytic target material of investigation in advance flow out during), control by control gear, valve 11 is switched to the state that flows to first path 10.
In Fig. 1, the solid-phase extraction column 14 that is adsorbed with the analytic target material is pulled down and is installed on second path 16 from first path 10, but as shown in Figure 5, also can constitute: place at first path 10 and 16 interflow, second path, transfer valve is set (is shown as rotary valve among the figure, but also can be the valve of other form of switching of for example sliding) 22, by manually or automatically switching this transfer valve 22, the analytic target material that is attracted on the solid-phase extraction column 14 gas chromatography 2 can be supplied with, and solid-phase extraction column 14 need not be mounted and dismounted.
In detail, in the reel (spool) (omitting sleeve pipe) of the movable side (rotation side) of above-mentioned transfer valve 22, forms 3 streams: be used to admit from first solution of above-mentioned mixer 13 or from the eluent of second pump 17 and to the first mobile stream 22A of the supply stream 22D that leads to solid-phase extraction column 14 as the shell that covers the reel periphery; Be used for by supplying with stream 22D, will supplying with the second stream 22C of above-mentioned escape hole 15 1 sides from the effluent of this first stream 22A; To supply with the 3rd stream 22B of entry needle 18 (gas chromatography 2) from the analytic target material of above-mentioned supply stream 22D outflow with being used for, supply condition can be switched to: will be by the analytic target material of above-mentioned first solution transfer, by the first stream 22A and supply stream 22D, supply with above-mentioned solid phase extraction column 14, it is adsorbed on this solid-phase extraction column 14, the moisture that will do not adsorbed etc., first supply condition (with reference to Fig. 6 (a)) of discharging by second stream 22C escape hole 15 downwards by solid-phase extraction column 14; With use manual or electronic, make direction of arrow rotation 60 degree of above-mentioned reel 22 to Fig. 6 (a), by the first path 22A and supply passageway 22D, supply with above-mentioned effluent to solid-phase extraction column 14, with the analytic target material wash-out that is attracted on this solid-phase extraction column 14, by second supply condition (with reference to Fig. 5 and Fig. 6 (b)) of the 3rd stream 22B, importing entry needle 18 (gas chromatography 2).When above-mentioned transfer valve 22 is set to second supply condition, entry needle 18 and its are moved downwards simultaneously, become the state that entry needle 18 is inserted in the gas chromatography 2.In addition, spend to the direction of arrow shown in the figure (in the other direction) rotation 60 from second supply condition of Fig. 6 (b), return above-mentioned first supply condition by making reel 22.At this moment, will contain the solution of derivatization reagent and the analytic target material that flows out from solid-phase extraction column 14 together in the injection gas chromatography 2, can be with analytic target material derivantization in storeroom 19.
Fig. 1 represents to be provided with the pump 12 that is used for supplying with to the eluate that contains the analytic target material that is separated by liquid chromatography 2 first solution, and Fig. 7 represents not supply with the analytical equipment of first solution in eluate.Other does not have the part and Fig. 1 identical of explanation.
As shown in Figure 8, the discharge side place in the lower end of the above-mentioned solid phase extraction column 14 in second path 16 is provided with the solid-phase extraction column 23 that snotter is removed usefulness, is used for adsorbing the snotter that contains from the eluent of this solid-phase extraction column 14 eluted analytic target materials.Thus, can analyze and omit the pre-treatment that purifies, the advantage that can shorten analysis time is arranged.Other does not have the part and Fig. 1 identical of explanation.
As shown in Figure 9, another solid-phase extraction column 24 of same structure can be installed freely in first path 10 also with loading and unloading, being used for adsorbing once more can not be by the analytic target material of above-mentioned solid phase extraction column 14 absorption.In Fig. 9, demonstrated 2 solid-phase extraction columns 14,24, the solid-phase extraction column more than 3 also can freely be installed in first path 10 with loading and unloading.Therefore, behind a plurality of by utilizing (being 2 among Fig. 8) solid-phase extraction column 14,24 adsorption analysis object materials, these solid-phase extraction columns 14,24 are pulled down and are installed in second path 16, utilize eluent to make analytic target material wash-out, with only compare with the situation of 1 solid-phase extraction column, 14 adsorption analysis object materials, adsorption analysis object material more, thus can analyze more reliably.Other does not have the part and Fig. 1 identical of explanation.
As shown in figure 10, also can be in first path 10 can second solid-phase extraction column 25 be installed freely with loading and unloading, being used to adsorb can not be by other analytic target material of above-mentioned solid phase extraction column 14 absorption.Like this, second pump 17,17A are installed in respectively among second path 16, the 16A, be used for supplying with different eluents to the solid-phase extraction column 14,25 that has adsorbed 2 kinds of different analytic target materials, from the different analytic target material of each solid-phase extraction column 14,25 wash-out, supply with different 2 vaporizers 20,20A respectively, can analyze different analytic target materials simultaneously.Represented to be provided with the situation of 2 solid-phase extraction columns 14,24 among Figure 10, but solid-phase extraction column more than 3 also can be set, to analyze the analytic target material more than 3 kinds.In addition, Figure 10 has represented to be provided with the situation of different vaporizer 20,20A, but carries out wash-out by making different analytic target materials have mistiming ground, also can analyze in same vaporizer.Other does not have the part and Fig. 1 identical of explanation.
As shown in figure 11, being provided with a plurality of in cylinder anchor clamps 28 (is 3 among the figure, also can be more than 2 or 4) solid-phase extraction column 14,26,27, use driving mechanisms such as motor, make the timing of the analytic target material that cylinder anchor clamps 28 and the analytic target material with a plurality of peaks flow out when each peak consistent (according to passage of time or from the detection signal of sensor), on the length direction of cylinder anchor clamps 28, move, can adsorb analytic target material thus with a plurality of peaks.Then, the cylinder anchor clamps 28 that kept being adsorbed with the solid-phase extraction column 14,26,27 of analytic target material are switched to second path 16 from first path 10, use driving mechanism such as motor, cylinder anchor clamps 28 are moved at length direction, can analyze the analytic target material at a plurality of peaks.When above-mentioned solid phase extraction column 14,26,27 adsorbs different analytic target materials, carry out wash-out, in different vaporizers, carry out the analysis of a plurality of analytic target materials with different eluents.In addition, during the analytic target material of a plurality of solid-phase extraction columns 14,26,27 absorption identical type, under the state that a plurality of solid-phase extraction columns 14,26,27 and second path 16 are connected in series, from a pump outflow eluent, with analytic target material wash-out.Other does not have the part and Fig. 1 identical of explanation.
In first path 10 and second path 16 all with solid line presentation graphs 1, Fig. 7, solid-phase extraction column 14 shown in Figure 8, but in fact, when it in first path 10 time, just not in second path 16, when it in second path 16 time, just not in first path 10, solid-phase extraction column 14 becomes the state that only is connected with the path of any one party.In addition, in the solid-phase extraction column of putting down in writing in Fig. 9~Figure 11 14,24,25,26,27, solid-phase extraction column (being 14,24 among Fig. 9, is 14,25 among Figure 10, is 14,26,27 among Figure 11) becomes the state that only is connected with the path of any one party similarly.
Embodiment 1
Utilize the interpolation recovery test to carry out the analysis of the remains of pesticide in the spinach.
(preparation of sample)
Weighing 20g spinach adds the 100ml acetonitrile, add the ethoprop of 0.02mg after, carry out homogenizing, to its carry out suction filtration, with filtrate as the spinach extract.
(analytical equipment)
Liquid chromatography (HPLC)
Post: ODS2.1 * 100mm
Mobile phase: 70% acetonitrile solution
Flow velocity: 0.2ml/min
Injection rate IR: 5 μ l
Measure wavelength: 254nm
Gas chromatography (GC/MS)
Storeroom: a large amount of injection with (using the gastric pattern lining)
Storeroom temperature: 60 ℃-100 ℃/min-250 ℃ (20min)
Column oven temperature: 60 ℃ of (4min)-10 ℃/min-260 ℃ (5min)
Interface
Solid-phase extraction column: solid phase C18
Add liquid: water, 2ml/min
Eluent: acetone, 50 μ l
(analytical approach)
In HPLC, inject 10 μ l spinach extracts, utilize liquid chromatography to separate.Valve is switched to the elution time of the ethoprop of investigation in advance, and the limit adds entry, solid-phase extraction column is passed through on the limit.At this moment, ethoprop is attracted on this solid-phase extraction column.Mounting of syringe on this solid-phase extraction column utilizes eluent acetone to make in its storeroom that directly is eluted to gas chromatography, is analyzed by GC/MS.Its result, ethoprop obtains the recovery more than 90% and good chromatogram as shown in Figure 3.The 21A of Fig. 3 represents the peak of ethoprop.
Embodiment 2
Utilize the interpolation recovery test to carry out the analysis of the remains of pesticide in the spinach.
(preparation of sample)
Weighing 20g spinach adds the 100ml acetonitrile, add the 0.02mg chlopyrifos after, carry out homogenizing, to its carry out suction filtration, with filtrate as the spinach extract.
(analytical equipment)
Liquid chromatography (HPLC)
Post: C23.0mm i.d. * 100mm
Parting liquid: 50% acetonitrile solution
Flow velocity: 0.5ml/min
Injection rate IR: 100 μ l
Measure wavelength: 210nm
Interface
Solid-phase extraction column: solid phase styrene-divinylbenzene
Eluent: hexane solution
Gas chromatography (GC/MS)
Storeroom: a large amount of injection with (using the gastric pattern lining)
Storeroom temperature: 70 ℃-120 ℃/min-220 ℃ (3min)-50 ℃/min-260 ℃ (10min)
Column oven temperature: 70 ℃ of (3min)-20 ℃/min-280 ℃ (4min)
MS mode: SCAN
(analytical approach)
In HPLC, inject 100 μ l spinach extracts, utilize liquid chromatography to separate.Valve is switched to the elution time of the chlopyrifos of investigation in advance, pass through solid-phase extraction column.At this moment, chlopyrifos is attracted on this solid-phase extraction column.Mounting of syringe on this solid-phase extraction column utilizes the eluent hexane to make in its storeroom that directly is eluted to gas chromatography, is analyzed by GC/MS.Its result, chlopyrifos obtains as shown in Figure 4 good SCAN chromatogram with the recovery more than 90%.21B shown in Figure 4 is the peak of chlopyrifos.
Embodiment 3
In storeroom, inject sample and derivatization reagent continuously, in storeroom, derive after the materialization, analyze.
(preparation of sample and derivatization reagent)
As sample, use pentachlorophenol and the bisphenol-A material after with acetone diluted.As derivatization reagent, use N, two (trimethyl silyl) trifluoroacetamides (BSTFA) of O-are with the material after the acetone diluted.
(analytical equipment)
Gas chromatography (GC/MS)
Post: DB-5ms 0.25mm i.d. * 30m, df=0.25 μ m
Vaporizer temperature: 50 ℃-30 ℃/min-180 ℃ (2min)
Furnace temp: 50 ℃ of (5min)-20 ℃/min-240 ℃ (4min)
Carrier gas: He
Shunting (split) initial stage flow: 30ml/min
Do not shunt the time (splitless time): 5min
Sample injection rate IR: 2 μ l
BSTFA injection rate IR: 1 μ l
(analytical approach)
Inject sample and hold it in the storeroom 19 of vaporizer 20.Then, derivatization reagent (BSTFA) is injected vaporizer 19.The temperature of vaporizer 20 is set at proper temperature, the materialization of deriving while concentrating.This derived material is imported gas chromatography.Figure 12 represents the chromatogram by this analysis generation.From this result as can be known, positively carried out deriving materialization.Use this derivatization reagent injection method, following advantage is arranged: can omit the pre-treatment operation of the materialization of deriving in advance, and can derive materialization and hand do not contact human body is brought dysgenic derivatization reagent, in addition, can after the materialization of deriving, analyze immediately.
Utilizability on the industry
The analytical approach of organic chemicals of the present invention can be rapidly and critically measure specific remains of pesticide and environmental hormone about a kind~20 kinds, is suitable for the security of evaluation object food etc. promptly.

Claims (14)

1. the analytical approach of an organic chemicals is characterized in that:
In the analysis of organic chemicals, lateral dominance with liquid chromatography to the assay sample that from the analytic target sample, extracts organic chemicals and preparation in advance separate, the limit adds different solution in this isolated eluate that contains the analytic target material, make this analytic target material be adsorbed on the solid-phase extraction column continuously from liquid chromatography, utilize eluent will be attracted to upright the connecing in the storeroom that is eluted to gas chromatography of material for testing on this solid-phase extraction column, utilize gas chromatography analysis.
2. the analytical approach of an organic chemicals is characterized in that:
In the analysis of organic chemicals, lateral dominance with liquid chromatography to the assay sample that from the analytic target sample, extracts organic chemicals and preparation in advance separate, the limit passes through solid-phase extraction column with this isolated eluate that contains the analytic target material, this analytic target material is adsorbed on this solid-phase extraction column continuously, utilize eluent will be attracted to upright the connecing in the storeroom that is eluted to gas chromatography of material for testing on this solid-phase extraction column, utilize gas chromatography analysis.
3. the analytical approach of organic chemicals as claimed in claim 1 or 2, it is characterized in that: utilize eluent will be attracted to analytic target material wash-out on the described solid-phase extraction column, when directly being eluted in the storeroom of gas chromatography, derivatization reagent is dissolved in this eluent, is injected in the storeroom of gas chromatography with the analytic target material, in storeroom, with after the analytic target material derivantization, utilize this derivant of gas chromatographic analysis.
4. the analytical approach of organic chemicals as claimed in claim 1 or 2, it is characterized in that: utilize eluent will be attracted to analytic target material wash-out on the described solid-phase extraction column, then, this eluent is passed through another solid-phase extraction column, the effluent of removing behind the snotter is injected in the storeroom of gas chromatography, utilizes gas chromatography analysis.
5. the analytical approach of organic chemicals as claimed in claim 4 is characterized in that:
Utilize eluent will be attracted to analytic target material wash-out on the described solid-phase extraction column, then, this eluent is passed through another solid-phase extraction column, when the effluent after will removing snotter is injected in the storeroom of gas chromatography, derivatization reagent is dissolved in this effluent, is injected in the storeroom of gas chromatography with the analytic target material, in storeroom, with after the analytic target material derivantization, utilize this derivant of gas chromatographic analysis.
6. as the analytical approach of each described organic chemicals in the claim 1~5, it is characterized in that: described analytic target material is a kind~20 kinds.
7. the analytical equipment of an organic chemicals is characterized in that, comprising:
Be used for importing and separating the liquid chromatography of organic chemicals extraction that the analytic target sample is comprised and the assay sample of preparing; Be used for according to this analytic target material by the isolated time that washes out of containing the eluate of analytic target material of this liquid chromatography, supply with first feed mechanism of first solution different automatically with this eluate; Be used to adsorb the solid-phase extraction column of the analytic target material that utilizes described first solution and shift by the mixed liquor of the isolated eluate of liquid chromatography; Be used for supplying with automatically second feed mechanism of the eluent that is used to make the analytic target material wash-out that is attracted on this solid-phase extraction column; With the entry needle that is used for described eluted analytic target material is imported gas chromatography, is connected with the flow export of described solid-phase extraction column.
8. the analytical equipment of organic chemicals as claimed in claim 7 is characterized in that:
Utilize described first solution and be adsorbed onto first path on the described solid-phase extraction column except being used to make by the analytic target material that the mixed liquor of the isolated eluate of liquid chromatography shifts, be provided with in addition being attracted to the analytic target material wash-out on the described solid-phase extraction column and importing second path of described gas chromatography, described solid-phase extraction column constituted 2 paths can freely mount and dismount separately.
9. the analytical equipment of organic chemicals as claimed in claim 8 is characterized in that:
Be provided with transfer valve, be used for supply condition is switched to second supply condition that will utilize described first solution and be supplied with described solid-phase extraction column and made it be adsorbed on first supply condition on this solid-phase extraction column and described eluent is supplied with described solid-phase extraction column, will be attracted to the analytic target material wash-out on this solid-phase extraction column and import described gas chromatography by the analytic target material that the mixed liquor of the isolated eluate of liquid chromatography shifts.
10. as the analytical equipment of each described organic chemicals in the claim 7~9, it is characterized in that: described gas chromatography is provided with the storeroom that does not contain the trapping agent that can store the analytic target material that imports from described entry needle for the time being in vaporizer.
11. the analytical equipment of an organic chemicals is characterized in that, comprising:
Be used for importing and separating the liquid chromatography of organic chemicals extraction that the analytic target sample is comprised and the assay sample of preparing; Be used to detect testing agency by the analytic target material of this liquid chromatography separation and transfer; Be used for surveying signal, will discharging the destination switches to predominating path one side from discharge path one side discharge destination transfer valve according to material for testing quality inspection from this testing agency; Be used to adsorb utilize described discharge destination transfer valve switch to predominating path one side, with the analytic target material that eluate shifts, be arranged on the solid-phase extraction column on this predominating path; Be used to supply with the feed mechanism that the analytic target material that will be attracted on this solid-phase extraction column imports the eluent of gas chromatography; Be used for import with the analytic target material of described eluent wash-out gas chromatography, be connected with the flow export of described solid-phase extraction column can knee-action entry needle.
12. the analytical equipment of organic chemicals as claimed in claim 11 is characterized in that:
Except being used to make the analytic target material that shifts with described eluate to be adsorbed onto first path on the described solid-phase extraction column, the eluent be used to from described feed mechanism is set in addition, will be attracted to the analytic target material wash-out on the described solid-phase extraction column and imports second path of described gas chromatography, described solid-phase extraction column is constituted 2 paths can freely mount and dismount separately.
13. the analytical equipment of organic chemicals as claimed in claim 11 is characterized in that:
Be provided with the supply condition transfer valve, be used for supply condition is switched to second supply condition that the analytic target material that shifts with described eluate is supplied with described solid-phase extraction column and made it be adsorbed on first supply condition on this solid-phase extraction column and supply with described eluent, will be attracted to the analytic target material wash-out on this solid-phase extraction column and import described gas chromatography to described solid-phase extraction column.
14. the analytical equipment as each described organic chemicals in the claim 11~13 is characterized in that:
Described gas chromatography is provided with the storeroom that does not contain the trapping agent that can store the analytic target material that imports from described entry needle for the time being in vaporizer.
CN 200480036198 2003-12-05 2004-12-03 Method of analyzing organic chemical substance and apparatus for analysis CN1890562A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
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CN102967495A (en) * 2012-11-21 2013-03-13 北京普立泰科仪器有限公司 Sample pretreatment device and sample treatment method
CN103189518A (en) * 2010-09-08 2013-07-03 Sk新技术株式会社 Method of preparing alkyl butyrate from fermented liquid using microorganisms
CN103278589A (en) * 2013-05-03 2013-09-04 云南烟草科学研究院 Detection method and device for volatile and semi-volatile components
CN105164527A (en) * 2013-04-26 2015-12-16 住友电气工业株式会社 Method for analysis for organic substance contained in solution to be examined

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103189518A (en) * 2010-09-08 2013-07-03 Sk新技术株式会社 Method of preparing alkyl butyrate from fermented liquid using microorganisms
CN103189518B (en) * 2010-09-08 2014-12-24 Sk新技术株式会社 Method of preparing alkyl butyrate from fermented liquid using microorganisms
CN102967495A (en) * 2012-11-21 2013-03-13 北京普立泰科仪器有限公司 Sample pretreatment device and sample treatment method
CN102967495B (en) * 2012-11-21 2015-04-01 北京普立泰科仪器有限公司 Sample pretreatment device and sample treatment method
CN105164527A (en) * 2013-04-26 2015-12-16 住友电气工业株式会社 Method for analysis for organic substance contained in solution to be examined
CN103278589A (en) * 2013-05-03 2013-09-04 云南烟草科学研究院 Detection method and device for volatile and semi-volatile components

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