CN104280491B - A kind of analytical approach detecting 11 kinds of ionic liquid cation in soil - Google Patents
A kind of analytical approach detecting 11 kinds of ionic liquid cation in soil Download PDFInfo
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- CN104280491B CN104280491B CN201310277864.3A CN201310277864A CN104280491B CN 104280491 B CN104280491 B CN 104280491B CN 201310277864 A CN201310277864 A CN 201310277864A CN 104280491 B CN104280491 B CN 104280491B
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Abstract
The invention discloses a kind of LC-MS/MS analytical approach simultaneously detecting 11 kinds of ionic liquid cation in soil.It is characterized in that: sample extracts through acetonitrile-ammonium chloride mixed solution, StrataX-CW solid phase extraction column purifies, and adopts chromatographic column to be separated, with the aqueous formic acid of acetonitrile+0.1% for mobile phase carries out gradient elution, with electron spray positive ion mode (ESI
+) ionization, multiple-reaction monitoring pattern (MRM) detects, quantified by external standard method.Detect and be limited to (S/N >=3) for 0.05-1.0ng/mL, quantitative limit (S/N >=10) is 0.15-3.0ng/mL, and 11 kinds of ionic liquid cation are good linear (r2 & gt within the scope of 2-500ng/mL; , and single injected sampling analysis only needs 12min 0.999).Take soil as matrix, the recovery of mark-on level is more than 90%, relative standard deviation & lt; 10%.The method have pre-treatment simple, detect the advantages such as quick, highly sensitive, qualitative, quantitative accurate, reproducible, be applicable to very much the retention analysis of micro ion liquid in ambient soil.
Description
Technical field
The present invention designs a kind of analyzing detecting method, specifically, relates to a kind of LC-MS/MS analytical approach simultaneously detecting 11 kinds of ionic liquid cation in soil.
Background technology
Ionic liquid (Ionicliquids, ILs), also known as ionic liquid at room temperature or room temperature molten salt, is generally made up of an organic cation and inorganic or organic anion.Owing to having unique physicochemical property, be widely used in the fields such as organic synthesis, galvanochemistry, new material, separating and extracting, living things catalysis by as " green " solvent.Although ILs decreases the pollution to air because of low vapour pressure, from environmental angle, ILs does not realize greenization completely.Because many ionic liquids have higher water-soluble and stability, along with its in a large number synthesis with use, ILs inevitably will be caused to discharge in environment, environment and ecological risk may be brought, to biology even the mankind produce potential hazard.There are some researches show at present, ionic liquid all has toxicity in various degree to algae, hydrobiont, microorganism, higher plant, fish and cell, and its toxicity and cation type, to replace side chain lengths relevant.And ILs has good chemical physical stability, its biodegradability is poor.Therefore, set up simply, efficiently, accurately the analytical technology of environment intermediate ion liquid cation is significant.
At present, the ILs kation assay method of bibliographical information mainly contains the chromatography of ions, ion pair chromatography, reversed phase liquid chromatography, capillary electrophoresis.But above method all has certain limitation, as low in chromatography of ions sensitivity, detection limit is generally 0.1-45mg/L, and be only suitable for separation side chain carbon atom number lower than 4 kation, comparatively strong to the cationic reservation of the ILs that alkyl side chain is longer, easily produce chromatographic peak hangover.Although reversed phase liquid chromatography improves detection sensitivity, the reservation and the selectivity that alkyl side chain carbon number are less than to the ionic liquid cation of 4 are more weak, and are subject to the impact of flowing Stationary liquid polarity and the equal factor of flowing.Aqueous favoring interaction chromatography (HILIC) is though can improve reverse-phase chromatography to the cationic selectivity of low carbon chain, and retain comparatively strong to strong polar, analysis time long (50-70min), efficiency is lower.
More than study be all adopt chromatographic technique, due to some ionic liquid cation without uv absorption or uv absorption more weak, traditional chromatogram just cannot detect the ionic liquid cation without uv absorption.Moreover above method only rests on basic skills establishment stage, the matrix too trace analysis of ILs in complex environment sample cannot be met, be necessary to carry out pre-treatment to environmental sample, to improve detection sensitivity and specificity.But about the analysis of soil intermediate ion liquid, after only having Nichthauser etc. to adopt saturated ammonium chloride-methyl alcohol (v/v1:9, PH=3) Extraction solvent to carry out ultrasonic extraction to soil intermediate ion liquid at present, the report it analyzed by liquid chromatography.But author only analyzes BMIM
+and HMIM
+two kinds of ILs kations, and HMIM
+the recovery lower (40%), may be the longer cause stronger with the adhesion of soil with organic matter of cationic side chain alkyl.Therefore, be necessary to study further pretreatment technology on this basis.
High performance liquid chromatography-tandem mass technology can according to characteristic ion and thus the fragments characteristic that produces of characteristic ion fracture as the fingerprint of a certain target chemical, it is chosen from the sample of complex matrices and carries out quantitative test, therefore, there is the advantages such as highly sensitive, selectivity is strong, qualitative, quantitative is accurate, make up the deficiency that chromatography detects.Therefore, the present invention can overcome the defect of above analytical approach, ultrasound wave extraction is carried out to soil intermediate ion liquid, after Solid-Phase Extraction column purification, in conjunction with Liquid Chromatography-Mass Spectrometry (HPLC-MS/MS) technology, accurate qualitative and quantitative analysis is carried out to target determinand, for the trace analysis of environment intermediate ion liquid cation provides technological means.
Summary of the invention
The object of this invention is to provide a kind of analytical approach simultaneously detecting different kinds of ions liquid cation in soil.Specifically to 1-ethyl-3-methylimidazole (EMIM in soil
+), 1-ethyl-2,3-methylimidazole (EMMIM
+), 1-propyl group-3-methylimidazole (PMIM
+); 1-butyl-3-methylimidazole (BMIM
+), 1-amyl group-3-methylimidazole (AMIM
+), 1-hexyl-3-methylimidazole (HMIM
+), 1-octyl group-3-methylimidazole (OMIM
+), 1-decyl-2,3-methylimidazole (DMMIM
+), N-ethylpyridine bromine salt (EPy
+), N-butyl-pyridinium (BPy
+), N-hexyl pyridine (HPy
+) 11 kinds of ionic liquid cation carry out extracting and developing purification and qualitative and quantitative analysis.The detectability (S/N >=3) of the present invention to 11 kinds of ionic liquid cation is 0.05-1.0ng/mL, and quantitative limit (S/N >=10) is 0.15-3.0ng/mL.Take soil as matrix, the recovery of mark-on level is more than 90%, and relative standard deviation <10%, 11 kinds of ILs kations realized baseline separation in 12 minutes.
Above-mentioned purpose is achieved through the following technical solutions, and key step is as follows.
1. extract: take soil sample that (1.00g ± 0.02) prepare in tool plug centrifuge tube, add mixed standard solution, 50 DEG C of oven dryings, (volume ratio is 8:2 to add acetonitrile-0.2M ammonium chloride, pH=3) solution 8mL is extracted, after vortex mixed, ultrasonic extraction 30min, extract is with the centrifugal 5min of 10000r/min, repeat extraction twice, merge supernatant, nitrogen blows down and removes organic solvent, 16mL is settled to water, to be clean.
2. purify: StrataX-CW solid phase extraction column carries out pre-service with acetonitrile, each 3mL of water successively, then accurately pipettes 16mL supernatant loading.Use 3mL water, acetonitrile drip washing pillar successively, with the acetonitrile-0.2mol/L ammonium chloride of 6mL, (volume ratio is 1: 1, PH3) wash-out, wash-out liquid nitrogen blows, with initial flow phase acetonitrile-0.1% formic acid water, (volume ratio is 1:9, v/v) be settled to 5mL, cross 0.22 μm of organic filter membrane, filtrate measures for HPLC-MS/MS.
3. the scavenging solution that institute's step 2 obtains is carried out liquid chromatography tandom mass spectrometry determination.Chromatographic condition: (1) chromatographic column: AgilentSB-C18(2.1mm × 50mm, 1.88 μm); (2) mobile phase: mobile phase A: acetonitrile, Mobile phase B: 0.1% aqueous formic acid; (3) gradient elution: (initially) 0min, A:B volume ratio is 10:90; 8min, A:B ratio becomes 90:10; 8-10min, A:B ratio is 90:10; After 10min, A:B ratio returns to 10:90; (4) flow velocity: 0.3mL/min; (5) chromatographic column temperature: 40 DEG C; (6) sampling volume: 5 μ L.Mass Spectrometry Conditions: (1) ESI positive ion scans; (2) capillary voltage 3.0kV; (3) desolventizing temperature degree 350 DEG C; (4) desolventizing gas (N2) flow 10L/h; (5) 350 DEG C, sheath gas; (6) sheath airshed 10L/h; (7) monitoring mode: reaction of high order is monitored, carries out quantitative test by reaction of high order monitoring.
The present invention establishes the LC-MS/MS analytical approach of 11 kinds of ionic liquid cation in soil, the method pre-treatment is simple, detect fast, highly sensitive, qualitative, quantitative is accurate, the recovery is stablized, be applicable to detect while components liquid multiple in soil environment sample.
Accompanying drawing explanation
Figure 111 plants ionic liquid standard solution total ion current figure.
The mark-on collection of illustrative plates of 11 kinds of ionic liquids in Fig. 2 pedotheque.
The mark-on collection of illustrative plates of 11 kinds of ionic liquids in Fig. 3 river silt.
Fig. 4 is EPY
+second order ms figure.
Fig. 5 is EMIM
+second order ms figure.
Fig. 6 is EMMIM
+second order ms figure.
Fig. 7 is PMIM
+second order ms figure.
Fig. 8 is BPY
+second order ms figure.
Fig. 9 is BMIM
+second order ms figure.
Figure 10 is AMIM
+second order ms figure.
Figure 11 is HPY
+second order ms figure.
Figure 12 is HMIM
+second order ms figure.
Figure 13 is OMIM
+second order ms figure.
Figure 14 is DMMIM
+second order ms figure.
Drawing reference numeral illustrates: peak 1.EPY
+, 2.EMIM
+, 3.EMMIM
+, 4.PMIM
+, 5.BPY
+, 6.BMIM
+, 7.AMIM
+, 8.HPY
+, 9.HMIM
+, 10.OMIM
+, 11.DMMIM
+.
Embodiment
Embodiment 1 agricultural land soil sample intermediate ion liquid detecting.
1. pedotheque preparation: natural air drying after soil collecting, removal of impurities, grinding, excessively 20 mesh sieves, for subsequent use.
2. the configuration of standard solution: preparation of (1) single mark storing solution: accurately take 11 kinds of each 50mg of ionic liquid respectively, becomes mass concentration to be the standard reserving solution of 5.0mg/mL with acetontrile, saves backup at-20 DEG C.(2) preparation of hybrid standard working fluid: draw a certain amount of often kind of standard reserving solution in same volumetric flask, is diluted to the required working solution of experiment with mobile phase, now with the current.
3. sample pre-treatments: (1) extracts: take soil sample that 1.00g (accurately to 0.01g) prepares in 50mL tool plug centrifuge tube, add certain density mixed standard solution 2mL, add EDTA solution 60 μ L(37.5g/L), room temperature places 60min, nitrogen blows, 50 DEG C of oven drying 4h, (volume ratio is 8:2 to add acetonitrile-0.2M ammonium chloride, pH=3) solution 8mL is extracted, after vortex mixed, ultrasonic extraction 30min, temperature 30 DEG C, extract is with the centrifugal 5min of 10000r/min, repeat extraction twice, merge supernatant, 40 DEG C of nitrogen blow down and remove organic solvent, 16mL is settled to water, to be clean.(2) purify: StrataX-CW solid phase extraction column carries out pre-service with acetonitrile, each 3mL of water successively, then accurately pipettes 16mL supernatant loading.Use 3mL water, acetonitrile drip washing pillar successively, with acetonitrile-0.2mol/L ammonium chloride (volume ratio is 1: 1, the PH3) wash-out of 6mL, wash-out liquid nitrogen blows, be settled to 5mL with mobile phase acetonitrile-0.1% formic acid water (volume ratio is 1:9), cross 0.22 μm of organic filter membrane, filtrate measures for HPLC-MS/MS.
4. chromatographic condition: (1) instrument and equipment: Agilent1200 liquid chromatography; (2) chromatographic column: AgilentSB-C18(2.1mm × 50mm, 1.88 μm); (3) mobile phase: mobile phase A: acetonitrile, Mobile phase B: 0.1% aqueous formic acid; (4) gradient elution: (initially) 0min, A:B volume ratio is 10:90; 8min, A:B ratio becomes 90:10; 8-10min, A:B ratio is 90:10; After 10min, A:B ratio returns to 10:90; (5) flow velocity: 0.3mL/min; (6) chromatographic column temperature: 40 DEG C; (7) sampling volume: 5 μ L.
5. Mass Spectrometry Conditions: (1) instrument and equipment: 6460TripleQuadLC/MS electron spray series connection quadrupole mass spectrometer; (2) ESI positive ion scanning; (3) capillary voltage 3.0kV; (4) desolventizing temperature degree 350 DEG C; (5) desolventizing gas (N2) flow 10L/h; (6) 350 DEG C, sheath gas; (7) sheath airshed 10L/h; (8) monitoring mode: reaction of high order is monitored, and compares carry out qualitative analysis with ion pair (parent ion and two daughter ions) information, carries out quantitative test with parent ion and the highest daughter ion of response.The MRM analytical parameters such as impact energy, monitoring ion of 11 kinds of ionic liquids and molecular structural formula are in table 1, and total ion current figure is shown in Fig. 1, and its second order ms scintigram is shown in Fig. 4-14.
6. typical curve, the range of linearity, detection limit and quantitative limit: the mixed solution of 11 kinds of ionic liquids is carried out gradient dilution and become 1.0,0.5,0.2,0.1,0.05,0.02,0.01,0.005,0.002,0.001 μ g/mL series standard working fluid, adopt above-mentioned instrument condition to analyze.With sample introduction mass concentration for horizontal ordinate, peak area is ordinate, carries out linear regression calculating, tries to achieve 11 kinds of cationic linear equations of ILs and related coefficient.Sample quality concentration corresponding when calculating 3 times of signal to noise ratio (S/N ratio)s (S/N >=3) and 10 times signal to noise ratio (S/N ratio) (S/N >=10), respectively as detection limit (LOD) and the quantitative limit (LOQ) of method.Continuous 9 replication mixed standard solutions under finite concentration, calculate relative standard deviation (RSD), the results are shown in Table 2.As can be seen from Table 2,11 kinds of ionic liquids are good in 2-500ng/mL scope internal linear relation, correlation coefficient r
2more than 0.999, detection limit (S/N>=3) is 0.05-1.0ng/mL, and quantitative limit (S/N>=10) is 0.15-3.0ng/mL, and can meet residual quantitative test requirement completely, method shows good accuracy and reappearance.
7. the recovery and Precision Experiment: adopt and mark-on recovery test is carried out to investigate accuracy and the precision of method to negative sample, namely background is not contained to the negative pedotheque of ionic liquid, add the ILs mixed standard solution being equivalent to 40ng/g, sample pre-treatments is carried out according to 2 joints, the condition in 3 and 4 joints is utilized to detect, 11 kinds of ionic liquid mark-on analysis chart spectrograms 2, average recovery and relative standard deviation (RSD) are in table 3.As can be seen from Table 3, the TIANZHU XINGNAO Capsul scope of 11 kinds of standard specimens is 92.1%-107.6%, and relative standard deviation (RSD) scope is 0.31-5.60%, shows that this analytical approach accurately, reliably.
Example 2 river silt sample intermediate ion liquid residue detects.
Have detected the ionic liquid liquid in river silt sample by the method for above-described embodiment 1, in embodiment 2, preprocess method, chromatographic mass spectrometry condition, detecting instrument, typical curve are all with reference to embodiment 1.
Sample mark-on is analyzed collection of illustrative plates and is seen Fig. 3, and recovery of standard addition is in table 4.The TIANZHU XINGNAO Capsul scope of 11 kinds of standard specimens is 93.0%-105.8%, and relative standard deviation (RSD) scope is 0.8-6.1%.
Embodiment illustrates that the present invention can detect the different kinds of ions liquid added in ambient soil simultaneously, and have the advantages such as resolution is high, quick, accurate, overcoming other detection methods cannot to the shortcoming of different kinds of ions fluid mark component analysis in environmental sample.
Claims (4)
1. detect a LC-MS/MS analytical approach for 11 kinds of ionic liquid cation in soil, it is characterized in that, said method comprising the steps of:
(1) extract: take soil sample in tool plug centrifuge tube, add 11 kinds of ionic liquid mixed standard solutions, room temperature places 60min, and nitrogen blows, 50 DEG C of oven dry, add acetonitrile-ammonium chloride and extract solution, vortex mixes, ultrasonic extraction, extract is centrifugal, gets supernatant, and nitrogen blows down and removes organic solvent, uses pure water constant volume;
(2) Solid-Phase Extraction: extraction solution step (1) obtained is after the good cationic solid phases extraction column of drip washing in advance, and with the mixed solution wash-out of acetonitrile and ammonium chloride, wash-out liquid nitrogen blows, and with initial flow phase constant volume, crosses 0.22 μm of organic filter membrane;
(3) liquid chromatograph-mass spectrometer measures: be separated, the filtrate that step (2) obtains with acetonitrile+aqueous formic acid for mobile phase carries out gradient elution through chromatographic column; With electron spray positive ion mode (ESI
+) ionization, multiple-reaction monitoring pattern (MRM) detects, and quantified by external standard method is analyzed;
In step (3), chromatographic condition is: chromatographic column: AgilentSB-C18, and specification is 2.1mm × 50mm, 1.88 μm; Mobile phase: acetonitrile A+0.1% aqueous formic acid B; Drip washing gradient is: initial flow phase A:B volume ratio is 10:90; In 8min, A:B ratio becomes 90:10; 8-10min, A:B ratio is 90:10; After 10min, A:B ratio returns to 10:90; Flow velocity is 0.3mL/min; Column temperature 40 DEG C; Sample size 5 μ L;
11 kinds of described ionic liquid cation are: 1-ethyl-3-methylimidazole EMIM
+, 1-ethyl-2,3-methylimidazole EMMIM
+, 1-propyl group-3-methylimidazole PMIM
+, 1-butyl-3-methylimidazole BMIM
+, 1-amyl group-3-methylimidazole AMIM
+, 1-hexyl-3-methylimidazole HMIM
+, 1-octyl group-3-methylimidazole OMIM
+, 1-decyl-2,3-methylimidazole DMMIM
+, N-ethylpyridine bromine salt EPy
+, N-butyl-pyridinium BPy
+, N-hexyl pyridine HPy
+.
2. a kind of LC-MS/MS analytical approach detecting 11 kinds of ionic liquid cation in soil as claimed in claim 1, is characterized in that: in step (1), the mixed volume of extract acetonitrile and ammonium chloride is 3.0 than being 8:2, pH; Ultrasonic extraction 10-30min, temperature 20-50 DEG C, the ratio of sample and extract is 1:5-10.
3. a kind of LC-MS/MS analytical approach detecting 11 kinds of ionic liquid cation in soil as claimed in claim 1, is characterized in that: in step (2), solid-phase extraction column is StrataX-CW post; Elute soln acetonitrile is 1:1, pH with the mixed volume ratio of ammonium chloride is 3.0; Constant volume solution is initial flow phase: acetonitrile+0.1% aqueous formic acid, and its volume ratio is 1:9.
4. a kind of LC-MS/MS analytical approach detecting 11 kinds of ionic liquid cation in soil as claimed in claim 1, is characterized in that: in step (3), Mass Spectrometry Conditions is positive ion scanning (ESI+); Multiple-reaction monitoring (MRM); Capillary voltage is 3.0kV; Desolventizing temperature degree is 350 DEG C; Sheath temperature degree is 350 DEG C, and desolventizing gas and sheath airshed are 10L/min; Multiple-reaction monitoring Mass Spectrometry Conditions is as follows:
。
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Non-Patent Citations (3)
| Title |
|---|
| Analysis of residual ionic liquids in environmental samples: Development of extraction methods;Joanna Nichthauser等;《Chemosphere》;20081122;第74卷;第2.3.2节、第2.4节、第3.2节 * |
| Reversed-phase liquid chromatographic method for the determination of selected room-temperature ionic liquid cations;Piotr Stepnowski等;《Journal of Chromatography A》;20031231;第993卷;第2.3节，表1，图1 * |
| Sorption of ionic liquids onto soils:Experimental and chemometric studies;Wojciech Mrozik等;《Chemosphere》;20120421;第88卷;第1202～1207页 * |
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