CN1326587C - Hanging drop type liquid-liquid micro-extraction method - Google Patents
Hanging drop type liquid-liquid micro-extraction method Download PDFInfo
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Abstract
The present invention relates to a hanging drop type liquid-liquid micro-extraction method which comprises the steps that liquid samples to be analyzed are added and stirred, and extractant is sucked quantificationally, so that the extractant drips on sample liquid; after set time is achieved, a sampler is used for sucking the extractant quantificationally from the liquid drop of the extractant, and the extractant is detected by an analytical instrument. The hanging drop type liquid-liquid micro-extraction method provided by the present invention has the characteristic of few sample requirement levels, and can effectively eliminate the interference of coexistent constituents in complex samples so as to realize high multiplying power concentration and lower analysis and detection limits and analysis cost. The present invention is combined and used with various color spectrum, spectrum and electrochemical analysis methods conveniently, and can be used for the analysis procedure of fields, such as food safety detection, environmental monitoring, natural resource extraction, drug and chemical production, etc. The present invention has strong technical superiority and wide application prospects.
Description
Technical field
The present invention relates to a kind of hanging drop type liquid-liquid micro-extraction method, particularly a kind of hanging drop type liquid-liquid micro-extraction method that is used for the analytic sample pre-treatment belongs to separating substances and analysis technical field.
Background technology
With analyzing detecting method efficiently quick, that high selectivity is feature is to realize cleaner production, the necessary condition of improving the quality of living.Along with improving constantly of social modernization's degree, people have higher requirement to the analytic process that is applied to fields such as food safety detection, environmental monitoring, traditional Chinese medicine quality control.The related system of these processes all has the characteristics of complex systems such as interference component is many, object content is low, and the direct quantitative analysis is very difficult.The key that realizes the complex system rapid analysis is to set up sample preparation technology fast and effectively, improves the efficient of sample concentration and purification process.
Liquid-liquid extraction is most widely used sample-pretreating methods because of it in the characteristics aspect system rerum natura and the operability, but traditional liquid-liquid extraction technology can't satisfy high enrichment, quick, Miniaturized requirement.For this reason, the micro-extraction sample making technology has received researcher's concern in recent years.This technology is divided into SPME (SPME) and liquid-phase micro-extraction (LPME) two classes, and common trait is to utilize the extraction phase of trace to extract synchronously and concentrate.The micro-extraction that at present business-like SPME technology is used is the polymeric coating layer on quartz fibre extracting head surface mutually, and SPME need not solvent, but exist extracting head costliness, rapid wear, easily cross pollution, with problem such as HPLC coupling difficulty.The micro-extraction that the LPME technology is used is the drop or the liquid film of micro updating mutually, and in existing bibliographical information, the method that forms little liquid phase comprises that capillary or syringe needle extension drip and liquid-film method.Compare with SPME,, favorable reproducibility low, be easy to and various Instrument crosslinkings based on mass-transfer efficiency height, the price of the LPME method of hang dripping technology, but owing to hang poor stability, the sampling of the process of dripping and easily carry secretly, to the requirement height of operating technology.
In sum, the LPME technology that comes from liquid-liquid extraction is significantly in the advantage aspect implementation cost, the scope of application, the detection speed, meets complex systems such as food samples, environmental samples, Chinese medicine sample are carried out conventional detection, popularize and detect and the on-the-spot requirement that detects.The key of LPME technology promotion and application is to set up stable, controlled LPME method, and then the GC-MS of development LPME and other efficient analysis method.
Summary of the invention
The objective of the invention is at the analytic process that is applied to fields such as food safety detection, environmental monitoring, natural resources extraction, medicine and chemicals production, develop and a kind ofly be used for that analytic sample concentrates and the hanging drop type liquid-liquid micro-extraction method of purification process.
A kind of hanging drop type liquid-liquid micro-extraction method, it comprises following steps:
The 1st step: in the extraction flask of temperature constant, built-in stirrer, add fluid sample to be analyzed;
The 2nd step: start agitating device and make stirring frequency constant;
The 3rd step: quantitatively draw extractant and make it to drip on sample liquid and to form hanging drop and pick up counting;
The 4th step: quantitatively draw the part extractant with sampler from extractant drop inside after reaching setting-up time, detect with analytical instrument.
The mass fraction of water is not less than 50% in the described fluid sample, can make this requirement of samples met by adding deionized water.
The scope of described stirring frequency is 1～50s
-1
The density of the extractant of described formation hanging drop is lower than the density of sample solution.
The extractant of described formation hanging drop is aromatic hydrocarbon and derivative, aliphatic ester class and ketone, the aliphatic hydrocarbon of C6～C16, the fatty alcohol of C4～C12.
The volume of the extractant of described formation hanging drop is 2～100 μ L.
Principle of the present invention is: trace organic phase splashes into when having the aqueous phase that stirs the field, being positioned at the whirlpool that stirs a center can suck solvent, at this moment solvent not only can be along with whirlpool rotates, and because the local depression that the whirlpool place exists, can make solvent under the effect of pressure, enter water, increase the contact area of two-phase, and remain on the whirlpool center with making solvent-stable, keep the stirring field to stablize and just can obtain stable organic facies form and flow condition.
Beneficial effect of the present invention: the sample requirement of the hanging drop type liquid-liquid micro-extraction method that the present invention proposes is few, only consume the organic solvent of micro updating, can effectively get rid of the interference of coexistence component in the complex sample, realize the high magnification enrichment, reduce analyzing and testing limit and analysis cost, very convenient with various chromatograms, spectrum, electrochemical analysis method coupling; Compare with other liquid-liquid micro-extraction method of having reported, have and make the characteristics simple and easy to do, that process stabilization is controlled, can be the degree of accuracy and the accuracy that improve the analyzing and testing result and give security.The hanging drop type liquid-liquid micro-extraction method that the present invention proposes can be used for the analytic process in fields such as food safety detection, environmental monitoring, natural resources extraction, medicine and chemicals production, has very strong technical advantage and wide application prospect.
Description of drawings
Fig. 1 is the operation chart of the hanging drop type liquid-liquid micro-extraction method of the present invention's proposition.
The HPLC spectrogram of Fig. 2 root of large-flowered skullcap extract.
The HPLC spectrogram of Fig. 3 root of large-flowered skullcap extract after the n-octyl alcohol micro-extraction is handled.
Fig. 4 root of large-flowered skullcap extract initial concentration and n-octyl alcohol micro-extraction be the correlation of ultimate density mutually.
Fig. 5 Radix Et Rhizoma Rhei extract dissociated anthraquinone initial concentration and benzene micro-extraction be the correlation of ultimate density mutually.
Fig. 6 acephatemet aqueous solution initial concentration and methyl isopropyl Ketone micro-extraction be the correlation of ultimate density mutually.
Fig. 7 phenalgin dish pyridine aqueous solution initial concentration and butyl acetate micro-extraction be the correlation of ultimate density mutually.
The initial concentration of benzene and the normal octane micro-extraction correlation of ultimate density mutually in Figure 85 0% acetonitrile-aqueous solution.
The specific embodiment
Further specify the present invention below in conjunction with embodiment.
Fig. 1 is the operation chart of the hanging drop type liquid-liquid micro-extraction method of the present invention's proposition.The present invention uses the extraction flask of built-in stirrer, it is constant that the extraction flask internal temperature keeps, heat preserving mode is to use insulation jacket, and the gas or the liquid of the temperature constant that is provided by thermostatic water-circulator bath (or other thermostat) is provided in the chuck, or extraction flask is placed isoperibol.
Its concrete implementation step comprises:
(1) use pipette (or other proportional sampling device) that fluid sample to be analyzed is joined in the extraction flask quantitatively, the sample addition will guarantee that liquid level did not have more than the stirrer 1cm, starts agitating device, regulates stirring frequency and makes it to remain on setting value.
(2) use pipette (or other proportional sampling device) to draw extractant, it is disposable, splash in the extraction flask quantitatively, reposefully, make extractant in sample liquid, form steady suspension and drip, pick up counting simultaneously.
(3) reach the extraction time of setting after, use microsyringe (or other proportional sampling device) from the inner part extraction phase solution of drawing of hanging drop, with high pressure liquid chromatography (or other analytical instrument) analyzing and testing.
The operating pressure of said process can be a normal pressure or near normal pressure, and operating temperature can be a normal temperature or near normal temperature.
Embodiment one
Water decocts and obtains the baikal skullcap root extract.Extract is divided into two parts.First part is diluted 10 times with methyl alcohol, draws 2 μ L and carry out efficient liquid phase chromatographic analysis behind 0.2 μ m micro-pore-film filtration.Handle with hanging drop type liquid-liquid micro-extraction for second part, step is as follows: get in the extraction flask that extract 10 μ L place strap clamp cover, add deionized water and be diluted to 100 times, 25 ℃ the water that provides by thermostatic water-circulator bath is provided in the chuck of extraction flask, start agitating device and make stirring frequency be stabilized in 10s
-1Get extractant n-octyl alcohol 10 μ L, splash in the extraction flask and promptly pick up counting; When timing reaches 300s, from hanging drop, draw 2 μ L extraction phases with microscale sampler and carry out efficient liquid phase chromatographic analysis.Fig. 2 is the spectrogram that first duplicate samples obtains, and wherein the baicalein peak area accounts for 6.67% of total peak area.Fig. 3 is the spectrogram that second duplicate samples obtains, and wherein the baicalein peak area accounts for 48.2% of total peak area.Through hanging drop type liquid-liquid micro-extraction, target component baicalein has obtained selectivity purifying effectively, has reduced the burden of subsequent analysis process.
Embodiment two
Obtain the baikal skullcap root extract with the ethanol lixiviate, wherein the concentration of baicalein is 462.3mg/L.Get 0.1,0.3,0.5,0.7 respectively, 0.9mL places the 100mL volumetric flask, adds deionized water and is diluted to scale, makes sample liquid.Sample liquid is carried out hanging drop type liquid-liquid micro-extraction, and step is as follows: get in the extraction flask that extract 1000 μ L place strap clamp cover, 25 ℃ the water that is provided by thermostatic water-circulator bath is provided in the chuck of extraction flask, start agitating device and make stirring frequency be stabilized in 1s
-1Get extractant n-octyl alcohol 2 μ L, splash in the extraction flask and promptly pick up counting; When timing reaches 3600s, from hanging drop, draw 1 μ L extraction phase, with high-performance liquid chromatogram determination baicalein concentration wherein with microscale sampler.The corresponding mapping with the concentration of the extraction phase that records of initial concentration with aqueous sample obtains Fig. 4.Can see both linearly dependent coefficient R
2Be 0.9997, the baicalein concentration of extraction phase reaches 25 times of initial sample.Hanging drop type liquid-liquid micro-extraction and the chromatograph joint used quantitative analysis that is suitable for trace constituent are described, the concentration effect that hanging drop type liquid-liquid micro-extraction is good makes chromatogram descend more than 10 times to the detectability of baicalein.
Embodiment three
Get the 5g Chinese herb rhubarb and add 100mL water logging bubble 24h, filter the Radix Et Rhizoma Rhei extract that obtains clarifying with filter paper then.Get 1mL, 2mL, 3mL, 4mL, 10mL extract respectively, add deionized water and be settled to 100mL, obtain sample liquid.Sample liquid is carried out hanging drop type liquid-liquid micro-extraction handle, step is as follows: sample thief liquid 5000 μ L place in the extraction flask of strap clamp cover, and 25 ℃ the water that is provided by thermostatic water-circulator bath is provided in the chuck of extraction flask, start agitating device and make stirring frequency be stabilized in 50s
-1Get extractant benzene 100 μ L, splash in the extraction flask and promptly pick up counting; When timing reaches 300s, from hanging drop, draw 50 μ L extraction phases with microscale sampler, join in the cuvette, the 1% magnesium acetate methanol solution that other gets 1000 μ L injects in the cuvette as developer, and the usefulness ultraviolet-visible spectrophotometer is measured dissociated anthraquinone concentration wherein under the 510nm wavelength.Fig. 5 is the relation curve of extraction phase dissociated anthraquinone concentration and the initial dissociated anthraquinone concentration of water behind the hanging drop type liquid-liquid micro-extraction, linearly dependent coefficient R
2Be 0.9983.
Embodiment four
Compound concentration is respectively 0.5,1,2, the acephatemet aqueous solution of 5mg/L, adopt hanging drop type liquid-liquid micro-extraction method to carry out example enrichment, step is as follows: sample thief 2000 μ L place in the extraction flask of strap clamp cover, 25 ℃ the water that provides by thermostatic water-circulator bath is provided in the chuck of extraction flask, starts agitating device and make stirring frequency be stabilized in 10s
-1Get extractant methyl iso-butyl ketone (MIBK) 10 μ L, splash in the extraction flask and promptly pick up counting; When timing reaches 300s, from hanging drop, draw 2 μ L extraction phases, with the gas chromatographic analysis micro-extraction acephatemet concentration in mutually with microscale sampler.The corresponding mapping with the concentration of the extraction phase that records of initial concentration with aqueous sample obtains Fig. 6.
Embodiment five
Compound concentration is respectively 0.5,1,2, the dyrenium aqueous solution of 5mg/L, wherein all contain coexistence component urea 1000mg/L, adopt hanging drop type liquid-liquid micro-extraction method to carry out example enrichment, operating condition is as follows: sample thief 5000 μ L place in the extraction flask of strap clamp cover, 25 ℃ the water that provides by thermostatic water-circulator bath is provided in the chuck of extraction flask, starts agitating device and make stirring frequency be stabilized in 10s
-1Get extractant butyl acetate 10 μ L, splash in the extraction flask and promptly pick up counting; When timing reaches 300s, from hanging drop, draw 2 μ L extraction phases, with efficient liquid phase chromatographic analysis phenalgin dish pyridine concentration wherein with microscale sampler.The corresponding mapping with the concentration of the extraction phase that records of initial concentration with aqueous sample obtains Fig. 7, and both linear relationships are better, the influence of the component urea that do not coexisted substantially, and the enrichment multiple reaches 56.
Embodiment six
With 50% acetonitrile-water is that the solvent compound concentration is respectively 0.5,1,2, the benzole soln of 5mg/L, adopt hanging drop type liquid-liquid micro-extraction method to carry out example enrichment, operating condition is as follows: sample thief 5000 μ L place in the extraction flask of strap clamp cover, 25 ℃ the water that provides by thermostatic water-circulator bath is provided in the chuck of extraction flask, starts agitating device and make stirring frequency be stabilized in 10s
-1Get extractant normal octane 10 μ L, splash in the extraction flask and promptly pick up counting; When timing reaches 300s, from hanging drop, draw 2 μ L extraction phases with microscale sampler, with the concentration of efficient liquid phase chromatographic analysis benzene wherein.The corresponding mapping with the concentration of the extraction phase that records of initial concentration with aqueous sample obtains Fig. 8, and both linear relationships are better.
Claims (6)
1, a kind of hanging drop type liquid-liquid micro-extraction method is characterized in that, it comprises following steps:
The 1st step: in the extraction flask of temperature constant, built-in stirrer, add fluid sample to be analyzed;
The 2nd step: start agitating device and make stirring frequency constant;
The 3rd step: quantitatively draw extractant and make it to drip on sample liquid and to form hanging drop and pick up counting;
The 4th step: quantitatively draw the part extractant with sampler from extractant drop inside after reaching setting-up time, detect with analytical instrument.
2, a kind of hanging drop type liquid-liquid micro-extraction method according to claim 1 is characterized in that, the mass fraction of water is not less than 50% in the described fluid sample.
3, a kind of hanging drop type liquid-liquid micro-extraction method according to claim 1 is characterized in that, the scope of described stirring frequency is 1～50s
-1
4, a kind of hanging drop type liquid-liquid micro-extraction method according to claim 1 is characterized in that, the density of the extractant of described formation hanging drop is lower than the density of sample solution.
5, a kind of hanging drop type liquid-liquid micro-extraction method according to claim 1 is characterized in that, the extractant of described formation hanging drop is aromatic hydrocarbon and derivative, aliphatic ester class and ketone, the aliphatic hydrocarbon of C6～C16, the fatty alcohol of C4～C12.
6, a kind of hanging drop type liquid-liquid micro-extraction method according to claim 1 is characterized in that, the volume of the extractant of described formation hanging drop is 2～100 μ L.
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| CN101762417B (en) * | 2010-01-18 | 2011-09-28 | 福州大学 | Dispersive liquid-liquid microextraction method for pretreatment of plant hormone |
| CN102313665A (en) * | 2010-06-30 | 2012-01-11 | 浙江工商大学 | Liquid-liquid micro extraction method for ultrasonic atomized and strengthened suspension drop type ion liquid |
| CN101915695A (en) * | 2010-08-11 | 2010-12-15 | 北京市农林科学院 | Centrifuge tube and method for micro-extraction of dispersion liquid |
| CN102590011A (en) * | 2011-11-22 | 2012-07-18 | 泸州北方化学工业有限公司 | Measuring method for monitoring content of siloxane in hydrochloride during organosilicone production process |
| CN103235066B (en) * | 2013-04-16 | 2014-06-04 | 云南省烟草公司大理州公司 | Hanging drop liquid phase micro-extraction method for extracting aroma component in tobacco leaf |
| CN106596796B (en) * | 2017-01-09 | 2019-05-17 | 国家烟草质量监督检验中心 | The method that GC-MS based on liquid-liquid micro-extraction surveys aromatic amine in cigarette smoke |
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