CN103127742B - Temperature gradient liquidliquid-liquid microextraction method - Google Patents
Temperature gradient liquidliquid-liquid microextraction method Download PDFInfo
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Abstract
The invention relates to a temperature gradient liquid-liquid-liquid microextraction method. The temperature gradient refers to that a temperature difference exists between a receiving phase and a supplying phase (sample) of the liquid-liquid-liquid microextraction, wherein the receiving phase is a hot end and the supplying phase is a cold end. The site of the liquid-liquid-liquid microextraction is a coaxial tube-shell-type channel. Liquid layer segregation is supplied by a hollow fiber pipe, wherein the lateral wall of the fiber pipe is provided with micropores or is free from pores. Liquid which is neither immiscible with the liquid of the supplying phase nor the receiving phase is arranged on the surface of the hollow fiber pipe in a loaded mode. An outer shell body is sleeved outside the hollow fiber pipe, wherein the inner diameter of the outer shell body is larger than the outer diameter of the hollow fiber pipe. The supplying phase passes through the interior of the hollow fiber pipe, and the receiving phase is filled in a cavity between the hollow fiber pipe and the outer shell body. The outer shell body is heated so that the receiving phase is heated, thus the temperature gradient between the receiving phase and the supplying phase is achieved and used as mass transfer power, and an extraction recovery rate is improved.
Description
Technical field
The present invention relates to a kind of liquid-liquid-liquid microextraction method.A kind of providing and the liquid-liquid-liquid microextraction method accepting to exist mutually thermograde is provided particularly.This micro-extraction device can be applied in the selective concentrated and enrichment of various heat-stable compound in complex sample.
Background technology
After nineteen ninety Pawliszyn (Analytical Chemistry62 2145 (1990)) SPME that begins one's study, micro-extraction technique starts to widely use in analytical chemistry, be mainly used in the pre-treatment of complex sample, have the features such as high, the simple to operate and environmental protection of enrichment times.Dasgupta (Analytical Chemistry68 1817 (1996)) and Cantwell (Analytical Chemistry68 in 1996, 2236. (1996)) micro-extraction technique is incorporated in liquid-phase extraction, what start that they adopt most is the form of single dropping liquid-phase microextraction, but owing to hanging the unstability of drop, at Pedersen-Bjergaard (Analytical Chemistry71 in 1999, 2650 (1999)) hollow-fibre membrane is introduced in liquid-phase micro-extraction, achieve with hollow-fibre membrane be the liquid film of support membrane is mesophase spherule simultaneously, hollow-fibre membrane inner chamber is for accepting phase, hollow-fibre membrane outside is the liquid-liquid-liquid microextraction method of supply phase.This method can be very little due to the phase volume that accepts injecting hollow-fibre membrane inner chamber, makes to provide and accept phase volume ratio and can reach several order of magnitude, thus reaching very high enrichment cycles of concentration.Meanwhile, because the mesophase spherule on support membrane has necessarily selective, the pH gradient accepted mutually between supply mutually also has certain exclusion ability to the material not within the scope of this ionization, system is had stronger selective.Have good enrichment and purification capacity for the ionizable compound in complex sample in this approach.A large amount of documents all reports in this way direct-detection analysis environments water sample, fruit juice, even blood plasma, the micro substance in the biological samples such as urine.(Journal?of?Chromatography?A,1184(2008)132–142)
Although liquid-liquid-liquid microextraction has many merits, the shortcomings such as it has extraction time long, and absolute recovery is low.For many years, some researchs were also done some to it and were improved, and than making acceptance aspirate back and forth mutually if any document by syringe pump thus reducing to accept the mass transfer layer of phase, achieved dynamic extraction.And for example system is put into ultrasonic wave pond and carry out ultrasound on extracting.These methods, from kinetically solving the slow problem of micro-extraction mass transfer rate, improve extraction efficiency.Rare article namely improves mass transfer rate and the extraction efficiency that distribution coefficient removes to improve liquid-liquid-liquid microextraction from thermodynamics.
A large amount of result by references all shows, in profit distributes, high temperature is conducive to the distribution of organic matter in water, and favors low temperature is in the distribution of organic matter in oil phase, and high temperature also will improve the ionizing efficiency of organic acids and base in water simultaneously.In sum, if can high temperature be remained on mutually by providing and accept to remain on mutually low temperature, a kind of mass transfer power will be increased in pH gradient, i.e. thermograde, and make liquid-liquid-liquid microextraction have higher extraction efficiency.
Summary of the invention
The object of the invention is to make acceptance phase and provide between phase to produce thermograde, accepting the distribution coefficient of phase with the mass transfer power and target components that improve liquid-liquid-liquid microextraction.Thus improve the extraction efficiency of liquid-liquid-liquid microextraction.Reach larger enrichment times within a short period of time.
Technical scheme of the present invention is:
Adopt liquid-liquid-liquid microextraction device, it comprises outer tube and hollow fiber film tube,
By accepting mutually or providing phase between outer tube with hollow membrane pipe, by providing mutually or accepting phase between hollow fiber film tube;
Accept and provide mutually for there is the liquid of temperature difference each other, accepting mutually or provide to be respectively hot junction or cold junction mutually.
Hollow membrane for be supported with the miillpore filter of mesophase spherule or atresia polymeric membrane or with the atresia polymeric membrane providing the side surface that contacts to be coated with mesophase spherule.
Hollow membrane is miillpore filter, and its surface is supported with the liquid as mesophase spherule, and this liquid does not dissolve each other with the liquid accepting phase with providing phase, but infiltrates mutually with hollow membrane, dissolves each other with providing the target components mutually; Liquid enters in the micro channel of miillpore filter, constitutes the transfer phase between providing mutually and accept mutually with the liquid being supported on microporous membrane surface.Such as provide mutually and to accept mutually be all aqueous phase time, mesophase spherule can time n-octyl alcohol, normal heptane, the water-insoluble organic solvent such as n-dodecanol, miillpore filter then can select hydrophobic polypropylene microporous filter membrane.
Hollow membrane is atresia polymeric membrane, and it mixes with providing the target molecule mutually; Or the atresia polymeric membrane that hollow membrane is coated with mesophase spherule for providing the side surface that contacts, the liquid as mesophase spherule that atresia polymeric membrane surface supports together form with atresia polymeric membrane the transfer phase providing mutually and accept target components between phase; This liquid does not dissolve each other with providing the liquid of phase, dissolves each other with providing the target components mutually.Such as atresia polymeric membrane can be silica gel, dimethyl silicone polymer etc., and the liquid that surface supports can be water-fast ion-pairing agent (trioctylphosphine amine, tri-n-butylamine) etc.
Accept mutually and provide and mutually flow in outer tube and hollow fiber film tube, they can mutually and stream or adverse current or one phase flow move and another is mutually static.
Described thermograde liquid-liquid-liquid microextraction device is coaxial sleeve tube structure, and with hollow fiber conduit as accepting phase and providing the separation layer between phase, have shell body in the outer surface cover of hollow fiber conduit, shell body internal diameter is greater than hollow fiber conduit external diameter; There is provided and flow through hollow fiber conduit mutually, doughnut outer tube layer is full of with the cavity between shell body and accepts phase.
Being provided with thermal source outside described shell body, shell body thermal source homogeneous heating, making the temperature accepting phase higher than providing phase, formation temperature gradient between the two phases; Thermal source is temperature-controlled box.
The entrance point of described hollow membrane pipe is provided with a cooling device, to provide by pump with certain speed by hollow membrane tube cavity, provides through apparatus for supercooling cooling before entering hollow membrane pipe, and formation temperature gradient between the acceptance be in shell body mutually; There is provided the low temperature of phase can meet the requirement of particular sample to temperature.
Tool of the present invention has the following advantages:
1, the extraction mode of existing hollow-fibre membrane liquid-liquid-liquid microextraction is substantially all accept mutually and provide the pH gradient of phase to be mass transfer power, and the present invention on the mass transfer power of pH gradient more in addition thermograde be auxiliary mass transfer power, its extract can be improved in the distribution ratio accepted mutually and improve extraction efficiency.Particularly some water-soluble less ionizable analysis things.
2, whole device achieves semi-automation, simple to operate, without the need to the troublesome operation process as normal static extraction flask stirring-type liquid-liquid-liquid microextraction, and has the potentiality that can become with the automatic on-line enriching apparatus of liquid chromatogram coupling.
Thermograde between accepting phase and providing mutually is provided, and as mass transfer power, improves recovery of extraction.The present invention is applicable to the ionogenic component such as agricultural chemicals residue of veterinary drug, small-molecule drug, plant hormone in extraction water matrix.
Accompanying drawing explanation
Fig. 1 is the principle schematic of temperature difference liquid-liquid-liquid microextraction;
In figure: 101 for accepting phase, 102 for providing phase, and 201 is mesophase spherule, and 301 is shell body, and 401 is thermal source;
Fig. 2 is the schematic diagram of coaxial-type extraction equipment 1;
In figure: 506 is sealing gasket, 505 is the peek pipe of external diameter 0.79mm, and 507 be polyfluortetraethylene pipe, and 502 is internal diameter 1.3mm, external diameter 2.2mm quartz ampoule, and 501 is threeway, and 504 is the Pvdf Microporous Hollow Fiber Membrane of internal diameter 0.8mm, external diameter 1.2mm;
Fig. 3 is the schematic diagram of coaxial-type extraction equipment 2;
In figure: 503 is PMMA square, 507 is external diameter 1/16 inch of peek pipe, and 505 is the stainless steel tube of external diameter 0.6mm, and 504 is polypropylene hollow fiber membrane, and 508 and 509 is diameter 1.05mm etched channels, and 510 is epoxy glue;
Fig. 4 carries out the chromatographic peak comparison diagram before and after enrichment to GA3 in embodiment 1;
Fig. 5 carries out the chromatographic peak comparison diagram before and after enrichment to GA1, GA3, GA4 in embodiment 2.
Detailed description of the invention
The mode of concrete employing is using shell-and-tube passage as extraction place, there is provided and pass through cooling in outside, made by peristaltic pump to provide the tube layer formed by hollow-fibre membrane inner chamber, and accept to be inactive state mutually, be positioned at shell, shell is controlled at higher temperature by cover cartridge heater outside.
Embodiment 1: the extraction and the enrichment that realize gibberellin GA3 in water with the extraction equipment shown in Fig. 1
Extraction equipment: this device connects into shell-and-tube passage by threeway and tubule.9cm every section (film internal diameter 800 μm, wall thickness 200 μm, 0.2 μm, aperture) will be cut into the ultrasonic Pvdf Microporous Hollow Fiber Membrane of drying of acetone.Coaxial configuration realizes by inner and outer tubes are nested.Interior pipe is hollow-fibre membrane, and outer tube is metal, inorganic material or macromolecular material composition, diameter 1.3mm.Outer tube two ends are connected with threeway and seal, and hollow-fibre membrane is then through the internal channel of threeway, and the thin metal pipe that two ends are suitable with internal diameter or macromolecular material pipe embed and dock and seal, and then draw from the other end of threeway.Accept to import from the C end of two threeways and derive.
There is provided phase configuration: be dissolved in acetonitrile by GA3 standard specimen and obtain 100 μ g/mL storing solutions, storing solution is diluted in 100 times to the aqueous solution and be configured to 1 μ g/mL the phase aqueous solution is provided, phase aqueous solution salt acid for adjusting pH will be provided to 2, then add the sodium chloride of 10%.
Accept the configuration of phase: by 5% sodium bicarbonate aqueous solution that obtains soluble in water for analysis pure sodium bicarbonate for accepting phase
The configuration of organic extractant: n-octyl alcohol and ethyl acetate are mixed to get mixed organic solvents with the ratio of 3:1;
The pretreatment of hollow-fibre membrane: the organic solvent prepared by 50 μ L injects hollow-fibre membrane inner chamber by stainless steel tube, passes into inner chamber respectively with distilled water after 30min and shell passage cleans unnecessary organic solvent.
Extraction process: extraction equipment is put into temperature control cylinder, the acceptance 100 μ L mutually injecting and configure are held from threeway C, be connected with syringe pump by the stainless steel tube that threeway B holds, what in syringe pump, suction 4 DEG C was cooled provides phase 10mL, and keeps its low temperature with the syringe that ice bag wraps on pump.Syringe pump flow velocity is 20mL/h, open temperature control module that temperature control cylinder connects first by temperature control cylinder constant temperature at 60 DEG C, and then open syringe pump and pump into phase is provided;
Detect: will provide after extraction and use syringe sucking-off mutually, sample introduction detects in HPLC-UV, take C18 as splitter, and mobile phase is 30% methyl alcohol-0.1% phosphate aqueous solution isocratic elution, and UV detect wavelength is 206nm.There is provided and contrast as shown in Figure 5 with the peak area accepting phase.Enrichment times GA3 is 27 times.
Embodiment 2: the extraction and the enrichment that realize gibberellin GA1, GA3, GA4 in water with the extraction equipment shown in Fig. 2
Extraction equipment: this device processes shell-and-tube passage by a whole block material.9cm every section (film internal diameter 600 μm is cut into by with the ultrasonic polypropylene hollow fiber membrane of drying of acetone, wall thickness 200 μm, 0.2 μm, aperture), dry film is held through the 1.05mm diameter channels AB gone out by PMMA materials processing, and passage AB holds the space epoxy glue between hollow-fibre membrane to cling and shut, hollow-fibre membrane two ends are connected with the stainless steel tube of external diameter 0.6mm also heated sealant respectively.
There is provided phase configuration: be dissolved in acetonitrile by GA1, GA3, GA4 mixed sample and obtain 100 μ g/mL storing solutions, storing solution is diluted in 100 times to the aqueous solution and be configured to 0.1 μ g/mL the phase aqueous solution is provided, phase aqueous solution salt acid for adjusting pH will be provided to 3, then add the sodium chloride of 20%.
Accept the configuration of phase: by 5% sodium bicarbonate aqueous solution that obtains soluble in water for analysis pure sodium bicarbonate for accepting phase;
The configuration of organic extractant: n-octyl alcohol and ethyl acetate are mixed to get mixed organic solvents with the ratio of 3:1;
The pretreatment of hollow-fibre membrane: the organic solvent prepared by 50 μ L injects hollow-fibre membrane inner chamber by stainless steel tube connector, passes into inner chamber respectively with distilled water after 30s and shell passage cleans unnecessary organic solvent.
Extraction process: extraction equipment is put into temperature control cylinder, hold the acceptance 50 μ L mutually injecting and configure from processing channel C, be connected with the silicone tube of peristaltic pump by the stainless steel tube that B holds, the stainless steel tube of A end is connected with polyfluortetraethylene pipe.Silicone tube provides phase from providing to lay in mutually bottle to extract out, and provides to be flow back into lay in bottle by polyfluortetraethylene pipe and form circulation.Peristaltic pump flow velocity is set to 1mL/min, opens the temperature control module that temperature control cylinder connects.First by temperature control cylinder constant temperature at 60 DEG C, and then open peristaltic pump and pump into and provide phase, extraction time is 1 hour, provides phase volume to be 10mL.
Detect: will provide phase sucking-off after extraction, sample introduction detects in HPLC-MS/MS, take C18 as splitter, and mobile phase is 10%-40% acetonitrile-0.05% aqueous formic acid gradient elution 30min.There is provided and contrast as shown in Figure 5 with the peak area accepting phase.Enrichment times GA1 is 47.2, GA3 be 39.8, GA4 is 43.3 times.
Claims (8)
1. a temperature gradient liquid-liquid-liquidmicroextraction microextraction method, is characterized in that:
Adopt liquid-liquid-liquid microextraction device, it comprises outer tube and hollow fiber film tube,
By accepting phase (101) or providing phase (102) between outer tube with hollow membrane pipe, by providing phase (102) or accepting phase (101) between hollow fiber film tube;
Accept and provide mutually for there is the liquid of temperature difference each other, accepting mutually or provide to be respectively hot junction or cold junction mutually.
2., according to extracting process according to claim 1, it is characterized in that:
Hollow membrane for be supported with the miillpore filter of mesophase spherule (201) or atresia polymeric membrane or with the atresia polymeric membrane providing the side surface that contacts to be coated with mesophase spherule (201).
3. according to extracting process according to claim 2, it is characterized in that: hollow membrane is miillpore filter, its surface is supported with the liquid (103) as mesophase spherule (201), this liquid does not dissolve each other with the liquid providing phase (102) and accept phase (101), but infiltrating mutually with hollow membrane, dissolving each other with providing the target components mutually; Liquid (103) enters in the micro channel of miillpore filter, constitutes with the liquid (103) being supported on microporous membrane surface the transfer phase providing phase (102) and accept between phase (101).
4. according to extracting process according to claim 2, it is characterized in that: hollow membrane is atresia polymeric membrane, it mixes with the target molecule provided in phase (102); Or the atresia polymeric membrane of hollow membrane for providing the side surface that contacts to be coated with mesophase spherule (201), the liquid as mesophase spherule (201) (103) that atresia polymeric membrane surface supports together form with atresia polymeric membrane the transfer phase providing phase (102) and accept target components between phase (101); This liquid does not dissolve each other with providing the liquid of phase (102), dissolves each other with providing the target components mutually.
5., according to the extracting process described in claim 1 or 2, it is characterized in that:
Accept phase (101) and provide phase (102) mutually to flow in outer tube and hollow fiber film tube, they can mutually and stream or adverse current or one phase flow are dynamic and another is mutually static.
6., according to extracting process according to claim 1, it is characterized in that:
Described thermograde liquid-liquid-liquid microextraction device is coaxial sleeve tube structure, with hollow fiber conduit (203) as accepting phase and providing the separation layer between phase, have shell body (301) in the outer surface cover of hollow fiber conduit, shell body internal diameter is greater than hollow fiber conduit (203) external diameter; There is provided phase (102) to flow through hollow fiber conduit, hollow fiber conduit (203) skin is full of with the cavity between shell body (301) and accepts phase (101).
7., according to extracting process according to claim 6, it is characterized in that:
Being provided with thermal source (401) outside described shell body (301), shell body (301) thermal source (401) homogeneous heating, making the temperature accepting phase higher than providing phase, formation temperature gradient between the two phases; Thermal source (401) is temperature-controlled box.
8., according to the extracting process described in claim 6 or 7, it is characterized in that:
The entrance point of described hollow membrane pipe is provided with a cooling device, to provide by pump with certain speed by hollow membrane tube cavity, provides through apparatus for supercooling cooling before entering hollow membrane pipe, and formation temperature gradient between the acceptance be in shell body mutually; There is provided the low temperature of phase can meet the requirement of particular sample to temperature.
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CN101462010A (en) * | 2007-12-19 | 2009-06-24 | 中国科学院大连化学物理研究所 | Bundling capillary pipe solid phase micro-extraction device |
CN101637668A (en) * | 2009-01-14 | 2010-02-03 | 中山大学 | Device and method for combined use of molecular imprinting solid phase microextraction and hollow fiber liquid phase microextraction, and application thereof |
CN101670190A (en) * | 2008-09-12 | 2010-03-17 | 天津工业大学 | Liquid-phase micro-extraction technology for electric field enhanced hollow fibrous membrane and device for same |
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CN101462010A (en) * | 2007-12-19 | 2009-06-24 | 中国科学院大连化学物理研究所 | Bundling capillary pipe solid phase micro-extraction device |
CN101670190A (en) * | 2008-09-12 | 2010-03-17 | 天津工业大学 | Liquid-phase micro-extraction technology for electric field enhanced hollow fibrous membrane and device for same |
CN101637668A (en) * | 2009-01-14 | 2010-02-03 | 中山大学 | Device and method for combined use of molecular imprinting solid phase microextraction and hollow fiber liquid phase microextraction, and application thereof |
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Effective date of registration: 20210210 Address after: No. 17, Yunkai Road, Beibei District, Chongqing 400711 Patentee after: CHONGQING NANPAC INSTRUMENT TECHNOLOGY Co.,Ltd. Address before: 116023 No. 457, Zhongshan Road, Liaoning, Dalian Patentee before: DALIAN INSTITUTE OF CHEMICAL PHYSICS, CHINESE ACADEMY OF SCIENCES |