CN102455330A - Head-space liquid-phase microextraction device based on semiconductor refrigeration technology - Google Patents
Head-space liquid-phase microextraction device based on semiconductor refrigeration technology Download PDFInfo
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- CN102455330A CN102455330A CN2010105228374A CN201010522837A CN102455330A CN 102455330 A CN102455330 A CN 102455330A CN 2010105228374 A CN2010105228374 A CN 2010105228374A CN 201010522837 A CN201010522837 A CN 201010522837A CN 102455330 A CN102455330 A CN 102455330A
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- heat conduction
- conduction rod
- extraction solvent
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Abstract
The invention relates to an improved head-space liquid-phase microextraction device, which comprises a semiconductor refrigeration body, a heat conduction stick, an extraction solvent carrier, namely a small cap, and a sleeve. The semiconductor refrigeration body indirectly cools an extraction solvent; an extraction solvent with a low boiling point can be used; furthermore, the extraction solvent is close to a tested sample, so the extraction dynamics process is improved and the extraction balance speed is increased. The device can efficiently extract volatile components in a solid sample and a liquid sample, and then transfer extract to an analysis instrument for analysis.
Description
Technical field
The invention belongs to liquid-phase micro-extraction (Liquid-phase microextraction, LPME) field.The present invention has designed a kind of novel head space formula liquid-phase micro-extraction device, utilizes semiconductor refrigerating technology, makes extraction solvent be in relative low temperature; Utilize the low-surface-energy of teflon small cap simultaneously, increased the extraction solvent volume that hangs on the sample top, improved extraction efficiency.The enrichment of volatility and half volatile component in suitable solution example of this device or the solid sample.
Background technology
The liquid-phase micro-extraction technology is continue SPME (Solid-phase microextraction, a kind of green that SPME) grows up afterwards, the sample pre-treatments technology that the enrichment multiple is high, easy and simple to handle.LPME mainly relies on the syringe needle of micro-sampling pin, and the extraction solvent of suspension certain volume is submerged into extraction solvent in the water sample then, or to place sample top (be head space formula liquid-phase micro-extraction, HS-LPME).According to the similar compatibility principle, sample will enrichment in the solvent of micro updating.After extraction is accomplished, air inlet phase chromatogram or liquid chromatography compartment analysis.LPME has overcome characteristics such as the SPME fiber is expensive, easy to break, finite sum cross pollution in serviceable life, has obtained widespread use in environment, biology, food and Pharmaceutical Analysis field.
The HS-LPME theory is thought, extraction quantity n and partition factor k
OdwWith extraction solvent volume V
dRelation below existing:
C wherein
0Be the original concentration of component in the sample, V
sBe sample volume, k
HsBe the Henry's constant of component, V
hBe the head space volume.
From above-mentioned formula, can find out the volume that increases extraction solvent, the temperature that reduces extraction solvent will improve extraction quantity.
In HS-LPME in the past, because the contact area of extraction solvent and micro-sampling pin is less, the volume that can hang is generally the 3-5 microlitre, and the sample size that can extract is limited.In order to increase extraction solvent, people are at syringe needle socket hollow-fibre membrane or polyfluortetraethylene pipe, and the volume of extraction solvent is increased to the 5-10 microlitre.But the repeatability of these modes of operation is often not high.
In extraction process, often want heated sample with the quickening rate of extraction, but high temperature is prone to cause the extraction solvent volatilization loss of suspension.The temperature that reduces extraction solvent can directly reduce losing of extraction solvent, also can improve the enrichment multiple simultaneously.Khajeh people such as (Talanta 69 (2006) 1088) take at the sample introduction needle position the to circulate method of frozen water reduces the extraction solvent temperature indirectly, has reduced the volatilization of extraction solvent.Reported that in patent CN200910265442.8 a kind of semiconductor refrigerating technology is used to cool off the device of extraction solvent.This device has been realized the direct temperature control to extraction solvent, need not cold-producing medium.But extraction solvent is positioned at the aperture of bottle cap top in this device, and volatile constituent and extraction solvent exchange rate are lower, and the extraction equilibrium difficulty in addition, need be cleaned the supporting body of extraction solvent after each extraction is accomplished, and has increased the extraction time.
Summary of the invention
The headspace liquid-phase microextraction device that the objective of the invention is a kind of based semiconductor Refrigeration Technique; Utilize semiconductor refrigerating technology that the extraction solvent among the HS-LPME is effectively freezed; Adopt the heat conduction rod that low temperature is conducted to the small cap that holds extraction solvent, and the inside of sample bottle is goed deep on the surface of extraction solvent, presses close to the sample upper surface; Strengthen the exchange velocity between extraction solvent and the target components, therefore improved the accumulation ability of HS-LPME.The teflon small cap can be changed after extraction simultaneously, avoids cross pollution fully.
It is as shown in Figure 1 that this installs main concrete structure.
This device semiconductor refrigeration system, heat conduction rod, extraction solvent supporting body---small cap and sleeve pipe composition.
The semiconductor refrigerating control system adopts traditional " sandwich " structure, and the semiconductor refrigerating body is clipped in the middle of heat radiator and the refrigeration base, and is through nylon screw that the three is fastening.The two sides of semiconductor refrigerating body all scribbles heat-conducting silicone grease, to improve heat transfer efficiency.Fan is installed on the heat radiator, strengthens radiating effect through flow air.The middle internal thread of refrigeration base cooperates with the external thread on heat conduction rod top, also scribbles heat-conducting silicone grease between them.Refrigeration base and heat conduction rod are processed by thermal capacity aluminium or copper product big, that heat conductivility is good.The refrigeration base has an aperture of laying platinum resistance temperature sensor.The bottom of heat conduction rod is processed with screw thread, is used to install the tetrafluoro small cap.The effect of heat conduction rod is that the low temperature that the semiconductor refrigerating body produces is conducted to the extraction solvent cap.
Sleeve pipe is processed by teflon, the external thread coupling at its internal thread and heat conduction rod middle part.The effect of sleeve pipe is the sealed sample bottle, and the insulation material for heat conduction rod and heat conduction rod outside provides inertia outer simultaneously.The central tube external diameter of tetrafluoro sleeve pipe is than the big 0.1-0.3mm of sample bottle internal diameter of the bottleneck that adopts, be used for and the sample bottleneck between sealing.The bottom caliber makes things convenient for the tetrafluoro sleeve pipe to insert sample bottle than the little 0.5-1mm of sample bottle internal diameter of the bottleneck that adopts.Be filled with closely knit insulation material between tetrafluoro sleeve pipe and the heat conduction rod, the heat conduction rod is played insulation effect, avoid water vapor in the sample solution simultaneously in tetrafluoro sleeve outer wall dewfall.
Tetrafluoro small cap top is processed with screw thread, with heat conduction rod lower thread coupling.Be processed with step aperture (403) in the tetrafluoro small cap, wherein the hole internal diameter of top is 2.0-3.5mm (solvent according to different is decided), and the degree of depth is 3-6mm.Aperture can hold extraction solvent.Because the contact area of extraction solvent and tetrafluoro small cap is bigger, and the surface tension that extraction solvent receives is bigger, has overcome the gravity of extraction solvent itself, so when aperture down the time, it is unsettled and do not flow out that extraction solvent can be stable.The low temperature that the semiconductor refrigerating body is produced is delivered to the tetrafluoro small cap through Metallic rod and screw thread surface of contact; Thereby the temperature of extraction solvent is reduced; Also make the upper surface of this tetrafluoro cap simultaneously near sample; Improved the dynamic process of extraction, shortened equilibration time, also improved the sample enrichment ability.
Temperature controller with commodity is realized accurate temperature controlling (± 0.2 ℃) to semiconductor cooler and miscellaneous part.Temperature control to extraction solvent is an indirect type, but as long as other condition is identical, the temperature of extraction solvent also can guarantee that temperature is accurate, has therefore guaranteed the precision and the repeatability of extraction process.
CN200910265442.8 compares with patent, the advantage of this device:
1, because the design of sleeve pipe; Make the heat conduction rod can conduct low temperature when guaranteeing sealing, and make extraction solvent give prominence to entering sample bottle inside, press close to sample surfaces, greatly improved the extraction kinetics process to extraction solvent; Quicken rate of extraction, improve the enrichment multiple;
2, utilize in polytetrafluoroethylmaterial material low surface tension and the aperture and the big characteristics of extraction solvent contact area, can carry the above extraction solvent of 40 microlitres;
3, the tetrafluoro small cap of carrying extraction solvent is replaceable after single extraction is accomplished, and has avoided cross pollution fully, and has saved the time of cleaning the tetrafluoro small cap.The tetrafluoro small cap quantity of mistake to be used can be concentrated cleaning for a long time.
Description of drawings
Fig. 1 is each block diagram of the present invention;
Wherein, 101-fan; The 102-heat radiator; 103-heat radiator screw thread fixed orifice; 200-semiconductor refrigerating body; 201-semiconductor refrigerating body heat end; 202-semiconductor refrigerating body cold junction; The 301-base that freezes; Surface of contact on the 302-refrigeration base; The 303-counterbore; 304-refrigeration base internal thread fixed orifice; The 305-nylon screw; 306-heat conduction rod; 307-heat conduction rod upper external thread; 308-heat conduction rod middle part screw thread; The 309-sleeve pipe; 310-sleeve pipe middle part caliber; 311-sleeve pipe top screw thread; 312-sleeve pipe bottom caliber; 313-heat conduction rod lower internal thread; 400-tetrafluoro small cap; 401-tetrafluoro small cap screw top; The 402-extraction solvent; 403-tetrafluoro small cap step aperture.
Fig. 2 is integral installation figure of the present invention, wherein 314-fill insulant material.
Fig. 3 is the installation drawing that the present invention is used to extract the middle-and-high-ranking alcohol of water sample.
Wherein, the 501-sample bottle, the internal diameter of bottleneck and tetrafluoro sleeve pipe middle part caliber closely cooperate; 502-contains the aqueous sample of higher alcohol; The 503-magneton.
Fig. 4 is the extraction equipment that adopts the present invention to describe, and the chromatogram of the middle-and-high-ranking alcohol of water sample has been analyzed in extraction.Containing higher alcohol concentration in the water is 1mg/L, comprises 2-amylalcohol, normal butyl alcohol, n-amyl alcohol, n-hexyl alcohol, phenmethylol, n-octyl alcohol, n-nonyl alcohol.Extraction conditions does, 70 ℃ of sample temperatures, and stirring rate 800rpm, sample contain the sodium chloride of saturation concentration; Extraction solvent is 6 μ L acetonitriles ,-1 ℃; The extraction time is 20min.
Embodiment
A kind of headspace liquid-phase microextraction device of based semiconductor Refrigeration Technique is by semiconductor refrigeration system, heat conduction rod, the extraction solvent supporting body---small cap and sleeve pipe are formed;
The semiconductor refrigerating control system is made up of fan 101, heat radiator 102, semiconductor refrigerating body 200, refrigeration base 301, screw 305, heat conduction rod 306 and sleeve pipe 309;
Below heat conduction rod 306, be connected with small cap 400, small cap 400 belows are provided with solvent and deposit a year hole.
Wherein freezing, base and heat conduction rod are big by thermal capacity, heat conductivility good metal material is processed, and like silver, aluminium or copper material, refrigeration base 304 closely cooperates with heat conduction rod top 307.
Through the screw thread fixed orifice 103 on nylon screw and the heat radiator, the cold junction 202 of the semiconductor refrigerating body hot junction 201 with refrigeration base surface of contact 302 and semiconductor refrigerating body is closely contacted with the heat radiator bottom surface.
The refrigeration base is processed with the aperture that can lay temperature sensor; Small cap 400 is installed in the bottom of heat conduction rod, and the low temperature that simultaneously the semiconductor refrigerating body is produced conducts to the extraction solvent 402 that is contained in the small cap; The semiconductor refrigerating body is by the temperature controller temperature control.
Said sleeve pipe is processed by teflon, and its top 311 is threaded with heat conduction rod middle part 308; Wherein central tube external diameter 310 is used for the sealed sample bottle than the big 0.1-0.3mm of specimen in use bottle internal diameter of the bottleneck; During application, the lower tube 312 of sleeve pipe is inserted sample bottle; Be filled with insulation material 314 between sleeve pipe and the heat conduction rod, reduce the external heat conduction, avoid water vapor in the sample solution simultaneously in tetrafluoro sleeve outer wall dewfall.
Described small cap 400 is processed by the low material teflon of surface energy, is used to carry extraction solvent; Small cap top 401 is connected with heat conduction rod lower thread 313; Be processed with step aperture 403 in the small cap, wherein the hole internal diameter of top is decided according to different solvents, can be 2.0-3.5mm, and the degree of depth is 3-6mm; Can hold extraction solvent 402 in the aperture.
The concrete operations step:
1) open each parts power supply, with the refrigeration base temperature be reduced to setting value;
2) the tetrafluoro small cap is installed on the heat conduction rod;
3) measure the extraction solvent of certain volume with the micro-sampling pin, with the aperture of tetrafluoro small cap up, the extraction solvent in the sample introduction needle is joined in the aperture simultaneously;
4) water sample and the magneton of adding certain volume in the sample bottle, the tetrafluoro sleeve pipe insertion sample bottle with this device makes the tetrafluoro small cap place the sample top;
5) sample bottle is placed the magnetic stirring apparatus of heating, make the magneton stirred sample, the extraction certain hour;
6) take out the extraction solvent in the tetrafluoro small cap with the gas chromatography sample introduction needle, air inlet phase chromatographic resolution is analyzed.
Claims (7)
1. the headspace liquid-phase microextraction device of a based semiconductor Refrigeration Technique is characterized in that: by semiconductor refrigeration system, heat conduction rod, extraction solvent supporting body---small cap and sleeve pipe;
The semiconductor refrigerating control system is made up of fan (101), heat radiator (102), semiconductor refrigerating body (200), refrigeration base (301), screw (305), heat conduction rod (306) and sleeve pipe (309);
Semiconductor refrigerating body (200) places refrigeration base (301) top, and heat radiator (102) and fan (101) place semiconductor refrigerating body (200) top successively; Fastening between refrigeration base (301) and heat radiator (102) through screw (305);
Refrigeration base (301) below is provided with heat conduction rod (306), and heat conduction rod (306) is set in the sleeve pipe (309), between heat conduction rod (306) and sleeve pipe (309), is provided with adiabator layer;
Be connected with small cap (400) in heat conduction rod (306) below, small cap (400) below is provided with solvent and deposits a year hole.
2. device according to claim 1 is characterized in that:
Wherein freezing, base and heat conduction rod are big by thermal capacity, heat conductivility good metal material is processed, and refrigeration base (304) closely cooperates with heat conduction rod top (307).
3. device according to claim 2 is characterized in that: wherein freeze base and heat conduction rod are processed by silver, aluminium or copper material.
4. device according to claim 1 is characterized in that:
Through the screw thread fixed orifice (103) on nylon screw and the heat radiator, the cold junction (202) of the semiconductor refrigerating body hot junction (201) with refrigeration base surface of contact (302) and semiconductor refrigerating body is closely contacted with the heat radiator bottom surface.
5. device according to claim 1 is characterized in that:
The refrigeration base is processed with the aperture that can lay temperature sensor; Small cap (400) is installed in the bottom of heat conduction rod, and the low temperature that simultaneously the semiconductor refrigerating body is produced conducts to the extraction solvent (402) that is contained in the small cap; The semiconductor refrigerating body is by the temperature controller temperature control.
6. device according to claim 1 is characterized in that: said sleeve pipe is processed by teflon, and its top (311) are threaded with heat conduction rod middle part (308); Wherein central tube external diameter (310) is used for the sealed sample bottle than the big 0.1-0.3mm of specimen in use bottle internal diameter of the bottleneck; During application, the lower tube of sleeve pipe (312) is inserted sample bottle; Be filled with insulation material (314) between sleeve pipe and the heat conduction rod, reduce the external heat conduction, avoid water vapor in the sample solution simultaneously in tetrafluoro sleeve outer wall dewfall.
7. device according to claim 1 is characterized in that: described small cap (400) is processed by the low material teflon of surface energy, is used to carry extraction solvent; Small cap top (401) is connected with heat conduction rod lower thread (313); Be processed with step aperture (403) in the small cap, wherein the hole internal diameter of top is decided according to different solvents, can be 2.0-3.5mm, and the degree of depth is 3-6mm; Can hold extraction solvent (402) in the aperture.
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| CN 201010522837 CN102455330B (en) | 2010-10-27 | 2010-10-27 | Head-space liquid-phase microextraction device based on semiconductor refrigeration technology |
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| CN 201010522837 CN102455330B (en) | 2010-10-27 | 2010-10-27 | Head-space liquid-phase microextraction device based on semiconductor refrigeration technology |
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| CN102455330B CN102455330B (en) | 2013-07-03 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1161056A (en) * | 1995-06-13 | 1997-10-01 | 日本石油化学株式会社 | Method of continuous extraction of crude wax and apparatus therefor |
| CN1412504A (en) * | 2001-10-08 | 2003-04-23 | 中国科学院生态环境研究中心 | Semiconductor refrigerated low-temp. chromatograph enrichment and separation equipment |
| CN1743049A (en) * | 2005-07-21 | 2006-03-08 | 上海交通大学 | Cyclic condensation solid-phase extraction apparatus |
| CN101053704A (en) * | 2007-03-02 | 2007-10-17 | 华中师范大学 | Ultrasonic auxiliary headspace liquid-phase microextraction method |
| CN201253503Y (en) * | 2008-09-11 | 2009-06-10 | 上海交通大学 | Effusion type cycle-condensation solid-phase micro-extraction device |
-
2010
- 2010-10-27 CN CN 201010522837 patent/CN102455330B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1161056A (en) * | 1995-06-13 | 1997-10-01 | 日本石油化学株式会社 | Method of continuous extraction of crude wax and apparatus therefor |
| CN1412504A (en) * | 2001-10-08 | 2003-04-23 | 中国科学院生态环境研究中心 | Semiconductor refrigerated low-temp. chromatograph enrichment and separation equipment |
| CN1743049A (en) * | 2005-07-21 | 2006-03-08 | 上海交通大学 | Cyclic condensation solid-phase extraction apparatus |
| CN101053704A (en) * | 2007-03-02 | 2007-10-17 | 华中师范大学 | Ultrasonic auxiliary headspace liquid-phase microextraction method |
| CN201253503Y (en) * | 2008-09-11 | 2009-06-10 | 上海交通大学 | Effusion type cycle-condensation solid-phase micro-extraction device |
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| CN102455330B (en) | 2013-07-03 |
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