CN102100976B - Headspace liquid phase micro-extraction device adopting volatile solvent - Google Patents
Headspace liquid phase micro-extraction device adopting volatile solvent Download PDFInfo
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- CN102100976B CN102100976B CN 200910265442 CN200910265442A CN102100976B CN 102100976 B CN102100976 B CN 102100976B CN 200910265442 CN200910265442 CN 200910265442 CN 200910265442 A CN200910265442 A CN 200910265442A CN 102100976 B CN102100976 B CN 102100976B
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Abstract
The invention relates to a headspace liquid phase micro-extraction device adopting a volatile solvent as an extraction phase, which comprises a polytetrafluoroethylene cap with a thread, a first hollow part, a second hollow part, an extraction solvent in the first hollow part, a semiconductor refrigerating system, a sample bottle and a magnetic stirrer, wherein the first hollow part and the second hollow part are arranged at the center of the cap. The volatile solvent is used as the extraction phase of headspace liquid phase micro-extraction, thus the application range of the headspace liquid phase micro-extraction is enlarged. A thread opening of the sample bottle is matched with the thread of the polytetrafluoroethylene cap, which plays a role of sealing a solution in the sample bottle. Under the action of the first hollow part, the volume of the suspended extraction solvent reaches 10-80 microlitres; meanwhile, due to the forced cooling of the semiconductor refrigerating system, the volatile solvent is at -10-20 DEG C, and can be positioned at the headspace of a sample for a long time, thus the extraction efficiency is improved. Due to the adoption, the interference on the sample by the solvent on the chromatograph peak exceeding time is greatly reduced, and the application field of the headspace liquid phase micro-extraction is widened.
Description
Technical field
The present invention relates to micro-extraction device of liquid phase, a kind of headspace liquid-phase microextraction device that adopts volatile solvent specifically, can adopt volatile organic solvent, widen the range of application of headspace liquid-phase microextraction, can reach especially the extracting and enriching of higher multiple to volatility in the water and half volatile material.
Background technology
Liquid-phase micro-extraction (Liquid Phase Microextraction, LPME) be that a kind of of being proposed in 1996 by Jeannot and Cantwell (Analytical Chemistry 68 (1996) 2236) adopts the micro updating solvent as extraction phase, target components is had the environmental friendliness of high enrichment times, efficient sample pre-treatments new technology.LPME has overcome extracting fiber costliness, easy to break in the SPME (SPME), and access times are limited, have the shortcomings such as memory effect (carry over), have simultaneously extractant polarity concurrently adjustable, and are simple to operate, the enrichment times advantages of higher.LPME has two kinds of operator schemes, and a kind of is immersion, and another kind is the head space formula.Wherein headspace liquid-phase microextraction is mainly used in extracting in the water sample enrichment of volatility and half volatile solvent.Then the general solvent that adopts chromatogram micro-sampling pin to draw the 2-5 microlitre utilizes the surface tension between solvent and the sample introduction syringe needle that it is suspended on the syringe needle place in headspace liquid-phase microextraction.After the extraction, regain extractant, can directly air inlet phase chromatogram or liquid chromatogram carry out compartment analysis.
Because extractant is in the head space position of sample, for preventing extractant volatilization loss in the extraction process, adopts the higher organic solvent of boiling point (generally being higher than 110 ℃) more.This just cause after gas-chromatography or liquid-phase chromatographic analysis in, have comparatively serious interference between solvent peak and the sample peak.This technical development so far, adopt more boiling point more high solvent extract low-boiling sample, or adopt selective detector to avoid the interference of solvent peak.Therefore traditional headspace liquid-phase microextraction is limited by very large when the slective extraction solvent, and range of application is not as head space formula SPME.The people such as Khajeh (Talanta 69 (2006) 1088) take at the sample introduction needle position the to circulate method of frozen water reduces the extractant temperature indirectly, reduced the volatilization of extractant, but its extractant boiling point that adopts also can't be lower than 100 ℃.The people such as Xu Hui (CN 100469412C, Journal of Chromatography A1167 (2007) 1) adopt the PCR pipe of 0.2mL internal diameter to do the extractant carrier, realized the direct cooling of extractant, but the cooling means that adopts is just placed ice bath, its temperature control inaccuracy causes extraction repeatability not good.Therefore in headspace liquid-phase microextraction, adopt volatile solvent to make extractant there are no report.
In addition, because sample introduction needle syringe needle thin (general 0.5-0.7mm) can be stablized the extractant finite volume of suspension, be generally less than 5 microlitres.Increase the extraction quantity that the extractant volume can improve sample, the sensitivity of raising method, and can improve the repeatability of headspace liquid-phase microextraction method.Someone is at pinhead sleeve polytetrafluoroethylene (PTFE) tubule or hollow-fibre membrane, and with the increase surface tension, but the extractant volume also is not more than 10 microlitres, and operation is comparatively loaded down with trivial details.The ionic liquid of employing is also arranged as extractant, its extraction volume can reach 20 microlitres, but ionic liquid and gas-chromatography compatibility are too poor, and universality is not high.Therefore, how to increase the volume of extractant and use becomes the liquid-phase micro extraction technique development than low boiling point solvent important topic.Utilize the PCR pipe of polypropylene material to be carrier in the document (Journal of Chromatography A 1167 (2007) 1), the stability of extractant is improved, but the volume that adopts is for can only arrive 8 microlitres, the extractant that can use is limited in scope, some common solvent all can't realize stable the suspension such as n-hexane, carrene etc.
Summary of the invention
The purpose of this invention is to provide a kind of volatile organic solvent that adopts as the device of headspace liquid-phase microextraction extractant, volatile organic solvent is carried out direct semiconductor refrigerating, when reducing its vapour pressure, improved the extraction efficiency of volatility target components.
A kind of headspace liquid-phase microextraction device that adopts volatile solvent comprises polytetrafluoroethylene (PTFE) cap, semiconductor refrigeration system and magnetic stirring apparatus that sample bottle, screw thread specification and sample bottle screw thread are complementary.
The bottleneck of sample bottle is provided with external screw thread; Sample bottle is vertically placed in the water-bath of magnetic stirring apparatus;
The polytetrafluoroethylene (PTFE) cap is the hollow step structure that is comprised of three parts; External diameter increases successively from top to bottom, is respectively the first hollow bulb, the second hollow bulb, the 3rd hollow bulb; The inner wall surface of the 3rd hollow bulb is provided with internal thread, and the 3rd hollow bulb of polytetrafluoroethylene (PTFE) cap and the bottleneck of sample bottle are screwed;
Semiconductor refrigeration system comprises semiconductor chilling plate, refrigeration cover, dc source; Semiconductor chilling plate is arranged at refrigeration cover top, and the cold junction of semiconductor chilling plate fits with the refrigeration cover, and semiconductor chilling plate is electrically connected with dc source by wire;
Refrigeration puts the through hole that offers the counterbore shape, and this through hole and polytetrafluoroethylene (PTFE) cap are that the external shape of the first hollow bulb, the second hollow bulb is corresponding, are matched in clearance between them.
Described polytetrafluoroethylene (PTFE) cap adopts the polytetrafluoroethylmaterial material with low critical surface tension to process; Add the screw thread specification of reference sample bottle bottleneck in man-hour, supporting with it; The internal diameter of the first hollow bulb of tetrafluoroethene cap is 1-3mm, dark 0.5-10mm; The internal diameter of the second hollow bulb is 6-10mm, dark 3-10mm.
Described refrigeration cover is to be made of the through hole that is processed with the counterbore shape in the middle part of the aluminium block; Described magnetic stirring apparatus is the heat collecting type constant-temperature heating magnetic stirring apparatus.
Described semiconductor refrigeration system is comprised of fan, fin, semiconductor chilling plate, nylon screw, refrigeration cover, platinum resistance temperature sensor, high precision temperature control table, solid-state relay and dc source;
Semiconductor chilling plate is arranged at refrigeration cover top, and the cold junction of semiconductor chilling plate fits with the refrigeration cover, and semiconductor chilling plate is electrically connected with dc source by wire;
Be provided with fin above semiconductor chilling plate, hot junction and the fin of semiconductor chilling plate fit; Above fin, be provided with fan;
Refrigeration cover, semiconductor chilling plate and radiator three closely compress by nylon screw;
Be provided with platinum resistance temperature sensor in refrigeration cover inside, RTD is connected with high precision temperature control table input end signal by wire, high precision temperature control table output by wire via in the connecting circuit between solid-state relay access semiconductor chilling plate and dc source.
Scribbling heat-conducting silicone grease between the cold junction of semiconductor chilling plate and the refrigeration cover and between the hot junction of semiconductor chilling plate and the fin.
The advantage of this device:
1, the volatile solvent that is in the head space place directly cools off temperature control by semiconductor refrigeration system, devolatilization greatly reduces, extraction time prolongs, the solvent that headspace liquid-phase microextraction can adopt is widened the volatile solvent scope by original high boiling solvent, such as acetone, carrene, n-hexane, cyclohexane, carbon disulfide etc.Reduce the interference of solvent peak and sample on the chromatogram, improved the compatibility between headspace liquid-phase microextraction and gas-chromatography or the liquid chromatogram.Also can adopt simultaneously the organic solvent of traditional higher, such as n-octyl alcohol, toluene, water etc.;
The volume of the volatility extractant that 2, can use rises to 40 microlitres-80 microlitre;
3, because distribution coefficient and the temperature of target components in organic solvent is inversely proportional to, relative low temperature has increased the meltage of target components in solvent, has improved extraction efficiency;
4, volatile solvent and sample all obtain accurate temperature controlling, and a plurality of factors of whole extraction process are controlled, the good reproducibility of extracting and enriching.
Description of drawings
Fig. 1 is the single unit system schematic diagram of patent of the present invention;
Wherein, 100-polytetrafluoroethylene (PTFE) cap; The 101-extractant; 102-the first hollow bulb; 103-the second hollow bulb; The internal thread of 104-polytetrafluoroethylene (PTFE) cap; The 201-fan; The 202-fin; The 203-semiconductor chilling plate; The 204-nylon screw; The 205-cover that freezes; 301-sample bottle whorl of bottleneck; The 302-sample solution; 303-stirs magneton; The 400-magnetic stirring apparatus.
Fig. 2 is the temperature control part schematic diagram of semiconductor refrigeration system;
Wherein, 206 platinum resistance temperature sensors; 207-high precision temperature control table; The 208-solid-state relay; The 209-dc source.
Fig. 3 utilizes this device that chlorobenzene compound in the water sample is carried out after the headspace liquid-phase microextraction, in conjunction with the large volume sample injection technology, adopts the spectrogram of gas chromatographic analysis.1-Chlorobenzene wherein, 2-1,4-dichlorobenzene, 3-1,2-dichlorobenzene, 4-1,2,4-trichlorobenzene.
The specific embodiment
This device concrete structure such as Fig. 1.
A kind of headspace liquid-phase microextraction device that adopts volatile solvent,
Comprise polytetrafluoroethylene (PTFE) cap 100, semiconductor refrigeration system 200 and magnetic stirring apparatus 400 that sample bottle 300, screw thread specification and sample bottle screw thread are complementary.
The bottleneck of sample bottle 300 is provided with external screw thread; Sample bottle 300 is vertically placed in the water-bath of magnetic stirring apparatus 400;
Polytetrafluoroethylene (PTFE) cap 100 is the hollow step structure that is comprised of three parts; External diameter increases successively from top to bottom, is respectively the first hollow bulb, the second hollow bulb, the 3rd hollow bulb; The inner wall surface of the 3rd hollow bulb is provided with internal thread, and the 3rd hollow bulb of polytetrafluoroethylene (PTFE) cap 100 and the bottleneck of sample bottle 300 are screwed;
Semiconductor refrigeration system 200 comprises semiconductor chilling plate 203, refrigeration cover 205, dc source 209; Semiconductor chilling plate 203 is arranged at refrigeration cover 205 tops, and the cold junction of semiconductor chilling plate fits with the refrigeration cover, and semiconductor chilling plate 203 is electrically connected with dc source 209 by wire;
Offer the through hole of counterbore shape on the refrigeration cover 205, this through hole and polytetrafluoroethylene (PTFE) cap 100 are that the external shape of the first hollow bulb, the second hollow bulb is corresponding, are matched in clearance between them.
Described polytetrafluoroethylene (PTFE) cap 100 adopts the polytetrafluoroethylmaterial material with low critical surface tension to process; Add the screw thread specification of reference sample bottle bottleneck in man-hour, supporting with it;
Described refrigeration cover 205 is to be made of the through hole that is processed with the counterbore shape in the middle part of the aluminium block; Described magnetic stirring apparatus 400 is the heat collecting type constant-temperature heating magnetic stirring apparatus.
Wherein the screw socket of polytetrafluoroethylene (PTFE) cap 100 is that screw thread specification and sample bottle screw thread 301 are complementary, and the internal diameter of the first hollow bulb of tetrafluoroethene cap is 1-3mm, dark 0.5-10mm; The internal diameter of the second hollow bulb is 6-10mm, dark 3-10mm.Wherein the second hollow bulb groove is offering sample target components and water vapour split tunnel being lower than under the zero degree environment, splendid attire volatile organic solvent 101 in the first hollow bulb.The thin pipe wall feature reduces the thermal resistance of polytetrafluoroethylene (PTFE) tubule greatly, energy fast cooling under the refrigeration system effect, and can guarantee certain intensity.Because polytetrafluoroethylmaterial material has extremely low critical surface tension, most solution can't wetting its surface, therefore has maximum surface tension component.
Described semiconductor refrigeration system 200 is comprised of fan 201, fin 202, semiconductor chilling plate 203, nylon screw 204, refrigeration cover 205, platinum resistance temperature sensor 206, high precision temperature control table 207, solid-state relay 208 and dc source 209;
Be provided with fin 202 above semiconductor chilling plate 203, hot junction and the fin of semiconductor chilling plate fit; Above fin 202, be provided with fan 201;
Refrigeration cover, semiconductor chilling plate and radiator three closely compress by nylon screw (204);
Be provided with platinum resistance temperature sensor 206 in refrigeration cover 205 inside, RTD 206 is connected with high precision temperature control table 207 input end signal by wire, and high precision temperature control table 207 output is by in the connecting circuit of wire via 209 of solid-state relay 208 access semiconductor chilling plates 203 and dc sources.
Wherein the refrigeration cover is processed by thermal capacity aluminium or copper product large, that heat conductivility is good; In the refrigeration cover, be processed with endoporus and the deep hole of laying platinum resistance temperature sensor with polytetrafluoroethylene (PTFE) crown end parts size coupling.Scribble heat-conducting silicone grease between the cold junction of semiconductor chilling plate and the refrigeration cover and between the hot junction of semiconductor chilling plate and the fin, in order to strengthen its heat conductivility, closely compress with will freeze cover, semiconductor chilling plate and radiator three of nylon screw.Temp controlled meter effectively freezes with the head portion to the polytetrafluoroethylene (PTFE) cap to refrigeration cover accurate temperature controlling.The fan air blast cooling of the upper end of radiator makes the cold junction temperature of semiconductor chilling plate can reach-20 ℃.The circuit part of semiconductor refrigeration system as shown in Figure 2.Under the control of high precision temperature control table, the volatile solvent that is positioned at polytetrafluoroethylene (PTFE) crown end parts can be refrigerated to and set temperature.
Sample bottle 300 in-built certain volumes with volatility or half volatile sample solution 302, in be placed with and stir magneton 303.When magnetic stirring apparatus 400 provides external heat source for sample solution, can stir sample, to accelerate the mass transfer rate in the sample solution, improve extraction rate.
Its operating procedure is as follows:
1) in sample bottle 300, pack into certain volume sample solution and stir magneton;
2) 100 mouthfuls on polytetrafluoroethylene (PTFE) cap accurately measures certain volume (10-80 microlitre) volatile solvent 101 with the micro-sampling pin, and joins in the first hollow bulb 102 of polytetrafluoroethylene (PTFE) cap up;
3) with polytetrafluoroethylene (PTFE) cap mouth down, its internal thread position cooperated with the sample bottle screw socket tighten;
4) above-mentioned sample bottle with polytetrafluoroethylene (PTFE) cap 100 is placed in the magnetic stirring apparatus, semiconductor refrigeration system is placed on the polytetrafluoroethylene (PTFE) cap afterwards, the first hollow bulb and the second hollow part are in the refrigeration cover at this moment, and temperature is reduced to and sets temperature under the effect of refrigeration cover;
5) turn on agitator begins timing simultaneously, after the extraction certain hour, turns on polytetrafluoroethylene (PTFE) cap 100, with the Liquid sample introduction pin extractant 101 is taken out, and gives gas chromatograph sampling, and separation detects.
Application examples
Getting 20 microlitre acetone with the micro liquid sample introduction needle is extractant, and design temperature is-10 ℃.Set 70 ℃ of sample temperatures, mixing speed 1200rpm, salinity 1M, sample concentration are the chlorobenzene compound of 1 μ g/L.The polytetrafluoroethylene (PTFE) cap that is added with 20 microlitre acetone is tightened at sample bottle, put into magnetic stirring apparatus, and fast semiconductor refrigeration system is enclosed within on the polytetrafluoroethylene (PTFE) cap, open magnetic stirring apparatus extraction 40min.Get afterwards the acetone air inlet phase chromatogram of 10 microlitres.Analysis of spectra is seen Fig. 3.
Triplicate calculates four kinds of chlorobenzene compound peak area repeatability RSD values and is respectively 1.82%, 2.29%, 3.10%, 2.29%.
Claims (6)
1. headspace liquid-phase microextraction device that adopts volatile solvent is characterized in that:
Comprise polytetrafluoroethylene (PTFE) cap (100), semiconductor refrigeration system (200) and magnetic stirring apparatus (400) that sample bottle (300), screw thread specification and sample bottle screw thread are complementary;
The bottleneck of sample bottle (300) is provided with external screw thread; Sample bottle (300) is positioned in the water-bath of magnetic stirring apparatus (400);
Polytetrafluoroethylene (PTFE) cap (100) is the hollow step structure that is comprised of three parts; External diameter increases successively from top to bottom, is respectively the first hollow bulb, the second hollow bulb, the 3rd hollow bulb; The inner wall surface of the 3rd hollow bulb is provided with internal thread, and the bottleneck of the 3rd hollow bulb of polytetrafluoroethylene (PTFE) cap (100) and sample bottle (300) is screwed;
Semiconductor refrigeration system (200) comprises semiconductor chilling plate (203), refrigeration cover (205), dc source (209); Semiconductor chilling plate (203) is arranged at refrigeration cover (205) top, and the cold junction of semiconductor chilling plate fits with the refrigeration cover, and semiconductor chilling plate (203) is electrically connected with dc source (209) by wire;
Offer the through hole of counterbore shape on the refrigeration cover (205), this through hole and polytetrafluoroethylene (PTFE) cap (100) are that the external shape of the first hollow bulb, the second hollow bulb is corresponding, are matched in clearance between them.
2. headspace liquid-phase microextraction device according to claim 1 is characterized in that: described polytetrafluoroethylene (PTFE) cap (100) adopts the polytetrafluoroethylmaterial material with low critical surface tension to process; Add the screw thread specification of reference sample bottle bottleneck in man-hour, supporting with it.
3. headspace liquid-phase microextraction device according to claim 2, it is characterized in that: the internal diameter of described the first hollow bulb (102) is 1-3mm, dark 0.5-10mm; The internal diameter of the second hollow bulb (103) is 6-10mm, dark 3-10mm.
4. headspace liquid-phase microextraction device according to claim 1 is characterized in that: described refrigeration cover (205) is to be made of the through hole that the aluminium block middle part is processed with the counterbore shape; Described magnetic stirring apparatus (400) is the heat collecting type constant-temperature heating magnetic stirring apparatus.
5. headspace liquid-phase microextraction device according to claim 1 is characterized in that:
Described semiconductor refrigeration system (200) is comprised of fan (201), fin (202), semiconductor chilling plate (203), nylon screw (204), refrigeration cover (205), platinum resistance temperature sensor (206), high precision temperature control table (207), solid-state relay (208) and dc source (209);
Semiconductor chilling plate (203) is arranged at refrigeration cover (205) top, and the cold junction of semiconductor chilling plate fits with the refrigeration cover, and semiconductor chilling plate (203) is electrically connected with dc source (209) by wire;
Be provided with fin (202) in semiconductor chilling plate (203) top, hot junction and the fin of semiconductor chilling plate fit; Be provided with fan (201) in fin (202) top;
Refrigeration cover, semiconductor chilling plate and radiator three closely compress by nylon screw (204);
Be provided with platinum resistance temperature sensor (206) in refrigeration cover (205) inside, RTD (206) is connected with high precision temperature control table (207) input end signal by wire, high precision temperature control table (207) output by wire via in the connecting circuit between solid-state relay (208) access semiconductor chilling plate (203) and dc source (209).
6. headspace liquid-phase microextraction device according to claim 1 is characterized in that: scribbling heat-conducting silicone grease between the cold junction of semiconductor chilling plate and the refrigeration cover and between the hot junction of semiconductor chilling plate and the fin.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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