CN105709457A - Solid-phase extraction device and application thereof - Google Patents
Solid-phase extraction device and application thereof Download PDFInfo
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- CN105709457A CN105709457A CN201410742143.XA CN201410742143A CN105709457A CN 105709457 A CN105709457 A CN 105709457A CN 201410742143 A CN201410742143 A CN 201410742143A CN 105709457 A CN105709457 A CN 105709457A
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Abstract
The invention provides a solid-phase extraction device and application thereof. The solid-phase extraction device consists of a solid carrier and an extraction solid phase, the solid carrier refers to porous titanium or porous titanium alloy, micron three-dimensional porous channels are formed on the inner surface of the carrier, and the extraction solid phase is immobilized to the inner surfaces of the three-dimensional porous channels by means of physical coating or chemical bonding and crosslinking. The device can be used for rapid extraction of liquid samples, and during extraction, a sample solution flows through the three-dimensional porous channels of the porous titanium or porous titanium alloy, a target component is enriched by the extraction solid phase on the inner surfaces of the three-dimensional porous channels, and then the solid-phase extraction device desorbs the target component for analysis and detection. The solid-phase extraction device is high in mechanical strength, high in plasticity and high in durability and can be used with separation analysis instruments such as chromatographs and the like.
Description
Technical field
The invention belongs to field of sample preparation, specifically, relate to a kind of solid-phase extraction device and application thereof.
Background technology
Owing to matrix and the composition of major part actual sample are sufficiently complex, therefore sample pre-treatments becomes important step indispensable in sample analysis.By pre-treatment, remove the interfering material in sample and concentrate object, to make up existing isolation technics and the deficiency of instrument detection sensitivity.In actual analysis, the time of sample pre-treatments cost often accounts for the 2/3rds even more of whole analysis process.Along with improving constantly of instrument level and analytical technology, sample pre-treatments becomes the bottleneck restricting whole analysis process.
Traditional sample-pretreating method has liquid-liquid extraction, soxhlet extraction, chromatography, distillation, absorption, a centrifugal and filtration etc., but these methods generally have and use a large amount of organic solvents, process time length and shortcoming that operating procedure is many.These methods are not only easily lost sample, are produced bigger error, and the use of toxic solvent can affect operator ' s health, contaminated environment.
Solid-phase microextraction (SPME) is the Sample Pretreatment Technique risen the nineties in 20th century.The maximum feature of SPME integrates sampling, extraction, enrichment, sample introduction exactly, thus it is easy and simple to handle, and do not need solvent, rate of extraction is fast, running cost is low, free from environmental pollution, facilitate implementation automatization and be prone to and the efficiently separation detection means coupling such as chromatograph, electrophoresis, therefore, it is widely used in chemistry, medicine, food, environmental area and pharmaceutical analysis.
But it is that absorption stirring rod technology (SBSE) its extraction time of fiber solid phase micro-extraction (Fiber-SPME), In-tube SPME (In-TubeSPME) or follow-up developments is all at more than 15min, and its extraction material major part is quartz or glass, material brittle；Major part extracting process is all manual operation, it is difficult to realize automatization.Therefore, these extracting process are all difficult to reach the sample pre-treatments requirement that big flux is rapid automatized.
Summary of the invention
In order to solve the problems referred to above, the present invention proposes a kind of solid-phase extraction device.Unlike the prior art, this extraction equipment uses POROUS TITANIUM or titanium alloy as carrier, the fixing phase of coated extraction on three-dimensional open-framework therein, can effectively utilize POROUS TITANIUM structure specific surface area big, and resistance is little, the advantage of acid-alkali-corrosive-resisting.Realize to sample quick, efficient, be automatically enriched with analytical analysis.
To achieve these goals, the technical solution adopted in the present invention is:
A kind of solid-phase extraction device, by the fixing phase composition of solid carrier and extraction, it is characterised in that: described solid carrier is POROUS TITANIUM or porous titanium alloy, and carrier inside exists micron-sized 3 D pore canal；The fixing inner surface being coated with or being bonded in 3 D pore canal mutually by Physical coating or chemical bonding mode of described extraction.
Cylindrically shaped, the tubular type of described solid carrier or cuboid.
The thickness of described solid carrier is 1mm-10mm, it is preferable that 2mm-5mm；The length of side of cylindrical diameter or tubular type diameter or cuboid is 1mm-50mm, it is preferable that diameter 2mm-10mm.
The diameter of described POROUS TITANIUM or porous titanium alloy interior three-dimensional passage is 1 micron～500 microns, it is preferable that 50-200 micron.
Described titanium alloy is Ti-Al-V, Ti-Ni or Ti-Ni-Fe alloy.
Described solid carrier is connecting the fixing phase front of extraction, can corrode with concentrated acid, increase porous and the specific surface area of interior three-dimensional passage, concentrated acid corrosion process is, the hydrochloric acid adopting mass concentration 10%-30% soaks carrier at 20 DEG C-80 DEG C, or utilizing the nitric acid of mass concentration 15-50% to soak at 20-60 DEG C, soak time is 2 minutes 2 hours.
A kind of application of described solid-phase extraction device, it is characterised in that: the liquid sample containing target components flows through solid-phase extraction device, the fixing phase adsorption and enrichment of extraction being immobilized on 3 D pore canal surface；Then solid-phase extraction device is carried out desorption, make target components parse and be analyzed detection.
Described fluid sample is natural gravity by the method for solid-phase extraction device, or malleation is tried hard to recommend, or negative pressure is taken out.Wherein, malleation is tried hard to recommend can be the manual way of propelling of gases at high pressure, peristaltic pump or syringe；It can be air pump evacuation mode that negative pressure is taken out.
Described desorption can adopt solvent by target components from eluting solid-phase extraction device, or adopts the mode of heating to make target components depart from from solid-phase extraction device.
Described target components be with extract fixing phase polarity close organic compound.
The character extracting fixing phase can select according to the chemical property of target components and sample substrate.Such as, sample is aqueous solution, and target components is low pole compound, then extracting fixing can be nonpolar or low pole mutually, such as the fixing phase that polymethyl siloxane and derivant thereof are formed.If target components is polar compound, then extracts and fix the fixing phase that can be middle polarity or polar compound formation mutually, such as the silicone of cyano-containing.
The invention have the advantages that
(1) present invention adopts POROUS TITANIUM or porous titanium alloy as the carrier of extraction equipment, effectively utilizing its robust advantage, mechanical strength is high, tolerance acid-base, avoid easily broken, the frangible problem adopting quartz carrier to cause in tradition SPME method, improve the ruggedness of extraction equipment.
(2) there is hydroxyl reactive group in POROUS TITANIUM or porous titanium alloy surface, can effectively be bonded/cross-link extraction phase, thus having significantly high temperature tolerance and organic solvent resistance.
(3) present invention adopts the three-dimensional open-framework within POROUS TITANIUM or porous titanium alloy, having specific surface area big, damping little advantage, thus having high bioaccumulation efficiency and enrichment rate.
(4) present invention adopts POROUS TITANIUM or porous titanium alloy as the carrier of extraction equipment, there is significantly high plasticity, the place of various sizes specification can be applicable to, and this structure easily is automated analysis, can carry out coupling with various gas chromatograies or liquid chromatography-mass spectrography system flexibly.
Accompanying drawing explanation
Fig. 1 adopts in POROUS TITANIUM solid-phase extraction device extraction water the gas chromatographic analysis spectrogram after polycyclic aromatic hydrocarbon, the collosol and gel that wherein solid-phase extraction device fixing is mutually is precursor synthesis with MTES.1-naphthalene in figure, 2-acenaphthene, 3-is luxuriant and rich with fragrance, 4-anthracene, 5-fluoranthene, 6-pyrene.
Fig. 2 adopts the gas chromatographic analysis spectrogram in POROUS TITANIUM solid-phase extraction device extraction water after polycyclic aromatic hydrocarbon, the collosol and gel that wherein solid-phase extraction device fixing is mutually is precursor synthesis with phenyl triethoxysilane.1-naphthalene in figure, 2-acenaphthene, 3-is luxuriant and rich with fragrance, 4-anthracene, 5-fluoranthene, 6-pyrene.
Detailed description of the invention
Describing the present invention in detail below in conjunction with drawings and Examples, illustrative examples and explanation in this present invention are used for explaining the present invention, but not as a limitation of the invention.
Embodiment 1
A kind of POROUS TITANIUM solid-phase extraction device, by the fixing phase composition of POROUS TITANIUM carrier and extraction.Wherein, POROUS TITANIUM carrier is cylindrical structural, post footpath 3.8mm, thick 3mm.In order to expose the hydroxyl reactive group of carrier inner surface more fully, it is possible to successively with pure water, carrier is carried out by dichloromethane, and is immersed in 1mol/LNaOH solution 2 hours.
Sol-gal process configuration is adopted to extract fixing phase: to take hydroxy-end capped polydimethylsiloxane (OH-PDMS), MTES (MTES), trifluoroacetic acid (TFA), dichloromethane (CH2Cl2) in after the ratio mixing of 500mg:500 μ l:125 μ l:1000 μ l, it is sufficiently stirred for 30min.
It is pressed into the 3 D pore canal within POROUS TITANIUM by the mode of malleation or negative pressure mutually by fixing for the extraction prepared, after standing a period of time, then extraction phase is extruded 3 D pore canal.After dilution extraction phase concentration, repeatedly repeatedly coated, to increase the coated thickness of extraction phase, reduce the probability in blocking duct.Treat that solgel reaction is sufficiently complete, POROUS TITANIUM carrier at high temperature can be carried out aging, make extraction fix solidifying, and be connected firmly with carrier, be derived from POROUS TITANIUM solid-phase extraction device.
The enrichment analysis being applied in water sample by POROUS TITANIUM solid-phase extraction device polycyclic aromatic hydrocarbon.By high pressure N2, the polycyclic aromatic hydrocarbon aqueous solution of 100ml20 μ g/l is pressed into POROUS TITANIUM solid-phase extraction device, and enrichment flow velocity is 50ml/min.After being enriched with, POROUS TITANIUM solid-phase extraction device is taken out, put into and hot parser carries out desorption, and use gas chromatograph to be analyzed detection.The chromatogram obtained is as shown in Figure 1.
Embodiment 2
Solid-phase extraction device and methods for using them as described in Example 1, the configuration wherein extracting fixing phase changes into: hydroxy-end capped polydimethylsiloxane (OH-PDMS), phenyl triethoxysilane (PTES), trifluoroacetic acid (TFA), after dichloromethane mixes in the ratio of 500mg:500ul:125ul:1000ul, coated POROUS TITANIUM solid-phase extraction device after being sufficiently stirred for 30min.The gas chromatogram obtained is as shown in Figure 2.
Embodiment 3
Solid-phase extraction device as described in Example 1, wherein, before the fixing phase of POROUS TITANIUM or the coated extraction of porous titanium alloy carrier, carries out strong acid corrosion.Mass concentration 10%-30% hydrochloric acid can be used to soak carrier at 20 DEG C-80 DEG C, or utilize the nitric acid of mass concentration 15-50% to soak at 20-60 DEG C, soak time is 2 minutes 2 hours, it is preferable that utilize mass concentration 15-25% hydrochloric acid to soak 30 minutes at 50-70 DEG C.Treated carrier, its internal 3 D pore canal has bigger specific surface area and more active active group than before processing, it is thus achieved that higher extraction efficiency and rate of extraction.
Embodiment 4
Solid-phase extraction device and methods for using them as described in Example 1, what wherein extract fixing phase is configured that PEG 20000 (PEG-20M), tetraethyl orthosilicate (TEOS), GY-202 containing hydrogen silicone oil (PHMS), trifluoroacetic acid (TFA), dichloromethane (CH2Cl2) mix in the ratio of 500mg:500 μ L:500mg:125 μ L:1000 μ L, for coated POROUS TITANIUM solid-phase extraction device after being sufficiently stirred for.
Wherein, extraction equipment is for the extraction polar compound in water, such as phenol, alcohols etc..After extraction completes, adopting methanol that solid-phase extraction device is carried out solvent elution, the methanol solution after eluting carries out chromatography.
Claims (10)
1. a solid-phase extraction device, by the fixing phase composition of solid carrier and extraction, it is characterised in that: described solid carrier is POROUS TITANIUM or porous titanium alloy, and carrier inside exists micron-sized 3 D pore canal；The fixing inner surface being coated with or being bonded in 3 D pore canal mutually by Physical coating or chemical bonding mode of described extraction.
2. solid-phase extraction device according to claim 1, it is characterised in that: cylindrically shaped, the tubular type of described solid carrier or cuboid.
3. solid-phase extraction device according to claim 2, it is characterised in that: the thickness of described solid carrier is 1mm-10mm, and the length of side of cylindrical diameter or tubular type diameter or cuboid is 1mm-50mm.
4. solid-phase extraction device according to claim 1, it is characterised in that: the diameter of described POROUS TITANIUM or porous titanium alloy interior three-dimensional passage is 1 micron～500 microns.
5. solid-phase extraction device according to claim 1, it is characterised in that: described titanium alloy is Ti-Al-V, Ti-Ni or Ti-Ni-Fe alloy.
6. solid-phase extraction device according to claim 1, it is characterized in that: described solid carrier is connecting the fixing phase front of extraction, corrode with concentrated acid, increase porous and the specific surface area of interior three-dimensional passage, concentrated acid corrosion process is, the hydrochloric acid adopting mass concentration 10%-30% soaks carrier at 20 DEG C-80 DEG C, or utilizes the nitric acid of mass concentration 15-50% to soak at 20-60 DEG C, and soak time is 2 minutes 2 hours.
7. one kind as arbitrary in claim 1-6 as described in the application of solid-phase extraction device, it is characterised in that: the liquid sample containing target components flows through solid-phase extraction device, the fixing phase adsorption and enrichment of extraction being immobilized on 3 D pore canal surface；Then solid-phase extraction device is carried out desorption, make target components parse and be analyzed detection.
8. application according to claim 7, it is characterised in that: described fluid sample is natural gravity by the method for solid-phase extraction device, or malleation is tried hard to recommend, or negative pressure is taken out.
9. application according to claim 7, it is characterised in that: described desorption is for adopting solvent by target components from eluting solid-phase extraction device, or adopts the mode of heating to make target components depart from from solid-phase extraction device.
10. application according to claim 7, it is characterised in that: described target components be with extract fixing phase polarity close organic compound.
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| CN110323123A (en) * | 2019-06-25 | 2019-10-11 | 知健生物分子研究院(南京)有限公司 | A kind of analysis method and the real-time direct mass spectrometer of Solid Phase Extraction and Direct Analysis in Real Time mass spectrometry |
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