CN105709457B - A kind of solid-phase extraction device and its application - Google Patents
A kind of solid-phase extraction device and its application Download PDFInfo
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- CN105709457B CN105709457B CN201410742143.XA CN201410742143A CN105709457B CN 105709457 B CN105709457 B CN 105709457B CN 201410742143 A CN201410742143 A CN 201410742143A CN 105709457 B CN105709457 B CN 105709457B
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Abstract
The invention provides a kind of solid-phase extraction device and its application.The solid-phase extraction device is by solid carrier and the fixed phase composition of extraction, wherein solid carrier is POROUS TITANIUM or porous titanium alloy, there is micron-sized 3 D pore canal in inner surface of the carrier, extraction stationary phase is immobilized on into 3 D pore canal inner surface by way of Physical coating or chemical bonding crosslinking inside 3 D pore canal.The device can be used for Rapid Extraction fluid sample, and during extraction, sample solution is enriched with by POROUS TITANIUM or the 3 D pore canal of porous titanium alloy, target components by the extraction stationary phase of 3 D pore canal inner surface；Then solid-phase extraction device is desorbed, parses target components and carry out analysis detection.The extraction equipment of the present invention has high mechanical properties, and plasticity is strong, and durability is high, can separate analytical instrument combination with chromatogram etc..
Description
Technical field
The invention belongs to field of sample preparation, specifically, is related to a kind of solid-phase extraction device and its application.
Background technology
Because the matrix and composition of most of actual sample are sufficiently complex, therefore sample pre-treatments turn into sample analysis not
The important step that can or lack.By pre-treatment, remove the interfering material in sample and concentrate object, to make up existing separation skill
The deficiency of art and instrument detection sensitivity.The time that sample pre-treatments are spent in actual analysis often accounts for whole analysis process
2/3rds is even more more.As instrument is horizontal and the continuous improvement of analytical technology, sample pre-treatments have turned into restricts whole point
The bottleneck of analysis process.
Traditional sample-pretreating method has liquid-liquid extraction, soxhlet extraction, chromatography, distillation, absorption, centrifugation and filtering
Deng, but these methods generally have the shortcomings that a large amount of organic solvents of use, processing time are long and operating procedure is more.These methods are not
But easily lose sample, produce larger error, and the use of toxic solvent can influence operator's health, pollute environment.
SPME (SPME) is the Sample Pretreatment Technique risen the 1990s.SPME maximum feature
Exactly integrate sampling, extraction, enrichment, sample introduction, thus it is easy to operate, and solvent is not required to, rate of extraction is fast, running cost
It is low, free from environmental pollution, be easy to implement automation and be easy to that efficiently separation detection means are combined with chromatogram, electrophoresis etc., therefore,
It is widely used in chemistry, medicine, food, environmental area and Pharmaceutical Analysis.
But either fiber solid phase micro-extraction (Fiber-SPME), In-tube SPME (In-Tube SPME) are still
Absorption stirring rod technology (SBSE) of follow-up developments its extraction time is all in more than 15min, and it is stone that it is most of, which to extract material, for it
English or glass, material brittle；Most of extracting process is all to be manually operated, it is difficult to realizes automation.Therefore, these extraction sides
Method is all difficult to reach the rapid automatized sample pre-treatments requirement of big flux.
The content of the invention
In order to solve the above problems, the present invention proposes a kind of solid-phase extraction device.Unlike the prior art, the extraction equipment
Using POROUS TITANIUM or titanium alloy as carrier, coated extraction stationary phase, can effectively be utilized on the three-dimensional open-framework inside it
POROUS TITANIUM structure specific surface area is big, and resistance is small, the advantages of acid-alkali-corrosive-resisting.Realize quick, efficient, the automatic enrichment solution to sample
Analysis analysis.
To achieve these goals, the technical solution adopted in the present invention is：
A kind of solid-phase extraction device, by solid carrier and the fixed phase composition of extraction, it is characterised in that：The solid carrier is
Micron-sized 3 D pore canal be present in POROUS TITANIUM or porous titanium alloy, carrier inside；The extraction stationary phase by Physical coating or
Person is chemically bonded the inner surface that mode coated or be bonded in 3 D pore canal.
The solid carrier is shaped as cylinder, tubular type or cuboid.
The thickness of the solid carrier is 1mm-10mm, preferably 2mm-5mm；Cylindrical diameter or tubular type diameter is long
The length of side of cube shape is 1mm-50mm, preferably diameter 2mm-10mm.
A diameter of 1 micron~500 microns of the POROUS TITANIUM or porous titanium alloy interior three-dimensional passage, preferably 50-200 is micro-
Rice.
The titanium alloy is Ti-Al-V, Ti-Ni or Ti-Ni-Fe alloy.
The solid carrier can be corroded before connection extracts stationary phase with concentrated acid, increase the porous of interior three-dimensional passage
Property and specific surface area, concentrated acid corrosion process are that carrier is soaked at 20 DEG C -80 DEG C using mass concentration 10%-30% hydrochloric acid,
Or soaked using mass concentration 15-50% nitric acid at 20-60 DEG C, soak time is -2 hours 2 minutes.
A kind of application of the solid-phase extraction device, it is characterised in that：Liquid sample containing target components flows through solid phase
Extraction equipment, it is immobilized on the extraction stationary phase adsorption and enrichment on 3 D pore canal surface；Then solid-phase extraction device is desorbed,
Parse target components and carry out analysis detection.
The method that the fluid sample passes through solid-phase extraction device is natural gravity, or malleation is pushed, or negative pressure is taken out.Its
In, it can be gases at high pressure, peristaltic pump or the manual way of propelling of syringe that malleation, which is pushed,；It can be that pumping pumping is true that negative pressure, which is taken out,
Short side formula.
The desorption can be eluted target components using solvent from solid-phase extraction device, or be made by the way of heating
Target components depart from from solid-phase extraction device.
The target components are the organic compound similar in extraction stationary phase polarity.
The property of extraction stationary phase can be selected according to the chemical property of target components and sample substrate.Such as sample
Product are the aqueous solution, and target components are low pole compound, then it can be nonpolar or low pole to extract stationary phase, such as poly- methyl silicon
The stationary phase that oxygen alkane and its derivative are formed.If target components are polar compound, extraction stationary phase can be middle polarity
Or the stationary phase that polar compound is formed, such as the silicone of cyano-containing.
The present invention has advantages below：
(1) present invention uses the carrier of POROUS TITANIUM or porous titanium alloy as extraction equipment, can be effectively firm resistance to using its
With the advantages of, high mechanical strength, tolerance acid-base, avoid in traditional SPME methods use quartzy carrier caused by it is easily broken, frangible
Problem, improve the durability of extraction equipment.
(2) there is hydroxyl reactive group in POROUS TITANIUM or porous titanium alloy surface, can effectively be bonded/extraction phase is crosslinked, so as to
With very high temperature tolerance and organic solvent resistance.
(3) present invention is had specific surface area big, damped using the three-dimensional open-framework inside POROUS TITANIUM or porous titanium alloy
The advantages of small, so as to have high bioaccumulation efficiency and enrichment rate.
(4) present invention uses the carrier of POROUS TITANIUM or porous titanium alloy as extraction equipment, has very high plasticity, energy
Enough be applied to the place of various sizes specification, and structure analysis easy to automate, can flexibly with various gas-chromatographies
Or liquid chromatography-mass spectrography system is combined.
Brief description of the drawings
Fig. 1 be using the gas chromatographic analysis spectrogram after polycyclic aromatic hydrocarbon in POROUS TITANIUM solid-phase extraction device extraction water, wherein
The stationary phase of solid-phase extraction device is the collosol and gel using MTES as precursor synthesis.1- naphthalenes in figure, 2- acenaphthenes,
3- is luxuriant and rich with fragrance, 4- anthracenes, 5- fluoranthene, 6- pyrenes.
Fig. 2 uses the gas chromatographic analysis spectrogram after polycyclic aromatic hydrocarbon in POROUS TITANIUM solid-phase extraction device extraction water, wherein solid
The stationary phase of phase extraction equipment is the collosol and gel using phenyl triethoxysilane as precursor synthesis.1- naphthalenes in figure, 2- acenaphthenes, 3-
Phenanthrene, 4- anthracenes, 5- fluoranthene, 6- pyrenes.
Embodiment
Describe the present invention in detail with reference to the accompanying drawings and examples, herein illustrative examples and explanation of the invention
For explaining the present invention, but it is not as a limitation of the invention.
Embodiment 1
A kind of POROUS TITANIUM solid-phase extraction device, by porous titanium carrier and the fixed phase composition of extraction.Wherein, porous titanium carrier is
Cylindrical structural, post footpath 3.8mm, thick 3mm.In order to more fully expose the hydroxyl reactive group of inner surface of the carrier, Ke Yiyi
Secondary to use pure water, dichloromethane cleans to carrier, and is immersed in 1mol/LNaOH solution 2 hours.
Extraction stationary phase is configured using sol-gal process：Take hydroxy-end capped dimethyl silicone polymer (OH-PDMS), methyl
Triethoxysilane (MTES), trifluoroacetic acid (TFA), dichloromethane (CH2Cl2) press 500mg:500μl:125μl:1000 μ l's
After ratio mixing, 30min is sufficiently stirred.
The extraction stationary phase prepared is pressed into the 3 D pore canal inside POROUS TITANIUM by way of malleation or negative pressure, stands one
After the section time, then extraction phase extruded into 3 D pore canal.Also it is repeatedly repeatedly coated after can be by diluting extraction phase concentration, with increase
The coated thickness of extraction phase, reduce the possibility for blocking duct.Treat that solgel reaction is fully completed, porous titanium carrier can be existed
Aging is carried out under high temperature, extraction is fixed solidifying, and is connected firmly with carrier, is derived from POROUS TITANIUM solid-phase extraction device.
The enrichment that POROUS TITANIUM solid-phase extraction device is applied to polycyclic aromatic hydrocarbon in water sample is analyzed.By the more of the μ g/l of 100ml 20
The PAH aqueous solution is pressed into POROUS TITANIUM solid-phase extraction device by high pressure N2, and enrichment flow velocity is 50ml/min.Will after the completion of enrichment
POROUS TITANIUM solid-phase extraction device takes out, and is put into hot parser and is desorbed, and carries out analysis detection using gas chromatograph.Obtain
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, wherein the configuration of extraction stationary phase is changed to：Hydroxyl seals
The dimethyl silicone polymer (OH-PDMS) at end, phenyl triethoxysilane (PTES), trifluoroacetic acid (TFA), dichloromethane is pressed
500mg:500ul:125ul:After 1000ul ratio mixing, coated POROUS TITANIUM solid-phase extraction device after 30min is sufficiently stirred.
The gas chromatogram arrived is as shown in Figure 2.
Embodiment 3
Solid-phase extraction device as described in Example 1, wherein, fixed in the coated extraction of POROUS TITANIUM or porous titanium alloy carrier
Before phase, strong acid corrosion is carried out.Carrier can be soaked at 20 DEG C -80 DEG C with use quality concentration 10%-30% hydrochloric acid, or is utilized
Mass concentration 15-50% nitric acid soaks at 20-60 DEG C, and soak time is -2 hours 2 minutes, preferably by mass concentration
15-25% hydrochloric acid soaks 30 minutes at 50-70 DEG C.Treated carrier, its internal 3 D pore canal have than before processing
Bigger specific surface area and more active active group, obtain higher extraction efficiency and rate of extraction.
Embodiment 4
Solid-phase extraction device and methods for using them as described in Example 1, wherein extraction stationary phase is configured to：Polyethylene glycol
20000 (PEG-20M), tetraethyl orthosilicate (TEOS), GY-202 containing hydrogen silicone oils (PHMS), trifluoroacetic acid (TFA), dichloromethane
(CH2Cl2) press 500mg:500μL:500mg:125μL:1000 μ L ratio mixing, consolidates after being sufficiently stirred for coated POROUS TITANIUM
Phase extraction equipment.
Wherein, the extraction polar compound that extraction equipment is used in water, such as phenol, alcohols etc..After the completion of extraction, using first
Alcohol carries out solvent elution to solid-phase extraction device, and the methanol solution after elution carries out chromatography.
Claims (10)
- A kind of 1. solid-phase extraction device, by solid carrier and the fixed phase composition of extraction, it is characterised in that：The solid carrier is more Micron-sized 3 D pore canal be present in hole titanium or porous titanium alloy, carrier inside；The extraction stationary phase is coated by Physical coating The inner surface of 3 D pore canal is bonded in by chemical bonding mode in the inner surface or extraction stationary phase of 3 D pore canal.
- 2. the solid-phase extraction device according to claim 1, it is characterised in that：The solid carrier be shaped as cylinder, Tubular type or cuboid.
- 3. solid-phase extraction device according to claim 2, it is characterised in that：The thickness of the solid carrier is 1 mm-10 Mm, the length of side of cylindrical diameter or tubular type diameter or cuboid is 1 mm-50 mm.
- 4. solid-phase extraction device according to claim 1, it is characterised in that：Three inside the POROUS TITANIUM or porous titanium alloy Tie up duct a diameter of 1 micron ~ 500 microns.
- 5. solid-phase extraction device according to claim 1, it is characterised in that：The titanium alloy be Ti-Al-V, Ti-Ni or Ti-Ni-Fe alloys.
- 6. solid-phase extraction device according to claim 1, it is characterised in that：The solid carrier extracts stationary phase in connection Before, corroded with concentrated acid, the porous and specific surface area in increase interior three-dimensional duct, concentrated acid corrosion process is, using mass concentration 10%-30% hydrochloric acid soaks carrier at 20 DEG C -80 DEG C, or utilizes mass concentration 15-50% nitric acid at 20-60 DEG C Immersion, soak time are -2 hours 2 minutes.
- A kind of 7. application of the solid-phase extraction device as described in claim 1-6 is any, it is characterised in that：Liquid containing target components Aspect product flow through solid-phase extraction device, are immobilized on the extraction stationary phase adsorption and enrichment on 3 D pore canal surface；Then solid phase is extracted Take device to be desorbed, parse target components and carry out analysis detection.
- 8. application according to claim 7, it is characterised in that：The method that the liquid sample passes through solid-phase extraction device is Natural gravity, or malleation are pushed, or negative pressure is taken out.
- 9. application according to claim 7, it is characterised in that：The desorption is to be extracted target components from solid phase using solvent Take and eluted on device, or target components is departed from from solid-phase extraction device by the way of heating.
- 10. application according to claim 7, it is characterised in that：The target components are close with extraction stationary phase polarity Organic compound.
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| CN101468306A (en) * | 2007-12-29 | 2009-07-01 | 中国科学院生态环境研究中心 | Titanium-containing solid phase micro-extraction head and preparation method thereof |
| CN101757898B (en) * | 2008-12-25 | 2011-10-19 | 中国科学院兰州化学物理研究所 | Preparation method of titanium oxide extraction bar for solid phase microextraction |
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