CN103418355B - Sol-gel molecularly-imprinted solid-phase microextraction head and preparation method thereof - Google Patents
Sol-gel molecularly-imprinted solid-phase microextraction head and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of chemical analysis test instruments, and discloses a sol-gel molecularly-imprinted solid-phase microextraction head and a preparation method thereof. Compared with a molecularly-imprinted extraction head prepared through a copolymerization method, the sol-gel molecularly-imprinted solid-phase microextraction head has the advantages that available functional monomers are various, the preparation process is simple and fast, the yield is high, the preparation reproducibility is good, and the thickness is controllable. The prepared sol-gel molecularly-imprinted solid-phase microextraction head has the outstanding characteristics of high heat stability, high solvent stability, long service life and the like. The sol-gel molecularly-imprinted solid-phase microextraction head can be used for aqueous-phase recognition directly, has high extraction capacity and selectivity in both headspace extraction or direct extraction, also has high extraction capacity and recognition capability on substances with high boiling points, and can be used for separation and concentration of complex samples such as foods, environments and biological medicine.
Description
Technical field
The present invention relates to a kind of SPME (Solid-phase microextraction, SPME) extracting head and preparation method thereof, specifically utilize sol-gel technique and the molecular imprinting extracting head preparing SPME and preparation method thereof, belong to chemical field, also belong to analytical chemistry field.Be applicable to the separation and consentration of microsphere in food, environmental sample, medicine and the complex matrices such as biological and the compound that structure is similar with it.
Technical background
SPME (SPME) is a kind of Sample Pretreatment Technique that last century, the nineties grew up, centralized procurement sample, extraction, concentrated, sample introduction are in one, have simple, fast, efficient, without the need to organic solvent, portable and be easy to and the advantage such as Other Instruments coupling, be widely applied in fields such as food.But, the situation complicated for sample composition and determinand content is low, existing commercialization SPME coating can not meet detection needs far away, except coat type is less, main cause is exactly that coating lacks high selectivity, in extraction process, there is competition and substitution reaction, the extraction quantity of determinand easily disturbs by sample matrices, thus affects the sensitivity of method, accuracy and the degree of accuracy.Thus, development has the effort target that high selectivity and even specific SPME coating become numerous scientific worker.
Molecularly imprinted polymer (Molecularly imprinted polymer, MIP) becomes a kind of novel extraction sorbing material by means of the recognition capability of its uniqueness.Its preparation method is normally: mixed with function monomer by template molecule (or being called microsphere), both form molecule aggregation body; Then add crosslinking agent, make molecule aggregation body form highly cross-linked polymer; Finally remove template molecule, just obtain MIP.MIP has with the complementation of original template spatial configuration of molecules and has " hole " in multiple action site, these " holes " have memory effect to microsphere, can microsphere optionally in separation and concentration sample or analogue, thus reach the object of separation, purifying.Current MIP obtains in fields such as chemistry, medical science, molecular biology and studies widely and use.The feature of easy with SPME technical operation, easy for the high selectivity of MIP automation is combined, SPME more efficiently separation and concentration target molecule from complex sample can be made, remove Matrix effects, improve sensitivity and the degree of accuracy of analytical method.
The method preparing molecular engram SPME extracting head of current bibliographical information is mainly copolymerization method (Xiaogang Hu, Jialiang Pan, Yuling Hu, Gongke Li, Journal of Chromatography A, 1216 (2009) 190-197; Juan He, Ruihe Lv, Haijun Zhan, Huizhi Wang, Jie Cheng, Kui Lu, Fengcheng Wang, Analytica Chimica Acta674 (2010) 53-58).And copolymerization method complicated operation, time-consuming, applying needs about 20h for 1 time, only can obtain about 1-2 μm of thick coating at every turn; coating repeatedly could use, and fiber preparation yields poorly, coating poor heat stability (being less than 290 DEG C); service life short (Xiaogang Hu, Guimei Dai, Jiajing Huang; Tingting Ye, Huajun Fan, TangYouwen; Ying Yu; Yong Liang, Journal of Chromatography A, 1217 (2010) 5875-5882; Xiaogang Hu, YulingHu, Gongke Li, Journal of Chromatography A, 1147 (2007) 1-9).And, this method can function monomer limited (being generally vinyl or acrylic acid derivative), coat type is fewer, and general needs identifies in non-aqueous media, greatly limit its range of application or adds analytical work amount (the analysis thing in water sample need be transferred to organic phase to extract again).In order to make molecular imprinting and material be widely used in SPME field, also having a large amount of research work to do, developing emphasis and focus that new function monomer and polymerization become research.
Sol-gel technique is a kind of new MIP technology of preparing.Utilize sol-gel process, can template molecule is incorporated in gel network structure, form a kind of rigid material of inorganic or inorganic-organic hybridization.Once template molecule removes from main body, can obtain that a kind of heat endurance is high, chemical stability good and there is the molecular engram collosol-gel polymer of unique adsorption selection ability.This polymer overcomes the rigidity of general molecular engram organic polymer and the poor shortcoming of inertia, take into account the advantage of both sol-gel and molecular engram, operating condition is gentle, the difform material of easy preparation (film, fiber, bulk and powder), specific organo-functional group can also be incorporated in network structure and improve selective and selectivity, and the stability of reinforcing material.In addition, collosol-gel polymer is three-dimensional netted loose structure, has larger specific area, is conducive to the wash-out of template molecule, also makes the more accessible avtive spot of analysis thing.This technology there is a small amount of report (Maggie Ka-Yi Li for the preparation of molecular engram SPME coating; Ngai-Yu Lei; Chengbin Gong; Yijun Yu; Ka-Ho Lam, Michael Hon-Wah Lam, Hongxia Yu; Paul Kwan-Sing Lam, Analytica Chimica Acta 633 (2009) 197 – 203; Mazyar Ahmadi Golsefidi, Zarrin Es ' haghi, Ali Sarafraz-Yazdi, Journal of Chromatography A, 1229 (2012) 24 – 29), but do not have the performance of one section of document to sol-gel molecular engram SPME extracting head comprehensively to study.
Summary of the invention
The object of the invention is to the defect overcoming prior art, a kind of sol-gel molecular engram SPME extracting head and preparation method thereof is provided.This method can function monomer kind many, preparation process is simple, fast, output high, preparation favorable reproducibility, extracting head thickness controlled (0-100 μm).The heat endurance (330-360 DEG C) that gained extracting head has had and solvent stability, long service life (more than 200 times); Can be directly used in Recognition in Aqueous Media, be headspace extraction or directly extraction all has good extracting power and selective; Also well extraction and recognition capability is had to high boiling material.
The technical solution adopted in the present invention is as follows:
A kind of sol-gel molecularly-imprintesolid-phase solid-phase microextraction head, it is prepared as follows:
By the template molecule of 5.2-82mg or 6-37 μ L, the function monomer of template molecule 1-8 times mol ratio, 300-800 μ L solvent supersonic 0-10min mixes, after oscillating reactions, add 25-50 μ L crosslinking agent 3-(2, 3-expoxy propane) propyl trimethoxy silicane or gamma-methyl allyl acyloxypropyl trimethoxysilane, 30-90mg hydroxy silicon oil, 30-100 μ L tetraethoxysilane, 5-10mg containing hydrogen silicone oil, 0-8mg initator benzophenone, the volume ratio adding water after mixing is 5%, trifluoroacetic acid volume ratio is the mixed liquor 30-80 μ L of 95%, centrifugal 3-8min, get supernatant for subsequent use, 0.5-60min in this supernatant is inserted in the quartz fibre one end removing the drying of protective layer, applies and obtain required coating for 1-15 time, after taking-up, in drier, place 8-24h, then photocuring 0-60min under uviol lamp, at N
2in 250-320 DEG C of aging 2-3h under protection, be the acetic acid/carbinol mixture eluted template molecule of 1:1-1:9 by volume ratio, dry, obtain described molecular blotting solid phase microextraction extracting head,
Wherein:
Above-mentioned functions monomer is polyethylene glycol 20,000 (PEG20000), butyl methacrylate/divinylbenzene (BMA/DVB), methacrylic acid (MAA), 5,11,17,23-tetra-tertiary butyl-25,27-diethyl itrile group-26,28-dihydroxy cup [4] aromatic hydrocarbons (is called for short acetonitrile cup [4], its preparation method reference literature Pavel Lhot á k, Miroslav Dudicc, Ivan Stibor, Hana Petr í ckov á, Jan Sykorab and Jana Hodacov á c, Chem.Commun., 2001,731 – 732; Nobuhiko Iki, Naoya Morohashi, Fumitaka Narumi, Toyohisa Fujimoto, the method synthesis of Tomohiro Suzuki and Sotaro Miyano, Tetrahedron Letters40 (1999) 7337-7341 report).Described template molecule is isocarbophos, Rogor, effective cypermethrin, basudin, parathion-methyl.Described solvent is selected from the mixture (volume ratio is 1:2) of toluene, carrene or toluene and carrene.Hydroxy silicon oil (OH-TSO), tetraethoxysilane, containing hydrogen silicone oil, crosslinking agent are purchased from organosilicon new material Co., Ltd of Wuhan University.BMA, DVB, MAA, PEG20000, benzophenone, trifluoroacetic acid are purchased from Shanghai Chemical Reagent Co., Ltd., Sinopharm Group.Above-mentioned agricultural chemicals is purchased from China National Measuring Science Research Inst..
Applicant provide a kind of preparation method of sol-gel molecularly-imprintesolid-phase solid-phase microextraction head, its step is as described below:
By the template molecule of 5.2-82mg or 6-37 μ L, the function monomer of template molecule 1-8 times mol ratio, 300-800 μ L solvent supersonic 0-10min mixes, after oscillating reactions, add 25-50 μ L crosslinking agent 3-(2, 3-expoxy propane) propyl trimethoxy silicane or gamma-methyl allyl acyloxypropyl trimethoxysilane, 30-90mg hydroxy silicon oil, 30-100 μ L tetraethoxysilane, 5-10mg containing hydrogen silicone oil, 0-8mg initator benzophenone, the volume ratio adding water after mixing is 5%, trifluoroacetic acid volume ratio is the mixed liquor 30-80 μ L of 95%, centrifugal 3-8min, get supernatant for subsequent use, 0.5-60min in this supernatant is inserted in the quartz fibre one end removing the drying of protective layer, applies and obtain required coating for 1-15 time, after taking-up, in drier, place 8-24h, then photocuring 0-60min under uviol lamp, at N
2in 250-320 DEG C of aging 2-3h under protection, be the acetic acid/carbinol mixture eluted template molecule of 1:1-1:9 by volume ratio, dry, obtain described molecular blotting solid phase microextraction extracting head,
Wherein:
Above-mentioned functions monomer is polyethylene glycol 20,000 (PEG20000), butyl methacrylate/divinylbenzene (BMA/DVB), methacrylic acid (MAA), 5,11,17,23-tetra-tertiary butyl-25,27-diethyl itrile group-26,28-dihydroxy cup [4] aromatic hydrocarbons (is called for short acetonitrile cup [4], its preparation method reference literature Pavel Lhot á k, Miroslav Dudicc, Ivan Stibor, Hana Petr í ckov á, Jan Sykorab and Jana Hodacov á c, Chem.Commun., 2001,731 – 732; Nobuhiko Iki, Naoya Morohashi, Fumitaka Narumi, Toyohisa Fujimoto, the method synthesis of Tomohiro Suzuki and Sotaro Miyano, Tetrahedron Letters40 (1999) 7337-7341 report).Described template molecule is isocarbophos, Rogor, effective cypermethrin, basudin, parathion-methyl.Described solvent is selected from the mixture (volume ratio is 1:2) of toluene, carrene or toluene and carrene.Hydroxy silicon oil (OH-TSO), tetraethoxysilane, containing hydrogen silicone oil, crosslinking agent are purchased from organosilicon new material Co., Ltd of Wuhan University.BMA, DVB, MAA, PEG20000, benzophenone, trifluoroacetic acid are purchased from Shanghai Chemical Reagent Co., Ltd., Sinopharm Group.Above-mentioned agricultural chemicals is purchased from China National Measuring Science Research Inst..
Accompanying drawing explanation
Fig. 1: comparing of sol-gel process the SPME extracting head prepared and the SPME extracting head extracting power prepared by bibliographical information copolymerization method.Wherein: MIP-10: molecular engram SPME extracting head prepared by sol-gel process; NIP-10: non-trace SPME extracting head MIP-11 prepared by sol-gel process: the molecular engram SPME extracting head prepared by the copolymerization method of bibliographical information; NIP-11: the non-trace SPME extracting head prepared by the copolymerization method of bibliographical information.
Fig. 2: the heat endurance of the BMA/DVB extracting head of basudin trace.
Fig. 3: the extracting power of BMA/DVB extracting head to template molecule and analogue thereof of effective cypermethrin trace compares.
Fig. 4: acetonitrile cup [the 4]/OH-TSO extracting head of parathion-methyl trace compares with commercial extracting head extracting power.
Fig. 5: the comparison of the different extraction mode of PEG20000/OH-TSO extracting head of Rogor trace.
Fig. 6: the gas-chromatography collection of illustrative plates of acetonitrile cup [4]/OH-TSO extracting head to organophosphorus pesticide extraction in mark-on pineapple of parathion-methyl trace compares.Wherein 1: Dyfonate; 2: parathion-methyl; 3: fenifrothion; 4: parathion.
Detailed description of the invention
Below in conjunction with specific embodiment, technical scheme of the present invention is further described, but is not restriction the present invention.
Embodiment 1:
Get 6 μ L basudin, 8 μ L methacrylic acids, are placed in 1.5mL centrifuge tube, add the ultrasonic 5min dissolving of 500 μ L toluene and mix.Add 50mg hydroxy silicon oil afterwards, 5mg containing hydrogen silicone oil, 30 μ L tetraethoxysilanes, 50 μ L gamma-methyl allyl acyloxypropyl trimethoxysilanes, 4mg benzophenone, ultrasonic mixing, then the volume ratio dripping water be 5%, trifluoroacetic acid volume ratio be 95% mixture 80 μ L, centrifugal after ultrasonic 6min (12000r/min) 6min.Get supernatant for subsequent use.The quartz fibre handled well is vertically inserted 5min in colloidal sol clear liquid, is coated with stain 10 times.The extracting head photocuring reaction 40min under uviol lamp being coated with stain good is placed in drier, aging at gas chromatographic sample introduction mouth after dry 20h, aging temperature 280 DEG C, ageing time 2.5h.With acetic acid/methyl alcohol (volume ratio is 1:3) wash-out, the template molecule that removing is residual, until gas-chromatography can't detect template molecule.
Embodiment 2:
Get 100mg PEG20000 and 82mg isocarbophos in centrifuge tube, add 800 μ L toluene it is fully dissolved, 90mg hydroxy silicon oil, 100 μ L tetraethoxysilanes, 40 μ L3-(2 are added after reaction, 3-expoxy propane) propyl trimethoxy silicane, 10mg containing hydrogen silicone oil, ultrasonic mixing, the mixture 80 μ L that the volume ratio dripping water is again 5%, trifluoroacetic acid volume ratio is 95%, ultrasonic 6min, then centrifugal 8min under 12000r/min, migrates out supernatant liquor for subsequent use.The quartz fibre handled well is vertically inserted 60min in colloidal sol clear liquid, is coated with stain 1 time.Aging at gas chromatographic sample introduction mouth after the extracting head coated being placed in the dry 18h of drier, aging temperature 280 DEG C, ageing time 2h.With acetic acid/methyl alcohol (volume ratio is 1:6) wash-out, the template molecule that removing is residual, until gas-chromatography can't detect template molecule.
Embodiment 3:
Get 80 μ LBMA, 40 μ LDVB, 34 μ L basudin (template molecule) are placed in 1.5mL centrifuge tube, add 200 μ LCH
2cl
2, the ultrasonic 5min of 100 μ L toluene dissolves and mixes.30mg hydroxy silicon oil is added after reaction, 5mg containing hydrogen silicone oil, 50 μ L tetraethoxysilanes, 25 μ L gamma-methyl allyl acyloxypropyl trimethoxysilanes, 6mg benzophenone, ultrasonic mixing, then the volume ratio dripping water be 5%, trifluoroacetic acid volume ratio be 95% mixture 30 μ L, centrifugal after ultrasonic 8min (12000r/min) 5min.Get supernatant for subsequent use.The quartz fibre handled well is vertically inserted 30min in colloidal sol clear liquid, is coated with stain 5 times.The extracting head photocuring reaction 20min under uviol lamp being coated with stain good is placed in drier, aging after dry 8h, aging temperature 280 DEG C, ageing time 2h.With acetic acid/methyl alcohol (volume ratio is 1:8) wash-out, the template molecule that removing is residual, until gas-chromatography can't detect template molecule.
Embodiment 4:
Get 80 μ LBMA, 40 μ LDVB, 50mg effective cypermethrin is placed in 1.5mL centrifuge tube, adds 200 μ LCH
2cl
2, the ultrasonic 10min of 100 μ L toluene dissolves and mixes.Add 45mg hydroxy silicon oil, 5mg containing hydrogen silicone oil, 50 μ L tetraethoxysilanes, 30 μ L gamma-methyl allyl acyloxypropyl trimethoxysilanes, the ultrasonic mixing of 4mg benzophenone, the mixture 40 μ L that the volume ratio dripping water is again 5%, trifluoroacetic acid volume ratio is 95%, centrifugal after ultrasonic 10min (12000r/min) 8min.Get supernatant for subsequent use.The quartz fibre handled well is vertically inserted 40min in colloidal sol clear liquid, is coated with stain 3 times.The extracting head photocuring reaction 60min under uviol lamp being coated with stain good is placed in drier, aging after dry 24h, aging temperature 320 DEG C, ageing time 2h.With acetic acid/methyl alcohol (volume ratio is 1:9) wash-out, until can't detect template molecule in gas-chromatography.
Embodiment 5:
Take 15mg acetonitrile cup [4] and 5.2mg parathion-methyl is placed in centrifuge tube, with 300 μ LCH
2cl
2dissolve, add 45mg hydroxy silicon oil, 8mg containing hydrogen silicone oil, 50 μ L tetraethoxysilanes, 25 μ L3-(2,3-expoxy propane) propyl trimethoxy silicane, ultrasonic mixing, the mixture 80 μ L that the volume ratio dripping water is again 5%, trifluoroacetic acid volume ratio is 95%, centrifugal after ultrasonic 5min (12000r/min) 8min, gets supernatant liquor for subsequent use.The quartz fibre handled well is vertically inserted 0.5min in clear liquid, is coated with stain 15 times.Aging at gas chromatographic sample introduction mouth after dry 20h by being coated with in the good extracting head drier of stain, aging temperature 250 DEG C, ageing time 3h.By extracting head acetic acid/methyl alcohol (volume ratio the is 1:9) wash-out after aging, until can't detect template molecule in gas-chromatography.
Embodiment 6:
Take PEG20000100mg and 65mg Rogor standard items, be dissolved in 600 μ L toluene solvants and mix.Add 90mg hydroxy silicon oil, 6mg containing hydrogen silicone oil, 50 μ L3-(2,3-expoxy propane) propyl trimethoxy silicane and 100 μ L tetraethoxysilanes, the mixture 60 μ L that the volume ratio slowly adding water after ultrasonic 8min is 5%, trifluoroacetic acid volume ratio is 95%.Ultrasonic 8min, then centrifugal 3min under 12000r/min, migrates out supernatant liquor for subsequent use.The quartz fibre handled well is vertically inserted 10min in clear liquid, is coated with stain 8 times.Aging after the extracting head coated being placed in the dry 16h of drier, aging temperature 250 DEG C, ageing time 3h.With acetic acid/methyl alcohol (volume ratio is 1:4) wash-out repeatedly, until gas-chromatography can't detect template molecule.
Embodiment 7:
50mg PEG20000 and 37 μ L basudin are claimed to be dissolved in 350 μ L toluene, ultrasonic 10min mixing, 5mg containing hydrogen silicone oil is added after reaction, 45mg hydroxy silicon oil, 50 μ L tetraethoxysilanes, 25 μ L3-(2,3-expoxy propane) propyl trimethoxy silicane, the mixture 50 μ L that the volume ratio adding water after ultrasonic mixing is 5%, trifluoroacetic acid volume ratio is 95%.Centrifugal after ultrasonic 5min (12000r/min) 8min, takes out supernatant liquor for subsequent use.The quartz fibre handled well is vertically inserted 20min in colloidal sol clear liquid, is coated with stain 6 times.Aging at gas chromatographic sample introduction mouth after the extracting head coated being placed in the dry 14h of drier, aging temperature 300 DEG C, ageing time 2h.With acetic acid/methyl alcohol (volume ratio is 1:1) wash-out, the template molecule that removing is residual, until gas-chromatography can't detect template molecule.
The preparation method of the non-trace SPME extracting head (NIP) corresponding with the various embodiments described above, except not adding except template molecule, all the other preparation methods are identical with the various embodiments described above.
Beneficial effect of the present invention is as described below:
Fig. 1 is comparing of the MAA extracting head extracting power of the basudin trace that the MAA/OH-TSO extracting head of the basudin trace adopting method of the present invention to prepare is prepared with the copolymerization method by bibliographical information.As shown in Figure 1, the extracting power of SPME extracting head that prepared by the present invention is greater than the SPME extracting head (being about 1.5 times) prepared by literature procedure.
Table 1 is the imprinting effect of the PEG20000/OH-TSO extracting head of the isocarbophos trace adopting method of the present invention to prepare.As shown in Table 1, to the template molecule of variable concentrations, trace multiple (ratio of the extraction quantity of IF, trace SPME extracting head and the extraction quantity of non-trace SPME extracting head) is between 1.38-3.29.Show that isocarbophos concentration is lower, imprinting effect is better.
The PEG20000/OH-TSO extracting head of table 1 isocarbophos trace is to the trace multiple of isocarbophos
Adopt molecular engram SPME extracting head prepared by the present invention, because coating and quartz fiber surface there occurs strong chemical bonding effect, therefore coating has very high heat endurance and solvent resistant immersion ability, improve the service life of extracting head, extend the range of application of molecular engram SPME extracting head.
Table 2 and Fig. 2 are solvent stability and the heat endurance of the BMA/DVB extracting head of the basudin trace adopting method of the present invention to prepare respectively.As shown in Table 2, after respectively this extracting head being soaked 30min in water, acetone, toluene, methyl alcohol, acetic acid, the extraction quantity of para-diazines agriculture and analogue parathion-methyl thereof, Entex, quinalphos does not all have significant change (with untreated extracting head gained peak area for 1.00).As shown in Figure 2, by this extracting head after 280-360 DEG C of aging 30min again para-diazines agriculture and analogue thereof extract, extraction quantity is no change almost, illustrates that extracting head prepared by the method has good heat endurance, serviceability temperature can reach 360 DEG C, is applicable to very much the extraction of high boiling substance.
The solvent stability of the BMA/DVB extracting head of table 2 basudin trace
Table 3 is the preparation reappearance of BMA/DVB extracting head and the comparison of precision of the effective cypermethrin trace adopting the present invention to prepare.Take pyrethrin pesticide as analytic target, random choose is that the SPME extracting head of 60 μm and same extracting head extract 5 times to evaluate with BMA/DVB with 3 thickness of a collection of preparation is fiber preparation reappearance and the precision of function monomer, as shown in table 3.RSD value between 3 extracting head is between 3.4-8.8%, and same extracting head extracts the RSD value of 5 times between 2.4-6.0%, illustrates that the extracting head prepared with this materials and methods has good reappearance and precision.
The preparation reappearance of table 3 same batch of extracting head and the precision of this extracting head
Fig. 3 be the BMA/DVB extracting head of effective cypermethrin trace that adopts the present invention to prepare to the extraction selectivity of high boiling pyrethrin pesticide (trace be designated as MIP, non-trace be designated as NIP).Have good effect during for detecting the pyrethrin pesticide in Tea Samples, detect and be limited to 1.65-5.04 μ g/kg, the range of linearity is 10-2000 μ g/kg.Detectability is lower than the 6.4-12.8 μ g/L of bibliographical information, and the range of linearity is wider than 50-2000 μ g/L (Lei Chen, the LiangMin ShangGuan of bibliographical information, YongNing Wu, LiangJun Xu, FengFu Fu, Food Control25 (2012) 433-440).
Fig. 4 is acetonitrile cup [the 4]/OH-TSO extracting head of the parathion-methyl trace adopting the present invention to prepare and non-trace SPME extracting head, do not add the blank SPME extracting head (blank control) of function monomer, commercial dimethyl silicone polymer (PDMS), dimethyl silicone polymer/divinylbenzene (PDMS/DVB), polyacrylate (PA), dimethyl silicone polymer/divinylbenzene/carbon adsorbent (PDMS/DVB/CAR) extracting head is to the comparison of parathion-methyl in water and analogue extracting power thereof.As shown in Figure 4, trace SPME extracting head to the extracting power of parathion-methyl and analogue thereof far above non-trace SPME extracting head and commercial extracting head.
Fig. 5 be Rogor trace prepared by the present invention PEG20000/OH-TSO extracting head headspace extraction (HS-SPME) with directly extract comparing Rogor extracting power under (DI-SPME) two kinds of extraction modes.As shown in Figure 5, the effect of extracting of directly extraction is better, expands the scope of application of extracting head.
Fig. 6 is that the gas-chromatography collection of illustrative plates of acetonitrile cup [4]/OH-TSO extracting head to organophosphorus pesticide extraction in mark-on pineapple sample of parathion-methyl trace prepared by the present invention compares with the spectrogram of corresponding non-trace extracting head.As shown in Figure 6, the extraction quantity of acetonitrile cup [4]/OH-TSO extracting head to parathion-methyl and analogue thereof of parathion-methyl trace is obviously greater than non-trace SPME extracting head.
PEG20000/OH-TSO extracting head (MIP) and the corresponding non-trace extracting head (NIP) of the isocarbophos trace that table 4 is prepared for the present invention extract the interpretation of result of peak area to isocarbophos in different substrates.Employing MIP extracting head overcomes the matrix difference between different fruit and vegetable, and NIP extracting head can not overcome matrix interference.
Table 4MIP and NIP extracting head is to the interpretation of result of isocarbophos extraction peak area in different substrates
The molecular engram SPME extracting head heat endurance prepared with the present invention and solvent stability high, the identification of microsphere and analogue in aqueous phase can be directly used in, detectability is low, the range of linearity is wide, favorable reproducibility, can matrix interference be overcome, in the field such as environmental monitoring, food security, all there is good application prospect.
Claims (1)
1. sol-gel molecular engram method is preparing the application in solid phase micro-extraction extraction head, it is characterized in that the following step:
By the template molecule of 5.2-82mg or 6-37 μ L, the function monomer of template molecule 1-8 times mol ratio, 300-800 μ L solvent supersonic 5-10min mixes, after oscillating reactions, add 25-50 μ L crosslinking agent 3-(2, 3-expoxy propane) propyl trimethoxy silicane or gamma-methyl allyl acyloxypropyl trimethoxysilane, 30-90mg hydroxy silicon oil, 30-100 μ L tetraethoxysilane, 5-10mg containing hydrogen silicone oil, 0-8mg initator benzophenone, the volume ratio adding water after mixing is 5%, trifluoroacetic acid volume ratio is the mixed liquor 30-80 μ L of 95%, centrifugal 3-8min, get supernatant for subsequent use, 0.5-60min in this supernatant is inserted in the quartz fibre one end removing the drying of protective layer, applies and obtain required coating for 1-15 time, after taking-up, in drier, place 8-24h, then photocuring 0-60min under uviol lamp, at N
2in 250-320 DEG C of aging 2-3h under protection, be the acetic acid/carbinol mixture eluted template molecule of 1:1-1:9 by volume ratio, dry, obtain described molecular blotting solid phase microextraction extracting head,
Wherein:
Described function monomer is PEG 20000, butyl methacrylate/divinylbenzene, 5,11,17,23-tetra-tertiary butyl-25,27-diethyl itrile group-26,28-dihydroxy cup [4] aromatic hydrocarbons and methacrylic acids; Described template molecule is isocarbophos, Rogor, effective cypermethrin, basudin and parathion-methyl; Described solvent is toluene, carrene or volume ratio is the toluene of 1:2 and the mixture of carrene.
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| CN111406975B (en) * | 2020-05-08 | 2022-05-31 | 河北瑞龙生物科技有限公司 | Preparation method of guarana extract for cigarettes |
| CN113385154B (en) * | 2021-07-15 | 2022-09-27 | 吉林化工学院 | Molecular imprinting sol-gel coating fiber tube internal solid phase micro-extraction device and preparation method thereof |
| CN113426159B (en) * | 2021-08-04 | 2022-06-17 | 华中农业大学 | Solid phase micro-extraction tube, preparation method thereof, extraction device and application |
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| CN101920193A (en) * | 2010-08-20 | 2010-12-22 | 华中农业大学 | Sol-gel ionic liquid solid phase microextraction extraction fiber and preparation method thereof |
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