CN100333815C - Solid phase micro extraction head and its preparation method - Google Patents
Solid phase micro extraction head and its preparation method Download PDFInfo
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- CN100333815C CN100333815C CN 200510018525 CN200510018525A CN100333815C CN 100333815 C CN100333815 C CN 100333815C CN 200510018525 CN200510018525 CN 200510018525 CN 200510018525 A CN200510018525 A CN 200510018525A CN 100333815 C CN100333815 C CN 100333815C
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Abstract
The present invention discloses an extraction head for solid-phase microextraction and a preparation method thereof. A double glycidyl calixarene /hydroxy silicon oil composite coating layer is bonded on a surface of quartz fiber. The extraction head for solid-phase microextraction provided by the present invention has the characteristics of resistance on solvent flushing, strong alkali resistance performance, high thermal stability, long service life, good reproducibility of the preparation of probe heads, good extraction capability on aromatic compounds and chlorine substituted aromatics, etc., and has the advantages of simple and quick preparation process, high yield, low preparation cost, easy commercialization, and significant application prospect on chemistry and environmental analysis aspects.
Description
Technical field
The present invention relates to a kind of SPME (SPME) extracting head and preparation method thereof, extracting head of specifically a kind of bisglycidyl base calixarenes and the SPME of hydroxy silicon oil composite bed and preparation method thereof, belong to chemical field, also belong to the analytical chemistry field.
Background technology
SPME (SPME) (R.P, Belardi and J.Pawlisyn, Water Pollution Research J.Canada.1989,24,179) developed into a kind of ripe relatively sample pretreatment technology, owing to its many advantage is widely used in various sample detection.Yet up to the present, the kind of solid phase micro-extraction extraction head coating is limited; Serviceability temperature is on the low side (200-280 ℃); Service life, short (being generally 40-100 time) limited its range of application greatly.Adopt sol-gel process (D.X.Wang, S.-L.Chong, A.Malik, Anal.Chem.69 (1997) 4566) preparation solid phase micro-extraction extraction head can effectively overcome above shortcoming, but most of sol-gel processes prepare the time of extracting head cost and grow (needing several hrs sometimes), and it is low to prepare productive rate, cost is higher, is difficult to satisfy the needs that actual detected is analyzed.Simultaneously, improve the important development direction that sensitivity for analysis and selectivity remain the SPME technology, for the many and extremely low environmental sample pollutant of complexity and content of kind, trace, trace analysis are particularly important.The SPME coating plays decisive role to the sensitivity and the selectivity of this technology, therefore, use that new coating material preparation manipulation is stable, extraction efficiency is high, selectivity good, long service life, new coating that preparation cost is low still be SPME Study on Technology focus.
Calixarenes (calixarene) is the macrocyclic compound that has special ring cavity structure by the tert-butyl group and the formaldehyde class that condensation forms under alkali condition, be described as third generation super molecular compound, ion and neutral molecule are had the selectivity mating reaction, it has been carried out broad research mutually as chromatographic stationary at analysis field.Use calixarenes and will have good application prospects as the solid phase micro-extraction extraction head coating.
Summary of the invention
The object of the present invention is to provide a kind of new solid phase micro-extraction extraction head and preparation method thereof, the solid phase micro-extraction extraction head of gained, have following characteristics: anti-solvent washing, strong alkali resistance, high heat endurance, long service life, probe preparation favorable reproducibility has good extracting power to aromatic and chlorine substituted aromatic; Preparation process is simple, quick, the productive rate height, and cost is low, is easy to commercialization.
For achieving the above object, the technical solution adopted in the present invention is as follows:
A kind of extracting head of SPME comprises that quartz fibre reaches the coating attached to the quartz fibre surface, and described coating is bisglycidyl base calixarenes and the hydroxy silicon oil composite bed that is bonded in the quartz fibre surface.
Above-mentioned calixarenes is cup [4] aromatic hydrocarbons.
The present invention also provides the preparation method of above-mentioned solid phase micro-extraction extraction head:
Getting 10-60mg bisglycidyl base calixarenes, add calixarenes molal quantity 1-5 3-aminopropyltriethoxywerene werene (KH-550) doubly, is solvent with 100-500 μ L carrene, reacts 10-60min in advance.Add bisglycidyl base calixarenes quality 1.5-15 hydroxy silicon oil doubly again, 60-120 μ L tetraethoxysilane or MTMS reach the 0-15mg containing hydrogen silicone oil and fully mix, and sonic oscillation 3-10 minute, centrifugal 0-10 minute, obtain the colloidal sol clear liquid; Quartz fibre one end that removes the drying of protective layer is inserted 1-30min in the colloidal sol clear liquid, took out the back dry 8-24 hour; N
2Protection promptly got required extracting head down in 250-380 ℃ of aging 2-3 hour.
Description of drawings
After Fig. 1 is alkali lye (up to the NaOH alkali lye of 4mol/L) the immersion 40min of extracting head of the present invention through variable concentrations, to the comparison of your extracting power of the general Lip river of hydrochloric acid naphthalene;
Fig. 2 is the comparison to nine kinds of chlorobenzene extracting powers of extracting head of the present invention and commercial dimethyl silicone polymer (PDMS) and dimethyl silicone polymer-divinylbenzene (PDMS-DVB) extracting head.
The specific embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is further described:
In the embodiment of the invention: bisglycidyl base cup [4] is 5,11,17,23-tetra-tert-25,27-dihydroxy-26,28-bisglycidyl base cup [4] aromatic hydrocarbons, this cup [4] but aromatic hydrocarbons reference literature method (C.D.Gutsche, M.Iqbal, Org.Synth.1990,68,234 and J.M.Klunder, T.Onami, K.B.Sharpless, J Org.Chem.1989,54,1295) prepare.Hydroxy silicon oil (OH-TSO, molecular weight is 3000-5000) use and the research center tetraethoxysilane, MTMS available from Chengdu silicon, 3-aminopropyltriethoxywerene werene (KH-550), containing hydrogen silicone oil (molecular weight is 1000-2000) is available from the Wuhan University chemical plant.
Embodiment 1:
Get 10mg bisglycidyl base cup [4] aromatic hydrocarbons, add the 3-aminopropyltriethoxywerene werene of 1 times of calixarenes molal quantity,, make its reaction 10min with the dissolving of 100 μ L carrene.Add 150mg hydroxy silicon oil (molecular weight is 3000) again, 60 μ L tetraethoxysilanes, 15mg containing hydrogen silicone oil (molecular weight is 1000) fully mixes, sonic oscillation 5 minutes, centrifugal (10000r/min) 8 minutes obtains the colloidal sol clear liquid.Quartz fibre one end that removes the drying of protective layer is inserted about 20min in the colloidal sol clear liquid (looking required extracting head thickness repeatable operation for several times), took out the back dry 8 hours.N
2Protection down in 320 ℃ aging 2 hours, make the solid phase micro-extraction extraction head that thickness is 10-100 μ m.
Embodiment 2:
Getting 60mg bisglycidyl base cup [4] aromatic hydrocarbons, add the 3-aminopropyltriethoxywerene werene (KH-550) of 3 times of calixarenes molal quantitys, is solvent with 500 μ L carrene, reacts 60min in advance.Add 90mg hydroxy silicon oil (molecular weight is 5000) again, 120 μ L tetraethoxysilanes fully mix, and sonic oscillation 10 minutes obtains the colloidal sol clear liquid.Quartz fibre one end that removes the drying of protective layer is inserted 2min in the colloidal sol clear liquid (looking required extracting head thickness repeatable operation for several times), took out the back dry 24 hours; N
2Protection makes the solid phase micro-extraction extraction head that thickness is 10-100 μ m down in 250 ℃ of aging 3h.
Embodiment 3:
Getting 30mg bisglycidyl base cup [4] aromatic hydrocarbons, add the 3-aminopropyltriethoxywerene werene (KH-550) of 5 times of calixarenes molal quantitys, is solvent with 400 μ L carrene, reacts 30min in advance.Add 120mg hydroxy silicon oil (molecular weight is 4000) again, 100 μ L MTMSs, 10mg containing hydrogen silicone oil (molecular weight is 2000) fully mixes, sonic oscillation 8 minutes, centrifugal (16000r/min) 3 minutes obtains the colloidal sol clear liquid.Quartz fibre one end that removes the drying of protective layer is inserted 30min in the colloidal sol clear liquid (looking required extracting head thickness repeatable operation for several times), took out the back dry 12 hours; N
2Protection makes the solid phase micro-extraction extraction head that thickness is 10-100 μ m down in 280 ℃ of aging 2.5h.
Adopt the obtained beneficial effect of technical scheme of the present invention:
The present invention adopts sol-gel to prepare the hydrolysis that relates to two kinds of monomers in the solid-phase micro-extraction coating process, a kind of is the three-dimensional silica gel skeleton that the tetraethoxysilane hydrolysis forms an inorganic medium, another kind is that the product hydrolysis after KH-550 and the bisglycidyl base calixarenes ring-opening reaction is introduced the silica gel skeleton with calixarenes and formed an organic whole, and this organism forms firm chemical bond with the hydroxyl of glass surface again.The contrast nuclear magnetic spectrogram finds, (3-GlyH), 3.02 and 3.06 (3-GlyH) the spectrum peak of these epoxy radicals disappears δ 2.96, proves calixarenes and silylating reagent complete reaction for m, 1Heach for m, 2H; The extracting head composite coating that scrapes after carrene soaks is done the infrared spectrum experiment, still contains the characteristic peak of calixarenes: 1488.1cm in the gained spectrogram
-1(ArC-C is flexible) and 871.1cm
-1(Ar-H bending) illustrates that calixarenes is bonded on the coating.
This extracting head embodies special advantages on the preparation method.Even bisglycidyl base on the calixarenes and KH-550 at room temperature also have good reactivity, the content of calixarenes is higher in the coating of feasible preparation, thereby selectivity is better; KH-550 has certain catalytic action to the so-gel process simultaneously, and reaction does not need to add in addition catalyst, and preparation process is more simple, quick.The introducing of bisglycidyl base calixarenes and KH-550 has very big effect to the filming performance of sol-gel mixture, prepare a solution and can be coated with many extracting head, measure the favorable reproducibility (relative standard deviation＜10%) of the sample of giving with the extracting head of several same thickness, same amount, the preparation productive rate improves greatly, cost reduces, and helps the commercialization of sol-gel probe.
Because coating and the strong bonding action of fiber surface, this extracting head has very high heat endurance and chemical stability, and the scope of application is widened, and the life-span prolongs greatly.With the general Luo Naier of a kind of beta blocker hydrochloric acid, six kinds of polycyclic aromatic hydrocarbons (PAHs) (indenes, naphthalene, biphenyl, acenaphthene, fluorenes and phenanthrene), six kinds of arylamine (aniline, ortho-aminotoluene, 2, the 4-dimethylaniline, 3, the 4-dimethylaniline, N-ethyl-m-toluidine and N, the N-diethyl-m-toluidine), six kinds of polarity phenol sample (phenol, orthoresol, paracresol, 3,5-xylenol, 1-naphthols and beta naphthal) and nine kinds of chlorobenzene compounds (1, the 4-dichloro-benzenes, 1, the 2-dichloro-benzenes, 1,3, the 5-trichloro-benzenes, 1,2, the 4-trichloro-benzenes, 1,2, the 3-trichloro-benzenes, 1,2,3, the 4-tetrachlorobenzene, 1,2,4, the 5-tetrachlorobenzene, pentachlorobenzene, hexachloro-benzene) for measuring sample, investigated the performance of extracting head of the present invention.Fig. 1 has investigated its alkaline-resisting ability, and wherein abscissa is a NaOH concentration, and ordinate is flame ionization ditector (FID) response signal.After the NaOH alkali lye (up to 4mol/L) through variable concentrations soaked 40min, the extracting power of this extracting head did not reduce, and trend slightly raises.The extracting head of the present invention that table 1 shows sol-gel process preparation through water, carrene, acetonitrile, methyl alcohol, n-hexane, toluene wash in succession each after 40 minutes its adsorbance do not have significant change, illustrate that its anti-solvent washing is very capable.This extracting head is through 280 ℃, 320 ℃, 340 ℃, 350 ℃ high temperature respectively after aging 30 minutes, and its extracting power does not obviously reduce yet.This extracting head is through behind 300 times the headspace solid-phase microextraction altogether, and its extraction quantity does not have too big variation, and sustainable use.Directly extract the general Luo Naier of hydrochloric acid with this extracting head, the extraction time is 30min, and temperature is 90 ℃, and desorption temperature is 280 ℃, under this condition, still has good effect of extracting after extracting head has been used 160 times altogether.
Table 1 solvent soaking is to the influence of extracting head extraction quantity of the present invention
| Solvent | Peak area (n=2) | |||||
| Indenes | Naphthalene | Biphenyl | Acenaphthene | Fluorenes | Luxuriant and rich with fragrance | |
| Not before the bubble | 13023168 | ?17691027 | ?47875682 | ?23575650 | ?32720757 | ?13457510 |
| Acetonitrile | 12019303 | ?18244720 | ?55871963 | ?30819818 | ?34220410 | ?13508662 |
| Methyl alcohol | 12768842 | ?18875742 | ?53528037 | ?28976414 | ?33151847 | ?14225005 |
| N-hexane | 12681500 | ?19164293 | ?51696345 | ?26505592 | ?34501484 | ?14662651 |
| Toluene | 11660932 | ?18310652 | ?55403971 | ?29853464 | ?33342804 | ?12716229 |
| Carrene | 11527453 | ?17126749 | ?51268572 | ?26621841 | ?30221075 | ?12399091 |
| Water | 12358836 | ?20451100 | ?57827187 | ?30086597 | ?30175818 | ?12480165 |
Because the ring cavity structure and the character of calixarenes uniqueness, it has very high extracting power to the compound of being tested, and has obtained lower detectability (SPME-gas chromatography).Polycyclic aromatic hydrocarbon (PAHs), arylamine, phenol and the chlorobenzene LDL measured with this extracting head are respectively 0.07-1.72ng/L, 1.53-4.50ng/L, 0.01-0.48 μ g/L, 0.21-71ng/L, can satisfy the needs of trace, trace analysis fully, adopt higher its sensitivity of detector of sensitivity further to reduce.Fig. 2 is the comparison to nine kinds of chlorobenzene extracting powers of this extracting head and commercial dimethyl silicone polymer (PDMS) and dimethyl silicone polymer-divinylbenzene (PDMS-DVB) extracting head, and wherein abscissa is chlorobenzene (A, 1, a 4-dichloro-benzenes; B, 1, the 2-dichloro-benzenes; C, 1,3, the 5-trichloro-benzenes; D, 1,2, the 4-trichloro-benzenes; E, 1,2, the 3-trichloro-benzenes; F, 1,2,3, the 4-tetrachlorobenzene; G, 1,2,4, the 5-tetrachlorobenzene; H, pentachlorobenzene; I, hexachloro-benzene), ordinate is electron capture detector (ECD) response signal.As seen from Figure 2, the extracting power of extracting head of the present invention (self-control extracting head) is far above two kinds of commercial extracting head.
Solid phase micro-extraction extraction head provided by the present invention, anti-solvent washing ability is strong, and anti-highly basic soaks, the heat endurance height, long service life, the preparation favorable reproducibility has good extracting power to aromatic and chlorine substituted aromatic; Preparation process is simple, quick, the productive rate height, and preparation cost is low, is easy to commercialization.Has important application prospects aspect chemistry and the environmental analysis.
Claims (3)
1. a solid phase micro-extraction extraction head comprises that quartz fibre reaches the coating attached to the quartz fibre surface, and it is characterized in that: described coating is bisglycidyl base calixarenes and the hydroxy silicon oil composite bed that is bonded in the quartz fibre surface; Described extracting head makes by following method: getting 10-60mg bisglycidyl base calixarenes, add calixarenes molal quantity 1-5 3-aminopropyltriethoxywerene werene doubly, is solvent with 100-500 μ L carrene, reacts 10-60min in advance; Add bisglycidyl base calixarenes quality 1.5-15 hydroxy silicon oil doubly again, 60-120 μ L tetraethoxysilane or MTMS reach the 0-15mg containing hydrogen silicone oil and fully mix, and sonic oscillation 3-10 minute, centrifugal 0-10 minute, obtain the colloidal sol clear liquid; Quartz fibre one end that removes the drying of protective layer is inserted 1-30min in the colloidal sol clear liquid, took out the back dry 8-24 hour; N
2Protection promptly got required extracting head down in 250-380 ℃ of aging 2-3 hour.
2. extracting head according to claim 1 is characterized in that: described calixarenes is cup [4] aromatic hydrocarbons.
3. the preparation method of the described solid phase micro-extraction extraction head of claim 1, it is characterized in that: get 10-60mg bisglycidyl base calixarenes, adding calixarenes molal quantity 1-5 3-aminopropyltriethoxywerene werene doubly, is solvent with 100-500 μ L carrene, reacts 10-60min in advance; Add bisglycidyl base calixarenes quality 1.5-15 hydroxy silicon oil doubly again, 60-120 μ L tetraethoxysilane or MTMS reach the 0-15mg containing hydrogen silicone oil and fully mix, and sonic oscillation 3-10 minute, centrifugal 0-10 minute, obtain the colloidal sol clear liquid; Quartz fibre one end that removes the drying of protective layer is inserted 1-30min in the colloidal sol clear liquid, took out the back dry 8-24 hour; N
2Protection promptly got required extracting head down in 250-380 ℃ of aging 2-3 hour.
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