CN100446833C - Making process of integral stirring rod for solid phase extraction - Google Patents
Making process of integral stirring rod for solid phase extraction Download PDFInfo
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- CN100446833C CN100446833C CNB2006101223411A CN200610122341A CN100446833C CN 100446833 C CN100446833 C CN 100446833C CN B2006101223411 A CNB2006101223411 A CN B2006101223411A CN 200610122341 A CN200610122341 A CN 200610122341A CN 100446833 C CN100446833 C CN 100446833C
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Abstract
The present invention relates to solid extraction stirring rod, and is especially the making process of integral solid extraction stirring rod. The making process is simple and may produce solid extraction stirring rod of high adsorption and desorption speed and in required sizes. The making process includes the following steps: making stirring magneton; pre-bonding through preparing mixture solution of gamma-methylic acid, propoxy trimethoxy silane and methanol, adding organic base to prepare pre-bonding solution, soaking the stirring magneton in the pre-bonding solution to react under nitrogen protection to bond one layer of silane matter with alkenyl group in the outer wall of the glass tube of stirring magneton; forming solid extraction stirring rod; setting the stirring magneton in mixture solution of mixed reaction monomer and pore creating agent inside a glass container in a sealed water bath to obtain stirring rod with coated polymer; and post-treatment.
Description
Technical field
The present invention relates to a kind of solid-phase extraction muddler, especially relate to and a kind ofly be used for SPE and based on the technology of preparing of integral material solid-phase extraction muddler (MSBSE).
Background of invention
Solid-phase extraction muddler technology (SBSE) is a kind of novel sample pre-treatments technology of development on SPME (SPME) basis, it is by (Baltussen E, Sandra P, David F such as Baltussen, Cramers C.J.Microcol.Sep., 1999,11 (10): 737～747) at first proposed in 1999, and by (the Frank D of Gerstel GmbH company, TienpontB, Sandra P.LC-GC North America, 2003,21 (2): 1～7) commercialization.The SBSE stirring rod is to apply the commercial dimethyl silicone polymer of one deck (PDMS) on the glass tube of interior envelope magnetic core, is used for the enrichment of fluid sample object.During extraction, stirring rod is the absorption object when stirring, can avoid among the SPME stirrer to the competitive Adsorption of object, the volume of extraction water sample is generally 55～250mL, bigger more than 50 times than Fiber SPME and general In-tube SPME extraction volume, therefore the corresponding raising of enrichment multiple is suitable for the analysis of trace components in the sample.This technology successfully is applied to environmental sample (1.Leon V M, Alvarez B, CobouoM A, Munoz S, Valor I.J.Chrom atogr.A, 2003,999:91～101 at present; 2.Vercauteren J, Peres C, Devos C, Sandra P, Vanhaecke F, Moens L.Anal.Chem., 2001,73:1509～1514; 3.Popp P, Bauer C, Wennrich L.Anal.Chim.Acta, 2001,436:1～9), pollutant (1.Sandra P, Tienpont B, David F.J.Chromatogr.A, 2003,1000:299～309 in the food; 2.Andreas G J, Lauer H L, Heideman T, Sandra P.J.highResolut.Chromatogr., 644～646) and residues of pesticides (Tienpont B 2000,23 (11):, David F, Kesmet K, Sandra P.Anal.Bioanal.Chem., 2002,373:46～55) and the analysis of biological sample, (Migaku K, Rie I, Koichi S such as Migaku, Hiroyuki N, J.Pharm.and Biomed.Anal., 2006,40:500-508) this is summarized.
In the SBSE technology, the extraction fixedly preparation of phase is very important, in order to improve accumulation ability, just must increase and extracts the fixedly thicknesses of layers of phase.But present used extraction fixedly phase coating still only limits to PDMS, increases thicknesses of layers difficulty relatively, and when rete was too thick on the one hand, resistance to mass tranfer strengthened, and the absorption and the rate of recovery of object all had a significant impact; In addition on the one hand, too thick rete in use ftractures easily, influences service life.(Liu Wenmin such as Guan, Wang Hanwen, Guan Yafeng, analytical chemistry, 2005,33 (1): 45～49) utilize fixedly phase coating of extraction that sol-gel technique prepared thickness 30 μ m first, adopt multistage temperature-programmed mode wear out mutually to avoid coating to chap to fixing, be used for the enrichment of the polycyclic aromatic hydrocarbon of seawater, obtained result preferably.
Summary of the invention
Being intended to of the object of the invention at the existing the problems referred to above of existing solid-phase extraction muddler technology, provide a kind of preparation process easy, easy to operate, adsorption and desorption speed is very fast, also can prepare the preparation method of the integral stirring rod for solid phase extraction of length, stirring rod that thickness is different in the practical application by demand.
For this reason, the present invention is by the following technical solutions: the integral post technology of preparing is incorporated in the fixing preparation mutually of SBSE extraction, the used monomer of integral material is an alkyl methacrylate, crosslinking agent is ethylene glycol dimethacrylate or pentaerythritol triacrylate or trimethoxy propane trimethyl acrylic ester, azodiisobutyronitrile (AIBN) or benzoyl peroxide are initator, normal propyl alcohol, 1,4-butanediol and water ternary mixture are cosolvent.Preparation-obtained integral stirring rod for solid phase extraction can carry out the extraction to object when stirring.
Integral stirring rod for solid phase extraction of the present invention is provided with iron bar, and iron bar is by glass capsulation, and glass outer layer scribbles polymeric layer.
The preparation method of integral stirring rod for solid phase extraction of the present invention is as follows:
1) preparation of stirring magneton: intercept an iron leg bar, behind the cleaning, drying, it is sealed, must stir magneton with glass.
2) the pre-bonding of stirring magneton:
A. operate routinely the glass tube exterior surface that stirs magneton is carried out cleaning, dry stand-by;
B. prepare γ-methacrylic acid oxygen propyl trimethoxy silicane (mixed solution of γ-MAPS) and methyl alcohol; press mass ratio γ-methacrylic acid oxygen propyl trimethoxy silicane (γ-MAPS) and methyl alcohol=1: (0.5～1.5); at γ-methacrylic acid oxygen propyl trimethoxy silicane (γ-MAPS) and in the mixed solution of methyl alcohol add organic base; make pre-bonding solution; the stirring magneton of handling well is immersed pre-bonding solution; after under nitrogen protection, reacting; oven dry; so far, stirred on the glass tube outer wall bonding of magneton the silanization material of one deck band thiazolinyl.
3) preparation of solid-phase extraction muddler:
A. prepare the reaction monomers intermixture, alkyl methacrylate is 59.5%～44.5% by mass percentage, and crosslinking agent is 39.5%～54.5%, and initator azobisisobutyronitrile (AIBN) or benzoyl peroxide are 0.5%～2%;
B. prepare the pore-foaming agent mixed solution, propyl alcohol is 50%～70%, 1 by mass percentage, and the 4-butanediol is 20%～40%, and water is 5%～20%;
C. take by weighing reaction monomers and pore-foaming agent, pour into behind the mixing in the glass container, the stirring magneton of handling is vertically put into glass container, sealing places water-bath to react, and removes glass container again, takes out the stirring rod that scribbles polymer.
4) post processing of solid-phase extraction muddler: the stirring rod that step 3 polymerization is good places solvent, obtains the integral stirring rod for solid phase extraction based on integral material again after the drying.
When magneton was stirred in preparation, the diameter of iron bar was preferably 0.1～3mm, and length is 0.5～5cm.
In the pre-bonding that stirs magneton; percentage by volume; the organic base that adds is γ-methacrylic acid oxygen propyl trimethoxy silicane (0.1%～0.3% of mixed solution of γ-MAPS) and methyl alcohol; described organic base is a pyridine, triethylamine, imidazoles etc.; after making pre-bonding solution; the stirring magneton of handling well is immersed pre-bonding solution, under nitrogen protection, place 30～50 ℃ the reaction 6～24h after, 30～60 ℃ of vacuum dryings.Pre-bonding reaction formula is as follows:
When the preparation solid-phase extraction muddler, the mass percent of reaction monomers intermixture and pore-foaming agent mixed liquor is preferably (35%: 65%)～(55%: 45%); The temperature of described water-bath is preferably 40～70 ℃, and the water-bath time is preferably 6～24h.If crosslinking agent is an example with the ethylene glycol dimethacrylate, then polymerization process is as follows:
R＝C
4H
9～C
18H
37
In the last handling process of solid-phase extraction muddler, can the stirring rod that step 3 polymerization is good place apparatus,Soxhlet's, with methyl alcohol or second eyeball or ethanol is solvent, extract 4～24h, with stirring rod dry 1～8h in 30～80 ℃ of vacuum, obtain integral stirring rod for solid phase extraction at last then based on integral material; Perhaps stirring rod is placed methyl alcohol or second eyeball or alcohol solvent, be dipped to that free from admixture detects in the liquid, with stirring rod dry 1～8h in 30～80 ℃ of vacuum, obtain integral stirring rod for solid phase extraction at last then based on integral material.
The present invention is incorporated into the technology of preparing of integral post in the preparation of solid-phase extraction muddler, because the integral post preparation is simple, permeability is good, stability is strong, it is easy, easy to operate to use the stirring rod preparation process that this technology makes, absorption and desorption rate are arranged faster, also can prepare length, stirring rod that thickness is different in the practical application by demand.The glass outer surface that stirs magneton is reacted with the γ-MAPS that has difunctional, so glass surface has two keys, can with monomer intermixture generation copolymerization, the stirring rod of gained becomes one like this, has good stability.
Description of drawings
Fig. 1 is the structural representation of solid-phase extraction muddler embodiment of the present invention.
Fig. 2 is the Electronic Speculum figure on stirring rod surface in the embodiment of the invention 1.
Fig. 3 is the Electronic Speculum figure of stirring rod section part in the embodiment of the invention 1.In Fig. 3, A. stirs magneton glass face, B. polymer.
Fig. 4 is extraction time and an extraction efficiency graph of a relation in the embodiment of the invention 4.In Fig. 4, abscissa is time t (min), and ordinate is peak area Peak area (mAU), a naphthalene, b fluoranthene, c naphthalene.
Fig. 5 is desorption time and a desorption efficiency graph of a relation in the embodiment of the invention 5.In Fig. 5, abscissa is time t (min), and ordinate is peak area Peak area (mAU), a naphthalene, b fluoranthene, c naphthalene.
Fig. 6 is that the HPLC-UV of (a) and back (b) separated spectrogram before the mark-on seawater extracted in the embodiment of the invention 6.In Fig. 6, abscissa is time t (min), and ordinate is absorption intensity Absorbance, and the ordinate scale value is 5mAU, the mark-on seawater before a extraction, b extract; 1. naphthalene, 2. acenaphthene, 3. phenanthrene, 4. anthracene, 5. fluoranthene, 6. pyrene, 7.
, 8. BaP.
Fig. 7 be in the embodiment of the invention 7 before the mark-on running water extraction (a) and afterwards (b) HPLC-UV separate spectrogram.In Fig. 7, abscissa is time t (min), and ordinate is absorption intensity Absorbance, and the ordinate scale value is 1mAU, the mark-on running water before a extraction, b extract; 1. nandrolone, 2. methyltestosterone, 3. testosterone propionate, 4. Nandrolone Phenylpropionate.
The specific embodiment
The present invention is further illustrated below by embodiment.
Referring to Fig. 1, when magneton was stirred in preparation, intercepting diameter was 0.1mm, and length is the iron bar 1 of 0.5cm, behind the cleaning, drying, with glass 2 with its seal the stirring magneton.
Stir the glass tube exterior surface of magneton and operate routinely, dry stand-by carrying out cleaning.By 1: 0.5 preparation γ-methacrylic acid oxygen propyl trimethoxy silicane (mixed solution 3.0mL of γ-MAPS) and methyl alcohol; add pyridine 3 μ L; the stirring magneton of handling well is immersed above-mentioned solution, under nitrogen protection, place 30 ℃ the reaction 24h after, 30 ℃ of vacuum dryings.So far, the silanization material of glass tube outer wall bonding last layer band thiazolinyl.
Composed as follows between the reaction monomers mixture: the quality percentage composition of butyl methacrylate is 59.5%, and pentaerythritol triacrylate quality percentage composition is 39.5%, and initator azobisisobutyronitrile (AIBN) is 0.5%; Ratio between the pore-foaming agent mixture is: propyl alcohol 50%, 1,4-butanediol 40%, water 10%; Ratio between monomer mixture and the pore-foaming agent mixture is 35%: 65%; Take by weighing respective reaction reagent according to the above ratio, behind the reactant liquor mixing, above-mentioned solution is poured in the teat glass of certain 4mm internal diameter, the stirring magneton that carefully will handle is vertically put into glass tube, and sealing places 40 ℃ of water-baths to react 24h.After reaction is finished, carefully remove glass tube, take out stirring rod.
The stirring rod that polymerization is good places apparatus,Soxhlet's, is solvent with methyl alcohol, extracts 4h, then with stirring rod at 30 ℃ of vacuum drying 8h, obtain integral stirring rod for solid phase extraction based on integral material.Fig. 2 is the Electronic Speculum figure on this stirring rod surface, and Fig. 3 is the stirring rod section part, the Electronic Speculum figure of glass and polymer.In Fig. 1, the external coating of glass 2 is a polymeric layer 3.
The preparation of stirring magneton is with embodiment 1, but the iron bar diameter is 2mm, and length is 3cm.In stirring the pre-bonding of magneton by 1: 1 preparation γ-methacrylic acid oxygen propyl trimethoxy silicane (mixed solution 6.0mL of γ-MAPS) and methyl alcohol; add triethylamine 12 μ L; the stirring magneton of handling well is immersed above-mentioned solution; after under nitrogen protection, placing 40 ℃ of reaction 12h, 50 ℃ of vacuum dryings.So far, on glass tube outer wall bonding the silanization material of one deck band thiazolinyl.Consisting of of reaction monomers intermixture: the quality percentage composition of 2-Propenoic acid, 2-methyl-, octyl ester is 49.5%, and ethylene glycol dimethacrylate quality percentage composition is 49.5%, and the initator benzoyl peroxide is 1%; Ratio between the pore-foaming agent mixture is: propyl alcohol 60%, 1,4-butanediol 30%, water 10%; Ratio between monomer intermixture and the pore-foaming agent mixture was at 40%: 60%; Take by weighing corresponding reagent according to the above ratio, behind the reactant liquor mixing, above-mentioned solution is poured in the teat glass of certain 6mm internal diameter, the stirring magneton that carefully will handle is vertically put into teat glass, and sealing places 60 ℃ of water-baths to react 16h.In the post processing of solid-phase extraction muddler, the stirring rod that polymerization is good places apparatus,Soxhlet's, is solvent with the second eyeball, extracts 8h, then with stirring rod at 50 ℃ of vacuum drying 6h.Obtain integral stirring rod for solid phase extraction at last based on integral material.
The preparation of stirring magneton is with embodiment 1, but the iron bar diameter is 3mm, and length is 5cm.In stirring the pre-bonding of magneton by 1: 1.5 preparation γ-methacrylic acid oxygen propyl trimethoxy silicane (γ-MAPS) and methyl alcohol mixed solution 9mL; add imidazoles 27 μ L; the stirring magneton of handling well is immersed above-mentioned solution, under nitrogen protection, place 60 ℃ the reaction 6h after, 60 ℃ of vacuum dryings.So far, the silanization material of glass tube outer wall bonding last layer band thiazolinyl.Ratio is between the reaction monomers mixture: the quality percentage composition of octadecyl methacrylate is 44.5%, and trimethoxy propane trimethyl acrylic ester quality percentage composition is 54.5%, and the initator benzoyl peroxide is 2%; Ratio between the pore-foaming agent mixture is: propyl alcohol 70%, 1,4-butanediol 25%, water 5%; Ratio between monomer mixture and the pore-foaming agent mixture was at 55%: 45%; Take by weighing respective reaction reagent according to the above ratio, behind the reactant liquor mixing, above-mentioned solution is poured in the teat glass of certain 8mm internal diameter, the stirring magneton that carefully will handle is vertically put into teat glass, and sealing places 70 ℃ of water-baths to react 6h.Carrying out in the post processing of solid-phase extraction muddler, is solvent with ethanol, stirring rod is dipped to free from admixture detects, then with stirring rod dry 1h in 80 ℃ of vacuum.Obtain integral stirring rod for solid phase extraction at last based on integral material.
Embodiment 4
The mixed aqueous solution 100mL (containing methyl alcohol 8mL) of preparation naphthalene, phenanthrene and fluoranthene, concentration is 2.0ppm, investigate the adsorption process of prepared extraction stirring rod to these three kinds of test compounds, the iron core diameter of the stirring rod of using is 1mm, length 1.5cm, stirring rod diameter 6mm, length 3em, other preparation process is with embodiment 2, stirring rod is placed the mixed aqueous solution of naphthalene, phenanthrene and fluoranthene, and 600r/min stirs certain hour under the room temperature, and chromatographic condition is: C18 integral post (100 * 4.6mm i.d.), flowing is acetonitrile and water mutually, and volume ratio is 75: 25; Flow velocity 2.0mL/min; Sample size 20 μ L; Detect wavelength 254nm.The residual quantity of naphthalene, phenanthrene and fluoranthene (representing) in extraction time and the sample with chromatographic peak area, as shown in Figure 4.
Embodiment 5
In embodiment 4, the stirring rod of having adsorbed naphthalene, phenanthrene and fluoranthene is taken out, and puts into 10mL methyl alcohol, 600r/min stirs certain hour under the room temperature, investigates the desorption process of stirring rod, and chromatographic condition is with embodiment 4, time and desorption efficiency (representing) with chromatographic peak area, as shown in Figure 5.
Embodiment 6
Prepare the sea water solution 200mL that 8 kinds of polycyclic aromatic hydrocarbon mark-on concentration are 10ppb, insert stirring rod, under 600r/min, extract 2h under the room temperature, take out stirring rod by embodiment 4 preparations, with 10mL methyl alcohol desorb 2h under 600r/min, nitrogen blowing is concentrated into 1mL then.Chromatographic condition is chromatographic column Waters spherosorb 5 μ m (250 * 4.6mm i.d.), and flowing is acetonitrile and water mutually, and volume ratio is 80: 20, flow velocity 1.5mL/min, and sample size 20 μ L, the detection wavelength is 254nm.Fig. 6 separates spectrogram for the HPLC-UV of mark-on seawater extraction preceding (a) and back (b).
Embodiment 7
Prepare the polymer solution in water 200mL that 4 kinds of anabolic hormone mark-on concentration are 10ppb, insert stirring rod by embodiment 4 preparations, extract 2h under the room temperature under 600r/min, take out stirring rod 10mL methyl alcohol desorb 2h under 600r/min, nitrogen blowing is concentrated into 1mL then.Chromatographic condition is chromatographic column Waters spherosorb 5 μ m (250 * 4.6mm i.d.), and flowing is acetonitrile and water mutually, and volume ratio is 85: 15, flow velocity 1.0mL/min, and sample size 20 μ L, the detection wavelength is 245nm.Fig. 7 separates spectrogram for the HPLC-UV of mark-on running water extraction preceding (a) and back (b).
Claims (9)
1. the preparation method of integral stirring rod for solid phase extraction is characterized in that the steps include:
1) preparation of stirring magneton: intercept an iron leg bar, behind the cleaning, drying, it is sealed, must stir magneton with glass;
2) the pre-bonding of stirring magneton:
A. operate routinely the glass tube exterior surface that stirs magneton is carried out cleaning, dry stand-by;
B. prepare the mixed solution of γ-methacrylic acid oxygen propyl trimethoxy silicane and methyl alcohol, press mass ratio γ-methacrylic acid oxygen propyl trimethoxy silicane and methyl alcohol=1: 0.5～1.5, in the mixed solution of γ-methacrylic acid oxygen propyl trimethoxy silicane and methyl alcohol, add organic base, make pre-bonding solution, the stirring magneton of handling well is immersed pre-bonding solution, under nitrogen protection after the reaction, the silanization material of one deck band thiazolinyl has been stirred on the glass tube outer wall bonding of magneton in oven dry;
3) preparation of solid-phase extraction muddler:
A. prepare the reaction monomers intermixture, alkyl methacrylate is 59.5%～44.5% by mass percentage, and crosslinking agent is 39.5%～54.5%, and initator azobisisobutyronitrile or benzoyl peroxide are 0.5%～2%;
B. prepare the pore-foaming agent mixed solution, propyl alcohol is 50%～70%, 1 by mass percentage, and the 4-butanediol is 20%～40%, and water is 5%～20%;
C. take by weighing reaction monomers and pore-foaming agent, pour into behind the mixing in the glass container, the stirring magneton of handling is vertically put into glass container, sealing places water-bath to react, and removes glass container again, takes out the stirring rod that scribbles polymer;
4) post processing of solid-phase extraction muddler: the stirring rod that step 3 polymerization is good places solvent, obtains the integral stirring rod for solid phase extraction based on integral material again after the drying.
2. the preparation method of integral stirring rod for solid phase extraction as claimed in claim 1 is characterized in that the diameter of iron bar is 0.1～3mm when magneton is stirred in preparation, and length is 0.5～5cm.
3. the preparation method of integral stirring rod for solid phase extraction as claimed in claim 1, it is characterized in that in the pre-bonding that stirs magneton, percentage by volume, the organic base of adding be γ-methacrylic acid oxygen propyl trimethoxy silicane and methyl alcohol mixed solution 0.1%～0.3%.
4. the preparation method of integral stirring rod for solid phase extraction as claimed in claim 1 is characterized in that described organic base is pyridine, triethylamine or imidazoles.
5. the preparation method of integral stirring rod for solid phase extraction as claimed in claim 1; after it is characterized in that making pre-bonding solution; the stirring magneton of handling well is immersed pre-bonding solution, under nitrogen protection, place 30～50 ℃ the reaction 6～24h after, 30～60 ℃ of vacuum dryings.
6. the preparation method of integral stirring rod for solid phase extraction as claimed in claim 1 is characterized in that the mass percent of reaction monomers intermixture and pore-foaming agent mixed liquor is 35%: 65%～55%: 45% when the preparation solid-phase extraction muddler.
7. the preparation method of integral stirring rod for solid phase extraction as claimed in claim 1, the temperature that it is characterized in that described water-bath is 40～70 ℃, the water-bath time is 6～24h.
8. the preparation method of integral stirring rod for solid phase extraction as claimed in claim 1, it is characterized in that in the last handling process of solid-phase extraction muddler, can the stirring rod that step 3 polymerization is good place apparatus,Soxhlet's, with methyl alcohol or second eyeball or ethanol is solvent, extract 4～24h, with stirring rod dry 1～8h in 30～80 ℃ of vacuum, obtain integral stirring rod for solid phase extraction at last then based on integral material.
9. the preparation method of integral stirring rod for solid phase extraction as claimed in claim 1, it is characterized in that in the last handling process of solid-phase extraction muddler, can the stirring rod that step 3 polymerization is good place methyl alcohol or second eyeball or alcohol solvent, be dipped to that free from admixture detects in the liquid, with stirring rod dry 1～8h in 30～80 ℃ of vacuum, obtain integral stirring rod for solid phase extraction at last then based on integral material.
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