CN104707584A - Preparation method for molecularly imprinted solid-phase extraction columns of anthraquinone sensitizing disperse dyes - Google Patents
Preparation method for molecularly imprinted solid-phase extraction columns of anthraquinone sensitizing disperse dyes Download PDFInfo
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Abstract
The invention relates to a preparation method for molecularly imprinted solid-phase extraction columns of anthraquinone sensitizing disperse dyes. As molecularly imprinted polymers are high in selectivity, and graphene and molecules provided with the aromatic structure can be separated, enriched and purified through the Pi-Pi bond interaction force, the preparation method combines the high selectivity of the molecularly imprinted polymers and the high adsorptive capacity of graphene on the anthraquinone sensitizing disperse dyes provided with the aromatic structure, and the prepared solid-phase extraction columns have the characteristics of being high in specific selectivity and high in enrichment efficiency on the anthraquinone sensitizing disperse dyes; the enrichment capability of the product on a target analyte is 50-500 times of that of the ordinary commercial solid-phase extraction pillaret; when being used for 10 times, the molecularly imprinted solid-phase extraction columns still have relatively high selectivity and high enrichment capability on the trace amount of the residual anthraquinone sensitizing disperse dyes in the sample, and the recovery rate is greater than 96.6%.
Description
Technical field
The present invention relates to a kind of preparation method of Anthraquinones sensitizing disperse dyes molecularly imprinted solid phase extraction column.
Background technology
Sensitizing disperse dyes (allergenic disperse dyes, ADDs) refers to the disperse dyes of some skin that can cause human body or animal, mucous membrane or respiratory tract anaphylaxis.ADDs is as the class chemical pollutant containing aromatic structure, and it, to the exposure of the pollution situation of water body and relevant food security incident, makes it be subject to extensive concern both domestic and external.Such chemical pollutant can be aromatic amine material by metabolic breakdown after entering human body, and has the side effect such as high poison, high residue and " three cause " (carcinogenic, teratogenesis, mutagenesis).List 20 kinds of sensitizing disperse dyes in European Union Oeko-Tex Standard Oeko.Tex Standard 1001151, and in prescribed product, sensitizing disperse dyes content must not more than 0.006%.But according to China integrated wastewater discharge standard GB 8978-1996, printing and dyeing enterprise discharge of wastewater major control index is pH value, colourity, BOD, COD and ammonia-nitrogen content, does not provide clear and definite limit value to the concentration of emission of sensitizing disperse dyes.Current research shows, 0.1 μ g/L even the sensitizing disperse dyes dyestuff of lower amounts level can cause the biological effect of animal used as test, and the research of its low dose effect has become an important directions of current sensitizing disperse dyes dyestuff research.Given this, enrichment purification and the detection technique research of carrying out trace sensitizing disperse dyes are of value to the progress promoting sanitary inspection technology.
Solid phase extraction techniques (Solid Phase Extraction, SPE) be a kind of traditional abstraction and purification means, superfine people (the Feng Yuechao of Feng Yue, Jia Li, He Yahui, waits .2013, and 31,1021) adopt WAX solid-phase extraction column to carry out enrichment purification to 24 kinds of residual traces industrial dyes in grain and meat products, obtain comparatively satisfied result.But common SPE post lacks selective to component to be measured, and reproducibility is poor, and the active force between traditional solid phase extraction adsorbents and component to be measured is nonspecific, limits further developing of SPE.
What molecularly imprinted polymer mainly utilized molecular imprinting to prepare have high-affinity and high selectivity can identify the special receptor with combining target molecule, the distribution of shape, size and chemical functional base can be relied on to identify template molecule, there is the precordainment of structure effect, the specificity of identification and practicality widely.
In prior art, have no the report about Anthraquinones sensitizing disperse dyes molecularly imprinted solid phase extraction column.
Summary of the invention
Technical problem to be solved by this invention is the present situation for prior art, provides the preparation method of the Anthraquinones sensitizing disperse dyes molecularly imprinted solid phase extraction column that a kind of specific selectivity is strong, bioaccumulation efficiency is high.
The present invention solves the problems of the technologies described above adopted technical scheme: a kind of preparation method of Anthraquinones sensitizing disperse dyes molecularly imprinted solid phase extraction column, is characterized in that comprising the following steps:
(1) 100 ~ 500mg Anthraquinones sensitization dispersion dye magnetic graphite thiazolinyl molecularly imprinted polymer is mixed with the pure organic solvent of 5 ~ 20mL, after vibration 5 ~ 30min, ultrasonic process 5 ~ 30min is to mixing, the capacity that moved to by this mixture is in the solid phase extraction column of 3mL, after filling evenly, sieve plate shutoff is used at the two ends of solid phase extraction column respectively;
(2) 100 ~ 500mg solid phase extraction filler is mixed with the pure organic solvent of 5 ~ 20mL, after vibration 5 ~ 30min, ultrasonic process 5 ~ 30min is to mixing, the Anthraquinones sensitization dispersion of having loaded this mixture being moved to step (1) contaminates in the solid phase extraction column of magnetic graphite thiazolinyl molecularly imprinted polymer, after filling evenly, by the sieve plate shutoff of the top of this solid phase extraction column, clean with the acidic organic solvent upper prop of 5 ~ 20mL, then with the pure organic solvent upper prop cleaning of 5 ~ 20mL;
(3) by step (2) the gains residual organic solvent of inert gas purge removing, and at 30 ~ 90 DEG C vacuum drying 1 ~ 24h, namely obtain Anthraquinones sensitization dispersion dye magnetic graphite thiazolinyl molecularly imprinted solid phase extraction column.
In such scheme, the preparation method of the dispersion of Anthraquinones sensitization described in step (1) dye magnetic graphite thiazolinyl molecularly imprinted polymer comprises the following steps:
A () is by FeSO
4and FeCl
36H
2o is dissolved in 100mL water, obtains Fe
2+, Fe
3+molar concentration be respectively the solution of 0.18 ~ 0.22mol/L, 0.58 ~ 0.62mol/L, add 45 ~ 55mg Graphene by after this solution ultrasonic disperse 10 ~ 20min, and continue ultrasonic disperse 1h ~ 2h;
B () adds 0.1 ~ 1.0moL Anthraquinones sensitizing disperse dyes template molecule in step (a) gains, and with ammoniacal liquor adjust ph to 10 ~ 12 at 80 DEG C ~ 82 DEG C, then 80 DEG C ~ 82 DEG C, with 600 ~ 650r/min stirring reaction, 1 ~ 1.5h, obtain the product with black solid powder;
C () product to step (b) carries out Magneto separate, gained black solid powder is not detected by Liquid Chromatography-Tandem Mass Spectrometry instrument to described Anthraquinones sensitizing disperse dyes template molecule with ultra-pure water and ethanol washing successively, then by black solid powder vacuum drying 12 ~ 16h at 60 ~ 65 DEG C, Anthraquinones sensitizing disperse dyes magnetic graphite thiazolinyl molecularly imprinted polymer is namely obtained.
As preferably, the pure organic solvent described in step (1), (2) is the one in methyl alcohol, ethanol, acetonitrile and acetone.
As improvement, acidic organic solvent described in step (2) is the mixed solution of at least one in formic acid, acetic acid and trifluoroacetic acid and methyl alcohol, and the volume ratio of one or more mixed solution in formic acid, acetic acid, trifluoroacetic acid and methyl alcohol is 1:5 ~ 20.
Preferably, solid phase extraction filler described in step (2) is at least one in Graphon, styrene-polystyrene copolymer, basic alumina, aliphatic quaternary ammonium salt bonded silica gel SAX, aliphatic quaternary ammonium salt bonded silica gel WAX.
Further improvement, the mass ratio of Anthraquinones sensitizing disperse dyes magnetic graphite thiazolinyl molecularly imprinted polymer described in step (1) and the middle solid phase extraction filler of step (2) is 1:1 ~ 5.
Preferably, the Anthraquinones sensitizing disperse dyes template molecule described in step (b) is at least one in disperse blue 1, disperse blue 3, disperse blue 7, disperse blue 26, disperse blue 35, dispersion red 11 and disperse orange 11.
Compared with prior art, the invention has the advantages that:
(1) because molecularly imprinted polymer has high selectivity, and the object of separation and consentration purification between Graphene and the molecule with aromatic structure, is reached by π – π key interaction force, the high selectivity of molecularly imprinted polymer combined with the strong adsorption capacity of Graphene to the Anthraquinones sensitizing disperse dyes with aromatic structure, to Anthraquinones sensitizing disperse dyes, prepared solid-phase extraction column has the advantages that specific selectivity is strong, bioaccumulation efficiency is high;
(2) it is large that the Anthraquinones sensitizing disperse dyes magnetic graphite thiazolinyl molecularly imprinted polymer in the present invention has specific area, adsorption site is many, the selective advantage such as by force, the solid-phase extraction column of preparation has excellent selective and accumulation ability to trace Anthraquinones sensitizing disperse dyes in environmental water sample, 50 ~ 500 times of general commercial solid phase extraction column to the accumulation ability of target analytes, molecularly imprinted solid phase extraction column is after use 10 times, to residual traces Anthraquinones sensitizing disperse dyes in sample, still there is higher selective and accumulation ability, the rate of recovery is greater than 96.6%,
(3) Anthraquinones sensitizing disperse dyes magnetic graphite thiazolinyl molecular imprinted solid phase extraction cartridge preparation method of the present invention is simple, and stable process conditions, production cost is low.
Accompanying drawing explanation
Fig. 1 is the TEM figure of Anthraquinones sensitization dispersion dye magnetic graphite thiazolinyl molecularly imprinted polymer in the embodiment of the present invention 1;
Fig. 2 is the SEM figure of Anthraquinones sensitization dispersion dye magnetic graphite thiazolinyl molecularly imprinted polymer in the embodiment of the present invention 1;
Fig. 3 is Anthraquinones sensitizing disperse dyes multiple-reaction monitoring (MRM) chromatogram in the embodiment of the present invention, wherein, peak (1) is disperse blue 1, (2) be disperse blue 3, (3) are disperse blue 7, (4) are disperse blue 26, (5) are disperse blue 35, (6) are dispersion red 11, (7) are disperse orange 11.
Detailed description of the invention
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.
Embodiment 1:
The preparation method of Anthraquinones sensitizing disperse dyes molecularly imprinted solid phase extraction column in the present embodiment, comprises the following steps:
The preparation of Anthraquinones sensitization dispersion dye magnetic graphite thiazolinyl molecularly imprinted polymer:
A () is by FeSO
4and FeCl
36H
2o is dissolved in 100mL water, obtains Fe
2+, Fe
3+molar concentration be respectively the solution of 0.2mol/L, 0.6mol/L, add 50mg Graphene by after this solution ultrasonic disperse 15min, and continue ultrasonic disperse 1h;
B () adds 0.1moL Anthraquinones sensitizing disperse dyes template molecule disperse blue 1 in step (a) gains, and by ammoniacal liquor adjust ph to 11 at 80 DEG C, then 80 DEG C, with 600r/min stirring reaction 1h, obtain the product with black solid powder;
C () product to step (b) carries out Magneto separate, gained black solid powder is not detected by Liquid Chromatography-Tandem Mass Spectrometry instrument to described Anthraquinones sensitizing disperse dyes template molecule disperse blue 1 with ultra-pure water and ethanol washing successively, then by black solid powder vacuum drying 12h at 60 DEG C, Anthraquinones sensitizing disperse dyes magnetic graphite thiazolinyl molecularly imprinted polymer is namely obtained.
The preparation of Anthraquinones sensitizing disperse dyes molecularly imprinted solid phase extraction column:
(1) above-mentioned for 100mg Anthraquinones sensitization dispersion dye magnetic graphite thiazolinyl molecularly imprinted polymer is mixed with 10mL methyl alcohol, after vibration 20min, ultrasonic process 20min is to mixing, the capacity that moved to by this mixture is in the solid phase extraction column of 3mL, after filling evenly, sieve plate shutoff is used at the two ends of solid phase extraction column respectively;
(2) 100mg styrene-polystyrene copolymer is mixed with 10mL methyl alcohol, after vibration 10min, ultrasonic process 10min is to mixing, the Anthraquinones sensitization dispersion of having loaded this mixture being moved to step (1) contaminates in the solid phase extraction column of magnetic graphite thiazolinyl molecularly imprinted polymer, after filling evenly, by the sieve plate shutoff of the top of this solid phase extraction column, clean with the formic acid of 15mL and the mixed solution upper prop of methyl alcohol, then with the cleaning of 15mL methyl alcohol upper prop; Wherein, the volume ratio of formic acid and methyl alcohol is 1:5;
(3) by step (2) the gains residual organic solvent of inert gas purge removing, and at 30 DEG C vacuum drying 24h, namely obtain Anthraquinones sensitization dispersion dye magnetic graphite thiazolinyl molecularly imprinted solid phase extraction column.
Adopt transmission electron microscope (TEM) and SEM (SEM) to characterize its pattern preparation-obtained for embodiment 1 Anthraquinones sensitizing disperse dyes magnetic graphite thiazolinyl molecularly imprinted polymer, result as shown in Figures 1 and 2.Comprehensive TEM and SEM characterization result, nanometer Fe immobilized on Anthraquinones sensitizing disperse dyes magnetic graphite thiazolinyl molecularly imprinted polymer
3o
4pattern rule, uniform particle diameter, good dispersion, and the orderly distribution at graphenic surface can be realized; Achieve crosslinked in order between single-layer graphene.
Embodiment 2:
The preparation method of Anthraquinones sensitizing disperse dyes molecularly imprinted solid phase extraction column in the present embodiment, comprises the following steps:
The preparation of Anthraquinones sensitization dispersion dye magnetic graphite thiazolinyl molecularly imprinted polymer:
(a) FeSO
4and FeCl
36H
2o is dissolved in 100mL water, obtains Fe
2+, Fe
3+molar concentration be respectively the solution of 0.18mol/L, 0.58mol/L, add 45mg Graphene by after this solution ultrasonic disperse 10min, and continue ultrasonic disperse 1.5h;
B () adds 1.0moL Anthraquinones sensitizing disperse dyes template molecule disperse blue 3 in step (a) gains, and by ammoniacal liquor adjust ph to 10 at 82 DEG C, then 82 DEG C, with 620r/min stirring reaction 1.2h, obtain the product with black solid powder;
C () product to step (b) carries out Magneto separate, gained black solid powder is not detected by Liquid Chromatography-Tandem Mass Spectrometry instrument to described Anthraquinones sensitizing disperse dyes template molecule disperse blue 3 with ultra-pure water and ethanol washing successively, then by black solid powder vacuum drying 14h at 63 DEG C, Anthraquinones sensitizing disperse dyes magnetic graphite thiazolinyl molecularly imprinted polymer is namely obtained.
The preparation of Anthraquinones sensitizing disperse dyes molecularly imprinted solid phase extraction column:
(1) above-mentioned for 200mg Anthraquinones sensitization dispersion dye magnetic graphite thiazolinyl molecularly imprinted polymer is mixed with 5mL ethanol, after vibration 5min, ultrasonic process 30min is to mixing, the capacity that moved to by this mixture is in the solid phase extraction column of 3mL, after filling evenly, sieve plate shutoff is used at the two ends of solid phase extraction column respectively;
(2) 500mg basic alumina is mixed with 20mL ethanol, after vibration 30min, ultrasonic process 5min is to mixing, the Anthraquinones sensitization dispersion of having loaded this mixture being moved to step (1) contaminates in the solid phase extraction column of magnetic graphite thiazolinyl molecularly imprinted polymer, after filling evenly, by the sieve plate shutoff of the top of this solid phase extraction column, clean with the acetic acid of 5mL and the mixed solution upper prop of methyl alcohol, then with the cleaning of 20mL ethanol upper prop; Wherein, the volume ratio of acetic acid and methyl alcohol is 1:20;
(3) by step (2) the gains residual organic solvent of inert gas purge removing, and at 90 DEG C vacuum drying 1h, namely obtain Anthraquinones sensitization dispersion dye magnetic graphite thiazolinyl molecularly imprinted solid phase extraction column.
Embodiment 3:
The preparation method of Anthraquinones sensitizing disperse dyes molecularly imprinted solid phase extraction column in the present embodiment, comprises the following steps:
The preparation of Anthraquinones sensitization dispersion dye magnetic graphite thiazolinyl molecularly imprinted polymer:
A () is by FeSO
4and FeCl
36H
2o is dissolved in 100mL water, obtains Fe
2+, Fe
3+molar concentration be respectively the solution of 0.22mol/L, 0.62mol/L, add 55mg Graphene by after this solution ultrasonic disperse 20min, and continue ultrasonic disperse 2h;
B () adds 0.5moL Anthraquinones sensitizing disperse dyes template molecule disperse blue 7 in step (a) gains, and by ammoniacal liquor adjust ph to 12 at 80 DEG C, then 80 DEG C, with 650r/min stirring reaction 1.5h, obtain the product with black solid powder;
C () product to step (b) carries out Magneto separate, gained black solid powder is not detected by Liquid Chromatography-Tandem Mass Spectrometry instrument to described Anthraquinones sensitizing disperse dyes template molecule disperse blue 7 with ultra-pure water and ethanol washing successively, then by black solid powder vacuum drying 16h at 65 DEG C, Anthraquinones sensitizing disperse dyes magnetic graphite thiazolinyl molecularly imprinted polymer is namely obtained.
The preparation of Anthraquinones sensitizing disperse dyes molecularly imprinted solid phase extraction column:
(1) above-mentioned for 500mg Anthraquinones sensitization dispersion dye magnetic graphite thiazolinyl molecularly imprinted polymer is mixed with 20mL acetonitrile, after vibration 30min, ultrasonic process 5min is to mixing, the capacity that moved to by this mixture is in the solid phase extraction column of 3mL, after filling evenly, sieve plate shutoff is used at the two ends of solid phase extraction column respectively;
(2) 500mg aliphatic quaternary ammonium salt bonded silica gel SAX is mixed with 5mL acetonitrile, after vibration 5min, ultrasonic process 30min is to mixing, the Anthraquinones sensitization dispersion of having loaded this mixture being moved to step (1) contaminates in the solid phase extraction column of magnetic graphite thiazolinyl molecularly imprinted polymer, after filling evenly, by the sieve plate shutoff of the top of this solid phase extraction column, clean with the trifluoroacetic acid of 20mL and the mixed solution upper prop of methyl alcohol, then with the cleaning of 5mL acetonitrile upper prop; Wherein, the volume ratio of trifluoroacetic acid and methyl alcohol is 1:10;
(3) by step (2) the gains residual organic solvent of inert gas purge removing, and at 60 DEG C vacuum drying 12h, namely obtain Anthraquinones sensitization dispersion dye magnetic graphite thiazolinyl molecularly imprinted solid phase extraction column.
Embodiment 4:
The preparation method of Anthraquinones sensitizing disperse dyes molecularly imprinted solid phase extraction column in the present embodiment, comprises the following steps:
The preparation of Anthraquinones sensitization dispersion dye magnetic graphite thiazolinyl molecularly imprinted polymer:
A () is by FeSO
4and FeCl
36H
2o is dissolved in 100mL water, obtains Fe
2+, Fe
3+molar concentration be respectively the solution of 0.2mol/L, 0.6mol/L, add 50mg Graphene by after this solution ultrasonic disperse 15min, and continue ultrasonic disperse 1h;
B () adds 0.8moL Anthraquinones sensitizing disperse dyes template molecule dispersion red 11 in step (a) gains, and by ammoniacal liquor adjust ph to 11.6 at 80 DEG C, then 80 DEG C, with 600r/min stirring reaction 1h, obtain the product with black solid powder;
C () product to step (b) carries out Magneto separate, gained black solid powder is not detected by Liquid Chromatography-Tandem Mass Spectrometry instrument to described Anthraquinones sensitizing disperse dyes template molecule dispersion red 11 with ultra-pure water and ethanol washing successively, then by black solid powder vacuum drying 13h at 60 DEG C, Anthraquinones sensitizing disperse dyes magnetic graphite thiazolinyl molecularly imprinted polymer is namely obtained.
The preparation of Anthraquinones sensitizing disperse dyes molecularly imprinted solid phase extraction column:
(1) above-mentioned for 300mg Anthraquinones sensitization dispersion dye magnetic graphite thiazolinyl molecularly imprinted polymer is mixed with 15mL acetone, after vibration 10min, ultrasonic process 15min is to mixing, this mixture is moved in solid phase extraction column, after filling evenly, sieve plate shutoff is used at the two ends of solid phase extraction column respectively;
(2) 400mg Graphon is mixed with 15mL acetone, after vibration 20min, ultrasonic process 15min is to mixing, the Anthraquinones sensitization dispersion of having loaded this mixture being moved to step (1) contaminates in the solid phase extraction column of magnetic graphite thiazolinyl molecularly imprinted polymer, after filling evenly, by the sieve plate shutoff of the top of this solid phase extraction column, clean with the mixed solution upper prop of the formic acid of 18mL, trifluoroacetic acid and methyl alcohol, then with the cleaning of 10mL acetone upper prop; Wherein, the volume ratio of formic acid, trifluoroacetic acid and methyl alcohol is 0.5:0.5:15;
(3) by step (2) the gains residual organic solvent of inert gas purge removing, and at 60 DEG C vacuum drying 12h, namely obtain Anthraquinones sensitization dispersion dye magnetic graphite thiazolinyl molecularly imprinted solid phase extraction column.
Embodiment 5:
The preparation method of Anthraquinones sensitizing disperse dyes molecularly imprinted solid phase extraction column in the present embodiment, comprises the following steps:
The preparation of Anthraquinones sensitization dispersion dye magnetic graphite thiazolinyl molecularly imprinted polymer:
A () is by FeSO
4and FeCl
36H
2o is dissolved in 100mL water, obtains Fe
2+, Fe
3+molar concentration be respectively the solution of 0.2mol/L, 0.6mol/L, add 50mg Graphene by after this solution ultrasonic disperse 20min, and continue ultrasonic disperse 2h;
B () adds 0.3moL Anthraquinones sensitizing disperse dyes template molecule disperse orange 11 in step (a) gains, and by ammoniacal liquor adjust ph to 12 at 80 DEG C, then 80 DEG C, with 600r/min stirring reaction 1.5h, obtain the product with black solid powder;
C () product to step (b) carries out Magneto separate, gained black solid powder is not detected by Liquid Chromatography-Tandem Mass Spectrometry instrument to described Anthraquinones sensitizing disperse dyes template molecule disperse orange 11 with ultra-pure water and ethanol washing successively, then by black solid powder vacuum drying 16h at 60 DEG C, Anthraquinones sensitizing disperse dyes magnetic graphite thiazolinyl molecularly imprinted polymer is namely obtained.
The preparation of Anthraquinones sensitizing disperse dyes molecularly imprinted solid phase extraction column:
(1) above-mentioned for 100mg Anthraquinones sensitization dispersion dye magnetic graphite thiazolinyl molecularly imprinted polymer is mixed with 20mL acetonitrile, after vibration 30min, ultrasonic process 10min is to mixing, the capacity that moved to by this mixture is in the solid phase extraction column of 3mL, after filling evenly, sieve plate shutoff is used at the two ends of solid phase extraction column respectively;
(2) 500mg aliphatic quaternary ammonium salt bonded silica gel WAX is mixed with 10mL acetonitrile, after vibration 10min, ultrasonic process 30min is to mixing, the Anthraquinones sensitization dispersion of having loaded this mixture being moved to step (1) contaminates in the solid phase extraction column of magnetic graphite thiazolinyl molecularly imprinted polymer, after filling evenly, by the sieve plate shutoff of the top of this solid phase extraction column, clean with the mixed solution upper prop of the formic acid of 20mL, acetic acid and methyl alcohol, then with the cleaning of 15mL acetonitrile upper prop; Wherein, the volume ratio of formic acid, acetic acid and methyl alcohol is 0.6:0.4:10;
(3) by step (2) the gains residual organic solvent of inert gas purge removing, and at 60 DEG C vacuum drying 12h, namely obtain Anthraquinones sensitization dispersion dye magnetic graphite thiazolinyl molecularly imprinted solid phase extraction column.
The Anthraquinones sensitizing disperse dyes magnetic graphite thiazolinyl molecularly imprinted solid phase extraction column post utilizing the various embodiments described above to prepare carries out accumulation and purification process to trace disperse blue 1, disperse blue 3, disperse blue 7, disperse blue 26, disperse blue 35, dispersion red 11 and disperse orange 11 in Drinking Water and food.Accurately take each Anthraquinones sensitizing disperse dyes standard items 10.0mg respectively in 7 10mL volumetric flasks, dissolve with methyl alcohol and be settled to scale, being prepared into the Anthraquinones sensitizing disperse dyes standard reserving solution of 1.0mg/mL, being placed in 4 DEG C of Refrigerator stores for subsequent use.
For Drinking Water, gather 50 ~ 500mL water sample respectively, add the Anthraquinones sensitizing disperse dyes standard reserving solution of appropriate 1.0mg/mL, make its concentration be respectively 0.01 μ g/L.Priority 5mL deionized water and methyl alcohol activate Anthraquinones sensitizing disperse dyes magnetic graphite thiazolinyl molecularly imprinted solid phase extraction column, loading, maintenance flow velocity is 1.0mL/min, with 6mL methanol/water mixed solution (1:10, V/V) drip washing, removing impurity, 10mL ammoniacal liquor and methyl alcohol (1:10V/V) solution is used to carry out wash-out again, eluent blows near dry through nitrogen, dissolve with methyl alcohol and be settled to 1mL, adopt supper-fast liquid chromatography-tandem mass spectrometry instrument (UFLC-MS/MS) to analyze, result as shown in Figure 3.
For food, accurately take food samples 1.0g, add the Anthraquinones sensitizing disperse dyes standard reserving solution of appropriate 1.0mg/mL, add formic acid and methyl alcohol (1:10V/V) mixed solution extracts, make its concentration be respectively 0.01 μ g/L.Priority 5mL deionized water and methyl alcohol activate Anthraquinones sensitizing disperse dyes magnetic graphite thiazolinyl molecularly imprinted solid phase extraction column, loading, maintenance flow velocity is 1.0mL/min, with 6mL methanol/water mixed solution (1:10, V/V) drip washing, removing impurity, 10mL ammoniacal liquor and methyl alcohol (1:10V/V) solution is used to carry out wash-out again, eluent blows near dry through nitrogen, dissolve with methyl alcohol and be settled to 1mL, adopting supper-fast liquid chromatography-tandem mass spectrometry instrument (UFLC-MS/MS) to analyze.
For evaluating the performance of the Anthraquinones sensitizing disperse dyes magnetic graphite thiazolinyl molecularly imprinted solid phase extraction column prepared by various embodiments of the present invention further, select respectively
solid-phase extraction column (3mL, 60mg) and
graphon solid-phase extraction column (3mL, 60mg) enrichment detection is carried out to 7 kinds of Anthraquinones sensitizing disperse dyes in water sample, keep other experiment condition consistent with Anthraquinones sensitizing disperse dyes magnetic graphite thiazolinyl molecularly imprinted solid phase extraction column, result is as shown in table 1, compared to commercial solid-phase extraction column (
solid-phase extraction column (3mL, 60mg) and
graphon solid-phase extraction column (3mL, 60mg)), the Anthraquinones sensitizing disperse dyes magnetic graphite thiazolinyl molecularly imprinted solid phase extraction column prepared by the present invention is adopted to have the high advantage of enrichment times high (being 50 ~ 500 times of prior art), detection limit low (0.01 ~ 0.1 μ g/L), the rate of recovery high (95.2 ~ 106.2%), good stability (precision is 0.8 ~ 3.6%) and recycling rate of waterused.
Table 1
In above detection:
Chromatographic condition: chromatographic column: X-Bridge C18 post (150mm × 2.1mm i.d., 5 μm); Flow velocity: 0.4mL/min; Sample size: 5.0 μ L; Mobile phase: A phase: include 0.08% ammoniacal liquor (v/v), B phase: include 0.08% ammoniacal liquor methyl alcohol (v/v).Gradient elution program: 0 ~ 2.00min, 60.0%A ~ 30.0%A; 2.00 ~ 3.20min, 30%A ~ 10%A; 3.20 ~ 4.00min, 10%A; 4.00 ~ 4.01min, 10.0%A ~ 60.0%A; 4.01 ~ 6.00min, 60.0%A.
Mass Spectrometry Conditions:
Ion gun: electric spray ion source; Scan mode: anion scans; Quantitative detection mode: multiple-reaction monitoring pattern (MRM); Electron spray voltage (IS): 4500V; Atomization gas pressure (GS1): 344.8kPa (50.0psi); Assisted gas flow velocity (GS2): 344.8kPa (50.0psi); Gas curtain atmospheric pressure (CUR): 275.9kPa (40.0psi); Collision gas (CAD): 41.4kPa (6.0psi); Ion source temperature (TEM): 650 DEG C; Sweep time: 20mS; Collision cell exit potential (CXP): 10.0V; Collision cell entrance potential (EP): 10.0V; Q1/Q3 ion pair, collision energy (CE) and go a bunch voltage (DP) specifically in table 2.
Table 2
* quota ion
Experiment shows: Anthraquinones sensitizing disperse dyes magnetic graphite thiazolinyl molecularly imprinted solid phase extraction column prepared by the present invention is evenly distributed, stable in properties; To trace disperse blue 1, disperse blue 3, disperse blue 7, disperse blue 26, disperse blue 35, dispersion red 11 and disperse orange 11 residual in water and food samples, there is good enrichment.
Claims (7)
1. a preparation method for Anthraquinones sensitizing disperse dyes molecularly imprinted solid phase extraction column, is characterized in that comprising the following steps:
(1) 100 ~ 500mg Anthraquinones sensitization dispersion dye magnetic graphite thiazolinyl molecularly imprinted polymer is mixed with the pure organic solvent of 5 ~ 20mL, after vibration 5 ~ 30min, ultrasonic process 5 ~ 30min is to mixing, the capacity that moved to by this mixture is in the solid phase extraction column of 3mL, after filling evenly, sieve plate shutoff is used at the two ends of solid phase extraction column respectively;
(2) 100 ~ 500mg solid phase extraction filler is mixed with the pure organic solvent of 5 ~ 20mL, after vibration 5 ~ 30min, ultrasonic process 5 ~ 30min is to mixing, the Anthraquinones sensitization dispersion of having loaded this mixture being moved to step (1) contaminates in the solid phase extraction column of magnetic graphite thiazolinyl molecularly imprinted polymer, after filling evenly, by the sieve plate shutoff of the top of this solid phase extraction column, clean with the acidic organic solvent upper prop of 5 ~ 20mL, then with the pure organic solvent upper prop cleaning of 5 ~ 20mL;
(3) by step (2) the gains residual organic solvent of inert gas purge removing, and at 30 ~ 90 DEG C vacuum drying 1 ~ 24h, namely obtain Anthraquinones sensitization dispersion dye magnetic graphite thiazolinyl molecularly imprinted solid phase extraction column.
2. preparation method according to claim 1, is characterized in that: the preparation method of the dispersion of Anthraquinones sensitization described in step (1) dye magnetic graphite thiazolinyl molecularly imprinted polymer comprises the following steps:
A () is by FeSO
4and FeCl
36H
2o is dissolved in 100mL water, obtains Fe
2+, Fe
3+molar concentration be respectively the solution of 0.18 ~ 0.22mol/L, 0.58 ~ 0.62mol/L, add 45 ~ 55mg Graphene by after this solution ultrasonic disperse 10 ~ 20min, and continue ultrasonic disperse 1h ~ 2h;
B () adds 0.1 ~ 1.0moL Anthraquinones sensitizing disperse dyes template molecule in step (a) gains, and with ammoniacal liquor adjust ph to 10 ~ 12 at 80 DEG C ~ 82 DEG C, then 80 DEG C ~ 82 DEG C, with 600 ~ 650r/min stirring reaction, 1 ~ 1.5h, obtain the product with black solid powder;
C () product to step (b) carries out Magneto separate, gained black solid powder is not detected by Liquid Chromatography-Tandem Mass Spectrometry instrument to described Anthraquinones sensitizing disperse dyes template molecule with ultra-pure water and ethanol washing successively, then by black solid powder vacuum drying 12 ~ 16h at 60 ~ 65 DEG C, Anthraquinones sensitizing disperse dyes magnetic graphite thiazolinyl molecularly imprinted polymer is namely obtained.
3. preparation method according to claim 1, is characterized in that: the pure organic solvent described in step (1), (2) is the one in methyl alcohol, ethanol, acetonitrile and acetone.
4. preparation method according to claim 1, it is characterized in that: the acidic organic solvent described in step (2) is the mixed solution of at least one in formic acid, acetic acid and trifluoroacetic acid and methyl alcohol, and the volume ratio of one or more mixed solution in formic acid, acetic acid, trifluoroacetic acid and methyl alcohol is 1:5 ~ 20.
5. preparation method according to claim 1, is characterized in that: solid phase extraction filler described in step (2) is at least one in Graphon, styrene-polystyrene copolymer, basic alumina, aliphatic quaternary ammonium salt bonded silica gel SAX, aliphatic quaternary ammonium salt bonded silica gel WAX.
6. preparation method according to claim 1, is characterized in that: the mass ratio of Anthraquinones sensitizing disperse dyes magnetic graphite thiazolinyl molecularly imprinted polymer described in step (1) and the middle solid phase extraction filler of step (2) is 1:1 ~ 5.
7. preparation method according to claim 2, is characterized in that: the Anthraquinones sensitizing disperse dyes template molecule described in step (b) is at least one in disperse blue 1, disperse blue 3, disperse blue 7, disperse blue 26, disperse blue 35, dispersion red 11 and disperse orange 11.
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