CN100540135C - The preparation method of benzene phenodiazine quasi-molecule surface print solid-phase extractant - Google Patents

The preparation method of benzene phenodiazine quasi-molecule surface print solid-phase extractant Download PDF

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CN100540135C
CN100540135C CNB2007100290574A CN200710029057A CN100540135C CN 100540135 C CN100540135 C CN 100540135C CN B2007100290574 A CNB2007100290574 A CN B2007100290574A CN 200710029057 A CN200710029057 A CN 200710029057A CN 100540135 C CN100540135 C CN 100540135C
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汤又文
金国有
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South China Normal University
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Abstract

The preparation method of benzene phenodiazine quasi-molecule surface print solid-phase extractant, earlier with benzene phenodiazine class template molecular melting in methyl alcohol, add function monomer A and function monomer B again, stir preact and obtain prepolymer, add tetramethoxy-silicane or tetraethoxysilane to above-mentioned solution, add silica gel particle after stirring again, add the acid-catalyzed hydrolysis condensation through the methanesulfonic acid solution activation, filtration drying obtains crude product, at last with crude product wash-out purifying.This method preparation process is simple, and prepared surface molecule print solid phase extraction agent has the selection identity to target molecule, can get rid of the interference of impurity in the sample fully, the mechanical strength height, and physicochemical properties are stable, and swelling coefficient is little.

Description

The preparation method of benzene phenodiazine quasi-molecule surface print solid-phase extractant
One, technical field
The present invention relates to a kind of benzene phenodiazine The preparation method of the molecule blotting solid phase extracter of class medicine promptly in conjunction with sol-gel process and surface imprinted technology, prepares a kind of to the benzene phenodiazine
Figure C20071002905700043
The class medicine has the hybrid inorganic-organic SPE material of selecting identity.This extractant is applied to the benzene phenodiazine in the separation and concentration biological sample
Figure C20071002905700044
The class medicine.Belong to separation and concentration and technical field of analysis and detection.
Two, background technology
The benzene phenodiazine
Figure C20071002905700045
The class medicine has calmness, hypnosis, lax maincenter skeletal muscle effect.The clinical manifestation of this medicine acute poisoning is mainly aspect muscle and central nervous system, as myasthenia, flesh hypotonia, coordinate movement imbalance, dysphonia, symptom such as drowsiness appear, show as stupor, mydriasis, respiration inhibition, shock during serious the poisoning, even cause death.Therefore accurately quick diagnosis is to formulate the key of effective emergency measures.
Method for separating and concentrating commonly used both at home and abroad is based on liquid-liquid extraction and SPE.Liquid-liquid extraction need consume relatively large organic solvent, and selectivity is not high enough, causes impurity serious interference in the mensuration process, often can't be accurately qualitative, quantitative.(as C18) carries out pre-treatment as solid extracting agent to body fluid with common sorbing material, also exists selectivity relatively poor, influences follow-up problems such as accurate qualitative and quantitative analysis.
Molecular engram is the high sorbing material technology of selecting of preparation that development in recent years is got up, and it is to be the method for template synthetic polymer with the target molecule.Have and the be complementary hole of space structure and peculiar recognition site of template molecule owing to exist in the molecularly imprinted polymer, can be target molecule or a certain compounds from the complicated substrate optionally absorption close with target molecular structure.Used function monomer and the crosslinking agent majority of molecular imprinting is organic compounds such as methacrylic acid, GDMA at present, and the solid extracting agent of preparation meets the easy swelling of machine solvent.Use synthetic method to be generally mass polymerization and precipitation polymerization method, many binding sites are wrapped in the rigid structure of molecularly imprinted polymer, cause it to select the mass transfer rate of absorption target molecule undesirable, template molecule is difficult to elute from polymer fully, the seepage of template molecule takes place in actual use, has a strong impact on accurately quantitatively detecting of micro-determinand.
At present, about the existing report of the document of sol-gel-molecular imprinted polymer on surface, but not with the benzene phenodiazine
Figure C20071002905700051
The class medicine is template and the report for preparing its surface imprinted polymer correlation technique with sol-gel process.The surface molecule print sol-gel material has been taken into account the two advantage of sol-gel and surface molecule print, has reduced " embedding " phenomenon of template molecule, is beneficial to the wash-out and the identification of template molecule, has improved the utilization rate of template molecule.Advantages such as the surface molecule print sol-gel material has Heat stability is good, selectivity height simultaneously, easy affine site is many, mass transfer rate is fast.
Three, summary of the invention
The object of the present invention is to provide a kind of benzene phenodiazine
Figure C20071002905700052
The preparation method of quasi-molecule surface print solid-phase extractant.The advantage of this method is: preparation process is simple, prepared molecular imprinted polymer on surface mechanical strength height, and physicochemical properties are stable, and swelling coefficient is little.
The present invention includes following concrete steps:
(1) activation of silica gel particle: get silica gel particle and add constant temperature stirring and refluxing in the methanesulfonic acid solution, filter and be washed with water to and be neutral, final drying obtains activated silica gel to constant weight.
(2) preact of function monomer and template molecule: with the benzene phenodiazine
Figure C20071002905700053
The class template molecular melting adds function monomer A and function monomer B again in methyl alcohol, stir preact and obtain prepolymer, and wherein, the mol ratio of three kinds of materials is: function monomer A: function monomer B: template molecule=1: (1~1.5): (0.15~0.5); Function monomer A adopts γ-An Jibingjisanyiyangjiguiwan or gamma-amino propyl trimethoxy silicane; Function monomer B adopts phenyltrimethoxysila,e or phenyl triethoxysilane.
(3) preparation of molecular imprinted polymer on surface: the volume with used function monomer A in the step (2) is as the criterion, the tetramethoxy-silicane or the tetraethoxysilane that in step (2) solution, add 1~2 times of volume, fully stir, add the activated silica gel that makes through step (1) of 0.5~2 times of function monomer A quality again, add the water of 1~2 times of volume and catalyzing hydrolysis condensation between pH 3~5 at last; Leave standstill after fully stirring and make its complete hydrolysis condensation, filter, be dried to constant weight, obtain the molecular imprinted polymer on surface crude product.
(4) wash-out of template molecule: remove template molecule with acetate/methyl alcohol or acetate/acetonitrile solution, with in methyl alcohol, ethanol, propyl alcohol or the acetonitrile more than one acetate residual on molecular imprinted polymer on surface crude product is removed again, drying obtains the pure product of required molecular imprinted polymer on surface---benzene phenodiazine
Figure C20071002905700061
The molecule blotting solid phase extracter of class medicine.
In said method, in the step (1), silica gel particle adopts ball-type or unformed; The mass fraction of methanesulfonic acid solution is generally 10%~90%; The concrete operations of constant temperature stirring and refluxing are: 100~120 ℃ of following stirring and refluxing of constant temperature 8~12 hours; Drying generally is to be dried to constant weight under 60~80 ℃ of vacuum conditions.
In the step (2), the benzene phenodiazine
Figure C20071002905700062
The class template molecule can be the benzene phenodiazine
Figure C20071002905700063
In the class material any one is as estazolam, stable, alprazolam, midazolam or triazolam etc.; Methyl alcohol is that analysis is pure at least; The time of stirring preact was generally 0.5~1 hour.
In the step (3), regulate pH and generally adopt HCl or H 2SO 4Deng; Hydrolytic condensation is generally carried out at normal temperatures; Dry general 90~110 ℃ of vacuum drying of adopting.
In the step (4), drying generally is vacuum drying under 60~80 ℃ of conditions.
The inventive method has following advantage and effect: this method not only can be used for the modification of unformed silica gel but also can be used for the modification of ball-type silica gel, and the particle diameter of the molecular imprinted polymer on surface of preparation is even, be difficult for producing fragment in the adsorption process, at room temperature to the selective absorption of target substance molecule, select the adsorbing separation ability preferably even in the water-methanol mixture of strong polarity, target molecule still had.In actual applications, compare with methods such as common SPE, liquid-liquid extraction, the solid extracting agent of this method preparation has the better choice adsorptivity to target molecule, can get rid of the interference of impurity in the biological sample fully.
Four, description of drawings
Fig. 1 is that embodiment 1 synthetic solid extracting agent amplifies 500 times SEM figure.
Fig. 2 is that embodiment 1 synthetic solid extracting agent amplifies 3000 times SEM figure.
Fig. 3 is the thermogravimetric curve of the synthetic solid extracting agent of embodiment 1.
Fig. 4 is the HPLC spectrogram that sample is handled in embodiment 2 synthetic solid extracting agent, C18 solid extracting agent and methyl alcohol liquid-liquid extraction.
Five, the specific embodiment
Following embodiment further specifies of the present invention, rather than limits the scope of the invention.
Embodiment 1
Getting the 0.19g estazolam is dissolved in the 5mL methyl alcohol, add the 1mL γ-An Jibingjisanyiyangjiguiwan again, 1.1mL phenyltrimethoxysila,e, stir about 0.5 hour, add the 2mL tetraethoxysilane, stirred then 5 minutes, adding 0.5g activated silica gel is (unformed, particle diameter 19~37 μ m), add 1mL water and regulate the condensation of pH to 3 catalyzing hydrolysis at last with hydrochloric acid.After treating that above-mentioned mixed liquor stirs fully, leave standstill and made its complete hydrolysis condensation about 24 hours, filter afterwards, 100 ℃ of vacuum drying are to constant weight.(1: 9, V/V) template molecule is removed in the extracting of solution Soxhlet, with methyl alcohol acetate residual on the molecular imprinted polymer on surface is removed again, and was last, standby after 80 ℃ of vacuum drying with acetate/methyl alcohol.
Fig. 1 and 2 is respectively that embodiment 1 synthetic 500 times of SEM with 3000 times of amplifications of solid extracting agent amplification scheme.As can be seen from the figure, this solid extracting agent is vesicular texture, and this helps shortening the time of solid extracting agent recognition objective molecule.
Fig. 3 is the thermogravimetric curve of the synthetic solid extracting agent of embodiment 1.The total weightlessness of (30~1000 ℃) this molecular imprinted polymer on surface only 16% in test specification, and particularly weightlessness is lower than 3% in 100~400 ℃ of scopes, shows the good heat endurance energy.
The solid extracting agent that makes with said method carries out adsorption experiment, experimentation is: the product that takes by weighing 100mg embodiment 1, install to (SUPELCO in the solid-phase extraction column of a sky, internal diameter 0.4cm), obtain solid-phase extraction column (MIP-SPE post), the activation of 5*1mL methyl alcohol, 1: 9 (V/V) balance of 5*1mL methanol.Estazolam, alprazolam, stable 1: 9 (V/V) solution of methanol that 2mL concentration is 1 μ g/mL load, the 3mL solution washing, and the 2mL methanol-eluted fractions directly detects with HPLC.The result shows, estazolam, alprazolam, the stable molecule of MIP-SPE in can 100% adsorbent solution.The present invention has prepared a kind of to the benzene phenodiazine
Figure C20071002905700081
The class medicine has the surface molecule print solid phase extraction agent of concentration effect.
Embodiment 2
Getting the 0.62g estazolam is dissolved in the 15mL methyl alcohol, add 1mL gamma-amino propyl trimethoxy silicane again, 0.8mL phenyltrimethoxysila,e, stir about 1 hour, add the 4mL tetramethoxy-silicane, stirred then 5 minutes, add 1.8g activated silica gel (ball-type, particle diameter is 5~10 μ m), add 1mL water at last and regulate the condensation of pH to 4 catalyzing hydrolysis with hydrochloric acid.After treating that above-mentioned mixed liquor stirs fully, leave standstill and made its complete hydrolysis condensation about 12 hours, filter afterwards, 90 ℃ of vacuum drying 8 hours.(1: 9, V/V) template molecule is removed in the extracting of solution Soxhlet, with methyl alcohol acetate residual on the molecular imprinted polymer on surface is removed again, and was last, standby after 60 ℃ of vacuum drying with acetate/acetonitrile.
Handle biological sample with the microballoon solid extracting agent that said method makes, experimentation is: get blood plasma that 1ml contains estazolam 2 μ g/ml and cross embodiment 2 synthetic solid extracting agent-SPE post and C18-SPE post respectively, after using the water wash of 3ml then, use the methanol-eluted fractions of 2ml again, wash-out receives liquid and directly measures its concentration with HPLC.In order to compare with SPE, we measure its concentration with HPLC with estazolam molecule in the 2ml methanol extraction 1ml plasma sample behind 0.45 μ m membrane filtration.Chromatogram as shown in Figure 4.
Fig. 4 is after sample is handled in embodiment 2 synthetic solid extracting agent, C18 and methyl alcohol liquid-liquid extraction, the spectrogram comparison diagram of sample introduction HPLC.Be followed successively by embodiment 2 synthetic solid extracting agents from top to bottom and handle the back sample introduction; Sample introduction after the C18 solid extracting agent is handled; Direct injected after the methyl alcohol liquid-liquid extraction.The estazolam rate of recovery of handling through the MIP-SPE post is about 98.7%.Experiment shows, the MIP-SPE post has its substrate and separates preferably and concentration effect, can reach baseline separation when utilizing high performance liquid chromatography to detect, can be quick, qualitative, this type of medicine in the detection of biological sample quantitatively.
Embodiment 3
Get that 0.27g is stable to be dissolved in the 15mL methyl alcohol, add the 1mL γ-An Jibingjisanyiyangjiguiwan again, the 1mL phenyl triethoxysilane, stir about 0.5 hour, add the 4mL tetraethoxysilane, stirred then 5 minutes, add 1.8g activated silica gel (ball-type, particle diameter is 5~10 μ m), add 2mL water at last and regulate the condensation of pH to 5 catalyzing hydrolysis with hydrochloric acid.After treating that above-mentioned mixed liquor stirs fully, leave standstill and made its complete hydrolysis condensation about 24 hours, filter afterwards, 110 ℃ of vacuum drying 8 hours.(1: 9, V/V) template molecule is removed in the extracting of solution Soxhlet, with methanol/ethanol acetate residual on the molecular imprinted polymer on surface is removed again, and was last, standby after 80 ℃ of vacuum drying with acetate/methyl alcohol.
In order to prove that the microballoon solid extracting agent that makes has the selection adsorptivity to template molecule, the spy does following experiment: with the accurate stable methanol-water (1: 9 of the 10mg/mL of preparation of 2mL, V/V) the microballoon solid extracting agent that makes of solution and 20mg said method is put into the ground conical flask of 10mL, vibrated about 6 hours at 25 ℃ of following shaking tables, getting the membrane filtration of supernatant, and detecting solution concentration with HPLC with 0.45 μ m.Experiment shows, the static absorption of this microballoon solid extracting agent distribution coefficient (K D=object is in the concentration of the concentration/object on the polymer in solution) reach 344.4; Its trace factor (I=K Di/ K DnK DiBe the static absorption of trace microballoon distribution coefficient, K DnBe the static absorption of non-trace microballoon distribution coefficient) be 6.1.

Claims (5)

1, a kind of benzene phenodiazine
Figure C2007100290570002C1
The preparation method of quasi-molecule surface print solid-phase extractant is characterized in that comprising the steps:
(1) activation of silica gel particle: get silica gel particle and add constant temperature stirring and refluxing in the methanesulfonic acid solution, filter and be washed with water to and be neutral, final drying obtains activated silica gel to constant weight;
(2) preact of function monomer and template molecule: template molecule estazolam, stable, alprazolam, midazolam or triazolam are dissolved in the methyl alcohol, add function monomer A and function monomer B again, stir preact and obtain prepolymer, wherein, the mol ratio of three kinds of materials is: function monomer A: function monomer B: template molecule=1: 1~1.5: 0.15~0.5; Function monomer A adopts γ-An Jibingjisanyiyangjiguiwan or gamma-amino propyl trimethoxy silicane; Function monomer B adopts phenyltrimethoxysila,e or phenyl triethoxysilane;
(3) preparation of molecular imprinted polymer on surface: the volume with used function monomer A in the step (2) is as the criterion, the tetramethoxy-silicane or the tetraethoxysilane that in step (2) solution, add 1~2 times of volume, fully stir, add the activated silica gel that makes through step (1) of 0.5~2 times of function monomer A quality again, add the water of 1~2 times of volume and catalyzing hydrolysis condensation between pH 3~5 at last; Leave standstill after fully stirring and make its complete hydrolysis condensation, filter, be dried to constant weight, obtain the molecular imprinted polymer on surface crude product;
(4) wash-out of template molecule: remove template molecule with acetate/methyl alcohol or acetate/acetonitrile solution, with in methyl alcohol, ethanol, propyl alcohol or the acetonitrile more than one acetate residual on molecular imprinted polymer on surface crude product is removed again, drying obtains the pure product of required molecular imprinted polymer on surface---benzene phenodiazine The molecule surface print solid-phase extractant of class medicine.
2, preparation method as claimed in claim 1 is characterized in that: in the step (1), silica gel particle adopts ball-type or unformed; The mass fraction of methanesulfonic acid solution is 10%-90%; The concrete operations of constant temperature stirring and refluxing are: 100~120 ℃ of following stirring and refluxing of constant temperature 8~12 hours; Drying is to be dried to constant weight under 60~80 ℃ of vacuum conditions.
3, preparation method as claimed in claim 1 is characterized in that: in step (2), methyl alcohol is that analysis is pure at least; The time of stirring preact is 0.5~1 hour.
4, preparation method as claimed in claim 1 is characterized in that: in the step (3), regulate pH and adopt HCl or H 2SO 4Hydrolytic condensation is carried out at normal temperatures; 90~110 ℃ of vacuum drying of dry employing.
5, as the described preparation method of the arbitrary claim of claim 1~4, it is characterized in that: in the step (4), vacuum drying under 60~80 ℃ of conditions of dry employing.
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CN105085924A (en) * 2014-04-24 2015-11-25 北京普析通用仪器有限责任公司 Metal ion imprinting polymer, preparation method and applications thereof
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