CN104874380A - Graphene oxide doped molecular imprinted polymer stirring rod as well as preparation method and application thereof - Google Patents
Graphene oxide doped molecular imprinted polymer stirring rod as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a graphene oxide doped molecular imprinted polymer stirring rod as well as a preparation method and application thereof. The graphene oxide doped molecular imprinted polymer stirring rod comprises a glass capillary tube, an iron core and an extraction coating; the iron core is arranged in the glass capillary tube with two hotly-sealed ends; and the extraction coating is a graphene oxide doped propranolol molecular imprinted polymer coating which is chemically bonded on the surface of the glass capillary tube. According to the graphene oxide doped molecular imprinted polymer stirring rod, a glass stirring rod which is activated by a sodium hydroxide solution is immersed into a mold containing a graphene oxide doped molecular imprinted prepolymerization solution; and after reaction is finished, the graphene oxide doped molecular imprinted polymer coating stirring rod is taken out. The graphene oxide doped molecular imprinted polymer stirring rod disclosed by the invention can be used for selectively extracting and analyzing medicines, and has the advantages of strong water-phase identification capability, good extraction selectivity, high adsorption capacity, rapid mass transfer rate, good mechanical stability, good heat stability, good chemical stability and the like.
Description
Technical field
The invention belongs to analytical chemistry Sample Pretreatment Technique field, relate to the extraction of a kind of absorbent-type stirring rod, molecularly imprinted polymer stirring rod being specifically related to a kind of graphene oxide doped and preparation method thereof and application.
Background technology
Stir bar sorptive extraction (SBSE) (Baltussen E., Sandra P., David F., Cramers C.Stir bar sorptiveextraction (SBSE), a novel extraction technique for aqueous samples:theory and principles [J] .Journal of Microcolumn Separations, 1999, 11 (10): 737-747) as a kind of novel Sample Pretreatment Technique, there is microminiaturization, easy and simple to handle, with low cost, extraction efficiency high, compared with solid phase micro-extraction technique, avoid the competitive Adsorption using and stir magneton and cause, larger coating volume enhances the extracting and enriching ability to target analytes, there is higher extraction efficiency, thus environment is widely used in, in food and biological sample analysis.But the development of stirring rod coating is comparatively slow, what current application was more is nonpolar for benzene homologues, polycyclic aromatic hydrocarbon etc. or the nonpolar coating dimethyl silicone polymer (PDMS) of low pole compound, and thus preparation is applicable to opposed polarity and the extraction coating with certain mechanical strength and chemical stability is one of development trend of current Stir bar sorptive extraction.
Molecular imprinting is a kind of molecular recognition technology of Novel high-sensitivity, the molecularly imprinted polymer that this technology prepares has the advantages such as specific recognition ability is strong, physicochemical properties stable, preparation method is simply various, it is combined with Stir bar sorptive extraction, the selectivity extracting and enriching of thing can be analyzed by realize target, the interference of effective reduction complicated substrate, thus the sensitivity of raising method.Molecular imprinting is incorporated in Stir Bar Sorptive Extraction coating by existing research worker, and the molecular imprinting stirring rod coating prepared has the feature of precordainment, identity and practicality to test analyte.Zhu etc. have prepared the two kinds of extraction of the molecular imprinting stirring rod based on nylon membrane coatings, be respectively used to the Monocrotophos Pesticides in testing environment and biological sample and chiral separation amino acid (Zhu, X.L., et al., Films coated with molecular imprinted polymers for the selective stirbar sorption extraction of monocrotophos.Journal of Chromatography A, 2006.1131 (1-2): p.37-44; Zhu, X.L.and Q.S.Zhu, Molecular imprinted Nylon-6 stir bar as a novel extractiontechnique for enantioseparation of amino acids.Journal of Applied Polymer Science, 2008.109 (4): p.2665-2670.).A series of molecular engram coating stirring rod has been prepared for complex sample analysis (Hu with Ractopamine, Garagard, sulfamerazine for template molecule respectively by chemical bonding by seminar of Li Gong section, Y.L., et al., Development ofselective and chemically stable coating for stir bar sorptive extraction by molecularly imprintedtechnique.Talanta, 2010.82 (2): p.464-470; Xu, Z.G., et al., Preparation of trimethoprimmolecularly imprinted stir bar sorptive extraction and its application for trace analysis oftrimethoprim and sulfonamides in complex samples.Chinese Journal of Analytical Chemistry, 2012.40 (7): p.1002-1009; Hu, Y.L., et al., Novel applications of molecularly-imprinted polymers insample preparation.Trac-Trends in Analytical Chemistry, 2013.43:p.37-52.).Gomez-Caballero etc. adopt the mode of burst of ultraviolel to synthesize a kind of molecular engram material has enantiomer-specific structure medicine (Gomez-Caballero for chiral separation, A., et al., Chiral imprinted polymers as enantiospecific coatings of stir barsorptive extraction devices.Biosensors & Bioelectronics, 2011.28 (1): p.25-32).
Along with the fast development of molecular imprinting in Sample Pretreatment Technique, some potential problems start to highlight, as poor in recognition capability in aqueous phase, adsorption capacity is little, and these problems limit molecularly imprinted polymer as the application of selective extraction coating in Stir Bar Sorptive Extraction field.For the problem of molecularly imprinted polymer Recognition in Aqueous Media ability, in document, adopt " solvent effect " to improve molecular engram coating recognition capability to target analytes in aqueous medium more, specific practice adopts the mixed solution of pure water or water and other solvents as pore-foaming agent, under aqueous environment, function monomer and template molecule realize pre-assembled, obtained molecular engram coating has the ability (Yan of certain tolerance water polar solvent, H.Y.and K.H.Row, Novel molecularlyimprinted monolithic column for selective on-line extraction of ciprofloxacin from human urine.Biomedical Chromatography, 2008.22 (5): p.487-493, He, L.M., et al., Novel cyromazineimprinted polymer applied to the solid-phase extraction of melamine from feed and milk samples.Journal of Chromatography A, 2009.1216 (34): p.6196-6203, Zheng, M.M., et al., Selective samplepretreatment by molecularly imprinted polymer monolith for the analysis of fluoroquinolones frommilk samples.Journal of Chromatography A, 2010.1217 (14): p.2075-2081, Mergola, L., et al., Developments in the synthesis of a water compatible molecularly imprinted polymer as artificialreceptor for detection of 3-nitro-L-tyrosine in neurological diseases.Biosensors & Bioelectronics, 2013.40 (1): p.336-341.).In addition, also there is the little problem of adsorption capacity in molecularly imprinted polymer, consider the Two-dimensional Carbon atomic layer structure of graphene oxide uniqueness and abundant oxy radical, there is large specific area, electron rich structure, the advantages such as good heat endurance and chemical stability, the molecular engram material preparing graphene oxide doped in molecular engram reaction pre-polymerization liquid can be entrained in, thus improve adsorption capacity and the mass transfer rate (Li of imprinted material, Y., X.Li, et al., A grapheneoxide-based molecularly imprinted polymer platform for detecting endocrine disrupting chemicals.Carbon 2010.48 (12): 3427-3433, Qiu, H., C.Luo, et al., A chemiluminescence sensor fordetermination of epinephrine using graphene oxide-magnetite-molecularly imprinted polymers.Carbon 2012.50 (11): 4052-4060, Peeters, M., S.Kobben, et al., Thermal detection of histaminewith a graphene oxide based molecularly imprinted polymer platform prepared by reversibleaddition-fragmentation chain transfer polymerization.Sensors and Actuators B-Chemical 2014.203:527-535.).
Summary of the invention
Primary and foremost purpose of the present invention is the Propranolol molecularly imprinted polymer coating stirring rod providing a kind of graphene oxide doped, this stirring rod is applicable to the selective extraction analysis of Propranolol medicine, has that Recognition in Aqueous Media ability is strong, extraction selectivity good, adsorption capacity is high, mass transfer rate is fast, good mechanical stability, heat endurance and good chemical stability.
Another object of the present invention is to the preparation method of the molecularly imprinted polymer coating stirring rod that above-mentioned graphene oxide doped is provided, reaction pre-polymerization liquid is that the mixed solution of template molecule, methyl alcohol and graphene oxide dispersion is pore-foaming agent, methacrylic acid is function monomer, ethylene glycol dimethacrylate is crosslinking agent, azodiisobutyronitrile is initator with Propranolol, there is home position polymerization reaction in reaction pre-polymerization liquid, obtained molecularly imprinted polymer is chemically bound in capillary glass tube rod surface under hot initiation conditions.Molecularly imprinted polymer is successfully incorporated in Stir bar sorptive extraction by the present invention, and solves molecularly imprinted polymer coating Recognition in Aqueous Media ability and the little problem of adsorption capacity.
Another object of the present invention is to the application of the molecularly imprinted polymer coating stirring rod that above-mentioned graphene oxide doped is provided.
Object of the present invention is achieved through the following technical solutions:
A kind of molecularly imprinted polymer coating stirring rod of graphene oxide doped, comprise capillary glass tube, iron core and extraction coating, iron core is placed in the capillary glass tube of two ends sealing by fusing, and extraction coating is coated in capillary glass tube outer surface; Described extraction coating is the molecularly imprinted polymer coating of the graphene oxide doped being chemically bound in capillary glass tube surface; The template molecule of the molecularly imprinted polymer of described graphene oxide doped is preferably Propranolol molecule.
Described capillary glass tube is preferably dimensioned to be long 2cm, internal diameter 0.9-1.1mm, wall thickness 0.10-0.15mm, and capillary glass tube two ends sealing by fusing forms dumbbell shape structure; Described iron core is preferably dimensioned to be 1.7cm, diameter 0.50mm.
The preparation method of the molecularly imprinted polymer coating stirring rod of above-mentioned graphene oxide doped, comprises the steps:
(1) capillary glass tube of two ends sealing by fusing is placed in sodium hydroxide solution to activate, cleaning, dry for standby;
(2) be the methyl alcohol/graphene oxide water solution of 7:3 by methacrylic acid, volume ratio, Propranolol, ethylene glycol dimethacrylate, azodiisobutyronitrile mix, ultrasonic, obtains the trace coating reaction pre-polymerization liquid of graphene oxide doped;
(3) the capillary glass tube rod pretreated through step (1) is vertically placed in mould, then the reaction pre-polymerization liquid of the molecularly imprinted polymer coating of graphene oxide doped is injected mould, cover lid, mould is placed in closed container, after sealing, logical nitrogen deoxygenation; Closed container is placed in water-bath thermal-initiated polymerization reaction, has reacted rear taking-up capillary glass tube rod, cated one section will be intercepted, inserted iron core, then on alcolhol burner flame, seal into dumbbell shaped;
(4) again capillary glass tube rod is placed in eluent more than ultrasonic cleaning 20min, after repeating wash-out 4 ~ 8 times, is placed in ultrasonic more than the 20min of methyl alcohol again, namely obtain the molecularly imprinted polymer coating stirring rod of graphene oxide doped;
Described mould is cylindrical, by bottom, main body and upper cover three part form, wherein bottom does not punch, upper cover central punch, and inner major diameter size is adjustable.
Described mould is made up of polytetrafluoroethylene (PTFE), and die length is 2cm, and main part internal diameter is 2.5mm.
In described step (1), the concentration of sodium hydroxide solution is 1mol/L, and the time of activation is more than 3h, and described cleaning way is successively by ultra-pure water, 0.1mol/L hydrochloric acid, ultra-pure water cleaning extremely neutrality.
The preparation process of the trace coating reaction pre-polymerization liquid of described graphene oxide doped is specially: get methacrylic acid successively, methyl alcohol/5mg/mL graphene oxide water solution that volume ratio is 7:3, evenly ultrasonic after vortex mixed, add Propranolol again, evenly ultrasonic after vortex mixed, add ethylene glycol dimethacrylate and azodiisobutyronitrile, evenly ultrasonic after vortex mixed, obtain the trace coating reaction pre-polymerization liquid of graphene oxide doped; The mol ratio of described Propranolol, methacrylic acid and ethylene glycol dimethacrylate is 1:10:24.
Described capillary glass tube is of a size of long 2cm, internal diameter 0.9-1.1mm, wall thickness 0.10-0.15mm, and capillary glass tube two ends sealing by fusing forms dumbbell shape structure; Described iron core is of a size of 1.7cm, diameter 0.50mm.
In described step (3), the time of logical nitrogen deoxygenation is 10min; Bath temperature is 60 DEG C, reaction 24h; The core length of described insertion is 1.7cm.
Described eluent is the methanol solution (v/v) containing 8% acetic acid.
A kind of molecularly imprinted polymer coating stirring rod of graphene oxide doped, is prepared by above-mentioned preparation method.
The application of molecularly imprinted polymer coating stirring rod in the selective extraction of medicine is analyzed of above-mentioned graphene oxide doped.
A kind of method of SPE Propranolol, comprise the following steps: the Propranolol solution molecularly imprinted polymer stirring rod of above-mentioned graphene oxide doped being placed in pH=9.0, extraction 40min is stirred under 800rpm rotating speed, extraction terminates rear taking-up stirring rod, the solution drying stirring rod surface with filter paper remains, transfer them to ultrasonic desorb 20min in methyl alcohol/10mmol/L hydrochloric acid solution that volume ratio is 3:2, gained stripping liquid is analyzed for follow-up HPLC-UV detection after 0.22 μm of membrane filtration; The molecularly imprinted polymer stirring rod of the graphene oxide doped after desorb is placed in methanol solution and the ultrasonic 5min of methyl alcohol of 8% acetic acid successively, reuses.
Tool of the present invention has the following advantages and effect:
Graphene oxide is introduced in molecularly imprinted polymer coating by the present invention, prepare a kind of can efficiently high selectivity extraction Propranolol and the molecularly imprinted polymer coating of the good graphene oxide doped of Recognition in Aqueous Media ability.The homogeneous porous of molecularly imprinted polymer coating morphology of the graphene oxide doped utilizing home position polymerization reaction to prepare, the aqueous solution of methyl alcohol is selected to be the Recognition in Aqueous Media ability that pore-foaming agent substantially increases extraction coating, avoid the sample extraction process of aqueous phase actual sample Analysis of Complex, the doping of graphene oxide had both improve the adsorption capacity of extraction coating, also enhanced the mechanical performance of extraction coating.Because this molecularly imprinted polymer coating has selectivity, specific extraction to template molecule and analog thereof, the selective extraction enrichment to certain drug in complex sample system can be realized, have actual application value.
The molecularly imprinted polymer stirring rod of graphene oxide doped of the present invention is applicable to the selective extraction analysis of medicine, has that Recognition in Aqueous Media ability is strong, extraction selectivity good, adsorption capacity is high, mass transfer rate is fast, good mechanical stability, heat endurance and good chemical stability.
Accompanying drawing explanation
Fig. 1 is the structural representation of the molecularly imprinted polymer coating stirring rod of graphene oxide doped prepared by embodiment 1; Wherein, 1-iron core; 2-capillary glass tube; 3-extraction coating.
Fig. 2 is the infrared spectrogram of the molecularly imprinted polymer coating stirring rod of graphene oxide doped prepared by embodiment 1.
Fig. 3 is the apparent form figure of the molecularly imprinted polymer stirring rod of graphene oxide doped prepared by embodiment 1; Wherein, the apparent form figure of molecularly imprinted polymer coating stirring rod that adulterates for non-oxidation Graphene of Fig. 3 (a); The apparent form figure of the molecularly imprinted polymer coating stirring rod that Fig. 3 (b) is graphene oxide doped.
Fig. 4 is the ESEM phenogram of polymer coating stirring rod, wherein, 500 × ESEM phenogram of the non-molecularly imprinted polymer coating stirring rod that Fig. 4 (a) is graphene oxide doped, 1000 × ESEM phenogram of the non-molecularly imprinted polymer coating stirring rod that Fig. 4 (b) is graphene oxide doped, 500 × ESEM phenogram of the molecularly imprinted polymer coating stirring rod that Fig. 4 (c) is the graphene oxide doped before template removal, 500 × ESEM phenogram of the molecularly imprinted polymer coating stirring rod that Fig. 4 (d) is the graphene oxide doped after template removal, 1000 × ESEM phenogram of the molecularly imprinted polymer coating stirring rod that Fig. 4 (e) is the graphene oxide doped after template removal.
Fig. 5 is the molecularly imprinted polymer coating stirring rod of graphene oxide doped prepared by embodiment 1 and does not have the thermogravimetric of the molecularly imprinted polymer coating stirring rod of graphene oxide doped to characterize comparison diagram.
Fig. 6 is the chemical stability investigation figure of the molecularly imprinted polymer coating of graphene oxide doped prepared by embodiment 1.
Fig. 7 is the Recognition in Aqueous Media ability comparison diagram of the molecularly imprinted polymer coating stirring rod of the graphene oxide doped that in embodiment 1 prepared by different pore-foaming agent.
Fig. 8 is the extraction efficiency comparison diagram of the molecularly imprinted polymer coating stirring rod of the graphene oxide doped of different graphene oxide content in embodiment 1.
Fig. 9 is investigation in the service life figure of the molecularly imprinted polymer stirring rod of graphene oxide doped prepared by embodiment 1.
Figure 10 is the extraction efficiency comparison diagram of four kinds of coating stirring rods to Propranolol medicine prepared by embodiment 1; Wherein, A represents the molecularly imprinted polymer coating stirring that molecularly imprinted polymer coating stirring is excellent, D the represents graphene oxide doped rod that the non-molecularly imprinted polymer coating stirring that non-molecularly imprinted polymer coating stirring is excellent, B represents graphene oxide doped is excellent, C represents the doping of non-oxidation Graphene of non-oxidation Graphene doping.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, further detailed description is done to the present invention, but embodiments of the present invention are not limited thereto.
A molecularly imprinted polymer stirring rod for graphene oxide doped, as shown in Figure 1, comprise capillary glass tube 2, iron core 1 and extraction coating 3, iron core 1 is placed in the capillary glass tube 2 of two ends sealing by fusing, and extraction coating 3 is coated in capillary glass tube outer surface.Extraction coating is the molecularly imprinted polymer coating of the graphene oxide doped being chemically bound in capillary glass tube surface, and described molecularly imprinted polymer template is Propranolol molecule.
Embodiment 1
(1) design of Teflon mould
The Teflon mould preparing the molecularly imprinted polymer coating stirring rod of graphene oxide doped by bottom, main body and upper cover three part form, wherein bottom does not punch, upper cover central punch, is in the center of mould for fixing glass capillary rod.The internal diameter size of die main body part is adjustable, thus obtains the GO/MIP coating stirring rod of different coating thickness.The die length that this example is selected is 2cm, and main part internal diameter is 2.5mm, capillary glass tube rod outside diameter 1.1mm, and extrapolating stirring rod coating layer thickness is 700 μm.
(2) activation of capillary glass tube rod
By capillary glass tube by about 6cm, with alcolhol burner flame by one end closure, other end sealing by fusing globulate, obtain the capillary glass tube rod of one end dumbbell.The capillary glass tube rod fired uses pure water and methyl alcohol ultrasonic cleaning successively, is then soaked in 1mol/L sodium hydroxide solution and activates 8h, makes its rich surface hydroxyl group.Take out afterwards successively by pure water, 1mol/L hydrochloric acid solution, pure water cleaning extremely neutrality, be placed in baking oven 60 DEG C of dry for standby.Be placed in KH-570/ acetone (1/3, v/v) solution by the capillary glass tube rod activated and soak 1.5h, take out afterwards and use washed with methanol several times, nitrogen dries up for subsequent use.
(3) preparation of the reaction pre-polymerization liquid of the molecularly imprinted polymer coating of graphene oxide doped
Be 1:10:24 according to a mole most ratio of greater inequality for template Propranolol, function monomer methacrylic acid and crosslinking agent ethylene glycol dimethacrylate, get 79.3 μ L methacrylic acids, 1mL methyl alcohol/5mg/mL graphene oxide water solution (70/30 successively, v/v), after vortex mixed, ultrasonic 30min makes it be uniformly dispersed, add 27.27mg Propranolol afterwards, ultrasonic 30min after vortex mixed, makes template molecule Propranolol and function monomer methacrylic acid carry out pre-assembled.Add 456 μ L ethylene glycol dimethacrylates and 14.55mg azodiisobutyronitrile afterwards, ultrasonic 30min after vortex mixed, obtain the reaction pre-polymerization liquid of the molecularly imprinted polymer coating of graphene oxide doped.
(4) preparation of the molecularly imprinted polymer coating stirring rod of graphene oxide doped
Capillary glass tube rod is vertically placed in Teflon mould, then the reaction pre-polymerization liquid of the molecularly imprinted polymer coating of the graphene oxide doped of ultrasonic mixing is injected the Teflon mould being placed with capillary glass tube rod, cover upper cover.Whole device is placed in teat glass, by rubber stopper seal, and logical nitrogen 10min deoxygenation.Afterwards teat glass is placed in water-bath and completes home position polymerization reaction under 60 DEG C of hot initiation conditions, after reaction 24h, capillary glass tube rod is taken out.Intercept cated one section of capillary glass tube rod, long 2cm, insert the iron core that 1.7cm is long, then use alcolhol burner flame sealing by fusing globulate, obtain dumbbell shape glass stirring rod, surface is coated with the molecularly imprinted polymer coating of graphene oxide doped.
(5) wash-out of template molecule Propranolol
Configure the methanol solution of 8% acetic acid (as eluent, the molecularly imprinted polymer coating stirring rod of graphene oxide doped is placed in 2mL eluent ultrasonic cleaning 30min, is placed in the ultrasonic 30min of methyl alcohol after repeating wash-out 6 times again and remains in order to the acetic acid on the molecularly imprinted polymer coating stirring rod surface of removing graphene oxide doped.Finally obtain the molecularly imprinted polymer coating stirring rod of the graphene oxide doped that cavity mates with Propranolol molecular structure.
Carried out a series of material to the molecularly imprinted polymer stirring rod of the graphene oxide doped prepared to characterize, as IR Characterization, ESEM sign, thermogravimetric analysis investigation etc., result is as follows:
Fig. 2 is the infrared spectrogram of the molecularly imprinted polymer coating of graphene oxide doped, 3443cm
-1locate to absorb for the stretching vibration of hydroxyl O-H, 1735cm
-1locate to absorb for the stretching vibration of C=O bond C=O, 1643cm
-1locate to absorb for the stretching vibration of carbon-carbon double bond C=C, 1450cm
-1locate to absorb for the flexural vibrations of hydroxyl O-H, 1387cm
-1locate to absorb for the flexural vibrations of C-H bond C-H, 1258cm
-1locate to absorb for the stretching vibration of carbon-oxygen bond C-O, 1151cm
-1locate to absorb for the stretching vibration of carbon oxygen carbon bond C-O-C, these characteristic peaks are consistent with the chemical constitution of the molecularly imprinted polymer of graphene oxide doped.Although can not determine the existence of graphene oxide from infrared peak, but the apparent form figure (Fig. 3) of the molecularly imprinted polymer coating stirring rod of contrast non-oxidation Graphene doping and the molecularly imprinted polymer coating stirring rod of graphene oxide doped can see, the molecularly imprinted polymer of non-oxidation Graphene doping is white solid, the molecularly imprinted polymer of graphene oxide doped is light gray solid, and visible graphene oxide Uniform Doped is in molecularly imprinted polymer coating.
Fig. 4 is the ESEM phenogram of polymer coating stirring rod; As can be seen from Figure 4, non-molecularly imprinted polymer coating stirring rod (a) (b) the surface uniform porous of graphene oxide doped, structure is relatively fine and close; Molecularly imprinted polymer coating stirring rod (c) the surface compact less porous of the graphene oxide doped before template removal; Molecularly imprinted polymer coating stirring rod (d) (e) surface uniform of the graphene oxide doped after template removal, presents good pore structure, has larger specific area, be beneficial to mass transfer compared with before template removal.
Fig. 5 is the molecularly imprinted polymer coating stirring rod of graphene oxide doped and does not have the thermogravimetric of the molecularly imprinted polymer coating stirring rod of graphene oxide doped to characterize comparison diagram.As can be seen from Figure 5, the molecularly imprinted polymer stirring rod coating of graphene oxide doped starts to occur obvious weightlessness at 280 DEG C, and whole Weight lose mainly occurs in 280 DEG C within the scope of 450 DEG C.Do not have the molecular imprinting stirring rod coating of graphene oxide doped then namely to start to occur obvious weightlessness at 250 DEG C, Weight lose mainly occurs in 250 DEG C within the scope of 450 DEG C.Visible, there is the doping of graphene oxide can the heat endurance of raising trace coating to a certain degree.
Embodiment 2
The stirring rod extraction desorption process of the molecularly imprinted polymer stirring rod of graphene oxide doped is as follows: the molecularly imprinted polymer stirring rod of graphene oxide doped is placed in 10mL sample solution (regulating sample solution pH 9.0 with sodium hydroxide solution), extraction 40min is stirred under 800rpm rotating speed, extraction terminates rear taking-up stirring rod, the solution drying stirring rod surface with filter paper remains, transfer them to ultrasonic desorb 20min in the desorption tube that 100 μ L methyl alcohol/10mmol/L hydrochloric acid (60/40, v/v) is housed.Stripping liquid is analyzed for the detection of follow-up high performance liquid chromatography-ultraviolet (HPLC-UV) after 0.22 μm of membrane filtration; Stirring rod after desorb is placed in methanol solution and the ultrasonic 5min of methyl alcohol of 8% acetic acid successively, reusable after regeneration.
Fig. 6 is the chemical stability investigation figure of the molecular engram coating stirring rod of graphene oxide doped.The molecular engram coating stirring of graphene oxide doped rod is soaked in respectively the methanol solution of 8% acetic acid, the methanol solution of 8% ammoniacal liquor, methyl alcohol, acetone, carrene and toluene, rinse well with water after soaking 24h, then test for Stir Bar Sorptive Extraction, the molecular engram coating stirring rod of its extraction efficiency and graphene oxide doped compares without blank group of solvent soaking, can see that the molecular engram coating stirring rod through the graphene oxide doped of different disposal is more or less the same to the extraction efficiency of Propranolol, illustrate that the molecular engram coating stirring rod of homemade graphene oxide doped has certain chemical stability.
Although molecular engram coating has the advantages such as structure precordainment, specific recognition, general applicability, also there is the problem that in aqueous phase, recognition capability is weak, this is mainly because water polar solvent can destroy the hydrogen bond action between function monomer and template molecule.The present invention selects the mixed solution of water and methyl alcohol as pore-foaming agent, relies on " solvent effect " to improve the Recognition in Aqueous Media ability of molecularly imprinted polymer coating, and optimizes the optimal proportion of water and methyl alcohol.The pore-foaming agent selecting participation molecularly imprinted polymer coating to prepare is respectively methanol/water volume ratio 10/0 (MIP1), 9/1 (MIP2), 8/2 (MIP3), 7/3 (MIP4), the reaction pre-polymerization liquid that the ratio continuing to reduce methyl alcohol obtains has lamination, the stable homogeneous of the obtained coating of impact.By the extraction for target analytes Propranolol of this four kinds of molecularly imprinted polymer coating stirrings rod and non-molecular engram coating stirring rod (NIP), sample solution is prepared with pure methyl alcohol, methanol/water (1/1, v/v) and pure water respectively.Experimental result is shown in Fig. 7, when pore-foaming agent is pure methyl alcohol (MIP1), the extraction efficiency of MIP1 coating stirring rod in pure methyl alcohol, methanol/water (1/1, v/v), pure water reduces gradually, its extraction efficiency in water compare with NIP coating stirring rod increase little; When in pore-foaming agent, the ratio of water improves gradually, the extraction efficiency of MIP coating stirring rod in water increases gradually, embodies good Recognition in Aqueous Media ability, and its extraction efficiency in water is significantly better than the extraction efficiency in methyl alcohol.Final selection pore-foaming agent is methanol/water (7/3, v/v).
The problem little for molecularly imprinted polymer coating adsorbs capacity, mechanical performance is general, the present invention is doped with graphene oxide in reaction pre-polymerization liquid, the molecularly imprinted polymer coating stirring rod concentration of the graphene oxide doped selected is respectively 0 (MIP5), 1mg/mL (MIP6), 3mg/mL (MIP7) and 5mg/mL (MIP8), reacts the uneven preparation reappearance affecting the molecularly imprinted polymer coating stirring rod of graphene oxide doped of pre-polymerization liquid dispersion after continuing to increase graphene oxide concentration.The molecularly imprinted polymer coating stirring of four kinds of graphene oxide dopeds of preparation rod is used for the Propranolol analysis in different solvents sample solution, experimental result is shown in Fig. 8.Visible, along with the Propranolol extraction efficiency of molecularly imprinted polymer coating stirring rod in same sample solution of the increase graphene oxide doped of graphene oxide content is also increasing gradually, the extraction selectivity of molecularly imprinted polymer coating stirring rod in pure methyl alcohol, methanol/water (1/1, v/v) and pure water sample solution of the graphene oxide doped of different graphene oxide content is consistent simultaneously.It can thus be appreciated that, the extraction efficiency increasing the molecularly imprinted polymer coating stirring rod that can improve graphene oxide doped of graphene oxide content and do not affect its extraction selectivity.Final selective oxidation Graphene concentration is 5mg/mL.
The investigation in service life is carried out to the molecularly imprinted polymer stirring rod of graphene oxide doped prepared by the present invention, has compared and repeatedly use the molecularly imprinted polymer stirring rod of rear oxidation Graphene doping to the extraction efficiency of Propranolol.Experimental result is shown in Fig. 9, known, after the molecularly imprinted polymer stirring rod extraction desorb 70 times of graphene oxide doped to the extraction efficiency of Propranolol without significant change, and to reuse in process stirring rod coating without wearing and tearing obscission, the molecularly imprinted polymer coating of visible graphene oxide doped has good mechanical performance and stable effect of extracting, can use at least 70 times.
Compare four kinds of coating stirring rods (the non-molecularly imprinted polymer coating stirring rod of non-oxidation Graphene doping, the non-molecularly imprinted polymer coating stirring rod of graphene oxide doped, the molecularly imprinted polymer coating stirring rod of non-oxidation Graphene doping, the molecularly imprinted polymer coating stirring rod of graphene oxide doped) to the extraction efficiency of seven kinds of cardiovascular drugses and extraction selectivity, the results are shown in Figure 10.As we know from the figure, trace coating stirring rod (the molecularly imprinted polymer coating stirring rod of non-oxidation Graphene doping, the molecularly imprinted polymer coating stirring rod of graphene oxide doped) to the extraction efficiency of seven kinds of cardiovascular drugses significantly better than non-trace coating stirring rod (the non-molecularly imprinted polymer coating stirring rod of non-oxidation Graphene doping, the non-molecularly imprinted polymer coating stirring rod of graphene oxide doped), wherein trace coating is significantly improved compared with other six kinds of cardiovascular drugses to the extraction efficiency of Propranolol, embody the selective extraction of trace coating to Propranolol.In addition, also can correspondingly improve the extraction efficiency of imprinted material and non-imprinted material and not affect extraction selectivity after being doped with graphene oxide.Integrated comparative, the molecularly imprinted polymer coating of the graphene oxide doped of this job design synthesis has good extraction efficiency and extraction selectivity to target analytes Propranolol in aqueous phase.
Imprinted material has good specific recognition to template molecule and template molecule analogue, thus investigated the molecularly imprinted polymer coating stirring rod of the homemade non-oxidation Graphene doping of this work and the cross reactivity of molecularly imprinted polymer coating stirring rod to seven kinds of cardiovascular drugses of graphene oxide doped, experimental result is in table 1.The standby trace coating of this duty take Propranolol as template, the molecularly imprinted polymer coating stirring rod adulterated by non-oxidation Graphene and the molecularly imprinted polymer coating stirring rod of graphene oxide doped are used for containing the extraction (sample solution be aqueous medium) of Propranolol at interior seven kinds of cardiovascular drugses, as can be seen from selectivity factor result, the molecularly imprinted polymer coating stirring rod of non-oxidation Graphene doping and the molecularly imprinted polymer coating stirring rod of graphene oxide doped are much better than other six kinds of cardiovascular drugses to the extraction selectivity of Propranolol, this is because the molecular structure of other six kinds of cardiovascular drugses and Propranolol have larger difference, do not mate with the cavity structure of the trace coating taking Propranolol as template, thus selective lower.In addition compared for the extraction selectivity difference of the molecularly imprinted polymer coating stirring rod of non-oxidation Graphene doping and the molecularly imprinted polymer coating stirring rod of graphene oxide doped, can see that the reduction of the doping of graphene oxide to trace coating is selective and not have a significant effect.
Table 1 is the cross reactivity investigation figure of the molecularly imprinted polymer stirring rod of graphene oxide doped prepared by embodiment 1.
Table 1
Wherein, A, B represent the molecularly imprinted polymer coating stirring rod of non-oxidation Graphene doping, the molecularly imprinted polymer coating stirring rod of graphene oxide doped respectively.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from Spirit Essence of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. a preparation method for the molecularly imprinted polymer coating stirring rod of graphene oxide doped, is characterized in that, comprise the steps:
(1) capillary glass tube of two ends sealing by fusing is placed in sodium hydroxide solution to activate, cleaning, dry for standby;
(2) be the methyl alcohol/graphene oxide water solution of 7:3 by methacrylic acid, volume ratio, Propranolol, ethylene glycol dimethacrylate, azodiisobutyronitrile mix, ultrasonic, obtains the trace coating reaction pre-polymerization liquid of graphene oxide doped;
(3) the capillary glass tube rod pretreated through step (1) is vertically placed in mould, then the reaction pre-polymerization liquid of the molecularly imprinted polymer coating of graphene oxide doped is injected mould, cover lid, mould is placed in closed container, after sealing, logical nitrogen deoxygenation; Closed container is placed in water-bath thermal-initiated polymerization reaction, has reacted rear taking-up capillary glass tube rod, cated one section will be intercepted, inserted iron core, then on alcolhol burner flame, seal into dumbbell shaped;
(4) again capillary glass tube rod is placed in eluent more than ultrasonic cleaning 20min, after repeating wash-out 4 ~ 8 times, is placed in ultrasonic more than the 20min of methyl alcohol again, namely obtain the molecularly imprinted polymer coating stirring rod of graphene oxide doped;
Described mould is cylindrical, by bottom, main body and upper cover three part form, wherein bottom does not punch, upper cover central punch, and inner major diameter size is adjustable.
2. the preparation method of the molecularly imprinted polymer coating stirring rod of graphene oxide doped according to claim 1, is characterized in that: described mould is made up of polytetrafluoroethylene (PTFE), and die length is 2cm, and main part internal diameter is 2.5mm.
3. the preparation method of the molecularly imprinted polymer coating stirring rod of graphene oxide doped according to claim 1, it is characterized in that: in described step (1), the concentration of sodium hydroxide solution is 1mol/L, the time of activation is more than 3h, and described cleaning way is successively by ultra-pure water, 0.1mol/L hydrochloric acid, ultra-pure water cleaning extremely neutrality.
4. the preparation method of the molecularly imprinted polymer coating stirring rod of graphene oxide doped according to claim 1, it is characterized in that: the preparation process of the trace coating reaction pre-polymerization liquid of described graphene oxide doped is specially: get methacrylic acid successively, volume ratio is the methyl alcohol/5mg/mL graphene oxide water solution of 7:3, evenly ultrasonic after vortex mixed, add Propranolol again, evenly ultrasonic after vortex mixed, add ethylene glycol dimethacrylate and azodiisobutyronitrile, evenly ultrasonic after vortex mixed, obtain the trace coating reaction pre-polymerization liquid of graphene oxide doped, the mol ratio of described Propranolol, methacrylic acid and ethylene glycol dimethacrylate is 1:10:24.
5. the preparation method of the molecularly imprinted polymer coating stirring rod of graphene oxide doped according to claim 1, it is characterized in that: described capillary glass tube is of a size of long 2cm, internal diameter 0.9-1.1mm, wall thickness 0.10-0.15mm, capillary glass tube two ends sealing by fusing forms dumbbell shape structure; Described iron core is of a size of 1.7cm, diameter 0.50mm.
6. the preparation method of the molecularly imprinted polymer coating stirring rod of graphene oxide doped according to claim 1, is characterized in that: in described step (3), and the time of logical nitrogen deoxygenation is 10min; Bath temperature is 60 DEG C, reaction 24h; The core length of described insertion is 1.7cm.
7. the preparation method of the molecularly imprinted polymer coating stirring rod of graphene oxide doped according to claim 1, is characterized in that: described eluent is the methanol solution containing 8% acetic acid.
8. the molecularly imprinted polymer coating stirring rod of a graphene oxide doped, is characterized in that: prepared by the preparation method described in any one of claim 1 to 7.
9. the application of molecularly imprinted polymer coating stirring rod in the selective extraction of medicine is analyzed of graphene oxide doped according to claim 8.
10. the method for a SPE Propranolol, it is characterized in that, comprise the following steps: the Propranolol solution molecularly imprinted polymer stirring rod of graphene oxide doped according to claim 8 being placed in pH=9.0, extraction 40min is stirred under 800rpm rotating speed, extraction terminates rear taking-up stirring rod, the solution drying stirring rod surface with filter paper remains, transfer them to ultrasonic desorb 20min in methyl alcohol/10mmol/L hydrochloric acid solution that volume ratio is 3:2, gained stripping liquid is analyzed for follow-up HPLC-UV detection after 0.22 μm of membrane filtration; The molecularly imprinted polymer stirring rod of the graphene oxide doped after desorb is placed in methanol solution and the ultrasonic 5min of methyl alcohol of 8% acetic acid successively, reuses.
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