CN104592446A - Preparation method and application of nano fiber molecularly-imprinted polymer of tetracycline antibiotics - Google Patents
Preparation method and application of nano fiber molecularly-imprinted polymer of tetracycline antibiotics Download PDFInfo
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Abstract
The invention discloses a preparation method and application of a nano fiber molecularly-imprinted polymer. The preparation method is characterized by comprising the following steps: carrying out silanization treatment and denaturation on nano fiber, and synthesizing the nano cellulose molecularly-imprinted polymer by using doxycycline as template molecules, acetonitrile/methanol as a pore-forming agent, methacrylic acid as a functional monomer, trimethylolpropane trimethyl acrylate as a crosslinking agent and azodiisobutyronitrile as an initiator. The application method comprises the following steps: characterizing the synthesized polymer material, filling in a solid-phase extraction column, and determining the concentration of tetracycline antibiotics in the sample to be detected according to the standard curve in combination with high-performance liquid chromatography. The application method has the advantages of high sensitivity, high detection speed, low detection limit, high efficiency and low price.
Description
Technical field
The present invention relates to field of detection of food safety, especially relating to a kind of nanofiber molecularly imprinted polymer preparation method and application for detecting teracycline antibiotic residues in food.
Background technology
The antimicrobial drug that tetracycline antibiotics (Tetracycline Antibiotic) is spectral type, be usually used in prevention and therapy livestock and poultry process, but due to the unreasonable use of medicine, often there is the residue problem of tetracycline medication in animal-derived food, harm humans is healthy.Conventional Fourth Ring four class microbiotic mainly contains tsiklomitsin (Tetracycline, TC), duomycin (Chlortetracycline, CTC), terramycin (Oxytetracycline, OTC) etc., part microbiotic also can be converted into epitetracycline through metabolism in animal body, not only cause drug effect to reduce, and its toxic side effect increase.FDA's above-mentioned three kinds of tetracycline antibiotics maximum residue limits of regulation are 2 μ g/g, and the Ministry of Agriculture's regulation microbiotic maximum residue limit is 100ng/g.Therefore, in food, the detection of tetracycline antibiotics is extremely urgent.Microbial method is the most frequently used method, but the method is complicated, consuming time, accuracy is not high.High performance liquid chromatography has highly sensitive, highly selective and accuracy in conjunction with the detection technique of additive method, can meet the qualitative and quantitative analysis to trace amount tetracycline antibiotics, but complicated operation, pre-treatment requires high, and sample introduction requires strict.Therefore, enrichment, purifying are carried out to sample, become step indispensable in trace analysis process.Solid phase extraction techniques, because its equipment is simple, level of automation advantages of higher, is widely used in sample pre-treatments.General sample composition is complicated, solid phase extraction procedure specificity is not high, and molecular engram solid phase extraction (Molecularly imprinted solid-phase extraction, MISPE) be that the highly selective that fast development is in recent years got up purifies and enrichment new technology, molecularly imprinted polymer is filled in solid phase extraction column, pre-treatment is carried out to sample, improves detection specificity, accuracy.
Nano-cellulose (Nanocrystalline Cellulose, NCC), also referred to as Cellulose nanocrystal body, be that a kind of diameter is at 1-100nm, length is plain to the rod-like fibre of hundreds of nanometer tens, has the advantages such as high purity, high-crystallinity, high strength.Mierocrystalline cellulose is natural polymers simultaneously, and NCC, because of the singularity on aggregated structure and physical property, makes it in high-performance polymer, demonstrate huge application prospect.At present, the correlative study report of the preparation method and application of any nanofiber molecularly imprinted polymer about tetracycline antibiotics is not also disclosed both at home and abroad.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method and application with the nanofiber molecularly imprinted polymer of highly sensitive, that detection speed is fast, detectability is low and efficient, cheap tetracycline antibiotics.
The present invention solves the problems of the technologies described above adopted technical scheme: a kind of preparation method of nanofiber molecularly imprinted polymer of tetracycline antibiotics, using nanofiber molecule as prop carrier, silanization is carried out to its surface, take doxycycline as template molecule, acetonitrile/methanol is pore-creating agent, methacrylic acid (MAA) is function monomer, trimethylol propane trimethyl vinylformic acid acid esters (TRIM) is linking agent, Diisopropyl azodicarboxylate (AIBN) is initiator, the nanofiber molecularly imprinted polymer of synthesis tetracycline antibiotics.
Specifically comprise the steps:
(1) preparation of nanofiber
Get 10g alpha-cellulose powder and be dissolved in the anhydrous N of 100mL, in N-N,N-DIMETHYLACETAMIDE (DMAC), after ultrasonic 20min, 2h is activated under 160 DEG C of conditions, revolve steaming 3-4h(and steam part N, N-N,N-DIMETHYLACETAMIDE), add 1mmol Lithium chloride (anhydrous), rotating speed 200rpm, fully 10h is stirred at 60 DEG C, and then revolve steaming 3-4h remove portion N, the emulsion that N-N,N-DIMETHYLACETAMIDE obtains, by emulsion under 8000 ~ 12000rmp rotating speed, centrifugal 15min, taking off layer gelinite, to be repeatedly washed to scavenging solution pH be 6.5-7.5, then dialysed overnight in distilled water, last under-40 DEG C of conditions, lyophilize 24h, process obtains the Mierocrystalline cellulose nanometer of loosening,
(2) preparation of silanization nanofiber
Getting 0.9g nano-cellulose is scattered in 300mL ethanol/water mixed solution, sonic oscillation 15min, then add 15mL ammoniacal liquor, 2.1mL tetraethoxy (TEOS) in reaction system, under 40 DEG C of conditions, stirring reaction 12h, with distilled water and ethanol drip washing repeatedly, under 8000 ~ 12000rmp rotating speed, centrifugal 15min, takes off layer gelinite under-40 DEG C of conditions, lyophilize 24h, obtains silanization nanofiber particle; Wherein ethanol/water mixed solution by ethanol and water by volume 4:1 mix;
(3) denaturing treatment of silanization nanofiber
Get 0.25mg silanization nanofiber particle join 30mL containing 3-mercaptopropyl trimethoxysilane (MPTS) volume fraction be in the toluene solution of 1/6, then under nitrogen protection, 120 DEG C of conditions, after back flow reaction 24h, wash 3 ~ 5 times with toluene and distilled water successively, then, under 8000 ~ 12000rmp rotating speed, centrifugal 15min, takes off layer gelinite under-40 DEG C of conditions, lyophilize 24h, obtains the silanization nano-fiber material of sex change;
(4) precipitation polymerization method synthesis of nano fiber molecule imprinted polymer
Get round-bottomed flask, add silanization nano-fiber material, 3.0mmol doxycycline, the 60mL acetonitrile/methanol mixed solution (35:30 of sex change in 30mg step (3) successively, V/V), the pretreated methacrylic acid of 0.68mL (MAA), after ultrasonic 15min, add 10mmol pretreated trimethylol propane trimethyl vinylformic acid acid esters (TRIM), ultrasonic 10min; Under nitrogen protection, add the pretreated Diisopropyl azodicarboxylate of 45mg (AIBN), in 60 DEG C of magnetic agitation polymerization 24h; after polyreaction terminates; decompress filter, washs 3 ~ 5 times by filter cake methyl alcohol/acetic acid mixture (7:1, V/V); use methyl alcohol/acetic acid mixture (7:1 again; V/V) surname extraction 24h, after extracting completes, sample is under-40 DEG C of conditions; lyophilize 24h, obtains the nanofiber molecularly imprinted polymer of tetracycline antibiotics.
Acetonitrile/methanol mixed solution described in step (5) by acetonitrile and methyl alcohol by volume 35:30 mix, described methyl alcohol/acetic acid mixture by methyl alcohol and acetic acid by volume 7:1 mix.
The preprocessing process of the methacrylic acid described in step (5) is by methacrylic acid underpressure distillation, and collect the cut of 69 DEG C ,-30 DEG C of Refrigerator stores are for subsequent use; The preprocessing process of described trihydroxy methyl propane trimethyl vinylformic acid acid esters is for using charcoal absorption removal of impurities, filtration, and collect filtrate ,-30 DEG C of Refrigerator stores are for subsequent use; The preprocessing process of described Diisopropyl azodicarboxylate is Diisopropyl azodicarboxylate and methyl alcohol after 1:10 mixes in mass ratio, and 50 DEG C of water-baths, while hot suction filtrations, filtrate leaves standstill 30min, again suction filtration, collects crystallized product, and sealing ,-40 DEG C save backup.
Described tetracycline antibiotics is tsiklomitsin, duomycin and terramycin.
Nanofiber molecularly imprinted polymer detects a method for tetracycline antibiotics concentration in sample, comprises the following steps:
(1) sample preparation
Testing sample tissue mashing machine is rubbed evenly, add the Mcllvaine buffered soln of testing sample 4 times of volumes, ultrasonic lixiviate 20min, centrifugal 15min gets supernatant liquor, and residue adds the Mcllvaine buffered soln of testing sample 4 times of volumes again, ultrasonic lixiviate 20min, centrifugal 15min gets supernatant liquor, merge two times centrifugal gained supernatant liquor, supernatant liquor is obtained analyte sample fluid with the filtering with microporous membrane of 0.45 μm, refrigerates for subsequent use;
(2) molecular imprinted solid phase extraction cartridge preparation
Accurately take 150mg nanofiber molecularly imprinted polymer, fill post with methanol wet, load well, with vacuum pump, solid phase extraction column is taken out tightly, obtain molecular imprinted solid phase extraction cartridge;
(3) tetracycline antibiotics concentration determination
Be under the condition of 2mL/min at flow velocity by molecular imprinted solid phase extraction cartridge 3mL methanol solution, repeatedly after drip washing activation, pure water cleans, be loaded into 2mL analyte sample fluid again, after absorption terminates, pure water cleaning 3-4 time, use methanol solution wash-out again 3 ~ 5 times, collect elutriant, by elutriant high-performance liquid chromatogram determination, record data, according to tsiklomitsin, the quantitative relationship of duomycin and terramycin 3 kinds of tetracycline antibiotics liquid chromatography peak areas and corresponding tetracycline antibiotics concentration, determine tsiklomitsin in testing sample, the concentration of duomycin and terramycin 3 kinds of tetracycline antibiotics.
The compound method of described Mcllvaine buffered soln is as follows: 7.10g disodium hydrogen phosphate (Na
2hPO
412H
2o, 12.9g ten citrate dihydrate (C
6h
8o
712H
2o), 3.72g disodium ethylene diamine tetraacetate, with diluting after water dissolution and being settled to 1000mL.
High-efficient liquid phase chromatogram condition: chromatographic column: ZORBAX Eclipse XDB-C18,4.6 × 150mm, 5 μm; Moving phase: the SODIUM PHOSPHATE, MONOBASIC of 0.01mol/L pH 2.8: acetonitrile=79:21; Determined wavelength: 355nm; Flow velocity: 0.8mL/min; Sample size: 20 μ L; Column temperature: 30 DEG C.
Principle: using nanofiber molecule as prop carrier, silanization is carried out to its surface, take doxycycline as template molecule, acetonitrile/methanol is pore-creating agent, methacrylic acid (MAA) is function monomer, trimethylol propane trimethyl vinylformic acid acid esters (TRIM) is linking agent, Diisopropyl azodicarboxylate (AIBN) is initiator, template molecule and function monomer are combined by covalent linkage or non covalent bond and produce functional group and space structure complementary action forms title complex, again under linking agent exists, cause template molecule-function monomer title complex polymerization reaction take place, the rigid macromolecule polymkeric substance that height of formation is crosslinked, then template molecule is removed, obtain functional group, space structure and template molecule complementation, and tetracycline antibiotics is had to the molecularly imprinted polymer of specific adsorption ability.Molecularly imprinted polymer is loaded in solid-phase extraction column, make solid phase extraction column, through these steps of overbalance, loading, drip washing and wash-out, in sample, the hole of target molecule (tetracycline antibiotics) in molecularly imprinted polymer is in conjunction with the trace residue of combined highly effective liquid phase chromatography Simultaneously test meat kind three kinds of tetracycline antibiotics.
Compared with prior art, the invention has the advantages that: the preparation method and application of the nanofiber molecularly imprinted polymer of tetracycline antibiotics of the present invention, make use of nano-cellulose and there is poly-hydroxy and surface is easy to the feature of chemical modification, to its surface silanization, take doxycycline as template molecule, acetonitrile/methanol is pore-creating agent, methacrylic acid (MAA) is function monomer, trimethylol propane trimethyl vinylformic acid acid esters (TRIM) is linking agent, Diisopropyl azodicarboxylate (AIBN) is initiator, synthesis of nano cellulosic molecule imprinted polymer, be filled in solid phase extraction column, and in conjunction with high performance liquid chromatography, the trace residue of tetracycline antibiotics in working sample.It utilizes molecularly imprinted polymer to have specific recognition and absorption property to target molecule, realizes detecting kind of the tetracycline antibiotics of 3 in sample simultaneously.The present invention using nanofiber surface molecularly imprinted polymer material as solid extracting agent, and in conjunction with the analytical procedure of high performance liquid chromatography, and utilize the specific adsorption characteristic of nanofiber surface molecularly imprinted polymer material, reach the object improving detection specificity, sensitivity, the present invention has specificity, the multiple advantage such as quick, cheap.
Accompanying drawing explanation
Fig. 1 is scanning (SEM) the Electronic Speculum figure of nanofiber molecularly imprinted polymer;
Fig. 2 is transmission (TEM) the Electronic Speculum figure of nanofiber molecularly imprinted polymer;
Fig. 3 is infrared chromatography analysis (FT-IR) figure of nanofiber and nanofiber molecularly imprinted polymer;
Fig. 4 is the liquid chromatogram of tetracycline antibiotics standard specimen;
Fig. 5 is the absorption of nanofiber molecularly imprinted polymer to three kinds of tetracycline antibiotics;
Fig. 6 is that nanofiber molecularly imprinted polymer and non-molecularly imprinted polymer are to the adsorption curve of terramycin;
Fig. 7 is the Scatchard analysis chart that nanofiber molecularly imprinted polymer adsorbs terramycin;
Fig. 8 is the Scatchard analysis chart that the non-molecularly imprinted polymer of nanofiber adsorbs terramycin.
Embodiment
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.
Specific embodiment one
A kind of using nanofiber molecule as prop carrier, silanization is carried out to its surface, take doxycycline as template molecule, acetonitrile/methanol is pore-creating agent, methacrylic acid (MAA) is function monomer, trimethylol propane trimethyl vinylformic acid acid esters (TRIM) is linking agent, Diisopropyl azodicarboxylate (AIBN) is initiator, synthesis of nano cellulosic molecule imprinted polymer, with this polymkeric substance for sorbent material, adopt Solid-Phase Extraction-liquid chromatography United Technologies, in detection food, tetracycline antibiotics is residual.
Specific embodiment two
The concrete preparation method of the nano-cellulose molecularly imprinted polymer of the tetracycline antibiotics of above-described embodiment one, experiment material is as follows:
Doxycycline (Aladdin reagent company limited); Tsiklomitsin (Aladdin reagent company limited); Terramycin (Aladdin reagent company limited); Duomycin (Aladdin reagent company limited), alpha-cellulose powder (Aladdin reagent company limited); Lithium chloride (anhydrous) (the upper smooth Science and Technology Co., Ltd. of Haitai); N,N-dimethylacetamide (DMAC, Aladdin reagent company limited); 3-mercaptopropyl trimethoxysilane (MPTS, Chemical Reagent Co., Ltd., Sinopharm Group); Methacrylic acid (MAA, Chemical Reagent Co., Ltd., Sinopharm Group); Trimethylol propane trimethyl vinylformic acid acid esters (TRIM, Mayan reagent company limited); Diisopropyl azodicarboxylate (AIBN, Tianjin recovery fine chemistry industry institute); Tetraethyl orthosilicate (TEOS, the smooth Science and Technology Co., Ltd. of upper Haitai); SODIUM PHOSPHATE, MONOBASIC (NaH
2pO
42H
2o, Yong great chemical reagent company limited); Sodium phosphate dibasic (Na
2hPO
412H
2o, Yong great chemical reagent company limited); Disodium ethylene diamine tetraacetate (Chemical Reagent Co., Ltd., Sinopharm Group); Citric acid (C
6h
8o
712H
2o, Yong great chemical reagent company limited); Acetonitrile (chromatographically pure, Di Ma Science and Technology Ltd.); Methyl alcohol (chromatographically pure, Di Ma Science and Technology Ltd.).Below the reagent of non-grade labeling is analytical pure, and deionized water is prepared from laboratory.
Specifically comprise the steps:
(1) preparation of nanofiber
Get 10g alpha-cellulose powder and be dissolved in the anhydrous N of 100mL, in N-N,N-DIMETHYLACETAMIDE (DMAC), after ultrasonic 20min, 2h is activated under 160 DEG C of conditions, revolve steaming 3-4h(and steam part N, N-N,N-DIMETHYLACETAMIDE), add 1mmol Lithium chloride (anhydrous), rotating speed 200rpm, fully 10h is stirred at 60 DEG C, and then revolve steaming 3-4h remove portion N, N-N,N-DIMETHYLACETAMIDE obtains emulsion, by emulsion under 8000 ~ 12000rmp rotating speed, centrifugal 15min, taking off layer gelinite, to be repeatedly washed to scavenging solution pH be 6.5-7.5, then dialysed overnight in distilled water, last under-40 DEG C of conditions, lyophilize 24h, process obtains the Mierocrystalline cellulose nanometer of loosening,
(2) preparation of silanization nanofiber
Get 0.9g nano-cellulose and be scattered in 300mL ethanol/water mixed solution (4:1, V/V) in, sonic oscillation 15min, then add 15mL ammoniacal liquor, 2.1mL tetraethoxy (TEOS) in reaction system, under 40 DEG C of conditions, stirring reaction 12h, with distilled water and ethanol drip washing repeatedly, under 8000 ~ 12000rmp rotating speed, centrifugal 15min, take off layer gelinite under-40 DEG C of conditions, lyophilize 24h, obtain silanization nanofiber particle;
(3) denaturing treatment of silanization nanofiber
Get 0.25mg silanization nanofiber particle join 30mL containing 3-mercaptopropyl trimethoxysilane (MPTS) volume fraction be in the toluene solution of 1/6, then under nitrogen protection, 120 DEG C of conditions, after back flow reaction 24h, wash 3 ~ 5 times with toluene and distilled water successively, then, under 8000 ~ 12000rmp rotating speed, centrifugal 15min, takes off layer gelinite under-40 DEG C of conditions, lyophilize 24h, obtains the silanization nano-fiber material of sex change;
(4) agent treated: 1. by methacrylic acid underpressure distillation, collect the cut of 69 DEG C ,-30 DEG C of Refrigerator stores are for subsequent use; 2. trihydroxy methyl propane trimethyl acrylic ester charcoal absorption removal of impurities, filtration, collect filtrate ,-30 DEG C of Refrigerator stores are for subsequent use; 3. Diisopropyl azodicarboxylate and methyl alcohol (mass ratio is 1:10) mix, 50 DEG C of water-baths, while hot suction filtrations, and filtrate leaves standstill 30min, again suction filtration, collect crystallized product, sealing, and-40 DEG C save backup;
(5) precipitation polymerization method synthesis of nano fiber molecule imprinted polymer
Get round-bottomed flask, add silanization nano-fiber material, 3.0mmol doxycycline, the 60mL acetonitrile/methanol mixed solution (35:30 of sex change in 30mg step (3) successively, V/V), the pretreated methacrylic acid of 0.68mL (MAA), after ultrasonic 15min, add 10mmol pretreated trimethylol propane trimethyl vinylformic acid acid esters (TRIM), ultrasonic 10min; Under nitrogen protection; add the pretreated Diisopropyl azodicarboxylate of 45mg (AIBN); in 60 DEG C of magnetic agitation polymerization 24h; after polyreaction terminates; decompress filter; by filter cake methyl alcohol/acetic acid mixture (7:1; V/V) wash 3 ~ 5 times; use methyl alcohol/acetic acid mixture (7:1, V/V) surname extraction 24h again, after extracting completes; sample is under-40 DEG C of conditions; lyophilize 24h, obtains the nanofiber molecularly imprinted polymer of tetracycline antibiotics, and wherein tetracycline antibiotics is tsiklomitsin, duomycin and terramycin 3 kinds.According to above method, do not add doxycycline, the non-molecularly imprinted polymer NIP of synthesis control group;
(6) sign of nanofiber molecularly imprinted polymer: the microscopic appearance structure of sample observed by scanning electronic microscope (SEM), transmission electron microscope (TEM), and Fourier transform infrared spectrometer (FT-IR) tests the chemical composition of sample.All characterizing sample are all pulverized, pressing potassium bromide troche, and wavelength region is 400 ~ 4000cm
-1, resolving power is 4 cm
-1.
Found out by scanning (SEM) the Electronic Speculum figure of Fig. 1 nanofiber molecularly imprinted polymer and transmission (TEM) the Electronic Speculum figure of Fig. 2 nanofiber molecularly imprinted polymer, the caliber of nanofiber molecularly imprinted polymer is between 500 ~ 600nm, nanofiber molecularly imprinted polymer is slightly reunited, nanofiber molecular imprinting surface irregularity, uneven, have a large amount of aperture to exist, micromolecular compound infiltrates the inside of polymkeric substance by hole.
In infrared chromatography analysis (FT-IR) figure of Fig. 3 nanofiber molecularly imprinted polymer and non-molecularly imprinted polymer, 1632cm
-1for the vibration performance peak of carbon-carbon double bond (C=C), 3428 cm
-1be the charateristic avsorption band of H-O, the content in nanofiber is all higher.806 cm
-1si-O-Si symmetric vibration absorption peak, 1096 cm
-1be the charateristic avsorption band of Si-O, and the activity of now Sauerstoffatom is comparatively strong, therefore, can infer nanofiber surface success silanization.In the charateristic avsorption band of molecular imprinting nanofiber, Si-O absorption intensity reduces, and can release the formation that more Si-O key participates in molecular imprinting hole.
Specific embodiment three
Bent and the detectability of the adsorption test of nanofiber molecularly imprinted polymer, mark, concrete steps are as follows:
(1) high-efficient liquid phase chromatogram condition: chromatographic column: ZORBAX Eclipse XDB-C18,4.6 × 150mm, 5 μm, Agilent; Moving phase: 0.01mol/L SODIUM PHOSPHATE, MONOBASIC (pH 2.8): acetonitrile=79:21; Determined wavelength: 355nm; Flow velocity: 0.8mL/min; Sample size: 20 μ L; Column temperature: 30 DEG C, as the liquid chromatogram that Fig. 4 is tetracycline antibiotics standard specimen, three kinds of tetracycline antibiotics, under above-mentioned liquid chromatography experiment condition, can analyze end within 15min, tsiklomitsin and terramycin can go out peak within front 7min, and duomycin went out peak before 12min;
(2) production standard curve: make solvent with methyl alcohol, compound concentration is 2.5 μ g/mL, 5.0 μ g/mL, 10 μ g/mL, 25 μ g/mL, 50 μ g/mL, the tsiklomitsin of 100 μ g/mL and terramycin, concentration is the mixed standard solution of 5.0 μ g/mL, 10 μ g/mL, 20 μ g/mL, 50 μ g/mL, 100 μ g/mL, 200 μ g/mL duomycin, by above-mentioned liquid phase chromatogram condition, do linear regression analysis, table 1 is the linear equation of tetracycline antibiotics standard specimen, relative coefficient and detection limit.Result shows, three kinds of tetracycline antibiotics are in this concentration range internal linear relation good (R2 is all greater than 0.999);
(3) mensuration of method detection limit: (concentration < 100 μ g/L) tests 5 concentration and a blank group under low concentration scope, each concentration tests 10 times respectively, calculate standard deviation, the tropic is drawn with standard deviation-concentration, the intersection point (standard deviation when namely concentration is zero) calculating the tropic and ordinate zou is exactly the detectability of the method, table 1 is the linear equation of tetracycline antibiotics standard specimen, relative coefficient and detection limit, wherein X represents concentration, and Y represents liquid chromatography peak area.Find out that method of design in invention is respectively 9.61 μ g/Kg, 7.84 μ g/Kg, 11.93 μ g/Kg for the detection limit of tsiklomitsin, terramycin, duomycin by table 1;
Table 1
| Composition | Linearity range (μ g/mL) | Detectability (μ g/Kg) | Linear equation | Relation conefficient (R2) |
| Tsiklomitsin (TC) | 0.05～1.1 | 9.61 | Y=19.995X-18.046 | 0.9991 |
| Terramycin (OTC) | 0.05～1.1 | 7.84 | Y=222.35X-0.3748 | 0.9992 |
| Duomycin (CTC) | 0.1～2.2 | 11.93 | Y=869.82X-13.32 | 0.9995 |
(4) adsorption test of molecularly imprinted polymer: get 10 10mL centrifuge tubes, add the nanofiber molecularly imprinted polymer of 50mg respectively, then in 1-10 pipe, add 5mL be successively respectively 0.2 mgmL containing tsiklomitsin, terramycin, duomycin 3 kinds of tetracycline antibiotics concentration
-1, 0.4 mgmL
-1, 0.6 mgmL
-1, 0.8 mgmL
-1, 1.0 mgmL
-1, 1.2 mgmL
-1, 1.4 mgmL
-1, 1.6 mgmL
-1, 1.8 mgmL
-1, 2.0 mgmL
-1methanol/water (95:5, V/V) solution (namely 3 kinds of tetracycline antibiotics all do above-mentioned 10 different concns), mixing vibration 8h after, the centrifugal 10min of 8000rmp, and collect supernatant liquor, measure with high performance liquid chromatography (HPLC), each concentration arranges three groups of repetitions.According to adsorption equilibrium formula 1., calculated equilibrium adsorptive capacity Q(mgg
-1):
In formula: V represents liquor capacity (mL); M represents nanofiber molecularly imprinted polymer quality (g); C
0represent initial concentration solution (mgmL
-1); C
erepresent solution absorbs equilibrium concentration (mgmL
-1);
Molecularly imprinted polymer, to the absorption of target compound, affects primarily of two kinds of factors, i.e. the matching degree of hole size and target compound Structure adaptation degree, function monomer and target compound.From Fig. 5 nanofiber molecularly imprinted polymer to the absorption of tetracycline antibiotics, molecularly imprinted polymer all has good adsorptivity to tsiklomitsin, terramycin and duomycin.Because employing doxycycline as template molecule, although it is in the same size with tetracycline molecule amount, recognition site or group property comparison in difference large, therefore relatively lower slightly to the adsorption of tsiklomitsin, and to the adsorption of duomycin and terramycin comparatively by force;
(5) nanofiber molecularly imprinted polymer is analyzed the Static Adsorption of terramycin and Scatchard: get 10 10mL centrifuge tubes, add the nanofiber molecularly imprinted polymer of 50mg respectively, then in 1-10 pipe, add 5mL terramycin concentration be successively respectively 0.2 mgmL
-1, 0.4 mgmL
-1, 0.6 mgmL
-1, 0.8 mgmL
-1, 1.0 mgmL
-1, 1.2 mgmL
-1, 1.4 mgmL
-1, 1.6 mgmL
-1, 1.8 mgmL
-1, 2.0 mgmL
-1methanol/water (95:5, V/V) solution, after mixing vibration 8h, the centrifugal 15min of 8000rmp, and collect supernatant liquor, measure with high performance liquid chromatography (HPLC), each concentration arranges three groups of repetitions.According to above-mentioned adsorption equilibrium formula 1., calculated equilibrium adsorptive capacity Q(mgg
-1), obtain the Scatchard analytical results of table 2 nanofiber molecularly imprinted polymer and non-molecularly imprinted polymer (preparation method is shown in shown in specific embodiment two),
Table 2
。
Fig. 6 is that nanofiber molecularly imprinted polymer and non-molecularly imprinted polymer are to the adsorption curve of terramycin.Visible, nanofiber molecularly imprinted polymer is to the adsorption of terramycin, and adsorptive capacity is all increase along with the increase of starting point concentration, and the adsorption of nanofiber molecularly imprinted polymer is obviously greater than non-molecularly imprinted polymer.Illustrate that the present invention has more good selective adsorption effect.
The Scatchard analysis chart adsorbed terramycin by Fig. 7 nanofiber molecularly imprinted polymer and upper table, can find out, nanofiber molecularly imprinted polymer equilibrium dissociation constant K
dat 0.17429 ~ 0.92533mgmL
-1between, maximal absorptive capacity Q
maxat 44.886 ~ 91.635mgg
-1between, and be 24.41 mgg by the non-molecularly imprinted polymer of Fig. 8 nanofiber to terramycin maximal absorptive capacity
-1.Therefore, the absorption of nanofiber molecularly imprinted polymer has two adsorption sites, and adsorptive power is obviously greater than non-molecularly imprinted polymer.
Specific embodiment four
Applying nano fiber molecule imprinted polymer detects the concentration of tetracycline antibiotics in sample simultaneously.
In the large white goose meat in Xiangshan, the extraction of tetracycline antibiotics adopts Mcllvaine buffered soln dilution method.Rubbed evenly by large white goose meat with tissue mashing machine, added the above-mentioned buffered soln of 4 times of volumes, ultrasonic lixiviate 20min, centrifugal 15min, residue same procedure repeats lixiviate 1 time, merges vat liquor, with the filtering with microporous membrane of 0.45 μm, refrigerates to be measured.In mark-on process of the test, need a certain amount of tetracycline antibiotics be dissolved in Mcllvaine buffered soln, make terramycin, tetracycline concentration be respectively 0.2 μ g/mL, 0.4 μ g/mL, 0.8 μ g/mL, chlortetracycline concentration is 0.4 μ g/mL, 0.8 μ g/mL, 1.6 μ g/mL, and each concentration does 5 repetitions simultaneously.Mixture prepared by investigation is to the recovery of standard addition of 3 kinds of tetracycline antibiotics.
Accurately take 150mg nanofiber molecularly imprinted polymer, fill post with methanol wet, load well, with vacuum pump, solid phase extraction column is taken out tightly, obtain molecular imprinted solid phase extraction cartridge.The repeatedly drip washing activation of 3mL methanol solution first used by pillar before using, flow velocity 2mL/min.Activation terminates, and pure water cleans, then is loaded into the sample mark-on vat liquor of the above-mentioned preparation of 2mL respectively, and after absorption terminates, pure water cleans, and use methanol solution wash-out, collect elutriant, HPLC is to be measured.Record data, mark linear equation according to corresponding liquid chromatography peak area with mixed, draw the concentration of 3 kinds of tetracycline antibiotics in mark-on sample respectively, and calculate often kind of antibiotic recovery of standard addition, as table 3,
Table 3
As can be seen from Table 3, the non-molecularly imprinted polymer of nanofiber is respectively 88.8%, 92.43%, 94.56% to the recovery of standard addition of terramycin, tsiklomitsin, duomycin medicine in the large white goose sample in Xiangshan; Nanofiber molecularly imprinted polymer is respectively 91.05%, 95.35%, 95.63% to the recovery of standard addition of terramycin, tsiklomitsin, duomycin medicine in the large white goose sample in Xiangshan, visible, nanofiber molecularly imprinted polymer slightly increases as rate of recovery during sorbent material.The variation coefficient is between 1.53 ~ 7.80, and show that the method for detecting residue designed is reliable, preci-sion and accuracy all can reach the requirement that teracycline antibiotic residues is analyzed.
Detect the residual of 3 kinds of tetracycline antibiotics in Xiangshan large white goose brisket, detected result shows, and in goose brisket, terramycin content is 0.027mg/kg, tsiklomitsin content is 0.21 mg/kg, duomycin does not detect.Illustrate that the residual quantity of 3 kinds of tetracycline antibiotics in the large white goose brisket in Xiangshan is all lower than national standard requirement.
Certainly, above-mentioned explanation is not limitation of the present invention, and the present invention is also not limited to above-mentioned citing.Those skilled in the art are in essential scope of the present invention, and the change made, remodeling, interpolation or replacement, also should belong to protection scope of the present invention.
Claims (8)
1. the preparation method of the nanofiber molecularly imprinted polymer of a tetracycline antibiotics, it is characterized in that: using nanofiber molecule as prop carrier, silanization is carried out to its surface, take doxycycline as template molecule, acetonitrile/methanol is pore-creating agent, methacrylic acid is function monomer, trimethylol propane trimethyl vinylformic acid acid esters is linking agent, Diisopropyl azodicarboxylate is initiator, the nanofiber molecularly imprinted polymer of synthesis tetracycline antibiotics.
2. the preparation method of the nanofiber molecularly imprinted polymer of tetracycline antibiotics according to claim 1, is characterized in that specifically comprising the steps:
(1) preparation of nanofiber
Get 10g alpha-cellulose powder and be dissolved in the anhydrous N of 100mL, in N-N,N-DIMETHYLACETAMIDE, after ultrasonic 20min, 2h is activated under 160 DEG C of conditions, revolve after steaming 3-4h, add 1mmol Lithium chloride (anhydrous), rotating speed 200rpm, at 60 DEG C, fully stir 10h, and then revolve steam 3-4h obtain emulsion, by emulsion under 8000 ~ 12000rmp rotating speed, centrifugal 15min, taking off layer gelinite, to be repeatedly washed to scavenging solution pH be 6.5-7.5, then dialysed overnight in distilled water, last under-40 DEG C of conditions, lyophilize 24h, process obtains the Mierocrystalline cellulose nanometer of loosening;
(2) preparation of silanization nanofiber
Getting 0.9g nano-cellulose is scattered in 300mL ethanol/water mixed solution, sonic oscillation 15min, then add 15mL ammoniacal liquor, 2.1mL tetraethoxy in reaction system, under 40 DEG C of conditions, stirring reaction 12h, with distilled water and ethanol drip washing repeatedly, under 8000 ~ 12000rmp rotating speed, centrifugal 15min, takes off layer gelinite under-40 DEG C of conditions, lyophilize 24h, obtains silanization nanofiber particle; Wherein ethanol/water mixed solution by ethanol and water by volume 4:1 mix;
(3) denaturing treatment of silanization nanofiber
Get 0.25mg silanization nanofiber particle join 30mL containing 3-mercaptopropyl trimethoxysilane volume fraction be in the toluene solution of 1/6, then under nitrogen protection, 120 DEG C of conditions, after back flow reaction 24h, wash 3 ~ 5 times with toluene and distilled water successively, then, under 8000 ~ 12000rmp rotating speed, centrifugal 15min, takes off layer gelinite under-40 DEG C of conditions, lyophilize 24h, obtains the silanization nano-fiber material of sex change;
(4) precipitation polymerization method synthesis of nano fiber molecule imprinted polymer
Get silanization nano-fiber material, 3.0mmol doxycycline, 60mL acetonitrile/methanol mixed solution, the pretreated methacrylic acid of 0.68mL that round-bottomed flask adds 30mg sex change successively, after ultrasonic 15min, add 10mmol pretreated trimethylol propane trimethyl vinylformic acid acid esters, ultrasonic 10min; Under nitrogen protection; add the pretreated Diisopropyl azodicarboxylate of 45mg; in 60 DEG C of magnetic agitation polymerization 24h, after polyreaction terminates, decompress filter; by filter cake methyl alcohol/acetic acid mixture washing 3 ~ 5 times; use methyl alcohol/acetic acid mixture surname extraction 24h again, after extracting completes, sample is under-40 DEG C of conditions; lyophilize 24h, obtains the nanofiber molecularly imprinted polymer of tetracycline antibiotics.
3. the preparation method of the nanofiber molecularly imprinted polymer of tetracycline antibiotics according to claim 2, it is characterized in that: the acetonitrile/methanol mixed solution described in step (5) by acetonitrile and methyl alcohol by volume 35:30 mix, described methyl alcohol/acetic acid mixture by methyl alcohol and acetic acid by volume 7:1 mix.
4. the preparation method of the nanofiber molecularly imprinted polymer of tetracycline antibiotics according to claim 2, it is characterized in that: the preprocessing process of the methacrylic acid described in step (5) is by methacrylic acid underpressure distillation, collect the cut of 69 DEG C ,-30 DEG C of Refrigerator stores are for subsequent use; The preprocessing process of described trihydroxy methyl propane trimethyl vinylformic acid acid esters is for using charcoal absorption removal of impurities, filtration, and collect filtrate ,-30 DEG C of Refrigerator stores are for subsequent use; The preprocessing process of described Diisopropyl azodicarboxylate is Diisopropyl azodicarboxylate and methyl alcohol after 1:10 mixes in mass ratio, and 50 DEG C of water-baths, while hot suction filtrations, filtrate leaves standstill 30min, again suction filtration, collects crystallized product, and sealing ,-40 DEG C save backup.
5. the preparation method of the nanofiber molecularly imprinted polymer of tetracycline antibiotics according to claim 2, is characterized in that described tetracycline antibiotics is tsiklomitsin, duomycin and terramycin.
6. application rights requires that the nanofiber molecularly imprinted polymer according to any one of 1-5 detects a method for tetracycline antibiotics concentration in sample, it is characterized in that comprising the following steps:
(1) sample preparation
Testing sample tissue mashing machine is rubbed evenly, add the Mcllvaine buffered soln of testing sample 4 times of volumes, ultrasonic lixiviate 20min, centrifugal 15min gets supernatant liquor, and residue adds the Mcllvaine buffered soln of testing sample 4 times of volumes again, ultrasonic lixiviate 20min, centrifugal 15min gets supernatant liquor, merge two times centrifugal gained supernatant liquor, supernatant liquor is obtained analyte sample fluid with the filtering with microporous membrane of 0.45 μm, refrigerates for subsequent use;
(2) molecular imprinted solid phase extraction cartridge preparation
Accurately take 150mg nanofiber molecularly imprinted polymer, fill post with methanol wet, load well, with vacuum pump, solid phase extraction column is taken out tightly, obtain molecular imprinted solid phase extraction cartridge;
(3) tetracycline antibiotics concentration determination
Be under the condition of 2mL/min at flow velocity by molecular imprinted solid phase extraction cartridge 3mL methanol solution, repeatedly after drip washing activation, pure water cleans, be loaded into 2mL analyte sample fluid again, after absorption terminates, pure water cleaning 3-4 time, use methanol solution wash-out again 3 ~ 5 times, collect elutriant, by elutriant high-performance liquid chromatogram determination, record data, according to tsiklomitsin, the quantitative relationship of duomycin and terramycin 3 kinds of tetracycline antibiotics liquid chromatography peak areas and corresponding tetracycline antibiotics concentration, determine tsiklomitsin in testing sample, the concentration of duomycin and terramycin 3 kinds of tetracycline antibiotics.
7. nanofiber molecularly imprinted polymer according to claim 6 detects the method for tetracycline antibiotics concentration in sample, it is characterized in that the compound method of described Mcllvaine buffered soln is as follows: 7.10g disodium hydrogen phosphate, 12.9g ten citrate dihydrate, 3.72g disodium ethylene diamine tetraacetate, with diluting after water dissolution and being settled to 1000mL.
8. nanofiber molecularly imprinted polymer according to claim 6 detects the method for tetracycline antibiotics concentration in sample, it is characterized in that high-efficient liquid phase chromatogram condition: chromatographic column: ZORBAX Eclipse XDB-C18,4.6 × 150mm, 5 μm; Moving phase: the SODIUM PHOSPHATE, MONOBASIC of 0.01mol/L pH 2.8: acetonitrile=79:21; Determined wavelength: 355nm; Flow velocity: 0.8mL/min; Sample size: 20 μ L; Column temperature: 30 DEG C.
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