CN105315408A - Synthetic method for molecular imprinting material and application of molecular imprinting material in separation of solanesol in tobacco leaves - Google Patents
Synthetic method for molecular imprinting material and application of molecular imprinting material in separation of solanesol in tobacco leaves Download PDFInfo
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- CN105315408A CN105315408A CN201510802583.4A CN201510802583A CN105315408A CN 105315408 A CN105315408 A CN 105315408A CN 201510802583 A CN201510802583 A CN 201510802583A CN 105315408 A CN105315408 A CN 105315408A
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Abstract
The invention relates to a synthetic method for a molecular imprinting material and application of the molecular imprinting material in separation of solanesol in tobacco leaves. The molecular imprinting technology and middle-low pressurepreparative chromatography are combined, high performance liquid chromatography serves as a detection means, and the molecular imprinting material is used for quickly preparing the high-purity target molecules, namely solanesol, in a large-scale mode in natural product tobacco leaves. Proper molecules serve as an imprinting template, a monomer, a crosslinking agent, surfactant and a pore-forming agent, an azo initiating agent is adopted, and an imprinting polymer is prepared through suspension polymerization. By means of formula optimization, the large-particle-size sphere imprinting polymer is prepared for preparing spectrum packing. By means of spectrum condition optimization, high-purity solanesol can be extracted from tobacco leaves with a small quantity of a solvent within a short time, and chromatographic columns can be recycled. According to the method, economic value is achieved, higher universality is achieved, the method can be used for extracting other active ingredients in natural products, and good application prospects are achieved.
Description
Technical field
Invent the extracting method of activeconstituents in a kind of natural product, by molecularly imprinted polymer for the preparation of chromatogram, the highly purified activeconstituents of extracting directly from natural product, i.e. molecularly imprinted polymer (MolecularlyImprintedPolymers, MIPs) in conjunction with the system of mesolow preparative chromatography (FlashChromatography), for activeconstituents in natural product quick, prepare in a large number.
Background technology
Molecularly imprinted polymer refers to and passes through by between function monomer, template molecule, linking agent the polymkeric substance formed that interacts.It carries more than one hundred million the specific binding sites to template, can identify and specific binding target compound.Molecularly imprinted polymer, because it is to the specific recognition of specific molecular and selective binding ability, can be used for various fields, comprises abstraction and purification, sensing and bio-sensing, catalysis, pharmaceutical carrier etc.With regard to the application of its abstraction and purification, molecular imprinting is widely used in Solid-Phase Extraction in recent years, for enrichment and the purifying of sample before analyzing and testing, but seldom has its application in preparation in enormous quantities.
The reported first of preparative chromatography is in 1879, is used for the purifying of target compound after organic synthesis by W.C.Still.Because it has the advantages such as low cost, short, high yield consuming time, be after this widely used in organic reaction aftertreatment, natural product extraction, example enrichment and purifying etc.But the inherent defect of traditional stationary phase (as silica gel, polymeric amide, aluminum oxide, hydrogel etc.) is as low in adsorptivity, the life-span is short etc. has a strong impact on purity and the separation costs of its product.
Highly purified effective constituent study hotspot is always extracted from natural product, Recent study person has developed a lot of chromatographic technique for this reason, as high speed adverse current chromatogram, supercritical fluid chromatography, simulated moving bed chromatography etc., be used successfully in natural product that activeconstituents is as the separation of saponin(e, Thymus vulgaris, Potenlini, desmosterol etc., product purity can reach 95%.But above chromatographic technique is because consuming time, solvent acquisition amount is large, high in cost of production, is not used widely in a large amount of preparation.
Summary of the invention
Molecular imprinting and preparative chromatography combine by the present invention, and object is the extraction for activeconstituents in natural product, provide a kind of quick, a large amount of preparation method, to solve the problems such as traditional method cost is high, step is complicated, product purity is low.
Technical scheme is as follows:
Forward suspension polymerization prepare Salanesol molecularly imprinted polymer: a certain amount of template, monomer, linking agent are dissolved in organic solvent, obtain disperse phase; External phase: a certain amount of tensio-active agent is dissolved in ultrapure water.Preparation condition: under certain mechanical stirring speed, rare gas element deoxygenation, at 50 ~ 90 DEG C, polyase 13 ~ 8 hour.
Molecular imprinting preparative chromatography condition after optimization, for extracting solanesol in tobacco leaves.The operation of its concrete grammar is as follows: the tobacco leaf extract organic solvent slightly carried is settled to finite concentration, with certain flow rate loading, switch moving phase eluting solvent with certain flow rate wash-out, finally use the eluting solvent in organic solvent purging system, collect elution fraction, through rotary evaporation, obtain white solid, i.e. Salanesol.
Advantage of the present invention:
(1) raw material of this experiment is tobacco leaf, and its steady sources is with low cost, and pretreatment process is easy;
(2) this extraction scheme extraction efficiency, product purity is up to 98%, and Extraction solvent can reclaim use, greatly reduces cost and avoids environmental pollution;
(3) molecularly imprinted polymer used in this experiment, adsorptivity is strong, selectivity is high, long service life, can reuse;
(4) extracting method of natural product set up of this experiment, has universality, can be used for the extraction of activeconstituents in other natural products, have a good application prospect.
Accompanying drawing explanation
Fig. 1 is the Salanesol imprinted polymer (MIP after optimization of C/C composites
3) Electronic Speculum figure.Salanesol imprinted polymer and non-imprinted polymer all have good sphericity as seen from the figure, and particle size range is 250-350 μm, and the non-imprinted polymer of imprinted polymer surface ratio is coarse.
Fig. 2 figure is Salanesol molecular imprinting preparative chromatography optimize chromatography condition, and wherein a) figure is the impact of loading flow velocity on adsorption rate.B) figure is the impact of elution flow rate on eluting rate, therefrom distinguishes known best loading flow velocity and elution flow rate.Scheme c) for eluting solvent is on the impact of eluting rate, therefrom known best eluting solvent ratio.
Fig. 3 a) figure is Salanesol molecular imprinting preparative chromatography, for separating of preparative chromatography figure during tobacco leaf crude extract.Wherein dotted line is this preparative chromatography loading dead time of toluene measurement; Bold portion is the preparative chromatography figure of tobacco leaf crude extract, and first peak is its overload peak; Second platform is the elution peak of Salanesol solution.
Fig. 3 b) be elutriant in experiment, cross the liquid chromatogram of carrier fluid, Salanesol mark product and tobacco leaf crude extract.As seen from the figure, there is interference in tobacco leaf crude extract complicated component, and the method for this experiment foundation therefrom can be separated and obtains highly purified Salanesol near Salanesol.
Embodiment
Below by some embodiments, the invention will be further described, but the present invention is not only limited to example below.
(1) Salanesol liquid phase chromatogram condition is determined
Salanesol high-efficient liquid phase chromatogram condition: chromatographic column and model PRONTOSIL300-5-C8 – SH (4.6 × 250mm, 5 μm); Moving phase is methanol/water (98/2, v/v); Flow velocity is 1ml/min, and column temperature is 25 DEG C; Sample size is 10 μ l; Ultraviolet detection wavelength is 210nm.Compound concentration is respectively 0.01,0.05,0.1,0.5,1, the Salanesol methyl alcohol standardized solution of 2mM, carry out high performance liquid chromatography (see Figure of description 3b) in order to upper chromatographic condition to detect, with peak area drawing standard curve corresponding to concentration for y=3 × 106x+104731, linearly dependent coefficient R
2=0.9988, good in this 0.01-2.0mM scope internal linear relation.
(2) preparation of Salanesol imprinted polymer
For preparing the good imprinted polymer of sphericity, the preparation of Salanesol molecularly imprinted polymer adopts suspension polymerization, and process is divided into the preparation of organic phase and aqueous phase.Through test recipe optimization (prioritization scheme is in table 1), MIP
3preparation process as follows, template, monomer, linking agent are mixed ultrasonic dissolution in organic solvent, then add initiator ultrasonic dissolution, pass into rare gas element and get rid of air in liquid; The preparation of aqueous phase: by surfactant dissolves in ultrapure water, and pass into the air in rare gas element eliminating liquid.After quarter-phase system is standby, by organic phase under mechanical stirring, is slowly added drop-wise in aqueous phase, is polymerized under the condition of protection of inert gas under certain temperature, reaction terminates rear filtration and obtains the Salanesol imprinted polymer that imprinting factor is 3.9.The preparation of non-imprinted polymer (NonimprintedPolymers, NIPs) except not adding template molecule, the same MIPs of preparation method.
Table 1
Table 1 is the formula of Salanesol four kinds of imprinted polymers, and adsorption rate, eluting rate and imprinting factor corresponding in Solid-Phase Extraction experiment.As shown in Table 1, the adsorption rate of MIP3 to Salanesol is the highest, and has the highest imprinting factor, therefore selects MIP3 to be polymkeric substance in subsequent experimental.
(3) absorption of Salanesol molecularly imprinted polymer and morphology characterization
The absorption representation of Salanesol MIPs: utilize molecular engram solid phase extraction to test to Salanesol trace and non-imprinted polymer to the dynamic adsorption of Salanesol, for follow-up preparative chromatography application lays the foundation.The preparation method of Salanesol molecularly imprinted polymer solid-phase extraction column is as follows: 25g polymkeric substance is closely placed in solid-phase extraction column, activates with organic solvent.Loading subsequently, with the non-adsorbent of organic solvent drip washing after sample drains off, and collect leacheate with dry centrifuge tube, after waiting it to drain off, use eluting solvent wash-out, and collect elutriant with dry centrifuge tube, after it drains off, leacheate and elutriant are dried up with Nitrogen evaporator at 35 DEG C, uses organic solvent constant volume, after ultrasonic dissolution, detect its concentration with high performance liquid chromatography.After three groups of parallel laboratory tests, measure and calculate eluting rate, adsorption rate, relative standard deviation (RSD) (Adsorption experimental results is shown in accompanying drawing table 1).Experimental result shows as polymkeric substance MIP
3the highest to the adsorption rate of Salanesol, and there is the highest imprinting factor, refer to MIP with MIPs in subsequent experimental
3.
The morphology characterization of Salanesol MIPs: by scanning electron microscope (SEM) to Salanesol polymkeric substance (MIP
3) pattern characterize.Electronic Speculum figure (see accompanying drawing 1) Salanesol imprinted polymer and non-imprinted polymer all have good sphericity, and particle size range is 250-350 μm, and the non-imprinted polymer of imprinted polymer surface ratio is coarse.Carried out BET specific surface area test to polymkeric substance in addition, test condition is as follows, and select heating-vacuumize degassing pattern, 50 DEG C of degassed 60min, nitrogen adsorption at 25 DEG C, saturated vapor pressure is 1.1140bar.BET result shows, Salanesol MIPs specific surface area is 136.5m
2g
-1, pore volume is 0.18mlg
-1, mean pore size is 5.4nm.
(4) adsorption solvent is on the impact of imprinted polymer adsorption rate
By the polymkeric substance filling solid-phase extraction column prepared.Prepare finite concentration Salanesol different solvents standardized solution respectively as sample solution to be separated, carry out Solid-Phase Extraction experiment, to determine suitable loading solvent, when testing sample is methanol solution, its Solid-Phase Extraction adsorption rate is 34% to the maximum.The solvent that adsorption selection rate is maximum is thus as the loading solvent of subsequent experimental.
(5) preparation of molecular imprinting preparative chromatography post
Bottom Flash void column pipe, seal up the polyethylene sieve plate in 20 μm of apertures, and filter membrane (0.22 μm) is placed in the middle of two-layer sieve plate, play a role in filtering.Accurately take a certain amount of MIPs (25g) slowly to load in Flash post, compress, flatten, one deck sieve plate is added by polymkeric substance compacting on filler top, ensure that MIPs is uniformly distributed in post, non-leakage, do not ftracture, and the molecular imprinting column prepared (MIPs-Flashcolumn) to be connected in preparative chromatography.
(6) determination in molecular imprinting preparative chromatography post dead time
The molecular imprinting preparative chromatography post prepared is connected in preparative chromatography, first with methyl alcohol activation, guarantees that the filler (polymkeric substance) in chromatographic column obtains uniform wet, complete activation.Adopt adsorption rate (amount) in this experiment to carry out the evaluation of extraction efficiency, calculate the dead time (or dead volume) that above data need to record Flash post.Because toluene is not adsorbed by imprinted polymer, so select toluene to measure the dead time of chromatographic column, the breakthrough time of toluene is the dead time of MIPs-Flash post.Chromatographic condition in this experiment is as follows, and determined wavelength is 210nm, moving phase: toluene (color atlas is shown in that Fig. 3 a)).
(7) optimization of molecular imprinting preparative chromatography chromatographic condition
In this experiment, the step of preparative chromatography experiment is divided into step; With methyl alcohol, chromatographic column is activated and pipeline balance, guarantee there is no bubble in the moistening of chromatographic column and system, until baseline punching is flat; Configure certain density Salanesol standardized solution, under certain flow rate, pump extracts loading certain volume.Organic solvent drip washing, washes away the impurity in sample to be separated, and not by the Salanesol molecule adsorbed; Switch eluting solvent wash-out 1h, with organic solvent, the eluent in system is washed down subsequently.
The optimization of wash-out and loading flow velocity: prepare certain density Salanesol standardized solution, with different loading speed pump loadings, use organic solvent drip washing certain hour subsequently, switch moving phase eluting solvent with different in flow rate wash-out same time, finally rinse certain hour with organic solvent, the eluting solvent in purging system.Respectively by adsorption rate and eluting rate evaluate loading flow velocity and elution flow rate (experimental result see Fig. 2 a) and Fig. 2 b)).
The optimization of eluting solvent ratio: prepare certain density Salanesol standardized solution, with different loading speed pump loadings, use organic solvent drip washing certain hour subsequently, the eluting solvent switching moving phase different ratios is with identical flow velocity wash-out equal time, finally rinse certain hour with organic solvent, eluting solvent in purging system, determines optimum proportion eluting solvent (experimental result is shown in Fig. 2 c) by eluting rate evaluation).Determined by experimental result, the best loading flow velocity of Salanesol molecular imprinting preparative chromatography and elution flow rate, best eluent ratio and ratio.
(8) loading capacity of Salanesol molecular imprinting preparative chromatography post
Prepare the Salanesol standardized solution of different concns respectively, with the flow velocity loading certain hour after optimization, switch moving phase eluting solvent wash-out 1h under certain flow rate, finally rinse certain hour with organic solvent, the eluting solvent in purging system, collect overload and elution fraction, detect with HPLC, and calculate the loading capacity of this molecular blotting column, determine the concentration loading with 10-100mM, it is saturated that this molecular imprinting preparative chromatography post can reach absorption.
(9) tobacco leaf pre-treatment
Extract is placed in apparatus,Soxhlet's, add certain volume organic solvent, be heated to 60-100 DEG C, extraction certain hour, leaves standstill and is cooled to room temperature, filter to obtain extraction liquid, extraction filter residue is continued with certain volume organic solvent, repeat aforesaid operations 3 times, merge and obtain crude extract, cross 0.22 μm of nylon leaching film stand-by.
(10) molecular imprinting preparative chromatography is utilized to extract Salanesol from tobacco leaf crude extract
The tobacco leaf extract organic solvent slightly carried is settled to finite concentration, to optimize rear flow velocity loading certain hour, switch the eluting solvent after moving phase optimization with the elution flow rate wash-out certain hour after optimization, finally rinse certain hour with organic solvent, eluting solvent in purging system, collect elution fraction (preparative chromatography figure is shown in that Fig. 3 a)), through rotary evaporation, obtain white solid.This solid is by liquid chromatography (liquid chromatogram is shown in Fig. 3 b)) and mass spectrum be defined as Salanesol further.
Through extracting, in 85min, this molecular imprinting preparative chromatography post (25g) can from the dry tobacco leaf of 66.8g, the Salanesol 1685.5mg that DNA purity is greater than 98%, and whole leaching process needs methyl alcohol 800ml, and can recycling after distillation.After measured, this molecular imprinting preparative chromatography post is after carrying out repeating experiment for 5 times, and its adsorption efficiency does not have obvious decline.
Claims (2)
1. the synthetic method of Salanesol molecularly imprinted polymer, is characterized in that concrete synthesis step is as follows:
(1) first template molecule, function monomer are dissolved in organic solvent, ultrasonic dissolution 10 minutes, place more than 12 hours at 25 DEG C, make solution pre-polymerization.Then in mixture, add linking agent and initiator, ultrasonic degas, more than filling with inert gas 15min with the oxygen in removing system, rear sealing.
Wherein the molar ratio of template molecule, function monomer and linking agent is 1:1:1 ~ 1:20:20; The quality of initiator is 0.5% ~ 2.0% of linking agent; 1mol template molecule adds 150 ~ 450ml non-polar organic solvent;
Described template molecule be following any one: Salanesol, inositol;
Described function monomer be following any one: 4-vinylphenylboronic acid, methacrylic acid, methyl methacrylate, to vinylbenzoic acid, p-ethyl-styrene, methylene-succinic acid, diacrylamine-2-methyl isophthalic acid-sulfonic acid, 1-vinyl imidazole, trifluoromethyl acrylate;
Described organic solvent be following any one: acetonitrile, DMF, dimethyl sulfoxide (DMSO), tetrahydrofuran (THF);
Described linking agent be following any one: trimethoxy oxypropyl trimethyl acrylate, ethyleneglycol dimethyacrylate, pentaerythritol triacrylate, trimethoxypropane gave, Viscoat 295, N, N '-methylene-bisacrylamide, Vinylstyrene, vinylbenzene;
Described initiator be following any one: Potassium Persulfate, azo-bis-iso-dimethyl, 2,2'-Azobis(2,4-dimethylvaleronitrile);
Described inert protective gas is nitrogen or argon gas.
(2) mixture obtained for the first step is gathered or polymerization more than 12 hours under hot polymerization condition at light, obtain molecularly imprinted polymer crude product, then with the methanol solution cleaning molecular engram material crude product containing formic acid or hydrochloric acid, the solid precipitation obtained is target product; The temperature of described hot polymerization condition is at 30 ~ 80 DEG C; In described formic acid or the methanol solution of hydrochloric acid, the volume ratio of formic acid or hydrochloric acid and methyl alcohol is 1:1 ~ 9.
2. the application of molecular cngram resin that obtains of synthetic method as claimed in claim 1, is characterized in that embody rule step is as follows:
(1) molecular imprinting (MIT) is combined with preparative chromatography, develop molecular imprinting preparative chromatography technology, possess the advantage of molecular imprinting and preparative chromatography technology; Polymerizing condition used, polymerization formula etc.
(2) by the optimization to Salanesol molecularly imprinted polymer formula, the polymer formulators to target compound adsorption efficiency the best is selected; By the optimization of the chromatographic condition to molecular imprinting preparative chromatography, obtain the optimal adsorption condition of chromatographic column; Actual sample tobacco leaf, after simple pre-treatment, is directly used in Salanesol molecular imprinting preparative chromatography and is separated, obtain Salanesol purity and be greater than 98%.
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| SE544779C2 (en) * | 2018-05-18 | 2022-11-15 | Henrik Kempe | Template-imprinted polymer particles |
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Cited By (3)
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| CN107383262A (en) * | 2017-07-28 | 2017-11-24 | 厦门大学 | A kind of preparation method of the porous adsorbent based on multifunctional monomer and crosslinking agent |
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Application publication date: 20160210 |