CN109880148A - A kind of preparation of surface imprinted material and its application in glutamic acid Chiral Separation - Google Patents
A kind of preparation of surface imprinted material and its application in glutamic acid Chiral Separation Download PDFInfo
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- CN109880148A CN109880148A CN201910057697.9A CN201910057697A CN109880148A CN 109880148 A CN109880148 A CN 109880148A CN 201910057697 A CN201910057697 A CN 201910057697A CN 109880148 A CN109880148 A CN 109880148A
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Abstract
The invention discloses a kind of preparation of surface imprinted material and its applications in glutamic acid Chiral Separation, implement the graft polymerization of function monomer sodium p styrene sulfonate in primary amine resin microsphere surface；Then the interaction of hydrogen bond between grafting macromolecular chain PSSS and acidic amino acid glutamate molecule is utilized, using surface imprinted method, in the chiral hole of primary amine resin microsphere surface building Pidolidone (L-Glu), imprinted material MIP-PSSS/PSA has been made in the molecular engram for implementing L-Glu;And imprinted material MIP-PSSS/PSA is deeply investigated to the evident characteristics of template molecule L-Glu and to the fractionation performance of glutamic acid racemic modification for control substance of plant drug with D-Glu (D-Glu).Imprinted material MIP-PSSS/PSA provided by the invention has good identification selection and binding affinity to template molecule L-Glu, while also having good desorption performance.
Description
Technical field
The present invention relates to a kind of preparation of surface imprinted material and its applications in glutamic acid Chiral Separation, belong to print
Mark Material Field.
Background technique
The molecularly imprinted polymer artificial synthesized for the first time of Wulff in 1972, with Wulff(WULFFG, SARHAN A.
Uber die anwendung von enzymanalog gebauten polymeren zur racem-attrennung
[J] Angew Chem, 1972,84 (8): 364-364.), Mosbach(Arshady R, Mosbach K. Synthesis
Of substrate-selective polymers by host-guest polymerization [J] Makromol
Chem, 1981,182:687-692.) etc. the innovation in covalent, non-covalent type, molecular engram have breakthrough progress.Point
Sub- imprinted polymer has many advantages that such as selectivity is strong, preparation is simple, environment tolerance is strong and practicability is extensive, therefore
Oneself is widely used in the fields such as chromatographic isolation, Solid Phase Extraction, sensor, drug release.But in terms of being applied to separation for amino acids
Report is few.The separation method of amino acid has chemical resolution method, crystallisation, enzyme process, membrane separation process and chromatography, and (including chirality is matched
Base exchange chromatography, high performance liquid chromatography, gas-chromatography and capillary electrophoresis etc.).The scope of application that these types of separation method has
It is narrow;Has plenty of cost costly;Some complex technical process;And some chromatographies, although selectivity is good and separation is imitated
Rate height (especially chiral ligands exchange chromatography), but it is all confined to analytical chemistry field, it still can not achieve quick, efficient, rule
The separation of modelling.Therefore, the efficient separating for realizing chiral enantiomer is an extremely challenging problem.
Molecular imprinting technology is selection target molecule as template molecule, the functionalization in structure with complementation
Polymer monomer is combined by covalent or non-covalent bond with template molecule, and crosslinking agent is then added and carries out cross-linking reaction, reaction
After template molecule elution is come out, leave it is a kind of with fixed cavitation shapes and sizes have stationary arrangement functional group friendship
Join high polymer.Molecular imprinted polymer on surface has special binding affinity and identification selection to template molecule.By people
The specific recognition material of biological acceptor can referred to as be simulated.This research attempts to introduce the novel surface molecule print technology
The molecular engram of amino acid constructs chiral hole on matrix particles surface, high-performance solid extracting agent is prepared, in molecule structure
The efficient separating to amino acid enantiomer is realized in type level.
Summary of the invention
The present invention is intended to provide a kind of preparation of surface imprinted material and its application in glutamic acid Chiral Separation, are adopted
The imprinted material MIP-PSSS/PSA prepared with molecular surface engram technology has apparent identification selection to L-Glu, is expected to
As solid extracting agent, effective fractionation of glutamic acid enantiomer is realized.
The present invention uses " picking out " method, and poly (sodium 4-styrenesulfonate) (SSS) is grafted on primary amine resin microsphere surface, prepares
Grafting particle MIP-SSS/PSA, using a kind of enantiomer L-Glu of glutamic acid as template molecule, N, N '-methylene bisacrylamide
Amide (MBA) uses novel surface molecular imprinting technology as crosslinking agent, implements L-Glu in the Silica Surface for being grafted with PSSS
Surface molecule print.Obtained surface imprinted material MIP-SSS/PSA, due to being distributed in the polymer foil on its surface
The chiral imprinted cavity of a large amount of L-Glu, thus to the L-Glu apparent identification selection having and good binding affinity；
These chiral holes in terms of space structure and action site with another enantiomer D-Glu due to mismatching, thus to D-Glu
Binding ability it is poor, binding capacity is low.For the racemic modification solution of two kinds of enantiomers, MIP-SSS/PSA shows good
Split performance.Since the trace hole of MIP-SSS/PSA is distributed in the polymer film of microparticle surfaces, cause to combine in hole
L-Glu elution property it is good, be conducive to the regeneration and reuse of imprinted material.
The present invention provides a kind of preparation methods of surface imprinted material, in solution polymerization system, using " picking out " method
Function monomer sodium p styrene sulfonate (SSS) is grafted on into primary amine resin microsphere surface, function grafting particle PSSS/ has been made
PSA, using the surface imprinted technology of novel molecular, using a kind of enantiomer L-Glu of glutamic acid (Glu) as template molecule, N, N '-are sub-
Bisacrylamide (MBA) is used as crosslinking agent, implements molecule to the macromolecular PSSS for being grafted on primary amine resin microsphere surface
Trace is prepared for L-Glu molecular surface engram material MIP-PSSS/PSA.It is pair with another enantiomer D-Glu of glutamic acid
Than object, MIP-PSSS/PSA is had extensively studied to the recognition performance of L-Glu molecule with two methods of dynamic using static, emphasis is visited
The feasibility that rope splits amino acid enantiomer using molecular surface engram material.
The preparation method of above-mentioned surface imprinted material, comprising the following steps:
(1) activation processing of polystyrene primary amine resin microballoon:
50mL-100mLN, dinethylformamide solution, at 20-30 DEG C is added in 20g-40g dry primary amine resin microballoon
At a temperature of impregnate 12-14 hours after filter, be put into vacuum drying oven and be dried, can be by primary amine resin microsphere surface ammonia
Base activation；
(2) in primary amine resin microsphere surface graft polymerization sodium p styrene sulfonate:
The 0.1g-0.3g primary amine resin microballoon activated is added in four-hole boiling flask, and 40mL-45mL solvent, 0.2500- is added
0.3500gSSS, logical nitrogen 20-40min start to be heated up with water-bath agitating and heating, and 0.04- is added after temperature reaches 50 DEG C
0.08g initiator ammonium persulfate starts to react；6-10h uses the repeated multiple times washing of distilled water after reaction, then with distillation water logging
It is filtered after bubble 22-26h, 22-26h then is dried at 40-60 DEG C of vacuum drying oven, grafting particle PSSS/PSA is made；
(3) molecular surface engram material MIP-PSSS/PSA is prepared:
Using the method for " be graft-polymerized carry out synchronous with crosslinking trace ", implement the surface of Pidolidone molecule in non-aqueous media
Trace: 0.3-0.5g monomer SSS and 0.005-0.02g template molecule glutamic acid is dissolved in 70mL solvent, its phase interaction is made
After 6-10h, move into the four-hole boiling flask equipped with reflux condensing tube, blender and thermometer；The modified primary amine resin of 1-3g is added
Ball PSA adds 0.1-0.2g initiator ammonium persulfate, 0.1-0.2g crosslinking agent MBA, stirs and leads to nitrogen 20-
On the one hand 40min excludes the air in reaction system, on the other hand make anionic monomer SSS and glutamic acid point in system
Son is sufficiently had an effect between each other；It is warming up to 50 DEG C and makes to be graft-polymerized under agitation and carry out 4-8h with cross-linking reaction；
After reaction, it filters while hot, the multiple washing by soaking trace microballoon of NaCl solution for being then 2 mol/L with concentration, with de-
Removing template molecule is dried under vacuum to constant weight to get trace microballoon MIP-PSSS/PSA.
Space structure is left in polymer MIP-PSSS/PSA obtained in above-mentioned preparation process can be with Pidolidone point
The three-dimensional hole that the space structure of son matches, these holes can only allow Pidolidone to enter, so utilizing the imprinted material
Identification selection absorption can be carried out to Pidolidone, the glutamic acid of mixed is split to reach.
In above-mentioned preparation method, in step (2), the solvent is the mixed solvent of first alcohol and water, and the volume ratio of the two is
5:1-5:3。
In above-mentioned preparation method, in step (2), when with distilled water immersion, 40-50mL distilled water is replaced every 4-6h.
In above-mentioned preparation method, the dosage of SSS is the 0.4-0.8% of all total mass of raw materiales；The use of initiator ammonium persulfate
Amount is the 20-22% of monomer mass.
The present invention provides using surface imprinted material made from above-mentioned preparation method.
The present invention provides application of the surface imprinted material in glutamic acid Chiral Separation.
In order to further investigate imprinted material to the evident characteristics of L-Glu, MIP-PSSS/PSA has been carried out to L-Glu and D-
The competitive adsorption of Glu is tested: compound concentration is L-Glu and D-Glu binary mixed solution (the i.e. racemic of 0.1 g/L
Liquid solution, optical activity zero), it takes 50 mL mixed solutions in stuffed conical flask, adds the trace microparticle material MIP- of 0.03 g
PSSS/PSA vibrates 2.5 h in constant temperature oscillator, so that absorption is reached balance, settle and separate is measured using spectrophotometry
The overall balance concentration of clear liquid Glutamic Acid, and with polarimeter measurement supernatant optical activity and specific rotatory power.Measurement discovery, this
When supernatant be provided with optical activity, optical direction is identical as D-Glu.This result shows that MIP-PSSS/PSA to racemic modification
L-Glu in solution has more absorption, i.e., produces fractionation effect to two kinds of enantiomers.It is calculated again with formula (1) molten
Then the equilibrium concentration of L-Glu and D-Glu in liquid presses formula (2), calculate the distribution coefficient of L-Glu and D-Glu.
(1)
In formula (1), CD, e(g/L) and CL, e(g/L) be respectively two enantiomers in supernatant equilibrium concentration;[α] is supernatant
The specific rotatory power of liquid;[α]D, markFor the standard specific rotatory power of enantiomer D-Glu;CE, always(g/L) dense for the overall balance of supernatant
Degree;
(2)
In formula, Kd(mL•g-1) be a certain enantiomer distribution coefficient; Ce (mg•mL-1) be the enantiomer in supernatant balance
Concentration; Qe (mg•g-1) be the enantiomer balance binding capacity.
Trace microparticle material MIP- is calculated according to formula (3) by the distribution coefficient data of two kinds of enantiomers in solution
Selectivity factor of the PSSS/PSA to L-Glu.
(3)
In formula, k is selectivity factor of the imprinted material MIP-PSSS/PSA to L-Glu for enantiomer D-Glu, k
The size of value indicates imprinted material MIP-PSSS/PSA to the identification selection of L-Glu.
Beneficial effects of the present invention:
(1) imprinted material MIP-PSSS/PSA has good identification selection and binding affinity, phase to template molecule L-Glu
For D-Glu, identification selection property coefficient is 3.97, shows good fractionation performance；
(2) imprinted material MIP-PSSS/PSA also has good desorption performance, using dilute NaOH aqueous solution as eluent, 13
Desorption efficiency can reach 98.62% in bed volume；
(3) since the trace hole of MIP-SSS/PSA is distributed in the polymer film of microparticle surfaces, cause to combine in hole
L-Glu elution property is good, is conducive to the regeneration and reuse of imprinted material.
Detailed description of the invention
Fig. 1 is the chemical reaction process schematic diagram that embodiment 1 prepares L-Glu imprinted material MIP-PSSS/PSA.
The infrared spectrogram for the MIP-PSSS/PSA that Fig. 2 is PSA and PSSS/PSA and prepared by embodiment 1.
Fig. 3 is imprinted material MIP-PSSS/PSA in embodiment 2 to the isothermal bonding wire of two kinds of enantiomers.
Fig. 4 is non-imprinted material PSSS/PSA in embodiment 2 to the isothermal bonding wire of two kinds of enantiomers.
Fig. 5 is non-imprinted material PSSS/PSA in embodiment 2 to the Dynamic Adsorption curve of glutamic acid enantiomer.
Fig. 6 is imprinted material MIP-PSSS/PSA in embodiment 2 to the dynamic bind curve of glutamic acid enantiomer.
Fig. 7 is elution curve in embodiment 4.
Specific embodiment
The present invention is further illustrated below by embodiment, but is not limited to following embodiment.
Primary amine resin of the invention has sulphur after being grafted again with sodium p styrene sulfonate (SSS) after being modified
Acid function group.During being crosslinked trace, due to existing between the oxygen atom on the hydroxyl of sulfonate radical and amino and glutamic acid
Hydrogen bonding interaction, therefore the binding site with specific binding performance can be formed.After washing away template molecule, it is polymerizeing
The three-dimensional hole that space structure can match with the space structure of Pidolidone molecule is left in object, forms L-Glu molecule
Surface imprinted material MIP-PSSS/PSA.
Embodiment 1: molecular surface engram material MIP-PSSS/PSA is prepared
Preparation process specifically includes the following steps:
(1) activation processing of polystyrene primary amine resin microballoon:
The n,N-Dimethylformamide solution of 100mL is added in the primary amine resin microballoon of the drying of 30g, is soaked at a temperature of 30 DEG C
It is filtered after bubble 12h, is put into vacuum drying oven and is dried, it can be by primary amine resin microsphere surface amino-reactive；
(2) in primary amine resin microsphere surface graft polymerization sodium p styrene sulfonate:
The 0.2g primary amine resin microballoon activated is added in four-hole boiling flask, and 42mL solvent (V is addedMethanol: VWater=5:2),
0.2887g (the 0.6235% of gross mass) SSS, logical nitrogen 30min starts to be heated up with water-bath agitating and heating, when temperature reaches 50
0.0600g initiator ammonium persulfate (the 20.78% of monomer mass) is added after DEG C to start to react；8h uses distilled water after reaction
Repeated multiple times washing, then (constantly change water) for 24 hours with distilled water immersion and filter afterwards, it is then dried with vacuum drying oven, temperature is
50 DEG C, for 24 hours, grafting particle PSSS/PSA is made in drying.
It uses the grafting amount of determination of acid-basetitration grafting particle: with the salt acid soak PSSS/PSA 8h of certain volume, making
It after hydrochloric acid is sufficiently reacted with the amino of primary amine resin ball surface, then is gone to titrate remaining hydrochloric acid with the NaOH of standard, passes through formula
Calculate the grafting degree of PSSS/PSA.It is 120mg/g that grafting amount can be made under the program.
(3) molecular surface engram material MIP-PSSS/PSA is prepared:
Using the method for " be graft-polymerized carry out synchronous with crosslinking trace ", implement the surface of Pidolidone molecule in non-aqueous media
Trace: 0.5232 monomer SSS and 0.01g template molecule glutamic acid is dissolved in 70mL solvent, makes its 6- that interacts
After 10h, move into the four-hole boiling flask equipped with reflux condensing tube, blender and thermometer；The modified primary amine resin ball of 1.2g is added
PSA adds 0.136 g initiator ammonium persulfate, 0.1565g crosslinking agent MBA, stirs and lead to nitrogen 30min, on the one hand
The air in reaction system is excluded, fills the anionic monomer SSS in system between each other with glutamate molecule
Divide and has an effect；It is warming up to 50 DEG C and makes to be graft-polymerized under agitation and carry out 6h with cross-linking reaction；After reaction, while hot
Filtering, the multiple washing by soaking trace microballoon of NaCl solution for being then 2 mol/L with concentration are dry to remove template molecule vacuum
It is dry to constant weight to get trace microballoon MIP-PSSS/PSA.
Preparation process principle is as shown in Figure 1.
Its infrared spectroscopy is measured with KBr pressed disc method, confirms its structure change.Infrared spectrogram is as shown in Figure 2.From spectrogram
In as can be seen that 1650cm-1There is the characteristic absorption peak of double bond at place, illustrates that substrate fails fully reacting, 3400cm-1Place is NH2's
Stretching vibration peak, 3750cm-1It is the stretching vibration peak of N-H, 1678cm-1Place is the stretching vibration absworption peak of amidocarbonylation,
1576cm-1Place is that the in-plane bending of amide N-H absorbs vibration peak, the two peaks carry out the MBA in self-cross-linking copolymers;1460cm-1
And 1410cm-1Place is respectively the characteristic absorption peak of methylene and methine, illustrates that the double bond in primary amine ball and monomer SSS has occurred
Polyaddition reaction, and 1190cm-1There is sulfonic group-SO at place3-Characteristic absorption peak obviously reinforce, illustrate that monomer successfully connects
Branch has arrived primary amine microsphere surface.
Embodiment 2: MIP-PSSS/PSA is investigated to the recognition performance of two kinds of enantiomers L-Glu and D-Glu
1, the measurement of isothermal binding performance
Two methods of static and dynamic are respectively adopted, measure surface imprinted material MIP-PSSS/PSA to two kinds of enantiomers of glutamic acid
Binding performance.Equally, first binding kinetics behavior of the measurement MIP-PSSS/PSA to L-Glu and D-Glu, determines that combination reaches
The time (also near 2h) of balance is combined the measurement of performance on this basis.
(1) static method: under 30 DEG C of steady temperature, 50 mL concentration series are changed from 0.03~0.30 g/L's
L-Glu solution is respectively placed in several stuffed conical flasks, and the trace microparticle material MIP- of about 0.03 g of precise is added
PSSS/PSA vibrates 2h in constant temperature oscillator, makes in conjunction with balance is reached, and stratification takes supernatant, uses according to formula (1)
Spectrophotometry measures the equilibrium concentration of L-Glu in supernatant, according to formula (4), calculates MIP-PSSS/PSA and puts down to L-Glu
Weigh binding capacity Qe(mg/g), and balance binding capacity is drawn to equilibrium concentration relation curve, i.e. isothermal binding curve.
(4)
C in formula (4)0(g/L), CeIt (g/L) is respectively the concentration for adsorbing L-Glu in the solution of front and back；V (mL) is adsorption liquid
Volume;M (g) is the quality of imprinted material MIP-PSSS/PSA.According to same method, L-Glu molecular engram material is measured
MIP-PSSS/PSA draws isothermal binding curve to the balance binding capacity of another enantiomer D-Glu.
(2) dynamic method: being mounted in internal diameter under room temperature, after the MIP-SSS/PSA of 1.5 g is swollen in water is 10 mm
Glass tube in, make packed column bed volume (Bed Volume, BV) be 2 mL.Make the L-Glu solution of 0.1 g/L of concentration with
4 BV•h-1Flow velocity adverse current pass through packed column, efflux is collected with the interval of 1 BV, measures the concentration of L-Glu in efflux,
Dynamic bind curve is drawn, and using the concentration and bed body product of efflux, calculates MIP-PSSS/PSA to the leakage knot of L-Glu
Resultant and saturation binding capacity.Using same method, the dynamic bind curve that measures and draw imprinted material MIP-SSS/PSA to D-Glu.
2, the evident characteristics of MIP-PSSS/PSA and the binding performance to two kinds of enantiomers
In conjunction with thermoisopleth and dynamic bind curve
Using static (batch method) and dynamic (columnmethod) two methods, respectively using grafting microparticle material
MIP-PSSS/PSA and L-Glu molecular engram material MIP-PSSS/PSA, to two kinds of enantiomers L-Glu and D- in aqueous medium
Glu has carried out adsorption isotherm experiment.
It is learnt by Fig. 3,4, non-trace particle NMIP-PSSS/PSA is to glutamic acid (D-Glu and Pidolidone) enantiomer
The suction-operated of equal extent is generated, adsorption capacity is up to 120mg/g, shows non-imprinted material NMIP-PSSS/PSA to D- paddy
Propylhomoserin and Pidolidone do not have identification selection.The enantiomer of chipal compounds has identical chemical formula and physico
Property is learned, only optical activity is different.So two kinds of glutamic acid enantiomers all can be with big point in non-imprinted material NMIP-PSSS/PSA
Hydrogen bond is formed between subchain PSSS, makes non-imprinted material that there is stronger adsorption capacity to D-Glu and Pidolidone, not
Adsorptive selectivity.And imprinted material MIP-PSSS/PSA to the suction-operated of D-Glu compare Pidolidone it is strong very much.L-
The adsorbance of glutamic acid is reduced to 48mg/g or so by the 120mg/g in right figure, and D-Glu still maintains high adsorbance, greatly
About 120mg/g.This variation illustrates the surface imprinted material MIP-PSSS/PSA of this experiment preparation to template molecule L- paddy
Propylhomoserin has good binding ability and identification selection, and very weak to the binding ability of D-Glu molecule.This is because trace
A large amount of Pidolidone imprinted cavity is distributed in the surface polymer thin layer of material MIP-PSSS/PSA, these chiral holes with
Pidolidone molecule matched in terms of space structure and action site, therefore, imprinted material MIP-PSSS/PSA is to template
Molecule L-glutamic acid has special chiral recognition, forms strong combination power, to generate high adsorption capacity.But
These chiral holes and D-Glu molecule mismatch.It is very difficult to make it into hole, causes MIP-PSSS/PSA to D- paddy
The adsorbance of propylhomoserin is very low.In short, passing through Staticadsorption experiment, it was demonstrated that surface imprinted material MIP-PSSS/PSA is to template molecule
Pidolidone has good chiral recognition.
Fig. 5 gives non-mark material PSSS/PSA to the Dynamic Adsorption curve of two kinds of enantiomers of glutamic acid, and Fig. 6 is shown
Dynamic bind curve of the L-Glu molecular engram material MIP-PSSS/PSA to two kinds of enantiomer molecules.As shown in Figure 5, for
PSSS/PSA packed column, when two kinds of mapping liquid solutions are with when the flow velocity of 4 BV/h countercurrently passes through packed column respectively, breakthrough curve is complete
It is exactly the same；Two kinds of solution start to leak in 29 BV；But see from Fig. 6, for MIP-PSSS/PSA packed column, L-Glu
The leakage curve of solution differs markedly from the leakage curve of D-Glu solution: (1) D-Glu solution starts to reveal in 25 BV, and
The leakage volume of L-Glu solution is 38 BV, differs 13BV；(2) D-Glu solution is worn in 40BV complete penetration, L-Glu solution
Saturating volume is 55BV；The fact that above-mentioned dynamic experiment, again shows that MIP-SSS/PSA shows apparent identification to L-Glu
Selective and excellent binding affinity, it is in comparison, then weaker to the identification and binding ability of D-Glu.
Embodiment 3: in conjunction with selective experiment (Chiral Separation experiment)
In order to further investigate imprinted material to the evident characteristics of L-Glu, MIP-PSSS/PSA has been carried out to L-Glu and D-Glu
Competitive adsorption experiment: compound concentration is that (i.e. racemic modification is molten for L-Glu and D-Glu the binary mixed solution of 0.1 g/L
Liquid, optical activity zero), it takes 50 mL mixed solutions in stuffed conical flask, adds the trace microparticle material MIP-PSSS/ of 0.03 g
PSA vibrates 2.5 h in constant temperature oscillator, and absorption is made to reach balance, and settle and separate measures supernatant using spectrophotometry
The overall balance concentration of Glutamic Acid, and with polarimeter measurement supernatant optical activity and specific rotatory power.Measurement discovery, at this time on
Clear liquid is provided with optical activity, and optical direction is identical as D-Glu.This result shows that MIP-PSSS/PSA to racemic modification solution
In L-Glu there are more absorption, i.e., fractionation effect is produced to two kinds of enantiomers.It is calculated in solution with formula (1) again
Then the equilibrium concentration of L-Glu and D-Glu presses formula (2), calculate the distribution coefficient of L-Glu and D-Glu.
(1)
In formula (1), CD, e(g/L) and CL, e(g/L) be respectively two enantiomers in supernatant equilibrium concentration;[α] is supernatant
The specific rotatory power of liquid;[α]D, markFor the standard specific rotatory power of enantiomer D-Glu;CE, always(g/L) dense for the overall balance of supernatant
Degree;
(2)
In formula, Kd(mL•g-1) be a certain enantiomer distribution coefficient; Ce (mg•mL-1) be the enantiomer in supernatant balance
Concentration; Qe (mg•g-1) be the enantiomer balance binding capacity.
Trace microparticle material MIP- is calculated according to formula (3) by the distribution coefficient data of two kinds of enantiomers in solution
Selectivity factor of the PSSS/PSA to L-Glu.
(3)
In formula, k is selectivity factor of the imprinted material MIP-PSSS/PSA to L-Glu for enantiomer D-Glu, k
The size of value indicates imprinted material MIP-PSSS/PSA to the identification selection of L-Glu.
Selectivity factor of the MIP-SSS/PSA to template enantiomer molecule and the fractionation performance to racemic modification:
L-Glu Binary Mixtures (i.e. racemic modification solution) identical with D-Glu concentration are prepared, imprinted material MIP- is used
SSS/PSA has carried out competitive Adsorption experiment.Table 1 lists the distribution coefficient K of two kinds of substancesdWith MIP-SSS/PSA to template pair
Reflect the selectivity factor k of body L-Glu.
The distribution coefficient and selection coefficient table of 1 two kinds of amino acid of table
From the data of table 1 it can be found that relative to D-Glu, imprinted material MIP-SSS/PSA is to the selectivity factor of L-Glu
3.97, show that there is apparent identification selection to L-Glu.Obviously, above-mentioned competitive experimental data also sufficiently discloses trace
Material MIP-SSS/PSA has apparent fractionation ability to two kinds of enantiomers of glutamic acid.
When temperature is 30 DEG C, MIP-PSSS/PSA is maximum to the selectivity factor of Pidolidone molecule.With trace temperature
Degree increases, and selectivity factor becomes larger；Temperature reaches maximum 8.1 when reaching 30 DEG C；And as temperature continues to rise, selectivity is
Number declines instead.
When the ratio between monomer SSS and crosslinking agent MBA are 5:1, selectivity of the MIP-PSSS/PSA to Pidolidone molecule
Coefficient reaches maximum 7.8.
When template molecule Pidolidone and monomer SSS with the ratio between be 250:1 when, MIP-PSSS/PSA is to template molecule
Selectivity factor k value reaches maximum 7.8.
L-Glu Binary Mixtures (i.e. racemic modification solution) identical with D-Glu concentration are prepared, imprinted material is used
MIP-SSS/PSA has carried out competitive Adsorption experiment.Relative to D-Glu, selectivity of the imprinted material MIP-SSS/PSA to L-Glu
Coefficient is 3.97, shows there is apparent identification selection to L-Glu.Obviously, above-mentioned competitive experimental data also sufficiently discloses
Having gone out imprinted material MIP-SSS/PSA has apparent fractionation ability to two kinds of enantiomers of glutamic acid.
Embodiment 4: the investigation of elution property
The imprinted material MIP-PSSS/PSA filling dress column for being saturated absorption L-Glu for being 1.1 g by quality, in room temperature condition
Under, use the sodium hydroxide that concentration is 0.1 mol/L as eluent, with 4 BV h-1Flow velocity adverse current pass through packed column, carry out
Desorption experiment collects eluate with the interval of 1 BV, measures the concentration of L-Glu in eluate, draw desorption curve, investigates
The elution property of imprinted material MIP-PSSS/PSA.
It uses the sodium hydroxide that concentration is 0. 1 mol/L as eluent, the print of L-Glu is upstream adsorbed by being saturated
Mark material MIP-PSSS/PSA packed column, dynamic analysis curve are as shown in Figure 7.
As seen from Figure 7, desorption curve is computed sharply without hangover, and desorption efficiency reaches 97.23% in 11 bed volumes,
Desorption efficiency can reach 98.62% in 13 bed volumes.Above-mentioned experimental data, which absolutely proves, is bonded to imprinted material MIP-
L-Glu molecule in the hole PSSS/PSA due to being distributed in the polymer foil of primary amine resin microsphere surface, thus has excellent
Good desorption performance, be conducive to the regeneration of extraction column with reuse.
Claims (9)
1. a kind of preparation method of surface imprinted material, it is characterised in that: in solution polymerization system, using picking out method for function
Monomer sodium p styrene sulfonate SSS grafts on primary amine resin microsphere surface, function grafting particle PSSS/PSA has been made, using new
Type molecular surface engram technology, using a kind of enantiomer L-Glu of glutamic acid Glu as template molecule, N, N '-methylene bisacrylamide acyl
Amine MBA implements molecular engram as crosslinking agent, to the macromolecular PSSS for being grafted on primary amine resin microsphere surface, is prepared for L-
Glu molecular surface engram material MIP-PSSS/PSA.
2. the preparation method of surface imprinted material according to claim 1, it is characterised in that: the following steps are included:
(1) activation processing of polystyrene primary amine resin microballoon:
50mL-100mLN, dinethylformamide solution, at 20-30 DEG C is added in 20g-40g dry primary amine resin microballoon
At a temperature of impregnate 12-14 hours after filter, be put into vacuum drying oven and be dried, can be by primary amine resin microsphere surface ammonia
Base activation；
(2) in primary amine resin microsphere surface graft polymerization sodium p styrene sulfonate:
The 0.1g-0.3g primary amine resin microballoon activated is added in four-hole boiling flask, and 40mL-45mL solvent, 0.2500- is added
0.3500gSSS, logical nitrogen 20-40min start to be heated up with water-bath agitating and heating, and 0.04- is added after temperature reaches 50 DEG C
0.08g initiator ammonium persulfate starts to react；6-10h uses the repeated multiple times washing of distilled water after reaction, then with distillation water logging
It is filtered after bubble 22-26h, 22-26h then is dried at 40-60 DEG C of vacuum drying oven, grafting particle PSSS/PSA is made；
(3) molecular surface engram material MIP-PSSS/PSA is prepared:
Using the method for " be graft-polymerized carry out synchronous with crosslinking trace ", implement the surface of Pidolidone molecule in non-aqueous media
Trace: 0.3-0.5g monomer SSS and 0.005-0.02g template molecule glutamic acid is dissolved in 70mL solvent, its phase interaction is made
After 6-10h, move into the four-hole boiling flask equipped with reflux condensing tube, blender and thermometer；The modified primary amine resin of 1-3g is added
Ball PSA adds 0.1-0.2g initiator ammonium persulfate, 0.1-0.2g crosslinking agent MBA, stirs and leads to nitrogen 20-
On the one hand 40min excludes the air in reaction system, on the other hand make anionic monomer SSS and glutamic acid point in system
Son is sufficiently had an effect between each other；It is warming up to 50 DEG C and makes to be graft-polymerized under agitation and carry out 4-8h with cross-linking reaction；
After reaction, it filters while hot, the multiple washing by soaking trace microballoon of NaCl solution for being then 2 mol/L with concentration, with de-
Removing template molecule is dried under vacuum to constant weight to get trace microballoon MIP-PSSS/PSA.
3. the preparation method of anionic PSSS/PSA microballoon according to claim 2, it is characterised in that: step (2) and
(3) in, the solvent is the mixed solvent of first alcohol and water, and the volume ratio of the two is 5:1-5:3.
4. the preparation method of anionic PSSS/PSA microballoon according to claim 2, it is characterised in that: in step (2),
When with distilled water immersion, 40-50mL distilled water is replaced every 4-6h.
5. the preparation method of anionic PSSS/PSA microballoon according to claim 2, it is characterised in that: the dosage of SSS
For the 0.4-0.8% of all total mass of raw materiales；The dosage of initiator ammonium persulfate is the 20-22% of monomer mass.
6. surface imprinted material made from a kind of described in any item preparation methods of claim 1 ~ 5.
7. a kind of application of surface imprinted material as claimed in claim 6 in glutamic acid Chiral Separation.
8. application according to claim 7, it is characterised in that: compound concentration is the L-Glu and D-Glu bis- of 0.1 g/L
First mixed solution takes 50 mL mixed solutions in stuffed conical flask, adds the trace microparticle material MIP-PSSS/PSA of 0.03 g,
2.5 h are vibrated in constant temperature oscillator, and absorption is made to reach balance, settle and separate, using paddy in spectrophotometry measurement supernatant
The overall balance concentration of propylhomoserin, and with polarimeter measurement supernatant optical activity and specific rotatory power；Show that MIP-PSSS/PSA is external
L-Glu in racemization liquid solution has more absorption, i.e., produces fractionation effect to two kinds of enantiomers.
9. application according to claim 8, it is characterised in that: in the application, the distribution coefficient of L-Glu and D-Glu meet
Following relationship:
In formula, k is selectivity factor of the imprinted material MIP-PSSS/PSA to L-Glu for enantiomer D-Glu, k
The size of value indicates imprinted material MIP-PSSS/PSA to the identification selection of L-Glu；In above formula:
Wherein, Kd(mL•g-1) be a certain enantiomer distribution coefficient；Ce (mg•mL-1) be the enantiomer in supernatant balance
Concentration； Qe (mg•g-1) be the enantiomer balance binding capacity.
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