CN102993209A - Method for separating camptothecin by use of molecular imprinting-matrix solid-phase dispersion technology - Google Patents

Method for separating camptothecin by use of molecular imprinting-matrix solid-phase dispersion technology Download PDF

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CN102993209A
CN102993209A CN2012105403508A CN201210540350A CN102993209A CN 102993209 A CN102993209 A CN 102993209A CN 2012105403508 A CN2012105403508 A CN 2012105403508A CN 201210540350 A CN201210540350 A CN 201210540350A CN 102993209 A CN102993209 A CN 102993209A
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imprinted polymer
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phase dispersion
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CN102993209B (en
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陈立钢
洪言锁
李斌
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Northeast Forestry University
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Abstract

The invention discloses a method for separating camptothecin by use of a molecular imprinting-matrix solid-phase dispersion technology, relates to a camptothecin separation method and aims at solving the problems that the existing camptothecin separation extraction technology has low selectivity and complicated steps and causes great consumption of organic solvents, a matrix solid-phase dispersion technology has low selectivity and an embedding method for preparing molecularly imprinted polymer needs repeated grinding and wastes time and labor. The method comprises the following steps of: (I) preparing mixed powder; (II) transferring the mixed powder into an injector; (III) performing drip washing; and (IV) eluting. Through the invention, the sample preparation process is simple, and the experiment time and the use of solvent are reduced; a molecularly imprinted polymer is used as a separation medium, and the selective effect of camptothecin extraction and separation is improved; a surface imprinting technology is used for preparing a molecularly imprinted polymer, the binding site is limited on a silicon dioxide surface with good accessibility, being favorable for the elution and recombination of template molecules; and the conditions are easy to control, and the production cost is low. The method disclosed by the invention is used for separating camptothecin.

Description

Utilize the method for molecular imprinting-matrix solid-phase dispersion technique separating common camptotheca fruit alkali
Technical field
The present invention relates to a kind of method of separating common camptotheca fruit alkali.
Background technology
Camptothecine (Camptothecin, CPT), light yellow needle crystal, molecular formula: C 20H 16N 2O 4, molecular weight 348.3.It is a kind of alkaloid that extensively is distributed in the Nyssaceae drought Nelumbo deciduous tree camplotheca acuminata (Camptotheca acuminata Decsne) of south China; The people such as Wall in 1966 isolate camptothecine and proved conclusively structure from the leaf of camplotheca acuminata and bark, and it has very strong anti-tumor activity, and are especially effective to digestive tract tumor, leukemia, chorioepithelioma, bladder cancer.Camptothecine is generally extracted from root, skin, stem and the seed of camplotheca acuminata and is obtained.But owing to except camptothecine, also contain other various ingredients in the camplotheca acuminata, cause camptothecine to extract separation difficulty.The tradition extraction and separation technology exists the shortcomings such as step complexity, energy consumption is high, selectivity is low, the organic solvent consumption is large.It is particularly important to set up a kind of novel effective camptothecine separating and extracting method.
Matrix solid-phase dispersion technique (Matrix Solid-phase Dispersion, MSPD) is the Barker professor of U.S. Louisiana state university proposed and gave theoretical explanation in 1989 a kind of quick sample preconditioning technique.Its advantage is to have concentrated the processes such as sample homogenize in traditional sample pretreatment, extraction, purification, has avoided the loss of sample, has improved purification efficiency.Yet the dispersion agent of matrix solid-phase dispersion technique commonly used is silica gel, silicon-dioxide, C18, gac etc., lacks selectivity.The selectivity that how to improve matrix solid-phase dispersion technique is present problem in the urgent need to address
Molecular imprinting also claims the template imprinting technology, refers to prepare a certain specific target molecule is had the process of the polymkeric substance of specific selectivity.It can be made by being depicted as of image " artificial lock " technology of identification " molecule key ".The polymkeric substance of this technology preparation is called as molecularly imprinted polymer (Molecularly Imprinted Polymer, MIP).Compare with the sample-pretreating method that tradition is commonly used, but the effective separation of molecular imprinting realize target component, and selectivity is high, applied widely.Yet traditional entrapping method prepares the molecularly imprinted polymer needs to be ground repeatedly, wastes time and energy, and productive rate is low, and has the part imprinted sites to be embedded in the particle, can not play a role, and has reduced the utilization ratio of imprinted sites.
Existing camptothecine separation and extraction technology exists that selectivity is low, step is complicated, the organic solvent consumption is large in sum, and the selectivity of matrix solid-phase dispersion technique is low, and entrapping method prepares the molecularly imprinted polymer needs and repeatedly grinds, the problem that wastes time and energy.
Summary of the invention
The present invention will solve existing camptothecine separation and extraction technology to have that selectivity is low, step is complicated, the organic solvent consumption is large, the selectivity of matrix solid-phase dispersion technique is low, entrapping method prepares the molecularly imprinted polymer needs and repeatedly grinds, the problem that wastes time and energy, and the method for utilizing molecular imprinting-matrix solid-phase dispersion technique separating common camptotheca fruit alkali that provides.
Utilize the method for molecular imprinting-matrix solid-phase dispersion technique separating common camptotheca fruit alkali, specifically finish according to following steps:
One, be 40 orders ~ 50 orders with camplotheca acuminata raw material pulverizing to fineness, obtain the camplotheca acuminata powder, mass ratio according to molecularly imprinted polymer and camplotheca acuminata powder is 1:1 ~ 4, take by weighing camplotheca acuminata powder and molecularly imprinted polymer, camplotheca acuminata powder and molecularly imprinted polymer are mixed, grind homogenizing 5min ~ 10min, obtain mixed powder;
Two, the mixed powder that step 1 is obtained moves into and is equipped with in the rebasing syringe of glass wool, and placing glass is cotton above mixed powder again, compacting;
Three, eluent is poured in the syringe of compacting, with the flow velocity drip washing of 1mL/min ~ 2mL/min, wherein the volume ratio of the quality of mixed powder and eluent is 1g:5mL ~ 25mL in the syringe;
Four, eluent is poured in the syringe after the drip washing, flow velocity wash-out with 1mL/min ~ 2mL/min, wherein the volume ratio of the quality of mixed powder and eluent is 1g:5mL ~ 25mL in the syringe, finishes the method for utilizing molecular imprinting-matrix solid-phase dispersion technique separating common camptotheca fruit alkali.
Wherein, the purpose of drip washing is that other component except camptothecine in the camplotheca acuminata raw material is fallen in drip washing in the step 3, and the wash-out target compound is camptothecine in the step 4.
The invention has the beneficial effects as follows: the present invention adopts matrix solid-phase dispersion technique as clastotype, extracts separating common camptotheca fruit alkali, finishes in an individual system so that extract and purify, and makes the sample preparation process simple, has reduced experimental period and solvent usage quantity; Use molecularly imprinted polymer as separating medium, improved camptothecine and extracted the selectivity effect of separating, this polymkeric substance has two kinds of combinations to camptothecine, total adsorptive capacity (Q Max1+ Q Max2) can reach 10 ~ 20mg g -1What adopt when the preparation molecularly imprinted polymer is surface imprinted technology, binding site is confined to have on the silica sphere of good accessibility, thereby is conducive to the wash-out of template molecule and again combination, and preparation process is simple, condition is easy to control, and production cost is low.
The present invention is for separating of camptothecine.
Description of drawings
Fig. 1 is the scanning electron microscope diagram of the molecularly imprinted polymer of embodiment one preparation;
Fig. 2 is the infrared spectrogram of the molecularly imprinted polymer of embodiment one preparation;
Fig. 3 is that the molecularly imprinted polymer of embodiment one preparation is to the adsorption isotherm line chart of camptothecine;
Fig. 4 is the Scatchard analysis chart of the molecularly imprinted polymer absorption camptothecine of embodiment one preparation;
Fig. 5 is that the molecularly imprinted polymer of embodiment one preparation is to the kinetic curve figure of template molecule camptothecine;
Fig. 6 is the pseudo-first-order kinetics fitted figure of the molecularly imprinted polymer absorption camptothecine of embodiment one preparation;
Fig. 7 is the accurate second-order kinetics fitted figure of the molecularly imprinted polymer absorption camptothecine of embodiment one preparation.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: present embodiment is utilized the method for molecular imprinting-matrix solid-phase dispersion technique separating common camptotheca fruit alkali, it is characterized in that utilizing the method for molecular imprinting-matrix solid-phase dispersion technique separating common camptotheca fruit alkali, specifically finishes according to following steps:
One, be 40 orders ~ 50 orders with camplotheca acuminata raw material pulverizing to fineness, obtain the camplotheca acuminata powder, mass ratio according to molecularly imprinted polymer and camplotheca acuminata powder is 1:1 ~ 4, take by weighing camplotheca acuminata powder and molecularly imprinted polymer, camplotheca acuminata powder and molecularly imprinted polymer are mixed, grind homogenizing 5min～10min, obtain mixed powder;
Two, the mixed powder that step 1 is obtained moves into and is equipped with in the rebasing syringe of glass wool, and placing glass is cotton above mixed powder again, compacting;
Three, eluent is poured in the syringe of compacting, with the flow velocity drip washing of 1mL/min ~ 2mL/min, wherein the volume ratio of the quality of mixed powder and eluent is 1g:5mL ~ 25mL in the syringe;
Four, eluent is poured in the syringe after the drip washing, flow velocity wash-out with 1mL/min ~ 2mL/min, wherein the volume ratio of the quality of mixed powder and eluent is 1g:5mL ~ 25mL in the syringe, finishes the method for utilizing molecular imprinting-matrix solid-phase dispersion technique separating common camptotheca fruit alkali.
Wherein, the purpose of drip washing is that other component except camptothecine in the camplotheca acuminata raw material is fallen in drip washing in the step 3, and the wash-out target compound is camptothecine in the step 4.
Present embodiment adopts matrix solid-phase dispersion technique as clastotype, extracts separating common camptotheca fruit alkali, finishes in an individual system so that extract and purify, and makes the sample preparation process simple, has reduced experimental period and solvent usage quantity; Use molecularly imprinted polymer as separating medium, improved camptothecine and extracted the selectivity effect of separating, this polymkeric substance has two kinds of combinations to camptothecine, total adsorptive capacity (Q Max1+ Q Max2) can reach 10 ~ 20mg g -1What adopt when the preparation molecularly imprinted polymer is surface imprinted technology, binding site is confined to have on the silica sphere of good accessibility, thereby is conducive to the wash-out of template molecule and again combination, and preparation process is simple, condition is easy to control, and production cost is low.
Embodiment two: what present embodiment and embodiment one were different is: the mass ratio of molecularly imprinted polymer and camptothecine sample powder is 1:1.1 ~ 2 in the step 1.Other is identical with embodiment one.
Embodiment three: what present embodiment was different from embodiment one or two is: the thickness of glass wool is 2mm ~ 3mm in the step 2.Other is identical with embodiment one or two.
Embodiment four: what present embodiment was different from one of embodiment one to three is: the volume ratio of the quality of mixed powder and eluent is 1g:10mL ~ 20mL in the step 3.Other is identical with one of embodiment one to three.
Embodiment five: what present embodiment was different from one of embodiment one to four is: eluent is methanol aqueous solution or aqueous ethanolic solution in the step 3, and wherein the volume ratio of methyl alcohol or ethanol and water is 1:10 ~ 20.Other is identical with one of embodiment one to four.
Embodiment six: what present embodiment was different from one of embodiment one to five is: the volume ratio of the quality of mixed powder and eluent is 1g:10mL ~ 20mL in the step 4.Other is identical with one of embodiment one to five.
Embodiment seven: what present embodiment was different from one of embodiment one to six is: eluent is the mixing solutions of acetic acid and methyl alcohol or ethanol in the step 4, and wherein the volume ratio of acetic acid and methyl alcohol or ethanol is 1:10 ~ 50.Other is identical with one of embodiment one to six.
Embodiment eight: what present embodiment and embodiment one were different is: the described molecularly imprinted polymer of step 1, specifically according to the following steps preparation:
A, silane coupling agent KH570, distilled water, toluene and the vitriol oil are mixed, be under 50 ℃ ~ 70 ℃ conditions in temperature, the control rotating speed is 200rmp ~ 300rmp, keep 3h ~ 5h, obtain mixed solution A, wherein the volume ratio of distilled water and toluene is 1:3 ~ 6, and the volume ratio of the vitriol oil and distilled water is 1:1 ~ 2, and silane coupling agent KH570 is 1:8 ~ 15 with the cumulative volume ratio of distilled water, toluene and the vitriol oil;
B, employing separating funnel carry out separatory with the mixed solution A that step 1 obtains, remove aqueous portion, obtain toluene layer, in toluene layer, add nano silicon, mix, be under 100 ℃ ~ 120 ℃ conditions in temperature, the control rotating speed is 200rmp ~ 300rmp, keeps 3h ~ 5h, carries out drip washing with pure methyl alcohol again, then be to dry under 50 ℃ ~ 70 ℃ conditions in temperature, obtain the SiO of silylation modification 2, wherein the silane coupling agent KH570 volume ratio of the quality of silicon-dioxide and step 1 is 1g:3mL ~ 5mL;
C, template molecule, solvent and function monomer are mixed, the control rotating speed is 200rmp ~ 300rmp, keep 1h ~ 3h, obtain mixing solutions B, wherein template molecule is 1:3 ~ 6 with the ratio of the amount of substance of function monomer, and the amount of substance of template molecule and the volume ratio of solvent are 1mmo1: 100mL ~ 300mL, and template molecule is camptothecine, solvent is methyl alcohol, acetonitrile or chloroform, and function monomer is methacrylic acid, vinylformic acid or acrylamide;
The SiO of D, silylation modification that step B is obtained 2Joining among the mixing solutions B that step C obtains, add linking agent and initiator again, is under 50 ℃ ~ 70 ℃ conditions in temperature, the control rotating speed is 200rmp ~ 300rmp, keep 20h ~ 30h, obtain containing the molecularly imprinted polymer of template molecule, wherein the SiO of silylation modification 2The ratio of quality and the amount of substance of linking agent be 1g:8mmol ~ 15mmol, template molecule is 1:10 ~ 30 with the ratio of the amount of substance of linking agent among the mixing solutions B that step C obtains, the volume ratio of the quality of initiator and mixing solutions B is 1g:1000mL ~ 2000mL, linking agent is ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate or Vinylstyrene, and initiator is Diisopropyl azodicarboxylate;
E, the molecularly imprinted polymer that contains template molecule that step D is obtained are put into apparatus,Soxhlet's, with eluent wash-out 20h ~ 30h, be to dry under 50 ℃ ~ 60 ℃ conditions in temperature again, obtain molecularly imprinted polymer, wherein eluent is the mixing solutions of methyl alcohol or ethanol and acetic acid, and the volume ratio of acetic acid and methyl alcohol or ethanol is 1:3 ~ 5.Other is identical with embodiment one.
Adopt following examples to verify beneficial effect of the present invention:
Embodiment one:
Present embodiment utilizes the method for molecular imprinting-matrix solid-phase dispersion technique separating common camptotheca fruit alkali, specifically finishes according to following steps:
One, adopting pulverizer is 40 orders ~ 50 orders with camplotheca acuminata raw material pulverizing to fineness, obtain the camplotheca acuminata powder, take by weighing 0.1g camplotheca acuminata powder and 0.1g molecularly imprinted polymer, camplotheca acuminata powder and molecularly imprinted polymer are mixed in mortar, grind homogenizing 5min, obtain mixed powder;
Two, the mixed powder that step 1 is obtained moves into and is equipped with in the rebasing syringe of glass wool, and placing glass is cotton above mixed powder again, compacting, and glass wool thickness is 2mm;
Three, be that 5% methanol aqueous solution is poured in the syringe of compacting with the 3mL volumetric concentration, with the flow velocity drip washing of 1mL/min;
Four, be in the syringe after 5% acetic acid methanol solution is poured drip washing into, with the flow velocity wash-out of 1mL/min, to finish the method for utilizing molecular imprinting-matrix solid-phase dispersion technique separating common camptotheca fruit alkali with the 3mL volumetric concentration.
The preparation method of the described molecularly imprinted polymer of step 1 specifically prepares according to following steps:
A, 4mL silane coupling agent KH570,8mL distilled water, 25mL toluene and the 6.5mL vitriol oil being mixed, is under 60 ℃ of conditions in temperature, and the control rotating speed is 250rmp, keeps 4h, obtains mixed solution A;
B, employing separating funnel carry out separatory with the mixed solution A that step 1 obtains, remove aqueous portion, obtain toluene layer, in toluene layer, add the 1g nano silicon, mix, be under 110 ℃ of conditions in temperature, the control rotating speed is 250rmp, keeps 4h, carries out drip washing with pure methyl alcohol again, then be to dry under 60 ℃ of conditions in temperature, obtain the SiO of silylation modification 2
C, 0.5mmol camptothecine, 100mL chloroform and 2mmol methacrylic acid are mixed, the control rotating speed is 250rmp, keeps 2h, obtains mixing solutions B;
The SiO of D, silylation modification that step B is obtained 2Joining among the mixing solutions B that step C obtains, add 10mmol ethylene glycol dimethacrylate and 0.06g Diisopropyl azodicarboxylate again, is under 60 ℃ of conditions in temperature, and the control rotating speed is 250rmp, keeps 24h, obtains containing the molecularly imprinted polymer of template molecule;
E, the molecularly imprinted polymer that contains template molecule that step D is obtained are put into apparatus,Soxhlet's, are 20% acetic acid methanol solution wash-out 24h with volume content, are to dry under 60 ℃ of conditions in temperature again, obtain molecularly imprinted polymer.
The scanning electron microscope diagram of the molecularly imprinted polymer of present embodiment preparation as shown in Figure 1, the MIP particle diameter that as can be seen from the figure prepares is less, and is evenly distributed.
The infrared spectrogram of the molecularly imprinted polymer of present embodiment preparation as shown in Figure 2, as can be seen from the figure, 3448cm -1The place is the stretching vibration absorption peak of O-H; 2991cm -1The place is the stretching vibration absorption peak of C-H; 1732cm -1The place is C=O stretching vibration absorption peak; 1455cm -1And 1390cm -1The place is C-H flexural vibration absorption peak; 1256cm -1The place is the stretching vibration absorption peak of C-O; 1148cm -1The place is the stretching vibration absorption peak of Si-O, and this result shows SiO 2Wrapped up by MIP.
The molecularly imprinted polymer of present embodiment preparation to the adsorption isotherm line chart of camptothecine as shown in Figure 3, the Scatchard analysis chart of molecularly imprinted polymer absorption camptothecine utilizes formula: Q/C=(Q as shown in Figure 4 Max-Q)/K d(Q be MIP to the adsorptive capacity of camptothecine, C is the equilibrium concentration in the adsorbent solution, Q MaxBe maximum apparent adsorption quantity, K dBe dissociation constant) as can be seen from Figure 4, MIP has two kinds of combinations, the K that obtains to camptothecine D1=25.5mg L -1, Q Max1=7.86mg g -1K D2=12.8mg L -1, Q Max2=6.25mg g -1, this result shows that the MIP for preparing has stronger adsorptive power to camptothecine.
The molecularly imprinted polymer of present embodiment preparation to the kinetic curve figure of template molecule camptothecine as shown in Figure 5, the pseudo-first-order kinetics fitted figure of molecularly imprinted polymer absorption camptothecine as shown in Figure 6, the accurate second-order kinetics fitted figure of MIP absorption camptothecine as shown in Figure 7, MIP meets accurate second-order kinetics model to the absorption of camptothecine as seen from the figure, and wherein the fitting formula of accurate second-order kinetics is: t/Q t=1/K 2Q e 2+ t/Q e(Q tBe equilibrium adsorption capacity, Q eBe theoretical maximal absorptive capacity, K 2Be kinetics secondary balancing speed constant), obtain the K of MIP 2=0.0596g mg -1Min -1, this result shows that the MIP for preparing has fast adsorption rate to camptothecine.
The present invention adopts matrix solid-phase dispersion technique as clastotype, extracts separating common camptotheca fruit alkali, finishes in an individual system so that extract and purify, and makes the sample preparation process simple, has reduced experimental period and solvent usage quantity; Use molecularly imprinted polymer as separating medium, improved camptothecine and extracted the selectivity effect of separating, this polymkeric substance has two kinds of combinations to camptothecine, total adsorptive capacity (Q Max1+ Q Max2) can reach 10 ~ 20mg g -1What adopt when the preparation molecularly imprinted polymer is surface imprinted technology, binding site is confined to have on the silica sphere of good accessibility, thereby is conducive to the wash-out of template molecule and again combination, and preparation process is simple, condition is easy to control, and production cost is low.

Claims (8)

1. utilize the method for molecular imprinting-matrix solid-phase dispersion technique separating common camptotheca fruit alkali, it is characterized in that utilizing the method for molecular imprinting-matrix solid-phase dispersion technique separating common camptotheca fruit alkali, specifically finish according to following steps:
One, be 40 orders ~ 50 orders with camplotheca acuminata raw material pulverizing to fineness, obtain the camplotheca acuminata powder, mass ratio according to molecularly imprinted polymer and camplotheca acuminata powder is 1:1 ~ 4, take by weighing camplotheca acuminata powder and molecularly imprinted polymer, camplotheca acuminata powder and molecularly imprinted polymer are mixed, grind homogenizing 5min ~ 10min, obtain mixed powder;
Two, the mixed powder that step 1 is obtained moves into and is equipped with in the rebasing syringe of glass wool, and placing glass is cotton above mixed powder again, compacting;
Three, eluent is poured in the syringe of compacting, with the flow velocity drip washing of 1mL/min ~ 2mL/min, wherein the volume ratio of the quality of mixed powder and eluent is 1g:5mL ~ 25mL in the syringe;
Four, eluent is poured in the syringe after the drip washing, flow velocity wash-out with 1mL/min ~ 2mL/min, wherein the volume ratio of the quality of mixed powder and eluent is 1g:5mL ~ 25mL in the syringe, finishes the method for utilizing molecular imprinting-matrix solid-phase dispersion technique separating common camptotheca fruit alkali.
2. the method for utilizing molecular imprinting-matrix solid-phase dispersion technique separating common camptotheca fruit alkali according to claim 1 is characterized in that the mass ratio of molecularly imprinted polymer and camptothecine sample powder is 1:1.1 ~ 2 in the step 1.
3. the method for utilizing molecular imprinting-matrix solid-phase dispersion technique separating common camptotheca fruit alkali according to claim 2, the thickness that it is characterized in that glass wool in the step 2 is 2mm ~ 3mm.
4. the method for utilizing molecular imprinting-matrix solid-phase dispersion technique separating common camptotheca fruit alkali according to claim 3 is characterized in that the quality of mixed powder in the step 3 and the volume ratio of eluent are 1g:10mL ~ 20mL.
5. the method for utilizing molecular imprinting-matrix solid-phase dispersion technique separating common camptotheca fruit alkali according to claim 4 is characterized in that eluent is methanol aqueous solution or aqueous ethanolic solution in the step 3, and wherein the volume ratio of methyl alcohol or ethanol and water is 1:10 ~ 20.
6. the method for utilizing molecular imprinting-matrix solid-phase dispersion technique separating common camptotheca fruit alkali according to claim 5 is characterized in that the quality of mixed powder in the step 4 and the volume ratio of eluent are 1g:10mL ~ 20mL.
7. the method for utilizing molecular imprinting-matrix solid-phase dispersion technique separating common camptotheca fruit alkali according to claim 6 is characterized in that eluent is the mixing solutions of acetic acid and methyl alcohol or ethanol in the step 4, and wherein the volume ratio of acetic acid and methyl alcohol or ethanol is 1:10 ~ 50.
8. the method for utilizing molecular imprinting-matrix solid-phase dispersion technique separating common camptotheca fruit alkali according to claim 1 is characterized in that the described molecularly imprinted polymer of step 1, specifically prepares according to following steps:
A, silane coupling agent KH570, distilled water, toluene and the vitriol oil are mixed, be under 50 ℃ ~ 70 ℃ conditions in temperature, the control rotating speed is 200rmp ~ 300rmp, keep 3h ~ 5h, obtain mixed solution A, wherein the volume ratio of distilled water and toluene is 1:3 ~ 6, and the volume ratio of the vitriol oil and distilled water is 1:1 ~ 2, and silane coupling agent KH570 is 1:8 ~ 15 with the cumulative volume ratio of distilled water, toluene and the vitriol oil;
B, employing separating funnel carry out separatory with the mixed solution A that step 1 obtains, remove aqueous portion, obtain toluene layer, in toluene layer, add nano silicon, mix, be under 100 ℃ ~ 120 ℃ conditions in temperature, the control rotating speed is 200rmp ~ 300rmp, keeps 3h ~ 5h, carries out drip washing with pure methyl alcohol again, then be to dry under 50 ℃ ~ 70 ℃ conditions in temperature, obtain the SiO of silylation modification 2, wherein the silane coupling agent KH570 volume ratio of the quality of silicon-dioxide and step 1 is 1g:3mL ~ 5mL;
C, template molecule, solvent and function monomer are mixed, the control rotating speed is 200rmp ~ 300rmp, keep 1h ~ 3h, obtain mixing solutions B, wherein template molecule is 1:3 ~ 6 with the ratio of the amount of substance of function monomer, and the amount of substance of template molecule and the volume ratio of solvent are 1mmol:100mL ~ 300mL, and template molecule is camptothecine, solvent is methyl alcohol, acetonitrile or chloroform, and function monomer is methacrylic acid, vinylformic acid or acrylamide;
The SiO of D, silylation modification that step B is obtained 2Joining among the mixing solutions B that step C obtains, add linking agent and initiator again, is under 50 ℃ ~ 70 ℃ conditions in temperature, the control rotating speed is 200rmp ~ 300rmp, keep 20h ~ 30h, obtain containing the molecularly imprinted polymer of template molecule, wherein the SiO of silylation modification 2The ratio of quality and the amount of substance of linking agent be 1g:8mmol ~ 15mmol, template molecule is 1:10 ~ 30 with the ratio of the amount of substance of linking agent among the mixing solutions B that step C obtains, the volume ratio of the quality of initiator and mixing solutions B is 1g:1000mL ~ 2000mL, linking agent is ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate or Vinylstyrene, and initiator is Diisopropyl azodicarboxylate;
E, the molecularly imprinted polymer that contains template molecule that step D is obtained are put into apparatus,Soxhlet's, with eluent wash-out 20h ~ 30h, be to dry under 50 ℃ ~ 60 ℃ conditions in temperature again, obtain molecularly imprinted polymer, wherein eluent is the mixing solutions of methyl alcohol or ethanol and acetic acid, and the volume ratio of acetic acid and methyl alcohol or ethanol is 1:3 ~ 5.
CN201210540350.8A 2012-12-14 2012-12-14 Method for separating camptothecin by use of molecular imprinting-matrix solid-phase dispersion technology Expired - Fee Related CN102993209B (en)

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CN108816194B (en) * 2018-06-15 2019-12-31 东北林业大学 Method for separating and enriching quercetin by using metal organic framework @ mesoporous silicon composite material-matrix solid phase dispersion technology
CN113996275A (en) * 2021-11-23 2022-02-01 东北林业大学 Preparation of camptothecin molecularly imprinted polymer and method for separating and purifying camptothecin from camptotheca acuminata fruits
CN113996275B (en) * 2021-11-23 2024-04-19 东北林业大学 Preparation of camptothecine molecularly imprinted polymer and method for separating and purifying camptothecine in camptotheca acuminata fruits

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