CN106334344A - Lycorine surface molecular imprinting nanomicrosphere solid-phase extraction column and application thereof - Google Patents
Lycorine surface molecular imprinting nanomicrosphere solid-phase extraction column and application thereof Download PDFInfo
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- CN106334344A CN106334344A CN201610977010.XA CN201610977010A CN106334344A CN 106334344 A CN106334344 A CN 106334344A CN 201610977010 A CN201610977010 A CN 201610977010A CN 106334344 A CN106334344 A CN 106334344A
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- lycorine
- nano microsphere
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
- B01D15/22—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the construction of the column
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/12—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains three hetero rings
- C07D491/16—Peri-condensed systems
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Abstract
The invention discloses preparation and application ofsurface molecular imprinting nanomicrospheres of lycorine selectively extracted and separated from plant extraction liquid. The nanomicrospheres can serve as a filling material to be prepared into a solid-phase extraction column for extracting, separating and purifying the lycorine from the plant extraction liquid. The solid-phase extraction column has the advantages that the selectivity is high, the column capacity is high and is up to 6.68 micro-mol/g, the target material recovery rate is high (92%-105%), the preparation cost is low, materials are easy to obtain, the functional process is simple, the adaptability is strong and large-batch production is easy, and has a very good application prospect.
Description
Technical field
The invention belongs to Nano microsphere preparation, sense dough and its technology neck applied in active ingredient of Chinese herbs separates
Domain, be related to a kind of preparation of lycorine surface molecule print Nano microsphere and using this nano material be solid extracting agent separately,
Lycorine in purifying natural product.
Background technology
Lycorine is the alkaloid component in traditional medicine plant Amaryllidaceae (amaryllidaceae).Bioactivity research
Show, lycorine and its derivative have anti-inflammatory, antiviral, anti-malarial, acetylcholine esterase inhibition, protection angiocarpy and lure
Lead multiple effect such as apoptosis of tumor cells.[referring to (a) a.jimenez, a.santos, g.alonso and
D.vazquez.biochim.biophys.acta (bba): nucleicacidsproteinsynth.1976,425,342-
348. (b) y.toriizuka, e.kinoshita, n.kogure, m.kitajima, a.ishiyama, k.otoguro,
H.yamada, s.omura and h.takayama.bioorgan.med.chem.2008,16,10182-10189. (c)
J.liu, y.yang, y.xu, c.ma, c.qin and l.zhang.virol.j.2011,8,483-491.]
Plant extraction liquid, various Chinese medicine compound prescription and biological specimen ingredient are sufficiently complex.Control curative effect in order to improve Chinese herbal medicine
Fruit, it is necessary to most effective component extracting to greatest extent, removes invalid components and toxic component.Therefore, Chinese herbal medicine active component is divided
From extract it is critical that.The research of centering herb sample pretreatment technology is also relatively more at present, is concentrated mainly on solid phase extraction
Take, liquid-phase extraction, supercritical fluid extraction, ultrafiltration centrifugation and microwave abstracting etc..Wherein solid phase extraction techniques due to simple to operate,
Quickly, use that organic solvent is few, low cost, few to the secondary pollution of environment the advantages of, have become as activity in current Chinese herbal medicine
Constituents extraction and the technical way of enrichment.The performance of SPE is generally closely related with the characteristic of its filler.Silicagel column,
c18Bonding phase column, al2o3Post development is relatively early, and its universality is stronger, has reasonable enrichment to most compounds, and application is compared
Extensively.But disadvantage is poor selectivity, enrichment capacity low [referring to Wang Hongyun, Jiang Ji, Hu Bei, etc. solid phase extraction techniques are entered
Exhibition and the application [j] in biopharmaceutical analysis. Pharmaceutical Analysis magazine, 2003,23 (3), 236].Molecular engram material is for mould
High molecular polymer or nano material that plate molecule is made to measure, because it is after eluted template molecule, can stay shape,
The hole that size and recognition site are all matched with template molecule, this hole can re-recognize template molecule, because it has concurrently
Efficiently, stable and specific selectivity and prepare cheap feature, thus there is wide application prospect.But it is extensive at present
The molecular engram material using is overall imprinted polymer, have including low adsorption capacity low, can not go completely into template and
It is difficult the significantly defect such as wash-out.
Content of the invention
In order to overcome the above-mentioned deficiencies of the prior art, the invention provides a kind of surface molecular with lycorine as template prints
Mark Nano microsphere be novel adsorption separation material, and in this, as the fixing phase of solid-phase extraction column orient from Chinese medicine crude extract divide
From, enrichment, purify lycorine method, thus can obtain the target component of high extraction.The present invention is by following technology
Scheme is realized.
Using technical scheme:
A kind of lycorine surface molecule print Nano microsphere solid-phase extraction column, the matrix of described solid-phase extraction column is short-tube lycoris
Alkali surface molecule print Nano microsphere, lycorine surface molecule print Nano microsphere is by vinylated sio2Nanometer is micro-
Ball surface carries out polymerisation and is obtained, and solid-phase extraction column blank pipe volume is 1～6ml, and loading height is 0.6～1.2cm, blank pipe material
Matter is polyolefin.
1. the preparation of lycorine surface molecule print Nano microsphere:
(1)sio2The preparation of Nano microsphere: ethanol, ammoniacal liquor mix all according to 1: 2～2: 1 ratio in round-bottomed flask
Even, cumulative volume controls in 50～200ml, and then tetraethyl orthosilicate (teos) 5～15ml, ethanol 60～120ml are rapidly added
In above-mentioned solution.Mixed solution continues to react 2～5h at room temperature.Centrifugation 5min after the completion of reaction, rotating speed is
9000 turns/min, use ethanol washing precipitate, centrifugation product vacuum is dried, and obtains dried sio2Nano microsphere；
(2)sio2Nano microsphere vinylated: will according to such scheme be obtained sio2Nano microsphere 0.3～1.5g adds
It is added to dispersion mixing in 40～150ml toluene solution, then add 3- (methacryloxy) propyl group-trimethoxy in the solution
Base silane (kh-570) 2～8ml, mixed solution reacts 8～15h at 80～95 DEG C under nitrogen protection, after the completion of reaction
Centrifugation 5min, rotating speed is 9000 turns/min, uses ethanol washing precipitate, centrifugation product vacuum is dried, and obtains dried second
The sio of alkenyl2Nano microsphere；
(3) preparation of the surface molecule print Nano microsphere with lycorine as template: lycorine surface molecule print nanometer
Microballoon is by vinylated sio2Nano microsphere surface carries out polymerisation and is obtained, and specifically comprises the following steps that 20～40mg
Lycorine, the acrylamide of 30～60mg and 500～1000mg ethylene glycol dimethacrylate be dissolved in 40～100ml's
In acetonitrile, then vinylated sio2Nano microsphere 50～120mg is also added into ultrasonic disperse in above-mentioned solution, add 5～
The azodiisobutyronitrile of 20mg, logical nitrogen 20～60min.Finally, under constant temperature oscillation, carry out two-stage polymerization reaction.The first step
React 6～7h at 40～50 DEG C, after finishing, carry out second step polymerisation, second step reacts 20～24h at 50～60 DEG C.Reaction
The product centrifugation obtaining, washs the unreacted chemical reagent in multiple removal surface simultaneously, receives in molecular engram with substantial amounts of ethanol
In meter Wei Qiu, the template molecule methyl alcohol/glacial acetic acid (ratio is 6: 1～1: 1) of remaining washes away, the surface molecular print being finally obtained
Mark microballoon is washed away with substantial amounts of methyl alcohol, 40～60 DEG C of vacuum drying, obtains lycorine surface molecule print Nano microsphere.
2. lycorine surface molecule print Nano microsphere solid-phase extraction column preparation:
(1) sieve plate under a piece of porous polyethylene is put into the bottom of solid-phase extraction column blank pipe, polyethylene hole diameter of sieve (perforated) plate is 5
～20 μm；
(2) the lycorine surface molecule print that will be equivalent to solid-phase extraction column blank pipe volume 2/1 to three/3rds is received
Meter Wei Qiu dry packing enters in post；
(3) put into another porous polyethylene upper sieve plate on the lycorine surface molecule print Nano microsphere loading,
Polyethylene hole diameter of sieve (perforated) plate is 5～20 μm, and compression filler makes filling pillar height degree be maintained at 0.6～1.2cm, prepares SPE
Post.
3. Solid phase extraction separation purifies the lycorine in plant extraction liquid: before carrying out SPE, use first (5～
20) ml methyl alcohol, second eyeball or corresponding cushioning liquid activating surface molecular engram Nano microsphere, then drives in vavuum pump negative pressure
Under make plant extraction liquid flow through pillar, wash away the impurity of matrix using appropriate volume cleaning fluid, using suitable eluent acetonitrile/
Methyl alcohol etc. is collected analyte wash-out in container, then carries out qualitative and quantitative analysis.
Compared with existing solid-phase extraction column, lycorine surface molecule print Nano microsphere solid phase extraction provided by the present invention
Post is taken to have the advantage that
(1) selectively good, column capacity is high, reaches 6.68 μm of ol/g.
(2) environmental friendliness: the lycorine surface molecule print Nano microsphere solid-phase extraction column of the present invention is environment friend in itself
Alright, and in extraction process, only need to consume minimal amount of organic solvent, other poisonous and harmful substances will not be introduced；
(3) complete invention during, select crinum asiaticum in lycorine as goal in research thing, to described SPE
The property indices of post are tested repeatedly.Result shows all can reach for the recovery of standard addition of above-mentioned alkaloid
92%-105%, desorption process sieve is single, and above-mentioned substance can be eluted by the methyl alcohol of 2ml.
Brief description
Fig. 1 is lycorine surface molecule print Nano microsphere synthesis schematic diagram and is applied in SPE plant extraction liquid
Lycorine schematic diagram；
Fig. 2 is lycorine surface molecule print Nano microsphere solid-phase extraction column schematic diagram, and in figure is: SPE column jecket 1,
Upper sieve plate 2, lower sieve plate 3, lycorine surface molecule print Nano microsphere filler 4；
Fig. 3 is the original sio that synthesis obtains2Nano microsphere and lycorine surface molecule print Nano microsphere transmission electron microscope picture
(tem).
Specific embodiment
Form by the following examples, is described in further detail to the above of the present invention again, but should not be by this
It is interpreted as that the scope of the above-mentioned theme of the present invention is only limitted to Examples below, all technology realized based on the above of the present invention are equal
Belong to the scope of the present invention.
Below in conjunction with the accompanying drawings, by specific embodiment, the present invention is described in further detail.
Embodiment 1: the preparation of lycorine surface molecule print Nano microsphere solid phase extraction filler
Experiment material: acrylamide, lot number is: a108465, purchased from Shanghai Aladdin reagent Co., Ltd；Azo two is different
Butyronitrile, lot number is a104256, purchased from Shanghai Aladdin reagent Co., Ltd；Ethylene glycol dimethacrylate, lot number is:
E106223, purchased from Shanghai Aladdin reagent Co., Ltd；Tetraethyl orthosilicate, lot number is: l1306074, purchased from Shanghai Aladdin
Reagent Co., Ltd；3- (methacryloxy) propyl-trimethoxysilane, lot number is: n136609, purchased from Shanghai I
Fourth reagent Co., Ltd；Hydrochloric acid lycorine, lot number is: l101559, purchased from Shanghai Aladdin reagent Co., Ltd；Toluene, lot number
For x112054, Shanghai Aladdin reagent Co., Ltd.
Laboratory apparatus and equipment: round-bottomed flask, kq-500de ultrasonic cleaner, dhg-9143bs electric heating forced air drying
Case, df-101s magnetic force heating stirrer, ay120 electronic analytical balance, tgl-16c centrifuge.
(1) original sio2The preparation of Nano microsphere
Ethanol, ammoniacal liquor mix in round-bottomed flask according to 3: 5 ratio, and cumulative volume controls in 100ml, then positive silicon
Sour tetra-ethyl ester (teos) 10ml, ethanol 90ml are rapidly added in above-mentioned solution.Mixed solution continues to react 3h at room temperature.
Centrifugation 5min after the completion of reaction, rotating speed is 9000 turns/min, uses ethanol washing precipitate, centrifugation product vacuum is dried, and obtains
Dried sio2Nano microsphere.Products obtained therefrom crystalline form Electronic Speculum is characterized, as shown in Figure 3 a.
(2) preparation of the surface molecule print Nano microsphere with lycorine as template
The sio that will be obtained2Nano microsphere 0.5g is added to dispersion mixing in 50ml toluene solution, then adds in the solution
3- (methacryloxy)-propyl-trimethoxysilane (kh-570) 2ml, 90 DEG C under nitrogen protection of mixed solution
Lower reaction 12h, centrifugation 5min after the completion of reaction, rotating speed is 9000 turns/min, uses ethanol washing precipitate, and centrifugation product is true
Empty dry, obtain dried vinylated sio2Nano microsphere.Lycorine surface molecule print Nano microsphere is by second
The sio of alkenyl2Nano microsphere surface carries out polymerisation and is obtained, and specifically comprises the following steps that the lycorine of 28.7mg, 56.8mg
Acrylamide and 634mg ethylene glycol dimethacrylate are dissolved in the acetonitrile of 50ml, vinylated sio2Nano microsphere
100mg is also added into ultrasonic disperse in above-mentioned solution, is subsequently adding the azodiisobutyronitrile of 10mg, logical nitrogen 30min.Finally,
Under constant temperature oscillation, carry out two-stage polymerization reaction.The first step reacts 6h at 50 DEG C, carries out second step polymerisation after finishing, the
Two steps react 24h at 60 DEG C.The product centrifugation that reaction obtains, washs multiple removal surface unreacted simultaneously with substantial amounts of ethanol
Chemical reagent, in surface molecule print Nano microsphere, the template molecule methyl alcohol/glacial acetic acid (ratio is 4: 1) of remaining washes away,
The molecularly imprinted microspheres on surface being finally obtained is washed away with substantial amounts of methyl alcohol, 50 DEG C of vacuum drying, obtains lycorine surface molecular print
Mark Nano microsphere.
Embodiment 2: the preparation of lycorine surface molecule print Nano microsphere solid-phase extraction column
1st, void column material and specification
Existing solid phase extraction column void column specification is from 1～6ml.Void column material is polypropylene, and pillar respectively has up and down
The polyethylene sieve plate in 20 μm of apertures, above-mentioned void column all can be used in the present invention.In following experimental example, the present invention adopts 3ml
Specification.
2nd, the filler of solid-phase extraction column
The filler of solid-phase extraction column is lycorine surface molecule print Nano microsphere.
3rd, amount of fill and the selection loading height
Load 3ml solid-phase extraction column, such as accompanying drawing 2 with the lycorine surface molecule print Nano microsphere of aforementioned preparation, by one
Under piece porous polyethylene, sieve plate 3 is placed in SPE column jecket 1 bottom, weigh be equivalent to solid-phase extraction column blank pipe volume two/
One lycorine surface molecule print Nano microsphere filler 4 is put in SPE column jecket 1, then puts porous upper sieve plate 2
On filler top, compressing filler makes filling pillar height degree be maintained at 0.8cm, obtains lycorine surface molecule print Nano microsphere solid phase
Extraction column.
Embodiment 3: Solid phase extraction separation purifies the lycorine in crinum asiaticum extract
Experiment material: hydrochloric acid lycorine, lot number is: l101559, purchased from Shanghai Aladdin reagent Co., Ltd, ammonium acetate
Purchased from Shanghai Shanghai Aladdin reagent Co., Ltd, lot number is: 20070622；It is public that the pure acetonitrile of high performance liquid chromatography is purchased from merck
Department, lot number: 1605030-138；Crinum asiaticum, purchased from Nanjing pharmaceutcal corporation, Ltd of Tongrentang.
Experimental instruments: waters company 2695/2996 high performance liquid chromatograph, ap-01p vavuum pump, by stating reality
Apply the lycorine surface molecule print Nano microsphere solid-phase extraction column of preparation in example 2.
Experimentation:
Take crinum asiaticum powder 20g, add 95% ethanol solution 200ml in round-bottomed flask, be heated to reflux 2.5h at 84 DEG C,
Totally 3 times, filter and obtain final product crinum asiaticum crude extract, crude extract dilution in acetonitrile different multiples.By the lycorine surface molecular being obtained print
Mark Nano microsphere solid-phase extraction column keeps 5min with 4ml acetonitrile complete wetting filler, then bleeds off liquid with the speed of 1/s,
Process rear pillar and be in the state of activation；Put up device, drive vavuum pump, mix up vacuum, taken with the speed of 2ml/min (20～
100) ml sample flows through extraction column, and suction filtration removes solvent composition, and again with methanol/acetonitrile (90: 10) elutes solid-phase extraction column, permissible
Obtain the eluent of different enrichment times, be analyzed detecting and quantitative analysis with high performance liquid chromatograph, concentrated, dry
To lycorine 7.2mg.
Above example is merely to illustrate the preferred embodiment of the present invention, but the present invention is not limited to above-mentioned embodiment party
Formula, in the ken that described field those of ordinary skill possesses, that is made within the spirit and principles in the present invention is any
Modification, equivalent substitute and improvement etc., it all should be within the scope of the technical scheme that the present invention is claimed.
Claims (3)
1. a kind of lycorine surface molecule print Nano microsphere solid-phase extraction column is it is characterised in that the base of described solid-phase extraction column
Matter is lycorine surface molecule print Nano microsphere, and lycorine surface molecule print Nano microsphere is by vinylated two
Silica Nano microsphere surface carry out polymerisation be obtained, solid-phase extraction column blank pipe volume be 1～6ml, load height be 0.6～
1.2cm, blank pipe material is polyolefin.
2. a kind of functionalization lycorine surface molecule print Nano microsphere solid-phase extraction column as claimed in claim 1, its feature
It is that preparation method is:
(1) sieve plate under a piece of porous polyethylene is put into the bottom of solid-phase extraction column blank pipe, polyethylene hole diameter of sieve (perforated) plate is 5～20
μm；
(2) the lycorine surface molecule print nanometer that will be equivalent to solid-phase extraction column blank pipe volume 2/1 to three/3rds is micro-
Ball dry packing enters in post；
(3) another porous polyethylene upper sieve plate, poly- second are put on the lycorine surface molecule print Nano microsphere loading
Alkene hole diameter of sieve (perforated) plate is 5～20 μm, and compression filler makes filling pillar height degree be maintained at 0.6～1.2cm, prepares solid-phase extraction column.
3. a kind of method preparing lycorine surface molecule print Nano microsphere is it is characterised in that micro- by primary silica nanometer
Ball warp is vinylated, obtained by surface aggregate, sequentially include the following steps:
(1) silicon dioxide nanosphere is vinylated: sio2Nano microsphere 0.3～1.5g is added in 40～150ml toluene solution
Mixing, then adds 3- (methacryloxy)-propyl-trimethoxysilane 2～8ml, mixed solution in the solution
React 8～15h, centrifugation 5min after the completion of reaction at 80～95 DEG C under nitrogen protection, rotating speed is 9000 turns/min, uses second
Alcohol washing precipitate, centrifugation product vacuum is dried, and obtains dried vinylated sio2Nano microsphere；
(2) with lycorine as template, in vinylated sio2Nano microsphere surface is polymerized: lycorine surface molecule print
Nano microsphere is by vinylated sio2Nano microsphere surface carries out polymerisation and is obtained, the lycorine of 20～40mg,
The acrylamide of 30～60mg and 500～1000mg ethylene glycol dimethacrylate are dissolved in the acetonitrile of 40～100ml, second
The sio of alkenyl2Nano microsphere 50～120mg is also added into ultrasonic disperse in above-mentioned solution, is subsequently adding the azo of 5～20mg
Bis-isobutyronitrile, logical nitrogen 20～60min.Finally, under constant temperature oscillation, carry out two-stage polymerization reaction.The first step is at 40～50 DEG C
Reaction 6～7h, carries out second step polymerisation after finishing, second step reacts 20～24h at 50～60 DEG C.The product that reaction obtains
Centrifugation, is washed repeatedly with substantial amounts of ethanol simultaneously, removes the unreacted chemical reagent in surface, in surface molecule print Nano microsphere
Template molecule methyl alcohol/the glacial acetic acid (ratio is 6: 1～1: 1) of middle remaining washes away, the surface molecule print nanometer being finally obtained
Microballoon is washed with substantial amounts of methyl alcohol, 40～60 DEG C of vacuum drying, obtains lycorine surface molecule print Nano microsphere.
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Cited By (1)
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| CN109647001A (en) * | 2018-11-30 | 2019-04-19 | 中国刑事警察学院 | A kind of Furadan carbon nano tube surface molecularly imprinted solid phase extraction column |
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