CN106334344B - Lycorine surface molecule print nanoparticle solid-phase extraction column and its application - Google Patents
Lycorine surface molecule print nanoparticle solid-phase extraction column and its application Download PDFInfo
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- CN106334344B CN106334344B CN201610977010.XA CN201610977010A CN106334344B CN 106334344 B CN106334344 B CN 106334344B CN 201610977010 A CN201610977010 A CN 201610977010A CN 106334344 B CN106334344 B CN 106334344B
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- Prior art keywords
- nanoparticle
- lycorine
- surface molecule
- phase extraction
- solid
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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
-
- 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
Abstract
The invention discloses the preparations and its application of the surface molecule print nanoparticle of selective extraction separating short-tube lycoris alkali from plant extraction liquid.Solid-phase extraction column can be made as filler material in the nanoparticle and extract separation, purifying lycorine from plant extraction liquid.Solid-phase extraction column of the present invention has highly selective, high column capacity, up to 6.68 μm of ol/g.(92% 105%) good to the target substance rate of recovery, manufacturing cost is low, and material is easy to get, and functionalization process is simple, adaptable, the characteristics of being easy to batch production, has good application prospect.
Description
Technical field
The invention belongs to nanoparticle preparation, function dough and its technology necks applied in active ingredient of Chinese herbs separation
Domain, be related to a kind of lycorine surface molecule print nanoparticle preparation and using the nano material be solid extracting agent separation,
Lycorine in purifying natural product.
Background technology
Lycorine is the alkaloid component in traditional medicinal phytobezoar garlic section (Amaryllidaceae).Bioactivity research
Show that lycorine and its derivative have anti-inflammatory, antiviral, anti-malarial, acetylcholine esterase inhibition, protection angiocarpy and lure
Lead a variety of effects 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 prescriptions and biological specimen ingredient are sufficiently complex.In order to improve the treatment effect of Chinese herbal medicine
Fruit removes invalid components and toxic component it is necessary to most effective component extracting to greatest extent.Therefore, to Chinese herbal medicine active constituent point
It is vital from extraction.The research of centering herb sample pretreatment technology at present is also relatively more, 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 it is easy to operate,
Quickly, the advantages that few using organic solvent, at low cost, few to the secondary pollution of environment, has become active in current Chinese herbal medicine
The technical way of constituents extraction and enrichment.The performance of Solid Phase Extraction is usually closely related with the characteristic of its filler.Silicagel column,
C18Bonding phase column, Al2O3Column development is more early, and universality is stronger, there is relatively good enrichment to most compounds, using comparing
Extensively.But disadvantage is poor selectivity, enrichment capacity it is low [referring to：Wang Hongyun, Jiang Ji, Hu Bei, wait solid phase extraction techniques into
Exhibition and application [J] Pharmaceutical Analysis magazines in biopharmaceutical analysis, 2003,23 (3), 236].Molecular engram material is for mould
The high molecular polymer or nano material that plate molecule is made to measure, since it is after eluted template molecule, can leave shape,
The hole that size and recognition site all match with template molecule, the hole can re-recognize template molecule, since it has concurrently
Efficiently, stablize and specific selectivity and prepares cheap feature, thus with wide application prospect.However at present extensively
The molecular engram material used is whole imprinted polymer, have include low adsorption ability is low, template cannot be gone completely into and
The apparent defect such as it is not easy to elute.
Invention content
In order to overcome the above-mentioned deficiencies of the prior art, the present invention provides a kind of using lycorine as the surface molecular of template print
Mark nanoparticle is novel adsorption separation material, and orients and divide from Chinese medicine crude extract in this, as the stationary phase of solid-phase extraction column
From, enrichment, purifying lycorine method, it is possible thereby to obtain the target component of high extraction.The present invention passes through technology below
What scheme was realized.
The technical solution of use：
The matrix of a kind of lycorine surface molecule print nanoparticle solid-phase extraction column, the solid-phase extraction column is short-tube lycoris
Alkali surface molecule print nanoparticle, lycorine surface molecule print nanoparticle are by vinylated SiO2Nanometer is micro-
Ball surface carries out polymerisation and is made, and solid-phase extraction column blank pipe volume is 1~6mL, and it is 0.6~1.2cm, blank pipe material to load height
Matter is polyolefin.
1. the preparation of lycorine surface molecule print nanoparticle：
(1)SiO2The preparation of nanoparticle：Ethyl alcohol, ammonium hydroxide mix according to 1: 2~2: 1 ratio in round-bottomed flask
Even, total volume is controlled in 50~200mL, and then tetraethyl orthosilicate (TEOS) 5~15mL, 60~120mL of ethyl alcohol are rapidly added
In above-mentioned solution.Mixed solution the reaction was continued at room temperature 2~5h.5min is centrifuged after the completion of reaction, rotating speed is
9000 turns/min, with ethyl alcohol washing precipitate, centrifugation product vacuum drying, the SiO after must drying2Nanoparticle；
(2)SiO2Nanoparticle it is vinylated：It will be according to SiO made from said program20.3~1.5g of nanoparticle adds
It is added to dispersion mixing in 40~150mL toluene solutions, 3- (methacryloxy) propyl-trimethoxy is then added 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
5min is centrifuged, rotating speed is 9000 turns/min, with ethyl alcohol washing precipitate, centrifugation product vacuum drying, the second after must drying
The SiO of alkenyl2Nanoparticle；
(3) using lycorine as the preparation of the surface molecule print nanoparticle of template：Lycorine surface molecule print nanometer
Microballoon is by vinylated SiO2Nanoparticle surface carries out polymerisation and is made, and is as follows：20~40mg
Lycorine, 30~60mg acrylamide and 500~1000mg ethylene glycol dimethacrylates be dissolved in 40~100mL's
In acetonitrile, then vinylated SiO250~120mg of nanoparticle is also added into ultrasonic disperse in above-mentioned solution, it is added 5~
The azodiisobutyronitrile of 20mg leads to 20~60min of nitrogen.Finally, under constant temperature oscillation, two-stage polymerization reaction is carried out.The first step
6~7h is reacted at 40~50 DEG C, after carry out second step polymerisation, second step reacts 20 at 50~60 DEG C~for 24 hours.Reaction
The product of acquisition centrifuges, while washing the repeatedly removal unreacted chemical reagent in surface with a large amount of ethyl alcohol, is received in molecular engram
Remaining template molecule is washed away with methanol/glacial acetic acid (ratio 6: 1~1: 1) in meter Wei Qiu, last surface molecular print obtained
Mark microballoon is washed away with a large amount of methanol, and 40~60 DEG C of vacuum drying obtain lycorine surface molecule print nanoparticle.
2. prepared by lycorine surface molecule print nanoparticle solid-phase extraction column：
(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 one third to 2/3rds is received
Meter Wei Qiu dry packings enter in column；
(3) it is put into another porous polyethylene upper sieve plate on the lycorine surface molecule print nanoparticle of filling,
Polyethylene hole diameter of sieve (perforated) plate is 5~20 μm, and compressing filler makes filling pillar height degree be maintained at 0.6~1.2cm, and Solid Phase Extraction is prepared
Column.
3. Solid phase extraction separation purifies the lycorine in plant extraction liquid：Before carrying out Solid Phase Extraction, use first (5~
20) then mL methanol, second eyeball or corresponding buffer solution activating surface molecular engram nanoparticle drive in vacuum pump negative pressure
Under so that plant extraction liquid is flowed through pillar, the impurity of matrix is washed away using appropriate volume cleaning solution, using suitable eluent acetonitrile/
Methanol etc. is collected into analyte elution in container, then carries out qualitative and quantitative analysis.
Compared with existing solid-phase extraction column, lycorine surface molecule print nanoparticle solid phase extraction provided by the present invention
Column is taken to has the following advantages：
(1) selectivity is good, and column capacity is high, reaches 6.68 μm of ol/g.
(2) environmental-friendly：The lycorine surface molecule print nanoparticle solid-phase extraction column of the present invention itself is environment friend
Alright, and in extraction process, minimal amount of organic solvent only need to be consumed, other poisonous and harmful substances will not be introduced；
(3) during completing invention, select in crinum asiaticum that lycorine is as goal in research object, to the Solid Phase Extraction
The property indices of column are tested repeatedly.The result shows that the recovery of standard addition for above-mentioned alkaloid can reach
92%-105%, desorption process sieve is single, and the methanol of 2mL can elute above-mentioned substance.
Description of the drawings
Fig. 1 is that lycorine surface molecule print nanoparticle synthesizes schematic diagram and applied in Solid Phase Extraction plant extraction liquid
Lycorine schematic diagram；
Fig. 2 is lycorine surface molecule print nanoparticle solid-phase extraction column schematic diagram, is in figure：Solid Phase Extraction column tube 1,
Upper sieve plate 2, lower sieve plate 3, lycorine surface molecule print nanoparticle filler 4；
Fig. 3 is the original SiO that synthesis obtains2Nanoparticle and lycorine surface molecule print nanoparticle transmission electron microscope picture
(TEM)。
Specific implementation mode
Form by the following examples is described in further detail the above of the present invention again, but should not be by this
The range for being interpreted as the above-mentioned theme of the present invention is only limitted to example below, and all technologies 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, the present invention is described in further detail by specific embodiment.
Embodiment 1：The preparation of lycorine surface molecule print nanoparticle solid phase extraction filler
Experiment material：Acrylamide, lot number are：A108465 is purchased from Shanghai Aladdin reagent Co., Ltd；Azo two is different
Butyronitrile, lot number A104256 are purchased from Shanghai Aladdin reagent Co., Ltd；Ethylene glycol dimethacrylate, lot number are：
E106223 is purchased from Shanghai Aladdin reagent Co., Ltd；Tetraethyl orthosilicate, lot number are：L1306074 is purchased from Shanghai Aladdin
Reagent Co., Ltd；3- (methacryloxy) propyl-trimethoxysilane, lot number are：N136609, purchased from Shanghai I
Fourth reagent Co., Ltd；Hydrochloric acid lycorine, lot number are：L101559 is 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 cleaners, DHG-9143BS electric heating forced air dryings
Case, DF-101S magnetic force heating stirrer, AY120 electronic analytical balances, TGL-16C centrifuges.
(1) original SiO2The preparation of nanoparticle
Ethyl alcohol, ammonium hydroxide are uniformly mixed according to 3: 5 ratio in round-bottomed flask, and total volume control is in 100mL, then positive silicon
Sour tetra-ethyl ester (TEOS) 10mL, ethyl alcohol 90mL are rapidly added in above-mentioned solution.Mixed solution the reaction was continued at room temperature 3h.
5min is centrifuged after the completion of reaction, rotating speed is 9000 turns/min, and with ethyl alcohol washing precipitate, centrifugation product vacuum drying obtains
SiO after drying2Nanoparticle.Products obtained therefrom crystalline form Electronic Speculum is characterized, as shown in Figure 3A.
(2) using lycorine as the preparation of the surface molecule print nanoparticle of template
By SiO obtained2Nanoparticle 0.5g is added to dispersion mixing in 50mL toluene solutions, is then added in the solution
3- (methacryloxy)-propyl-trimethoxysilane (KH-570) 2mL, 90 DEG C under nitrogen protection of mixed solution
Lower reaction 12h centrifuges 5min after the completion of reaction, rotating speed is 9000 turns/min, and with ethyl alcohol washing precipitate, centrifugation product is true
Sky is dry, the vinylated SiO after must drying2Nanoparticle.Lycorine surface molecule print nanoparticle is by second
The SiO of alkenyl2Nanoparticle surface carries out polymerisation and is made, and is as follows：The lycorine of 28.7mg, 56.8mg
Acrylamide and 634mg ethylene glycol dimethacrylates are dissolved in the acetonitrile of 50mL, vinylated SiO2Nanoparticle
100mg is also added into ultrasonic disperse in above-mentioned solution, and the azodiisobutyronitrile of 10mg is then added, and leads to nitrogen 30min.Finally,
Under constant temperature oscillation, two-stage polymerization reaction is carried out.The first step reacts 6h at 50 DEG C, after carry out second step polymerisation, the
Two steps are reacted for 24 hours at 60 DEG C.The product centrifugation that reaction obtains, while wash with a large amount of ethyl alcohol that multiple to remove surface unreacted
Chemical reagent, remaining template molecule is washed away with methanol/glacial acetic acid (ratio 4: 1) in surface molecule print nanoparticle,
Last molecularly imprinted microspheres on surface obtained is washed away with a large amount of methanol, and 50 DEG C of vacuum drying obtain lycorine surface molecular print
Mark nanoparticle.
Embodiment 2：The preparation of lycorine surface molecule print nanoparticle solid-phase extraction column
1, void column material and specification
Existing solid phase extraction column void column specification is from 1~6mL etc..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 can be used in the present invention.The present invention uses 3mL in following experimental example
Specification.
2, the filler of solid-phase extraction column
The filler of solid-phase extraction column is lycorine surface molecule print nanoparticle.
3, the selection of amount of fill and filling height
3mL solid-phase extraction columns are loaded with the lycorine surface molecule print nanoparticle of aforementioned preparation, such as attached drawing 2, by one
Sieve plate 3 is placed in 1 bottom of Solid Phase Extraction column tube under piece porous polyethylene, weigh be equivalent to solid-phase extraction column blank pipe volume two/
One lycorine surface molecule print nanoparticle filler 4 is put into Solid Phase Extraction column tube 1, then puts porosity upper sieve plate 2
On filler top, compressing filler makes filling pillar height degree be maintained at 0.8cm, obtains lycorine surface molecule print nanoparticle solid phase
Extraction column.
Embodiment 3：Solid phase extraction separation purifies the lycorine in crinum asiaticum extracting solution
Experiment material：Hydrochloric acid lycorine, lot number are：L101559 is purchased from Shanghai Aladdin reagent Co., Ltd, ammonium acetate
Purchased from Shanghai Shanghai Aladdin reagent Co., Ltd, lot number is：20070622；The pure acetonitrile of high performance liquid chromatography is public purchased from Merck
Department, lot number：1605030-138；Crinum asiaticum is purchased from Nanjing pharmaceutcal corporation, Ltd of Tongrentang.
Experimental instruments：2695/2996 high performance liquid chromatograph of Waters companies, AP-01P vacuum pumps, by stating reality
Apply the lycorine surface molecule print nanoparticle solid-phase extraction column prepared in example 2.
Experimentation：
Crinum asiaticum powder 20g is taken, 95% ethanol solution 200mL is added in round-bottomed flask, 2.5h is heated to reflux at 84 DEG C,
It totally 3 times, filters up to crinum asiaticum crude extract, crude extract dilution in acetonitrile different multiples.Lycorine surface molecular obtained is printed
Mark nanoparticle solid-phase extraction column keeps 5min with 4mL acetonitrile complete wetting fillers, then bleeds off liquid with the speed of 1 drop/s,
Pillar is in the state of activation after having handled；Device is put up, vacuum pump is opened, mixes up vacuum degree, taken with the speed of 2mL/min (20~
100) mL samples flow through extraction column, filter and remove solvent composition, and again with methanol/acetonitrile (90: 10) elutes solid-phase extraction column, can be with
The eluent of different enrichment times is obtained, analysis detection and quantitative analysis is carried out 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, the field those of ordinary skill within the scope of knowledge, within the spirit and principles in the present invention made by it is any
Modification, equivalent substitute and improvement etc., should all be within the claimed technical proposal scope of the present invention.
Claims (2)
1. a kind of lycorine surface molecule print nanoparticle solid-phase extraction column, it is characterised in that the base of the solid-phase extraction column
Matter is lycorine surface molecule print nanoparticle, and lycorine surface molecule print nanoparticle is by vinylated two
Silica nanoparticle surface carries out polymerisation and is made, and solid-phase extraction column blank pipe volume is 1~6mL, load height for 0.6~
1.2cm, blank pipe material are polyolefin, and wherein lycorine surface molecule print nanoparticle is passed through by primary silica nanoparticle
Obtained by vinylated, surface aggregate, carry out according to the following steps：
(1) silicon dioxide nanosphere is vinylated：SiO20.3~1.5g of nanoparticle is added in 40~150mL toluene solutions
Then 3- (methacryloxy) -2~8mL of propyl-trimethoxysilane, mixed solution is added in mixing in the solution
8~15h is reacted at 80~95 DEG C under nitrogen protection, 5min is centrifuged after the completion of reaction, rotating speed is 9000 turns/min, uses second
Alcohol washing precipitate, centrifugation product vacuum drying, the vinylated SiO after must drying2Nanoparticle；
(2) using lycorine as template, in vinylated SiO2Nanoparticle surface is polymerize：Lycorine surface molecule print
Nanoparticle is by vinylated SiO2Nanoparticle surface carries out polymerisation and is made, the lycorine of 20~40mg,
The acrylamide and 500~1000mg ethylene glycol dimethacrylates of 30~60mg is dissolved in the acetonitrile of 40~100mL, second
The SiO of alkenyl250~120mg of nanoparticle is also added into ultrasonic disperse in above-mentioned solution, and the azo of 5~20mg is then added
Bis-isobutyronitrile leads to 20~60min of nitrogen；Finally, under constant temperature oscillation, two-stage polymerization reaction is carried out；The first step is at 40~50 DEG C
React 6~7h, after carry out second step polymerisation, second step reacts 20 at 50~60 DEG C~for 24 hours；React the product obtained
Centrifugation, while being washed repeatedly with a large amount of ethyl alcohol, the unreacted chemical reagent in surface is removed, in surface molecule print nanoparticle
The template molecule of middle remaining is washed away with methanol/glacial acetic acid, and its ratio be 6：1~1：1, last surface molecule print obtained is received
Meter Wei Qiu is washed with a large amount of methanol, and 40~60 DEG C of vacuum drying obtain lycorine surface molecule print nanoparticle.
2. a kind of lycorine surface molecule print nanoparticle solid-phase extraction column as described in claim 1, it is characterised in that system
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) will be equivalent to solid-phase extraction column blank pipe volume one third to 2/3rds lycorine surface molecule print nanometer it is micro-
Ball dry packing enters in column；
(3) another porous polyethylene upper sieve plate, poly- second are put on the lycorine surface molecule print nanoparticle of filling
Alkene hole diameter of sieve (perforated) plate is 5~20 μm, and compressing filler makes filling pillar height degree be maintained at 0.6~1.2cm, and solid-phase extraction column is prepared.
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