CN106390948B - A kind of grafting has silicon wafer of poly ion liquid and its preparation method and application - Google Patents
A kind of grafting has silicon wafer of poly ion liquid and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of silicon wafers and its preparation method and application grafted and have poly ion liquid, the grafting has the silicon wafer of poly ion liquid with 1- vinyl -3- phenylpropyl imidazoles villaumite and 1,1- (1,6- hexane)-two-two kinds of ionic liquids of (1- vinyl imidazole) bromide be monomer, it is reacted by atom transfer radical polymerization (ATRP), it is grafted onto the silicon chip surface of modified, it being capable of three kinds of curcumin substances of Solid Phase Extraction: single Demethoxycurcumin, Bisdemethoxycurcumin, curcumin.The silicon wafer for the load poly ion liquid that the present invention synthesizes improves the stability of extraction process, enhances extraction adsorbance, can accurately detect curcumin, and favorable reproducibility by high performance liquid chromatography.
Description
Technical field
The invention belongs to solid phase extraction techniques field, particular by synthesizing a kind of new solid extracting agent and with the solid phase
Extractant is enriched with single Demethoxycurcumin, Bisdemethoxycurcumin, curcumin and the method for detection curcumin obtained.
Background technique
Curcumin (C21H2O6) it is from a kind of chemical component extracted in plant roots and stems in part Zingiber, Araeceae, tool
There is the effects of reducing blood lipid, anticoagulant, anti-oxidant, cholagogue, anticancer, arthrocele, arthritis can be prevented, to cardiovascular disease, cancer
Etc. diseases also have certain therapeutic effect.The enrichment of curcumin is of great significance to clinical diagnosis with detection, still, existing
Curcumin detection method poor reproducibility, interference are more, cannot accurately and effectively detect curcumin.
In recent years, ionic liquid at room temperature especially glyoxaline ion liquid is played an important role in chemical field.Room temperature
Ionic liquid is a kind of fuse salt being made of macromolecule organic cation and inorganic or organic anion, and fusing point is lower than 100
DEG C, it is generally near room temperature, has good dissolubility to many inorganic salts and organic matter.It is ion, polycyclic in high performance liquid chromatography
The substances such as aromatic hydrocarbons, amine, nucleosides mainly use the silicon wafer of Ionic Liquid Modified to be separated as solid extracting agent.By polyion liquid
Vegetative grafting is based on solid phase micro-extraction technique and load poly ion liquid technology to silicon chip surface.Poly ion liquid utilizes physics
Ionic liquid is fixed on solid, liquid, polymer or aeroge by absorption, self assembly or polymerization, to avoid ion
Leaching of the liquid in extraction process, has saved cost, also improves the stability of extraction process.However, by single imidazoles
Ionic liquid synthesis load poly ion liquid is often ineffective during modifying solid.Therefore, it further increases and extracted
The stability and enhancing extraction adsorbance of journey have great scientific research value.
Summary of the invention
In view of the deficiencies of the prior art, an object of the present invention be with 1- vinyl -3- phenylpropyl imidazoles villaumite and 1,
1- (1,6- hexane)-two-(1- vinyl imidazole) two kinds of ionic liquids of bromide are monomer, pass through atom transfer radical polymerization
(ATRP) it reacts, is grafted onto the silicon chip surface of modified, synthesis grafting has the silicon wafer of poly ion liquid, being capable of Solid Phase Extraction turmeric
Element improves the stability of extraction process, enhances extraction adsorbance.
It is a kind of stable with extraction efficiency height, extraction process the second object of the present invention is to be synthesized with method of the invention
Grafting has the silicon wafer of poly ion liquid.
The third object of the present invention is that the grafting for using the present invention to synthesize has the silicon wafer of poly ion liquid as extractant, with this
Extractant extracts curcumin, then detects curcumin with high performance liquid chromatography, and this method can not only accurately detect curcumin, and
Favorable reproducibility has very big scientific research value to clinical application.
Technical solution used by one of achieving the object of the present invention is as follows:
It is a kind of to graft the silicon wafer for having poly ion liquid, including silicon wafer, it is characterised in that: the surface of the silicon wafer is successively passed through
Hydroxylating processing, amination processing and bromination processing；Grafting has poly ion liquid on the silicon chip surface.
Technical solution used by two achieved the object of the present invention is as follows:
It is a kind of to graft the silicon wafer for having poly ion liquid, characterized by the following steps:
1) detailed process is as follows for silicon chip surface moditied processing:
1-1) hydroxylating is handled: silicon wafer is placed in sodium hydroxide solution after impregnating 8-10min and is rinsed well with deionization,
Then silicon wafer is placed in nitric acid solution and impregnates 15-20min, complete silicon wafer hydroxylating；
1-2) amination is handled: will be completed hydroxylated silicon wafer in step 1-1) with being dried with nitrogen, is subsequently placed in 500 μ L's
In the mixed solution of 97%3- TSL 8330 and 10mL dehydrated alcohol, it is protected from light 24-28h, i.e. completion silicon
Piece amination；
1-3) bromination is handled: step 1-2) the amidized silicon wafer being washed and used is dried with nitrogen, be placed in boiling flask
In, the mixed solution of 1.6mL pyridine and 20mL methylene chloride is added, 1mL bromo isobutyryl bromine solutions and 15mL bis- is then added dropwise
Chloromethanes solution after being added dropwise, reacts 12-14h in ice-water bath；
2) detailed process is as follows for grafting processing:
2-1) cuprous bromide purifies: weighing 1.5g cuprous bromide in small beaker, 8mL glacial acetic acid is added, stirs at room temperature
It is filtered after mixing 2 hours, glacial acetic acid is removed, then washed cuprous bromide solid 3 times with 8mL glacial acetic acid, then by cuprous bromide solid
It is transferred in 9mL methanol solution, is filtered after 1h is stirred at room temperature, remove methanol solution, again with methanol washs cuprous bromide solid extremely
Filtrate is colourless, the cuprous bromide that will filter 50 DEG C of obtained solid vacuum drying 48 hours to get purifying；
2-2) silicon chip surface polymerization grafting poly ion liquid: the 1- vinyl -3- benzene of 5mmol is added in 25mL three-necked bottle
Propyl imidazole villaumite and 1,1- (1,6- hexane)-two-(1- vinyl imidazole) bromide cross-linking ion liquid, adds 5mL N, N-
Dimethyl formamide solution, heating are passed through argon gas after making ion liquid dissolving and continue 20min, and reaction flask is then placed in liquid nitrogen
In, the cuprous bromide and 0.0032g copper powder of purifying described in 0.0072g is added, argon gas is passed through after vacuumizing, is added simultaneously
0.1mmoL is dissolved in 1mLN, N, N, N', the N of dinethylformamide, ' N "-five methyl diethylentriamine, continue logical argon gas simultaneously
Continue 10min, reacts 4-5h at 95 DEG C then to get the silicon wafer grafted and have poly ion liquid.
Preferably, the step 1-1) further include Wafer Cleaning, Wafer Cleaning process is as follows before silicon wafer hydroxylation procedures:
The silicon wafer of well cutting is put into ethanol solution after ultrasound 5min and is rinsed well with deionized water, is then 7:3's with volume ratio
It is rinsed well after the mixed solution ultrasound 10min of the concentrated sulfuric acid and hydrogen peroxide with deionized water, then ultrasonic with deionized water
10min is finally rinsed well with after 5% hydrofluoric acid solution ultrasound 10min with deionized water, then with deionized water ultrasound 5min,
It is put into ethanol solution and saves.
Preferably, the step 1-1) silicon wafer hydroxylating processing in, the silicon wafer of cleaning is placed in 0.1mol/L hydrogen-oxygen
Change and rinsed well after impregnating 8min in sodium solution with deionization, then silicon wafer is placed in 0.1mol/L nitric acid solution and is impregnated
15min completes silicon wafer hydroxylating.
Preferably, the step 1-2) in silicon wafer amination processing, hydroxylated silicon wafer nitrogen will be completed in step 1-1)
Air-blowing is dry, is subsequently placed in the 97%3- TSL 8330 of 500 μ L and the mixed solution of 10mL dehydrated alcohol, keeps away
Light reaction 24, i.e. completion silicon wafer amination.
Preferably, the step 1-3) silicon wafer bromination processing in, step 1-2) the amidized silicon wafer is washed and is used in combination
It is dried with nitrogen, is placed in boiling flask, the mixed solution of 1.6mL pyridine and 20mL methylene chloride is added, 1mL bromo is then added dropwise
Isobutyryl bromine solutions and 15mL dichloromethane solution after being added dropwise, react 12h in ice-water bath, i.e. completion silicon wafer bromination.
Preferably, the step 2-2) silicon chip surface polymerization grafting poly ion liquid during, in 25mL three-necked bottle plus
Enter 1- vinyl -3- phenylpropyl imidazoles villaumite and the crosslinking of-two-(1- vinyl imidazole) bromide of 1,1- (1,6- hexane) of 5mmol
Ionic liquid, adds 5mL n,N-Dimethylformamide solution, and heating is passed through argon gas after making ion liquid dissolving and continues
Then reaction flask is placed in liquid nitrogen by 20min, the cuprous bromide and 0.0032g copper powder of purifying described in 0.0072g is added, and is taken out true
It is passed through argon gas after sky, while 0.1mmoL is added and is dissolved in 1mLN, N, N, N', the N of dinethylformamide, ' two Asia of N "-pentamethyl
Ethyl triamine continues logical argon gas and continues 10min, and reacting 5h at 95 DEG C then to get the grafting has poly ion liquid
Silicon wafer.
Technical solution used by three achieved the object of the present invention is as follows:
A method of there is the silicon wafer of poly ion liquid to detect curcumin, feature as extractant using the grafting
It is: the following steps are included:
1) standard sample curcumin the extraction of curcumin: is diluted to 10 with the mixed solution of ethanol/water-5G/L takes 1mL
Curcumin solution after dilution extracts 20min under 35 DEG C of waters bath with thermostatic control in the centrifuge tube equipped with grafting poly ion liquid silicon wafer,
Silicon wafer and drying are taken out, surplus solution is analyzed by UFLC；
2) elution of curcumin: by treated in step 1), the silicon wafer mixed solution of 0.5mL methanol and acetic acid is eluted,
Eluent passes through efficient liquid phase chromatographic analysis.
Preferably, in the extraction process of the step 1) curcumin, ethyl alcohol in ethanol/water: the volume ratio of water is 1:4.
Preferably, in the elution process of the step 2) curcumin, methanol in the mixed solution of methanol and acetic acid: acetic acid
Volume ratio is 9:1, and used high-efficient liquid phase chromatogram condition is: C18Reverse-phase chromatographic column, flow velocity 0.3mL/min, ultraviolet detection
Wavelength is 426nm, and 35 DEG C of column temperature, mobile phase is the acetonitrile that volume ratio is 1:1: water, wherein contains volume ratio in acetonitrile and water
For 0.5% acetic acid.
The beneficial effects of the present invention are:
Novel crosslinking poly ion liquid is successfully grafted on silicon wafer, the silicon wafer of the grafting poly ion liquid realizes pair
Curcumin chemical compounds are rapidly enriched with and detect, with the operating time is short, amount of samples is small, is not necessarily to extractant, extraction item
The advantages that part is mild.The more single glyoxaline ion liquid of crosslinking poly ion liquid that the present invention is grafted has more stable, reproduction
More preferable, the stronger advantage of adsorption capacity of property.It is extracted using ionic liquid of the invention, greatly reduces the use of organic solvent
Amount, the advantage with low-carbon environment-friendly.
Detailed description of the invention
Fig. 1 is that silicon wafer bromination of the present invention handles photoelectricity subgraph.
Fig. 2 is silicon wafer of the present invention treated contact angle figure, and a is that silicon wafer hydroxylating handles contact angle, and b is silicon wafer amination
Contact angle is handled, c is that silicon wafer bromination handles contact angle, and d is contact angle after silicon wafer polymerization.
Fig. 3 is chromatogram of the invention, and (a) is the chromatogram of three kinds of curcumin solution, is (b) three kinds of ginger after Solid Phase Extraction
The chromatogram of flavine is (c) chromatogram after three kinds of curcumin elutions；1 is Bisdemethoxycurcumin, and 2 be single de-methoxy
Curcumin, 3 be curcumin.
Specific embodiment
In the following, being described further in conjunction with attached drawing and specific embodiment to the present invention:
Specific embodiment one:
The disclosed grafting of the present embodiment has the preparation method of the silicon wafer of poly ion liquid, which is characterized in that including walking as follows
It is rapid:
1) detailed process is as follows for silicon chip surface moditied processing:
1-1) cleaning silicon chip: the silicon wafer of well cutting is put into ethanol solution after ultrasound 5min to be rinsed with deionized water and is done
Only, it the concentrated sulfuric acid for being then 7:3 with volume ratio: is rinsed well, then spent with deionized water after hydrogenperoxide steam generator ultrasound 10min
Ionized water ultrasound 10min is finally rinsed well with deionized water with after 5% hydrofluoric acid solution ultrasound 10min, then is used deionized water
Ultrasonic 5min, is put into ethanol solution and saves.
1-2) hydroxylating is handled: silicon wafer described in step 1-1) is placed in 0.1molL-1Sodium hydroxide solution (0.2g hydrogen
Sodium oxide molybdena, 50 ml deionized waters) in impregnate 8min after rinsed well with deionization, silicon wafer is then placed in 0.1molL-1Nitre
15min is impregnated in acid solution (126uL concentrated nitric acid is dissolved in 30 milliliters of distilled water), is completed hydroxylating, is had silicon chip surface
Great amount of hydroxy group.
1-3) amination is handled: by the silicon wafer for completing hydroxylating in step 1-2) with being dried with nitrogen, being subsequently placed in 500
In the mixed solution of μ L3- TSL 8330 (97%) and 10mL dehydrated alcohol, it is protected from light for 24 hours, utilizes hydroxyl
Bonding action, silicon chip surface have a large amount of amino.
1-4) bromination is handled: step 1-3) the amidized silicon wafer being washed and used is dried with nitrogen, be placed in boiling flask
In, the mixed solution of 1.6mL pyridine and 20mL methylene chloride is added, 1mL bromo isobutyryl bromine solutions and 15mL bis- is then added dropwise
Chloromethanes solution after being added dropwise, reacts 12h, bromo on silicon chip surface bonded end band in ice-water bath.As shown in Figure 1, silicon
Piece passes through aforementioned four step process, successfully grafts bromo.
2) silicon chip surface grafts poly ion liquid, and detailed process is as follows:
2-1) cuprous bromide purifies: weighing 1.5g cuprous bromide in small beaker, 8mL glacial acetic acid is added, stirs at room temperature
It is filtered after mixing 2 hours, glacial acetic acid is removed, then washed cuprous bromide solid 3 times with 8mL glacial acetic acid, then by cuprous bromide solid
It is transferred in 9mL methanol solution, is filtered after being stirred at room temperature 1 hour, remove methanol solution, again with methanol washs cuprous bromide solid
Cuprous bromide colourless to filtrate, 50 DEG C of obtained solid vacuum drying will being filtered 48 hours to get purifying.
2-2) silicon chip surface polymerization grafting poly ion liquid: the 1- vinyl -3- benzene of 5mmol is added in 25mL three-necked bottle
Propyl imidazole villaumite and 1, the ionic liquid of-two-(1- vinyl imidazole) bromide of 1- (1,6- hexane) crosslinking, adds 5mL N,
Dinethylformamide solution, heating make ion liquid dissolving, and logical argon gas simultaneously continues 20min, and reaction flask is then placed in liquid nitrogen
In, the cuprous bromide and 0.0032g copper powder of 0.0072g purifying is added, argon gas is passed through after vacuumizing, while it is molten that 0.1mmoL is added
In 1mLN, N, N, N', the N of dinethylformamide, ' N "-five methyl diethylentriamine, continue logical argon gas and continue 10min,
Then the silicon wafer that 5h has poly ion liquid to get grafting is reacted at 95 DEG C.
As shown in Fig. 2, silicon wafer successively through hydroxylating, amination, bromination, grafting four steps of poly ion liquid, silicon wafer
Contact angle is gradually increased, and contact angle increase helps to promote the accumulation ability of curcumin, improves the stability of extraction process.
Specific embodiment two
The disclosed grafting of the present embodiment has the preparation method of the silicon wafer of poly ion liquid, which is characterized in that including walking as follows
It is rapid:
1) detailed process is as follows for silicon chip surface moditied processing:
1-1) cleaning silicon chip: the silicon wafer of well cutting is put into ethanol solution after ultrasound 5min to be rinsed with deionized water and is done
Only, it the concentrated sulfuric acid for being then 7:3 with volume ratio: is rinsed well, then spent with deionized water after hydrogenperoxide steam generator ultrasound 10min
Ionized water ultrasound 10min is finally rinsed well with deionized water with after 5% hydrofluoric acid solution ultrasound 10min, then is used deionized water
Ultrasonic 5min, is put into ethanol solution and saves.
1-2) hydroxylating is handled: silicon wafer described in step 1-1) is placed in 0.1molL-1Sodium hydroxide solution (0.2g hydrogen
Sodium oxide molybdena, 50 ml deionized waters) in impregnate 9min after rinsed well with deionization, silicon wafer is then placed in 0.1molL-1Nitre
18min is impregnated in acid solution (126uL concentrated nitric acid is dissolved in 30 milliliters of distilled water), is completed hydroxylating, is had silicon chip surface
Great amount of hydroxy group.
1-3) amination is handled: by the silicon wafer for completing hydroxylating in step 1-2) with being dried with nitrogen, being subsequently placed in 500
In the mixed solution of μ L3- TSL 8330 (97%) and 10mL dehydrated alcohol, it is protected from light 26h, utilizes hydroxyl
Bonding action, silicon chip surface have a large amount of amino.
1-4) bromination is handled: step 1-3) the amidized silicon wafer being washed and used is dried with nitrogen, be placed in boiling flask
In, the mixed solution of 1.6mL pyridine and 20mL methylene chloride is added, 1mL bromo isobutyryl bromine solutions and 15mL bis- is then added dropwise
Chloromethanes solution after being added dropwise, reacts 13h, bromo on silicon chip surface bonded end band in ice-water bath.As shown in Figure 1, silicon
Piece passes through aforementioned four step process, successfully grafts bromo.
2) silicon chip surface grafts poly ion liquid, and detailed process is as follows:
2-1) cuprous bromide purifies: weighing 1.5g cuprous bromide in small beaker, 8mL glacial acetic acid is added, stirs at room temperature
It is filtered after mixing 2 hours, glacial acetic acid is removed, then washed cuprous bromide solid 3 times with 8mL glacial acetic acid, then by cuprous bromide solid
It is transferred in 9mL methanol solution, is filtered after being stirred at room temperature 1 hour, remove methanol solution, again with methanol washs cuprous bromide solid
Cuprous bromide colourless to filtrate, 50 DEG C of obtained solid vacuum drying will being filtered 48 hours to get purifying.
2-2) silicon chip surface polymerization grafting poly ion liquid: the 1- vinyl -3- benzene of 5mmol is added in 25mL three-necked bottle
Propyl imidazole villaumite and 1, the ionic liquid of-two-(1- vinyl imidazole) bromide of 1- (1,6- hexane) crosslinking, adds 5mL N,
Dinethylformamide solution, heating make ion liquid dissolving, and logical argon gas simultaneously continues 20min, and reaction flask is then placed in liquid nitrogen
In, the cuprous bromide and 0.0032g copper powder of 0.0072g purifying is added, argon gas is passed through after vacuumizing, while it is molten that 0.1mmoL is added
In 1mLN, N, N, N', the N of dinethylformamide, ' N "-five methyl diethylentriamine, continue logical argon gas and continue 10min,
Then the silicon wafer that 4h has poly ion liquid to get grafting is reacted at 95 DEG C.
Specific embodiment three:
The disclosed grafting of the present embodiment has the preparation method of the silicon wafer of poly ion liquid, which is characterized in that including walking as follows
It is rapid:
1) detailed process is as follows for silicon chip surface moditied processing:
1-1) cleaning silicon chip: the silicon wafer of well cutting is put into ethanol solution after ultrasound 5min to be rinsed with deionized water and is done
Only, it the concentrated sulfuric acid for being then 7:3 with volume ratio: is rinsed well, then spent with deionized water after hydrogenperoxide steam generator ultrasound 10min
Ionized water ultrasound 10min is finally rinsed well with deionized water with after 5% hydrofluoric acid solution ultrasound 10min, then is used deionized water
Ultrasonic 5min, is put into ethanol solution and saves.
1-2) hydroxylating is handled: silicon wafer described in step 1-1) is placed in 0.1molL-1Sodium hydroxide solution (0.2g hydrogen
Sodium oxide molybdena, 50 ml deionized waters) in impregnate 10min after rinsed well with deionization, silicon wafer is then placed in 0.1molL-1
20min is impregnated in nitric acid solution (126uL concentrated nitric acid is dissolved in 30 milliliters of distilled water), is completed hydroxylating, is made silicon chip surface band
There is great amount of hydroxy group.
1-3) amination is handled: by the silicon wafer for completing hydroxylating in step 1-2) with being dried with nitrogen, being subsequently placed in 500
In the mixed solution of μ L3- TSL 8330 (97%) and 10mL dehydrated alcohol, it is protected from light 28h, utilizes hydroxyl
Bonding action, silicon chip surface have a large amount of amino.
1-4) bromination is handled: step 1-3) the amidized silicon wafer being washed and used is dried with nitrogen, be placed in boiling flask
In, the mixed solution of 1.6mL pyridine and 20mL methylene chloride is added, 1mL bromo isobutyryl bromine solutions and 15mL bis- is then added dropwise
Chloromethanes solution after being added dropwise, reacts 14h, bromo on silicon chip surface bonded end band in ice-water bath.As shown in Figure 1, silicon
Piece passes through aforementioned four step process, successfully grafts bromo.
2) silicon chip surface grafts poly ion liquid, and detailed process is as follows:
2-1) cuprous bromide purifies: weighing 1.5g cuprous bromide in small beaker, 8mL glacial acetic acid is added, stirs at room temperature
It is filtered after mixing 2 hours, glacial acetic acid is removed, then washed cuprous bromide solid 3 times with 8mL glacial acetic acid, then by cuprous bromide solid
It is transferred in 9mL methanol solution, is filtered after being stirred at room temperature 1 hour, remove methanol solution, again with methanol washs cuprous bromide solid
Cuprous bromide colourless to filtrate, 50 DEG C of obtained solid vacuum drying will being filtered 48 hours to get purifying.
2-2) silicon chip surface polymerization grafting poly ion liquid: the 1- vinyl -3- benzene of 5mmol is added in 25mL three-necked bottle
Propyl imidazole villaumite and 1, the ionic liquid of-two-(1- vinyl imidazole) bromide of 1- (1,6- hexane) crosslinking, adds 5mL N,
Dinethylformamide solution, heating make ion liquid dissolving, and logical argon gas simultaneously continues 20min, and reaction flask is then placed in liquid nitrogen
In, the cuprous bromide and 0.0032g copper powder of 0.0072g purifying is added, argon gas is passed through after vacuumizing, while it is molten that 0.1mmoL is added
In 1mLN, N, N, N', the N of dinethylformamide, ' N "-five methyl diethylentriamine, continue logical argon gas and continue 10min,
Then the silicon wafer that 4.5h has poly ion liquid to get grafting is reacted at 95 DEG C.
Application Example
There is the silicon wafer of poly ion liquid to detect curcumin as extractant using grafting disclosed by the invention, detailed process is such as
Under:
1) extraction of curcumin: the ethyl alcohol for being 1:4 with volume ratio: standard sample curcumin is diluted to by the mixed solution of water
10-5G/L, the curcumin solution after taking 1mL to dilute is in the centrifuge tube equipped with grafting poly ion liquid silicon wafer, 35 DEG C of waters bath with thermostatic control
Lower extraction 20min, takes out silicon wafer and drying, and surplus solution is analyzed by UFLC.
2) elution of curcumin: by treated in step 1) silicon wafer 0.5mL methanol: acetic acid volume ratio is the molten of 9:1
Liquid elution, eluent pass through efficient liquid phase chromatographic analysis.
Liquid phase chromatogram condition of the present invention is: C18Reverse-phase chromatographic column, flow velocity 0.3mL/min, ultraviolet detection wave
A length of 426nm, 35 DEG C of column temperature, mobile phase is the acetonitrile that volume ratio is 1:1: water, is wherein containing volume ratio in acetonitrile and water
0.5% acetic acid.Testing result as shown in figure 3, using the silicon wafer of grafting poly ion liquid disclosed by the invention as extractant,
Three kinds of curcumins can be effectively enriched with, and bioaccumulation efficiency is high, can accurately detect curcumin by high performance liquid chromatography, be answered for clinic
With providing scientific research value.
For those skilled in the art, it can make other each according to the above description of the technical scheme and ideas
Kind is corresponding to be changed and deforms, and all these change and deform the protection model that all should belong to the claims in the present invention
Within enclosing.
Claims (9)
1. a kind of graft the silicon wafer for having poly ion liquid, including silicon wafer, it is characterised in that: hydroxyl is successively passed through on the surface of the silicon wafer
Base processing, amination processing and bromination processing；Grafting has poly ion liquid on the silicon chip surface;
It is described to graft the preparation method for having the silicon wafer of poly ion liquid, include the following steps:
1) detailed process is as follows for silicon chip surface moditied processing:
1-1) hydroxylating is handled: silicon wafer being placed in sodium hydroxide solution after impregnating 8-10min and is rinsed well with deionization, then
Silicon wafer is placed in nitric acid solution and impregnates 15-20min, completes silicon wafer hydroxylating；
1-2) amination is handled: will be completed hydroxylated silicon wafer in step 1-1) with being dried with nitrogen, is subsequently placed in the 97% of 500 μ L
In the mixed solution of 3- TSL 8330 and 10mL dehydrated alcohol, it is protected from light 24-28h, i.e. completion silicon wafer ammonia
Base；
1-3) bromination is handled: step 1-2) the amidized silicon wafer being washed and used is dried with nitrogen, be placed in boiling flask, add
Enter the mixed solution of 1.6mL pyridine and 20mL methylene chloride, 1mL bromo isobutyryl bromine solutions and 15mL methylene chloride is then added dropwise
Solution after being added dropwise, reacts 12-14h in ice-water bath；
2) detailed process is as follows for grafting processing:
2-1) cuprous bromide purifies: weighing 1.5g cuprous bromide in small beaker, 8mL glacial acetic acid is added, it is small to stir 2 at room temperature
When after filter, remove glacial acetic acid, then washed cuprous bromide solid 3 times with 8mL glacial acetic acid, be then transferred to cuprous bromide solid
In 9mL methanol solution, filtered after 1h is stirred at room temperature, remove methanol solution, again with methanol wash cuprous bromide solid to filtrate without
Color, the cuprous bromide that 50 DEG C of obtained solid vacuum drying will be filtered 48 hours to get purifying；
2-2) silicon chip surface polymerization grafting poly ion liquid: the 1- vinyl -3- phenylpropyl of 5mmol is added in 25mL three-necked bottle
Imidazoles villaumite and 1,1- (1,6- hexane)-two-(1- vinyl imidazole) bromide cross-linking ion liquid, adds 5mL N, N- diformazan
Base formamide solution, heating are passed through argon gas after making ion liquid dissolving and continue 20min, then reaction flask is placed in liquid nitrogen,
The cuprous bromide and 0.0032g copper powder of purifying described in 0.0072g is added, argon gas is passed through after vacuumizing, while 0.1mmoL is added
It is dissolved in 1mLN, N, N, N', the N of dinethylformamide, ' N''- five methyl diethylentriamine, continue logical argon gas and continues
Then 10min reacts 4-5h at 95 DEG C to get the silicon wafer grafted and have poly ion liquid.
2. according to claim 1 graft the silicon wafer for having poly ion liquid, it is characterised in that: the step 1-1) hydroxylating
Further include Wafer Cleaning before processing, Wafer Cleaning process is as follows: the silicon wafer of well cutting is put into ethanol solution after ultrasound 5min
It is rinsed well with deionized water, is used after the mixed solution ultrasound 10min of the concentrated sulfuric acid and hydrogen peroxide that are then 7:3 with volume ratio
Deionized water is rinsed well, then with deionized water ultrasound 10min, finally with using deionization after 5% hydrofluoric acid solution ultrasound 10min
Water is rinsed well, then with deionized water ultrasound 5min, is put into ethanol solution and is saved.
3. according to claim 2 graft the silicon wafer for having poly ion liquid, it is characterised in that: the step 1-1) hydroxylating
In processing, the silicon wafer of cleaning is placed in 0.1mol/L sodium hydroxide solution after impregnating 8min and is rinsed well with deionization,
Then silicon wafer is placed in 0.1mol/L nitric acid solution and impregnates 15min, complete silicon wafer hydroxylating.
4. according to claim 1 graft the silicon wafer for having poly ion liquid, it is characterised in that: the step 1-2) amination
In processing, hydroxylated silicon wafer will be completed in step 1-1) with being dried with nitrogen, be subsequently placed in the 97%3- aminopropyl three of 500 μ L
It in the mixed solution of methoxy silane and 10mL dehydrated alcohol, is protected from light for 24 hours, i.e. completion silicon wafer amination.
5. according to claim 1 graft has the silicon wafer of poly ion liquid, it is characterised in that: the step 1-3) at bromination
It in reason, step 1-2) the amidized silicon wafer is washed and used is dried with nitrogen, be placed in boiling flask, 1.6mL pyridine is added
With the mixed solution of 20mL methylene chloride, 1mL bromo isobutyryl bromine solutions and 15mL dichloromethane solution is then added dropwise, drips
Bi Hou reacts 12h in ice-water bath, i.e. completion silicon wafer bromination.
6. according to claim 1 graft the silicon wafer for having poly ion liquid, it is characterised in that: the step 2-2) silicon wafer table
During face polymerization grafting poly ion liquid, the 1- vinyl -3- phenylpropyl imidazoles villaumite of 5mmol is added in 25mL three-necked bottle
With 1,1- (1,6- hexane)-two-(1- vinyl imidazole) bromide cross-linking ion liquid, 5mL n,N-Dimethylformamide is added
Solution, heating are passed through argon gas after making ion liquid dissolving and continue 20min, then reaction flask is placed in liquid nitrogen, are added
The cuprous bromide and 0.0032g copper powder of purifying described in 0.0072g, are passed through argon gas, while 0.1mmoL is added and is dissolved in after vacuumizing
1mLN, N, N, N', the N of dinethylformamide, ' N''- five methyl diethylentriamine, continue logical argon gas and continue 10min,
Then 5h is reacted at 95 DEG C to get the silicon wafer grafted and have poly ion liquid.
7. a kind of have side of the silicon wafer of poly ion liquid as extractant detection curcumin using grafting described in claim 1
Method, it is characterised in that: the following steps are included:
1) standard sample curcumin the extraction of curcumin: is diluted to 10 with the mixed solution of ethanol/water-5G/L takes 1mL to dilute
Curcumin solution afterwards extracts 20min under 35 DEG C of waters bath with thermostatic control in the centrifuge tube equipped with grafting poly ion liquid silicon wafer, takes out
Silicon wafer and drying, surplus solution are analyzed by UFLC；
2) elution of curcumin: by treated in step 1), the silicon wafer mixed solution of 0.5mL methanol and acetic acid is eluted, elution
Liquid passes through efficient liquid phase chromatographic analysis.
8. grafting according to claim 7 has method of the silicon wafer of poly ion liquid as extractant detection curcumin,
Be characterized in that: in the extraction process of the step 1) curcumin, ethyl alcohol in ethanol/water: the volume ratio of water is 1:4.
9. grafting according to claim 7 has method of the silicon wafer of poly ion liquid as extractant detection curcumin,
It is characterized in that: in the elution process of the step 2 curcumin, methanol in the mixed solution of methanol and acetic acid: the volume ratio of acetic acid
For 9:1, used high-efficient liquid phase chromatogram condition is: C18Reverse-phase chromatographic column, flow velocity 0.3mL/min, ultraviolet detection wavelength are
426nm, 35 DEG C of column temperature, mobile phase be in the acetonitrile that volume ratio is 1:1: water, wherein acetonitrile and water containing volume ratio be 0.5%
Acetic acid.
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