CN106390948A - Silicon wafer grafted with polyionic liquid, preparation method and application thereof - Google Patents
Silicon wafer grafted with polyionic liquid, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a silicon wafer grafted with a polyionic liquid, a preparation method and application thereof. The silicon wafer grafted with the polyionic liquid is formed by that 1-vinyl-3-phenylpropyl imidazole chloride salt and 1,1-(1, 6-hexane) bis (1-vinyl imidazole) bromide salt as two kinds of the polyionic liquid are used as monomers and grafted on the modified silicon wafer surface by atom transfer radical polymerization (ATRP) reaction, three curcumin substances including mono-demethoxy curcumin, bis-demethoxy curcumin and curcumin can be obtained by solid phase extraction. By use of the synthesized silicon wafer loaded with the polyionic liquid, the stability of extraction process can be improved, the extraction adsorption amount can be enhanced, the curcumin can be accurately detected through high performance liquid chromatography, and the reproducibility is good.
Description
Technical field
The invention belongs to solid phase extraction techniques field, extract particular by synthesizing a kind of new solid phase
Take agent and with this solid extracting agent be enriched with single demethoxycurcumin, bisdemethoxycurcumin,
Curcumin and obtain detection curcumin method.
Background technology
Curcumin (C21H2O6) it is to extract in plant roots and stems from part Zingiberaceae, Araeceae
A kind of chemical composition, has the effect such as blood fat reducing, anticoagulant, antioxidation, function of gallbladder promoting, anticancer, can
Prevention arthroncuss, arthritis, also have to diseases such as cardiovascular disease, cancers and necessarily control curative effect
Really.The enrichment of curcumin is significant to clinical diagnosises with detection, but, existing
How curcumin detection method poor reproducibility, interference are it is impossible to accurately and effectively detect curcumin.
In recent years, ionic liquid at room temperature especially glyoxaline ion liquid plays in chemical field
Important function.Ionic liquid at room temperature is a kind of by macromolecule organic cation and inorganic or organic
The fuse salt of anion composition, fusing point is less than 100 DEG C, is generally near room temperature, inorganic to many
Salt and Organic substance have good dissolubility.In high performance liquid chromatography, ion, polycyclic aromatic hydrocarbon,
The materials such as amine, nucleoside are mainly carried out point as solid extracting agent with the silicon chip of Ionic Liquid Modified
From.Poly ion liquid is grafted onto silicon chip surface, is poly- based on solid phase micro-extraction technique and load
Ionic liquids technologies.Poly ion liquid utilizes physical absorption, self assembly or polymerization by ion
Liquid is fixed on solid, liquid, polymer or aeroge, thus avoiding ionic liquid in extraction
Leaching during taking, has saved cost, also improves the stability of extraction process.However,
By single glyoxaline ion liquid synthesize load poly ion liquid modify solid during often
Effect on driving birds is not good.Therefore, improve the stability of extraction process further and strengthen extraction absorption measurer
There is great scientific research value.
Content of the invention
For the deficiencies in the prior art, an object of the present invention is with 1- vinyl -3- phenylpropyl alcohol
Base imidazoles villaumite and 1,1- (1,6- hexane)-two-(1- vinyl imidazole) two kinds of ionic liquid of bromide
Body is monomer, is reacted by atom transfer radical polymerization (ATRP), is grafted onto modified
Silicon chip surface, synthesis grafting has the silicon chip of poly ion liquid, can Solid-Phase Extraction curcumin, carry
The high stability of extraction process, enhances extraction adsorbance.
The second object of the present invention be with the method for the present invention synthesize one kind have extraction efficiency high,
The stable grafting of extraction process has the silicon chip of poly ion liquid.
The third object of the present invention is that have the silicon chip of poly ion liquid with the grafting of present invention synthesis
As extractant, extract curcumin with this extractant, then detect Rhizoma Zingiberis Recens with high performance liquid chromatography
Flavin, the method accurately can not only detect curcumin, and favorable reproducibility, and clinical practice is had very
Big scientific research value.
Realize the technical scheme that an object of the present invention adopted as follows：
A kind of grafting has the silicon chip of poly ion liquid, including silicon chip it is characterised in that：Described silicon
The surface of piece sequentially passes through hydroxylating process, amination process and bromination and processes；Described silicon chip table
On face, grafting has poly ion liquid.
Realize the technical scheme that the second object of the present invention adopted as follows：
A kind of grafting have poly ion liquid silicon chip it is characterised in that：Comprise the steps：
1) detailed process of silicon chip surface moditied processing is as follows：
1-1) hydroxylating is processed：Silicon chip is placed in sodium hydroxide solution and soaks after 8-10min
Rinsed well with deionization, then silicon chip is placed in immersion 15-20min in salpeter solution, complete
Become silicon chip hydroxylating；
1-2) amination is processed：By step 1-1) in complete hydroxylated silicon chip nitrogen and blow
Dry, it is subsequently placed in 97%3- TSL 8330 and the anhydrous second of 10mL of 500 μ L
In the mixed solution of alcohol, lucifuge reacts 24-28h, that is, complete silicon chip amination；
1-3) bromination is processed：By step 1-2) described amidized silicon chip washs and uses nitrogen
Dry up, be placed in boiling flask, the mixing of addition 1.6mL pyridine and 20mL dichloromethane is molten
Liquid, then Deca 1mL bromo isobutyryl bromine solutions and 15mL dichloromethane solution, drip
Bi Hou, reacts 12-14h in ice-water bath；
2) detailed process that grafting is processed is as follows：
2-1) cuprous bromide purification：Weigh 1.5g cuprous bromide in small beaker, add 8mL
Glacial acetic acid, stirring at room temperature was filtered after 2 hours, removes glacial acetic acid, then uses 8mL glacial acetic acid
Washing cuprous bromide solid 3 times, then cuprous bromide solid is transferred in 9mL methanol solution,
Filter after 1h is stirred at room temperature, remove methanol solution, again with methanol washing cuprous bromide solid is extremely
Filtrate is colourless, will filter 50 DEG C of gained solid and be vacuum dried 48 hours, and obtain final product the bromination of purification
Cuprous；
2-2) silicon chip surface polymerization grafting poly ion liquid：5mmol is added in 25mL three-necked bottle
1- vinyl -3- phenylpropyl imidazoles villaumite and 1,1- (1,6- hexane)-two-(1- vinyl miaow
Azoles) bromide cross-linking ion liquid, add 5mL DMF solution, heating makes
It is passed through argon after ion liquid dissolving and continues 20min, then reaction bulb is placed in liquid nitrogen,
Add the cuprous bromide of purification and 0.0032g copper powder described in 0.0072g, be passed through after evacuation
Argon, is simultaneously introduced 0.1mmoL and is dissolved in 1mLN, dinethylformamide
N, N, N', N, ' N "-five methyl diethylentriamine, continue logical argon and continue 10min, so
React 4-5h at 95 DEG C, obtaining final product described grafting has the silicon chip of poly ion liquid.
Preferably, described step 1-1) before silicon chip hydroxylation procedures, also include Wafer Cleaning,
Wafer Cleaning process is as follows：The silicon chip of well cutting is put into and uses after ultrasonic 5min in ethanol solution
Deionized water rinsing is clean, then uses volume ratio to be 7:3 concentrated sulphuric acid and the mixing of hydrogen peroxide
After the ultrasonic 10min of solution, deionized water is rinsed well, the more ultrasonic 10min of deionized water,
Finally rinsed well with deionized water after the ultrasonic 10min of 5% hydrofluoric acid solution, then spend from
The ultrasonic 5min of sub- water, puts in ethanol solution and preserves.
Preferably, described step 1-1) silicon chip hydroxylating process in, will cleaning described silicon chip
It is placed in and rinsed well with deionization, then after soaking 8min in 0.1mol/L sodium hydroxide solution
Silicon chip is placed in immersion 15min in 0.1mol/L salpeter solution, completes silicon chip hydroxylating.
Preferably, described step 1-2) silicon chip amination process in, by step 1-1) in complete
Become hydroxylated silicon chip nitrogen to dry up, be subsequently placed in the 97%3- aminopropyl front three of 500 μ L
In the mixed solution of TMOS and 10mL dehydrated alcohol, lucifuge reaction 24, that is, complete silicon chip
Amination.
Preferably, described step 1-3) silicon chip bromination process in, by step 1-2) described ammonia
The silicon chip washing of base is simultaneously dried up with nitrogen, is placed in boiling flask, add 1.6mL pyridine and
The mixed solution of 20mL dichloromethane, then Deca 1mL bromo isobutyryl bromine solutions and 15mL
Dichloromethane solution, after completion of dropping, reacts 12h in ice-water bath, that is, completes silicon chip bromination.
Preferably, described step 2-2) silicon chip surface polymerization grafting poly ion liquid during,
In 25mL three-necked bottle add 5mmol 1- vinyl -3- phenylpropyl imidazoles villaumite and
1,1- (1,6- hexane)-two-(1- vinyl imidazole) bromide cross-linking ion liquid, adds 5mL
DMF solution, heating is passed through argon and continues after making ion liquid dissolving
20min, then reaction bulb is placed in liquid nitrogen, adds the protobromide of purification described in 0.0072g
Copper and 0.0032g copper powder, are passed through argon after evacuation, are simultaneously introduced 0.1mmoL and are dissolved in
1mLN, N, N, N', the N of dinethylformamide, ' N "-five methyl diethylentriamine, continue
Logical argon simultaneously continues 10min, then at 95 DEG C react 5h, obtain final product described grafting have gather from
The silicon chip of sub- liquid.
Realize the technical scheme that the third object of the present invention adopted as follows：
A kind of have the silicon chip of poly ion liquid as extractant detection Rhizoma Curcumae Longae using described grafting
Element method it is characterised in that：Comprise the following steps：
1) extraction of curcumin：With the mixed solution of ethanol/water, standard sample curcumin is diluted
To 10-5G/L, takes the curcumin solution after 1mL dilution in equipped with grafting poly ion liquid silicon chip
Centrifuge tube in, under 35 DEG C of waters bath with thermostatic control extract 20min, take out silicon chip and be dried, residue molten
Liquid is analyzed by UFLC；
2) eluting of curcumin：By step 1) in process after silicon chip with 0.5mL methanol and
The mixed solution eluting of acetic acid, eluent passes through efficient liquid phase chromatographic analysis.
Preferably, described step 1) curcumin extraction process in, ethanol in ethanol/water：
The volume ratio of water is 1:4.
Preferably, described step 2) curcumin elution process in, the mixing of methanol and acetic acid
Methanol in solution：The volume ratio of acetic acid is 9:1, the high-efficient liquid phase chromatogram condition being adopted is：
C18Reversed phase chromatographic column, flow velocity is 0.3mL/min, and ultraviolet detection wavelength is 426nm, 35 DEG C of column temperature,
Mobile phase is 1 for volume ratio:1 acetonitrile：In water, wherein acetonitrile and water containing volume ratio it is all
0.5% acetic acid.
The beneficial effects of the present invention is：
The new crosslinked poly ion liquid of successful grafting, this grafting poly ion liquid on silicon chip
Silicon chip achieve and curcumin chemical compounds be rapidly enriched with and detect that there is the operating time
Short, amount of samples is little, without extractant, extraction conditionss gentle the advantages of.The present invention is transferred
The more single glyoxaline ion liquid of crosslinked poly ion liquid connecing has more stable, repeatability more
Advantage good, that absorbability is higher.Ionic liquid using the present invention is extracted, and significantly drops
The low consumption of organic solvent, has the advantage of low-carbon environment-friendly.
Brief description
Fig. 1 is that silicon chip bromination of the present invention processes photoelectricity subgraph.
Fig. 2 process for silicon chip of the present invention after contact angle figure, a be silicon chip hydroxylating process contact
Angle, b processes contact angle for silicon chip amination, and c processes contact angle for silicon chip bromination, and d is silicon
Contact angle after piece polymerization.
Fig. 3 is the chromatogram of the present invention, and (a) is the chromatogram of three kinds of curcumin solution, (b)
For the chromatogram of three kinds of curcumins after Solid-Phase Extraction, (c) is the color after three kinds of curcumin eluting
Spectrogram；1 is bisdemethoxycurcumin, and 2 is single demethoxycurcumin, and 3 is curcumin.
Specific embodiment
Below, in conjunction with accompanying drawing and specific embodiment, the present invention is described further：
Specific embodiment one：
Grafting disclosed in the present embodiment has the preparation method of the silicon chip of poly ion liquid, and its feature exists
In comprising the steps：
1) detailed process of silicon chip surface moditied processing is as follows：
1-1) cleaning silicon chip：The silicon chip of well cutting is put into and uses after ultrasonic 5min in ethanol solution
Deionized water rinsing is clean, then uses volume ratio to be 7:3 concentrated sulphuric acid：Hydrogenperoxide steam generator surpasses
After sound 10min, deionized water is rinsed well, the more ultrasonic 10min of deionized water, finally uses
After the ultrasonic 10min of 5% hydrofluoric acid solution, deionized water is rinsed well, then deionized water is ultrasonic
5min, puts in ethanol solution and preserves.
1-2) hydroxylating is processed：By step 1-1) described in silicon chip be placed in 0.1mol L-1Hydrogen-oxygen
Change spend after soaking 8min in sodium solution (0.2g sodium hydroxide, 50 ml deionized water) from
Son is rinsed well, then silicon chip is placed in 0.1mol L-1(126uL concentrated nitric acid is molten for salpeter solution
In 30 milliliters of distilled water) middle immersion 15min, complete hydroxylating, make silicon chip surface band
There is great amount of hydroxy group.
1-3) amination is processed：By step 1-2) in complete the silicon chip nitrogen of hydroxylating
Air-blowing is done, and is subsequently placed in 500 μ L3- TSL 8330 (97%) and 10mL anhydrous
In the mixed solution of ethanol, lucifuge reacts 24h, using the bonding action of hydroxyl, silicon chip surface
With a large amount of amino.
1-4) bromination is processed：By step 1-3) described amidized silicon chip washs and uses nitrogen
Dry up, be placed in boiling flask, the mixing of addition 1.6mL pyridine and 20mL dichloromethane is molten
Liquid, then Deca 1mL bromo isobutyryl bromine solutions and 15mL dichloromethane solution, drip
Bi Hou, reacts 12h, bromo on silicon chip surface bonded end band in ice-water bath.As Fig. 1 institute
Show, silicon chip is through aforementioned four step process, successful grafting bromo.
2) silicon chip surface grafting poly ion liquid, detailed process is as follows：
2-1) cuprous bromide purification：Weigh 1.5g cuprous bromide in small beaker, add 8mL
Glacial acetic acid, stirring at room temperature was filtered after 2 hours, removes glacial acetic acid, then uses 8mL glacial acetic acid
Washing cuprous bromide solid 3 times, then cuprous bromide solid is transferred in 9mL methanol solution,
Filter after being stirred at room temperature 1 hour, remove methanol solution, again with methanol washs cuprous bromide solid
Colourless to filtrate, 50 DEG C of gained solid will be filtered and be vacuum dried 48 hours, obtain final product the bromine of purification
Change cuprous.
2-2) silicon chip surface polymerization grafting poly ion liquid：5mmol is added in 25mL three-necked bottle
1- vinyl -3- phenylpropyl imidazoles villaumite and 1,1- (1,6- hexane)-two-(1- vinyl miaow
Azoles) the crosslinked ionic liquid of bromide, add 5mL DMF solution, heating
Make ion liquid dissolving, logical argon simultaneously continues 20min, then reaction bulb is placed in liquid nitrogen,
Add cuprous bromide and the 0.0032g copper powder of 0.0072g purification, after evacuation, be passed through argon,
It is simultaneously introduced 0.1mmoL and be dissolved in 1mLN, N, N, N', the N of dinethylformamide, ' N "-five first
Base diethylenetriamines, continue logical argon and continue 10min, then react 5h at 95 DEG C,
Obtaining final product grafting has the silicon chip of poly ion liquid.
As shown in Fig. 2 through hydroxylating, amination, bromination, grafting polyion liquid after silicon chip elder generation
Four steps of body, the contact angle of silicon chip is gradually increased, and contact angle increases and contributes to lifting curcumin
Accumulation ability, improve the stability of extraction process.
Specific embodiment two
Grafting disclosed in the present embodiment has the preparation method of the silicon chip of poly ion liquid, and its feature exists
In comprising the steps：
1) detailed process of silicon chip surface moditied processing is as follows：
1-1) cleaning silicon chip：The silicon chip of well cutting is put into and uses after ultrasonic 5min in ethanol solution
Deionized water rinsing is clean, then uses volume ratio to be 7:3 concentrated sulphuric acid：Hydrogenperoxide steam generator surpasses
After sound 10min, deionized water is rinsed well, the more ultrasonic 10min of deionized water, finally uses
After the ultrasonic 10min of 5% hydrofluoric acid solution, deionized water is rinsed well, then deionized water is ultrasonic
5min, puts in ethanol solution and preserves.
1-2) hydroxylating is processed：By step 1-1) described in silicon chip be placed in 0.1mol L-1Hydrogen-oxygen
Change spend after soaking 9min in sodium solution (0.2g sodium hydroxide, 50 ml deionized water) from
Son is rinsed well, then silicon chip is placed in 0.1mol L-1(126uL concentrated nitric acid is molten for salpeter solution
In 30 milliliters of distilled water) middle immersion 18min, complete hydroxylating, make silicon chip surface band
There is great amount of hydroxy group.
1-3) amination is processed：By step 1-2) in complete the silicon chip nitrogen of hydroxylating
Air-blowing is done, and is subsequently placed in 500 μ L3- TSL 8330 (97%) and 10mL anhydrous
In the mixed solution of ethanol, lucifuge reacts 26h, using the bonding action of hydroxyl, silicon chip surface
With a large amount of amino.
1-4) bromination is processed：By step 1-3) described amidized silicon chip washs and uses nitrogen
Dry up, be placed in boiling flask, the mixing of addition 1.6mL pyridine and 20mL dichloromethane is molten
Liquid, then Deca 1mL bromo isobutyryl bromine solutions and 15mL dichloromethane solution, drip
Bi Hou, reacts 13h, bromo on silicon chip surface bonded end band in ice-water bath.As Fig. 1 institute
Show, silicon chip is through aforementioned four step process, successful grafting bromo.
2) silicon chip surface grafting poly ion liquid, detailed process is as follows：
2-1) cuprous bromide purification：Weigh 1.5g cuprous bromide in small beaker, add 8mL
Glacial acetic acid, stirring at room temperature was filtered after 2 hours, removes glacial acetic acid, then uses 8mL glacial acetic acid
Washing cuprous bromide solid 3 times, then cuprous bromide solid is transferred in 9mL methanol solution,
Filter after being stirred at room temperature 1 hour, remove methanol solution, again with methanol washs cuprous bromide solid
Colourless to filtrate, 50 DEG C of gained solid will be filtered and be vacuum dried 48 hours, obtain final product the bromine of purification
Change cuprous.
2-2) silicon chip surface polymerization grafting poly ion liquid：5mmol is added in 25mL three-necked bottle
1- vinyl -3- phenylpropyl imidazoles villaumite and 1,1- (1,6- hexane)-two-(1- vinyl miaow
Azoles) the crosslinked ionic liquid of bromide, add 5mL DMF solution, heating
Make ion liquid dissolving, logical argon simultaneously continues 20min, then reaction bulb is placed in liquid nitrogen,
Add cuprous bromide and the 0.0032g copper powder of 0.0072g purification, after evacuation, be passed through argon,
It is simultaneously introduced 0.1mmoL and be dissolved in 1mLN, N, N, N', the N of dinethylformamide, ' N "-five first
Base diethylenetriamines, continue logical argon and continue 10min, then react 4h at 95 DEG C,
Obtaining final product grafting has the silicon chip of poly ion liquid.
Specific embodiment three：
Grafting disclosed in the present embodiment has the preparation method of the silicon chip of poly ion liquid, and its feature exists
In comprising the steps：
1) detailed process of silicon chip surface moditied processing is as follows：
1-1) cleaning silicon chip：The silicon chip of well cutting is put into and uses after ultrasonic 5min in ethanol solution
Deionized water rinsing is clean, then uses volume ratio to be 7:3 concentrated sulphuric acid：Hydrogenperoxide steam generator surpasses
After sound 10min, deionized water is rinsed well, the more ultrasonic 10min of deionized water, finally uses
After the ultrasonic 10min of 5% hydrofluoric acid solution, deionized water is rinsed well, then deionized water is ultrasonic
5min, puts in ethanol solution and preserves.
1-2) hydroxylating is processed：By step 1-1) described in silicon chip be placed in 0.1mol L-1Hydrogen-oxygen
Change and spend after soaking 10min in sodium solution (0.2g sodium hydroxide, 50 ml deionized water)
Ion is rinsed well, then silicon chip is placed in 0.1mol L-1Salpeter solution (126uL concentrated nitric acid
It is dissolved in 30 milliliters of distilled water) middle immersion 20min, complete hydroxylating, make silicon chip surface
With great amount of hydroxy group.
1-3) amination is processed：By step 1-2) in complete the silicon chip nitrogen of hydroxylating
Air-blowing is done, and is subsequently placed in 500 μ L3- TSL 8330 (97%) and 10mL anhydrous
In the mixed solution of ethanol, lucifuge reacts 28h, using the bonding action of hydroxyl, silicon chip surface
With a large amount of amino.
1-4) bromination is processed：By step 1-3) described amidized silicon chip washs and uses nitrogen
Dry up, be placed in boiling flask, the mixing of addition 1.6mL pyridine and 20mL dichloromethane is molten
Liquid, then Deca 1mL bromo isobutyryl bromine solutions and 15mL dichloromethane solution, drip
Bi Hou, reacts 14h, bromo on silicon chip surface bonded end band in ice-water bath.As Fig. 1 institute
Show, silicon chip is through aforementioned four step process, successful grafting bromo.
2) silicon chip surface grafting poly ion liquid, detailed process is as follows：
2-1) cuprous bromide purification：Weigh 1.5g cuprous bromide in small beaker, add 8mL
Glacial acetic acid, stirring at room temperature was filtered after 2 hours, removes glacial acetic acid, then uses 8mL glacial acetic acid
Washing cuprous bromide solid 3 times, then cuprous bromide solid is transferred in 9mL methanol solution,
Filter after being stirred at room temperature 1 hour, remove methanol solution, again with methanol washs cuprous bromide solid
Colourless to filtrate, 50 DEG C of gained solid will be filtered and be vacuum dried 48 hours, obtain final product the bromine of purification
Change cuprous.
2-2) silicon chip surface polymerization grafting poly ion liquid：5mmol is added in 25mL three-necked bottle
1- vinyl -3- phenylpropyl imidazoles villaumite and 1,1- (1,6- hexane)-two-(1- vinyl miaow
Azoles) the crosslinked ionic liquid of bromide, add 5mL DMF solution, heating
Make ion liquid dissolving, logical argon simultaneously continues 20min, then reaction bulb is placed in liquid nitrogen,
Add cuprous bromide and the 0.0032g copper powder of 0.0072g purification, after evacuation, be passed through argon,
It is simultaneously introduced 0.1mmoL and be dissolved in 1mLN, N, N, N', the N of dinethylformamide, ' N "-five first
Base diethylenetriamines, continue logical argon and continue 10min, then react 4.5h at 95 DEG C,
Obtaining final product grafting has the silicon chip of poly ion liquid.
Application Example
Rhizoma Zingiberis Recens are detected as extractant using the silicon chip that grafting disclosed by the invention has poly ion liquid
Flavin, detailed process is as follows：
1) extraction of curcumin：It is 1 with volume ratio:4 ethanol：The mixed solution of water will be marked
Quasi- sample curcumin is diluted to 10-5G/L, takes the curcumin solution after 1mL dilution in equipped with transferring
Connect in the centrifuge tube of poly ion liquid silicon chip, under 35 DEG C of waters bath with thermostatic control, extract 20min, take out silicon
Piece is simultaneously dried, and surplus solution is analyzed by UFLC.
2) eluting of curcumin：By step 1) in process after silicon chip 0.5mL methanol：
Acetic acid volume ratio is 9:1 eluant solution, eluent passes through efficient liquid phase chromatographic analysis.
Liquid phase chromatogram condition of the present invention is：C18Reversed phase chromatographic column, flow velocity is
0.3mL/min, ultraviolet detection wavelength is 426nm, 35 DEG C of column temperature, and mobile phase for volume ratio is
1:1 acetonitrile：The acetic acid being all 0.5% containing volume ratio in water, wherein acetonitrile and water.Detection
Result is as shown in figure 3, adopt the silicon chip of grafting poly ion liquid disclosed by the invention as extraction
Agent, can effectively be enriched with three kinds of curcumins, and bioaccumulation efficiency is high, can pass through high-efficient liquid phase color Prepenem
Accurately detection curcumin, is that clinical practice provides scientific research value.
For a person skilled in the art, can technical scheme as described above and structure
Think, make other various corresponding changes and deform, and all these changes and deforms
All should belong within the protection domain of the claims in the present invention.
Claims (10)
1. a kind of grafting has the silicon chip of poly ion liquid, including silicon chip it is characterised in that：Institute
The surface stating silicon chip sequentially passes through hydroxylating process, amination process and bromination process；Described silicon
Grafting on piece surface has poly ion liquid.
2. a kind of grafting as claimed in claim 1 has the preparation side of the silicon chip of poly ion liquid
Method is it is characterised in that comprise the steps：
1) detailed process of silicon chip surface moditied processing is as follows：
1-1) hydroxylating is processed：Silicon chip is placed in sodium hydroxide solution and soaks after 8-10min
Rinsed well with deionization, then silicon chip is placed in immersion 15-20min in salpeter solution, complete
Become silicon chip hydroxylating；
1-2) amination is processed：By step 1-1) in complete hydroxylated silicon chip nitrogen and blow
Dry, it is subsequently placed in 97%3- TSL 8330 and the anhydrous second of 10mL of 500 μ L
In the mixed solution of alcohol, lucifuge reacts 24-28h, that is, complete silicon chip amination；
1-3) bromination is processed：By step 1-2) described amidized silicon chip washs and uses nitrogen
Dry up, be placed in boiling flask, the mixing of addition 1.6mL pyridine and 20mL dichloromethane is molten
Liquid, then Deca 1mL bromo isobutyryl bromine solutions and 15mL dichloromethane solution, drip
Bi Hou, reacts 12-14h in ice-water bath；
2) detailed process that grafting is processed is as follows：
2-1) cuprous bromide purification：Weigh 1.5g cuprous bromide in small beaker, add 8mL
Glacial acetic acid, stirring at room temperature was filtered after 2 hours, removes glacial acetic acid, then uses 8mL glacial acetic acid
Washing cuprous bromide solid 3 times, then cuprous bromide solid is transferred in 9mL methanol solution,
Filter after 1h is stirred at room temperature, remove methanol solution, again with methanol washing cuprous bromide solid is extremely
Filtrate is colourless, will filter 50 DEG C of gained solid and be vacuum dried 48 hours, and obtain final product the bromination of purification
Cuprous；
2-2) silicon chip surface polymerization grafting poly ion liquid：5mmol is added in 25mL three-necked bottle
1- vinyl -3- phenylpropyl imidazoles villaumite and 1,1- (1,6- hexane)-two-(1- vinyl miaow
Azoles) bromide cross-linking ion liquid, add 5mL DMF solution, heating makes
It is passed through argon after ion liquid dissolving and continues 20min, then reaction bulb is placed in liquid nitrogen,
Add the cuprous bromide of purification and 0.0032g copper powder described in 0.0072g, be passed through after evacuation
Argon, is simultaneously introduced 0.1mmoL and is dissolved in 1mLN, dinethylformamide
N, N, N', N, ' N "-five methyl diethylentriamine, continue logical argon and continue 10min, so
React 4-5h at 95 DEG C, obtaining final product described grafting has the silicon chip of poly ion liquid.
3. grafting according to claim 2 has the silicon chip of poly ion liquid, and its feature exists
In：Described step 1-1) hydroxylating before processing, also include Wafer Cleaning, Wafer Cleaning process
As follows：The silicon chip of well cutting is put into deionized water after ultrasonic 5min in ethanol solution rinse
Totally, volume ratio is then used to be 7:3 concentrated sulphuric acid and the mixed solution of hydrogen peroxide are ultrasonic
After 10min, deionized water is rinsed well, the more ultrasonic 10min of deionized water, finally with 5%
After the ultrasonic 10min of hydrofluoric acid solution, deionized water is rinsed well, then deionized water is ultrasonic
5min, puts in ethanol solution and preserves.
4. grafting according to claim 3 has the silicon chip of poly ion liquid, and its feature exists
In：Described step 1-1) hydroxylating process in, by cleaning described silicon chip be placed in 0.1mol/L
Rinsed well with deionization after soaking 8min in sodium hydroxide solution, then silicon chip is placed in
Soak 15min in 0.1mol/L salpeter solution, complete silicon chip hydroxylating.
5. grafting according to claim 2 has the silicon chip of poly ion liquid, and its feature exists
In：Described step 1-2) amination process in, by step 1-1) in complete hydroxylated silicon
Piece nitrogen dries up, be subsequently placed in 500 μ L 97%3- TSL 8330 and
In the mixed solution of 10mL dehydrated alcohol, lucifuge reaction 24, that is, complete silicon chip amination.
6. grafting according to claim 2 has the silicon chip of poly ion liquid, and its feature exists
In：Described step 1-3) during bromination processes, by step 1-2) described amidized silicon chip washes
Wash and dried up with nitrogen, be placed in boiling flask, add 1.6mL pyridine and 20mL dichloromethane
The mixed solution of alkane, then Deca 1mL bromo isobutyryl bromine solutions and 15mL dichloromethane are molten
Liquid, after completion of dropping, reacts 12h in ice-water bath, that is, completes silicon chip bromination.
7. grafting according to claim 2 has the silicon chip of poly ion liquid, and its feature exists
In：Described step 2-2) silicon chip surface polymerization grafting poly ion liquid during, in 25mL
In three-necked bottle, (1,6- is own for the 1- vinyl -3- phenylpropyl imidazoles villaumite of addition 5mmol and 1,1-
Alkane)-two-(1- vinyl imidazole) bromide cross-linking ion liquid, add 5mL N, N- dimethyl
Formamide solution, heating is passed through argon after making ion liquid dissolving and continues 20min, then will
Reaction bulb is placed in liquid nitrogen, adds the cuprous bromide of purification and 0.0032g described in 0.0072g
Copper powder, is passed through argon after evacuation, is simultaneously introduced 0.1mmoL and is dissolved in 1mLN, N- dimethyl methyl
N, N, N', the N of amide, ' N "-five methyl diethylentriamine, continue logical argon and continue
10min, then reacts 5h, obtaining final product described grafting has the silicon chip of poly ion liquid at 95 DEG C.
8. a kind of have the silicon chip of poly ion liquid as extraction using the grafting described in claim 1
Take agent detect curcumin method it is characterised in that：Comprise the following steps：
1) extraction of curcumin：With the mixed solution of ethanol/water, standard sample curcumin is diluted
To 10-5G/L, takes the curcumin solution after 1mL dilution in equipped with grafting poly ion liquid silicon chip
Centrifuge tube in, under 35 DEG C of waters bath with thermostatic control extract 20min, take out silicon chip and be dried, residue molten
Liquid is analyzed by UFLC；
2) eluting of curcumin：By step 1) in process after silicon chip with 0.5mL methanol and
The mixed solution eluting of acetic acid, eluent passes through efficient liquid phase chromatographic analysis.
9. according to claim 8 enrichment detection curcumin method it is characterised in that：
Described step 1) curcumin extraction process in, ethanol in ethanol/water：The volume ratio of water is
1:4.
10. the method for enrichment detection curcumin according to claim 8, its feature exists
In：Described step 2) curcumin elution process in, first in the mixed solution of methanol and acetic acid
Alcohol：The volume ratio of acetic acid is 9:1, the high-efficient liquid phase chromatogram condition being adopted is：C18Anti-phase color
Spectrum post, flow velocity is 0.3mL/min, and ultraviolet detection wavelength is 426nm, 35 DEG C of column temperature, flowing
Mutually for volume ratio be 1:1 acetonitrile：In water, wherein acetonitrile and water all containing volume ratio be 0.5%
Acetic acid.
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