CN105601938B - A kind of preparation method of the molecularly imprinted polymer of pH and temperature double stimuli responsive - Google Patents
A kind of preparation method of the molecularly imprinted polymer of pH and temperature double stimuli responsive Download PDFInfo
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- CN105601938B CN105601938B CN201610063579.5A CN201610063579A CN105601938B CN 105601938 B CN105601938 B CN 105601938B CN 201610063579 A CN201610063579 A CN 201610063579A CN 105601938 B CN105601938 B CN 105601938B
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- 229920000344 molecularly imprinted polymer Polymers 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 31
- 239000010703 silicon Substances 0.000 claims abstract description 31
- -1 poly(N-isopropylacrylamide) Polymers 0.000 claims abstract description 28
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229920003213 poly(N-isopropyl acrylamide) Polymers 0.000 claims abstract description 24
- 238000007789 sealing Methods 0.000 claims abstract description 13
- 125000003368 amide group Chemical group 0.000 claims abstract description 12
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000003287 optical effect Effects 0.000 claims abstract description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 6
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 229910004613 CdTe Inorganic materials 0.000 claims description 4
- 239000000908 ammonium hydroxide Substances 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims 2
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 10
- 150000004753 Schiff bases Chemical group 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 229920001109 fluorescent polymer Polymers 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- 230000004044 response Effects 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 238000010791 quenching Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 102000004169 proteins and genes Human genes 0.000 description 6
- 108090000623 proteins and genes Proteins 0.000 description 6
- 239000002096 quantum dot Substances 0.000 description 6
- 230000000171 quenching effect Effects 0.000 description 6
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002262 Schiff base Substances 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000011095 buffer preparation Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 241000283690 Bos taurus Species 0.000 description 1
- 102000001554 Hemoglobins Human genes 0.000 description 1
- 108010054147 Hemoglobins Proteins 0.000 description 1
- 244000178870 Lavandula angustifolia Species 0.000 description 1
- 235000010663 Lavandula angustifolia Nutrition 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 1
- AJVCUHHHRPBRHU-UHFFFAOYSA-N cadmium nitric acid Chemical compound [Cd].[N+](=O)(O)[O-] AJVCUHHHRPBRHU-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011557 critical solution Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229960003638 dopamine Drugs 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000001102 lavandula vera Substances 0.000 description 1
- 235000018219 lavender Nutrition 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005316 response function Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Luminescent Compositions (AREA)
Abstract
The present invention discloses a kind of preparation method of the molecularly imprinted polymer of pH and temperature double stimuli responsive, including, by the poly(N-isopropylacrylamide) (PNIPAAm) of benzaldehyde sealing end and amido modified mesoporous silicon molecular engram fluorescent polymer hybrid reaction to get the molecularly imprinted polymer for arriving pH and temperature double stimuli responsive.The present invention is using the Schiff base group and PNIPAAm polymer on mesoporous silicon molecularly imprinted polymer surface to the stimuli responsive of pH and temperature, play the role of gate valve, to which the condition for entering recognition site inside mesoporous silicon to target molecule control effectively, it can be used for molecular engram fluorescent optical sensor.
Description
Technical field
The present invention relates to the preparation method and applications of a kind of pH and the molecularly imprinted polymer of temperature double stimuli responsive.
Background technique
Fluorescent optical sensor has high sensitivity, and instrument is simple, the advantages such as easy to operate；Molecularly imprinted polymer has selection
Property high, the features such as performance is stablized.In conjunction with the high sensitivity of fluorescent optical sensor and highly selective, the molecule print of molecularly imprinted polymer
Mark fluorescent optical sensor was rapidly developed in the more than ten years in past.The building of molecular engram fluorescent optical sensor is mainly by fluorescent material
If quantum dot is coated on inside molecularly imprinted polymer, when measured object enters recognition site, quenching quantum dot fluorescence, to establish
Quantitative analysis method.
Stimulus responsive polymers, the ability with response external stimulation, such as the change of temperature, pH, light is responded.
In the less building applied to fluorescent molecule trace sensor of stimulus responsive polymers.It is only a small number of to report temperature-responsive function
Monomer or pH response function monomer are used for the preparation of molecularly imprinted polymer, and target is discharged and identified by the contraction of recognition site
Object is responded.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the existing defects, provides a kind of pH and temperature double stimuli responsive
Molecularly imprinted polymer preparation method.
In order to solve the above-mentioned technical problems, the present invention provides the following technical solutions:
A kind of preparation method of the molecularly imprinted polymer of pH and temperature double stimuli responsive, including,
The poly(N-isopropylacrylamide) that benzaldehyde blocks is mixed with amido modified mesoporous silicon molecularly imprinted polymer
Reaction is closed to get the molecularly imprinted polymer of pH and temperature double stimuli responsive is arrived.
Further, under alkaline condition, by N-hydroxy-succinamide ester sealing end poly(N-isopropylacrylamide) with
Parahydroxyben-zaldehyde reacts to obtain the poly(N-isopropylacrylamide) of the benzaldehyde sealing end.
Further, the amido modified mesoporous silicon molecularly imprinted polymer is attached to carrier surface.
Further, the preparation process of amido modified mesoporous silicon molecularly imprinted polymer includes:
(I) cetyl trimethylammonium bromide, ethyl orthosilicate, 3- aminopropyl-triethoxy are added into support dispersion
Silane, fluorescence quantum and template molecule, after reacting 1-30 hours under alkaline condition, separation is situated between on the surface of the carrier
Hole silicon layer；
(II) ammonium hydroxide and 3- aminopropyl-triethoxy silicon is added in medium in the support dispersion by step (I) processing
Alkane, after reaction 1-30 hours, separation is eluted to get amido modified mesoporous silicon molecularly imprinted polymer is arrived.
Further, the fluorescence quantum is CdTe quantum.
Detailed description of the invention
Attached drawing is used to provide further understanding of the present invention, and constitutes part of specification, with reality of the invention
It applies example to be used to explain the present invention together, not be construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the electricity before and after the poly(N-isopropylacrylamide) of mesoporous silicon molecularly imprinted polymer modification benzaldehyde sealing end
Mirror figure；
Fig. 2 is the pH before and after the poly(N-isopropylacrylamide) of mesoporous silicon molecularly imprinted polymer modification benzaldehyde sealing end
Response curve.
Fig. 3 is the temperature before and after the poly(N-isopropylacrylamide) of mesoporous silicon molecularly imprinted polymer modification benzaldehyde sealing end
Spend response curve.
Fig. 4 is the preparation flow figure of pH of the present invention and temperature double stimuli molecularly imprinted polymer.
Fig. 5 is the route for the poly(N-isopropylacrylamide) that mesoporous silicon molecularly imprinted polymer modifies benzaldehyde sealing end
Figure.
Fig. 6 is schematic illustration of the mesoporous silicon molecularly imprinted polymer to pH and temperature double stimuli responsive.
Specific embodiment
Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings, it should be understood that preferred reality described herein
Apply example only for the purpose of illustrating and explaining the present invention and is not intended to limit the present invention.
Embodiment 1
1. antiphase method prepares nano silica: 22.5 mL hexamethylenes, 5.3 mL Triton X-100,5.4 mL are just
Hexanol, 1.5mL water, 0.35mL ammonium hydroxide are added sequentially in 50 mL round-bottomed flasks, are stirred 30 min or more, are added 0.4mL
Ethyl orthosilicate (TEOS) reacts 24 h at 25 DEG C.Reaction product with second alcohol and water respectively wash three times (14000 rpm, 30
Min), finally it is dispersed in water, with 3000 turns of 5 min of centrifugation, takes supernatant, be scattered in the secondary water of 9 mL, obtain nanometer two
Silica dispersion liquid.
2. the preparation of CdTe quantum solution: the sodium borohydride of the tellurium powder and 40 mg that weigh 38.0 mg is added to 2mL's
In sharp bottom Huang lid bottle, the ethyl alcohol of 2mL is added, closes the lid rapidly, keeps system closed, a syringe needle is inserted on lid, in syringe needle
On with water to carry out fluid-tight oxygen barrier.It is placed on 30-50 DEG C of isothermal reaction, reacts 3-5h, until the tellurium powder of black completely disappears, supernatant is
Until lavender.The cadmium nitrate of 90-100mg is added in the secondary water of 75 mL simultaneously, the sulfydryl second of 63 μ L is then added
Acid, then pH is transferred to 9-10 with the sodium hydroxide solution of 1mol/L, 10-30min deoxygenation is blown with nitrogen.By the supernatant of tellurium powder product
Liquid 1mL is added in nitric acid cadmium solution, and flow back 1-3h under nitrogen protection, and the quantum dot of yellow green can be obtained.One under the solution
It is directly used in step.
2. surface imprinted prepare meso-hole structure molecular engram layer: taking above-mentioned 1 mL of nano silicon dioxide dispersion sample dilute
It releases in the 18 PBS buffer solutions of mL pH=7.4,2 mL CdTe quantum solution, is then added 0.8 mL 0.2mol/L's
Cetyl trimethylammonium bromide (CTAB) adds the configured good 0.2mol/L NaOH of about 0.1 mL after mixing evenly
After stirring 10 min, 0.2 mL of TEOS/ ethanol solution of 20% volume ratio, 3-aminopropyltriethoxysilane is added in aqueous solution
(APTES) 20 μ L, template molecule bovine hemoglobin (BHb) 20 mg, after being protected from light 24 h at 25 DEG C, centrifuge separation is obtained
Solid particle.
3. molecularly imprinted polymer surface amination: above-mentioned solid particle is added in 20 mL water, and 0.5mL ammonium hydroxide is added,
20 μ L of APTES is added, reacts 12h at room temperature.It is obtained by filtration solid product, product methanol and ethanol solution centrifuge washing 3 times
More than, CTAB and template molecule BHb is removed, is finally scattered in 5 mL water, obtains amido modified mesoporous silicon molecular engram
Polymer (M-MIPs).
4. the preparation of the molecularly imprinted polymer of double stimuli responsive: 0.10 g N-hydroxy-succinamide ester sealing end
Poly(N-isopropylacrylamide) (PNIPAAm) (purchase is in Sigma company, molecular weight 2000 or so) is added in 50mL water, adds
Enter 30 mg parahydroxyben-zaldehydes, (a small amount of Na is added in alkalescent2CO3, adjust pH 8.0) under react for 24 hours, reaction solution dialyse
Bag (molecular cut off 1000) dialysis for 24 hours, removes unreacted parahydroxyben-zaldehyde, obtains poly- (the N- isopropyl of benzaldehyde sealing end
Base acrylamide).Solution after dialysis is added amido modified mesoporous silicon molecularly imprinted polymer, stirs 48 h at room temperature, from
Heart washing, obtains the fluorescent molecule imprinted polymer (pH-T-M-MIPs) with temperature and pH double stimuli responsive.
As shown in Figure 1, after the poly(N-isopropylacrylamide) of modification benzaldehyde sealing end, mesoporous silicon molecularly imprinted polymer
Interface thickens.
PH response test:
It with the PBS buffer preparation of different pH at concentration is respectively 40 mg/L by pH-T-M-MIPs and M-MIPs
Solution makes 0.5 μM of its concentration respectively to BHb is added inside it.Maintain solution temperature at 37 DEG C, to BHb and imprinted material
It interacts after 30min, surveys the fluorescence intensity of imprinted polymer solution response front and back, calculate it and quench efficiency, examine or check pH-T-M-
The pH response performance of MIPs.As a result as shown in Fig. 2, M-MIPs(symbol " ■ " indicates) highest is shown in pH 7.4 or so
Fluorescent quenching efficiency.After pH gradually weakens to acidity, since protein can be denaturalized in acid condition, enter print
The protein amounts of mark polymer recognition site are reduced, and cause to quench efficiency reduction.It compares, pH-T-M-MIPs(symbol "●"
Indicate) it is very low in the quenching efficiency of 6.0 or more pH.Reason is 6.0 or more pH, and Schiff base stable structure is deposited
So that the PNIPAAm for playing gate valve is covered on mesoporous trace layer surface, protein is being hindered to enter recognition site, therefore nothing
Method quenches quantum dot fluorescence.After pH is lower than 6.0, Schiff base starts to hydrolyze, and causes PNIPAAm from imprinted material
Surface is detached from, so that protein enters recognition site, quenches fluorescence, so that quenching efficiency greatly improves, the above results show
Stimulus response performance of the pH-T-M-MIPs to pH.
Temperature-responsive test:
Use the PBS buffer preparation of pH 7.4 at concentration for 40 mg/L's respectively pH-T-M-MIPs and M-MIPs
Solution makes 0.5 μM of its concentration respectively to BHb is added inside it.Change the temperature of solution from 20-40 DEG C, to BHb and trace
Material interacts after 30min, surveys the fluorescence intensity of imprinted polymer solution response front and back, calculates it and quenches efficiency, examines or check pH-
The temperature response performance of T-M-MIPs.As a result as shown in figure 3, M-MIPs(is indicated with symbol " ■ ") table within the scope of 20-40 DEG C
Reveal higher quenching performance.And pH-T-M-MIPs(is indicated with symbol "●") temperature be higher than 32 DEG C, fluorescent quenching efficiency compared with
It is low.Reason is that PNIPAAm exists in the form of random coil to roll up at this time, hinders the entrance of protein molecule.When temperature is low
When 32 DEG C, with the presence of extended chain state, protein can enter recognition site and quench quantum dot fluorescence PNIPAAm, therefore sudden
Efficiency of going out greatly improves.The above results show pH-T-M-MIPs to the stimulus response performance of temperature.
Fig. 4 is the preparation flow figure of pH of the present invention and temperature double stimuli molecularly imprinted polymer.Fig. 5 is mesoporous silicon molecule
Imprinted polymer modifies the route map of the poly(N-isopropylacrylamide) of benzaldehyde sealing end.Fig. 6 is poly- for mesoporous silicon molecular engram
Object is closed to the schematic illustration of pH and temperature double stimuli responsive.
It introduces on mesoporous silicon molecularly imprinted polymer surface to the Schif base group of pH stimuli responsive and to temperature
The polyisopropyl acrylamide of stimuli responsive.At pH 7.4 and 37 DEG C, Schiff base is stabilized, and PNIPAAm is poly-
It closes object to exist in the form of a random ball of string, is blocked in mesoporous silicon face, plays the role of gate valve, target molecule is made to cannot be introduced into Jie
Recognition site inside the silicon of hole.As the pH < 6.0 for changing solution, Schiff base hydrolysis leads to the polymer as gate valve
PNIPAAm is detached from from mesoporous material surface, and target molecule enters mesoporous silicon layer, quenches quantum dot fluorescence, to realize that fluorescence is examined
It surveys.In the case where not changing pH value of solution, the detection of object can also be realized by changing temperature.System temperature is reduced to be lower than
The critical solution temperature (32 DEG C) of PNIPAAm, PNIPAAm is with the presence of extended chain state, and target molecule can equally enter and be situated between at this time
Hole silicon layer is identified.It is achieved in temperature and pH double stimuli responsive.
Amido modified mesoporous silicon molecularly imprinted polymer of the invention is not limited to using method system of the present invention
It is standby, conventional method preparation can also be used, such as " research of dopamine friend's sequence mesoporous silicon surface molecule print sensor ", Gong Wei etc.,Analysis test journal, the 4th phase of volume 31 in April, 2012,417-422 pages." preparation of two kinds of mesoporous silicon molecularly imprinted polymers and
Its application study ", Tang Fei etc.,Agricultural University Of Anhui, 2013.
Finally, it should be noted that the foregoing is only a preferred embodiment of the present invention, it is not intended to restrict the invention,
Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features.
All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in of the invention
Within protection scope.
Claims (8)
1. a kind of preparation method of the molecularly imprinted polymer of pH and temperature double stimuli responsive, including,
The poly(N-isopropylacrylamide) that benzaldehyde blocks is mixed instead with amido modified mesoporous silicon molecularly imprinted polymer
It should be to get the molecularly imprinted polymer for arriving pH and temperature double stimuli responsive.
2. preparation method according to claim 1, which is characterized in that under alkaline condition, by n-hydroxysuccinimide
The poly(N-isopropylacrylamide) of ester sealing end reacts to obtain poly- (the N- isopropyl of the benzaldehyde sealing end with parahydroxyben-zaldehyde
Base acrylamide).
3. preparation method according to claim 1, which is characterized in that the amido modified mesoporous silicon molecular engram polymerization
Object is attached to carrier surface.
4. preparation method according to claim 3, which is characterized in that the carrier is nano silica.
5. preparation method according to claim 1 or 3, which is characterized in that amido modified mesoporous silicon molecular engram polymerization
The preparation process of object includes:
(I) cetyl trimethylammonium bromide, ethyl orthosilicate, 3- aminopropyl-triethoxy silicon are added into support dispersion
Alkane, fluorescence quantum and template molecule, after reacting 1-30 hours under alkaline condition, separation obtains mesoporous on the surface of the carrier
Silicon layer；
(II) in medium ammonium hydroxide and 3- aminopropyl triethoxysilane is added, instead in the support dispersion by step (I) processing
After answering 1-30 hours, separation is eluted to get amido modified mesoporous silicon molecularly imprinted polymer is arrived.
6. preparation method according to claim 5, which is characterized in that the fluorescence quantum is CdTe quantum.
7. the pH of any the method preparation of claim 1-6 and the molecularly imprinted polymer of temperature double stimuli responsive.
8. molecularly imprinted polymer described in claim 7 is used to prepare molecular engram fluorescent optical sensor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610063579.5A CN105601938B (en) | 2016-01-29 | 2016-01-29 | A kind of preparation method of the molecularly imprinted polymer of pH and temperature double stimuli responsive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610063579.5A CN105601938B (en) | 2016-01-29 | 2016-01-29 | A kind of preparation method of the molecularly imprinted polymer of pH and temperature double stimuli responsive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105601938A CN105601938A (en) | 2016-05-25 |
| CN105601938B true CN105601938B (en) | 2019-02-26 |
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| EP3689820A1 (en) * | 2019-01-30 | 2020-08-05 | KIST-Europe Forschungsgesellschaft mbH | Sensors comprising mesoporous silica particles |
| CN109964927B (en) * | 2019-04-04 | 2021-12-03 | 江南大学 | Preparation method of temperature/pH dual-response nano antibacterial system |
| CN110437451B (en) * | 2019-06-21 | 2023-07-21 | 临沂大学 | Preparation method of molecularly imprinted fluorescent polymer |
| CN112619435B (en) * | 2020-12-02 | 2022-04-29 | 石河子大学 | Preparation method of molecularly imprinted hybrid membrane for separating phenylethanoid glycosides |
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