CN106397664B - It is a kind of can be to up-conversion nano material that pH value responds and preparation method thereof - Google Patents
It is a kind of can be to up-conversion nano material that pH value responds and preparation method thereof Download PDFInfo
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- CN106397664B CN106397664B CN201610883720.6A CN201610883720A CN106397664B CN 106397664 B CN106397664 B CN 106397664B CN 201610883720 A CN201610883720 A CN 201610883720A CN 106397664 B CN106397664 B CN 106397664B
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- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
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- 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
- C08F8/42—Introducing metal atoms or metal-containing groups
Abstract
The invention discloses it is a kind of can be to up-conversion nano material that pH value responds and preparation method thereof.This method synthesizes pH sensitive high molecular weight materials first, then upper conversion nano particle is protected to be prepared by ligand exchange with oleic acid.The present invention is using up-conversion nano material as base material, by compound with poly- three-level amine pH responsive polymers, realizes the pH response performances of anti-Stokes displacement optical material.The material is in low pH aqueous solutions, under near-infrared laser excitation, nano material shines weaker, after higher than certain ph, nano material can enhance 20 times relative to low ph value light intensity, and pH converts the variation that section is only proton concentration closely 2 times of generation in 0.3 pH section and aqueous solution and may be such that up-conversion nano material light intensity enhances 20 times.The intelligent response up-conversion nano material that the present invention is prepared has good water solubility, and optical signalling is strong, hypotoxicity and the sensitive response performance to environmental pH.
Description
Technical field
The invention belongs to technical field of nano material, and in particular to a kind of upper conversion nano material that can be responded to pH value
Material and preparation method thereof, the material using up-conversion nano material as matrix, using intelligent response macromolecule for controlled material preparation and
Into as converting biological marker material on the novel intelligent that pH responses are carried out for microenvironment in water.
Background technology
For biomedicine field, multi-functional nano material can be by good water solubility, Spectral Properties due to it
Property and to extraneous stimulation in response to the advantages that roll into one and obtained extensive research.
Rear-earth-doped up-conversion nano material is based upon two-photon or multi-photon mechanism converts long wavelength laser
Emit the nano particle of the anti-Stokes displacement mechanism of light for short wavelength, in infrared acquisition, light emitting diode, solar-electricity
The fields such as pond, biomarker, living imaging, drug therapy are with a wide range of applications.
Although existing up-conversion nano material has been provided with good optical characteristics, but do not have for microenvironment also
Intelligent response characteristic.
Invention content
In order to overcome the above-mentioned deficiencies of the prior art, the present invention provides a kind of upper conversions that can be responded to pH value to receive
Rice material and preparation method thereof.The material is by synthesizing pH sensitive high molecular weight materials, and upper conversion nano is then protected with oleic acid
Particle is obtained by ligand exchange.
It is of the present invention to be to the preparation method for the up-conversion nano material that pH value responds：
1), the synthesis of up-conversion nano material：Rare earth-iron-boron, 4-10mL oleic acid and 10-20mL octadecylenes is weighed to add in
In three-necked flask, 30-50 DEG C vacuumizes deoxidation, is filled with nitrogen, is warming up to 60-80 DEG C and vacuumizes again；110-130 DEG C is warming up to,
React 40-60min；30-50 DEG C is naturally cooling to after being finally warming up to 150-170 DEG C of maintenance 4-10min；Add 0.12-
The NH of 0.16g4F, the NaOH of 0.08-0.12g, 30-50 DEG C vacuumizes deoxidation, is filled with nitrogen, is warming up to 60-80 DEG C and takes out again very
It is empty；Then 280-320 DEG C of reaction 40-70min, is naturally cooling to 30-50 DEG C；By reaction solution under the rotating speed of 12000r/min from
The heart removes supernatant, adds in volume ratio 1:2-2:1 hexamethylene and ethyl alcohol, ultrasonic disperse, the hexamethylene of end product 5-10mL
Alkane disperses, and is packed into sample bottle；
2), the synthesis of pH responsive polymers monomer：0.2-0.3g hydroquinones, 15-25g tertiary amines, 30- are weighed successively
40g N, N '-di-n-butyl ethyl alcohol and 150-250mL tetrahydrofurans, 50-60 DEG C of reflux, is added dropwise 18- in three-necked flask
25g methacrylic chlorides or acryloyl chloride react 0.5-1.5h after dripping off；After reaction solvent is removed with alumina filter, revolving
Tetrahydrofuran is finally evaporated under reduced pressure, and collects fraction up to pH responsive polymer monomers；
3) synthesis, containing the pH responsive polymers that can coordinate group with up-conversion nano material：Respectively into reaction bulb
The pH responsive polymer monomers of addition 0.8-1.5g, 15-40mg azo-bis-isobutyl cyanide initiators, 0.05-0.3g methacrylic acids,
And 3-6mL tetrahydrofurans, the water and oxygen in reaction bulb are removed by 2-6 freezing degassing, after being filled with nitrogen, in 50-80
24-72h is reacted at DEG C, is obtained containing the pH responsive polymers that can coordinate group with up-conversion nano material；
It 4), can be to the compound of the up-conversion nano material that pH value responds：Take it is synthesized obtain containing can with upper turn
The pH responsive polymers 100-200mg for changing nano material cooperation group is dissolved in the DMF of 2-6mL, and step 1) institute is added dropwise
The up-conversion nano material 40-80mg of synthesis, 2-6h is stirred at room temperature after dripping；Under conditions of 16000-20000r/min from
Heart 15-25min is washed with the hydrochloric acid solution of pH=2-5 and is removed not compound macromolecule, is finally dispersed in the acidity of pH=2-5
In solution.
The rare earth of the rare earth-iron-boron be selected from lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm),
Europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), scandium (Sc) and yttrium (Y)
One or more of.
The molar concentration of the rare earth-iron-boron is 0.02-2.00mol/L, preferably 0.2mol/L or 0.25mol/L.
The tertiary amine is triethylamine.
The N, N '-di-n-butyl ethyl alcohol replace with N, N '-dimethyl ethyl alcohol, N, N '-diethylaluminum ethoxide, N, N '-two
Propyl ethyl alcohol, N, N '-diisopropyl ethyl alcohol, N, N '-diisobutyl ethyl alcohol, N, N '-pyrrolidinyl ethyl alcohol, N, N '-piperidine ethanol,
One or more of N, N '-azacycloheptyl ethyl alcohol.
The present invention by select different intelligent response high molecular materials and with it is different excitation and launch wavelength upper turn
Change nano material, carry out that ligand exchange is compound under different proportionings, so as to obtain that pH value can be responded upper turn
Change nano material.Intelligent macromolecule different pH value can be occurred the groups such as quick response, carboxylic acid can by polymer with
Up-conversion nano material be coordinated compound, and copolymerization ratios are needed in OK range, so as to obtained by neither influencing macromolecule with
Up-conversion nano material it is compound, and the response of pH responsive polymers cannot be changed.
Compared with prior art, the present invention is poly- by being responded with poly- three-level amine pH using up-conversion nano material as base material
It is compound to close object, realizes the pH response performances of anti-Stokes displacement optical material.The characteristics of intelligent pH response nano material
Be in low pH aqueous solutions, near-infrared laser excitation under, nano material shine it is weaker, after higher than certain ph, nanometer material
Material can enhance 20 times relative to low ph value light intensity, and pH conversions section be only in 0.3 pH section and aqueous solution proton concentration it is near
2 times of variation occurs and may be such that up-conversion nano material light intensity enhances 20 times.The preparation method of the present invention is easy, general, system
Standby obtained intelligent response up-conversion nano material has good water solubility, and optical signalling is strong, hypotoxicity and to environment pH
The sensitive response performance of value, can be applied to biomarker field.
Description of the drawings
Fig. 1 can prepare schematic diagram for the present invention's to the up-conversion nano material that pH value responds.
Fig. 2 is the transmission electron microscope picture of up-conversion nano material synthesized in embodiment 1.
Fig. 3 is to be compounded with the up-conversion nano material of poly- (N, N '-dimethyl ethyl) methacrylate in different pH items
UCL spectrograms under part.
Fig. 4 is to be compounded with the up-conversion nano material of poly- (N, N '-dimethyl ethyl) methacrylate in different pH items
UCL spectrum most strong spectral variation diagram under part.
Fig. 5 is to be compounded with the up-conversion nano material of poly- (N, N '-dimethyl ethyl) methacrylate in different pH items
Grain-size graph under part.
Fig. 6 exists to be compounded with the up-conversion nano material of poly- (N, N '-diethyl ethyl) methacrylate in embodiment 2
UCL spectrograms under condition of different pH.
Fig. 7 exists to be compounded with the up-conversion nano material of poly- (N, N '-diethyl ethyl) methacrylate in embodiment 2
UCL spectrum most strong spectral variation diagram under condition of different pH.
Fig. 8 exists to be compounded with the up-conversion nano material of poly- (N, N '-diethyl ethyl) methacrylate in embodiment 2
Grain-size graph under condition of different pH.
Fig. 9 is to be compounded with the up-conversion nano material of poly- (N, N '-diisopropyl ethyl) methacrylate in different pH
Under the conditions of UCL spectrograms.
Figure 10 is compounded with the up-conversion nano material of poly- (N, N '-diisopropyl ethyl) methacrylate in difference in being
UCL spectrum most strong spectral variation diagram under the conditions of pH.
Figure 11 is compounded with the up-conversion nano material of poly- (N, N '-diisopropyl ethyl) methacrylate in difference in being
Grain-size graph under the conditions of pH.
Figure 12 is the up-conversion nano material that poly- (N, N '-dibutylethyl) methacrylate is compounded in embodiment 1
UCL spectrograms under condition of different pH.
Figure 13 is the up-conversion nano material that poly- (N, N '-dibutylethyl) methacrylate is compounded in embodiment 1
UCL spectrum most strong spectral variation diagram under condition of different pH.
Figure 14 is the up-conversion nano material that poly- (N, N '-dibutylethyl) methacrylate is compounded in embodiment 1
Grain-size graph under condition of different pH.
Figure 15 is the cytotoxicity figure of composite material.
Specific embodiment
Below by specific embodiment, the present invention will be described, but the present invention is not limited thereto.
Experimental method used in following embodiments is conventional method unless otherwise specified；Institute in following embodiments
Reagent, material etc., are commercially available unless otherwise specified.
Embodiment 1：Response be pH 5.0 can be to up-conversion nano material that pH value responds
(1) LuCl is weighed3(0.2251g)、YbCl3(0.0503g) and ErCl3(0.0055g) and oleic acid (6mL), ten
Eight alkene (15mL), vacuumize deoxidation at 40 DEG C in three-necked flask, are filled with nitrogen, are warming up to 70 DEG C and vacuumize again；It is warming up to 120
DEG C, react 40min；40 DEG C are naturally cooling to after being finally warming up to 160 DEG C of maintenance 5min；Add in NH4F(4mmol)、NaOH
After (2.5mmol), 40 DEG C vacuumize deoxidation, are filled with nitrogen, are warming up to 70 DEG C and vacuumize again；It is natural after 300 DEG C of reaction 60min
It is cooled to 40 DEG C；Reaction solution under the rotating speed of 12000r/min is centrifuged, removes supernatant, adds in volume ratio 1:1 hexamethylene
And ethyl alcohol, ultrasonic disperse, end product are disperseed with the hexamethylene of 6mL, are packed into sample bottle, are proved by transmission electron microscope
To grain size 80nm or so up-conversion nanoparticles；
(2) hydroquinone (0.23g), triethylamine (20.2g), N, N '-dibutyl ethyl alcohol (34.6g) and tetrahydrochysene are weighed successively
Furans (200mL), 56 DEG C of reflux, are added dropwise methacrylic chloride (20.8g), react 1h after dripping off in three-necked flask；Production
It rotates after object alumina filter, is evaporated under reduced pressure after filtering, collect fraction, obtain monomer methacrylic acid N, N '-dibutyl second
Ester, yield about 52%.
(3) methacrylic acid N, N '-dibutyl ethyl ester (1g), azo-bis-isobutyl cyanide (AIBN) are added in into reaction bulb respectively
(22mg) initiator, methacrylic acid (90mg) and tetrahydrofuran (4mL) are removed by 3 freezing degassings in reaction bulb
Water and oxygen after being filled with nitrogen, react 48h at 60 DEG C, obtain poly- (N, N '-dibutylethyl) methacrylate；
(4) poly- (N, N '-dibutylethyl) methacrylate (150mg) is taken to be dissolved in the DMF of 4mL, be added dropwise
The up-conversion nano material (50mg) of oleic acid protection, 4h is stirred at room temperature after dripping；It is centrifuged under conditions of 18000r/min
20min is washed with the hydrochloric acid solution of pH=4 and is removed not compound macromolecule, is finally dispersed in the hydrochloric acid solution of pH 4.0.
(5) the compound up-conversion nano material of obtained polymer is dissolved in pH 5.0 and pH with same concentrations
In 5.5 aqueous solution, measure UCL spectrum, UCL spectral intensities in pH 5.5 for pH 5.0 when about 20 times (pass through 980nm
Laser excitation).
(6) obtaining the material by MTT cytotoxicity assays can to the toxicity of cell in the range of institute's test concentrations
Ignore.
Embodiment 2
(1) YCl is weighed3(0.0976g)、YbCl3(0.0503g) and ErCl3(0.0055g) and oleic acid (6mL) and ten
Eight alkene (15mL), 40 DEG C of deoxidations, are filled with nitrogen, are warming up to 70 DEG C and vacuumize again；130 DEG C are warming up to, reacts 60min；It is warming up to
40 DEG C are naturally cooling to after 160 DEG C of maintenance 10min；Add in 0.1481g NH4F, after 0.1g NaOH, 40 DEG C of deoxidations are filled with nitrogen
Gas is warming up to 70 DEG C and vacuumizes again；After 300 DEG C of reaction 60min, it is naturally cooling to 40 DEG C；By reaction solution 12000r/min's
It is centrifuged under rotating speed, removes supernatant, add in volume ratio 1:1 hexamethylene and ethyl alcohol, ultrasonic disperse, the ring of end product 9mL
Hexane disperses, and elutes oleic acid, obtains the up-conversion nano material that can be dissolved in aqueous solution；
(2) hydroquinone (0.0494g), triethylamine (4.3382g), N, N '-diethyl ethyl alcohol are weighed successively
(6.2402g) and tetrahydrofuran (50mL), 56 DEG C of reflux, are added dropwise 4.4671g methacrylic chlorides in three-necked flask, drip
Reaction 1h after complete；It rotates after product alumina filter, is evaporated under reduced pressure after filtering, collect fraction, obtain monomer methacrylic acid
N, N '-diethyl base-ethyl ester.
(3) methacrylic acid N, N '-diethyl ethyl phosphonate (1g), azo-bis-isobutyl cyanide (AIBN) are added in into reaction bulb respectively
(22mg) initiator, methacrylic acid (117mg) and tetrahydrofuran (4mL) are removed by 3 freezing degassings in reaction bulb
Water and oxygen, after being filled with nitrogen, react 48h at 60 DEG C, obtain poly- (N, N '-diethyl ethyl) methacrylate；
(4) poly- (N, N '-diethyl ethyl) methacrylate (150mg) is taken to be dissolved in 4mL DMF, be added dropwise and wash
The up-conversion nano material (50mg) of de-oiling acid, 4h is stirred at room temperature after dripping；It is centrifuged under conditions of 18000r/min
20min is washed with the hydrochloric acid solution of pH=4 and is removed not compound macromolecule, is finally dispersed in the hydrochloric acid solution of pH 4.0.
(5) the compound up-conversion nano material of obtained polymer is dissolved in pH 7.0 and pH with same concentrations
In 7.3 aqueous solution, measure UCL spectrum, UCL spectral intensities in pH 7.3 for pH 7.0 when about 20 times (pass through 980nm
Laser excitation).
(6) obtaining the material by MTT cytotoxicity assays can to the toxicity of cell in the range of institute's test concentrations
Ignore.
The UCL spectrum tests for the up-conversion nano material that pH value responds can be shown obtained by above-mentioned less than height
During molecule pKa value, the UCL spectral intensities of pH response nano up-conversions are weaker, and when pH value is higher than macromolecule pKa,
Jumping then occurs for UCL spectral intensities, reaches 20 times of low ph value or more, signal strength greatly enhances.Jumping institute occurs for its light intensity
Corresponding pH value is corresponding with the pKa of institute's composite high-molecular.
Claims (5)
1. a kind of can be to the preparation method for the up-conversion nano material that pH value responds, which is characterized in that its specific steps are：
1）, up-conversion nano material synthesis：It weighs rare earth-iron-boron, 4-10 mL oleic acid and 10-20 mL octadecylenes and adds in three
In mouth flask, 30-50 DEG C vacuumizes deoxidation, is filled with nitrogen, is warming up to 60-80 DEG C and vacuumizes again；110-130 DEG C is warming up to, instead
Answer 40-60 min；30-50 DEG C is naturally cooling to after being finally warming up to 150-170 DEG C of maintenance 4-10 min；Add 0.12-
The NH of 0.16 g4F, the NaOH of 0.08-0.12 g, 30-50 DEG C vacuumizes deoxidation, is filled with nitrogen, is warming up to 60-80 DEG C and takes out again very
It is empty；Then 280-320 DEG C of reaction 40-70 min, is naturally cooling to 30-50 DEG C；By reaction solution 12000 r/min rotating speed
Supernatant is removed in lower centrifugation, adds in volume ratio 1:2-2:1 hexamethylene and ethyl alcohol, ultrasonic disperse, end product 5-10 mL
Hexamethylene dispersion, be packed into sample bottle；
2）, pH responsive polymer monomers synthesis：0.2-0.3 g hydroquinones, 15-25 g tertiary amines, 30-40 g are weighed successively
N, N '-di-n-butyl ethyl alcohol and 150-250 mL tetrahydrofurans, 50-60 DEG C of reflux, is added dropwise 18-25 in three-necked flask
G methacrylic chlorides or acryloyl chloride react 0.5-1.5 h after dripping off；After reaction solvent four is removed with alumina filter, revolving
Hydrogen furans, is finally evaporated under reduced pressure, and collects fraction up to pH responsive polymer monomers；
3）, containing can with up-conversion nano material coordinate group pH responsive polymers synthesis：It is added in respectively into reaction bulb
The pH responsive polymer monomers of 0.8-1.5 g, 15-40 mg azo-bis-isobutyl cyanide initiators, 0.05-0.3 g methacrylic acids,
And 3-6 mL tetrahydrofurans, the water and oxygen in reaction bulb are removed by 2-6 freezing degassing, after being filled with nitrogen, in 50-80
24-72 h are reacted at DEG C, are obtained containing the pH responsive polymers that can coordinate group with up-conversion nano material；
4）, can be to the compound of the up-conversion nano material that pH value responds：Containing for being obtained synthesized by taking can be received with upper conversion
The pH responsive polymers 100-200mg of rice material mating group is dissolved in the DMF of 2-6mL, and step 1 is added dropwise）It is synthesized
Up-conversion nano material 40-80mg, 2-6 h are stirred at room temperature after dripping；It is centrifuged under conditions of 16000-20000 r/min
15-25 min are washed with the hydrochloric acid solution of pH=2-5 and are removed not compound macromolecule, are finally dispersed in the acid solution of pH=2-5
In.
2. preparation method according to claim 1, which is characterized in that the rare earth of the rare earth-iron-boron is selected from lanthanum
(La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium
(Er), one or more of thulium (Tm), ytterbium (Yb), lutetium (Lu), scandium (Sc) and yttrium (Y).
3. preparation method according to claim 1, which is characterized in that the molar concentration of the rare earth-iron-boron is 0.02-
2.00 mol/L。
4. preparation method according to claim 1, which is characterized in that the tertiary amine is triethylamine.
5. preparation method according to claim 1, which is characterized in that the N, N '-di-n-butyl ethyl alcohol replace with N,
N '-dimethyl ethyl alcohol, N, N '-diethylaluminum ethoxide, N, N '-dipropyl ethyl alcohol, N, N '-diisopropyl ethyl alcohol, N, N '-diisobutyl
One or more of ethyl alcohol, N, N '-pyrrolidinyl ethyl alcohol, N, N '-piperidine ethanol, N, N '-azacycloheptyl ethyl alcohol.
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| CN102060957A (en) * | 2010-11-23 | 2011-05-18 | 吉林大学 | Preparation method of nano-scale microsphere with controllable fluorescence property and temperature sensibility |
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