CN106397664A - Up-conversion nano material capable of responding to pH value and preparation method thereof - Google Patents
Up-conversion nano material capable of responding to pH value and preparation method thereof Download PDFInfo
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- CN106397664A CN106397664A CN201610883720.6A CN201610883720A CN106397664A CN 106397664 A CN106397664 A CN 106397664A CN 201610883720 A CN201610883720 A CN 201610883720A CN 106397664 A CN106397664 A CN 106397664A
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- 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
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Abstract
The invention discloses an up-conversion nano material capable of responding to pH value and a preparation method thereof. The method includes: synthesizing a pH-sensitive high molecular material; subjecting the pH-sensitive high molecular material and oleic acid protected up-conversion nanoparticles to ligand exchange to obtain the up-conversion nano material. The up-conversion nano material is used as a substrate and combined with polytertiary amine pH responding polymer to realize pH responding performance of an anti-Stokes shift optical material. In a low-pH water solution, under excitation of near infrared laser, the nano material emits light weakly; after being higher than a specific pH value, light intensity of the nano material can be enhanced by 20 times relative to that when pH value is low; pH conversion interval is only 0.3 pH interval, in other words, the light intensity of the up-conversion nano material can be enhanced by 20 times by only changing proton concentration in a water solution by 2 times. The intelligent-responding up-conversion nano material prepared by the method has high water solubility, high optical signal intensity, low toxicity and sensitive responding performance to pH value of environment.
Description
Technical field
The invention belongs to technical field of nano material is and in particular to a kind of can be to the upper conversion nano material of pH value generation response
Material and preparation method thereof, this material with up-conversion nano material as matrix, with intelligent response macromolecule for controlled material prepare and
Become, as carrying out converting biological marker material on the novel intelligent of pH response for microenvironment in water.
Background technology
For biomedicine field, multi-functional nano material can be by good water solublity, Spectral Properties due to it
Property, and roll into one and obtained extensive research the advantages of stimulation to external world occurs response.
Rear-earth-doped up-conversion nano material is based upon two-photon or long wavelength laser is converted by multi-photon mechanism
For the nano-particle of the anti-Stokes displacement mechanism of short wavelength's launching light, in infrared acquisition, light emitting diode, solar-electricity
Pond, biomarker, living imaging, the field such as Drug therapy is with a wide range of applications.
Although existing up-conversion nano material has been provided with good optical characteristics, also do not possess for microenvironment
Intelligent response characteristic.
Content of the invention
In order to overcome the above-mentioned deficiencies of the prior art, the invention provides a kind of upper conversion that to pH value, response can occur is received
Rice material and preparation method thereof.This material is by synthesizing pH sensitive high molecular weight material, then the upper conversion nano with Oleic acid protection
Granule is obtained by ligand exchange.
Of the present invention response can occur to pH value the preparation method of up-conversion nano material be：
1), the synthesis of up-conversion nano material：Weigh rare earth chloride, 4-10mL Oleic acid and 10-20mL octadecylene to add
In there-necked flask, 30-50 DEG C of evacuation deoxidation, it is filled with nitrogen, be warmed up to 60-80 DEG C of evacuation again；It is warmed up to 110-130 DEG C,
Reaction 40-60min；It is naturally cooling to 30-50 DEG C after being finally warmed up to 150-170 DEG C of maintenance 4-10min；Add 0.12-
The NH of 0.16g4The NaOH of F, 0.08-0.12g, 30-50 DEG C of evacuation deoxidation, it is filled with nitrogen, be warmed up to 60-80 DEG C and take out very again
Empty；Then 280-320 DEG C of reaction 40-70min, is naturally cooling to 30-50 DEG C；By reactant liquor under the rotating speed of 12000r/min from
The heart, removes supernatant, adds volume ratio 1:2-2:1 hexamethylene and ethanol, ultrasonic disperse, the end product hexamethylene of 5-10mL
Alkane disperses, and loads sample bottle；
2), the synthesis of pH responsive polymer monomer：Weigh 0.2-0.3g hydroquinone, 15-25g tertiary amine, 30- successively
40g N, N '-di-n-butyl ethanol and 150-250mL oxolane, in there-necked flask, 50-60 DEG C of backflow, is added dropwise over 18-
25g methacrylic chloride or acryloyl chloride, react 0.5-1.5h after dripping off；Alumina filter is used, revolving removes solvent after reaction
Oxolane, last vacuum distillation, collect fraction and obtain final product pH responsive polymer monomer；
3), contain the synthesis of the pH responsive polymer that can coordinate group with up-conversion nano material：Respectively in reaction bulb
The pH responsive polymer monomer of addition 0.8-1.5g, 15-40mg azo-bis-isobutyl cyanide initiator, 0.05-0.3g methacrylic acid,
And 3-6mL oxolane, remove water and the oxygen in reaction bulb through 2-6 freezing degassing, after being filled with nitrogen, in 50-80
React 24-72h at DEG C, obtain containing the pH responsive polymer that can coordinate group with up-conversion nano material；
4), pH value can be occurred with being combined of the up-conversion nano material responding：Obtain synthesized by taking containing can with upper turn
Changing nano material coordinates the pH responsive polymer 100-200mg of group to be dissolved in the DMF of 2-6mL, is added dropwise over step 1) institute
The up-conversion nano material 40-80mg of synthesis, is stirred at room temperature 2-6h after dripping；Under conditions of 16000-20000r/min from
Heart 15-25min, is washed with the hydrochloric acid solution of pH=2-5 and removes the macromolecule not being combined, be finally dispersed in the acidity of pH=2-5
In solution.
The rare earth of described rare earth chloride 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), lutecium (Lu), scandium (Sc) and yttrium (Y)
One or more of.
The molar concentration of described rare earth chloride is 0.02-2.00mol/L, preferably 0.2mol/L or 0.25mol/L.
Described tertiary amine is triethylamine.
Described N, N '-di-n-butyl ethanol replaces with N, N '-dimethyl ethanol, N, N '-diethylaluminum ethoxide, N, N '-two
Propyl group ethanol, N, N '-diisopropyl ethanol, N, N '-diisobutyl ethanol, N, N '-pyrrolidinyl ethanol, N, N '-piperidine ethanol,
One or more of N, N '-azacycloheptyl ethanol.
The present invention pass through to select different intelligent response macromolecular materials and have difference excite with launch wavelength upper turn
Change nano material, carry out under different proportionings ligand exchange be combined, thus obtain can for pH value occur response upper turn
Change nano material.Intelligent macromolecule can occur quick response for different pH value, the group such as carboxylic acid can by polymer with
Up-conversion nano material carries out that coordination is compound, and copolymerization ratios need in OK range, thus obtained by neither affecting macromolecule with
Being combined of up-conversion nano material, can not change the response value of pH responsive polymer again.
Compared with prior art, the present invention, with up-conversion nano material as base material, is gathered by being responded with poly- three-level amine pH
Compound is combined it is achieved that the pH response performance of anti-Stokes displacement optical material.The feature of this intelligent pH response nano material
It is in low pH aqueous solution, under near-infrared laser excites, nano material is luminous weaker, after higher than certain ph, nanometer material
Material can strengthen 20 times with respect to low ph value light intensity, and the interval only 0.3 pH interval of pH conversion, and in aqueous solution, proton concentration is near
The change occurring 2 times can make up-conversion nano material light intensity strengthen 20 times.The preparation method is simple of the present invention, general, system
The standby intelligent response up-conversion nano material obtaining has good water solublity, and optical signalling is strong, hypotoxicity, and to environment pH
The sensitive response performance of value, can be applicable to biomarker field.
Brief description
Fig. 1 prepares schematic diagram for the up-conversion nano material that pH value can be occurred with response of the present invention.
Fig. 2 is the transmission electron microscope picture of the up-conversion nano material of synthesis in embodiment 1.
Fig. 3 is the up-conversion nano material being compounded with poly- (N, N '-dimethyl ethyl) methacrylate in different pH bars
UCL spectrogram under part.
Fig. 4 is the up-conversion nano material being compounded with poly- (N, N '-dimethyl ethyl) methacrylate in different pH bars
UCL spectrum under part strong spectral variation diagram.
Fig. 5 is the up-conversion nano material being compounded with poly- (N, N '-dimethyl ethyl) methacrylate in different pH bars
Grain-size graph under part.
Fig. 6 is that the up-conversion nano material being compounded with poly- (N, N '-diethyl ethyl) methacrylate in embodiment 2 exists
UCL spectrogram under condition of different pH.
Fig. 7 is that the up-conversion nano material being compounded with poly- (N, N '-diethyl ethyl) methacrylate in embodiment 2 exists
UCL spectrum under condition of different pH strong spectral variation diagram.
Fig. 8 is that the up-conversion nano material being compounded with poly- (N, N '-diethyl ethyl) methacrylate in embodiment 2 exists
Grain-size graph under condition of different pH.
Fig. 9 is the up-conversion nano material being compounded with poly- (N, N '-diisopropyl ethyl) methacrylate in different pH
Under the conditions of UCL spectrogram.
Figure 10 is compounded with the up-conversion nano material of poly- (N, N '-diisopropyl ethyl) methacrylate in difference in being
UCL spectrum under the conditions of pH strong spectral variation diagram.
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 being compounded with poly- (N, N '-dibutylethyl) methacrylate in embodiment 1
UCL spectrogram under condition of different pH.
Figure 13 is the up-conversion nano material being compounded with poly- (N, N '-dibutylethyl) methacrylate in embodiment 1
UCL spectrum under condition of different pH strong spectral variation diagram.
Figure 14 is the up-conversion nano material being compounded with poly- (N, N '-dibutylethyl) methacrylate in embodiment 1
Grain-size graph under condition of different pH.
Figure 15 is the cytotoxicity figure of composite.
Specific embodiment
Below by specific embodiment, the present invention will be described, but the invention is not limited in this.
Experimental technique used in following embodiments if no special instructions, is conventional method；Institute in following embodiments
Reagent, material etc., if no special instructions, all commercially obtain.
Embodiment 1：Response value is the up-conversion nano material that pH value can be occurred with response of pH 5.0
(1) weigh LuCl3(0.2251g)、YbCl3(0.0503g) and ErCl3(0.0055g), and Oleic acid (6mL), ten
Eight alkene (15mL), in 40 DEG C of evacuation deoxidations in there-necked flask, are filled with nitrogen, are warmed up to 70 DEG C of evacuation again；It is warmed up to 120
DEG C, react 40min；It is naturally cooling to 40 DEG C after being finally warmed up to 160 DEG C of maintenance 5min；Add NH4F(4mmol)、NaOH
(2.5mmol) after, 40 DEG C of evacuation deoxidations, it is filled with nitrogen, be warmed up to 70 DEG C of evacuation again；After 300 DEG C of reaction 60min, natural
It is cooled to 40 DEG C；Reactant liquor is centrifuged under the rotating speed of 12000r/min, removes supernatant, add volume ratio 1:1 hexamethylene
And ethanol, ultrasonic disperse, end product is disperseed with the hexamethylene of 6mL, loads sample bottle, is proved by transmission electron microscope
To particle diameter in 80nm about up-conversion nanoparticles；
(2) hydroquinone (0.23g), triethylamine (20.2g), N, N '-dibutyl ethanol (34.6g) and tetrahydrochysene are weighed successively
Furan (200mL), in there-necked flask, 56 DEG C of backflows, are added dropwise over methacrylic chloride (20.8g), react 1h after dripping off；Produce
Revolving after thing alumina filter, vacuum distillation after filtration, 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 respectively in reaction bulb
(22mg) initiator, methacrylic acid (90mg), and oxolane (4mL), remove in reaction bulb through 3 freezing degassings
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 over
The up-conversion nano material (50mg) of Oleic acid protection, is stirred at room temperature 4h after dripping；It is centrifuged under conditions of 18000r/min
20min, is washed with the hydrochloric acid solution of pH=4 and removes the macromolecule not being combined, be finally dispersed in the hydrochloric acid solution of pH 4.0.
(5) up-conversion nano material being combined obtained polymer is dissolved in pH 5.0 and pH with same concentrations
In 5.5 aqueous solution, measure UCL spectrum, its UCL spectral intensity in pH 5.5 be pH 5.0 when about 20 times (by 980nm
Laser excitation).
(6) obtaining this material by MTT cytotoxicity assay can to the toxicity of cell in the range of institute's test concentrations
Ignore.
Embodiment 2
(1) weigh YCl3(0.0976g)、YbCl3(0.0503g) and ErCl3, and Oleic acid (6mL) and ten (0.0055g)
Eight alkene (15mL), 40 DEG C of deoxidations, it is filled with nitrogen, be warmed up to 70 DEG C of evacuation again；It is warmed up to 130 DEG C, react 60min；It is warmed up to
It is naturally cooling to 40 DEG C after 160 DEG C of maintenance 10min；Add 0.1481g NH4After F, 0.1g NaOH, 40 DEG C of deoxidations, it is filled with nitrogen
Gas, is warmed up to 70 DEG C of evacuation again；After 300 DEG C of reaction 60min, it is naturally cooling to 40 DEG C；By reactant liquor 12000r/min's
It is centrifuged under rotating speed, removes supernatant, add volume ratio 1:1 hexamethylene and ethanol, ultrasonic disperse, the end product ring of 9mL
Hexane disperses, and eluting Oleic acid obtains the up-conversion nano material that can dissolve in aqueous；
(2) hydroquinone (0.0494g), triethylamine (4.3382g), N, N '-diethyl ethyl alcohol are weighed successively
(6.2402g) with oxolane (50mL), in there-necked flask, 56 DEG C of backflows, are added dropwise over 4.4671g methacrylic chloride, drip
Reaction 1h after complete；Revolving after product alumina filter, vacuum distillation after filtration, 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 respectively in reaction bulb
(22mg) initiator, methacrylic acid (117mg), and oxolane (4mL), remove in reaction bulb through 3 freezing degassings
Water and oxygen, after being filled with nitrogen, at 60 DEG C, react 48h, 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 over washing
The up-conversion nano material (50mg) of removing oil acid, is stirred at room temperature 4h after dripping；It is centrifuged under conditions of 18000r/min
20min, is washed with the hydrochloric acid solution of pH=4 and removes the macromolecule not being combined, be finally dispersed in the hydrochloric acid solution of pH 4.0.
(5) up-conversion nano material being combined obtained polymer is dissolved in pH 7.0 and pH with same concentrations
In 7.3 aqueous solution, measure UCL spectrum, its UCL spectral intensity in pH 7.3 be pH 7.0 when about 20 times (by 980nm
Laser excitation).
(6) obtaining this material by MTT cytotoxicity assay can to the toxicity of cell in the range of institute's test concentrations
Ignore.
The above-mentioned obtained UCL spectrum test that to pH value, the up-conversion nano material of response can occur shows, less than height
During molecule pKa value, the UCL spectral intensity of pH response nano up-conversion is weaker, and when pH value is higher than macromolecule pKa, its
Then there is hop in UCL spectral intensity, reach more than 20 times of low ph value, signal intensity greatly enhances.There is hop institute in its light intensity
Corresponding pH value is corresponding with the pKa of institute's composite high-molecular.
Claims (5)
1. a kind of preparation method of the up-conversion nano material that pH value can be occurred with response is it is characterised in that it concretely comprises the following steps：
1), the synthesis of up-conversion nano material：Weigh rare earth chloride, 4-10mL Oleic acid and 10-20mL octadecylene and add three mouthfuls
In flask, 30-50 DEG C of evacuation deoxidation, it is filled with nitrogen, be warmed up to 60-80 DEG C of evacuation again；It is warmed up to 110-130 DEG C, reaction
40-60min；It is naturally cooling to 30-50 DEG C after being finally warmed up to 150-170 DEG C of maintenance 4-10min；Add 0.12-0.16g's
NH4The NaOH of F, 0.08-0.12g, 30-50 DEG C of evacuation deoxidation, it is filled with nitrogen, be warmed up to 60-80 DEG C of evacuation again；Then
280-320 DEG C of reaction 40-70min, is naturally cooling to 30-50 DEG C；Reactant liquor is centrifuged under the rotating speed of 12000r/min, goes
Supernatant, adds volume ratio 1:2-2:1 hexamethylene and ethanol, ultrasonic disperse, end product is disperseed with the hexamethylene of 5-10mL,
Load sample bottle；
2), the synthesis of pH responsive polymer monomer：Weigh 0.2-0.3g hydroquinone, 15-25g tertiary amine, 30-40g N successively,
N '-di-n-butyl ethanol and 150-250mL oxolane, in there-necked flask, 50-60 DEG C of backflow, is added dropwise over 18-25g methyl
Acryloyl chloride or acryloyl chloride, react 0.5-1.5h after dripping off；Alumina filter is used, revolving removes solvent tetrahydrochysene furan after reaction
Mutter, last vacuum distillation, collect fraction and obtain final product pH responsive polymer monomer；
3), contain the synthesis of the pH responsive polymer that can coordinate group with up-conversion nano material：Add in reaction bulb respectively
The pH responsive polymer monomer of 0.8-1.5g, 15-40mg azo-bis-isobutyl cyanide initiator, 0.05-0.3g methacrylic acid, and
3-6mL oxolane, removes water and the oxygen in reaction bulb, after being filled with nitrogen, at 50-80 DEG C through 2-6 freezing degassing
Reaction 24-72h, is obtained containing the pH responsive polymer that can be coordinated group with up-conversion nano material；
4), pH value can be occurred with being combined of the up-conversion nano material responding：Obtain synthesized by taking containing can receive with upper conversion
The pH responsive polymer 100-200mg of rice material fit group is dissolved in the DMF of 2-6mL, is added dropwise over step 1) synthesized
Up-conversion nano material 40-80mg, 2-6h is stirred at room temperature after dripping；It is centrifuged under conditions of 16000-20000r/min
15-25min, is washed with the hydrochloric acid solution of pH=2-5 and removes the macromolecule not being combined, and the acidity being finally dispersed in pH=2-5 is molten
In liquid.
2. preparation method according to claim 1 is it is characterised in that the rare earth of described rare earth chloride 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), lutecium (Lu), scandium (Sc) and yttrium (Y).
3. preparation method according to claim 1 is it is characterised in that the molar concentration of described rare earth chloride is 0.02-
2.00mol/L, preferably 0.2mol/L or 0.25mol/L.
4. preparation method according to claim 1 is it is characterised in that described tertiary amine is triethylamine.
5. it is characterised in that described N, N '-di-n-butyl ethanol replaces with N to preparation method according to claim 1,
N '-dimethyl ethanol, N, N '-diethylaluminum ethoxide, N, N '-dipropyl ethanol, N, N '-diisopropyl ethanol, N, N '-diisobutyl
One or more of ethanol, N, N '-pyrrolidinyl ethanol, N, N '-piperidine ethanol, N, N '-azacycloheptyl ethanol.
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Cited By (1)
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| CN109632751A (en) * | 2019-01-08 | 2019-04-16 | 苏州科技大学 | Method and pH detector based on triplet state-triplet state annihilation up-conversion fluorescence detection pH value |
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