CN100491425C - Temperature-sensitive fluorescent nano material synthesis method - Google Patents
Temperature-sensitive fluorescent nano material synthesis method Download PDFInfo
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- CN100491425C CN100491425C CNB2006101664753A CN200610166475A CN100491425C CN 100491425 C CN100491425 C CN 100491425C CN B2006101664753 A CNB2006101664753 A CN B2006101664753A CN 200610166475 A CN200610166475 A CN 200610166475A CN 100491425 C CN100491425 C CN 100491425C
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Abstract
The invention discloses a synthesizing method of temperature-sensitive fluorescent nanometer material, which comprises the following steps: adding C5-8 naphthene, TritonX-100 as surface activator and normal hexanol in the reacting pond; adding rhodamine B, TEOS and ammonia; stirring continuously to form nanometer particle; decorating through excessive MPS; collecting the rhodamine B with the weight rate of rhodamine B and SiO2 at 0.5%; adopting modified rhodamine B/SiO2 as seed; adding N-isopropyl acrylamide as monomer and MBA as crosslinking agent; adding solution with ammonium persulphate in the nuclear case structural particle; adding fluohydric acid solution in the pure nuclear case structural particle; dialyzing; obtaining the temperature sensitive water dispersing liquid of rhodamine B/PolyNIPAM microball.
Description
Technical field
The present invention relates to synthetic method, be specifically related to a kind of synthetic method of temperature-sensitive fluorescent nano material.
Background technology
Poly N-isopropyl acrylamide (PolyNIPAM) is a kind of polymkeric substance with temperature sensitivity, and according to the literature, its lower critical solution temperature is about 32 ℃.The hydrogel fines based on PolyNIPAM of reported first is to be monomer with NIPAM, N, N '-methylene-bisacrylamide (MBA) is a linking agent, adopt emulsifier-free emulsion polymerization method synthetic, reaction must be carried out the formation colloidal particle so that the PolyNIPAM chain that increases is separated being higher than on about 32 ℃ of the lowest critical solution temperature of linear PolyNIPAM (LCST).
Poly-N-the N-isopropylacrylamide hydrogel is to study maximum thermo-responsive polymeric drug delivery systems up to now, finds that by changing temperature the PolyNIPAM hydrogel can reversibly absorb or discharge vitamins B as Hoffman etc.
12Okano etc. are with NIPAM and synthetic Poly (NIPAM-co-BMA) copolymer aquagel of butyl methacrylate (BMA) copolymerization, carrier as indomethacin (Indomethacin) medicine, when temperature alternately changes between 20 ℃ and 30 ℃, but aquogel system switched attenuator switched-mode ground control drug release; Nearest Hsihe etc. are made into the glaucomatous eye drops of treatment with Poly NIPAM hydrogel nanoparticle packing suprarenin with water, and its intraocular effect of easing stress is 8 times of medicine commonly used.
Summary of the invention
The objective of the invention is to: the synthetic method that a kind of temperature-sensitive fluorescent nano material is provided, the synthetic temperature sensitive fluorescent nano particles of rhodamine B/PNIPAM of this synthetic method with fluorescence and temperature sensitive bi-functional, make the polymer particles of environment sensitive not only have single stimuli responsive performance, nanoparticle with fluorescence and temperature sensitive double-response can be used at protein, the controlled separation of enzyme, research such as controlled delivery of pharmaceutical agents guiding and release and use in carry out fluorescent mark, help research system is followed the tracks of and detected, widened temperature sensing material in Application for Field such as biology and medical researches.
Technical solution of the present invention is that this synthetic method may further comprise the steps:
(1) in reaction tank be with carbon number 5-8 naphthenic hydrocarbon, tensio-active agent TritonX-100 and n-hexyl alcohol by volume 1-7:1:0.5-2 mix, the water that adds 20-50mL is as disperse phase;
(2) behind stirring 5-20min, form the water in oil microemulsion of transparent and stable in properties, add the concentration 0.05-0.3mol L of 1-10ml
-1The wetting ability inner nuclear material of commodity rhodamine B by name stirs 1h, finishes core-shell nano particulate nucleation;
(3) with silylating reagent TEOS and ammoniacal liquor by volume 1-4:0.05-2 join in the microemulsion system, continuously stirring 20-30h, under the catalysis of ammoniacal liquor, TEOS is hydrolysis gradually, generates Si (OH)
4Polycondensation formation nano particle also takes place in precipitation in the nanometer reaction tank;
(4) particle of gained is modified with the MPS that is in excess in 3-8 times on particle, then by dehydrated alcohol repeatedly centrifugal with separate the rhodamine B/SiO of collection
2Disperse with redistilled water, making its massfraction is 0.5%;
(5) with the 30g solid content be the rhodamine B/SiO of 0.1%-0.7% above-mentioned MPS modification
2Particle water dispersion liquid is as seed, add 0.2-5g N-N-isopropylacrylamide NIPAM as monomer, 0.01 MBA is as linking agent for-0.4g butyl methacrylate, 40-80 ℃ of logical nitrogen reaction of insulation 0.5h, add the aqueous solution 1-10mL that is dissolved with the 0.007g ammonium persulphate, 70 ℃ of insulation reaction 4h obtain the nucleocapsid structure particle, remove water-soluble polymers and the residual monomer that is dissolved in the water through separation;
(6) in the purified nucleocapsid structure particle of gained, add 5-30% hydrofluoric acid solution, room temperature reaction 2-6h, pack into and dialyse in the dialysis tubing, up to aqueous dispersions pH=6, obtain having the aqueous dispersions of the rhodamine B/PolyNIPAM microballoon of fluorescence and temperature sensitive property at last.
The present invention has the following advantages: 1. the temperature sensitive fluorescent nano particles of synthetic rhodamine B/PNIPAM has fluorescence and temperature sensitive double-response performance; 2. nanoparticle has nucleocapsid structure; 3. synthetic method mild condition, a step has prepared rhodamine B/SiO
2Fluorescent core; 4. do not use emulsifying agent owing in the building-up process, thereby particle surface is cleaner; 5. remove SiO with hydrofluoric acid solution
2Layer, method is simple.
Description of drawings
Fig. 1 is the rhodamine B/PNIPAM particle of the nanoscale of TEM test.
Fig. 2 is the fluorescence spectrum of the rhodamine B/PNIPAM nano material under the different excitation wavelengths.
Fig. 3 is the turbidity figure of rhodamine B/PNIPAM.
Embodiment
Example 1: according to the temperature sensitive fluorescent nano particles of the bright B/PNIPAM of following steps synthesizing rhodamine:
(1) with carbon number be 5 naphthenic hydrocarbon, tensio-active agent TritonX-100 and n-hexyl alcohol by volume 1:1:0.5 mix, the water that adds 20mL is as disperse phase;
(2) behind the stirring 5min, form the water in oil microemulsion of transparent and stable in properties, add the concentration 0.05-0.3mol L of 1ml
-1Commodity are called rhodamine B wetting ability inner nuclear material, stir 1h, finish core-shell nano particulate nucleation;
(3. with silylating reagent TEOS and ammoniacal liquor by volume 1:0.05 join in the microemulsion system, continuously stirring 20h, under the catalysis of ammoniacal liquor, TEOS is hydrolysis gradually, generates Si (OH)
4Polycondensation formation nano particle also takes place in precipitation in the nanometer reaction tank;
(4) particle of gained is modified with the MPS that is in excess in 3 times on particle, then by dehydrated alcohol repeatedly centrifugal with separate the rhodamine B/SiO of collection
2Disperse with redistilled water, making its massfraction is 0.5%;
(5) with the 30g solid content be the rhodamine B/SiO of 0.1% above-mentioned MPS modification
2Particle water dispersion liquid is as seed, add 0.2g N-N-isopropylacrylamide NIPAM as monomer, 0.01g butyl methacrylate MBA is as linking agent, the 40 ℃ of logical nitrogen reaction of insulation 0.5h, add the aqueous solution 1mL that is dissolved with the 0.007g ammonium persulphate, 70 ℃ of insulation reaction 4h obtain the nucleocapsid structure particle, remove water-soluble polymers and the residual monomer that is dissolved in the water through separation;
(6) add 5% hydrofluoric acid solution in the purified nucleocapsid structure particle of gained, room temperature reaction 2h dialyses in the dialysis tubing of packing into, up to aqueous dispersions pH 〉=6, the aqueous dispersions of temperature-sensitive fluorescent rhodamine B/PolyNIPAM microballoon obtained at last.
As shown in Figure 1, the rhodamine B/PNIPAM of TEM test shows nucleocapsid structure is the particle of nanoscale.
As shown in Figure 2, measure the fluorescence spectrum of the rhodamine B/PNIPAM nano material under the different excitation wavelengths, the result shows that the maximum emission wavelength of the fluorescence emission spectrum of nano particle adds 350nm cut-off all at 365nm, does not almost move.
As shown in Figure 3, in water medium, along with temperature raises, the turbidity of rhodamine B/PNIPAM solution has a hop in the time of 33 ℃, when temperature is lower than 33 ℃, and particulate swelling capacity height, water regain is big, and is transparence; When temperature during more than or equal to 33 ℃, the particulate swelling capacity is low, discharges the moisture that is absorbed, and its turbidity increases, and illustrates that fluorescent nano particles rhodamine B/PNIPAM has temperature sensitive property.
Example 2: according to the temperature sensitive fluorescent nano particles of the bright B/PNIPAM of following steps synthesizing rhodamine:
(1) in reaction tank be with carbon number 6 naphthenic hydrocarbon, tensio-active agent TritonX-100 and n-hexyl alcohol by volume 4:1:1.2 mix, the water that adds 35mL is as disperse phase;
(2) behind the stirring 12min, form the water in oil microemulsion of transparent and stable in properties, add the concentration 0.05-0.3mol L of 5ml
-1Commodity are called rhodamine B wetting ability inner nuclear material, stir 1h, finish core-shell nano particulate nucleation;
(3) with silylating reagent TEOS and ammoniacal liquor by volume 2.5:1 join in the microemulsion system, continuously stirring 25h, under the catalysis of ammoniacal liquor, TEOS is hydrolysis gradually, generates Si (OH)
4Polycondensation formation nano particle also takes place in precipitation in the nanometer reaction tank;
(4) particle of gained is modified with the MPS that is in excess in 5 times on particle, then by dehydrated alcohol repeatedly centrifugal with separate the rhodamine B/SiO of collection
2Disperse with redistilled water, making its massfraction is 0.5%;
(5) with the 30g solid content be the rhodamine B/SiO of 0.4% above-mentioned MPS modification
2Particle water dispersion liquid is as seed, add 2.6g N-N-isopropylacrylamide NIPAM as monomer, 0.2g butyl methacrylate MBA is as linking agent, the 60 ℃ of logical nitrogen reaction of insulation 0.5h, add the ammonium persulfate aqueous solution 5mL that is dissolved with 0.007g, 70 ℃ of insulation reaction 4h, the nucleocapsid structure particle that obtains is removed water-soluble polymers and the residual monomer that is dissolved in the water through separation;
(6) add 16% hydrofluoric acid solution in the purified nucleocapsid structure particle of gained, room temperature reaction 4h dialyses in the dialysis tubing of packing into, up to aqueous dispersions pH 〉=6, the aqueous dispersions of temperature-sensitive fluorescent rhodamine B/PolyNIPAM microballoon obtained at last.
Example 3: according to the temperature sensitive fluorescent nano particles of the bright B/PNIPAM of following steps synthesizing rhodamine:
(1) in reaction tank be with carbon number 8 naphthenic hydrocarbon, tensio-active agent TritonX-100 and n-hexyl alcohol in proportion volume ratio 7:1:2 mix, the water that adds 50mL is as disperse phase;
(2) behind the stirring 20min, form the water in oil microemulsion of transparent and stable in properties, add the concentration 0.05-0.3mol L of 10ml
-1Commodity are called rhodamine B wetting ability inner nuclear material, stir 1h, finish core-shell nano particulate nucleation;
(3) with silylating reagent TEOS and ammoniacal liquor by volume 4:2 join in the microemulsion system, continuously stirring 30h, under the catalysis of ammoniacal liquor, TEOS is hydrolysis gradually, generates Si (OH)
4Polycondensation formation nano particle also takes place in precipitation in the nanometer reaction tank;
(4) particle of gained is modified with the MPS that is in excess in 8 times on particle, then by dehydrated alcohol repeatedly centrifugal with separate the rhodamine B/SiO of collection
2Disperse with redistilled water, making its massfraction is 0.5%;
(5) with the 30g solid content be the rhodamine B/SiO of 0.7% above-mentioned MPS modification
2Particle water dispersion liquid is as seed, add 5g N-N-isopropylacrylamide NIPAM as monomer, 0.4g butyl methacrylate MBA is as linking agent, the 80 ℃ of logical nitrogen reaction of insulation 0.5h, add the aqueous solution 10mL that is dissolved with the 0.007g ammonium persulphate, 70 ℃ of insulation reaction 4h, the nucleocapsid structure particle that obtains is removed water-soluble polymers and the residual monomer that is dissolved in the water through separation;
(6) add 30% hydrofluoric acid solution in the purified nucleocapsid structure particle of gained, room temperature reaction 6h dialyses in the dialysis tubing of packing into, up to aqueous dispersions pH 〉=6, the aqueous dispersions of temperature-sensitive fluorescent rhodamine B/PolyNIPAM microballoon obtained at last.
Claims (1)
1. the synthetic method of a temperature-sensitive fluorescent nano material, this synthetic method may further comprise the steps: (1) in reaction tank be with carbon number 5-8 naphthenic hydrocarbon, tensio-active agent TritonX-100 and n-hexyl alcohol by volume 1-7:1:0.5-2 mix, the water that adds 20-50mL is as disperse phase;
(2) behind stirring 5-20min, form the water in oil microemulsion of transparent and stable in properties, add the concentration 0.05-0.3mol L of 1-10ml
-1Commodity rhodamine B wetting ability inner nuclear material by name, stir 1h, finish core-shell nano particulate nucleation;
(3) with silylating reagent TEOS and ammoniacal liquor by volume 1-4:0.05-2 join in the microemulsion system, continuously stirring 20-30h, under the catalysis of ammoniacal liquor, TEOS is hydrolysis gradually, generates Si (OH)
4Polycondensation formation nano particle also takes place in precipitation in the nanometer reaction tank;
(4) particle of gained is modified with the MPS that is in excess in 3-8 times on particle, then by dehydrated alcohol repeatedly centrifugal with separate the rhodamine B/SiO of collection
2Disperse with redistilled water, making its massfraction is 0.5%;
(5) the 30g solid content is the rhodamine B/SiO of 0.1%-0.7% above-mentioned MPS modification
2Particle water dispersion liquid is as seed, add 0.2-5g N, N '-N-isopropylacrylamide NIPAM is as monomer, 0.01 MBA is as linking agent for-0.4g butyl methacrylate, 40-80 ℃ of logical nitrogen reaction of insulation 0.5h add the aqueous solution 1-10mL that is dissolved with the 0.007g ammonium persulphate, 70 ℃ of insulation reaction 4h, the nucleocapsid structure particle that obtains is removed water-soluble polymers and the residual monomer that is dissolved in the water through separation;
(6) add 5-30% hydrofluoric acid solution in the purified nucleocapsid structure particle of gained, room temperature reaction 2-6h dialyses in the dialysis tubing of packing into, up to aqueous dispersions pH 〉=6, the aqueous dispersions of temperature-sensitive fluorescent rhodamine B/PolyNIPAM microballoon obtained at last.
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| CN101775112B (en) * | 2010-02-05 | 2012-01-11 | 苏州大学 | Preparation method of magnetic fluorescence dual functional thermo-sensitive nano particle |
| 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 |
| CN102489232B (en) * | 2011-12-13 | 2013-06-12 | 扬州大学 | Method for preparing fluorescence labeling polyactic acid nanometer microsphere |
| CN104861928A (en) * | 2015-05-21 | 2015-08-26 | 长安大学 | Thermosensitive salt-releasing material as well as preparation method and application thereof |
| CN108157369B (en) * | 2018-01-18 | 2019-10-15 | 浙江大学 | A kind of cold-resistant counterfeit-proof type seed coat agent and its application |
| CN110373918A (en) * | 2019-08-02 | 2019-10-25 | 浙江工业职业技术学院 | A kind of rhodamine B fluorescent paint and the preparation method and application thereof |
| CN112079950B (en) * | 2020-08-28 | 2022-03-15 | 长春理工大学 | Thermal activation delayed fluorescence temperature-sensitive polymer and preparation method thereof |
| CN115432707B (en) * | 2022-07-21 | 2024-05-07 | 复旦大学 | Synthesis method of patch-shaped hybrid nanoparticle with polar small molecular configuration |
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