CN103374346A - Method for improving water solubility of nanomaterial through surface modification and nanomaterial modified by method - Google Patents
Method for improving water solubility of nanomaterial through surface modification and nanomaterial modified by method Download PDFInfo
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- CN103374346A CN103374346A CN2012101104189A CN201210110418A CN103374346A CN 103374346 A CN103374346 A CN 103374346A CN 2012101104189 A CN2012101104189 A CN 2012101104189A CN 201210110418 A CN201210110418 A CN 201210110418A CN 103374346 A CN103374346 A CN 103374346A
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Abstract
The invention relates to a nanomaterial and particularly discloses a method for improving the water solubility of the nanomaterial through surface modification. The method comprises the following steps of: (1) dissolving the nanomaterial in an organic solvent to prepare a solution A; (b) adding a tween-series surfactant into the solution A, stirring to dissolve, adding a water or saline solution, and reacting for 3-5 hours at 40-80 DEG C; and (c) carrying out centrifugal separation on the solution obtained in the step (b) to obtain a solid, washing the solid by using water, and then drying the solid. The nanomaterial modified by the modification method disclosed by the invention has the advantages of good water solubility and low toxicity. Therefore, the nanomaterial can be potentially and widely applied to the fields of bio-labeling, biological detection, biological imaging, treatment of diseases and the like.
Description
Technical field
The present invention relates to nano material, relate in particular to a kind of nano material of improving the water miscible method of nano material and the method modification by finishing.
Background technology
Rare earth luminous nano material has many good performances and purposes widely, its optical property is mainly derived from electronics at the part forbidden transition jing of 4f shell inside, its emmission spectrum is wire, has the characteristics of long, high temperature resistant, the high excitation energy density of luminescent lifetime, high lumen equivalent.In addition, rare earth luminescent material has that the not available luminosity of other luminescent material is high, time of persistence is long, wavelength of transmitted light is adjustable, the radiationless advantage such as pollution-free, so it is widely used at colour televistion phosphor, three primary colours lamp phosphor, medical image fluorescent material, graphoscope, nuclear physics, radiation field and the aspect such as military.Because excellent properties and the broad prospect of application of Nano-scale Rare-earth Luminescent Materials, its development research has caused people's extensive concern.
At present, the method for the rare earth luminous nano material of preparation that adopted of people has: hydro-thermal and solvent-thermal method, organic/inorganic precursors thermal decomposition method, ultrasonic householder method, the precipitator method, sol-gel method, polyvalent alcohol method, microemulsion method etc.
But in the middle of the method that can synthesize the less and good luminous performance of particle diameter, the solvent that usage comparison is many is organic solvent, and the water-soluble of the nanoparticle that obtains all can't be satisfied nano material in the application of biological field.In many synthetic methods, all can carry out certain modification to synthetic nano material in the middle of many documents.With regard to rare earth luminous nano material, usually adopt silicon-dioxide and some hydrophilic polymkeric substance (such as polyacrylic acid, polyethyene diamine, polyoxyethylene glycol etc.) to modify in nanoparticle surface, to strengthen the dispersiveness of particle in polar solvent.Yet these are reunited than being easier in polar solvent and biological buffer with the resulting particle of these coating means at present, and these polymkeric substance are also relatively more expensive, and some polymkeric substance toxicity is larger.
The chemical name of tween is the polyoxyethylene sorbitan fatty acid ester, is called for short polysorbate (Polysorbate).Tween is the transliteration of English TWEEN, is the condenses of sapn (Span, Span) and oxyethane, is a class nonionic surface active agent.Because sapn is sorbyl alcohol and the formed ester of different higher fatty acid, so tween is actually series product of the same type, generally be divided into polysorbas20,40,60,80 etc. get well multiple.For example polysorbas20 is laurate, and polysorbate60 is stearate, and tween 80 is oleic acid ester, etc.The toxicity of the tensio-active agent of tween series is very low, and less expensive, therefore has been applied at present the aspects such as foodstuffs industry and biological chemistry detection.
Summary of the invention
The present invention aims to provide and a kind ofly improves the water miscible method of nano material by finishing.
Of the present inventionly improve the water miscible method of nano material by finishing, comprise the steps:
(a), nano material is dissolved in makes solution A in the organic solvent;
(b), add tween series of surfactants stirring and dissolving in the solution A after, add entry or salt brine solution, reaction 3-5 hour to organic solvent is evaporated completely under 40-80 ℃ of condition;
(c), gained substance B in the step (b) is carried out centrifugation after water clean post-drying;
Wherein, the volume of the tween series of surfactants used of the nano material of every modification 3-5mg is 20-50 μ L.
Optionally, the method that in the step (a) nano material is dissolved in the organic solvent is: after joining nano material in the organic solvent, nano material was dissolved in supersound process 20-30 minute.
Optionally, the nano material of every modification 3-5mg, the volume of the organic solvent that uses in the step (a) is 2-10ml; The water that adds in the step (b) or the volume of salt brine solution are 8-12ml.
Optionally, described nano material is up-conversion fluorescence nanoparticle or ferriferrous oxide nano-particle.
Optionally, described organic solvent is hexanaphthene or chloroform.
Optionally, the water described in step (b) or the step (c) is distilled water or deionized water.
Optionally, the described salt brine solution phosphate buffered saline buffer that is concentration 0.01-0.1mol/L.
Optionally, described tween series of surfactants is one or more the mixture in polysorbas20, polysorbate40, polysorbate60 or the tween 80.
Optionally, in the step (c) during centrifugal treating centrifuge speed be 10000-12000 rev/min.
The invention still further relates to a kind of by above-mentioned either method modify and nano material.
Beneficial effect of the present invention is as follows:
(1) method provided by the present invention is simple, by simple ultrasonic and stirring, can obtain water-soluble extraordinary nanoparticle.And the nanoparticle that obtains has good dispersiveness (seeing accompanying drawing 1) in the multiple solution with biocompatibility and damping fluid.
(2) nanoparticle that obtains has lower toxicity, therefore can not produce harm (seeing accompanying drawing 2) to organism.
(3) modify up-conversion fluorescence nanoparticle afterwards with modifying method of the present invention, it can't gone out much by tween essence with the relative intensity of fluorescence under the isoconcentration, fluorescent effect difference little (seeing accompanying drawing 3) before and after modifying, and the up-conversion fluorescence nanoparticle fluorescence essence of traditional method after the modifying rate of going out is higher.
(4) use the nanoparticle of modifying method of the present invention after modifying because good wetting ability, and the shortcoming such as cytotoxicity is low, and it is poor to have overcome nanoparticle wetting ability aspect biocompatibility, and cytotoxicity is large.Therefore in fields such as biomarker, biological detection, bio-imaging and disease treatments potential widespread use is being arranged.
Description of drawings
Fig. 1 is the deployment conditions of up-conversion fluorescence nanoparticle in phosphate buffered saline buffer (PBS), foetal calf serum (FBS) and cell culture medium (DMEM) after modifying by the method among the embodiment 1.
Fig. 2 is the cytotoxicity to human pneumonocyte (A549) under different concns of the up-conversion fluorescence nanoparticle after modifying by the method among the embodiment 1;
Fig. 3 is relative intensity of fluorescence under same isoconcentration (1mg/mL) of the up-conversion fluorescence nanoparticle of the up-conversion fluorescence nanoparticle (a following line) after modifying by the method among the embodiment 1 and unmodified (above a line).
Embodiment
The present invention will be described in detail below in conjunction with specific embodiment.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.Should be understood that in addition after having read content disclosed by the invention, various changes or modification that those skilled in the art do the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
The below is take up-conversion fluorescence nanoparticle and ferriferrous oxide nano-particle as example, provide several specific embodiments, the present invention is equally applicable to the finishing of other nano material except up-conversion fluorescence nanoparticle and ferriferrous oxide nano-particle, and the water-soluble and lower toxicity that after modifying nano material is obtained.
Up-conversion fluorescence nanoparticle of the present invention can adopt the preparation of one of following two kinds of methods:
(1) adopting oleic acid (Oleic acid) and octadecylene (Octadecyl ene) is solvent, and Rare Earths salt is that reactant carries out pyrolysis:
Take by weighing YCl
3XH
2O, YbCl
3XH
2O and ErCl
3XH
2O is 1mmol (YCl altogether
3XH
2O, YbCl
3XH
2O and ErCl
3XH
2The mol ratio of O is 80: 18: 2 or 78: 20: 2), and add in the 2mL methyl alcohol ultrasonic dissolution.In addition 6mL oleic acid and 15mL octadecylene are mixed in the 50mL single port flask, above-mentioned methanol solution is poured in time mixed solution, be heated to 100 ℃ and stirring, behind the solution that makes its dissolving and formation homogeneous transparent, be cooled to room temperature.With 2.5mmol NaOH and 4mmolNH
4F is dissolved in the 5mL methyl alcohol, and ultrasonic dissolution slowly splashes in the above-mentioned system with constant pressure funnel.After adding, as for heating 30min in 100 ℃ the heating jacket, purpose is with methyl alcohol volatilization complete (this step is extremely important, and can whether fully the methyl alcohol volatilization affects the reaction final product luminous) with the single port flask.After treating that methyl alcohol volatilizees fully, insert prolong, remove air, logical water of condensation and argon gas, constant temperature to 300 ℃ also stirring, the reaction times is 1h.After the question response end temp descends, the particle in the system is out centrifugal and use ethanol or water to clean for several times, oven dry, it is for subsequent use to collect powder.
(2) adopting oleic acid and oleyl amine is solvent, and the rare earth trifluoroacetate is reactant, the rare earth up-conversion fluorescence nanoparticle (NaYF of preparation core-shell structure
4: Yb, Er@NaYF
4):
Take by weighing Y (CF
3COO)
3, Yb (CF
3COO)
3And Er (CF
3COO)
31mmo l (Y (CF altogether
3COO)
3, Yb (CF
3COO)
3And Er (CF
3COO)
3Mol ratio be 80: 18: 2 or 78: 20: 2), and take by weighing 1.5mmol Na (CF
3COO).Other gets 30mL oleic acid and 8mL oleyl amine, is mixed in the 50mL single port flask, adds high temperature magneton, zeolite and above-mentioned powder.System is removed air, passes into argon gas, is heated to 120 ℃, stirs about 30min to salt to be dissolved in the organic solvent, after the dissolving system is warming up to 250 ℃-300 ℃.Reaction times is 30min.
When treating above-mentioned reaction, take by weighing 1mmolY (CF
3COO)
3And 1.5mmolNa (CF
3COO), add in 3mL oleic acid and the 3mL oleyl amine, be heated to about 120 ℃, stir 20min and make its dissolving.After above-mentioned reaction was complete, system was cooled to below 200 ℃, and in fast adding system of this solution, laying equal stress on newly is warming up to 320 ℃, reaction 30min.After reaction finishes, cooling, for subsequent use after cleaning several and the oven dry.
The below provides several about the embodiment that improves the water miscible method of nano material by finishing of the present invention.
Embodiment 1
Take by weighing up-conversion fluorescence nanoparticle 3mg, join in the 2mL hexanaphthene, make the up-conversion fluorescence nano-particle solution.Then supersound process 20 minutes is until in the described organic solvent that the up-conversion fluorescence nanoparticle is dissolved in fully, add 20 μ L tween 20s, stirring 1h is dissolved in fully to tween 20 and must goes up conversion nano fluorescent nano particles solution in the organic solvent under the 1250r/min rotating speed.Then described upper conversion nano fluorescent nano particles solution is placed water-bath, heated and stirred adds the deionized water of 10mL, constant temperature in 70 ℃ 4 hours, complete to the organic solvent volatilization, the solution clear, reaction finishes.Reaction is later with reaction solution centrifugal treating under the rotating speed of 12000 rev/mins of centrifuge speeds, up-conversion nanoparticles after centrifugal treating post-drying of washed with de-ionized water, collect powder, be the up-conversion nanoparticles after the finishing, this up-conversion nanoparticles has good water-soluble, and have lower toxicity, therefore can not produce harm to organism.
Embodiment 2
Take by weighing up-conversion fluorescence nanoparticle 5mg, join in the 3mL hexanaphthene, make the up-conversion fluorescence nano-particle solution.Then supersound process 30 minutes until the up-conversion fluorescence nanoparticle be dissolved in fully in the described organic solvent, add 50 μ L Tween-40s, stirring 2h is dissolved in fully to Tween-40 and must goes up conversion nano fluorescent nano particles solution in the organic solvent under the 1700r/min rotating speed.Then described upper conversion nano fluorescent nano particles solution is placed water-bath, heated and stirred, the concentration that adds 8mL is the phosphate buffered saline buffer of 0.01mol/L, constant temperature in 40 ℃ 5 hours, complete to the organic solvent volatilization, the solution clear, reaction finishes.Reaction is later with reaction solution centrifugal treating under the rotating speed of 10000 rev/mins of centrifuge speeds, up-conversion nanoparticles after centrifugal treating post-drying of washed with de-ionized water, collect powder, be the up-conversion nanoparticles after the finishing, this up-conversion nanoparticles has good water-soluble, and have lower toxicity, therefore can not produce harm to organism.
Embodiment 3
Take by weighing up-conversion fluorescence nanoparticle 5mg, join in the 10mL hexanaphthene, make the up-conversion fluorescence nano-particle solution.Then supersound process 25 minutes until the up-conversion fluorescence nanoparticle be dissolved in fully in the described organic solvent, add 30 μ L Tween-60s, stirring 2h is dissolved in fully to Tween-60 and must goes up conversion nano fluorescent nano particles solution in the organic solvent under the 2400r/min rotating speed.Then described upper conversion nano fluorescent nano particles solution is placed water-bath, heated and stirred adds the distilled water of 12mL, and constant temperature was in 80 degree 3 hours, and is complete to the organic solvent volatilization, the solution clear, and reaction finishes.Reaction is later with reaction solution centrifugal treating under the rotating speed of 11000 rev/mins of centrifuge speeds, up-conversion nanoparticles after the centrifugal treating cleans a post-drying with distilled water, collect powder, be the up-conversion nanoparticles after the finishing, this up-conversion nanoparticles has good water-soluble, and have lower toxicity, therefore can not produce harm to organism.
Embodiment 4
Take by weighing up-conversion fluorescence nanoparticle 5mg, join in the 7mL hexanaphthene, make the up-conversion fluorescence nano-particle solution.Then supersound process 25 minutes until the up-conversion fluorescence nanoparticle be dissolved in fully in the described organic solvent, add 40 μ L tween-80s, stirring 2h is dissolved in fully to tween-80 and must goes up conversion nano fluorescent nano particles solution in the organic solvent under the 2400r/min rotating speed.Then described upper conversion nano fluorescent nano particles solution is placed water-bath, heated and stirred adds the deionized water of 12mL, constant temperature in 75 ℃ 3 hours, complete to the organic solvent volatilization, the solution clear, reaction finishes.Reaction is later with reaction solution centrifugal treating under the rotating speed of 11000 rev/mins of centrifuge speeds, up-conversion nanoparticles after centrifugal treating post-drying of washed with de-ionized water, collect powder, be the up-conversion nanoparticles after the finishing, this up-conversion nanoparticles has good water-soluble, and have lower toxicity, therefore can not produce harm to organism.
Embodiment 5
Take by weighing ferriferrous oxide nano-particle 5mg, join in the 4mL chloroform, make ferriferrous oxide nano-particle solution.Then supersound process 25 minutes adds 40 μ L tween-80s until Z 250 is dissolved in the described organic solvent fully, and stirring 1.5h is dissolved in fully to tween-80 and must goes up ferriferrous oxide nano-particle solution in the organic solvent under the 1600r/min rotating speed.Then ferriferrous oxide nano-particle solution is placed water-bath, heated and stirred adds the deionized water of 10mL, constant temperature in 65 ℃ 3.5 hours, complete to the organic solvent volatilization, the solution clear, reaction finishes.Reaction is later with the reaction solution centrifugal treating, up-conversion nanoparticles after centrifugal treating post-drying of washed with de-ionized water, collect powder, be the up-conversion nanoparticles after the finishing, this up-conversion nanoparticles has good water-soluble, and have lower toxicity, therefore can not produce harm to organism.
Claims (10)
1. one kind is improved the water miscible method of nano material by finishing, it is characterized in that, comprises the steps:
(a), nano material is dissolved in makes solution A in the organic solvent;
(b), add tween series of surfactants stirring and dissolving in the solution A after, add entry or salt brine solution, reaction 3-5 hour to organic solvent is evaporated completely to get substance B under 40-80 ℃ of condition;
(c), gained substance B in the step (b) is carried out centrifugal treating after water clean post-drying;
Wherein, the volume of the tween series of surfactants used of the nano material of every modification 3-5mg is 20-50 μ L.
2. the water miscible method of nano material of improving according to claim 1, it is characterized in that, the method that in the step (a) nano material is dissolved in the organic solvent is: after joining nano material in the organic solvent, nano material was dissolved in supersound process 20-30 minute.
3. the water miscible method of nano material of improving according to claim 1 is characterized in that, the nano material of every modification 3-5mg, and the volume of the organic solvent that uses in the step (a) is 2-10ml; The water that adds in the step (b) or the volume of salt brine solution are 8-12ml.
4. the water miscible method of nano material of improving according to claim 1 is characterized in that described nano material is up-conversion fluorescence nanoparticle or ferriferrous oxide nano-particle.
5. the water miscible method of nano material of improving according to claim 1 is characterized in that described organic solvent is hexanaphthene or chloroform.
6. the water miscible method of nano material of improving according to claim 1 is characterized in that, the water described in step (b) or the step (c) is distilled water or deionized water.
7. the water miscible method of nano material of improving according to claim 1 is characterized in that, described salt brine solution is the superphosphate damping fluid of concentration 0.01-0.1mol/L.
8. the water miscible method of nano material of improving according to claim 1 is characterized in that, described tween series of surfactants is one or more the mixture in tween 20, Tween-40, Tween-60 or the tween-80.
9. the water miscible method of nano material of improving according to claim 1 is characterized in that, centrifuge speed is 10000-12000 rev/min during the middle centrifugal treating of step (c).
10. one kind was carried out the surface finish nano material, it is characterized in that, was modified and was got by each described method of claim 1-9.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111269720A (en) * | 2020-03-06 | 2020-06-12 | 厦门稀土材料研究所 | Rare earth doped double long afterglow nano material and its preparation method and use |
| CN111454591A (en) * | 2019-01-22 | 2020-07-28 | 北京化工大学 | Method for modifying silicon dioxide, modified silicon dioxide and application |
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| CN1588006A (en) * | 2004-07-16 | 2005-03-02 | 北京博奥生物芯片有限责任公司 | Calibration chip for fluorescent instrument calibration measurement and its preparing method |
| CN1775429A (en) * | 2005-09-29 | 2006-05-24 | 江苏大学 | Method for preparing nano nickel |
| CN102241968A (en) * | 2011-06-28 | 2011-11-16 | 吉林大学 | Method for implementing transfer of up-conversion nanocrystals from oil phase to aqueous phase |
-
2012
- 2012-04-13 CN CN2012101104189A patent/CN103374346A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1588006A (en) * | 2004-07-16 | 2005-03-02 | 北京博奥生物芯片有限责任公司 | Calibration chip for fluorescent instrument calibration measurement and its preparing method |
| CN1775429A (en) * | 2005-09-29 | 2006-05-24 | 江苏大学 | Method for preparing nano nickel |
| CN102241968A (en) * | 2011-06-28 | 2011-11-16 | 吉林大学 | Method for implementing transfer of up-conversion nanocrystals from oil phase to aqueous phase |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111454591A (en) * | 2019-01-22 | 2020-07-28 | 北京化工大学 | Method for modifying silicon dioxide, modified silicon dioxide and application |
| CN111269720A (en) * | 2020-03-06 | 2020-06-12 | 厦门稀土材料研究所 | Rare earth doped double long afterglow nano material and its preparation method and use |
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Application publication date: 20131030 |