CN108359093A - A kind of organic fluorescence poly-dopamine nano-particle solution and preparation method thereof with pH instruction functions - Google Patents

A kind of organic fluorescence poly-dopamine nano-particle solution and preparation method thereof with pH instruction functions Download PDF

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CN108359093A
CN108359093A CN201810190281.XA CN201810190281A CN108359093A CN 108359093 A CN108359093 A CN 108359093A CN 201810190281 A CN201810190281 A CN 201810190281A CN 108359093 A CN108359093 A CN 108359093A
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solution
dopamine
poly
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preparation
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CN108359093B (en
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熊华玉
王升富
张修华
文为
董超
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Hubei University
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Abstract

The present invention relates to a kind of organic fluorescence poly-dopamine nano-particle solutions and preparation method thereof indicating function with pH, and preparation method includes the following steps:S1. dopamine is dissolved in the water to obtain aqueous dopamine solution;S2. ferrous salt or molysite aqueous solution are added into aqueous dopamine solution, while hydrogen peroxide is added, reaction solution is obtained after being sufficiently mixed;S3. reaction solution reacts 5 8h at room temperature, be then charged into molecular cut off be 100 500Da bag filter in, dialysis 36 48h to get.The beneficial effects of the invention are as follows:After ferrous or iron ion is added in aqueous dopamine solution, it is only necessary to can be obtained the poly-dopamine nano-particle with fluorescent characteristic using the oxidation of one step of suitable hydrogen peroxide, preparation method is relatively simpler;The fluorescence intensity of organic fluorescence poly-dopamine nano-particle solution prepared by the present invention shows the characteristic changed with the variation of pH value of solution, that is, has the function of indicating pH value of solution.

Description

It is a kind of with pH instruction function organic fluorescence poly-dopamine nano-particle solution and its Preparation method
Technical field
The invention belongs to chemistry and bioscience technology fields, and in particular to a kind of organic fluorescence with pH instruction functions Poly-dopamine nano-particle solution and preparation method thereof.
Background technology
Organic fluorescence nano material has advantage outstanding in biodegradable, bio-compatibility and photostability etc.. Dopamine is that a kind of neurotransmitter is widely present for helping the chemical substance of cell transfer pulse in human body.DOPA Amine is a kind of small molecule for being easy to that autohemagglutination occurs under Oxygen Condition, with it come prepare organic fluorescence nano material be it is a kind of very Attractive and application prospect material.
So far, also fewer about the relevant report of the synthesis of fluorescence poly-dopamine nano material.The text reported Two-step method is usually used in offering to be synthesized.The first step:Dopamine is under alkaline condition by the dioxygen oxidation in water at big Poly-dopamine nano-particle;Second step:A large amount of H is added2O2, by big poly-dopamine nano-particle be etched into it is small have it is glimmering Fluorescence poly-dopamine nano-particle [X.Zhang, S.Wang, L.Xu, L.Feng, Y.Ji, L.Tao, the S.Li and of optical property Y.Wei,Nanoscale,2012,4,5581-5584].Disadvantage is that when carrying out oxidation polymerization to dopamine with oxygen Extent of polymerization is difficult control, therefore synthesized fluorescence poly-dopamine nano material is by different extent of polymerization groups in the prior art At mixture [A.Yildirim and M.Bayindir, Anal.Chem., 2014,86,5508-5512..J.-H.Lin, C.-J.Yu,Y.-C.Yang and W.-L.Tseng,Phys.Chem.Chem.Phys.,2015,17,15124-15130]。
Invention content
The present invention provides a kind of organic fluorescence poly-dopamine nano-particle solution with pH instruction functions and its preparation side Method, it is desirable to provide a kind of new method preparing organic fluorescence poly-dopamine nano-particle solution simultaneously expands its application.
The technical solution that the present invention solves above-mentioned technical problem is as follows:A kind of organic fluorescence with pH instruction functions is poly- more The preparation method of bar amine nano-particle solution comprising following steps:
S1. dopamine is dissolved in the water to obtain aqueous dopamine solution;
S2. ferrous salt or molysite aqueous solution are added into aqueous dopamine solution, while hydrogen peroxide is added, after being sufficiently mixed Reaction solution, dopamine, Fe in reaction solution2+Or Fe3+、H2O2The ratio between the amount of substance of three be 2:0.001-0.004:0.5- 1.2;
S3. reaction solution reacts 5-8h at room temperature, is then charged into the bag filter that molecular cut off is 100-500Da, thoroughly Analyse 36-48h to get.
Based on the above technical solution, the present invention can also do specific choice further below or optimal selection.
Specifically, in S1 aqueous dopamine solution a concentration of 10-50mM.
Specifically, a concentration of 1-4mM of ferrous salt or molysite aqueous solution in S2.
Specifically, the molysite in S2 is iron chloride or ferric sulfate, ferrous salt is frerrous chloride or ferrous sulfate.
Specifically, a concentration of 0.5-1.5M of the hydrogen peroxide in S2.
Best, dopamine, Fe in the reaction solution of S22+Or Fe3+、H2O2The ratio between the amount of substance of three be 2:0.002- 0.003:1.
In addition, the present invention also provides a kind of organic fluorescence poly-dopamine nano-particle solution indicating function with pH, It is prepared by above-mentioned method.
Compared with prior art, the beneficial effects of the invention are as follows:
After ferrous or iron ion is added in aqueous dopamine solution, it is only necessary to be aoxidized using suitable one step of hydrogen peroxide The poly-dopamine nano-particle with fluorescent characteristic is obtained, preparation method is relatively simpler;Organic fluorescence prepared by the present invention is poly- The fluorescence intensity of dopamine nano-particle solution shows the characteristic changed with the variation of pH value of solution, therefore can be strong by its fluorescence Degree qualitatively reflects the acid-base property of solution, further also can be (right according to the pH sizes of the size quantitative response solution of fluorescence intensity Solution of the pH less than 8 is relatively applicable in), i.e., organic fluorescence poly-dopamine nano-particle prepared by the method provided through the invention is not only Having the function of fluorescent characteristic also has pH instructions.
Description of the drawings
Fig. 1 be the excitation figure of raw material and poly-dopamine nano-particle solution obtained used in the embodiment of the present invention 1 and Transmitting figure, wherein a is that excitation figure (Ex.=484nm), the b of poly-dopamine nano-particle solution are that poly-dopamine nano-particle is molten The transmitting figure (Em.=541nm) of liquid, c are raw material aqueous dopamine solution and molysite aqueous solution mixing and are stored at room temperature after 6h Transmitting figure under 484nm excitations, d are raw material aqueous dopamine solution and hydrogen peroxide mixing and are excited in 484nm after being stored at room temperature 6h Under transmitting figure;
Fig. 2 be the excitation figure of raw material and poly-dopamine nano-particle solution obtained used in the embodiment of the present invention 2 and Transmitting figure, wherein a is that excitation figure (Ex.=454nm), the b of poly-dopamine nano-particle solution are that poly-dopamine nano-particle is molten The transmitting figure (Em.=483nm) of liquid, c are raw material aqueous dopamine solution and perferrite solution mixing and are stored at room temperature after 6h Transmitting figure under 454nm excitations, d are raw material aqueous dopamine solution and hydrogen peroxide mixing and are excited in 454nm after being stored at room temperature 6h Under transmitting figure;
Fig. 3 is the transmission electron microscope picture for the poly-dopamine nano-particle solution that the embodiment of the present invention 1 obtains;
Fig. 4 is the feelings that the poly-dopamine nano-particle solution fluorescence intensity that the embodiment of the present invention 1 obtains changes with pH value of solution Condition.
Specific implementation mode
Technical solution provided by the invention is described in further detail below in conjunction with drawings and the specific embodiments, is lifted Example is served only for explaining the present invention, is not intended to limit the scope of the present invention.
The drug used in following embodiment is then commercial product unless otherwise noted, if the method used is without especially saying It is bright, it is the conventional method that those skilled in the art use.
Embodiment 1
A kind of organic fluorescence poly-dopamine nano-particle solution with pH instruction functions, is made by the steps It arrives:
S1. dopamine is dissolved in the water to obtain aqueous dopamine solution, a concentration of 0.005g/mL of aqueous dopamine solution, That is 32mM;
S2. the ferric chloride in aqueous solution and 10 a concentration of 1M of μ L of 10 a concentration of 2mM of μ L are added into 600 μ L aqueous dopamine solutions Hydrogen peroxide and be sufficiently mixed to obtain reaction solution, dopamine, Fe in reaction solution3+And H2O2The ratio between the amount of substance about 2:0.002: 1;
S3. reaction solution reacts 6h at room temperature, is then charged into the bag filter that molecular cut off is 100-500Da, dialysis 40h to get.
Embodiment 2
A kind of organic fluorescence poly-dopamine nano-particle solution with pH instruction functions, is made by the steps It arrives:
S1. dopamine is dissolved in the water to obtain aqueous dopamine solution, a concentration of 10mM of aqueous dopamine solution;
S2. the ferrous chloride aqueous solution and 10 μ L concentration of 10 a concentration of 4mM of μ L are added into 2000 μ L aqueous dopamine solutions For 1.2M hydrogen peroxide and be sufficiently mixed to obtain reaction solution, dopamine, Fe in reaction solution2+And H2O2The ratio between the amount of substance about 2: 0.004:1.2;
S3. reaction solution reacts 8h at room temperature, is then charged into the bag filter that molecular cut off is 100-500Da, dialysis 36h to get.
Embodiment 3
A kind of organic fluorescence poly-dopamine nano-particle solution with pH instruction functions, is made by the steps It arrives:
S1. dopamine is dissolved in the water to obtain aqueous dopamine solution, a concentration of 50mM of aqueous dopamine solution;
S2. ferrous chloride aqueous solution and the 10 μ L that 10 a concentration of 1mM of μ L are added into 400 μ L aqueous dopamine solutions are a concentration of The hydrogen peroxide of 0.5M is simultaneously sufficiently mixed to obtain reaction solution, dopamine, Al in reaction solution3+And H2O2The ratio between the amount of substance about 2: 0.001:0.5;
S3. reaction solution reacts 5h at room temperature, is then charged into the bag filter that molecular cut off is 100-500Da, dialysis 48h to get.
Respectively using organic fluorescence poly-dopamine nano-particle solution is test sample made from embodiment 1 to 3, after testing respectively Sample all has apparent fluorescent effect and has pH instructions function (fluorescence intensity changes with pH and changed).Respectively with embodiment 1 and embodiment 2 made from organic fluorescence poly-dopamine nano-particle solution be representative, test its fluorescent effect such as Fig. 1 and Fig. 2 It is shown, the present invention known to Fig. 1 and Fig. 2 successfully synthesize poly-dopamine nano-particle and its with fluorescent effect, (a and b have bright Aobvious excitation peak and emission peak, c and d non-emissives peak as a comparison);As can be seen from Figure 3, what prepared by the embodiment of the present invention 1 is poly- more Bar amine nano-particle sample has nano-scale and its size is relatively uniform;As can be seen from Figure 4, prepared by the embodiment of the present invention 1 The fluorescence intensity of poly-dopamine nano-particle solution change with the pH of solution and change, therefore can be anti-by the size of fluorescence intensity The pH for reflecting solution, when the pH of solution is less than 8, fluorescence intensity becomes larger with pH and is reduced, and correlation is good and variation is more apparent, It is contemplated that quantitatively obtaining the size of pH value of solution with the size of fluorescence intensity, in addition see can determine whether roughly according to the size of fluorescence intensity The acid-base property of solution (fluorescence intensity hour solution is alkalinity, and solution is acid or partial neutral when fluorescence intensity is big).
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all the present invention spirit and Within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention.

Claims (7)

1. a kind of preparation method of the organic fluorescence poly-dopamine nano-particle solution with pH instruction functions, which is characterized in that Include the following steps:
S1. dopamine is dissolved in the water to obtain aqueous dopamine solution;
S2. ferrous salt or molysite aqueous solution are added into aqueous dopamine solution, while hydrogen peroxide is added, must be reacted after being sufficiently mixed Liquid, dopamine, Fe in reaction solution2+Or Fe3+、H2O2The ratio between the amount of substance of three be 2:0.001-0.004:0.5-1.2;
S3. reaction solution reacts 5-8h at room temperature, is then charged into the bag filter that molecular cut off is 100-500Da, and dialyse 36- 48h to get.
2. a kind of system of organic fluorescence poly-dopamine nano-particle solution with pH instruction functions according to claim 1 Preparation Method, which is characterized in that a concentration of 10-50mM of aqueous dopamine solution in S1.
3. a kind of system of organic fluorescence poly-dopamine nano-particle solution with pH instruction functions according to claim 1 Preparation Method, which is characterized in that a concentration of 1-4mM of ferrous salt or molysite aqueous solution in S2.
4. a kind of system of organic fluorescence poly-dopamine nano-particle solution with pH instruction functions according to claim 1 Preparation Method, which is characterized in that the molysite in S2 is iron chloride or ferric sulfate, and ferrous salt is frerrous chloride or ferrous sulfate.
5. a kind of system of organic fluorescence poly-dopamine nano-particle solution with pH instruction functions according to claim 1 Preparation Method, which is characterized in that a concentration of 0.5-1.5M of the hydrogen peroxide in S2.
6. a kind of system of organic fluorescence poly-dopamine nano-particle solution with pH instruction functions according to claim 1 Preparation Method, which is characterized in that dopamine, Fe in the reaction solution of S22+Or Fe3+、H2O2The ratio between the amount of substance of three be 2: 0.002-0.003:1.
7. a kind of organic fluorescence poly-dopamine nano-particle solution with pH instruction functions, which is characterized in that wanted by right 1 to 6 any one of them method is asked to be prepared.
CN201810190281.XA 2018-03-08 2018-03-08 Organic fluorescent polydopamine nanoparticle solution with pH indicating function and preparation method thereof Expired - Fee Related CN108359093B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080247984A1 (en) * 2007-04-09 2008-10-09 Nerites Corporation Dopa-functionalized, branched, poly(aklylene oxide) adhesives
CN103908682A (en) * 2014-04-29 2014-07-09 中国科学院长春应用化学研究所 Application of poly-dopamine nano-particles
CN105514378A (en) * 2015-12-22 2016-04-20 湘潭大学 Lithium-sulfur battery positive-pole composite material with imitated cellular structure and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080247984A1 (en) * 2007-04-09 2008-10-09 Nerites Corporation Dopa-functionalized, branched, poly(aklylene oxide) adhesives
CN103908682A (en) * 2014-04-29 2014-07-09 中国科学院长春应用化学研究所 Application of poly-dopamine nano-particles
CN105514378A (en) * 2015-12-22 2016-04-20 湘潭大学 Lithium-sulfur battery positive-pole composite material with imitated cellular structure and preparation method thereof

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