CN107603595A - Load the up-conversion fluorescence three-dimensional porous sponge composite of graphene oxide - Google Patents
Load the up-conversion fluorescence three-dimensional porous sponge composite of graphene oxide Download PDFInfo
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- CN107603595A CN107603595A CN201710836769.0A CN201710836769A CN107603595A CN 107603595 A CN107603595 A CN 107603595A CN 201710836769 A CN201710836769 A CN 201710836769A CN 107603595 A CN107603595 A CN 107603595A
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Abstract
The invention discloses a kind of up-conversion fluorescence three-dimensional porous sponge composite for loading graphene oxide, using the pretreated sponge of cationic compound as carrier, pass through electrostatic interaction LBL self-assembly rare earth up-conversion luminescence nanomaterial, final load graphene oxide.The present invention guides the three-dimensional macro self assembly of rare earth up-conversion luminescence nanomaterial and graphene oxide using business sponge as template, prepares the three-dimensional macro nano structured unit assembly can in photoelectric device, biomedicine field with wide application prospect.
Description
Technical field
The present invention relates to a kind of up-conversion fluorescence three-dimensional porous sponge composite for loading graphene oxide, category nanometer is answered
Condensation material field.
Background technology
Rare earth upconversion nano luminescent material（UCNPs）Can be by two-photon or multi-photon mechanism the long amplitude of low energy
Penetrate and be converted into high-energy shortwave radiation, it possesses, and toxicity is low, chemical stability is high, photostability is strong, signal to noise ratio is high, emission band
Light penetration depth narrow, fluorescence lifetime is long, anti-Stokes displacement is big, larger, without photobleaching, without background fluorescence and to biology
Many advantages, such as organizing not damaged, controls in immunoassay, biomarker, bio-sensing, bio-imaging, pharmaceutical carrier, light power
The fields such as treatment, photo-thermal therapy, photoconductive switch, information storage, food safety detection, photocatalysis and solar cell have extensively
Research and application.Wherein NaYF4:Yb, Er/Tm are one of luminous efficiency highest UCNPs.
In past ten years, researcher is to the assembly research interest more and more higher of nano particle, and they are in nanometer
Substantial amounts of work has been done in terms of one-dimensional, two-dimentional, the three-dimensional self assembly and guide assembling of construction unit.Led specific to UCNPs
Domain, the document of one-dimensional, the two-dimentional self assembly about UCNPs is more, such as Changchun University of Science and Technology's chemistry and Environmental Engineering School's Dong's phase
The court of a feudal ruler prepares Y using electrostatic spinning technique2O3:Yb3+,Er3+Upper conversion nano fiber（SCI, 2010,31
(01):20-25）；Tan uses direct blending by CeF3:Yb, Er and PMMA are mixed, and mixed solution then is poured into mould, molten
PMMA laminated films are obtained after agent volatilization（ACS Applied Materials & Interfaces, 2010, 2(7):
1884-1891）.But it yet there are no macroscopical self-assembly system using three-dimensional porous material sponge as carrier.
The content of the invention
In view of the above problems, the present invention provides a kind of up-conversion fluorescence three-dimensional porous sponge for loading graphene oxide is compound
Material.
The technical scheme is that：（1）After sponge is cleaned, square is cut into, is immersed in quality
24h in the cationic compound aqueous solution of fraction 1%, bath raio 1:50, vacuum drying after taking-up；（2）Amine-terminated hyperbrancedization is polymerize
Thing modifies NaYF4:Yb, Er/Tm and Hyperbranched Polymer with Terminal Hydroxyl modification NaYF4:Yb, Er/Tm are configured to 1-10g/L's respectively
The aqueous solution；（3）Hyperbranched Polymer with Terminal Hydroxyl of the above-mentioned sponge impregnating at 80 DEG C is modified into NaYF4:In Yb, the Er/Tm aqueous solution
10-60min, bath raio 1:10, rinsed, dried repeatedly with deionized water after taking-up；Then by end of the above-mentioned sponge impregnating at 80 DEG C
Amino dissaving polymer modifies NaYF4:10-60min in Yb, the Er/Tm aqueous solution, bath raio 1:10, use deionized water after taking-up
Rinse, dry, so far by one layer of NaYF repeatedly4:Yb, Er/Tm are assembled into the surface of sponge, then overspend successively in terminal hydroxy group
Fluidized polymer modifies NaYF4:Yb, Er/Tm and Hyperbranched Polymer with Terminal Amido modification NaYF4:0- is repeated in Yb, Er/Tm assembles concentration
9 aforesaid operations；（4）By above-mentioned sponge impregnating in 80 DEG C, 1-10g/L graphene oxide water solution 10-60min, bath raio
1:50, reaction is washed, after drying repeatedly after terminating with ethanol and deionized water, obtains loading the up-conversion fluorescence of graphene oxide
Three-dimensional porous sponge composite.
Preferably, the cationic compound is Hyperbranched Polymer with Terminal Amido, PAMAM, chitosan, divinyl
Triamine, triethylene tetramine, TEPA, poly-dopamine, 2,3- epoxypropyltrimethylchloride chlorides, octyldodecyl diformazan
One or more in ammonium chloride, polyethyleneimine.
The synthesis of Hyperbranched Polymer with Terminal Amido refers to following open source literatures：Hyperbranched Polymer with Terminal Amido and its quaternary ammonium
The preparation of salt and performance [J] polymer material sciences and engineering, 2009,25 (8): 141-144；CN200710020794.8
A kind of super-branching reactive dye salt-free dyeing auxiliary；Coloration Technology, 2007, 123(6): 351-357；
AATCC Review, 2010, 10(6): 56-60；Biomacromolecules, 2010, 11(1): 245-251；
Chemical Research in Chinese Universities, 2005, 21(3): 345-354。
The synthesis of Hyperbranched Polymer with Terminal Hydroxyl refers to following open source literatures：The such as Yang Baoping, Zhang Pengfei, Cui Jinfeng ends
The study on the modification of hydroxyl dissaving polymer and its application [J] the China coating in coating, 2011,26 (3):53-57；King
River is learned, the Hyperbranched Polymer with Terminal Hydroxyl such as Hu Yanxin, Zheng Shujie is to Fe3+Absorption behavior studies [J] New Chemical Materials,
2011,39(9):26-29,47；The synthesis of the strong Hyperbranched Polymer with Terminal Hydroxyl such as torrential, Zhang Guoguo, Wang Xuechuan and modification [J]
Daily chemical industry, 2012,42 (6):413-417.
Hyperbranched Polymer with Terminal Amido modifies NaYF4:Yb, Er/Tm and Hyperbranched Polymer with Terminal Hydroxyl modification NaYF4:Yb,
Er/Tm preparation processes refer to document：A kind of water-soluble upper conversion nano particles of Chinese invention patent CN201410701945.6
And preparation method thereof.
Compared with prior art, the advantage of the invention is that：Rare earth up-conversion luminescence is guided using business sponge as template
The three-dimensional macro self assembly of nano material, NaYF is modified using electronegative Hyperbranched Polymer with Terminal Hydroxyl4:Yb, Er/Tm, oxygen
The Hyperbranched Polymer with Terminal Amido of graphite alkene and positively charged modifies NaYF4:Electrostatic interaction between Yb, Er/Tm is as film forming
Motive force, prepare the three-dimensional macro nano structured unit can in photoelectric device, biomedicine field with wide application prospect
Assembly.
Embodiment
The invention will be further elucidated with reference to specific embodiments.
Embodiment 1
（1）After sponge is cleaned, square is cut into, is immersed in 24h in the PAMAM aqueous solution of mass fraction 1%, bath raio 1:50, take
Go out rear vacuum drying；（2）Hyperbranched Polymer with Terminal Amido is modified into NaYF4:Yb, Er/Tm and Hyperbranched Polymer with Terminal Hydroxyl are repaiied
Adorn NaYF4:Yb, Er/Tm are configured to the 1g/L aqueous solution respectively；；（3）By superbrnaching end-hydroxy of the above-mentioned sponge impregnating at 80 DEG C
Polymer-modified NaYF4:10min in Yb, the Er/Tm aqueous solution, bath raio 1:10, rinsed, dried repeatedly with deionized water after taking-up；
Then Hyperbranched Polymer with Terminal Amido of the above-mentioned sponge impregnating at 80 DEG C is modified into NaYF4:10min in Yb, the Er/Tm aqueous solution,
Bath raio 1:10, rinsed, dried repeatedly with deionized water after taking-up；（4）By above-mentioned sponge impregnating in 80 DEG C, 1g/L graphite oxide
60min in aqueous solution, bath raio 1:50, reaction is washed, after drying repeatedly after terminating with ethanol and deionized water, obtains loading oxygen
The up-conversion fluorescence three-dimensional porous sponge composite of graphite alkene.
Embodiment 2
（1）After sponge is cleaned, square is cut into, is immersed in 24h in the triethylene tetramine aqueous solution of mass fraction 1%, bath raio 1:
50, vacuum drying after taking-up；（2）Hyperbranched Polymer with Terminal Amido is modified into NaYF4:Yb, Er/Tm and superbrnaching end-hydroxy polymerization
Thing modifies NaYF4:Yb, Er/Tm are configured to the 5g/L aqueous solution respectively；（3）Terminal hydroxy group of the above-mentioned sponge impregnating at 80 DEG C is surpassed
Branched polymer modifies NaYF4:30min in Yb, the Er/Tm aqueous solution, bath raio 1:10, rinsed repeatedly with deionized water after taking-up,
Drying；Then Hyperbranched Polymer with Terminal Amido of the above-mentioned sponge impregnating at 80 DEG C is modified into NaYF4:In Yb, the Er/Tm aqueous solution
30min, bath raio 1:10, rinsed, dried, so far by one layer of NaYF repeatedly with deionized water after taking-up4:Yb, Er/Tm are assembled into
The surface of sponge, then modify NaYF in Hyperbranched Polymer with Terminal Hydroxyl successively4:Yb, Er/Tm and Hyperbranched Polymer with Terminal Amido
Modify NaYF4:Aforesaid operations are repeated 2 times in Yb, Er/Tm assembles concentration；（4）By above-mentioned sponge impregnating in 80 DEG C, 5g/L oxidation
30min in graphene aqueous solution, bath raio 1:50, reaction is washed, after drying repeatedly after terminating with ethanol and deionized water, is born
Carry the up-conversion fluorescence three-dimensional porous sponge composite of graphene oxide.
Embodiment 3
（1）After sponge is cleaned, square is cut into, 2, the 3- epoxypropyltrimethylchloride chlorides for being immersed in mass fraction 1% are water-soluble
24h in liquid, bath raio 1:50, vacuum drying after taking-up；（2）Hyperbranched Polymer with Terminal Amido is modified into NaYF4:Yb, Er/Tm and end
Hydroxyl dissaving polymer modifies NaYF4:Yb, Er/Tm are configured to the 10g/L aqueous solution respectively；（3）Above-mentioned sponge impregnating is existed
80 DEG C of Hyperbranched Polymer with Terminal Hydroxyl modification NaYF4:60min in Yb, the Er/Tm aqueous solution, bath raio 1:10, spent after taking-up from
Sub- water rinses repeatedly, drying；Then Hyperbranched Polymer with Terminal Amido of the above-mentioned sponge impregnating at 80 DEG C is modified into NaYF4:Yb,
60min in the Er/Tm aqueous solution, bath raio 1:10, rinsed, dried, so far by one layer of NaYF repeatedly with deionized water after taking-up4:
Yb, Er/Tm are assembled into the surface of sponge, then modify NaYF in Hyperbranched Polymer with Terminal Hydroxyl successively4:Yb, Er/Tm and end ammonia
Base dissaving polymer modifies NaYF4:Aforesaid operations are repeated 4 times in Yb, Er/Tm assembles concentration；（4）By above-mentioned sponge impregnating 80
DEG C, 10min in 10g/L graphene oxide water solution, bath raio 1:50, reaction is washed repeatedly after terminating with ethanol and deionized water
Wash, after drying, obtain loading the up-conversion fluorescence three-dimensional porous sponge composite of graphene oxide.
Obviously, the above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not pair
The restriction of embodiments of the present invention.For those of ordinary skill in the field, may be used also on the basis of the above description
To make other changes in different forms.Here all embodiments can not be exhaustive.It is every to belong to this hair
Row of the obvious changes or variations that bright technical scheme is amplified out still in protection scope of the present invention.
Claims (5)
1. load the up-conversion fluorescence three-dimensional porous sponge composite of graphene oxide, it is characterised in that：By cationic compound
The pretreated sponge of thing, by electrostatic interaction LBL self-assembly rare earth up-conversion luminescence nanomaterial, is finally born as carrier
Carry graphene oxide.
2. the up-conversion fluorescence three-dimensional porous sponge composite of load graphene oxide according to claim 1, it is special
Sign is that the rare earth up-conversion luminescence nanomaterial is NaYF4:Yb, Er or NaYF4:Yb,Tm（That is NaYF4:Yb,Er/Tm）.
3. the up-conversion fluorescence three-dimensional porous sponge composite of load graphene oxide according to claim 1 or 2, its
It is characterised by, the rare earth up-conversion luminescence nanomaterial is that Hyperbranched Polymer with Terminal Hydroxyl modifies NaYF4:Yb, Er/Tm and end
Amino dissaving polymer modifies NaYF4:Yb,Er/Tm。
4. the up-conversion fluorescence three-dimensional porous sponge composite of load graphene oxide according to claim 1, it is special
Sign is that the cationic compound is Hyperbranched Polymer with Terminal Amido, PAMAM, chitosan, diethylenetriamine, triethylene four
Amine, TEPA, poly-dopamine, 2,3- epoxypropyltrimethylchloride chlorides, octyldodecyl alkyl dimethyl ammonium chloride, poly- second
One or more in alkene imines.
5. the up-conversion fluorescence three-dimensional porous sponge composite of load graphene oxide according to claim 1, it is special
Sign is that preparation process is as follows：（1）After sponge is cleaned, square is cut into, is immersed in the cationic compound of mass fraction 1%
24h in the aqueous solution, bath raio 1:50, vacuum drying after taking-up；（2）Hyperbranched Polymer with Terminal Amido is modified into NaYF4:Yb,Er/Tm
NaYF is modified with Hyperbranched Polymer with Terminal Hydroxyl4:Yb, Er/Tm are configured to the 1-10g/L aqueous solution respectively；（3）By above-mentioned sponge
It is immersed in 80 DEG C of Hyperbranched Polymer with Terminal Hydroxyl modification NaYF4:10-60min in Yb, the Er/Tm aqueous solution, bath raio 1:10, take
Rinsed, dried repeatedly with deionized water after going out；Then Hyperbranched Polymer with Terminal Amido of the above-mentioned sponge impregnating at 80 DEG C is modified
NaYF4:10-60min in Yb, the Er/Tm aqueous solution, bath raio 1:10, rinsed, dried, so far repeatedly with deionized water after taking-up
By one layer of NaYF4:Yb, Er/Tm are assembled into the surface of sponge, then modify NaYF in Hyperbranched Polymer with Terminal Hydroxyl successively4:Yb,
Er/Tm and Hyperbranched Polymer with Terminal Amido modification NaYF4:0-9 aforesaid operations are repeated in Yb, Er/Tm assembles concentration；（4）Will be upper
State sponge impregnating 10-60min, bath raio 1 in 80 DEG C, 1-10g/L graphene oxide water solution:50, reaction uses second after terminating
Alcohol and deionized water are washed, after drying repeatedly, obtain loading the up-conversion fluorescence three-dimensional porous sponge composite wood of graphene oxide
Material.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114874355A (en) * | 2022-05-19 | 2022-08-09 | 安徽农业大学 | Amino-terminated hyperbranched chitosan quaternary ammonium salt and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104371714A (en) * | 2014-11-28 | 2015-02-25 | 赵兵 | Molybdenum trioxide-graphene oxide composite material and preparation method thereof |
| CN104449714A (en) * | 2014-11-28 | 2015-03-25 | 赵兵 | UCNP (up-conversion nanoparticle)-graphene oxide composite material and preparation method thereof |
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2017
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104371714A (en) * | 2014-11-28 | 2015-02-25 | 赵兵 | Molybdenum trioxide-graphene oxide composite material and preparation method thereof |
| CN104449714A (en) * | 2014-11-28 | 2015-03-25 | 赵兵 | UCNP (up-conversion nanoparticle)-graphene oxide composite material and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| CHAO WU ET AL.: "Three-dimensional highly conductive grapheme-silver nanowire hybrid foams for flexible and stretchable conductors", 《ACS APPLIED MATERIALS & INTERFACES》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114874355A (en) * | 2022-05-19 | 2022-08-09 | 安徽农业大学 | Amino-terminated hyperbranched chitosan quaternary ammonium salt and preparation method thereof |
| CN114874355B (en) * | 2022-05-19 | 2023-01-03 | 安徽农业大学 | Amino-terminated hyperbranched chitosan quaternary ammonium salt and preparation method thereof |
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Application publication date: 20180119 |