CN107558187A - A kind of up-conversion fluorescence silk of graphene oxide cladding - Google Patents
A kind of up-conversion fluorescence silk of graphene oxide cladding Download PDFInfo
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- CN107558187A CN107558187A CN201710836629.3A CN201710836629A CN107558187A CN 107558187 A CN107558187 A CN 107558187A CN 201710836629 A CN201710836629 A CN 201710836629A CN 107558187 A CN107558187 A CN 107558187A
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Abstract
The invention discloses a kind of up-conversion fluorescence silk of graphene oxide cladding, by the use of electrostatic interaction as film forming motive force, in silk fabric surface layer self assembly NaYF4:The up-conversion fluorescence silk of graphene oxide cladding is prepared in Yb, Er/Tm, final impregnating in graphene oxide water solution.NaYF4:Silk fabric surface is attached to by the combination of negative ions key between Yb, Er/Tm, avoided using chemical cross-linking agent, reduces the influence to silk fabric strength.Modified silk fabric has excellent up-conversion fluorescence performance and good washable, wearability.
Description
Technical field
The present invention relates to a kind of up-conversion fluorescence silk of graphene oxide cladding, category fibrous material field.
Background technology
Silk is a kind of very important fibrous material, and its application has been not solely restricted to textile industry.Natural silkworm
The color of silk has white and yellow, and with the development of science and technology, people have obtained the silk with different colours, such as red
Color, green, orange etc..In addition, the silk after functionalization, also with some specific functions, such as fluorescence, UV resistance, antibacterial
Deng, available for weave, biomedical, anti-counterfeit field.
Preparation fluorescent natural silk method at present, including genetic engineering, feeding method, nano material associated methods and two-photon are glimmering
Light technology etc..Color fluorescence silk is prepared for example with feeding method, is had the advantages that simple to operate, efficient, environmentally friendly.But fluorescence contaminates
Expect that transport in silkworm body is complicated, it is efficiently entering in silk gland, so as to fibroin strong bonded, and ensure fluorescence
The materials such as dyestuff it is harmless on silkworm and on silk yield without influence, be still the difficult point overcome needed for feeding method production function silk（Cao Li
Common vetch, Lin Naibo, Liu Xiangyang optical function silk fiber material [J] Chinese materials progress, 2014,33 (11):669-676
+689）.
In recent years, the application of nano particle was widely paid close attention to, and because its particle diameter is small, specific surface area is big, shows
Dimensional effect, skin effect, there is the special performances such as light, electricity, magnetic, be applied to medicine, photoelectric device, biology sensor etc.
Field.The potential application that silk is combined with inorganic nanoparticles has been subjected to by silk as a kind of natural large biological molecule
The concern of people.But the limitation of the method preparation fluorescent natural silk combined using nano particle is the nanometer that silk surface bonds
Granule stability is bad, and washability is poor.
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.
At present by UCNPs and the compound document report of fibroin albumen, Zhao is with NaYF4:Exemplified by Yb, Er, by fibroin
Albumen is as flexible base material and Na YF4:Yb, Er are compound to be prepared for up-conversion fluorescence laminated film（Up-conversion fluorescence fibroin
The preparation of film and its performance study [D] University Of Suzhou, 2016；Physical Chemistry Chemical Physics,
2016, 18, 15289）.Song by UCNPs with fibroin is compound is prepared for fibroin support（Advanced Functional
Materials, 2017, 27(26): 1700628）.But do not see also arrange UCNPs to the report on silk fiber at present
Road.
The content of the invention
In view of the above problems, the present invention provides a kind of up-conversion fluorescence silk of graphene oxide cladding.
The technical scheme is that：（1）Hyperbranched Polymer with Terminal Amido is modified into NaYF4:Yb,
Er/Tm and Hyperbranched Polymer with Terminal Hydroxyl modification NaYF4:Yb, Er/Tm are configured to the 0.1-5g/L aqueous solution respectively, then will
Silk fabric 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, rinsed, dried repeatedly with deionized water after taking-up；Then above-mentioned silk fabric is immersed in 80 DEG C of amine-terminated hyperbrancedization
Polymer-modified NaYF4:10-60min in Yb, the Er/Tm aqueous solution, bath raio 1:10, rinsed, dried repeatedly with deionized water after taking-up
It is dry, so far by one layer of NaYF4:Yb, Er/Tm arrange the surface to silk fabric, then polymerize successively in superbrnaching end-hydroxy
Thing modifies NaYF4:Yb, Er/Tm and Hyperbranched Polymer with Terminal Amido modification NaYF4:Above-mentioned behaviour is repeated in Yb, Er/Tm dressing liquid
Make, determine silk fabric surface NaYF as needed4:The number of plies that Yb, Er/Tm are arranged；（2）Above-mentioned silk fabric is immersed in 80
DEG C, 10-60min in 1-10g/L graphene oxide water solution, bath raio 1:50, reaction is anti-with ethanol and deionized water after terminating
After backwashing washs, the up-conversion fluorescence silk of graphene oxide cladding is obtained after drying.
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：Modified using electronegative Hyperbranched Polymer with Terminal Hydroxyl
NaYF4:Yb, Er/Tm, graphene oxide and positively charged Hyperbranched Polymer with Terminal Amido modification NaYF4:Between Yb, Er/Tm
Silk fabric is immersed in Hyperbranched Polymer with Terminal Hydroxyl modification NaYF by electrostatic interaction successively as film forming motive force4:Yb,Er/
The Tm aqueous solution and Hyperbranched Polymer with Terminal Amido modification NaYF4:In Yb, the Er/Tm aqueous solution, silk fabric is determined as needed
Surface NaYF4:Graphene oxide bag is prepared in the number of plies that Yb, Er/Tm are arranged, final impregnating in graphene oxide water solution
The up-conversion fluorescence silk covered.NaYF4:Silk fabric table is attached to by the combination of negative ions key between Yb, Er/Tm
Face, avoid using harmful chemical cross-linking agent, reduce the influence to silk fabric strength.Modified silk fabric has
Excellent up-conversion fluorescence performance and good washable, wearability.
Embodiment
The invention will be further elucidated with reference to specific embodiments.
Embodiment 1
（1）Hyperbranched Polymer with Terminal Amido is modified into NaYF4:Yb, Er/Tm and Hyperbranched Polymer with Terminal Hydroxyl modification NaYF4:
Yb, Er/Tm are configured to the 0.1g/L aqueous solution respectively, and silk fabric is then immersed in 80 DEG C of Hyperbranched Polymer with Terminal Hydroxyl
Modify NaYF4:10min in Yb, the Er/Tm aqueous solution, bath raio 1:10, rinsed, dried repeatedly with deionized water after taking-up；Then will
Above-mentioned silk fabric is immersed in 80 DEG C of Hyperbranched Polymer with Terminal Amido modification NaYF4:10min in Yb, the Er/Tm aqueous solution, bath
Than 1:10, rinsed, dried repeatedly with deionized water after taking-up；（2）Above-mentioned silk fabric is immersed in 80 DEG C, 1g/L oxidation stone
10min in black aqueous solution, bath raio 1:50, reaction is washed, aoxidized after drying repeatedly after terminating with ethanol and deionized water
The up-conversion fluorescence silk of graphene coated.
Embodiment 2
（1）Hyperbranched Polymer with Terminal Amido is modified into NaYF4:Yb, Er/Tm and Hyperbranched Polymer with Terminal Hydroxyl modification NaYF4:
Yb, Er/Tm are configured to the 1g/L aqueous solution respectively, and silk fabric is then immersed in 80 DEG C of Hyperbranched Polymer with Terminal Hydroxyl and repaiied
Adorn NaYF4:30min in Yb, the Er/Tm aqueous solution, bath raio 1:10, rinsed, dried repeatedly with deionized water after taking-up；Then will be upper
State the Hyperbranched Polymer with Terminal Amido modification NaYF that silk fabric is immersed in 80 DEG C4:30min in Yb, 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 arranged and are arrived silk fabric
Surface, then modify NaYF in Hyperbranched Polymer with Terminal Hydroxyl successively4:Yb, Er/Tm and Hyperbranched Polymer with Terminal Amido modification
NaYF4:Aforesaid operations are repeated twice in Yb, Er/Tm dressing liquid；（2）Above-mentioned silk fabric is immersed in 80 DEG C, 5g/L oxidation
30min in graphene aqueous solution, bath raio 1:50, reaction is washed, obtains oxygen after drying repeatedly after terminating with ethanol and deionized water
The up-conversion fluorescence silk of graphite alkene cladding.
Embodiment 3
（1）Hyperbranched Polymer with Terminal Amido is modified into NaYF4:Yb, Er/Tm and Hyperbranched Polymer with Terminal Hydroxyl modification NaYF4:
Yb, Er/Tm are configured to the 5g/L aqueous solution respectively, and silk fabric is then immersed in 80 DEG C of Hyperbranched Polymer with Terminal Hydroxyl and repaiied
Adorn NaYF4:60min in Yb, the Er/Tm aqueous solution, bath raio 1:10, rinsed, dried repeatedly with deionized water after taking-up；Then will be upper
State the Hyperbranched Polymer with Terminal Amido modification NaYF that silk fabric is immersed in 80 DEG C4:60min in Yb, 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 arranged and are arrived silk fabric
Surface, then modify NaYF in Hyperbranched Polymer with Terminal Hydroxyl successively4:Yb, Er/Tm and Hyperbranched Polymer with Terminal Amido modification
NaYF4:Aforesaid operations are repeated eight times in Yb, Er/Tm dressing liquid；（2）Above-mentioned silk fabric is immersed in 80 DEG C, 10g/L oxygen
60min in graphite aqueous solution, bath raio 1:50, reaction is washed, obtained after drying repeatedly after terminating with ethanol and deionized water
The up-conversion fluorescence silk of graphene oxide cladding.
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 (2)
- A kind of 1. preparation method of the up-conversion fluorescence silk of graphene oxide cladding, it is characterised in that：Step 1：Hyperbranched Polymer with Terminal Amido is modified into NaYF4:Yb, Er/Tm and Hyperbranched Polymer with Terminal Hydroxyl modification NaYF4:Yb, Er/Tm are configured to the 0.1-5g/L aqueous solution respectively, and silk fabric is then immersed in 80 DEG C of terminal hydroxy group and overspend Fluidized polymer modifies NaYF4:10-60min in Yb, the Er/Tm aqueous solution, bath raio 1:10, rinsed repeatedly with deionized water after taking-up, Drying；Then the Hyperbranched Polymer with Terminal Amido for above-mentioned silk fabric being immersed in 80 DEG C modifies NaYF4:Yb, the Er/Tm aqueous solution Middle 10-60min, bath raio 1:10, rinsed, dried, so far by one layer of NaYF repeatedly with deionized water after taking-up4:Yb,Er/Tm The surface of silk fabric is arranged, then modifies NaYF in Hyperbranched Polymer with Terminal Hydroxyl successively4:Yb, Er/Tm and Amino End Group surpass Branched polymer modifies NaYF4:Aforesaid operations are repeated in Yb, Er/Tm dressing liquid, determine silk fabric surface as needed NaYF4:The number of plies that Yb, Er/Tm are arranged；Step 2：Above-mentioned silk fabric is immersed in 80 DEG C, 10-60min in 1-10g/L graphene oxide water solution, bath raio 1:50, reaction is washed, the up-conversion fluorescence of graphene oxide cladding is obtained after drying repeatedly after terminating with ethanol and deionized water Silk.
- 2. the up-conversion fluorescence silk that a kind of graphene oxide obtained by claim 1 preparation method coats.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020259490A1 (en) * | 2019-06-26 | 2020-12-30 | 浙江大学 | Preparation method for mulberry silk that fluoresces under near-infrared light and product |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102352251A (en) * | 2011-07-29 | 2012-02-15 | 黑龙江大学 | Graphene/rare earth fluoride nanoscale composite material and intercalation stripping synthesis method thereof |
| CN102919263A (en) * | 2012-11-05 | 2013-02-13 | 江苏大学 | Nanometer composite material and preparation method and application thereof |
| CN104371714A (en) * | 2014-11-28 | 2015-02-25 | 赵兵 | Molybdenum trioxide-graphene oxide composite material and preparation method thereof |
-
2017
- 2017-09-17 CN CN201710836629.3A patent/CN107558187A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102352251A (en) * | 2011-07-29 | 2012-02-15 | 黑龙江大学 | Graphene/rare earth fluoride nanoscale composite material and intercalation stripping synthesis method thereof |
| CN102919263A (en) * | 2012-11-05 | 2013-02-13 | 江苏大学 | Nanometer composite material and preparation method and application thereof |
| CN104371714A (en) * | 2014-11-28 | 2015-02-25 | 赵兵 | Molybdenum trioxide-graphene oxide composite material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 沈青著: "《分子酸碱化学》", 31 March 2012, 上海科学技术文献出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020259490A1 (en) * | 2019-06-26 | 2020-12-30 | 浙江大学 | Preparation method for mulberry silk that fluoresces under near-infrared light and product |
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