CN106701065A - Plant micro-nano cellulose fluorescence labeling method - Google Patents
Plant micro-nano cellulose fluorescence labeling method Download PDFInfo
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- CN106701065A CN106701065A CN201710004230.9A CN201710004230A CN106701065A CN 106701065 A CN106701065 A CN 106701065A CN 201710004230 A CN201710004230 A CN 201710004230A CN 106701065 A CN106701065 A CN 106701065A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6439—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" with indicators, stains, dyes, tags, labels, marks
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Abstract
The invention discloses a plant micro-nano cellulose fluorescence labeling method which comprises the following specific steps of: (1) performing ultrasonic treatment of a suspension of plant micro-nano cellulose; (2) adding an activator to the micro-nano cellulose suspension, adjusting the pH and activating; and then dialyzing until the solution is neutral; (3) performing amination treatment, namely adding an amine solution into the activated micro-nano cellulose suspension, and stirring for reacting in a room-temperature condition, and after the reacting, dialyzing the suspension to neutrality; and (4) dissolving a fluorescent substance in an organic solvent, adding into the micro-nano cellulose suspension, adjusting the pH, and stirring for reacting for 12h in a dark condition; dialyzing the mixture suspension until no fluorescent substance is detected in the water; and performing freeze drying of the suspension. The micro-nano cellulose fluorescence labeling disclosed by the invention has the advantages of good uniformity, high fluorescence intensity, long fluorescent lifetime, high quantum yield, strong fluorescence bleaching resistance and good fluorescence stability.
Description
Technical field
The invention belongs to nano-cellulose colouring art, more particularly, to the side of plant micro-nano cellulose fluorescence labeling
Method.
Background technology
The preparation method of plant nanometer cellulose including enzyme hydrolysis, sour water solution or mechanical treatment etc., by the above method
The cellulose at least unidimensional scale that treatment wood fibre is obtained is Nano grade.The diameter of nano-cellulose within 100nm,
It is the minimum physical arrangement unit of cellulose.Nano-cellulose and plant cellulose have same excellent property, environmental protection,
Natural reproducible, biocompatibility, while also having excellent optical property and mechanical performance.At present, nano-cellulose base material
Material has been applied in all trades and professions, such as cosmetics, biological medicine, building, food, military project, papermaking, environmental protection field, there is non-
The application prospect of Chang Ju great.
The fluorescent nano-fiber element of current studies in China, is mostly that polymer is mixed from different fluorescent materials, then
Nano fluorescence fiber element is produced by the method for electrostatic spinning.Sun Liguo etc. by preparing the CdSe quantum dot of different emission peaks,
Then mix with polystyrene, ultrasonic disperse paper is uniform, obtains polymer dope.It is poly- by what is obtained finally by spinning technique
Compound spinning solution is spun into fiber；Obtain the colorful fiber of polymer fluorescent.And obtained fluorescent fiber is applied prevent in fluorescence
The aspect such as counterfeit trade-mark, paper and fluorescent decoration, fluorescent ink, clothing products.It is micro- that Long Yunze et al. has invented a kind of rare-earth fluorescent
The preparation method of nano-cellulose, first by europium oxide and watery hydrochloric acid reaction generation Europium chloride, then by Europium chloride, second phthalein salicylic acid
Lanthanide complexes are made by a certain percentage with adjacent phenol Luo Lin, then, Rare Earth Europium Complex and polystyrene are mixed, prepare
Going out precursor solution carries out electrostatic spinning, and gained fiber can be widely used for the Material Fields such as electricity, optics, chemistry.But it is domestic
The report for carrying out fluorescent staining to plant micro-nano cellulose is rarely found.
The content of the invention
The present invention solves the technical problem of a kind of fluorescent staining method of plant micro-nano cellulose of offer.Use
The material with fluorescent characteristic all of in the market, treatment is modified by plant micro-nano cellulose, makes fluorescence
Material can be marked on plant micro-nano cellulose, can be in a certain section of ultraviolet light by the plant micro-nano cellulose for marking
Color is shown under wavelength, plant micro-nano cellulose is widely applied in every profession and trade field.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：
A kind of method of plant micro-nano cellulose fluorescence labeling, comprises the following steps that：
(1) pre-treatment：The suspension of plant micro-nano cellulose is carried out ultrasonically treated；
(2) activation process：To activator is added in micro-nano cellulose suspension, pH value is then adjusted to 10-10.5, enter
Row activation process；Then it is neutrality that dialysis removes unnecessary reagent to solution；
(3) amination treatment：To amine solution is added in activation micro-nano cellulose suspension, then stirred under room temperature condition
Reaction, after completion of the reaction, suspension is dialysed to neutrality；
(4) fluorescence labeling：Fluorescent material is dissolved in organic solvent first, is subsequently adding micro-nano cellulose suspension
In, pH value is adjusted to 10-10.5, stirring reaction 12h under the conditions of dark lucifuge；Then mixture suspension is dialysed, directly
To UV spectrophotometer measuring is used less than containing fluorescent material in water, then by suspension freeze-drying.
In the step (1), the ultrasound is batch (-type) ultrasound, and treatment conditions are：Ultrasonic time 3s, off time 3s,
Power 300W, 0-4 DEG C of temperature, ultrasound total effective time 15-30min.
Activator used is epoxychloropropane in the step (2).
The condition of activation process is in the step (2)：Magnetic agitation, 3h is reacted in 60~70 DEG C of waters bath with thermostatic control.
Amine solution used is ethylenediamine in the step (3), and the reaction time is 6h.
Fluorescent material used is 2- (6- hydroxyl -3- oxo -3H- xanthene -9- bases) benzoic acid in the step (4), is swashed
Hair wavelength X=490nm.
Organic solvent used is the mixed liquor of DMF (DMF) and acetone in the step (4), both
Volume ratio is 3:1.
The amount of the activator is 5-10ml/g celluloses；The amount of the amine solution is 8-10ml/g celluloses；It is described
The amount of fluorescent material >=0.01g/g celluloses.
Compared with prior art, the invention has the advantages that：
Micro-nano cellulose fluorescence labeling homogeneity of the present invention is good, and fluorescence intensity is high, and fluorescence lifetime is long, and quantum yield is high,
Fluorescence bleach-resistant ability is strong, and fluorescent stability is good.
Brief description of the drawings
Fig. 1 is the fluorescence spectra of NCC in embodiment 1.
Fig. 2 is the fluorescence spectra of NFC in embodiment 2.
Specific embodiment
With reference to embodiments, the present invention will be described in further detail.So that advantages and features of the invention can be more
It is easy to be readily appreciated by one skilled in the art, apparent is clearly defined so as to be made to protection scope of the present invention.Should manage
Solution, specific embodiment described herein is only used to explain the present invention, is not intended to limit the present invention.
Embodiment 1
The NCC of oven-dry weight 1g is weighed first, then to the NCC ultrasonically treated 30min of suspension batch (-type), ultrasonically treated condition
It is ultrasonic time 3s, off time 3s, power 300W, 0-4 DEG C of temperature.Addition 10ml epoxies in backward NCC suspension are processed
Chloropropane, is subsequently adding 5% NaOH solution 20ml, and regulation pH value is stirring reaction 3h in 10,60 DEG C of waters bath with thermostatic control.Then it is saturating
It is neutrality that analysis removes unnecessary reagent to solution, until spectrophotometer contains reagent in can't detect water, pH value is 7.Then
To adding 10ml ethylenediamines, then stirring reaction 6h under room temperature condition in activation NCC suspension.After completion of the reaction, by suspension
Dialyse to neutrality.2- (6- hydroxyl -3- oxo -3H- xanthene -9- bases) benzoic acid of 0.01g is dissolved in 10ml DMF and acetone
(volume ratio of DMF and acetone is 3 in mixed liquor:1), it is subsequently adding in NCC suspension, stirring reaction under the conditions of dark lucifuge
12h.Then mixture suspension is dialysed, until with UV spectrophotometer measuring less than being containing fluorescent material in water
Only, then by suspension freeze-drying.The NCC fluorescence intensities marked using the method can be seen that by the fluorescence spectra of Fig. 1
Height, after it is placed into one week indoors, still with stronger fluorescence intensity, illustrates that the NCC fluorescent stabilities of the method mark are good,
Anti-light bleaching power is strong.
Embodiment 2
The NFC (or being MFC) of oven-dry weight 1g is weighed first, and it is ultrasonically treated then to carry out batch (-type) to NFC suspension
30min, ultrasonically treated condition is ultrasonic time 3s, off time 3s, power 300W, 0-4 DEG C of temperature.Backward NFC has been processed to hang
8ml epoxychloropropane is added in supernatant liquid, 5% NaOH solution 20ml is subsequently adding, regulation pH value is 10.5,60 DEG C of waters bath with thermostatic control
Middle stirring reaction 3h.Then it is neutrality that dialysis removes unnecessary reagent to solution, until spectrophotometer contains in can't detect water
There is reagent, pH value is 7.Then to adding 8ml ethylenediamine solutions, then stirring reaction under room temperature condition in activation NFC suspension
6h.After completion of the reaction, suspension is dialysed to neutrality.By 2- (6- hydroxyl -3- oxo -3H- xanthene -9- bases) benzene first of 0.01g
(volume ratio of DMF and acetone is 3 during acid is dissolved in 10ml DMF and acetone mixture:1), it is subsequently adding in NFC suspension, it is black
Stirring reaction 12h under the conditions of dark lucifuge.Then mixture suspension is dialysed, until with UV spectrophotometer measuring not
To in water containing fluorescent material, then by suspension freeze-drying.
Claims (8)
1. a kind of method of plant micro-nano cellulose fluorescence labeling, it is characterised in that comprise the following steps that：
(1) pre-treatment：The suspension of plant micro-nano cellulose is carried out ultrasonically treated；
(2) activation process：To activator is added in micro-nano cellulose suspension, pH value is then adjusted to 10-10.5, lived
Change is processed；Then it is neutrality that dialysis removes unnecessary reagent to solution；
(3) amination treatment：To amine solution is added in activation micro-nano cellulose suspension, then stir anti-under room temperature condition
Should, after completion of the reaction, suspension is dialysed to neutrality；
(4) fluorescence labeling：Fluorescent material is dissolved in organic solvent first, is subsequently adding in micro-nano cellulose suspension,
PH value is adjusted to 10-10.5, stirring reaction 12h under the conditions of lucifuge；Then mixture suspension is dialysed, until detection is not
To in water containing fluorescent material, then by suspension freeze-drying.
2. method according to claim 1, it is characterised in that in the step (1), the ultrasound is batch (-type) ultrasound,
Treatment conditions are：Ultrasonic time 3s, off time 3s, power 300W, 0-4 DEG C of temperature, ultrasound total effective time 15-
30min。
3. method according to claim 1, it is characterised in that activator used is epoxy chloropropionate in the step (2)
Alkane.
4. method according to claim 1, it is characterised in that the condition of activation process is in the step (2)：Magnetic force is stirred
Mix, 3h is reacted in 60~70 DEG C of waters bath with thermostatic control.
5. method according to claim 1, it is characterised in that amine solution used is ethylenediamine in the step (3),
Reaction time is 6h.
6. method according to claim 1, it is characterised in that fluorescent material used is 2- (6- hydroxyls in the step (4)
Base -3- oxo -3H- xanthene -9- bases) benzoic acid, excitation wavelength lambda=490nm.
7. method according to claim 1, it is characterised in that organic solvent used is N, N- bis- in the step (4)
The mixed liquor of NMF and acetone, both volume ratios are 3:1.
8. method according to claim 1, it is characterised in that the amount of the activator is 5-10ml/g celluloses；It is described
The amount of amine solution is 8-10ml/g celluloses；The amount of the fluorescent material >=0.01g/g celluloses.
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| CN201710004230.9A CN106701065A (en) | 2017-01-04 | 2017-01-04 | Plant micro-nano cellulose fluorescence labeling method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108517712A (en) * | 2018-03-12 | 2018-09-11 | 华南理工大学 | A kind of paper grade (stock) micro nanometer fiber mill base and the preparation method and application thereof |
| CN108642860A (en) * | 2018-04-26 | 2018-10-12 | 深圳市裕同包装科技股份有限公司 | A kind of environment-friendly biomass base rare earth down-conversion fluorescent fiber and preparation method |
| WO2019010897A1 (en) * | 2017-07-14 | 2019-01-17 | 华南理工大学 | Dynamic characterization method for micro-nano celluloses |
| CN110106736A (en) * | 2019-04-18 | 2019-08-09 | 华南理工大学 | A kind of environmental type anti-counterfeiting paper and preparation method thereof |
| CN111116760A (en) * | 2018-10-31 | 2020-05-08 | 航天特种材料及工艺技术研究所 | Fluorescent nano-cellulose and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019010897A1 (en) * | 2017-07-14 | 2019-01-17 | 华南理工大学 | Dynamic characterization method for micro-nano celluloses |
| CN108517712A (en) * | 2018-03-12 | 2018-09-11 | 华南理工大学 | A kind of paper grade (stock) micro nanometer fiber mill base and the preparation method and application thereof |
| CN108642860A (en) * | 2018-04-26 | 2018-10-12 | 深圳市裕同包装科技股份有限公司 | A kind of environment-friendly biomass base rare earth down-conversion fluorescent fiber and preparation method |
| CN108642860B (en) * | 2018-04-26 | 2021-08-27 | 深圳市裕同包装科技股份有限公司 | Environment-friendly biomass-based rare earth down-conversion fluorescent fiber and preparation method thereof |
| CN111116760A (en) * | 2018-10-31 | 2020-05-08 | 航天特种材料及工艺技术研究所 | Fluorescent nano-cellulose and preparation method thereof |
| CN110106736A (en) * | 2019-04-18 | 2019-08-09 | 华南理工大学 | A kind of environmental type anti-counterfeiting paper and preparation method thereof |
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Application publication date: 20170524 |