CN104237187A - Water-sensitive fluorescence enhanced test paper as well as preparation method and application thereof - Google Patents

Water-sensitive fluorescence enhanced test paper as well as preparation method and application thereof Download PDF

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CN104237187A
CN104237187A CN201410478909.8A CN201410478909A CN104237187A CN 104237187 A CN104237187 A CN 104237187A CN 201410478909 A CN201410478909 A CN 201410478909A CN 104237187 A CN104237187 A CN 104237187A
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water
test paper
sensitive fluorescence
carbon nano
increasing test
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CN104237187B (en
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曲松楠
娄庆
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Changchun Institute of Optics Fine Mechanics and Physics of CAS
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Changchun Institute of Optics Fine Mechanics and Physics of CAS
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Abstract

The invention discloses water-sensitive fluorescence enhanced test paper as well as a preparation method and an application thereof, and belongs to the field of the application of a fluorescent carbon nanomaterial. The application of carbon dots is further broadened. The fluorescence enhanced test paper is composited by nano particles and paper, wherein the nano particles are formed by gathering amphiphilic carbon dots dissolved in a non-polar solvent, and the amphiphilic carbon dots have hydrophilic groups and lipophilic groups on the surfaces. The water-sensitive fluorescence enhanced test paper is used for jetting fluorescent printing, so that ink-free jet printing can be realized; the water-sensitive fluorescence enhanced test paper is used for sweat pore fluorescent imaging, so that the sweat pore perspiration function can be monitored; the water-sensitive fluorescence enhanced test paper can further be used for detecting humidity, thus, the application of the carbon dots is further broadened; and besides, the water-sensitive fluorescence enhanced test paper has higher photobleaching resistance, is low in manufacturing cost, and can be widely applied to industrial production.

Description

Water-sensitive Fluorescence Increasing test paper and preparation method thereof and application
Technical field
The present invention relates to fluorescent carbon applications to nanostructures field, be specifically related to a kind of water-sensitive Fluorescence Increasing test paper and preparation method thereof and application.
Background technology
Carbon nano dot (Carbon dots, CDs) be a kind of carbon nanomaterial that can be luminous, compare with organic-fuel with semiconductor-quantum-point, have that molecular weight is low, particle diameter is little, fluorescent stability is high, without optical flare, exciting light spectrum width and continuously, emission wavelength is tunable, good biocompatibility, low toxin, have broad application prospects in fields such as biomolecular labeling, living imaging, sensing, photoelectricity.
Water spray printing is a kind of environmental protection printing technique, and it utilizes water for marking ink, clearly can print information needed, thus avoids because lacking fluorescent ink, changing the next a series of economy of fluorescent ink tape and environmental issue.In prior art, the paper that water spray fluorescent printing adopts is the compound of printer paper, polyglycol and water-sensitive Fluorescence Increasing organic dyestuff, there is processing technology complexity, the defects such as unstable properties.
Pore imaging can be used as third generation fingerprint identification technology, and it can utilize 20-40 pore position just can confirm to differentiate individual fingerprint, can greatly simplify calculated amount needed for fingerprint automation recognition program, improves recognition accuracy.In addition, can monitoring human amount of sweat by pore fluorescence imaging, thus monitoring and warning is carried out to individual health level.
Humidity detection general resistance or capacitance variation monitor humidity.Utilize spectral intensity variation monitoring humidity comparatively directly perceived quick.
In prior art, do not realize the technology of water spray fluorescent printing, pore fluorescence imaging or humidity detection based on carbon nano dot compound substance.
Summary of the invention
The object of the invention is to overcome above-mentioned the deficiencies in the prior art, a kind of water-sensitive Fluorescence Increasing test paper and preparation method thereof and application are provided.
Water-sensitive Fluorescence Increasing test paper of the present invention is composited by nano particle and paper; Described nano particle is dissolved in non-polar solvent to assemble by amphipathic carbon nano dot and is formed; Described amphipathic carbon nano dot surface has hydrophilic radical and lipophilic group.
Preferably, described non-polar solvent is toluene, benzene or chloroform.
Preferably, described hydrophilic radical is one or more in amino, amide group, carboxyl, sulfydryl and hydroxyl.
Preferably, described lipophilic group is one or more in alkyl, alkylene and aryl radical.
Preferably, described amphipathic carbon nano dot is by becoming lipophilic group to prepare the part hydrophilic radical functionalization on water-soluble carbon nano dot surface.
The invention provides a kind of preparation method of above-mentioned water-sensitive Fluorescence Increasing test paper, comprise the following steps:
(1) amphipathic carbon nano dot is dissolved in non-polar solvent, obtains the solution containing nano particle;
(2) paper is immersed in the solution containing nano particle, takes out dry, obtain water-sensitive Fluorescence Increasing test paper;
Or by the solution spraying containing nano particle on paper, after drying, obtain water-sensitive Fluorescence Increasing test paper.
The present invention also provides the preparation method of another kind of above-mentioned water-sensitive Fluorescence Increasing test paper, comprises the following steps:
(1) amphipathic carbon nano dot is dissolved in non-polar solvent, obtains the solution containing nano particle;
(2) dip the solution containing nano particle, paper is write pattern or figure, after drying, obtain water-sensitive Fluorescence Increasing test paper.
Water-sensitive Fluorescence Increasing test paper of the present invention can be used in fluorescent printing of spraying water.
Water-sensitive Fluorescence Increasing test paper of the present invention can be used in pore fluorescence imaging.
Water-sensitive Fluorescence Increasing test paper of the present invention can be used in humidity detection.
Compared with prior art, beneficial effect of the present invention:
Water-sensitive Fluorescence Increasing test paper of the present invention, for fluorescent printing of spraying water, can realize unstressed configuration ink water spray fluorescent printing, print gained clear picture; For pore fluorescence imaging, can realize monitoring pore perspiration functions; Can also Humidity Detection be used for, expand the application of carbon nano dot further; Water-sensitive Fluorescence Increasing test paper of the present invention has stronger resistance to photobleaching Properties, cheap, can be widely used in commercial production.
Accompanying drawing explanation
In Fig. 1, a amphipathic carbon nano dot that () is embodiment under solar radiation 2 is dissolved in the photo in toluene, b amphipathic carbon nano dot that () is embodiment under solar radiation 2 is dissolved in the photo in water, c amphipathic carbon nano dot that () is embodiment under UV-irradiation 2 is dissolved in the photo in toluene, and the amphipathic carbon nano dot that (d) is embodiment under UV-irradiation 2 is dissolved in the photo in water;
Fig. 2 is the water-soluble carbon nano dot of the embodiment of the present invention 1 and the hydrogen nuclear magnetic resonance spectrogram of amphipathic carbon nano dot;
In Fig. 3, the toluene solution of a amphipathic carbon nano dot that () is embodiment 1 drips and is coated in field emission scanning electron microscope photo before treatment that silicon chip sprays, and the toluene solution of the amphipathic carbon nano dot that (b) is embodiment 1 drips the field emission scanning electron microscope photo be coated on silicon chip after spraying process;
Fig. 4 is the structural representation of amphipathic carbon nano dot of the present invention, wherein represent hydrophilic radical, represent lipophilic group;
In Fig. 5, (a) is under ultra violet lamp, the fluorescence photo of water-sensitive Fluorescence Increasing test paper before spraying of embodiment 5; B () is under ultra violet lamp, the water-sensitive Fluorescence Increasing test paper fluorescence photo after spraying of embodiment 5;
Fig. 6 is under ultra violet lamp, the fluorescence spectrum of water-sensitive Fluorescence Increasing test paper before spraying of embodiment 5 and the fluorescence spectrum after spraying;
In Fig. 7, (a) is under ultra violet lamp, the fluorescence photo of letter C before spraying of embodiment 6; B () is under ultra violet lamp, the letter C fluorescence photo after spraying of embodiment 6;
Fig. 8 is the water spray fluorescent printing photo of the embodiment of the present invention 9 water-sensitive Fluorescence Increasing test paper under UV-irradiation;
Fig. 9 is the water spray fluorescent printing photo of the embodiment of the present invention 9 water-sensitive Fluorescence Increasing test paper under UV-irradiation;
In Figure 10, (a) is the fingerprint picture of embodiment 10 under UV-irradiation on water-sensitive Fluorescence Increasing test paper, and (b) is the digital photograph of the fingerprint through image software process superposition;
Figure 11 is the fluorescence photo of water-sensitive Fluorescence Increasing test paper under different spray time that the fluorescence pattern of embodiment 11 is fixed;
Figure 12 is in embodiment 12, and after the different irradiation time of 500W mercury xenon lamp, the water-sensitive fluorescence pattern (left side) of water-sensitive Fluorescence Increasing test paper and commercial e-Pointer write identical fluorescence pattern (right side) fluorescence photo under ultraviolet light.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiments of the invention are described, but should be appreciated that these describe just to further illustrate the features and advantages of the present invention instead of limiting to the claimed invention.
Water-sensitive Fluorescence Increasing test paper of the present invention is composited by nano particle and paper; Wherein, nano particle is dissolved in non-polar solvent to assemble by amphipathic carbon nano dot and is formed; Amphipathic carbon nano dot surface has hydrophilic radical and lipophilic group, and under UV-irradiation, this test paper and the contacted position of water can manifest fluorescence.
In the present invention, the preferred toluene of non-polar solvent, benzene or chloroform.
In the present invention, the hydrophilic radical of amphipathic carbon nano dot is one or more in amino, amide group, carboxyl, sulfydryl and hydroxyl; Lipophilic group is one or more in alkyl, alkylene and aryl radical, and on the surface of amphipathic carbon nano dot, lipophilic group can account for 30-80%; The carbon atom of alkyl is preferably 1-36, the carbon number of alkylene is preferably 1-36, the carbon number of aryl radical is preferably 1-36, and this amphipathic carbon nano dot can self assembly be the medicine ball aggregation of micro-or nano size in non-polar solvent, i.e. nano particle.
Amphipathic carbon nano dot in the present invention can by becoming lipophilic group to prepare the part hydrophilic radical functionalization on water-soluble carbon nano dot surface; Water-soluble carbon nano dot is prior art, as the carbon nano dot in patent CN201210312844.0.
The present invention also provides the preparation method of above-mentioned amphipathic carbon nano dot: the part hydrophilic radical functionalization on water-soluble carbon nano dot surface is become lipophilic group, generally 30-80% hydrophilic radical functionalization is become lipophilic group.
The invention provides a kind of preparation method of amphipathic carbon nano dot, but be not limited thereto:
(1) by water-soluble carbon nano dot, add in reaction unit containing substituent lipophilic cpd, catalysts and solvents, after stirring, add hot reflux, make water-soluble carbon nano dot and lipophilic cpd generation condensation reaction or substitution reaction, obtain reacting rear solution;
Wherein, water-soluble carbon nano dot and the mass ratio containing substituent lipophilic cpd are 1:(5-30), catalyzer is pressed corresponding proportion according to prior art and is added, the consumption of solvent does not limit, and can dissolve water-soluble carbon nano dot and contain substituent lipophilic cpd (catalyzer can be insoluble);
Water-soluble carbon nano dot be carbon nano dot surface containing the carbon nano dot of hydrophilic radical, in the present invention, one or more preferably in amino, amide group, carboxyl, sulfydryl, hydroxyl of hydrophilic radical;
Substituting group containing substituent lipophilic cpd is generally halogen, carboxyl, amino, hydroxyl or sulfonic group, and lipophilic cpd is generally alkyl, alkylene or aryl radical; The carbon number of alkyl is preferably 1-36, and the carbon number of alkylene is preferably 1-36, and the carbon number of aryl radical is preferably 1-36;
When the hydrophilic substituent of water-soluble carbon nano dot is one or both in amino, amide group, when the substituting group of lipophilic cpd is halogen, there is substitution reaction, solvent is dimethyl formamide or acetone, catalyzer is potassium iodide and Anhydrous potassium carbonate, generally add hot reflux 4-12h, temperature is 60-180 DEG C;
When the hydrophilic substituent of water-soluble carbon nano dot is one or both in amino, amide group, sulfydryl, hydroxyl, the substituting group of lipophilic cpd be carboxyl or sulfonic group time, there is condensation reaction, solvent is dimethyl formamide, dimethyl sulfoxide (DMSO), tetrahydrofuran or acetone, catalyzer is the concentrated sulphuric acid or highly basic (as KOH, NaOH), add hot reflux 4-24h, heating-up temperature is 60-180 DEG C;
When the hydrophilic substituent of water-soluble carbon nano dot is one or more in carboxyl, sulfydryl, hydroxyl, the substituting group of lipophilic cpd be amide group or hydroxyl time, there is condensation reaction, solvent is dimethyl formamide, dimethyl sulfoxide (DMSO), tetrahydrofuran or acetone, catalyzer is the concentrated sulphuric acid or highly basic (as KOH, NaOH), add hot reflux 4-24h, heating-up temperature is 60-180 DEG C;
(2) by reacted solution Suction filtration device suction filtration, removing inorganic salts wherein, then decompression distillation is to the whole evaporate to dryness of solvent, the solid obtained can dissolve and centrifugal acquisition sediment in non-polar organic solvent, also can by the dissolution of solid that obtains in the mixed solution of water and non-polar solvent and centrifugal acquisition sediment, sediment after drying, obtains amphipathic carbon nano dot; Wherein, non-polar organic solvent is benzene, toluene, chloroform, normal hexane etc., and mixed solution can be toluene and the deionized water mixed liquor of volume ratio 1:9.
The preparation method of the present invention's above-mentioned water-sensitive Fluorescence Increasing test paper, comprises the following steps:
(1) be dissolved in non-polar solvent by amphipathic carbon nano dot, amphipathic carbon nano dot can self assembly be the medicine ball aggregation (i.e. nano particle) of micro-or nano size in non-polar solvent, obtains the solution containing nano particle;
The preferred toluene of non-polar solvent, benzene or chloroform, amphipathic carbon nano dot concentration in non-polar solvent is not particularly limited, as long as can be dissolved in non-polar solvent, as when non-polar solvent is toluene, concentration is generally at 0.25-2.5mg/mL, and concentration is higher, and fluorescent effect is more obvious;
(2) be immersed in by paper in the solution containing nano particle, soak time, generally at more than 1min, is taken out dry, is obtained water-sensitive Fluorescence Increasing test paper;
Or, by the solution spraying containing nano particle on paper, can even application, also can spray certain pattern or shape, after drying, obtain water-sensitive Fluorescence Increasing test paper;
The present invention also provides a kind of preparation method of above-mentioned water-sensitive Fluorescence Increasing test paper, can prepare the water-sensitive Fluorescence Increasing test paper with fixing phosphor pattern, comprise the following steps:
(1) be dissolved in non-polar solvent by amphipathic carbon nano dot, amphipathic carbon nano dot can self assembly be the medicine ball aggregation (i.e. nano particle) of micro-or nano size in non-polar solvent, obtains the solution containing nano particle;
The preferred toluene of non-polar solvent, benzene or chloroform, amphipathic carbon nano dot concentration in non-polar solvent is not particularly limited, as long as can be dissolved in non-polar solvent, as when non-polar solvent is toluene, concentration is generally at 0.25-2.5mg/mL, and concentration is higher, and fluorescent effect is more obvious;
(2) dip the solution containing nano particle, paper is write pattern or figure, after drying, obtain water-sensitive Fluorescence Increasing test paper, the process of dipping can select pen.
In above-mentioned preparation method, paper does not have particular/special requirement, generally adopts filter paper, and can be cut into any shape as required, drying means generally adopts air-dry.
Water-sensitive Fluorescence Increasing test paper of the present invention can be used in spray water fluorescent printing, pore fluorescence imaging and humidity detection.For spray water fluorescent printing time, water is loaded in blank ink jet print cartridge, and computer is connected with printer, replace black liquid to print with water (generally adopting deionized water), after printing, under the irradiation of ultraviolet light, the writing of printing can be found out; During for pore fluorescence imaging, directly press water-sensitive Fluorescence Increasing test paper with finger, under ultraviolet lighting, by fluorescent microscope, distribution shape and the perspiring state figure of finger sweat discharging hole can be seen; During for humidity detection, water-sensitive Fluorescence Increasing test paper is put into testing environment, distinguishes for convenience, general employing has the water-sensitive Fluorescence Increasing test paper of fixing word or pattern, and along with the increase of humidity, under ultraviolet light, the fluorescence of word or pattern can strengthen gradually.
Principle of the present invention is: the medicine ball aggregation that amphipathic carbon nano dot is self-assembled into fluorescent quenching in non-polar organic solvent is evenly compounded on paper.After outside moisture contacts with this extrusion coating paper, hydrone permeates this carbon nano dot medicine ball aggregation, the hydrogen bond action that hydrone destroys between carbon nano dot makes amphipathic carbon nano dot medicine ball aggregation decompose, and on carbon nano dot, hydrophilic radical makes its scattered adsorption on paper fiber.Now, amphipathic carbon nano dot is interact with each other to be weakened, Fluorescence Increasing.Finally, this water-sensitive Fluorescence Increasing test paper and water contact portion fluorescence intensity increase thus information needed are displayed.
Below in conjunction with embodiment and accompanying drawing, the present invention is set forth further.
Embodiment 1
1-4 illustrates embodiment 1 by reference to the accompanying drawings
The preparation of amphipathic fluorescent carbon nano dot:
(1) 3g citric acid (C is taken 6h 8o 7h 2o) blended in clean beaker with 6g urea (CH4N2O), add 20mL deionized water and fully stir and make it dissolve; Then be transferred in micro-wave oven, under 1000w power, heat 4min, obtain the coke shape pasty solid of black; Then beaker is placed on dry 1h in air dry oven, namely obtains water-soluble carbon nano dot;
(2) 0.6g water-soluble carbon nano dot is taken, 4g Anhydrous potassium carbonate (Tianjin recovery fine chemistry industry research institute), 0.4g potassium iodide (Tianjin Fengchuan Chemical Reagent Science & Technology Co., Ltd.), 60mLN, dinethylformamide (Xilong Chemical Co., Ltd), 2.4mL bromododecane (Tianjin recovery fine chemistry industry research institute) is blended in 250mL conical flask, at 180 DEG C, add hot reflux 12h under 4cm cylinder stirrer 600 rpms of stirring conditions; Reaction terminate after, by reacted solution Suction filtration device suction filtration twice, then under 150 DEG C of conditions decompression distillation to the whole evaporate to dryness of solvent; Solid will be obtained and add 20mL toluene dissolving (oleophylic carbon nano dot is dissolved in toluene), add 20mL deionized water vigorous stirring 10min again, by toluene and water mixing carbon nanodot solution 8000 turns of every min centrifugal, obtain required amphipathic carbon nano dot;
In Fig. 1, a amphipathic carbon nano dot that () is embodiment under solar radiation 1 is dissolved in the photo in toluene, b amphipathic carbon nano dot that () is embodiment under solar radiation 1 is dissolved in the photo in water, c amphipathic carbon nano dot that () is embodiment under UV-irradiation 1 is dissolved in the photo in toluene, and the amphipathic carbon nano dot that (d) is embodiment under UV-irradiation 1 is dissolved in the photo in water; As can be seen from Figure 1, amphipathic carbon nano dot all presents clear solution state in toluene and water, and under ultraviolet irradiation, the luminescence of amphipathic carbon aqueous nanodot solutions is stronger.
Fig. 2 is the water-soluble carbon nano dot of the embodiment of the present invention 1 and the hydrogen nuclear magnetic resonance spectrogram of amphipathic carbon nano dot; As can be seen from Figure 2, amphipathic carbon nano dot has alkyl chain groups and amino group, and show that it not only contains hydrophilic radical but also contain hydrophobic grouping, structure as shown in Figure 4.
In Fig. 3, the toluene solution of a amphipathic carbon nano dot that () is embodiment 1 drips and is coated in field emission scanning electron microscope photo before treatment that silicon chip sprays, and the toluene solution of the amphipathic carbon nano dot that (b) is embodiment 1 drips the field emission scanning electron microscope photo be coated on silicon chip after spraying process; As can be seen from Figure 3, amphipathic carbon nano dot is gathered into the medicine ball particle of 200-400 nanosized at toluene solution, and after water spray, amphipathic carbon nano dot scatter gradually.
Embodiment 2
The hydrophilic radical of amphipathic carbon nano dot is carboxyl and/or hydroxyl, and lipophilic group is propenyl;
The preparation method of above-mentioned amphipathic carbon nano dot:
Take 0.6g water-soluble carbon nano dot, 60mLN, dinethylformamide (Xilong Chemical Co., Ltd), 1.4mL allylamine (Tianjin recovery fine chemistry industry research institute) is blended in 250mL conical flask, add concentrated sulphuric acid 2mL, heating reflux reaction 8h; Reaction terminate after, by reacted solution Suction filtration device suction filtration twice, then under 150 DEG C of conditions decompression distillation to the whole evaporate to dryness of solvent; Reaction product is added in 20mL normal hexane and dissolve (lipophilicity carbon nano dot and amphipathic carbon nano dot are dissolved in normal hexane); To the hexane solution high speed centrifugation of carbon nano dot be dissolved with, obtain required amphipathic carbon nano dot.
Embodiment 3
The hydrophilic radical of amphipathic carbon nano dot is one or more in amino, amide group, carboxyl, and lipophilic group is dodecyl;
The preparation method of above-mentioned amphipathic carbon nano dot:
Take 0.6g water-soluble carbon nano dot, 60mL acetone (Beijing Chemical Plant), the 1mL concentrated sulphuric acid, 2.1mL lauryl alcohol (Tianjin recovery fine chemistry industry research institute) is blended in 250mL conical flask, at 80 DEG C of reaction 24h; Reaction terminate after, by reacted solution Suction filtration device suction filtration twice, then under 80 DEG C of conditions decompression distillation to the whole evaporate to dryness of solvent; The solid obtained is added in 20mL normal hexane and dissolve (lipophilicity carbon nano dot and amphipathic carbon nano dot are dissolved in normal hexane); To the hexane solution high speed centrifugation of carbon nano dot be dissolved with, obtain required amphipathic carbon nano dot.
Embodiment 4
The hydrophilic radical of amphipathic carbon nano dot is one or more in amino, amide group, sulfydryl, hydroxyl, and lipophilic group is dodecyl benzene;
The preparation method of above-mentioned amphipathic carbon nano dot:
Take 0.6g water-soluble carbon nano dot, 60mL tetrahydrofuran (Beijing Chemical Plant), the 1mL concentrated sulphuric acid, 2.5mL dodecylbenzene sulfonic acid (Tianjin recovery fine chemistry industry research institute) is blended in 250mL conical flask, at 120 DEG C of reaction 9h; To react afterwards solution Suction filtration device suction filtration twice after reaction terminates, then under 80 DEG C of conditions decompression distillation to the whole evaporate to dryness of solvent; The solid obtained is added in 20mL normal hexane and dissolve (lipophilicity carbon nano dot and amphipathic carbon nano dot are dissolved in normal hexane); To the hexane solution high speed centrifugation of carbon nano dot be dissolved with, obtain required amphipathic carbon nano dot.
Embodiment 5
5 and 6 embodiment 5 is described by reference to the accompanying drawings
The preparation of water-sensitive Fluorescence Increasing test paper:
(1) be dissolved in toluene by amphipathic for embodiment 1 carbon nano dot, the concentration of amphipathic carbon nano dot in toluene is 2.5mg/mL, and the self assembly in toluene of amphipathic carbon nano dot is nano particle, obtains the toluene solution containing nano particle;
(2) filter paper (production of Hangzhou Wo Hua filter paper company limited) is cut into A4 specification, and is soaked in the toluene solution 1min containing nano particle, then, dry 30min in drying box, obtains water-sensitive Fluorescence Increasing test paper.
(3) quick Fluorescence Increasing test paper spraying plant of fetching water carries out spraying process.
In Fig. 5, (a) is under ultra violet lamp, the fluorescence photo of water-sensitive Fluorescence Increasing test paper before spraying of embodiment 5; B () is under ultra violet lamp, the water-sensitive Fluorescence Increasing test paper fluorescence photo after spraying of embodiment 5; As can be seen from Figure 5, before spraying, fluorescence is very weak; After spraying, fluorescence significantly strengthens.
Fig. 6 is under ultra violet lamp, the fluorescence spectrum of the water-sensitive Fluorescence Increasing test paper of embodiment 5 before spraying and after spraying; Can find out, after spraying, fluorescence intensity increases obviously.
Embodiment 6
7 embodiment 6 is described by reference to the accompanying drawings
The preparation method of the water-sensitive Fluorescence Increasing test paper that fluorescence pattern is fixed:
(1) be dissolved in toluene by amphipathic carbon nano dot, the concentration of amphipathic carbon nano dot in toluene is 2.5mg/mL, and the self assembly in toluene of amphipathic carbon nano dot is nano particle, obtains the toluene solution containing nano particle;
(2) use pen picks the toluene solution containing nano particle, submits a written statement to a higher authority write out letter C at filter paper, can obtain the water-sensitive Fluorescence Increasing test paper that fluorescence pattern is fixing;
(3) the water-sensitive Fluorescence Increasing test paper spraying plant that this fluorescence pattern is fixing is carried out spraying process.
In Fig. 7, (a) is under ultra violet lamp, the fluorescence photo of letter C before spraying of embodiment 6; B () is under ultra violet lamp, the letter C fluorescence photo after spraying of embodiment 6; Can find out, before spraying, letter C does not manifest; After spraying, letter C is clear to be manifested.
Embodiment 7
The preparation of water-sensitive Fluorescence Increasing test paper:
(1) be dissolved in benzene by amphipathic for embodiment 3 carbon nano dot, the concentration of amphipathic carbon nano dot in benzene is 1.5mg/mL, and the self assembly in benzene of amphipathic carbon nano dot is nano particle, obtains the benzole soln containing nano particle;
(2) filter paper (production of Hangzhou Wo Hua filter paper company limited) is cut into A4 specification, and is soaked in the benzole soln 1min containing nano particle, then, dry 30min in drying box, obtains water-sensitive Fluorescence Increasing test paper.
Embodiment 8
The preparation of water-sensitive Fluorescence Increasing test paper:
(1) be dissolved in benzene by amphipathic for embodiment 4 carbon nano dot, the concentration of amphipathic carbon nano dot in benzene is 1.5mg/mL, and the self assembly in benzene of amphipathic carbon nano dot is nano particle, obtains the benzole soln containing nano particle;
(2) filter paper (production of Hangzhou Wo Hua filter paper company limited) is cut into A4 specification, and is soaked in the benzole soln 1min containing nano particle, then, dry 30min in drying box, obtains water-sensitive Fluorescence Increasing test paper.
Embodiment 9
Composition graphs 8 and 9 illustrates embodiment 9
Water-sensitive Fluorescence Increasing test paper can be used in fluorescent printing of spraying water:
(1) deionized water is injected the printer ink cartridge of ethanol purge as ink;
(2) water spray fluorescent printing machine put into by water-sensitive Fluorescence Increasing test paper embodiment 5 prepared, and carries out water spray fluorescent printing, after printing, under ultraviolet light, namely shows the fluoroscopic image of printing, as shown in Figure 8 and Figure 9.
Embodiment 10
In conjunction with Figure 10, embodiment 10 is described
Water-sensitive Fluorescence Increasing test paper can be used in pore fluorescence imaging:
By finger print by being pressed on water-sensitive Fluorescence Increasing test paper prepared by embodiment 5, under fluorescent microscope, the distribution shape figure pointing sweat discharging hole can be obtained, as shown in (a) in Figure 10.
In Figure 10, the image of this finger print that (b) obtains for high-definition digital camera, can find out, both can coincide preferably, illustrates that the present invention may be used for pore fluorescence imaging, is further used for monitoring perspiring state.
Embodiment 11
In conjunction with Figure 11, embodiment 11 is described
The water-sensitive Fluorescence Increasing test paper that fluorescence pattern is fixed can be used in monitoring humidity:
The water-sensitive Fluorescence Increasing test paper that the fluorescence pattern of Example 6 is fixing, utilizes sprayer, promotes the humidity of the water-sensitive Fluorescence Increasing examination that this fluorescence pattern is fixed by increasing spray time; Can find out, under ultra violet lamp, along with spray time extends, humidity increases, and on test paper, the fluorescence intensity of fluorescence pattern strengthens, and as shown in figure 11, can find out, water-sensitive Fluorescence Increasing test paper of the present invention can be used in monitoring humidity.
Embodiment 12
In conjunction with Figure 12, embodiment 12 is described
The water-sensitive Fluorescence Increasing test paper that fluorescence pattern is fixed has resistance to photobleaching Properties:
The water-sensitive Fluorescence Increasing test paper that the fluorescence pattern of Example 6 is fixing, utilizes atomizers spray water smoke that its fluorescence pattern is displayed under ultra violet lamp;
Get the female C of commercial e-Pointer written word on another filter paper,
The fluorescence letter C on two filter paper is irradiated with 500W mercury xenon lamp.
In Figure 12, four width figure are respectively the fluorescence photo of fluorescence letter C after 500W mercury xenon lamp irradiates 0,0.5,1,1.5 hour on two filter paper, often open in figure, left side is the water-sensitive fluorescence pattern of water-sensitive Fluorescence Increasing test paper, right side is the fluorescence pattern with commercial e-Pointer book, as can be seen from Figure 12, along with 500W mercury xenon lamp irradiation time rises to 1.5 hours, the fluorescence pattern that the commercial e-Pointer in right side is write almost disappears, and the change of the water-sensitive fluorescence pattern of water-sensitive Fluorescence Increasing test paper is very little.This illustrates that the water-sensitive Fluorescence Increasing test paper that this fluorescence pattern is fixed has higher resistance to photobleaching Properties.
Obviously, the explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that the those of ordinary skill for described technical field, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.

Claims (10)

1. water-sensitive Fluorescence Increasing test paper, is characterized in that, is composited by nano particle and paper;
Described nano particle is dissolved in non-polar solvent to assemble by amphipathic carbon nano dot and is formed;
Described amphipathic carbon nano dot surface has hydrophilic radical and lipophilic group.
2. the preparation method of water-sensitive Fluorescence Increasing test paper according to claim 1, is characterized in that, described non-polar solvent is toluene, benzene or chloroform.
3. the preparation method of water-sensitive Fluorescence Increasing test paper according to claim 1, is characterized in that, described hydrophilic radical is one or more in amino, amide group, carboxyl, sulfydryl and hydroxyl.
4. the preparation method of water-sensitive Fluorescence Increasing test paper according to claim 1, is characterized in that, described lipophilic group is one or more in alkyl, alkylene and aryl radical.
5. the preparation method of water-sensitive Fluorescence Increasing test paper according to claim 1, is characterized in that, described amphipathic carbon nano dot is by becoming lipophilic group to prepare the part hydrophilic radical functionalization on water-soluble carbon nano dot surface.
6. the preparation method of the water-sensitive Fluorescence Increasing test paper of claim 1-5 described in any one, is characterized in that, comprise the following steps:
(1) amphipathic carbon nano dot is dissolved in non-polar solvent, obtains the solution containing nano particle;
(2) paper is immersed in the solution containing nano particle, takes out dry, obtain water-sensitive Fluorescence Increasing test paper;
Or, by the solution spraying containing nano particle on paper, after drying, obtain water-sensitive Fluorescence Increasing test paper.
7. the preparation method of the water-sensitive Fluorescence Increasing test paper of claim 1-5 described in any one, is characterized in that, comprise the following steps:
(1) amphipathic carbon nano dot is dissolved in non-polar solvent, obtains the solution containing nano particle;
(2) dip the solution containing nano particle, paper is write pattern or figure, after drying, obtain water-sensitive Fluorescence Increasing test paper.
8. the water-sensitive Fluorescence Increasing test paper of claim 1-5 described in any one can be used in fluorescent printing of spraying water.
9. the water-sensitive Fluorescence Increasing test paper of claim 1-5 described in any one can be used in pore fluorescence imaging.
10. the water-sensitive Fluorescence Increasing test paper of claim 1-5 described in any one can be used in humidity detection.
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