CN106957646A - A kind of gallate long-persistence nano-luminescent materials and its preparation method and application - Google Patents
A kind of gallate long-persistence nano-luminescent materials and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of gallate long-persistence nano-luminescent materials, methods described is a series of gallate long-persistence nano-luminescent materials for preparing different-grain diameters using solvent-thermal method using long chain organic acid as surfactant.This method prepare long-persistence nano-luminescent materials scale topography is homogeneous, good dispersion, with good long-persistence luminous performance, it is possible to achieve repeatability excites the acquisition overlength afterglow time again.The oil-soluble gallate long-persistence nano-luminescent materials can use at least one method in pickling processes and ligand exchange to carry out surface modification, and modified water miscible gallate long-persistence nano-luminescent materials can be coupled with biomolecule, utilize the characteristics of luminescence of long afterglow, biological technical field is can be applied to, out-phase fluoroscopic examination field is especially applicable to.
Description
Technical field
The invention belongs to long-persistence nano-luminescent materials technical field, and in particular to a kind of gallate long-persistence nano lights
Material and preparation method and application.
Background technology
Long after glow luminous material, which has to remove, remains in that characteristic luminous for a long time after excitation source, extensively should at present
For Emergency Light, safety emergent instruction, night vision investigation, industrial art coating, decorative appearance, information Store and high-energy ray
The fields such as detection.Because long-persistence nano-luminescent materials can be excited before fluorescence imaging and biological detection, in " exempting to excite " bar
Bio-sensing and imaging are realized under part, thus effectively prevent original position excites reasons for its use to disturb, in biological technical field tool
Have broad application prospects.The application study for the long-persistence nano-luminescent materials reported at present is concentrated mainly on fluorescence imaging neck
Domain, the research report only few in number in fluorescence-labeled bio detection, and the detection of these fluorescence-labeled bios is all base
The homogeneous biological detection of (FRET) is transmitted in fluorescence resonance energy.But due to there is biological substrate pair in homogeneous biological detection system
The competition of exciting light absorbs, while also there is mutual energy transmission with fluorescent marker causes autofluorescence interference effect, significantly
Reduce the accuracy and sensitivity of detection.Compared with homogeneous detection, out-phase biological detection will detect sample and biological substrate point
From the influence of biological substrate can be excluded, so that detection sensitivity and accuracy is greatly improved.In addition, report is long remaining both at home and abroad
The synthesis of brightness nano luminescent material mainly using hydro-thermal method, sol-gel process and combines high-temperature heat treatment, but high-temperature heat treatment
Process synthesized long-persistence nano-luminescent materials can be caused to reunite, and pattern and bad dispersibility.Simultaneously because receiving
The problem of afterglow intensity is weak under metrical scale, persistence is short, it is impossible to meet the active demand of monitoring for a long time in organism.Cause
This, develops a kind of simple method and synthesizes homogeneous appearance and size, good dispersion and the excellent long-persistence nano hair of afterglow property
Luminescent material is it biomedical sector towards practical application premise.
The content of the invention
In order to overcome the problem of prior art is present, an object of the present invention is to provide a kind of gallate long-persistence nano
The preparation method of luminescent material.The synthesis condition of the preparation method is easily controlled, and can synthesize appearance and size homogeneous, scattered
The property high water-soluble or oil-soluble gallate long-persistence nano-luminescent materials of preferable, repetitive rate.
The second object of the present invention is to provide the gallate long-persistence nano-luminescent materials that the above method is prepared, described
Material can be water-soluble or oil-soluble, with good long-persistence luminous performance, it is possible to achieve repeatability excites acquisition again
The overlength afterglow time.
The third object of the present invention is to provide the application of above-mentioned water miscible gallate long-persistence nano-luminescent materials, mainly
It is to be applied to biological technical field；Specifically, it is especially applicable to can be applied to biological detection after biomolecule coupling
Out-phase fluorescence-labeled bio detection field.
Inventor's research discovery, the long afterglow of long-persistence nano-luminescent materials especially near-infrared luminous (650-1000nm)
Nano luminescent material gradually causes the extensive concern of people.Compared with other traditional fluorescence labeling materials, near-infrared long afterglow
Nano luminescent material is it is possible to prevente effectively from the interference such as biological tissue's autofluorescence, background noise caused by directly exciting, together
When near infrared emission there is higher biological tissue's penetration power, therefore near-infrared long-persistence nano-luminescent materials in fluorescence imaging and
The fields such as biological detection have broad application prospects.In particular by preparation method of the present invention prepare it is water-soluble
The gallate long-persistence nano-luminescent materials of property have homogeneous appearance and size, good dispersion, without any reunion the features such as, this is exactly
An important guarantee is provided for application of the material in fluorescence imaging and biological detection.Meanwhile, there is presently no grind
Study carefully the out-phase life reported and the long-persistence nano-luminescent materials are used as without the realization of background fluorescence nano-probe to biomolecule
Application in analyte detection field.
Based on such thinking, we complete the present invention.
The present invention is achieved through the following technical solutions：
A kind of preparation method of gallate long-persistence nano-luminescent materials, the preparation method comprises the following steps：
(1) alcohol solution of the hydroxide of alkali metal is prepared；
(2) gallium salt, other metal salts and the optionally mixed aqueous solution of chromic salts are prepared；
(3) mixed aqueous solution of long chain organic acid and step (2) is sequentially added into the alcohol solution of above-mentioned steps (1),
Solvent thermal reaction is carried out, that is, prepares oil-soluble gallate long-persistence nano-luminescent materials.
According to the present invention, the hydroxide of the alkali metal used in step (1) is NaOH, potassium hydroxide, hydroxide
At least one in lithium；Preferably NaOH.
According to the present invention, the water used in step (1) and step (2) be deionized water, ultra-pure water, distilled water at least
It is a kind of；Preferably deionized water.
According to the present invention, the alcohol used in step (1) is at least one in methanol, ethanol, ethylene glycol, propyl alcohol, butanol；
Preferably ethanol；Also preferably absolute ethyl alcohol.
According to the present invention, in above-mentioned steps (1), the volume ratio of the water and alcohol is 1:2~10, the hydrogen-oxygen of the alkali metal
The mass ratio of compound and water is 0.05~0.2:1.
According to the present invention, in above-mentioned steps (2), the gallium salt is in gallium nitrate, gallium chloride, acetic acid gallium, gallium sulfate
It is at least one；At least one of the chromic salts in chromic nitrate, chromium chloride, chromic acetate, chromium sulfate.
According to the present invention, other described metal salts are selected from other metal salts in addition to gallium salt and chromic salts；Preferably, it is described
At least one of other metal salts in zinc salt, magnesium salts；It is further preferred that the zinc salt is selected from zinc nitrate, zinc chloride, acetic acid
At least one in zinc, zinc sulfate；At least one of the magnesium salts in magnesium nitrate, magnesium chloride, magnesium acetate, magnesium sulfate.
According to the present invention, in above-mentioned steps (2), other metal salts, gallium salt, the mol ratio of chromic salts in the mixed aqueous solution
For (0.7~2):2:(0~0.1)；The concentration of gallium salt is 0.5~2mol/L in the mixed aqueous solution.
According to the present invention, in step (3), at least one of the long chain organic acid in oleic acid, linoleic acid etc.；It is preferred that
Ground, the long chain organic acid is selected from oleic acid.
According to the present invention, in above-mentioned steps (3), the volume ratio of the long chain organic acid and alcohol solution is 1:1~7；Institute
The volume ratio for stating mixed aqueous solution and alcohol solution is 1:1~7.
According to the present invention, in above-mentioned steps (3), the temperature of the solvent thermal reaction is 150~280 DEG C；The solvent heat
The time of reaction is 4-48h；Preferably, the temperature of the solvent thermal reaction is 170~210 DEG C；The solvent thermal reaction when
Between be 5-24h.
According to the present invention, above-mentioned preparation method is further comprising the steps of：
(4) the oil-soluble gallate long-persistence nano-luminescent materials prepared to step (3) carry out surface modification, i.e.,
Prepare water miscible gallate long-persistence nano-luminescent materials.
According to the present invention, in above-mentioned steps (4), the surface, which is modified, includes at least one in pickling processes and ligand exchange
The method of kind.
According to the present invention, described pickling processes method is specially：The oil-soluble gallate that step (3) is prepared
Long-persistence nano-luminescent materials are dissolved in the alcoholic solution of hydrochloric acid (pH=1~2 of the alcoholic solution of the hydrochloric acid), stirring, are centrifuged and are received
Collect nano particle, then washed with alcohol, that is, prepare water miscible gallate long-persistence nano-luminescent materials.
Wherein, the alcohol and washing alcohol in the alcoholic solution of hydrochloric acid, are ethanol, preferably absolute ethyl alcohol.
According to the present invention, described ligand exchange processes are specially：The oil-soluble gallate that step (3) is prepared
Long-persistence nano-luminescent materials are dissolved in hexamethylene, are mutually mixed with the dichloromethane that is dissolved with tetrafluoro boric acid nitrous, after stirring
Centrifuge washing, and sediment is dispersed in dimethylformamide, phosphoethanolamine is added, continues centrifuge washing after stirring, i.e.,
Prepare water miscible gallate long-persistence nano-luminescent materials.
The present invention also provides a kind of gallate long-persistence nano-luminescent materials, and the material is prepared into by the above method
Arrive.
According to the present invention, the gallate long-persistence nano-luminescent materials are oil-soluble, and the chemical formula of its body is
MGa2O4:X%Cr3+；Wherein, M is Zn or Mg；0≤x≤10；There is long chain organic acid on its surface.
Preferably, 0 ＜ x≤5；It is further preferred that 0 ＜ x≤1；It is further preferred that 0 ＜ x≤0.6.
According to the present invention, the gallate long-persistence nano-luminescent materials are water miscible, and the chemical formula of its body is
MGa2O4:X%Cr3+；Wherein, M is Zn or Mg；0≤x≤10；There is amino on its surface or its surface is acidified modification.
Preferably, 0 ＜ x≤5；It is further preferred that 0 ＜ x≤1；It is further preferred that 0 ＜ x≤0.6.
That is, the water miscible long-persistence nano-luminescent materials can be amidized gallate or be tables
The acidified modified gallate in face.
Wherein, the gallate has Emission in Cubic spinel structure.
Wherein, the nano luminescent material is form of nanoparticles and scale topography is homogeneous, in subsphaeroidal, and particle size range exists
3-30nm。
The nano luminescent material of the present invention is form of nanoparticles, its dispersiveness, homogeneity and reproducible；In addition, this
The luminescent material of invention has good long-persistence luminous performance,
Invention further provides the above-mentioned water miscible gallate long-persistence nano-luminescent materials of one kind in biotechnology
Application in field.
Preferably, it will be examined after the water miscible gallate long-persistence nano-luminescent materials and biomolecule coupling in biology
The application in survey field.
It is further preferred that in out-phase after the water miscible gallate long-persistence nano-luminescent materials and biomolecule are coupled
The application in fluoroscopic examination field.
It is further preferred that being visited using the water miscible gallate long-persistence nano-luminescent materials as without background fluorescence
Pin realizes the detection of out-phase biological.
The beneficial effects of the present invention are：
1. the invention provides a kind of preparation method of gallate long-persistence nano-luminescent materials, methods described is with long-chain
Organic acid (such as oleic acid) is surfactant, and a series of gallate long afterglow for preparing different-grain diameters using solvent-thermal method is received
Rice luminescent material.The particle size range of long-persistence nano-luminescent materials prepared by this method is in 3-30nm, and its scale topography is homogeneous, divide
Property is dissipated good, with good long-persistence luminous performance, it is possible to achieve repeatability excites the acquisition overlength afterglow time again.
2. for the oil-soluble gallate long-persistence nano-luminescent materials that prepare of the present invention can using pickling processes and
At least one method in ligand exchange carries out surface modification, and the method simple practical of the surface modification, cycle time is short.And
Modified water miscible gallate long-persistence nano-luminescent materials can be coupled with biomolecule, utilize the luminous of long afterglow
Characteristic, can be applied to biological technical field, specifically applied to field of biological detection, be especially applicable to out-phase fluorescin quality testing
Survey field.
Brief description of the drawings
Fig. 1 is the ZnGa that embodiment 1 is prepared2O4:0.4%Cr3+The x-ray powder of long-persistence nano-luminescent materials spreads out
Penetrate figure.
Fig. 2 is the ZnGa that embodiment 1 is prepared2O4:0.4%Cr3+The transmission electron microscope picture of long-persistence nano-luminescent materials.
Fig. 3 is the ZnGa that embodiment 1 is prepared2O4:0.4%Cr3+The Emission at Room Temperature light of long-persistence nano-luminescent materials
Spectrogram.
Fig. 4 is the ZnGa that embodiment 1 is prepared2O4:0.4%Cr3+The long afterglow decay of long-persistence nano-luminescent materials
Curve.
Fig. 5 is the ZnGa that embodiment 1 is prepared2O4:0.4%Cr3+The multiple long afterglow of long-persistence nano-luminescent materials
Decay-excitation curve figure again.
(a), (b) in Fig. 6 is respectively the ZnGa that embodiment 2 is prepared2O4:0.4%Cr3+Long-persistence nano lights material
The X-ray powder diffraction figure of material, in aqueous place one month before and after hydration grain size distribution.
The ZnGa that Fig. 7 prepares for Examples 1 and 22O4:0.4%Cr3+The long afterglow of long-persistence nano-luminescent materials declines
Subtract curve comparison figure.
Fig. 8 is the ZnGa that embodiment 1 and 3 is prepared2O4:0.4%Cr3+The infrared spectrum of long-persistence nano-luminescent materials
Comparison diagram.
Fig. 9 be embodiment 4 in utilize biotinylated ZnGa2O4:0.4%Cr3+Long-persistence nano-luminescent materials are to affine
Fibroin carries out the calibration curve of out-phase detection, and illustration is the range of linearity curve of calibration curve.
Embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than for limiting the scope of the invention.Furthermore, it is to be understood that after described content of the invention has been read, this
Art personnel can make various changes or modifications to the present invention, and these equivalent form of values equally fall such as the protection model of the present invention
Enclose.
In the present invention, the X-ray powder diffraction figure (XRD) of the nano material, tester model MiniFlex 2,
Producer is Rigaku, and copper target radiation wavelength is λ=0.154187nm.
In the present invention, the transmission electron microscope photo (TEM) of described nano material, tester model JEM-2010, factory
Family is JEOL.
In the present invention, the launching light spectrogram of the nano material, tester model FLS980, producer is
Edinburgh, excitation source is 450W xenon lamp.
In the present invention, the hydration grain size distribution of the nano material, tester model Nano ZS ZEN3600,
Producer is Malvern.
In the present invention, the infrared spectrogram of the nano material, tester model Magna 750, producer is
Nicolet。
Embodiment 1
Oil-soluble ZnGa2O4:0.4%Cr3+The preparation of long-persistence nano-luminescent materials
(1) 8mL deionized waters, 18mL absolute ethyl alcohols and 0.6g NaOH are mixed into ultrasound, makes NaOH complete
Dissolving, that is, prepare the ethanol water for obtaining NaOH；
(2) in the ethanol water for the NaOH that 6mL oleic acid is added in step (1), 15min is stirred；
(3) by 1mL zinc nitrate solutions (1mol/L), 2mL gallium nitrate solutions (1mol/L) and 8 μ L chromium nitrate solutions
(0.5mol/L) is mutually mixed, and ultrasound obtains transparent mixed aqueous solution, is then added dropwise to the mixed liquor of step (2) acquisition
In, uniform stirring 0.5h at room temperature；
(4) obtained mixed solution is transferred in the water heating kettle of 40mL volumes (interior village is polytetrafluoroethylene (PTFE)), by hydro-thermal
Kettle is sealed, and carries out solvent thermal reaction, is put into the baking oven that preset temperature is 210 DEG C and is heated 16h；
(5) water heating kettle for naturally cooling to room temperature is taken out from baking oven, bottom white precipitate is obtained through centrifugation, washing
Oil-soluble long-persistence nano-luminescent materials, the chemical formula of its body is ZnGa2O4:0.4%Cr3+。
From figure 1 it appears that the oil-soluble long-persistence nano-luminescent materials have good crystallinity, its diffraction maximum
Position and ZnGa2O4PDF standard cards (JCPDS No.86-0415) it is consistent, be pure Emission in Cubic spinel structure, without miscellaneous
Phase.
As shown in Fig. 2 the oil-soluble long-persistence nano-luminescent materials are subsphaeroidal, good dispersion, pattern in hexamethylene
Homogeneous, particle diameter is about 7nm.
As shown in figure 3, under 271nm excitation wavelength, the oil-soluble long-persistence nano-luminescent materials have efficient near
Infrared light emission.
As shown in figure 4, after ultraviolet excitation is stopped, the near-infrared long afterglow of the oil-soluble long-persistence nano-luminescent materials
Still there is higher long afterglow signal after 2h.
As shown in figure 5, the near-infrared long afterglow of the oil-soluble long-persistence nano-luminescent materials uses house after 40min
3min is irradiated in advance with formula white LED lamp, is excited after stopping it is observed that long afterglow signal can recover and almost not have again
Obvious signal weakens, and can at least realize the excitation process of decay of afterglow as 6 times-again.
Embodiment 2
Water-soluble ZnGa2O4:0.4%Cr3+Preparation-pickling processes of long-persistence nano-luminescent materials
(1) 15mL absolute ethyl alcohols are taken in conical flask, 115 μ L concentrated hydrochloric acids is added, makes its pH=1；
(2) the oil-soluble long-persistence nano-luminescent materials that 40mg above-described embodiments 1 are prepared are added into step (1) to match somebody with somebody
In the solution of system, 30min is stirred, centrifugation, absolute ethanol washing prepares the water-soluble long-persistence nano and lighted for several times, that is,
Material, is the acidified modified ZnGa in surface2O4:0.4%Cr3+。
As can be seen that position and the ZnGa of the diffraction maximum of the water-soluble long-persistence nano-luminescent materials from Fig. 6 (a)2O4's
PDF standard cards (JCPDS No.86-0415) are consistent, are pure Emission in Cubic spinel structure, no dephasign.
As shown in Fig. 6 (b), the water-soluble long-persistence nano-luminescent materials possess the colloid-stabilised of height in deionized water
Property, it is hydrated particle diameter and almost not changed after placing one month.
The ZnGa that Fig. 7 prepares for Examples 1 and 22O4:0.4%Cr3+The long afterglow of long-persistence nano-luminescent materials declines
Subtract curve comparison figure, as seen from the figure, the long-persistence luminous performance of the nano material does not almost change before and after pickling processes,
Illustrate that the pickling processes used do not influence the long-persistence luminous performance of the nano material.
Embodiment 3
Water-soluble ZnGa2O4:0.4%Cr3+Preparation-ligand exchange of long-persistence nano-luminescent materials
(1) the oil-soluble long-persistence nano-luminescent materials that 40mg above-described embodiments 1 are prepared are dissolved in 5mL hexamethylenes
In, 26mg tetrafluoro boric acid nitrous is dissolved in 5mL dichloromethane, and both are mutually mixed, and stirs 10min, centrifugation, washing are finally produced
Thing is dispersed in 10mL dimethylformamides；
(2) 100mg phosphoethanolamines are added in the dimethyl formamide solution of above-mentioned steps (1), 1h is stirred, third is added
Ketone is precipitated, and is washed for several times with dimethylformamide and deionized water, is obtained the water-soluble long-persistence nano-luminescent materials, i.e. ammonia
The ZnGa of base2O4:0.4%Cr3+。
Fig. 8 is the ZnGa that embodiment 1 and 3 is prepared2O4:0.4%Cr3+The infrared spectrum of long-persistence nano-luminescent materials
Comparison diagram, as seen from the figure, after ligand exchange, it is observed that the long-persistence nano-luminescent materials are in 1633cm-1With
1079cm-1There is strong infrared absorption peak at place, while corresponding to the 2921cm in the long alkyl chain of oleic acid molecular-1And 2853cm-1
The characteristic absorption peak at place almost disappears, and illustrates by ligand exchange success amino on the Surface-modification of Nanoparticles.
Embodiment 4
Utilize water-soluble ZnGa2O4:0.4%Cr3+Long-persistence nano-luminescent materials carry out affinity prime detection
1. water solubility ZnGa2O4:0.4%Cr3+The biotinylation of long-persistence nano-luminescent materials：
(1) take 10mg biotin (buying from Sigma (China)) to be dissolved in 2mL deionized waters, add the 200 dense ammonia of μ L
Water is simultaneously ultrasonic to the transparent clarification of solution；
(2) the water-soluble ZnGa for preparing 20mg above-described embodiment 22O4:0.4%Cr3+Long-persistence nano lights
Material is added in above-mentioned solution, stirs 30min, centrifugation, washing disperse standby in deionized water.
2. based on biotinylation ZnGa2O4:0.4%Cr3+The out-phase biological detection of long-persistence nano-luminescent materials：
(1) the 100 μ L gradient standard liquid of Avidin is added in the microwell plate in 96 holes (by pH=9.6 coating buffer
It is formulated), 1h is incubated at 37 DEG C；
(2) microwell plate is washed 3 times with PBST, is added at 200 μ L monoethanolamine confining liquid, 37 DEG C and is incubated 1h；
(3) 100 μ L 50 μ g/mL biotinylated ZnGa is added in each hole2O4:0.4%Cr3+Long-persistence nano is sent out
Luminescent material solution, 1h is incubated at 37 DEG C, and PBST is washed 3 times；
(4) long afterglow of nano material is carried out using light-emitting mode on multi-function microplate reader (Synergy 4, BioTeK)
Signal record, the time of integration is set to 2s.
As shown in figure 9, biotinylation ZnGa2O4:0.4%Cr3+The long-persistence luminous enhancing signal of nano material is with micro-
On orifice plate in each hole the increase of affinity prime concentration and increase, illustrate that biotinylation long-persistence nano-luminescent materials can
Combined well with affinity prime, estimate that lowest detection is limited to 150pM with blank averages plus 3 times of standard deviations.
Embodiment 5
Oil-soluble ZnGa2O4The preparation of long-persistence nano-luminescent materials
(1) 8mL deionized waters, 18mL absolute ethyl alcohols and 0.6g NaOH are mixed into ultrasound, makes NaOH complete
Dissolving, that is, prepare the ethanol water for obtaining NaOH；
(2) in the ethanol water for the NaOH that 6mL oleic acid is added in step (1), 15min is stirred；
(3) 1mL zinc nitrate solutions (1mol/L), 2mL gallium nitrate solutions (1mol/L) are mutually mixed, ultrasound obtains transparent
Mixed aqueous solution, in the mixed liquor for being then added dropwise to step (2) acquisition, uniform stirring 0.5h at room temperature；
(4) obtained mixed solution is transferred in the water heating kettle of 40mL volumes (interior village is polytetrafluoroethylene (PTFE)), by hydro-thermal
Kettle is sealed, and carries out solvent thermal reaction, is put into the baking oven that preset temperature is 210 DEG C and is heated 16h；
(5) water heating kettle for naturally cooling to room temperature is taken out from baking oven, bottom white precipitate is obtained through centrifugation, washing
Oil-soluble long-persistence nano-luminescent materials, the chemical formula of its body is ZnGa2O4。
Embodiment 6
Oil-soluble MgGa2O4:0.5%Cr3+The preparation of long-persistence nano-luminescent materials
(1) 6mL deionized waters, 15mL absolute ethyl alcohols and 0.6g NaOH are mixed into ultrasound, makes NaOH complete
Dissolving, that is, prepare the ethanol water for obtaining NaOH；
(2) in the ethanol water for the NaOH that 6mL oleic acid is added in step (1), 15min is stirred；
(3) by 1mL magnesium nitrate solutions (1mol/L), 2mL gallium nitrate solutions (1mol/L) and 10 μ L chromium nitrate solutions
(0.5mol/L) is mutually mixed, and ultrasound obtains transparent mixed aqueous solution, is then added dropwise to the mixed liquor of step (2) acquisition
In, uniform stirring 0.5h at room temperature；
(4) obtained mixed solution is transferred in the water heating kettle of 40mL volumes (interior village is polytetrafluoroethylene (PTFE)), by hydro-thermal
Kettle is sealed, and carries out solvent thermal reaction, is put into the baking oven that preset temperature is 200 DEG C and is heated 24h；
(5) water heating kettle for naturally cooling to room temperature is taken out from baking oven, bottom white precipitate is obtained through centrifugation, washing
Oil-soluble long-persistence nano-luminescent materials, the chemical formula of its body is MgGa2O4:0.5%Cr3+。
Embodiment 7
Oil-soluble MgGa2O4The preparation of long-persistence nano-luminescent materials
(1) 6mL deionized waters, 15mL absolute ethyl alcohols and 0.6g NaOH are mixed into ultrasound, makes NaOH complete
Dissolving, that is, prepare the ethanol water for obtaining NaOH；
(2) in the ethanol water for the NaOH that 6mL oleic acid is added in step (1), 15min is stirred；
(3) 1mL magnesium nitrate solutions (1mol/L), 2mL gallium nitrate solutions (1mol/L) are mutually mixed, ultrasound obtains transparent
Mixed aqueous solution, in the mixed liquor for being then added dropwise to step (2) acquisition, uniform stirring 0.5h at room temperature；
(4) obtained mixed solution is transferred in the water heating kettle of 40mL volumes (interior village is polytetrafluoroethylene (PTFE)), by hydro-thermal
Kettle is sealed, and carries out solvent thermal reaction, is put into the baking oven that preset temperature is 200 DEG C and is heated 24h；
(5) water heating kettle for naturally cooling to room temperature is taken out from baking oven, bottom white precipitate is obtained through centrifugation, washing
Oil-soluble long-persistence nano-luminescent materials, the chemical formula of its body is MgGa2O4。
More than, embodiments of the present invention are illustrated.But, the present invention is not limited to above-mentioned embodiment.It is all
Within the spirit and principles in the present invention, any modifications, equivalent substitutions and improvements done etc., should be included in the guarantor of the present invention
Within the scope of shield.
Claims (10)
1. a kind of preparation method of gallate long-persistence nano-luminescent materials, it is characterised in that the preparation method includes as follows
Step：
(1) alcohol solution of the hydroxide of alkali metal is prepared；
(2) gallium salt, other metal salts and the optionally mixed aqueous solution of chromic salts are prepared；
(3) mixed aqueous solution of long chain organic acid and step (2) is sequentially added into the alcohol solution of above-mentioned steps (1), is carried out
Solvent thermal reaction, that is, prepare oil-soluble gallate long-persistence nano-luminescent materials.
2. preparation method according to claim 1, it is characterised in that the hydroxide of the alkali metal used in step (1)
For at least one in NaOH, potassium hydroxide, lithium hydroxide；Preferably NaOH.
Preferably, the alcohol used in step (1) is at least one in methanol, ethanol, ethylene glycol, propyl alcohol, butanol；Preferably second
Alcohol；Also preferably absolute ethyl alcohol.
Preferably, in above-mentioned steps (1), the volume ratio of the water and alcohol is 1:2~10, the hydroxide and water of the alkali metal
Mass ratio be 0.05~0.2:1.
Preferably, in above-mentioned steps (2), at least one of the gallium salt in gallium nitrate, gallium chloride, acetic acid gallium, gallium sulfate；
At least one of the chromic salts in chromic nitrate, chromium chloride, chromic acetate, chromium sulfate.
Preferably, other described metal salts are selected from other metal salts in addition to gallium salt and chromic salts；Preferably, other described metals
At least one of the salt in zinc salt, magnesium salts；It is further preferred that the zinc salt is selected from zinc nitrate, zinc chloride, zinc acetate, zinc sulfate
In at least one；At least one of the magnesium salts in magnesium nitrate, magnesium chloride, magnesium acetate, magnesium sulfate.
Preferably, in above-mentioned steps (2), other metal salts in the mixed aqueous solution, gallium salt, chromic salts mol ratio for (0.7~
2):2:(0~0.1)；The concentration of gallium salt is 0.5~2mol/L in the mixed aqueous solution.
3. preparation method according to claim 1 or 2, it is characterised in that in step (3), the long chain organic acid is selected from
At least one in oleic acid, linoleic acid etc.；Preferably, the long chain organic acid is selected from oleic acid.
Preferably, in above-mentioned steps (3), the volume ratio of the long chain organic acid and alcohol solution is 1:1~7；The mixing water
The volume ratio of solution and alcohol solution is 1:1~7.
Preferably, in above-mentioned steps (3), the temperature of the solvent thermal reaction is 150~280 DEG C；The solvent thermal reaction when
Between be 4-48h；Preferably, the temperature of the solvent thermal reaction is 170~210 DEG C；The time of the solvent thermal reaction is 5-
24h。
4. the preparation method according to claim any one of 1-3, it is characterised in that above-mentioned preparation method also includes following step
Suddenly：
(4) the oil-soluble gallate long-persistence nano-luminescent materials prepared to step (3) carry out surface modification, that is, prepare
Obtain water miscible gallate long-persistence nano-luminescent materials.
Preferably, in above-mentioned steps (4), the surface, which is modified, includes at least one method in pickling processes and ligand exchange.
5. preparation method according to claim 4, it is characterised in that described pickling processes method is：By step (3) system
Standby obtained oil-soluble gallate long-persistence nano-luminescent materials are dissolved in the alcoholic solution (pH=of the alcoholic solution of the hydrochloric acid of hydrochloric acid
1~2) in, stirring centrifuges and collects nano particle, then washed with alcohol, that is, prepares water miscible gallate long-persistence nano
Luminescent material.
Wherein, described ligand exchange processes are：The oil-soluble gallate long-persistence nano that step (3) is prepared lights
Material is dissolved in hexamethylene, is mutually mixed with the dichloromethane that is dissolved with tetrafluoro boric acid nitrous, centrifuge washing after stirring, and will be heavy
Starch is dispersed in dimethylformamide, adds phosphoethanolamine, is continued centrifuge washing after stirring, that is, is prepared water miscible
Gallate long-persistence nano-luminescent materials.
6. a kind of gallate long-persistence nano-luminescent materials, it is characterised in that the material is by any one of claim 1-5
What described method was prepared.
7. long-persistence nano-luminescent materials according to claim 6, it is characterised in that the gallate long-persistence nano hair
Luminescent material is oil-soluble, and the chemical formula of its body is MGa2O4:X%Cr3+；Wherein, M is Zn or Mg；0≤x≤10；Its surface
There is long chain organic acid.
Preferably, 0 ＜ x≤5；It is further preferred that 0 ＜ x≤1；It is further preferred that 0 ＜ x≤0.6.
8. long-persistence nano-luminescent materials according to claim 6, it is characterised in that the gallate long-persistence nano hair
Luminescent material is water miscible, and the chemical formula of its body is MGa2O4:X%Cr3+；Wherein, M is Zn or Mg；0≤x≤10；Its surface
It is acidified modification to have amino or its surface.
Preferably, 0 ＜ x≤5；It is further preferred that 0 ＜ x≤1；It is further preferred that 0 ＜ x≤0.6.
Preferably, the water miscible long-persistence nano-luminescent materials are amidized gallate or are that surface is acidified modified
Gallate.
9. the long-persistence nano-luminescent materials according to claim any one of 6-8, it is characterised in that the gallate has
Emission in Cubic spinel structure.
Preferably, the nano luminescent material is form of nanoparticles and scale topography is homogeneous, in subsphaeroidal, and particle size range is in 3-
30nm。
10. the answering in biological technical field of the water miscible gallate long-persistence nano-luminescent materials described in claim 8 or 9
With.
Preferably, it will be led after the water miscible gallate long-persistence nano-luminescent materials and biomolecule coupling in biological detection
The application in domain.
Preferably, it will be examined after the water miscible gallate long-persistence nano-luminescent materials and biomolecule coupling in out-phase fluorescence
The application in survey field.
Preferably, it is different using the water miscible gallate long-persistence nano-luminescent materials as being realized without background fluorescence probe
Phase biological is detected.
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| CN111187620A (en) * | 2020-01-19 | 2020-05-22 | 南京邮电大学 | Novel Zn2GeO4Base green long afterglow nano material and its preparation method |
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| CN116042215A (en) * | 2022-12-23 | 2023-05-02 | 鲁东大学 | Solid solution type near infrared long afterglow luminescent material and preparation method thereof |
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| CN110272732A (en) * | 2018-03-14 | 2019-09-24 | 中国科学院福建物质结构研究所 | Based on the luminous nano material of transition metal ions, preparation method and the usage |
| CN110272732B (en) * | 2018-03-14 | 2020-10-02 | 中国科学院福建物质结构研究所 | Transition metal ion luminescence-based nano material, preparation method and application thereof |
| CN110041919A (en) * | 2019-05-23 | 2019-07-23 | 东北大学 | A kind of non-rare earth doping fluorescent powder of the gallic acid zinc-base of white light emission and preparation method |
| CN111187620A (en) * | 2020-01-19 | 2020-05-22 | 南京邮电大学 | Novel Zn2GeO4Base green long afterglow nano material and its preparation method |
| CN111253937A (en) * | 2020-03-10 | 2020-06-09 | 武汉工程大学 | Cr3+、Bi3+Double-doped gallate long-afterglow fluorescent powder material and preparation method and application thereof |
| CN116478687A (en) * | 2022-12-01 | 2023-07-25 | 南开大学 | Long afterglow material based on MOF template method and preparation method and application thereof |
| CN116042215A (en) * | 2022-12-23 | 2023-05-02 | 鲁东大学 | Solid solution type near infrared long afterglow luminescent material and preparation method thereof |
| CN116042215B (en) * | 2022-12-23 | 2023-11-07 | 鲁东大学 | Solid solution type near infrared long afterglow luminescent material and preparation method thereof |
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