CN106957646B - 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, the method is that a series of gallate long-persistence nano-luminescent materials of different-grain diameters are prepared using solvent-thermal method using long chain organic acid as surfactant.The long-persistence nano-luminescent materials scale topography of this method preparation is uniform, good dispersion may be implemented repeatability and excite the acquisition overlength afterglow time again with good long-persistence luminous performance.The oil-soluble gallate long-persistence nano-luminescent materials can be used at least one of pickling processes and ligand exchange method and be surface modified, and modified water-soluble gallate long-persistence nano-luminescent materials can be coupled with biomolecule, utilize the characteristics of luminescence of long afterglow, it can be applied to field of biotechnology, be especially applied to out-phase fluorescence detection field.
Description
Technical field
The invention belongs to long-persistence nano-luminescent materials technical fields, and in particular to a kind of gallate long-persistence nano is luminous
Material and the preparation method and application thereof.
Background technique
Long after glow luminous material still maintains characteristic luminous for a long time after having removal excitation light source, answers extensively at present
For Emergency Light, the instruction of safety emergency, night vision investigation, industrial art coating, decorative appearance, information storage and high-energy ray
The fields such as detection.Since long-persistence nano-luminescent materials can excite before fluorescence imaging and biological detection, in " exempting to excite " item
Bio-sensing and imaging are realized under part, thus effectively prevents excitation reasons for its use interference in situ, are had in field of biotechnology
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
In the homogeneous biological detection of fluorescence resonance energy transmitting (FRET).But since there are biological substrates pair in homogeneous biological detection system
The competition of exciting light absorbs, while also there are mutual energy transmissions to cause autofluorescence interference effect with fluorescent marker, significantly
Reduce the accuracy and sensitivity of detection.Compared with homogeneous detection, out-phase biological detection will test sample and biological substrate point
From the influence of biological substrate can be excluded, so that detection sensitivity and accuracy be greatly improved.In addition, both at home and abroad more than report length
The synthesis of brightness nano luminescent material mainly using hydro-thermal method, sol-gel method and combines high-temperature heat treatment, however high-temperature heat treatment
Process will lead to synthesized long-persistence nano-luminescent materials and reunite, and pattern and bad dispersibility.Simultaneously because receiving
The problem that afterglow intensity is weak under metrical scale, persistence is short is unable to satisfy in organism the urgent need of monitoring for a long time.Cause
This, develops a kind of simple method and synthesizes uniform appearance and size, good dispersion and the excellent long-persistence nano hair of afterglow property
Luminescent material is it in premise of the field of biomedicine towards practical application.
Summary of the invention
Of the existing technology in order to overcome the problems, such as, 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 easy to control, can synthesize appearance and size it is uniform, dispersion
The water-soluble or oil-soluble gallate long-persistence nano-luminescent materials that property is preferable, repetitive rate is high.
The gallate long-persistence nano-luminescent materials being prepared the second object of the present invention is to provide the above method, it is described
Material can be water solubility or oil-soluble, have good long-persistence luminous performance, and repeatability may be implemented and excite acquisition again
The overlength afterglow time.
The third object of the present invention is to provide the application of above-mentioned water-soluble gallate long-persistence nano-luminescent materials, mainly
It is to be applied to field of biotechnology；Specifically, it can be applied to biological detection after it being coupled with biomolecule, be especially applied to
Out-phase fluorescence-labeled bio detection field.
Inventor the study found that long-persistence nano-luminescent materials especially near-infrared luminous (650-1000nm) long afterglow
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 because biological tissue's autofluorescence, the background noise etc. caused by directly exciting interfere, together
When near infrared emission biological tissue's penetration power with higher, therefore near-infrared long-persistence nano-luminescent materials in fluorescence imaging and
The fields such as biological detection have broad application prospects.It is prepared in particular by preparation method of the present invention water-soluble
The gallate long-persistence nano-luminescent materials of property have the characteristics that uniform appearance and size, good dispersion, without any reunion, this is exactly
It is that application of the material in fluorescence imaging and biological detection provides an important guarantee.Meanwhile there is presently no grind
Study carefully the out-phase life reported and realized using the long-persistence nano-luminescent materials as no 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 include the following steps:
(1) alcohol solution of the hydroxide of alkali metal is prepared；
(2) mixed aqueous solution of gallium salt, other metal salts and optionally chromic salts is 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, oil-soluble gallate long-persistence nano-luminescent materials are prepared.
According to the present invention, the hydroxide of alkali metal used in step (1) is sodium hydroxide, potassium hydroxide, hydroxide
At least one of lithium；Preferably sodium hydroxide.
According to the present invention, water used in step (1) and step (2) be deionized water, ultrapure water, in distilled water at least
It is a kind of；Preferably deionized water.
According to the present invention, alcohol used in step (1) is at least one of methanol, ethyl alcohol, ethylene glycol, propyl alcohol, butanol；
Preferably ethyl alcohol；Also preferably dehydrated 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；The chromic salts is selected from least one of 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, described
Other metal salts are selected from least one of zinc salt, magnesium salts；It is further preferred that the zinc salt is selected from zinc nitrate, zinc chloride, acetic acid
At least one of zinc, zinc sulfate；The magnesium salts is selected from least one of magnesium nitrate, magnesium chloride, magnesium acetate, magnesium sulfate.
According to the present invention, in above-mentioned steps (2), the molar ratio of other metal salts, gallium salt, 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), the long chain organic acid is selected from least one of oleic acid, linoleic acid etc.；It is preferred that
Ground, the long chain organic acid are 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) it carries out surface to the oil-soluble gallate long-persistence nano-luminescent materials that step (3) is prepared to be modified, i.e.,
Water-soluble gallate long-persistence nano-luminescent materials are prepared.
According to the present invention, in above-mentioned steps (4), modified at least one including in pickling processes and ligand exchange in the surface
Kind method.
According to the present invention, the pickling processes method specifically: the oil-soluble gallate that step (3) is prepared
Long-persistence nano-luminescent materials are dissolved in the alcoholic solution (pH=1~2 of the alcoholic solution of the hydrochloric acid) of hydrochloric acid, and stirring is centrifuged and receives
Collect nano particle, then washed with alcohol, that is, water-soluble gallate long-persistence nano-luminescent materials are prepared.
Wherein, the pure and mild washing alcohol in the alcoholic solution of hydrochloric acid is ethyl alcohol, preferably dehydrated alcohol.
According to the present invention, the ligand exchange processes specifically: the oil-soluble gallate that step (3) is prepared
Long-persistence nano-luminescent materials are dissolved in hexamethylene, are mutually mixed with the methylene chloride 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.,
Water-soluble gallate long-persistence nano-luminescent materials are prepared.
The present invention also provides a kind of gallate long-persistence nano-luminescent materials, the material is prepared by the above method
It arrives.
According to the present invention, the gallate long-persistence nano-luminescent materials are oil-soluble, and the chemical formula of ontology is
MGa2O4: x%Cr3+；Wherein, M is Zn or Mg；0≤x≤10；There is long chain organic acid on its surface.
Preferably, x≤5 0 <；It is further preferred that x≤1 0 <；It is further preferred that x≤0.6 0 <.
According to the present invention, the gallate long-persistence nano-luminescent materials are water-soluble, and the chemical formula of ontology 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, x≤5 0 <；It is further preferred that x≤1 0 <；It is further preferred that x≤0.6 0 <.
That is, the water-soluble long-persistence nano-luminescent materials can be amidized gallate or be tables
The acidified modified gallate in face.
Wherein, the gallate has cubic phase spinel structure.
Wherein, the nano luminescent material is form of nanoparticles and scale topography is uniform, and in subsphaeroidal, particle size range exists
3-30nm。
Nano luminescent material of the invention is form of nanoparticles, dispersibility, homogeneity and reproducible；In addition, this
The luminescent material of invention has good long-persistence luminous performance,
Invention further provides a kind of above-mentioned water-soluble gallate long-persistence nano-luminescent materials in biotechnology
Application in field.
Preferably, it will be examined after the water-soluble 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-soluble gallate long-persistence nano-luminescent materials and biomolecule are coupled
The application in fluorescence detection field.
It is further preferred that the water-soluble gallate long-persistence nano-luminescent materials is used to visit as no background fluorescence
Needle realizes the detection of out-phase biological.
The beneficial effects of the present invention are:
1. the present invention provides a kind of preparation method of gallate long-persistence nano-luminescent materials, the method is with long-chain
Organic acid (such as oleic acid) is surfactant, is received using a series of gallate long afterglow that different-grain diameters are prepared in solvent-thermal method
Rice luminescent material.For the particle size range of the long-persistence nano-luminescent materials of this method preparation in 3-30nm, scale topography is uniform, divides
It is good to dissipate property, there is good long-persistence luminous performance, repeatability may be implemented and excite the acquisition overlength afterglow time again.
2. for oil-soluble gallate long-persistence nano-luminescent materials prepared by the present invention can using pickling processes and
At least one of ligand exchange method is surface modified, the method simple practical of the surface modification, and cycle time is short.And
Modified water-soluble gallate long-persistence nano-luminescent materials can be coupled with biomolecule, utilize shining for long afterglow
Characteristic can be applied to field of biotechnology, specifically be applied to field of biological detection, be especially applied to the inspection of out-phase biological
Survey field.
Detailed description of the invention
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 of long-persistence nano-luminescent materials is decayed
Curve.
Fig. 5 is the ZnGa that embodiment 1 is prepared2O4: 0.4%Cr3+The multiple long afterglow of long-persistence nano-luminescent materials
Decaying-excitation curve figure again.
(a), (b) in Fig. 6 are respectively the ZnGa that embodiment 2 is prepared2O4: 0.4%Cr3+Long-persistence nano shines material
The X-ray powder diffraction figure of material, the hydration grain size distribution for placing a month front and back in aqueous solution.
Fig. 7 is the ZnGa that Examples 1 and 2 are prepared2O4: 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 spectroscopy of long-persistence nano-luminescent materials
Comparison diagram.
Fig. 9 is that biotinylated ZnGa is utilized in embodiment 42O4: 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.
Specific embodiment
Present invention will be further explained below with reference to specific examples.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 having read documented content of the invention, this
Field technical staff can make various changes or modifications the present invention, and such equivalent forms are equally fallen such as protection model of the invention
It encloses.
In the present invention, the X-ray powder diffraction figure (XRD) of the nano material, test equipment 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 the nano material, test equipment model JEM-2010, factory
Family is JEOL.
In the present invention, the launching light spectrogram of the nano material, test equipment model FLS980, producer is
Edinburgh, excitation light source are the xenon lamp of 450W.
In the present invention, the hydration grain size distribution of the nano material, test equipment model Nano ZS ZEN3600,
Producer is Malvern.
In the present invention, the infrared spectrogram of the nano material, test equipment 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 water, 18mL dehydrated alcohol and 0.6g sodium hydroxide are mixed into ultrasound, keeps sodium hydroxide complete
Dissolution prepares and obtains the ethanol water of sodium hydroxide；
(2) in the ethanol water for the sodium hydroxide that 6mL oleic acid is added in step (1), 15min is stirred；
(3) by 1mL zinc nitrate solution (1mol/L), 2mL gallium nitrate solution (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 to in the water heating kettle of 40mL volume (interior village is polytetrafluoroethylene (PTFE)), by hydro-thermal
Kettle sealing, carries out solvent thermal reaction, is put into the baking oven that preset temperature is 210 DEG C and heats 16h；
(5) water heating kettle of cooled to room temperature is taken out from baking oven, bottom white precipitate is centrifuged, is washed, and is obtained
Oil-soluble long-persistence nano-luminescent materials, the chemical formula of ontology are ZnGa2O4: 0.4%Cr3+。
From figure 1 it appears that the oil-soluble long-persistence nano-luminescent materials have good crystallinity, diffraction maximum
Position and ZnGa2O4PDF standard card (JCPDS No.86-0415) unanimously, be pure cubic phase 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
Uniform, partial size is about 7nm.
As shown in figure 3, the oil-soluble long-persistence nano-luminescent materials have efficient close under the excitation wavelength of 271nm
Infrared light emission.
As shown in figure 4, after stopping ultraviolet excitation, the near-infrared long afterglow of the oil-soluble long-persistence nano-luminescent materials
In long afterglow signal still with higher 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
Irradiate 3min in advance with formula white LED lamp, after excitation stops it can be observed that long afterglow signal can restore again and almost without
Apparent signal weakens, and the excitation process again of decay of afterglow-as at least may be implemented 6 times.
Embodiment 2
Water-soluble ZnGa2O4: 0.4%Cr3+Preparation-pickling processes of long-persistence nano-luminescent materials
(1) it takes 15mL dehydrated alcohol in conical flask, 115 μ L concentrated hydrochloric acids is added, make its pH=1；
(2) the oil-soluble long-persistence nano-luminescent materials that 40mg above-described embodiment 1 is prepared step (1) is added to match
In the solution of system, 30min, centrifugation are stirred, dehydrated alcohol washs for several times, that is, the water-soluble long-persistence nano is prepared and shines
Material is the acidified modified ZnGa in surface2O4: 0.4%Cr3+。
As can be seen that the position of the diffraction maximum of the water solubility long-persistence nano-luminescent materials and ZnGa from Fig. 6 (a)2O4's
PDF standard card (JCPDS No.86-0415) is pure cubic phase spinel structure, no miscellaneous phase unanimously.
As shown in Fig. 6 (b), which possesses the colloid-stabilised of height in deionized water
Property, it is hydrated partial size almost without changing after placing one month.
Fig. 7 is the ZnGa that Examples 1 and 2 are prepared2O4: 0.4%Cr3+The long afterglow of long-persistence nano-luminescent materials declines
Subtract curve comparison figure, as seen from the figure, before and after pickling processes the long-persistence luminous performance of the nano material almost without changing,
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 embodiment 1 is prepared are dissolved in 5mL hexamethylene
In, 26mg tetrafluoro boric acid nitrous is dissolved in 5mL methylene chloride, and the two is mutually mixed, and stirs 10min, and centrifugation, washing finally produce
Object is dispersed in 10mL dimethylformamide；
(2) 100mg phosphoethanolamine is added in the dimethyl formamide solution of above-mentioned steps (1), stirs 1h, is added third
Ketone precipitating, is washed for several times with dimethylformamide and deionized water, obtains 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 spectroscopy of long-persistence nano-luminescent materials
Comparison diagram, as seen from the figure, after ligand exchange, it can be 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) it takes the biotin (buying from Sigma (China)) of 10mg to be dissolved in 2mL deionized water, the 200 dense ammonia of μ L is added
Water is simultaneously ultrasonic to the transparent clarification of solution；
(2) the water-soluble ZnGa that above-described embodiment of 20mg 2 is prepared2O4: 0.4%Cr3+Long-persistence nano shines
Material is added in above-mentioned solution, stirs 30min, and centrifugation, washing disperse spare in deionized water.
2. being based on biotinylation ZnGa2O4: 0.4%Cr3+The out-phase biological detection of long-persistence nano-luminescent materials:
(1) the gradient standard solution of the Avidin of 100 μ L is added in the microwell plate in 96 holes (by the coating buffer of pH=9.6
It is formulated), 1h is incubated at 37 DEG C；
(2) microwell plate is washed 3 times with PBST, and the ethanol amine confining liquid of 200 μ L is added, is incubated for 1h at 37 DEG C；
(3) the biotinylated ZnGa of the 50 μ g/mL of 100 μ L is added in each hole2O4: 0.4%Cr3+Long-persistence nano hair
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 are set as 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
Well in conjunction 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 water, 18mL dehydrated alcohol and 0.6g sodium hydroxide are mixed into ultrasound, keeps sodium hydroxide complete
Dissolution prepares and obtains the ethanol water of sodium hydroxide；
(2) in the ethanol water for the sodium hydroxide that 6mL oleic acid is added in step (1), 15min is stirred；
(3) 1mL zinc nitrate solution (1mol/L), 2mL gallium nitrate solution (1mol/L) are mutually mixed, ultrasound obtains transparent
Mixed aqueous solution, be then added dropwise in the mixed liquor of step (2) acquisition, uniform stirring 0.5h at room temperature；
(4) obtained mixed solution is transferred to in the water heating kettle of 40mL volume (interior village is polytetrafluoroethylene (PTFE)), by hydro-thermal
Kettle sealing, carries out solvent thermal reaction, is put into the baking oven that preset temperature is 210 DEG C and heats 16h；
(5) water heating kettle of cooled to room temperature is taken out from baking oven, bottom white precipitate is centrifuged, is washed, and is obtained
Oil-soluble long-persistence nano-luminescent materials, the chemical formula of ontology are ZnGa2O4。
Embodiment 6
Oil-soluble MgGa2O4: 0.5%Cr3+The preparation of long-persistence nano-luminescent materials
(1) 6mL deionized water, 15mL dehydrated alcohol and 0.6g sodium hydroxide are mixed into ultrasound, keeps sodium hydroxide complete
Dissolution prepares and obtains the ethanol water of sodium hydroxide；
(2) in the ethanol water for the sodium hydroxide that 6mL oleic acid is added in step (1), 15min is stirred；
(3) by 1mL magnesium nitrate solution (1mol/L), 2mL gallium nitrate solution (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 to in the water heating kettle of 40mL volume (interior village is polytetrafluoroethylene (PTFE)), by hydro-thermal
Kettle sealing, carries out solvent thermal reaction, is put into the baking oven that preset temperature is 200 DEG C and heats for 24 hours；
(5) water heating kettle of cooled to room temperature is taken out from baking oven, bottom white precipitate is centrifuged, is washed, and is obtained
Oil-soluble long-persistence nano-luminescent materials, the chemical formula of ontology are MgGa2O4: 0.5%Cr3+。
Embodiment 7
Oil-soluble MgGa2O4The preparation of long-persistence nano-luminescent materials
(1) 6mL deionized water, 15mL dehydrated alcohol and 0.6g sodium hydroxide are mixed into ultrasound, keeps sodium hydroxide complete
Dissolution prepares and obtains the ethanol water of sodium hydroxide；
(2) in the ethanol water for the sodium hydroxide that 6mL oleic acid is added in step (1), 15min is stirred；
(3) 1mL magnesium nitrate solution (1mol/L), 2mL gallium nitrate solution (1mol/L) are mutually mixed, ultrasound obtains transparent
Mixed aqueous solution, be then added dropwise in the mixed liquor of step (2) acquisition, uniform stirring 0.5h at room temperature；
(4) obtained mixed solution is transferred to in the water heating kettle of 40mL volume (interior village is polytetrafluoroethylene (PTFE)), by hydro-thermal
Kettle sealing, carries out solvent thermal reaction, is put into the baking oven that preset temperature is 200 DEG C and heats for 24 hours；
(5) water heating kettle of cooled to room temperature is taken out from baking oven, bottom white precipitate is centrifuged, is washed, and is obtained
Oil-soluble long-persistence nano-luminescent materials, the chemical formula of ontology are MgGa2O4。
More than, embodiments of the present invention are illustrated.But the present invention is not limited to above embodiment.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention
Within the scope of shield.
Claims (27)
1. a kind of preparation method of gallate long-persistence nano-luminescent materials, which is characterized in that the preparation method includes as follows
Step:
(1) alcohol solution of the hydroxide of alkali metal is prepared；
(2) mixed aqueous solution of gallium salt, other metal salts and optionally chromic salts is 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
Oil-soluble gallate long-persistence nano-luminescent materials are prepared in solvent thermal reaction；The gallate long-persistence nano hair
The chemical formula of luminescent material ontology is MGa2O4:x%Cr3+；Wherein, M is Zn or Mg；0≤x≤10；There is long chain organic acid on its surface；
The gallate has cubic phase spinel structure；
In step (1), the volume ratio of the water and alcohol is 1:2 ~ 10, and the hydroxide of the alkali metal and the mass ratio of water are
0.05~0.2:1；
The concentration of gallium salt is 0.5 ~ 2 mol/L in the mixed aqueous solution；
In step (2), other described metal salts are selected from zinc salt or magnesium salts；
In step (3), the long chain organic acid is selected from least one of oleic acid, linoleic acid；
In step (3), the temperature of the solvent thermal reaction is 150 ~ 280 °C；The time of the solvent thermal reaction is 4-48 h.
2. preparation method according to claim 1, which is characterized in that the hydroxide of alkali metal used in step (1)
For at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, alcohol used in step (1) be methanol, ethyl alcohol, ethylene glycol,
At least one of propyl alcohol, butanol.
3. preparation method according to claim 1, which is characterized in that the hydroxide of alkali metal used in step (1)
For sodium hydroxide, alcohol used in step (1) is ethyl alcohol.
4. preparation method according to claim 1, which is characterized in that in above-mentioned steps (2), the gallium salt is selected from nitric acid
At least one of gallium, gallium chloride, acetic acid gallium, gallium sulfate；The chromic salts is in chromic nitrate, chromium chloride, chromic acetate, chromium sulfate
At least one.
5. preparation method according to claim 1, which is characterized in that the zinc salt is selected from zinc nitrate, zinc chloride, acetic acid
At least one of zinc, zinc sulfate；The magnesium salts is selected from least one of magnesium nitrate, magnesium chloride, magnesium acetate, magnesium sulfate.
6. preparation method according to claim 1, which is characterized in that in above-mentioned steps (2), its in the mixed aqueous solution
His metal salt, gallium salt, chromic salts molar ratio be (0.7 ~ 2): 2:(0 ~ 0.1).
7. preparation method according to claim 1, which is characterized in that the long chain organic acid is selected from oleic acid.
8. preparation method according to claim 1, which is characterized in that in above-mentioned steps (3), the long chain organic acid and alcohol
The volume ratio of aqueous solution is 1:1 ~ 7；The volume ratio of the mixed aqueous solution and alcohol solution is 1:1 ~ 7.
9. preparation method according to claim 1, which is characterized in that the temperature of the solvent thermal reaction is 170 ~ 210 °
C；The time of the solvent thermal reaction is 5-24 h.
10. -9 described in any item preparation methods according to claim 1, which is characterized in that above-mentioned preparation method further includes following
Step:
(4) surface is carried out to the oil-soluble gallate long-persistence nano-luminescent materials that step (3) is prepared to be modified, that is, prepare
Obtain water-soluble gallate long-persistence nano-luminescent materials；
The chemical formula of the water-soluble gallate long-persistence nano-luminescent materials ontology is MGa2O4:x%Cr3+；Wherein, M Zn
Or Mg；0≤x≤10；There is amino on its surface or its surface is acidified modification.
11. preparation method according to claim 10, which is characterized in that in above-mentioned steps (4), the surface modification includes
At least one of pickling processes and ligand exchange method.
12. preparation method according to claim 11, which is characterized in that the pickling processes method are as follows: by step (3)
The oil-soluble gallate long-persistence nano-luminescent materials being prepared are dissolved in the alcoholic solution of hydrochloric acid, and stirring is centrifuged and collects
Nano particle, then washed with alcohol, that is, water-soluble gallate long-persistence nano-luminescent materials are prepared.
13. preparation method according to claim 11, which is characterized in that the ligand exchange processes are as follows: by step (3)
The oil-soluble gallate long-persistence nano-luminescent materials being prepared are dissolved in hexamethylene, and dissolved with tetrafluoro boric acid nitrous
Methylene chloride is mutually mixed, centrifuge washing after stirring, and sediment is dispersed in dimethylformamide, and phosphoric acid ethyl alcohol is added
Amine continues centrifuge washing after stirring, that is, water-soluble gallate long-persistence nano-luminescent materials is prepared.
14. a kind of gallate long-persistence nano-luminescent materials, which is characterized in that the material is any by claim 1-13
What the method described in was prepared.
15. long-persistence nano-luminescent materials according to claim 14, which is characterized in that the gallate long-persistence nano
Luminescent material be it is oil-soluble, the chemical formula of ontology is MGa2O4:x%Cr3+；Wherein, M is Zn or Mg；0≤x≤10；Its table
There is long chain organic acid in face.
16. long-persistence nano-luminescent materials according to claim 15, which is characterized in that 0 x≤5 <.
17. long-persistence nano-luminescent materials according to claim 16, which is characterized in that 0 x≤1 <.
18. long-persistence nano-luminescent materials according to claim 17, which is characterized in that 0 x≤0.6 <.
19. long-persistence nano-luminescent materials according to claim 14, which is characterized in that the gallate long-persistence nano
Luminescent material be it is water-soluble, the chemical formula of ontology is MGa2O4:x%Cr3+；Wherein, M is Zn or Mg；0≤x≤10；Its table
There is amino in face or its surface is acidified modification.
20. long-persistence nano-luminescent materials according to claim 19, which is characterized in that 0 x≤5 <.
21. long-persistence nano-luminescent materials according to claim 20, which is characterized in that 0 x≤1 <.
22. long-persistence nano-luminescent materials according to claim 21, which is characterized in that 0 x≤0.6 <.
23. the described in any item long-persistence nano-luminescent materials of 4-22 according to claim 1, which is characterized in that the nanometer hair
Luminescent material is form of nanoparticles and scale topography is uniform, and in subsphaeroidal, particle size range is in 3-30nm.
24. the described in any item water-soluble gallate long-persistence nano-luminescent materials of claim 19-22 are led in biotechnology
Application in domain, the application is non-medical diagnosis on disease and non-disease is treated.
25. application according to claim 24, which is characterized in that the water-soluble gallate long-persistence nano shines
In the application of field of biological detection after material and biomolecule coupling.
26. application according to claim 24, which is characterized in that the water-soluble gallate long-persistence nano shines
In the application in out-phase fluorescence detection field after material and biomolecule coupling.
27. application according to claim 26, which is characterized in that sent out using the water-soluble gallate long-persistence nano
Luminescent material realizes the detection of out-phase biological as no background fluorescence probe.
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