CN101864298A - Double rare earth coordination compound, Ag at SiO2 fluorescent nano particle doped with the same and preparation method thereof - Google Patents
Double rare earth coordination compound, Ag at SiO2 fluorescent nano particle doped with the same and preparation method thereof Download PDFInfo
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- CN101864298A CN101864298A CN201010185553A CN201010185553A CN101864298A CN 101864298 A CN101864298 A CN 101864298A CN 201010185553 A CN201010185553 A CN 201010185553A CN 201010185553 A CN201010185553 A CN 201010185553A CN 101864298 A CN101864298 A CN 101864298A
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Abstract
The invention relates to a double rare earth coordination compound, an Ag at SiO2 fluorescent nano particle doped with the same and a preparation method thereof. The fluorescent nano particle takes Ag doped with the double rare earth coordination compound Eu3<+>/Tb3<+>-PABA-DTPA-APTMS as an inner core; silicon dioxide with a mesh structure is covered on the surface of the inner core; an active amino group is arranged on the surface of the silicon dioxide, wherein the ratio of the double rare earth coordination Eu3<+>/Tb3<+>-PABA-DTPA-APTMS to the Ag is 1:0.176-0.2; and the mass ratio of the inner core to the silicon dioxide is 1:5-12 and each milligram of nano particle contains 595-630nmol of amino groups. The fluorescence intensity of Eu3<+> and Tb3<+> in the nano particle at the maximum transmitting peak is improved by 3.0 and 3.4 times compared with the fluorescence intensity of a SiO2 fluorescent nano particle doped with the Eu3<+>/Tb3<+>-PABA-DTPA-APTMS without an Ag core; the prepared nano particle is regularly spherical, is uniform in size with the particle size of 120+/-5nm and has favorable monodispersity and light stability; and an amino group is arranged on the surface of the nano particle and directly reacts with a biomolecule without surface modification. The nano particle is expected to be used as a novel rare earth fluorescent probe which is applied to the time distinguishing fluorescent immunoassay for high-sensitivity detection, a biosensor, a biological chip and the like.
Description
Technical field
The present invention relates to a kind of Ag@SiO
2Fluorescent nano particles and preparation method thereof.Particularly a kind of double rare earth coordination compound, its adulterated Ag@SiO
2Fluorescent nano particles and preparation method thereof.
Background technology
Rare earth compounding has the characteristics of long lifetime fluorescence and big Stokes displacement, in recent years, it is prepared into have good aqueous solubility, hud typed silicon nano that good biological intermiscibility, surface are easily modified and be applied to time resolved fluoro-immunoassay, DNA detection and cell imaging
[5]Deng a research focus that becomes rare earth compound.
In at present prepared rare earth compounding fluorescent nano particles, the rare earth compounding of most of nanoparticles parcels only contains a kind of rare earth ion, and the fluorescent nano particles that contains two or more rare earth ion simultaneously seldom has report.Different rare earth ions can send characteristic fluorescence spectrum separately under the exciting of same wavelength light source
[9], and the kind of rare earth ion is different with proportion of composing, presents distinct colors.This special fluorescence phenomenon makes the type nanoparticle have the advantage of only thing in fields such as multiplex fluorescence immunoassay, cell imagings.In recent years, there is report to utilize the metal of silver to strengthen fluorescent effect, rare earth compounding is prepared into hud typed Ag@SiO
2Nanoparticle can improve the fluorescence intensity and the light stability of rare earth compounding silicon nano, and then improves its detection sensitivity as fluorescent probe.This provides new thinking for preparation novel rare-earth complex fluorescent nanoparticle.
Summary of the invention
One of purpose of the present invention is to provide a kind of double rare earth coordination compound.
Two of purpose of the present invention is to provide this complex doped Ag@SiO
2Fluorescent nano particles.
Two of purpose of the present invention is to provide the preparation method of this fluorescent nano particles.
For achieving the above object, the present invention adopts following technical scheme:
The adulterated Ag@SiO of a kind of double rare earth coordination compound
2Fluorescent nano particles is characterized in that this fluorescent nano particles is with double rare earth coordination compound Eu
3+/ Tb
3+The adulterated silver of-PABA-DTPA-APTMS is kernel, is coated with cancellated silicon-dioxide at core surface, has the active amino group on surface, titanium dioxide osmanthus, wherein double rare earth coordination compound Eu
3+/ Tb
3+-PABA-DTPA-APTMS with the mass ratio of silver is: 1: 0.176～0.2; The mass ratio of kernel and silicon-dioxide is: 1: 5～12, and every milligram of nanoparticle contains 595～630nmol amino.
Above-mentioned fluorescent nano particles is a regular spherical, and median size is 115～125nm nm, and wherein the thickness of the particle diameter of kernel and silicon shell is respectively: 16nm and 52nm.
A kind of adulterated Ag@SiO of above-mentioned double rare earth coordination compound for preparing
2The method of fluorescent nano particles is characterized in that the concrete steps of this method are:
A) with soluble E u salt and soluble T b salt by mixing in the water-soluble solution of 1: 0.8～1.3 mol ratio, add again and cooperate presoma PABA-DTPA-APTMS, make the presoma and the ratio of the total mole number of two kinds of rare earth ions be: 1: 0.9～1.1, stirring reaction keeps in Dark Place after spending the night, and gets double rare earth coordination compound Eu
3+/ Tb
3+-PABA-DTPA-APTMS solution;
B) Triton X-100, n-hexyl alcohol, hexanaphthene, 3-aminopropyl trimethoxysilane and redistilled water were pressed 448: 446: 1864: 1～500: 500: 2000: 1 volume ratio is mixed the back and is formed the w/o type microemulsion, adds step a gained double rare earth coordination compound Eu then
3+/ Tb
3+-PABA-DTPA-APTMS solution and AgNO
3The aqueous solution, wherein double rare earth coordination compound Eu
3+/ Tb
3+-PABA-DTPA-APTMS and AgNO
3Mol ratio be 1: 10～15, AgNO
3With the mol ratio of above-mentioned n-hexyl alcohol be 1: 437～500, stirring at room is even, adds reductive agent, this reductive agent and AgNO
3Mol ratio be 178～200: 1, add tetraethoxy and ammoniacal liquor, wherein tetraethoxy, ammoniacal liquor and AgNO
3Mol ratio be 96:: 572:: 1～100: 600: 1, stirring reaction is 23～26 hours under the room temperature, add tetraethoxy, ammoniacal liquor and 3-aminopropyl trimethoxysilane again, wherein the mol ratio of tetraethoxy, ammoniacal liquor and 3-aminopropyl trimethoxysilane is 17.1: 102: 1～20: 110: 1,3-aminopropyl trimethoxysilane and AgNO
3Mol ratio be 5.6: 1～10: 1; Continue stirring reaction after 24 hours, add the acetone breakdown of emulsion, the centrifugal supernatant liquor of removing alternately washs with dehydrated alcohol and redistilled water then and removes tensio-active agent and unreacted raw material impurity, after the vacuum-drying, obtains Eu
3+/ Tb
3+The adulterated Ag@SiO of-PABA-DTPA-APTMS
2Fluorescent nano particles.
Above-mentioned soluble E u salt is: EuCl
3
Above-mentioned soluble T b salt is: TbCl
3
Above-mentioned reductive agent is: hydrazine hydrate, Trisodium Citrate or sodium borohydride.
The concrete preparation method of above-mentioned cooperation presoma PABA-DTPA-APTMS is: para-amino benzoic acid PABA is dissolved in the methyl-sulphoxide, under the vigorous stirring, add diethylene triamine pentacetic acid (DTPA) DTPA, stirring reaction is after 8 hours, add 3-aminopropyl trimethoxysilane APTMS again, stirring is spent the night; Wherein the mol ratio of PABA, DTPA and APTMS is: 1.1: 1: 1.55～1.5: 1: 2.0, described cooperation presoma PABA-DTPA-APTMS structural formula be:
The present invention utilizes reverse microemulsion process successfully to prepare and characterizes the surface and has amino double rare earth coordination compound Eu
3+/ Tb
3+The adulterated Ag@SiO of-PABA-DTPA-APTMS
2Fluorescent nano particles.The result shows Eu in this nanoparticle
3+With Tb
3+In the fluorescence intensity at maximum emission peak place than Eu
3+/ Tb
3+The adulterated SiO that does not have galactic nucleus of-PABA-DTPA-APTMS
2Fluorescent nano particles has improved 3.0 and 3.4 times respectively, and it is spherical that prepared nanoparticle is rule, and size evenly, particle diameter is 120 ± 5nm, have good monodispersity and light stability, nanoparticle surface has amino, can not need to carry out finishing and direct and biomolecular reaction.This nanoparticle is expected time resolved fluoro-immunoassay, biosensor, biochip of being applied to as a kind of novel rare-earth fluorescent probe highly sensitive detection etc.
Description of drawings
Fig. 1 is Eu of the present invention
3+/ Tb
3+The adulterated SiO of-DTPA-PABA
2The TEM photo of fluorescent nano particles.
Fig. 2 is Eu of the present invention
3+/ Tb
3+The adulterated SiO of-DTPA-PABA
2The transmission electron microscope photo of fluorescent nano particles.
Fig. 3 is uv-visible absorption spectra figure, and wherein (A) is Eu
3+/ Tb
3+The adulterated Ag@SiO of-PABA-DTPA-APTMS
2Fluorescent nano particles (B) is Eu
3+/ Tb
3+The adulterated SiO of-PABA-DTPA-APTMS
2Fluorescent nano particles.
Fig. 4 is Eu
3+/ Tb
3+The time resolution fluorescence spectral figure of-PABA-DTPA-APTMS title complex (1.0mg/mL) in water
Fig. 5 is Eu
3+/ Tb
3+The adulterated Ag@SiO of-PABA-DTPA-APTMS
2Fluorescent nano particles (B, 1.0mg/mL) and Eu
3+/ Tb
3+The adulterated SiO of-PABA-DTPA-APTMS
2Fluorescent nano particles (C, 1.0mg/mL) time resolution fluorescence spectral in water.
Fig. 6 is Eu
3+/ Tb
3+The adulterated SiO of-PABA-DTPA-APTMS
2Nanoparticle (A) and Eu
3+/ Tb
3+The adulterated Ag@SiO of-PABA-DTPA-APTMS
2The light stability curve of nanoparticle (B).
Fig. 7 is APTMS (A), Eu
3+/ Tb
3+The adulterated Ag@SiO of-PABA-DTPA-APTMS
2Fluorescent nano particles (B) and Eu
3+/ Tb
3+The adulterated SiO of-PABA-DTPA-APTMS
2Uv-visible absorption spectra behind fluorescent nano particles (C) and the ninhydrin reaction.
The working curve that Fig. 8 measures for amino group concentration.
Embodiment
One, reagent and instrument:
U-3010 ultraviolet-visible spectrophotometer, CR21GII supercentrifuge (Japanese Hitachi company); JEM-2010F high resolution transmission electron microscopy (Jeol Ltd.); The multi-functional microplate reader of Varioskan flash (U.S. Thermo company).PABA, DTPA, APTMS, Triton X-100 and TbCl
6.6H
2O purchases the company in Sigma; Eu
2O
3(99.99%) purchases in Tongna Environment Protection Sci. ﹠ Tech. Co., Ltd., Shanghai; All the other reagent are purchased the Shanghai chemical reagents corporation in Chinese Medicine group, and mentioned reagent is analytical pure.Experimental water is a redistilled water.
Two, experimentation
1. cooperate the preparation of presoma PABA-DTPA-APTMS: 0.019 gram PABA is dissolved among the DMSO of 0.6mL, then 0.05 gram DTPA is joined in the DMSO solution that above-mentioned vigorous stirring, after the stirring at room 8 hours, 0.035mLAPTMS is joined in the said mixture, stirring is spent the night.
2. double rare earth coordination compound Eu
3+/ Tb
3+The preparation of-PABA-DTPA-APTMS: with 0.01mol/L EuCl
3With 0.01mol/L TbCl
3Anhydrous solution by the mixing of 1 to 1 volume ratio after, add a certain amount of cooperation presoma PABA-DTPA-APTMS, make presoma equate with the amount of substance of two kinds of rare earth ions, keep in Dark Place after stirring reaction spends the night.
3.Eu
3+/ Tb
3+The adulterated Ag@SiO of-DTPA-PABA
2The preparation of fluorescent nano particles
The redistilled water of hexanaphthene, 5 μ LAPTMS and the 0.25mL of the n-hexyl alcohol of Triton X-100, the 2.23mL of 2.24mL, 9.32mL is mixed the back form (W/O) type microemulsion, in above-mentioned microemulsion, add the presoma Eu of 50 μ L then
3+/ Tb
3+The AgNO of-PABA-DTPA-APTMS solution and 25 μ L0.02mol/L
3The aqueous solution, stirring at room added hydrazine hydrate 50 μ L after 30 minutes, then added TEOS and the 100uL ammoniacal liquor initiated polymerization of 100 μ L.Stirring reaction is 24 hours under the room temperature, add 100 μ L TEOS, 100 μ L ammoniacal liquor and 5 μ L APTMS, continue stirring reaction after 24 hours, adding about 20mL acetone is precipitated out Nano microsphere, remove supernatant liquor after centrifugal (about 12000 rev/mins), it is inferior to remove impurity such as tensio-active agent and unreacted raw material alternately to give a baby a bath on the third day after its birth with dehydrated alcohol and redistilled water then, after the vacuum-drying, obtains Eu
3+/ Tb
3+The adulterated Ag@SiO of-PABA-DTPA-APTMS
2Fluorescent nano particles.
Adopt and use the same method, do not adding AgNO
3Situation under prepare Eu
3+/ Tb
3+The adulterated SiO of-PABA-DTPA-APTMS
2Fluorescent nano particles.
The adulterated SiO of double rare earth coordination compound
2And the adulterated Ag@SiO of double rare earth coordination compound
2The fluorescent nano particles transmission electron microscope photo as shown in Figure 1.As seen from the figure, the adulterated SiO of double rare earth coordination compound
2Nanoparticle presents spherical particle, and its particle diameter is 90 ± 5nm, does not assemble mutually between the nanoparticle, has good monodispersity.Fig. 2 is the adulterated Ag@SiO of double rare earth coordination compound
2The high power Electronic Speculum figure of nanoparticle, it is spherical that nanoparticle is, and its particle diameter is 120 ± 5nm, and wherein the particle diameter of galactic nucleus is 16nm, and the thickness of silicon shell is about 52nm.
Fig. 3 is Eu
3+/ Tb
3+The adulterated Ag@SiO of-PABA-DTPA-APTMS
2Fluorescent nano particles and Eu
3+/ Tb
3+The adulterated SiO of-PABA-DTPA-APTMS
2The fluorescent nano particles uv-visible absorption spectra.As can be seen from the figure: Eu
3+/ Tb
3+The adulterated Ag@SiO of-PABA-DTPA-APTMS
2Fluorescent nano particles has argent to produce the surface plasma body resonant vibration charateristic avsorption band at the 415nm place, and Eu
3+/ Tb
3+The adulterated SiO of-PABA-DTPA-APTMS
2Fluorescent nano particles does not have absorption peak at the 415nm place.
Eu
3+/ Tb
3+-PABA-DTPA-APTMS title complex, Eu
3+/ Tb
3+The adulterated Ag@SiO of-PABA-DTPA-APTMS
2Fluorescent nano particles and Eu
3+/ Tb
3+The adulterated SiO of-PABA-DTPA-APTMS
2The time resolution fluorescence spectral of fluorescent nano particles as shown in Figure 4 and Figure 5.Their maximum excitation wavelength is respectively 258nm, 273nm and 258nm, because terbium ion
5D
4→
7F
6,5,4With europium ion
5D
0→
7F
2,4The cause of transition, double rare earth coordination compound and two kinds of nanoparticles all 489,543, there is emission peak at 589nm, 615nm and 694nm place, wherein the emission peak at 543nm and 615nm place is respectively the maximum emission peak of terbium ion and europium ion.And double rare earth coordination compound and two kinds of fluorescent nano particles all have the excitation band of broad, sharp-pointed emission peak, all about 10～15nm, the fluorescigenic Stokes displacement of nanoparticle institute is very big for peak width at half height, and this is highly beneficial to the interference of measuring for overcoming the light at random that causes because of exciting light.
In addition, from figure, can also draw: Eu
3+/ Tb
3+The adulterated Ag@SiO of-PABA-DTPA-APTMS
2In the fluorescent nano particles terbium ion and europium ion in the fluorescence intensity at maximum emission peak place than Eu
3+/ Tb
3+The adulterated SiO of-PABA-DTPA-APTMS
2Fluorescent nano particles has improved 3.4 and 3.0 times respectively, and this is because at Eu
3+/ Tb
3+The adulterated Ag@SiO of-PABA-DTPA-APTMS
2In the nanoparticle, because metal strengthens fluorescent effect, i.e. the interaction of the surface plasma body resonant vibration of argent and rare earth compounding fluorescence molecule strengthens the fluorescence intensity of rare earth compounding fluorescence molecule.
After measured, Eu
3+/ Tb
3+-PABA-DTPA-APTMS title complex, Eu
3+/ Tb
3+The adulterated Ag@SiO of-PABA-DTPA-APTMS
2Fluorescent nano particles and Eu
3+/ Tb
3+The adulterated SiO of-PABA-DTPA-APTMS
2The fluorescence lifetime of fluorescent nano particles is respectively 0.81,0.93 and 0.91ms, show that three kinds of materials all have long fluorescence lifetime, but the fluorescence lifetime of two kinds of fluorescent nano particles is all than Eu
3+/ Tb
3+-PABA-DTPA-APTMS title complex is long, and this may be because the silicon-dioxide shell has played the provide protection to inner nuclear material.
Eu
3+/ Tb
3+The adulterated SiO of-PABA-DTPA-APTMS
2Nanoparticle and Eu
3+/ Tb
3+The adulterated Ag@SiO of-PABA-DTPA-APTMS
2Nanoparticle under xenon lamp irradiation its fluorescence intensity along with time changing curve as shown in Figure 6.As seen from the figure, obvious variation does not take place its fluorescence intensity of xenon lamp irradiation back of 60 minutes in the fluorescence intensity of two kinds of nanoparticles, illustrates that they all have strong anti-photobleaching sexuality.Reason is because the provide protection of silica shell can reduce the photobleaching of external light source to fluorescence molecule effectively.
1.2.4 the mensuration of nanoparticle surface amino
In 3 5.0mL centrifuge tubes, add 5 μ L APTMS, 1.0mg Eu respectively
3+/ Tb
3+The adulterated Ag@SiO of-PABA-DTPA-APTMS
2And 1.0mg Eu
3+/ Tb
3+The adulterated SiO of-PABA-DTPA-APTMS
2Nanoparticle, the ninidrine solution and the 1.5mL water that add 0.5mL 0.056mol/L then to every centrifuge tube, the last NaOH solution that in centrifuge tube, adds 0.1mL 0.1mol/L respectively, 80 ℃ of heating in water bath 5 minutes, the cooling back is measured its uv-visible absorption spectra respectively with the U-3010 ultraviolet-visible spectrophotometer and is reached absorption value at the 570nm place.
Utilizing aminocompound and ninhydrin reaction to generate the bluish voilet material has the principle of obvious absorption peaks to measure amino existence at the 570nm place.Experimental result as shown in Figure 7, generating the bluish voilet material behind APTMS and the ninhydrin reaction has tangible absorption peak at the 570nm place, and Eu
3+/ Tb
3+The adulterated Ag@SiO of-PABA-DTPA-APTMS
2Fluorescent nano particles and Eu
3+/ Tb
3+The adulterated SiO of-PABA-DTPA-APTMS
2Fluorescent nano particles has absorption peak too at the 570nm place.Experimental result shows that all there is amino existence on two kinds of fluorescent nano particles surfaces.Because prepared nanoparticle surface directly has amino active group, it can be directly and biomolecular reaction, so this nanoparticle can be directly used in the mark of biomolecules, saved loaded down with trivial details steps such as finishing.
In addition, the surface amino groups of nanoparticle is carried out quantitative assay, done standard working curve with the absorbancy that APTMS measures the 570nm place as reference material, as shown in Figure 8.Nanoparticle used the same method measure the absorbancy at 570nm place, substitution straight-line equation y=0.001x-0.011 can calculate the quantity of nanoparticle surface amino.It is Eu about 120nm that experiment records adding prepared diameter under the condition of 5 μ LAPTMS
3+/ Tb
3+The adulterated Ag@SiO of-PABA-DTPA-APTMS
2Fluorescent nano particles contains the amino of the 611nmol that has an appointment for every milligram.
Claims (7)
1. adulterated Ag@SiO of double rare earth coordination compound
2Fluorescent nano particles is characterized in that this fluorescent nano particles is with double rare earth coordination compound Eu
3+/ Tb
3+The adulterated silver of-PABA-DTPA-APTMS is kernel, is coated with cancellated silicon-dioxide at core surface, has the active amino group on surface, titanium dioxide osmanthus, wherein double rare earth coordination compound Eu
3+/ Tb
3+-PABA-DTPA-APTMS with the mass ratio of silver is: 1: 0.176～0.2; The mass ratio of kernel and silicon-dioxide is: 1: 5～12, and every milligram of nanoparticle contains 595～630nmol amino.
2. the adulterated Ag@SiO of double rare earth coordination compound according to claim 2
2Fluorescent nano particles is characterized in that this fluorescent nano particles is a regular spherical, and median size is 115～125nm nm, and wherein the thickness of the particle diameter of kernel and silicon shell is respectively: 16nm and 52nm.
3. one kind prepares the adulterated Ag@SiO of double rare earth coordination compound according to claim 1
2The method of fluorescent nano particles is characterized in that the concrete steps of this method are:
A. with soluble E u salt and soluble T b salt by mixing in the water-soluble solution of 1: 0.8～1.3 mol ratio, add again and cooperate presoma PABA-DTPA-APTMS, make the presoma and the ratio of the total mole number of two kinds of rare earth ions be: 1: 0.9～1.1, stirring reaction keeps in Dark Place after spending the night, and gets double rare earth coordination compound Eu
3+/ Tb
3+-PABA-DTPA-APTMS solution;
B. Triton X-100, n-hexyl alcohol, hexanaphthene, 3-aminopropyl trimethoxysilane and redistilled water were pressed 448: 446: 1864: 1～500: 500: 2000: 1 volume ratio is mixed the back and is formed the w/o type microemulsion, adds step a gained double rare earth coordination compound Eu then
3+/ Tb
3+-PABA-DTPA-APTMS solution and AgNO
3The aqueous solution, wherein double rare earth coordination compound Eu
3+/ Tb
3+-PABA-DTPA-APTMS and AgNO
3Mol ratio be 1: 10～15, AgNO
3With the mol ratio of above-mentioned n-hexyl alcohol be 1: 437～500, stirring at room is even, adds reductive agent, this reductive agent and AgNO
3Mol ratio be 178～200: 1, add tetraethoxy and ammoniacal liquor, wherein tetraethoxy, ammoniacal liquor and AgNO
3Mol ratio be 96:: 572:: 1～100: 600: 1, stirring reaction is 23～26 hours under the room temperature, add tetraethoxy, ammoniacal liquor and 3-aminopropyl trimethoxysilane again, wherein the mol ratio of tetraethoxy, ammoniacal liquor and 3-aminopropyl trimethoxysilane is 17.1: 102: 1～20: 110:1,3-aminopropyl trimethoxysilane and AgNO
3Mol ratio be 5.6: 1～10: 1; Continue stirring reaction after 24 hours, add the acetone breakdown of emulsion, the centrifugal supernatant liquor of removing alternately washs with dehydrated alcohol and redistilled water then and removes tensio-active agent and unreacted raw material impurity, after the vacuum-drying, obtains Eu
3+/ Tb
3+The adulterated Ag@SiO of-PABA-DTPA-APTMS
2Fluorescent nano particles.
4. the adulterated Ag@SiO of double rare earth coordination compound according to claim 3
2The method of fluorescent nano particles is characterized in that described soluble E u salt is: EuCl
3
5. the adulterated Ag@SiO of double rare earth coordination compound according to claim 3
2The method of fluorescent nano particles is characterized in that described soluble T b salt is: TbCl
3
6. the adulterated Ag@SiO of double rare earth coordination compound according to claim 3
2The method of fluorescent nano particles is characterized in that described reductive agent is: hydrazine hydrate, Trisodium Citrate or sodium borohydride.
7. the adulterated Ag@SiO of double rare earth coordination compound according to claim 3
2The method of fluorescent nano particles, the concrete preparation method who it is characterized in that described cooperation presoma PABA-DTPA-APTMS is: para-amino benzoic acid PABA is dissolved in the methyl-sulphoxide, under the vigorous stirring, add diethylene triamine pentacetic acid (DTPA) DTPA, behind the stirring reaction 8 hours, add 3-aminopropyl trimethoxysilane APTMS again, stirring is spent the night; Wherein the mol ratio of PABA, DTPA and APTMS is: 1.1: 1: 1.55～1.5: 1: 2.0, described cooperation presoma PABA-DTPA-APTMS structural formula be:
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102650596A (en) * | 2011-02-24 | 2012-08-29 | 中国科学技术大学 | Time-resolved fluorescence spectrofluorometer boron measuring instrument control unit and boron measuring method applying same |
| CN103143721A (en) * | 2013-03-14 | 2013-06-12 | 山东大学 | Preparation method of Ag@SiO2 core-shell structure nano composite |
| CN104447524A (en) * | 2014-11-20 | 2015-03-25 | 陕西师范大学 | Amphiphilic Eu (III) complex, preparation method thereof and application thereof in sensing identification of citric acid/isocitric acid |
| CN104946236A (en) * | 2015-04-28 | 2015-09-30 | 上海大学 | Silver/graphene-coated silicon dioxide composite upconversion nanocrystal and preparation method thereof |
| WO2016020939A1 (en) | 2014-08-06 | 2016-02-11 | Council Of Scientific & Industrial Research | Para-aminobenzoic acid sensitized terbium doped laf3 nanoparticles for detection of explosive nitro compounds |
| CN112341502A (en) * | 2020-10-14 | 2021-02-09 | 内蒙古大学 | Preparation method of core-shell type rare earth complex |
-
2010
- 2010-05-26 CN CN201010185553A patent/CN101864298A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| KADIR等: "Fluorescent Core-Shell Ag@SiO2 Nanocomposites for Metal-Enhanced Fluorescence and Single Nanoparticle Sensing Platforms", 《J. A. C. S.》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102650596A (en) * | 2011-02-24 | 2012-08-29 | 中国科学技术大学 | Time-resolved fluorescence spectrofluorometer boron measuring instrument control unit and boron measuring method applying same |
| CN102650596B (en) * | 2011-02-24 | 2014-06-18 | 中国科学技术大学 | Time-resolved fluorescence spectrofluorometer boron measuring instrument control unit and boron measuring method applying same |
| CN103143721A (en) * | 2013-03-14 | 2013-06-12 | 山东大学 | Preparation method of Ag@SiO2 core-shell structure nano composite |
| CN103143721B (en) * | 2013-03-14 | 2014-08-06 | 山东大学 | Preparation method of Ag@SiO2 core-shell structure nano composite |
| WO2016020939A1 (en) | 2014-08-06 | 2016-02-11 | Council Of Scientific & Industrial Research | Para-aminobenzoic acid sensitized terbium doped laf3 nanoparticles for detection of explosive nitro compounds |
| CN104447524A (en) * | 2014-11-20 | 2015-03-25 | 陕西师范大学 | Amphiphilic Eu (III) complex, preparation method thereof and application thereof in sensing identification of citric acid/isocitric acid |
| CN104447524B (en) * | 2014-11-20 | 2016-05-04 | 陕西师范大学 | Amphipathic Eu (III) complex and preparation method thereof and the application in the identification of citric acid/isocitric acid sensing |
| CN104946236A (en) * | 2015-04-28 | 2015-09-30 | 上海大学 | Silver/graphene-coated silicon dioxide composite upconversion nanocrystal and preparation method thereof |
| CN112341502A (en) * | 2020-10-14 | 2021-02-09 | 内蒙古大学 | Preparation method of core-shell type rare earth complex |
| CN112341502B (en) * | 2020-10-14 | 2023-10-24 | 内蒙古大学 | Preparation method of core-shell rare earth complex |
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