CN107384375B - A kind of rare earth luminous silicon dioxide hybrid materials and its preparation method and application - Google Patents
A kind of rare earth luminous silicon dioxide hybrid materials and its preparation method and application Download PDFInfo
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Abstract
Rare earth luminous silicon dioxide hybrid materials disclosed in this invention and its preparation method and application, stablize the method for oily phase (γ-glycidyl ether oxygen propyl trimethoxy silicane (γ-MPS)) using nano silica, make TEOS slowly in oil droplets polycondensation, to which the rare earth compounding to shine is successfully wrapped in inorganic matrix, the SiO 2 hybrid nanosphere to shine based on rare-earth europium ion is obtained, and controls the homogeneity and grain size of optimization rare earth ion to shine with hybridized nanometer ball by condition；And rare-earth hybridized nanosphere is used as fluorescent optical sensor, go the content of copper ion in qualitative and quantitative detection water；Rare earth luminous silicon dioxide hybrid materials provided by the present invention also show relatively better monodispersity, and future is expected to the fields such as fluorescence imaging and the bio-sensing detection applied to cell.
Description
Technical field
The invention belongs to technical field of biological, and in particular to a kind of rare earth luminous silicon dioxide hybrid materials and its system
Preparation Method and application.
Background technique
Heavy metal pollution is always the topic that the mankind earnestly worry, heavy in environment with the industrialized aggravation of society
The content of metal is also being continuously increased, and wherein copper ion may in the exceeded of people's in-vivo content as a kind of important metal
It will cause human metabolism function's disorder, seriously endanger health, or even the life security of people can be threatened.As a kind of micro
Element, copper ion are widely present in the internal of plant, animal and people, at the same it can auxiliary enzymes and protein participate in it is various
Metabolic process.Its physicochemical properties results in various special-purposes of the copper in human lives.Copper has good conduction, leads
It is hot, it can be used as excellence conductor electrically and thermally, ductility can be used for making copper wire, transmit electric power, and be widely used in each in life
A field.It investigates according to incompletely statistics, every year since the copper that artificial or other reasons flow into natural environment flow promoter system contains
Amount can reach more than one hundred million tons.The standard of Drinking Water in China is that the content of copper ion must not exceed 20 μM.Copper is teleorganic micro
One of element, lack and it is excessive body can be damaged, lead to internal metabolic dysfunction, physiological dysfunctions and other
Pathological state.When Copper in Body ion concentration is higher, it is easy to cause body intracorporal organ great burden, common cirrhosis,
Two kinds of diseases of liver ascites are precisely due to content of copper ion is excessively high causes in vivo.Conversely, will lead to when lacking copper ion in human body
Pigmented enzyme in brain cell is reduced, and activity decline leads to confusion of thinking, decrease of memory.Human body hematopoiesis be unable to do without and needs copper
The forming process of the ceruloplasmin of ion synthesis, cardiovascular elastin laminin and Collagen is also required to the ginseng of copper ion
With.In addition, containing certain copper ion in superoxide dismutase, the life of tumour cell can be inhibited to a certain extent
It is long, and can boost metabolism, delay senescence.Copper ion is suitably the precondition of dimension life entity normal function in concentration,
Therefore, the content of accurate analysis measurement copper ions in sample detects the health of the mankind, drinking water and food safety, environmental quality
Deng with direct relation.And by direct method and the deployable detection to copper ion of indirect method, for utilizing Cu2+The object of itself
Reason and chemical property and the method directly tested determinand is known as direct method, common include molecular absorption spectrometry,
Chemical sensitisation method, atomic absorption method, electrochemical methods；And indirect method is the signal intensity or copper generated using supermolecular mechanism
Specific chemical between ion and indicator (chemical molecular probe) reacts the method tested and analyzed to copper ion, including
Copper ion fluorescent molecular probe method (fluorescent spectrometry) and copper ion indicator method.
In recent years, various functional materials are increasingly developed out with the development of science and technology, especially with rare earth luminous function material
Expect especially noticeable.4f5d electron configuration in the atom of rare earth element containing underfill, therefore, the 4f electronics of rare earth ion
Transition can be carried out in f layers, can also the generation transition from f layers to d layers, to show spectrum abundant, can cover from
The full bands of a spectrum fluorescent emission of ultraviolet, visible infrared region.In addition, also just because of this transition regime, so that rare earth luminous material
There is material longer fluorescence lifetime, excitation purity height, emission peak to be distributed, and wide, absorbing ability is strong, narrowband fluorescent emission；Anti-light bleaching energy
Power is strong, is able to maintain longer service life, make rare earth and rare earth luminous correlation function material get growing concern for and
Research.In addition to other than LED illumination, display and biological NMR imaging field are widely applied, with the demand and scale in market
Constantly expand, Rare Earth Functional Materials also start to be able to development and application on the light sources equipment such as medical treatment disinfection, natural radiant.
Summary of the invention
In order to solve the problems in the existing technology, the present invention provide a kind of rare earth luminous silicon dioxide hybrid materials and
Preparation method and application.
The technical solution adopted by the invention is as follows:
In a first aspect, the present invention provides a kind of preparation method of rare earth luminous silicon dioxide hybrid materials, including it is as follows
Step:
(1) ratio for being 0.01~0.05:1 according to the volume ratio of tetraethyl orthosilicate and L-arginine solution, by positive silicon
It is stirred to react 16~30h after L-arginine solution is added in sour tetra-ethyl ester, then under the conditions of 40~80 DEG C, silicon dioxde solution is made；
(2) existing for the organic solvent and water under the conditions of, by rare-earth salt solution and 4,4,4- tri- fluoro- 1-2- naphthalene -1,3- fourths
After the mixing of alkane diketone, 10~14h of insulation reaction under the conditions of 60~100 DEG C is filtered, is dried to obtain rare earth luminescent material,
In, the molar ratio of rare earth element is 1~5:1's in described 4,4,4- tri- fluoro- 1-2- naphthalene -1,3- butanediones and rare-earth salt solution
Ratio；
(3) step (2) resulting rare earth luminescent material is dissolved in after tetrahydrofuran and obtains mixed solution, then by the mixing
Solution is mixed with γ-glycidyl ether oxygen propyl trimethoxy silicane, step (1) resulting silicon dioxde solution, is stirred to react
10~60min adds ethyl orthosilicate, reacts 16~30h, and rare earth luminous titanium dioxide sila is made through centrifugation, cleaning, drying
Change material；Wherein, the volume ratio of the quality of the resulting rare earth luminescent material of the step (2) and the tetrahydrofuran be 0.04~
1:1(g/ml)；The quality of the resulting rare earth luminescent material of the step (2) and the body of the step (1) resulting silica
Product is than being 30~40:1 (g/ml).
Preferably, in the step (1), the volume ratio of the tetraethyl orthosilicate and L-arginine solution is 0.02:1.
Preferably, in the step (1), in the L-arginine solution concentration of L-arginine be 1~10mmol/L (into
One step is preferably 6mmol/L).
It is understood that the present invention is to described in step (1) mixing tetraethyl orthosilicate with L-arginine solution
Method is not particularly limited, using the mixed method of this field routine.
Preferably, in the step (1), described the step of mixing tetraethyl orthosilicate with L-arginine solution, tool
Body includes: that tetraethyl orthosilicate is added in L-arginine solution to mix.
Preferably, the rate stirred in the step (1) is 50~1500r/min (further preferably 1000r/min).
Preferably, in the step (1), the partial size of silica is 10~20nm (into one in the silicon dioxde solution
Step is preferably 15nm).
It is understood that the present invention is not particularly limited the dosage of water described in the step (2).Optionally,
The molar ratio of rare earth element and the water is 1:1~6 in the rare-earth salt solution.
It is understood that the present invention is not particularly limited the dosage of organic solvent described in the step (2).It is excellent
Selection of land, in the step (2), described 4,4,4- tri- fluoro- 1-2- naphthalene -1,3- butanedione solution are by 4,4,4- tri- fluoro- 1-2-
Naphthalene -1,3- butanedione be dissolved in organic solvent be made, wherein 4,4,4- tri- fluoro- 1-2- naphthalene -1,3- butanediones mole with have
The ratio of the volume of solvent is 0.02~0.5:1 (mmol/ml) (further preferably 0.1:1 (mmol/ml)).
It will be appreciated that rare-earth salts is dissolved in water, 4,4,4- tri- fluoro- 1-2- naphthalene -1,3- butanediones are dissolved in organic solvent, lead to
4,4,4- tri- fluoro- 1-2- naphthalene -1,3- butanediones in rare earth ion and the organic phase that stirs and may make in water phase are crossed to be sufficiently mixed,
Accelerate reaction, improves the yield of final product.
Preferably, in the step (2), described 4,4,4- tri- fluoro- 1-2- naphthalene -1,3- butanediones and rare earth element rub
You are than being 3:1.
Preferably, in the step (2), the organic solvent includes but is not limited to ethyl alcohol, methanol, propyl alcohol, butanol, acetone
One or more of.
It is further preferred that the organic solvent is ethyl alcohol in the step (2).
Preferably, in the step (2), the rare-earth salt solution includes but is not limited to rare earth nitrate solution, rare earth chlorine
One or more of compound solution, rare-earth oxalate solution.
Preferably, in the step (2), the rare earth element in the rare-earth salt solution include but is not limited to europium, dysprosium, samarium,
One or more of terbium.
It is further preferred that the rare earth element in the rare-earth salt solution is europium in the step (2).
Preferably, the step (2), specifically includes:
4,4,4- tri- fluoro- 1-2- naphthalene -1,3- butanediones are dissolved in organic solvent, be added alkaline solution, adjust pH to
6.5~7.5 (further preferably 7), according still further to mole of 4,4,4- tri- fluoro- 1-2- naphthalene -1,3- butanediones and rare earth element
Than the ratio for 1~5:1, by rare-earth salt solution and 4, after 4,4- tri- fluoro- 1-2- naphthalene -1,3- butanedione mixing, 60~100
10~14h of insulation reaction under the conditions of DEG C (further preferably 80 DEG C), is filtered, is dried to obtain rare earth luminescent material.
It is understood that step (2) neutral and alkali solution is well known to those skilled in the art for adjusting the alkali of pH value
Property solution.It is further preferred that the alkaline solution includes but is not limited to sodium hydroxide solution, hydroxide in the step (2)
One or more of potassium solution, ammonium hydroxide.
It is further preferred that the alkaline solution is sodium hydroxide solution, wherein the hydrogen-oxygen in the step (2)
The concentration for changing the sodium hydroxide of sodium solution is 0.2~2mol/L.
It is further preferred that in the step (2), the molecular structural formula of the rare earth luminescent material are as follows:
Preferably, in the step (3), the quality of the resulting rare earth luminescent material of the step (2) and the tetrahydro furan
The volume ratio muttered is 0.043~0.086:1 (g/ml) (further preferably 0.043~0.078:1 (g/ml)).
Preferably, in the step (3), the quality of the resulting rare earth luminescent material of the step (2) and the step (1)
The volume ratio of resulting silica is 32.5:1 (g/ml).
It is understood that the present invention in step (3) " by the mixed solution and γ-glycidyl ether oxygen propyl three
The method of the resulting silicon dioxde solution mixing of methoxy silane, step (1) " does not have special limitation, can be using using this
The technical solution mixed known to the technical staff of field.Preferably, described " by the mixed solution and γ-glycidol
It the step of resulting silicon dioxde solution mixing of ether oxygen propyl trimethoxy silicane, step (1) ", specifically includes: by the mixing
Solution, silicon dioxde solution are added sequentially to mix in γ-glycidyl ether oxygen propyl trimethoxy silicane.
Preferably, in the step (3), the rare earth luminous silicon dioxide hybrid materials are near-spherical.
Preferably, in the step (3), the partial size of the rare earth luminous silicon dioxide hybrid materials is 100~300nm.
It is further preferred that in the step (3), the partial size of the rare earth luminous silicon dioxide hybrid materials is 110~
130nm。
Second aspect is using such as first party of the present invention the present invention provides a kind of rare earth luminous silicon dioxide hybrid materials
The preparation method of rare earth luminous silicon dioxide hybrid materials described in face is made.
The third aspect, rare earth luminous silicon dioxide hybrid materials as described in second aspect answering in terms of cation recognition
With.
Preferably, the cation is copper ion.
It is understood that rare earth luminous silicon dioxide hybrid materials disclosed in this invention, utilize nano silica
The method for stablizing oil phase (γ-glycidyl ether oxygen propyl trimethoxy silicane (γ-MPS)), so that tetraethyl orthosilicate is slow
In oil droplets polycondensation, so that luminous rare earth compounding is successfully wrapped in inorganic matrix, obtain based on rare-earth europium ion
Luminous SiO 2 hybrid nanosphere (as shown in Figure 1), and received by the luminous and hydridization that condition controls optimization rare earth ion
The homogeneity and grain size of rice ball；And rare-earth hybridized nanosphere is used as fluorescent optical sensor, remove copper in qualitative and quantitative detection water
The content of ion.
Compared with prior art, the beneficial effects of the present invention are:
Instrument and equipment used by the preparation method of rare earth luminous silicon dioxide hybrid materials provided by the present invention is simple,
High-temperature high-voltage reaction condition is not needed, synthetic method is simple, and yield is high, and pollution is small, at low cost.Rare earth hair provided by the present invention
Light silicon dioxide hybrid materials have good dissolubility in water, soluble easily in water, are suitable for analysis detection cationic in water；
And the application of storage for a long time, transport and analysis detection can be suitable at room temperature with long-term preservation；It is provided by the present invention
Rare earth luminous silicon dioxide hybrid materials also show relatively better monodispersity, and future is expected to the fluorescence applied to cell
The fields such as imaging and bio-sensing detection.
Detailed description of the invention
In order to illustrate the technical solutions in the embodiments of the present application or in the prior art more clearly, will be described below to embodiment
Needed in attached drawing be briefly described, it should be apparent that, the accompanying drawings in the following description is only some of the application
Embodiment for those of ordinary skill in the art without creative efforts, can also be attached according to these
Figure obtains other attached drawings.
The rare-earth hybridized material of the preparation coated with silica of pickering emulsion method provided by Fig. 1 embodiment of the present invention shows
It is intended to
The digital photograph of aqueous silica solution provided by Fig. 2 embodiment of the present invention；
The digital pictures of pik woods solution provided by Fig. 3 embodiment of the present invention；
Rare earth luminous silicon dioxide hybrid materials SiO provided by Fig. 4 embodiment of the present invention2@Eu(NTA)3And organic ligand
The infrared spectrogram of molecule；
Complex Eu (NTA) provided by Fig. 5 embodiment of the present invention3With hybrid material SiO2@Eu(NTA)3Thermogravimetric analysis
Spectrogram；
Hybrid material SiO under difference THF content provided by Fig. 6 embodiment of the present invention2@Eu(NTA)3Fluorescent emission figure
Spectrum；
Provided by Fig. 7 embodiment of the present invention after various concentration copper ion is added, hybrid material SiO2@Eu(NTA)3's
Fluorescent emission map；
Rare earth luminous silicon dioxide hybrid materials SiO provided by Fig. 8 embodiment of the present invention2@Eu(NTA)3Transmission electron microscope
Photo；
Rare earth luminous silicon dioxide hybrid materials SiO provided by Fig. 9 embodiment of the present invention2@Eu(NTA)3Copper ion is rung
The invertibity answered.
Specific embodiment
The present invention is described in further details with example with reference to the accompanying drawing.
Embodiment 1
The present invention provides a kind of preparation methods of rare earth luminous silicon dioxide hybrid materials, include the following steps:
(1) preparation of nanometer grade silica
0.0527 gram of L-arginine powder is weighed with assay balance, is dissolved in 50mL distilled water, until completely dissolved, solution
It prepares and completes；The 25mL solution is taken out in wide-mouth bottle with the graduated cylinder of 10mL, sizeable magneton is put into, using magnetic agitation
Device stirring.The tetraethyl orthosilicate (TEOS) of 0.5mL is accurately pipetted with liquid-transfering gun, blend compounds head dropper is slowly added into static
In solution.After completion to be added, the careful revolving speed for controlling magnetic stirring apparatus makes solution be divided into two-phase, and the lower interface shape of TEOS
It is advisable at a taper, and makes its reaction simultaneously controlled at 60 DEG C.After 24 hours, stop reacting and being cooled to room temperature,
Product is collected, as shown in Figure 2.
(2) rare earth luminescent material Eu (NTA)3Preparation
Europium chloride is prepared firstly, being reacted at high temperature heat with the europiumsesquioxide of high-purity with concentrated hydrochloric acid, when three oxidations
After europium is completely dissolved, further heating removes extra hydrochloric acid, is obtained after vacuum drying containing there are six the colourless trichlorines of the crystallization water
Change europium powder.Then, suitable 4,4,4- tri- fluoro- 1-2- naphthalene -1,3- butanediones (399.3mg, 1.5mmol, NTA) is taken to be dissolved in
In 15ml dehydrated alcohol, suitable sodium hydrate aqueous solution (1mol/L) is then added and adjusts the pH of solution to neutral, then to
The aqueous solution (223.0mg, 0.5mmol) of europium chloride is added dropwise in above-mentioned solution, is warming up to 80 degree of 12 hours of reaction, stops
It only reacts and is cooled to room temperature, there is a large amount of Precipitations, precipitated after filtering with a large amount of distilled water flushings, finally the vacuum under 60 degree
Dry 12 hours obtain yellow powder Eu (NTA)3。
(3) preparation of rare earth luminous silicon dioxide hybrid materials
The Eu (NTA) of 0.0078g is weighed with assay balance3, it is dissolved in the tetrahydrofuran of 90 μ L, dissolution is complete molten
Liquid is slowly added into γ-glycidyl ether oxygen propyl trimethoxy silicane (γ-MPS) of 0.24 μ L；Step (1) is measured to prepare
Partial size 15nm or so silicon dioxde solution in bottle, select suitable magneton and be placed on magnetic stirring apparatus quickly
It stirs energetically, configured γ-glycidyl ether oxygen propyl trimethoxy silicane (γ-MPS) solution is rapidly added, by revolving speed tune
To 1000r/min, stir about 15 minutes, and numbering is 1.Phenomenon is observed, when solution colour is by nattier blue transparent to presenting
When milky white solution, as shown in figure 3, can stop stirring.The solution being stirred is added in flask, magneton, Yu Hengwen are put into
The good device of frame, adjusts temperature and revolving speed in oil bath, and the TEOS of 0.6mL is slowly added to rubber head dropper, solution is made to be divided into two-phase；
Continue to be stirred to react for 24 hours, i.e. the complete end of reaction of the TEOS on upper layer；It takes out product to be centrifuged, washes of absolute alcohol, then from
The heart；Collect product.The partial size and granularity of solution after measurement reaction, if partial size is less than in 100nm or so, size distribution PDI
0.1, as comparatively ideal experimental data.If partial size, granularity is above ideal value, then continues to test and optimize correlative
The dosage of matter.
Embodiment 2~4
Beneficial effect in order to further illustrate the present invention optimizes the luminous intensity of rare earth and the microcosmic ruler of hybridized nanometer ball
Very little, repeatedly " tetrahydrofurans of 90 μ L " in (3) the step of embodiment 1 are substituted for " the four of 100 μ L by the step of embodiment 1 respectively
Hydrogen furans ", " tetrahydrofurans of 150 μ L ", " tetrahydrofurans of 180 μ L ", and numbering is 2,3,4, investigates the result of parallel laboratory test.
Above-mentioned four groups of sample datas are depicted as following table:
The microscopic dimensions of hybridized nanometer ball under 1 difference THF dosage of table
Using and performance test
(1) visual analysis: the embodiment of the present invention 1~4 passes through the items such as the dosage of control reaction time, reaction temperature and TEOS
Part has accurately synthesized size in the water soluble silica nanoparticle of 15nm or so, in water with the slow diffusion method of two-phase
High degree of dispersion is kept, and at placement one month or more still it can be observed that as clear as crystal liquid (as shown in Figure 2)；Secondly,
Stablize γ-glycidyl ether oxygen propyl trimethoxy silicane containing rare earth luminous component using hydrophilic nano silica
(γ-MPS) oil droplet, and pickering emulsion as shown in Figure 3 is obtained by high-speed stirred；It is finally slow into static lotion again
Suitable TEOS is added, heating makes TEOS in the slow polycondensation in surface in lotion, so that obtaining kernel contains rare earth luminous cooperation
The silicon dioxide hybrid materials SiO of object2@Eu(NTA)3(Fig. 1).
(2) infrared analysis: the step of detecting the embodiment of the present invention 2 respectively using infrared spectrometer (2) resulting Eu
(NTA)3And the structure (i.e. sample two) of the resulting rare earth luminous silicon dioxide hybrid materials of step (3), test result such as Fig. 4.
It can be observed that being located at 2927,2840cm in the infrared spectrum (as shown in a in Fig. 4) of ligand molecular-1In the carbon-carbon double bond at place
C-H stretching vibration characteristic peak and 1606cm-1Locate the stretching vibration peak of corresponding carbonyl.When ligand is coordinated and introduces with europium ion
After into silica, find hybrid material in 1080cm-1There is the Si-O-Si eigen vibration peak of silica (such as in place
In Fig. 4 shown in b).It is obtained through analysis, the resulting rare earth luminescent material Eu (NTA) of the step (2)3Structural formula are as follows:
The structural formula of the resulting rare earth luminous silicon dioxide hybrid materials of step (3) is as follows:
(3) thermogravimetric analysis: stability is to evaluate an a kind of important indicator of new material performance, and therefore, the present invention chooses
2 step of embodiment (2) resulting Eu (NTA)3And resulting rare earth luminous silicon dioxide hybrid materials SiO2@Eu(NTA)3Heat
Stability, which has been done, to be detected (shown in Fig. 5).It can be observed that its aerial equilibrium temperature exists from the thermogravimetric curve of complex
200 degree or so, however be once introduced into after the inorganic network of silica, the thermal stability of composite material is rapid to be obtained
To raising (being greater than 300 degree), to widen the use temperature and range of complex.
(4) spectrofluorimetry: due to Eu (NTA) in experiment3γ-glycidyl ether oxygen propyl front three cannot be directly dissolved in
In the oily phase of oxysilane (γ-MPS), this invention takes first dissolved then to be added drop-wise to γ-glycidyl ether oxygen third again with THF
In base trimethoxy silane (γ-MPS), them can be made to become unified oily phase in this way.But in actual operation, find THF
The number of dosage can seriously affect the fluorescence intensity of final composite material.Respectively by 1~4 step of the embodiment of the present invention (3) institute
The rare earth luminous silicon dioxide hybrid materials SiO obtained2@Eu(NTA)3It is dispersed in water with the concentration of 0.1mg/ml, 360nm's
Its launching light spectrogram is measured under monitoring wavelength, test results are shown in figure 8.From steady-state fluorescence spectrum (Fig. 6) and ultraviolet light irradiation
Under fluorescence digital photograph in, it can be observed that the fluorescent emission intensity of No. 2 samples (100 μ L tetrahydrofuran) is most strong, wherein 1
Bluish violet fluorescence is presented in number sample under ultraviolet light irradiation, and red fluorescence is presented in 2,3, No. 4 samples.
(5) copper ion discriminance analysis: selection strongest No. two samples of luminous intensity test the fluorescence response row of its copper ion
To detect influence of the copper ion to fluorescence with fluorescence titration spectrum.No. 2 samples with water are diluted to obtain concentration to be 100 μM
Solution to be measured, copper chloride is dissolved in be configured in aqueous solution various concentration copper chloride solution (concentration be respectively 1mM, 2mM,
5mM, 10mM, 20mM, 30mM, 40mM, 50mM, 60mM, 70mM, 80mM, 90mM, 100mM, within the scope of 1-100mM), so
The copper ion for pipetting micro (100 μ l) various concentration respectively with liquid-transfering gun afterwards is added in luminescent solution to be measured, is made in mixed liquor
The concentration of copper ion maintains within the scope of 1-100 μM, and then different mixed liquors is added separately in cuvette, and successively examines
Survey its excitation spectrum and launching light spectrogram.Test results are shown in figure 7, grinds the red fluorescence of No. two samples provided by the present invention
Occur gradually weakening with being continuously increased for copper ion concentration until completely disappearing；And when copper ion is in a certain concentration range
In (1-100 μM) when variation, fluorescence intensity of the europium ion at 615nm shows Negative correlation, to realize to copper ion
Detection.
(6) Morphology analysis: the present invention sees the pattern of composite hybridization material using projection electron microscope
It examines.As shown in figure 8, SiO2@Eu(NTA)3Uniform ball shaped nano pattern is showed, the diameter of average grain about exists
110nm, and show relatively better monodispersity.It is this to be expected to be applied to based on rare earth luminous nano-hybrid material future
The fields such as fluorescence imaging and the bio-sensing detection of cell.
(7) to the reversibility Analysis of copper ion response: No. two samples of selection test its invertibity point to copper ion detection
Analysis.As shown in figure 9, fixed excitation wavelength is in 360nm, the fluorescent emission peak intensity of No. two sample solutions is very big, when depositing in solution
In bivalent cupric ion, apparent quenching occurs for the fluorescence emission peak of solution；The present invention is investigated it to copper ion response
Invertibity, EDTA have the ability of stronger chelated metal ions, can be coordinated with the copper ion in solution, so that sample
The fluorescence of middle rare earth is restored, and the detection of copper ion, fast response time, repeatable circulation can be re-used for after centrifuge separation
After 10 times, higher fluorescence intensity is still maintained.
Comparative example
Beneficial effect in order to further illustrate the present invention, repeatedly the step of embodiment of the present invention 1 (1) and step (2), divides
It Zhi get not nanosilica solution and rare earth luminescent material Eu (NTA)3；And rare earth luminous titanium dioxide is made in accordance with the following steps
Silicon hybridization material: the Eu (NTA) of step (2) resulting 0.0078g is weighed with assay balance3, it is dissolved in the tetrahydrofuran of 90 μ L
In, 0.6ml tetraethyl orthosilicate is added, and suitable water and alkaline solution is added, adjusts pH to 7.0, then under room temperature
It is stirred to react for 24 hours, centrifuge separation, and cleaned twice with water and ethyl alcohol respectively, obtains rare earth luminous SiO 2 hybrid after dry
Material is observed by projection electron microscope, which shows irregular big blocky-shaped particle, and is shown a large amount of
Aggregation phenomenon；Partial size is excessive, bad dispersibility can not be applied to the fields such as fluorescence imaging and the bio-sensing detection of cell.
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be said that
Specific implementation of the invention is only limited to these instructions.For those of ordinary skill in the art to which the present invention belongs, exist
Under the premise of not departing from present inventive concept, a number of simple deductions or replacements can also be made, all shall be regarded as belonging to of the invention
Protection scope.
Claims (10)
1. a kind of preparation method of rare earth luminous silicon dioxide hybrid materials, which comprises the steps of:
(1) ratio for being 0.01~0.05:1 according to the volume ratio of tetraethyl orthosilicate and L-arginine solution, by positive silicic acid four
It is stirred to react 16~30h after L-arginine solution is added in ethyl ester, then under the conditions of 40~80 DEG C, silicon dioxde solution is made；
(2) existing for the organic solvent and water under the conditions of, by rare-earth salt solution and 4,4,4- tri- fluoro- 1-2- naphthalene -1,3- butane two
After the mixing of ketone solution, 10~14h of insulation reaction under the conditions of 60~100 DEG C is filtered, is dried to obtain rare earth luminescent material,
In, the molar ratio of rare earth element is 1~5:1 in described 4,4,4- tri- fluoro- 1-2- naphthalene -1,3- butanediones and rare-earth salt solution；
(3) step (2) resulting rare earth luminescent material is dissolved in after tetrahydrofuran and obtains mixed solution, then by the mixed solution
It is mixed with γ-glycidyl ether oxygen propyl trimethoxy silicane, step (1) resulting silicon dioxde solution, it is stirred to react 10~
60min adds ethyl orthosilicate, reacts 16~30h, and rare earth luminous SiO 2 hybrid material is made through centrifugation, cleaning, drying
Material；Wherein, the quality of the resulting rare earth luminescent material of the step (2) and the volume ratio of the tetrahydrofuran are 0.04~1:
1g/ml；The quality of the resulting rare earth luminescent material of the step (2) and the volume ratio of the step (1) resulting silica
For 30~40:1g/ml.
2. the preparation method of rare earth luminous silicon dioxide hybrid materials as described in claim 1, which is characterized in that the step
(2) in, described 4,4,4- tri- fluoro- 1-2- naphthalene -1,3- butanedione solution are by 4,4,4- tri- fluoro- 1-2- naphthalene -1,3- butane two
Ketone is dissolved in organic solvent and is made, wherein the volume mole with organic solvent of 4,4,4- tri- fluoro- 1-2- naphthalene -1,3- butanediones
Ratio be 0.02~0.5:1mmol/ml.
3. the preparation method of rare earth luminous silicon dioxide hybrid materials as described in claim 1, which is characterized in that the step
(2) in, the organic solvent includes one or more of ethyl alcohol, methanol, propyl alcohol, butanol, acetone.
4. the preparation method of rare earth luminous silicon dioxide hybrid materials as described in claim 1, which is characterized in that the step
(2) in, the rare-earth salt solution includes one of rare earth nitrate solution, rare-earth chloride solution, rare-earth oxalate solution
Or it is several.
5. the preparation method of rare earth luminous silicon dioxide hybrid materials as described in claim 1, which is characterized in that the step
(2) in, the rare earth element in the rare-earth salt solution includes one or more of europium, dysprosium, samarium, terbium.
6. the preparation method of rare earth luminous silicon dioxide hybrid materials as described in claim 1, which is characterized in that the step
(2), it specifically includes:
4,4,4- tri- fluoro- 1-2- naphthalene -1,3- butanediones are dissolved in organic solvent, addition alkaline solution, adjusting pH to 6.5~
7.5, the ratio for being 1~5:1 according still further to the molar ratio of 4,4,4- tri- fluoro- 1-2- naphthalene -1,3- butanediones and rare earth element will be dilute
Earth salt solution and 4, after 4,4- tri- fluoro- 1-2- naphthalene -1,3- butanediones mixing, under the conditions of 60~100 DEG C insulation reaction 10~
14h is filtered, is dried to obtain rare earth luminescent material.
7. the preparation method of rare earth luminous silicon dioxide hybrid materials as described in claim 1, which is characterized in that the step
(3) in, the volume ratio of the quality of the resulting rare earth luminescent material of the step (2) and the tetrahydrofuran is 0.043~
0.086:1g/ml。
8. the preparation method of rare earth luminous silicon dioxide hybrid materials as described in claim 1, which is characterized in that the step
(3) in, the rare earth luminous silicon dioxide hybrid materials are near-spherical, and partial size is 100~300nm.
9. a kind of rare earth luminous silicon dioxide hybrid materials are using rare earth luminous SiO 2 hybrid as described in claim 1
The preparation method of material is made.
10. a kind of application of the rare earth luminous silicon dioxide hybrid materials in terms of copper ion identification as claimed in claim 9, institute
It states to apply and is not related to medical diagnosis on disease and disease treatment field.
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| CN109876157B (en) * | 2019-02-27 | 2020-12-15 | 浙江大学 | Composite material of ion-specific filter membrane/mesoporous silicon, nano sensor, product of nano sensor and application of nano sensor |
| CN110272645B (en) * | 2019-06-25 | 2021-06-01 | 东南大学 | Recoating anti-reflection super-hydrophobic coating and preparation method and application thereof |
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