CN109504366A - A kind of rare-earth complex cladding nano-hollow SiO2With cladded type rare-earth complex and preparation method thereof - Google Patents
A kind of rare-earth complex cladding nano-hollow SiO2With cladded type rare-earth complex and preparation method thereof Download PDFInfo
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- CN109504366A CN109504366A CN201910012547.6A CN201910012547A CN109504366A CN 109504366 A CN109504366 A CN 109504366A CN 201910012547 A CN201910012547 A CN 201910012547A CN 109504366 A CN109504366 A CN 109504366A
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/59—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing silicon
- C09K11/592—Chalcogenides
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
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Abstract
The invention discloses a kind of rare-earth complexs to coat nano-hollow SiO2, it is hollow silicon dioxide surface to be coated on as shell and in a manner of Electrostatic Absorption using rare-earth complex and the shot-like particle that is formed using nano-hollow silica as core.Product of the invention solves the problems, such as rare-earth complex stability and fluorescence intensity, not only greatly improves the fluorescence intensity of the rare-earth complex of core-shell structure, can also save the dosage of rare-earth complex.The higher biocompatibility of silica is used for reference simultaneously, the hollow silicon dioxide for coating rare-earth complex can be used for bio-carrier and fluorescence probe.
Description
Technical field
The present invention relates to a kind of rare-earth complex and hollow silicon dioxides more particularly to a kind of rare-earth complex to coat nanometer
Hollow SiO2With cladded type rare-earth complex and preparation method thereof.Belong to hybrid material and its preparation field.
Background technique
In recent years, the research in relation to tiny balloon has become the research hotspot in materialogy field.Partial size is in nanoscale to micro-
Characteristics, the hollow spaces such as the tiny balloon of meter level has large specific surface area, density is low, stability and filterability are good can accommodate
A large amount of guest molecule or large-sized object, and generate some peculiar properties based on microcosmic " package " effect.Therefore, empty
Heart microballoon has been widely used for such as being used as urging in chemistry, biological medicine and Material Field as a kind of new function material
Agent carrier, filler, coating, control release microencapsulation material (drug, pigment, cosmetics, ink and bioactive agents) etc..
So far, it is empty that a variety of preparations such as micella self-assembly method, template, emulsion method and spray reaction are had reported in document
The method of heart microballoon, wherein template is the most commonly used.In template, and develop a variety of methods for preparing shell, including layer
Layer self-assembly method (Layer by Layer) and sol-gel method (Sol-gel) etc..But it in reported template, all adopts
Template particles are removed with the method for the other solvent dissolutions of addition or high-temperature calcination, to obtain hollow structure microballoon.
When rare earth solid luminescent material is acted on by electron bombardment, X-ray, ultraviolet light equal excitation, the spokes such as fluorescence can be generated
Penetrate phenomenon.Show following advantage: bright in luster, excitation purity is high, and photoluminescent band is narrow；Light absorpting ability is strong, high conversion efficiency, can
To prepare the illuminator of various different characteristics；Launch wavelength distributed area field width；In the rare earth ion being excited, it is in excitation state
Much longer than the common atomic excitation service life of electron lifetime.Chemical stability is good, it is resistance to burn and also its physical property relatively
Stablize, preparation process is relatively easy, and it can bear the electron beam of relatively high power, stronger ultraviolet light and high-energy radiation again
Effect.By the end of currently, rare earth luminescent material has been widely used for food inspection, textile, illuminating material and display material
In equal fields, and extended to other emerging technology areas.
Luminescent material finished product and its various products (such as luminous paint, plastic foil or plate, fiber, ceramics, glass) can answer
Various fields for national economy.The application of luminescent material mainly has light source, display, the spy of optoelectronics device, radiation field
Survey and the record of dose of radiation etc..Fluorescent lamp, high-pressure sodium lamp, light emitting diode etc. are used in as light source；As display,
It is shown (such as numerical chracter (such as mortgage fluorescent character-display tube, shine digital diode, electroluminescent digital screen) and plate image
Electroluminescent simulative display, matrix are shown)；In terms of radiation detection, record, for scintillation crystal, the detection of electromagnetic field of high frequency
And as dosage facility；For opto-electronic device, the element etc. of photoelectroluminescence element and photoelectric double control is obtained；Daily
It can play the role of low emergency lighting, Warning Mark and decoration effect in life.
If research finds that coating one layer of rare-earth complex on the surface of silica is used to prepare novel rare earth luminous material
The new advantages such as there is material cost performance to improve, solvent resistance improves, provide for materials such as Development of Novel functional rareearth complexes
Development space.Significant the most, the SiO of this rare-earth complex cladding2New material has inorganic-organic hybrid material
The characteristics of material, suffers from important scientific valence to its formation mechenism and fluorescence enhancement mechanism and its functional mechanism study
Value.
Research also found coated with silica rare earth compounding, and not only rare-earth usage can economize on resources less, and certain
It can solve the problem of rare earth compounding stability in degree.Not only there is important application in terms of anti-counterfeiting mark, fluorescence probe
Value, and also have certain application prospect in terms of electroluminescent device.If further controlled this for silica
The granular size of the rare earth compounding of cladding, and it is used for the luminescent layer of electroluminescent device, it is possible to it can be in the stability of device
Aspect is improved.
However, although the technology in relation to this coated with silica rare earth compounding it has been reported that but retrieval discovery about
Rare-earth complex coats nano-hollow SiO2It is had not been reported with the patent of cladded type rare-earth complex and preparation method thereof.
Summary of the invention
In view of the deficiencies of the prior art, the problem to be solved in the present invention is to provide a kind of rare-earth complexs to coat nano-hollow
SiO2With cladded type rare-earth complex and preparation method thereof.
Rare-earth complex of the present invention coats nano-hollow SiO2, be using nano-hollow silica as core, with
Rare-earth complex is coated on hollow silicon dioxide surface and the shot-like particle that is formed as shell and in a manner of Electrostatic Absorption；Its feature exists
In: the particle size range of the shot-like particle is 2.1~2.3 microns, and compression strength is between 20~30MPa；It is hollow in its center
Part is in the spheroidal cavity of class, and it is silicon dioxide layer, layer other than core hollow parts that diameter range, which is 1.9~2.0 microns,
Thickness is 150~200 nanometers, and it is 5-10 nanometers that the rare-earth complex shell thickness of shell is used as outside core；In shot-like particle silica with
The mass ratio of rare-earth complex is 224.307:1, and the rare-earth complex is the Tb (acac) that can emit fluorescence3Phen, Eu
(TTA)3Phen or Tm (acac)3Phen, phen therein are 1-10 phenanthrolines, and TTA is 2- thioyl trifluoroacetone, acac
It is acetylacetone,2,4-pentanedione.
It is further it is preferable that: the rare-earth complex selects Tb (acac)3Phen, the nano-hollow dioxy of cladding
The shot-like particle that SiClx is formed is expressed as SiO2@Tb(acac)3Phen has sharp emission peak at 545nm.
Alternatively, the rare-earth complex selects Eu (TTA)3Phen, the nano-hollow silica of cladding form granular
Object is expressed as SiO2@Eu(TTA)3Phen has sharp emission peak at 612nm.
The invention discloses one kind for coating nano-hollow SiO2Cladded type rare-earth complex, it is characterised in that: institute
Stating rare-earth complex is the Tb (acac) that can emit fluorescence3Phen, Eu (TTA)3Phen or Tm (acac)3Phen, it is therein
Phen is 1-10 phenanthroline, and TTA is 2- thioyl trifluoroacetone, and acac is acetylacetone,2,4-pentanedione.
Wherein: the rare-earth complex is preferably Tb (acac)3phen。
Above-mentioned rare-earth complex coats nano-hollow SiO2Preparation method, step is:
(1) spherical calcium carbonate is prepared；
(2) using spherical calcium carbonate obtained as template, with the solution NaSiO containing silicon3、K2SiO3Or ethyl orthosilicate
(TEOS) solution mixes in the reactor, it is agitated after centrifugation, sediment is washed, it is dry after, removed and used using acid etching method
Make the calcium carbonate of template, finally calcining obtains nano-scale hollow silica dioxide granule；
(3) hollow silicon dioxide obtained dissolution is dispersed in ethanol, concentrated ammonia liquor, which is added, makes solution alkaline；It adds
First ligand, ultrasound mix, and then continuously add Ligands and rare earth metal salt into solution again, make the first ligand: second
Ligand: the molar ratio of rare earth metal salt is 1:3:1, and rare-earth complex cladding nano-hollow SiO is obtained after lasting stirring2?
Grain；Wherein first ligand is 1-10 phenanthroline (phen), and Ligands are acetylacetone,2,4-pentanedione (acac) or 2- thenoyl three
Fluorine acetone (TTA), the rare earth metal salt are the compounds of europium, terbium or thulium.
Further, the rare-earth complex coats nano-hollow SiO2Preferred preparation method is with following steps and ratio
Example dosage preparation:
(1) synthesizing spherical calcium carbonate: taking 50mL concentration is 0.6molL-1Calcium chloride solution, it is 1% that 100mL concentration, which is added,
Carboxymethyl cellulose (CMC) solution be uniformly mixed, then ultrasound, be added with stirring with calcium chloride solution it is isometric, etc. it is dense
The sodium carbonate liquor of degree, is centrifuged after ten minutes, and sediment is successively washed 3 times with distilled water, dehydrated alcohol respectively, at 80 ± 2 DEG C
Obtain spherical calcium carbonate within lower drying 24 ± 2 hours；
(2) preparation of nano-scale hollow silica dioxide granule: spherical calcium carbonate made from 1g is weighed as template, is added to
In the round-bottomed flask of 100mL, 30mL ethyl alcohol, 20mL water, 1.0mL concentrated ammonia liquor, 0.10g cetyl trimethyl bromination are sequentially added
Ammonium (CTAB), 1.0mL ethyl orthosilicate (TEOS) are stirred to react 4 hours；Centrifugation, precipitates washed with EtOH, preliminarily dried 6
It is heated 2 ± 0.5 hours at 250 ± 10 DEG C again after hour, 0.1molL is used after natural cooling-1Salt acid soak 24 hours with
Upper removal is used as the calcium carbonate of template, finally calcines 4 ± 1 hours at 600 ± 20 DEG C, obtains nano-scale hollow silica
Grain；
(3) rare-earth complex coats nano-hollow SiO2Synthesis: take hollow silicon dioxide made from 0.1g to be dissolved in
In the ethyl alcohol of 20mL, two hours of ultrasonic disperse, the concentrated ammonia liquor of 1mL is added, makes solution alkaline；Adding 0.2ml concentration is
0.1moL·L-1First ligand, continues ultrasound 30 minutes, then continuously adds isometric, concentration 0.3moL into solution again
L-1Ligands and 0.2ml concentration are 0.1moLL-1TbCl3·6H2O obtains rare-earth complex after persistently stirring 4 hours
Coat nano-hollow SiO2Particle；Wherein first ligand is 1-10 phenanthroline (phen), and Ligands are acetylacetone,2,4-pentanedione
(acac)。
The present inventor has found after study, if using the hollow silicon dioxide of silica precursor hydrolysis as core, with tool
The rare-earth complex for having fluorescence property is surface cover, can be self-assembly of a kind of hollow dioxy of rare-earth complex cladding
SiClx.Hollow silicon dioxide before uncoated is insoluble in organic solvent, and the silica for coating rare-earth complex is molten
In organic solvent, this shows that surface coated the good results are evident.
Rare-earth complex of the present invention coats nano-hollow SiO2As fluorescent marker in research silicon rubber system
The application of filler distribution situation.
The rare-earth complex that the present invention prepares coats nano-hollow SiO2The fluorescent microsphere of structure can be used for silicon rubber
Fluorescent marker in glue.Enhance field in filled rubber, the reinforcing effect of filler is in addition to one dependent on filler and rubber itself
Outside a little properties, the mutually synergistic effect also between filler and rubber matrix is related.Inorganic particulate as filler is in rubber matrix
In be not evenly distributed, but certain network structure is differently formed according to preparation method.It is filled out in research silicon rubber system
The distribution situation of material is to describe an important link of gum filler network.The hollow dioxy with fluorescence that will be prepared
Filler of the SiClx as silicon rubber prepares the silicon rubber with fluorescent functional, and hollow silica shells are due to endless
Whole property, rare-earth complex a part are attached to the surface of ball, some enters the inside of ball, and it is attached to increase rare-earth complex
Surface area, and sample is characterized by means of laser scanning co-focusing microscope, studies the distribution shape of filler in rubber
Condition characterizes composite material microstructure by fluorescent labelling techniques realization.
Rare-earth complex of the present invention coats nano-hollow SiO2As DNA fluorescence probe in research polynucleotide conformation
Application in variation.
Fluorescence probe is the optical physics and photochemical characteristics using fluorescent probe compounds, is studied on a molecular scale certain
(as intracellular) the physically or chemically mechanism, dynamics of change procedure and physicochemical characteristic of certain particular surroundings in system
Or the method for the structure of certain material or compound, conformation and its physicochemical properties.Rare-earth complex packet prepared by the present invention
Cover nano-hollow SiO2The fluorescent microsphere of structure, which is further processed, to be allowed to combine DNA, when fluorescent microsphere and contains mismatch
When base pair nucleotide combines, the variation of fluorescence spectrum reflects the variation of polynucleotide conformation, which can be used as DNA
Application of the fluorescence probe in research polynucleotide conformation change.
Rare-earth complex prepared by the present invention coats nano-hollow SiO2The fluorescent microsphere of structure can be also used for drug sieve
Choosing.Traditional drug screening method is that the medicine of medicinal sample is evaluated by internal, external Multiple experiments using pharmacological method
Learn activity.With going deep into functional polymer microballoon research, fluorescent microsphere has obtained the wide of people as a kind of new material
General concern.Fluorescent microsphere surface can be connected with the receptor in conjunction with determinand, while determinand is carried out labelled with radioisotope.
After the two mixing, fluorescent material can be excited to generate fluorescence with the radioactive ray of the determinand in conjunction with microballoon；And cannot with it is micro-
The determinand that chou closes cannot excite fluorescence since farther out, radiant is buried in oblivion in the solution apart from microballoon.This method without
Marker that is free and combining need to be separated, operation automation greatly shortens detection time, uses manpower and material resources sparingly.
The hollow silicon dioxide of rare-earth complex disclosed by the invention cladding is prepared according to the methods of the invention this
Cladded type rare-earth complex is a kind of novel rare-earth luminescent material, shows new advantage, relative to not embedding silica
For rare-earth complex, the characteristics of compatibility higher due to silica, solvent resistance is improved, and cost performance is also able to
It improves, the consumption of rare earth is conserved.
As a kind of novel rare-earth complex, cladded type rare-earth complex disclosed by the invention has organic and inorganic
Common feature can not only save expensive rare earth resources, but also the stability of rare-earth complex can be improved.It is dilute using this
For the hollow silicon dioxide of native complex compound cladding due to its non-toxic and non-radioactive, fluorescence intensity is high, has very strong hydrophily and life
Object compatibility, may be used as fluorescence probe.Meanwhile hollow silica is for solid silicon dioxide microsphere, it can be with
The microballoon of functionalization is placed in the cavity of hollow silica, is applied to mass transfer, becomes functionalization as carrier
Silicon dioxide microsphere.
To sum up, the hollow silicon dioxide of rare-earth complex cladding prepared by the present invention not only solves rare-earth complex and stablizes
The problem of property and fluorescence intensity, while also making public for the first time a kind of a kind of novel organic inorganic hybridization that can be used for mass transfer
Material.Since rare-earth complex is coated on the surface of hollow silica in a manner of physical absorption, so the structure ensure that
Rare-earth complex has very high stability.Meanwhile silica can be dissolved in organic solvent, facilitate rare-earth complex and exist
Disperse more uniform in organic solvent, improves rare-earth complex and be easy to the phenomenon that reuniting.Fluorescence pattern shows core-shell structure
The fluorescence intensity of rare-earth complex greatly improves, and can save the use of rare-earth complex in this way.And use for reference silica compared with
High biocompatibility, the hollow silicon dioxide for coating rare-earth complex can be used for bio-carrier and fluorescence probe.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of calcium carbonate template, and as can be seen from the figure calcium carbonate template is the spherical shape of standard, surface
Smoother.
Fig. 2 is the infared spectrum of calcium carbonate template, it can be seen from the figure that there are ν for calcium carbonate3Face asymmetric stretching vibration
Peak, this peak are Qiang Kuanfeng, and wave number is in 1463.5cm-1Place.ν2Out-of-plane bending vibration peak, wave number 874.91cm-1。ν1In-plane bending
Vibration peak, wave number is in 713.17cm-1。
Fig. 3 is to pass through calcined CaCO3@SiO2, it can be seen from the figure that calcium carbonate is removed after calcining, remain
Under hollow silica, have apparent cavity.
Fig. 4 is the infared spectrum of hollow silica.
It can be seen from the figure that 1083.93,796.30 and 462.33.cm-1The peak value at place is by Si-O-Si respectively
Antisymmetric stretching vibration, caused by symmetrical stretching vibration and bending vibration, 958.09cm-1The absorption peak at place corresponds to Si-OH
The stretching vibration of key, 1636.14,3428.22cm-1Then correspond to the absorption peak of constitution water.
Fig. 5 is that rare-earth complex wraps up hollow silicon dioxide.It can be seen from the figure that the surface ratio of hollow silicon dioxide ball
It is rougher, i.e. the complex compound surface that has been sticked to ball, and also internal is in hollow out.
Fig. 6 is rare-earth complex Tb (acac)3The chemical structural formula of phen.
Fig. 7 is the energy level transition schematic diagram of ligand and rare earth ion.
Fig. 8 is the exciting light spectrogram for the hollow silicon dioxide that rare-earth complex and rare-earth complex coat.What dotted line indicated
It is SiO2@Tb(acac)3The excitation spectrum of phen, solid line are Tb (acac)3The excitation spectrum of phen.
Fig. 9 is the launching light spectrogram for the hollow silicon dioxide that rare-earth complex and rare-earth complex coat.What dotted line indicated
It is SiO2@Tb(acac)3The emission spectrum of phen, solid line are Tb (acac)3The emission spectrum of phen.
Specific embodiment
The following are preferred specific embodiment and in conjunction with attached drawing come the present invention is further explained, the features of the present invention and
Advantage will become more apparent with these explanations.But these embodiments are merely illustrative, simultaneously to protection scope of the present invention
It is not limited in any way.Those skilled in the art and scientific research personnel understand, without departing from or deviate protection model of the invention
In enclosing, there are many alternative, modification and improvement for specific embodiments of the present invention, should be included in protection scope of the present invention
It is interior.
Following embodiment is rare-earth complex Tb (acac)3The preparation of phen and using TEOS as the hollow dioxy of presoma
The preparation of SiClx and the synthesis of last rare-earth complex package hollow silicon dioxide.It will be understood by those skilled in the art that with this
Rare-earth complex Tb (acac)3Other phen similar rare-earth complexs, such as Eu (TTA)3phen,Tb(acac)3Phen and Tm
(acac)3Phen can equally prepare rare-earth complex package hollow silicon dioxide, spectral signature with following implementation method
Similar, the present invention will no longer be illustrated one by one.Agents useful for same is commercial product in embodiment.
1 rare-earth complex Tb (acac) of embodiment3The preparation of phen
By Tb4O7Powder is dissolved in a certain amount of hydrogenperoxide steam generator, reacts the product obtained after a period of time through filtering
It after evaporation, is re-dissolved in dilute hydrochloric acid, then slow evaporation, until there is the crystal TbCl of white3·6H2O is subsequently placed in
It is continued drying out in drier, until quality does not change.
The TbCl that will be prepared3·6H2O, acac and phen dissolution in ethanol, is configured to certain density solution, rare earth
The preparation of complex compound is according to TbCl3·6H2O, the molar concentration rate of acac and phen is 1:3:1, adjusts pH value between 7-8.
2 rare-earth complex of embodiment coats nano-hollow SiO2Preparation
The preparation of hollow silicon dioxide uses template.
(1) synthesizing spherical calcium carbonate: taking 50mL concentration is 0.6molL-1Calcium chloride solution, it is 1% that 100mL concentration, which is added,
Carboxymethyl cellulose (CMC) solution be uniformly mixed, then ultrasound, be added with stirring with calcium chloride solution it is isometric, etc. it is dense
The sodium carbonate liquor of degree, is centrifuged after ten minutes, and sediment is successively washed 3 times with distilled water, dehydrated alcohol respectively, does at 80 DEG C
Obtain spherical calcium carbonate within dry 24 hours；
(2) preparation of nano-scale hollow silica dioxide granule: spherical calcium carbonate made from 1g is weighed as template, is added to
In the round-bottomed flask of 100mL, 30mL ethyl alcohol, 20mL water, 1.0mL concentrated ammonia liquor, 0.10g cetyl trimethyl bromination are sequentially added
Ammonium (CTAB), 1.0mL ethyl orthosilicate (TEOS) are stirred to react 4 hours；Centrifugation, precipitates washed with EtOH, preliminarily dried 6
It is heated 2 hours at 250 DEG C again after hour, 0.1molL is used after natural cooling-1Removals in salt acid soak 24 hours or more be used as
The calcium carbonate of template is finally calcined 4 hours at 600 DEG C, obtains nano-scale hollow silica dioxide granule；
(3) rare-earth complex coats nano-hollow SiO2Synthesis: take hollow silicon dioxide made from 0.1g to be dissolved in
In the ethyl alcohol of 20mL, two hours of ultrasonic disperse, the concentrated ammonia liquor of 1mL is added, makes solution alkaline；Adding 0.2ml concentration is
0.1moL·L-1First ligand, continues ultrasound 30 minutes, then continuously adds isometric, concentration 0.3moL into solution again
L-1Ligands and 0.2ml concentration are 0.1moLL-1TbCl3·6H2O obtains rare earth complex after persistently stirring 4 hours
Object coats nano-hollow SiO2Particle is expressed as SiO2@Tb(acac)3phen；Wherein first ligand is 1-10 phenanthroline
(phen), Ligands are acetylacetone,2,4-pentanedione (acac).
Rare-earth complex obtained above coats nano-hollow SiO2, it is using nano-hollow silica as core, with dilute
Native complex compound is coated on hollow silicon dioxide surface and the shot-like particle that is formed as shell and in a manner of Electrostatic Absorption；Its feature exists
In: the particle size range of the shot-like particle is 2.1~2.3 microns, and compression strength is between 20~30MPa；It is hollow in its center
Part is in the spheroidal cavity of class, and it is silicon dioxide layer, layer other than core hollow parts that diameter range, which is 1.9~2.0 microns,
Thickness is 150~200 nanometers, and it is 5-10 nanometers that the rare-earth complex shell thickness of shell is used as outside core；In shot-like particle silica with
The mass ratio of rare-earth complex is 224.307:1, and the rare-earth complex selects Tb (acac)3Phen, the nano-hollow of cladding
The shot-like particle that silica is formed is expressed as SiO2@Tb(Hacac)3Phen has sharp emission peak at 545nm.
3 SiO of embodiment2@Tb(acac)3The fluorescence spectrometry of phen
Fluorescence spectrum measures on fluorescence protractor, and exciting slit and transmite slit are both configured to 5nm, in order to more intuitive
Compare the fluorescence intensity of hollow silicon dioxide embedding front and back, fluoremetry carries out under same time, same concentration.
Fig. 9 is rare-earth complex Tb (acac)3The hollow silicon dioxide SiO of phen and rare-earth complex package2@Tb
(acac)3The launching light spectrogram of phen obtains excitation spectrum with the wavelength deexcitation of 545nm.It chooses and swashs from excitation spectrum again
Wavelength is sent out, emission spectrum is obtained.As can be seen from the figure the two has apparent main emission peak at 545nm, and emits
The position at peak does not vary widely.This illustrates not cause shadow to the energy level of rare-earth complex after wrapping up hollow silicon dioxide
It rings.
According to rare earth ion Tb3+Energy diagram, the emission spectrum of rare earth Tb should there are four the emission peaks of feature, in Tb
(acac)3Phen and SiO2@Tb(acac)3It can be clearly seen that in the launching light spectrogram of phen, be located at 490nm, 545nm,
585nm and 619nm, the energy level jump for respectively corresponding Tb are5D4→7F6,5D4→7F5,5D4→7F4,5D4→7F3Noticeable
It is the rare-earth complex SiO after wrapping up hollow silicon dioxide2@Tb(acac)3Phen is compared to pure rare-earth complex Tb
(acac)3For phen, under identical concentration, fluorescence intensity has greatly improved.
Fig. 8 is Tb (acac)3Phen and SiO2@Tb(acac)3The exciting light spectrogram of phen, Detection wavelength 545nm.From
As can be seen that the excitation wavelength of the two does not have apparent difference in figure, compared to the excitation spectrum of pure rare-earth complex, package
Rare-earth complex after silica has had more a peak at 270nm, this is the characteristic peak of hollow silicon dioxide, to rare earth complex
The molecular composition of object does not have an impact.This shows that the package of rare-earth complex is physical absorption and simultaneously chemically non-reactive.
The rare-earth complex of the present invention of embodiment 4 coats nano-hollow SiO2As fluorescent marker in research silicon rubber
The application of filler distribution situation in colloid system.
The rare-earth complex that the present invention prepares coats nano-hollow SiO2The fluorescent microsphere of structure can be used for silicon rubber
Fluorescent marker in glue.
Inorganic particulate as filler is not evenly distributed in rubber matrix, but according to the not similar shape of preparation method
At certain network structure.The distribution situation of filler is one of description gum filler network important in research silicon rubber system
Link.Using the hollow silicon dioxide with fluorescence prepared as the filler of silicon rubber, prepare with fluorescent functional
Silicon rubber, hollow silica shells are since imperfection, rare-earth complex a part are attached to the surface of ball, there are also one
Part enters the inside of ball, increases the surface area of rare-earth complex attachment, and by means of laser scanning co-focusing microscope pair
Sample is characterized, and the distribution situation of filler in rubber is studied, i.e., is realized by fluorescent labelling techniques to the microcosmic knot of composite material
Structure is characterized.
The rare-earth complex of the present invention of embodiment 5 coats nano-hollow SiO2As DNA fluorescence probe in research poly-nuclear
Application in thuja acid conformation change.
Rare-earth complex prepared by the present invention is coated into nano-hollow SiO2The fluorescent microsphere of structure, which is further processed, makes it
Can be in conjunction with DNA, when fluorescent microsphere is with containing mismatching in conjunction with base pair nucleotide, the variation of fluorescence spectrum reflects poly-nuclear
The variation of thuja acid conformation, the fluorescent microsphere can be used as application of the DNA fluorescence probe in research polynucleotide conformation change.
Combining specific embodiment above, the present invention is described, but these embodiments are only illustratives
, to protection scope of the present invention and do not constitute a limitation.It will be understood by those skilled in the art that without departing from or deviate the present invention
Protection scope under, there are many modification and improved method, these all should be at this for technical solution of the present invention and its implementation method
In the protection scope of invention.
Claims (9)
1. a kind of rare-earth complex coats nano-hollow SiO2, it is to be made using nano-hollow silica as core with rare-earth complex
The shot-like particle for being coated on hollow silicon dioxide surface for shell and in a manner of Electrostatic Absorption and being formed；It is characterized by: described granular
The particle size range of object is 2.1~2.3 microns, and compression strength is between 20~30MPa；Hollow parts are in similar ball in its center
The cavity of shape, diameter range are 1.9~2.0 microns, are silicon dioxide layer other than core hollow parts, and thickness is 150~200
Nanometer, it is 5-10 nanometers that core is used as the rare-earth complex shell thickness of shell outside；Silica and rare-earth complex in shot-like particle
Mass ratio is 224.307:1, and the rare-earth complex is the Tb (acac) that can emit fluorescence3Phen, Eu (TTA)3Phen or Tm
(acac)3Phen, phen therein are 1-10 phenanthrolines, and TTA is 2- thioyl trifluoroacetone, and acac is acetylacetone,2,4-pentanedione.
2. rare-earth complex according to claim 1 coats nano-hollow SiO2, it is characterised in that: the rare-earth complex
Select Tb (acac)3Phen, the shot-like particle that the nano-hollow silica of cladding is formed are expressed as SiO2@Tb(Hacac)3Phen,
It has sharp emission peak at 545nm.
3. rare-earth complex according to claim 1 coats nano-hollow SiO2, it is characterised in that: the rare-earth complex
Select Eu (TTA)3Phen, the shot-like particle that the nano-hollow silica of cladding is formed are expressed as SiO2@Eu(TTA)3Phen,
There is sharp emission peak at 612nm.
4. one kind is for coating nano-hollow SiO2Cladded type rare-earth complex, it is characterised in that: the rare-earth complex is energy
Enough emit the Tb (acac) of fluorescence3Phen, Eu (TTA)3Phen or Tm (acac)3Phen, phen therein are 1-10 phenanthrolines,
TTA is 2- thioyl trifluoroacetone, and acac is acetylacetone,2,4-pentanedione.
5. according to claim 4 for coating nano-hollow SiO2Cladded type rare-earth complex, it is characterised in that: institute
Stating rare-earth complex is Tb (acac)3phen。
6. claim 1,2 or 3 rare-earth complexs coat nano-hollow SiO2Preparation method, step is:
(1) spherical calcium carbonate is prepared；
(2) using spherical calcium carbonate obtained as template, with the solution NaSiO containing silicon3、K2SiO3Or ethyl orthosilicate
(TEOS) solution mixes in the reactor, it is agitated after centrifugation, sediment is washed, it is dry after, removed and used using acid etching method
Make the calcium carbonate of template, finally calcining obtains nano-scale hollow silica dioxide granule；
(3) hollow silicon dioxide obtained dissolution is dispersed in ethanol, concentrated ammonia liquor, which is added, makes solution alkaline；Add first
Ligand, ultrasound mix, then continuously add Ligands and rare earth metal salt into solution again, make the first ligand: Ligands:
The molar ratio of rare earth metal salt is 1:3:1, and rare-earth complex cladding nano-hollow SiO is obtained after lasting stirring2Particle；Wherein
First ligand is 1-10 phenanthroline (phen), and Ligands are acetylacetone,2,4-pentanedione (acac) or 2- thioyl trifluoroacetone
(TTA), the rare earth metal salt is the compound of europium, terbium or thulium.
7. rare-earth complex described in claim 2 coats nano-hollow SiO2Preparation method, which is characterized in that with following steps
And ratio dosage preparation:
(1) synthesizing spherical calcium carbonate: taking 50mL concentration is 0.6molL-1The carboxylic that 100mL concentration is 1% is added in calcium chloride solution
Methylcellulose (CMC) solution is uniformly mixed, then ultrasound, be added with stirring it is isometric, isoconcentration with calcium chloride solution
Sodium carbonate liquor is centrifuged after ten minutes, and sediment is successively washed 3 times with distilled water, dehydrated alcohol respectively, is done at 80 ± 2 DEG C
Obtain spherical calcium carbonate within dry 24 ± 2 hours；
(2) preparation of nano-scale hollow silica dioxide granule: spherical calcium carbonate made from 1g is weighed as template, is added to
In the round-bottomed flask of 100mL, 30mL ethyl alcohol, 20mL water, 1.0mL concentrated ammonia liquor, 0.10g cetyl trimethyl bromination are sequentially added
Ammonium (CTAB), 1.0mL ethyl orthosilicate (TEOS) are stirred to react 4 hours；Centrifugation, precipitates washed with EtOH, preliminarily dried 6
It is heated 2 ± 0.5 hours at 250 ± 10 DEG C again after hour, 0.1molL is used after natural cooling-1Salt acid soak 24 hours with
Upper removal is used as the calcium carbonate of template, finally calcines 4 ± 1 hours at 600 ± 20 DEG C, obtains nano-scale hollow silica
Grain；
(3) rare-earth complex coats nano-hollow SiO2Synthesis: take hollow silicon dioxide made from 0.1g to be dissolved in the second of 20mL
In alcohol, two hours of ultrasonic disperse, the concentrated ammonia liquor of 1mL is added, makes solution alkaline；Adding 0.2ml concentration is 0.1moL
L-1First ligand, continues ultrasound 30 minutes, then continuously adds isometric, concentration 0.3moLL into solution again-1Second
Ligand and 0.2ml concentration are 0.1moLL-1TbCl3·6H2O obtains rare-earth complex cladding and receives after persistently stirring 4 hours
The hollow SiO of rice2Particle；Wherein first ligand is Phen (phen), and Ligands are acetylacetone,2,4-pentanedione (acac).
8. claim 1,2 or 3 rare-earth complexs coat nano-hollow SiO2As fluorescent marker in research silicon rubber body
The application of filler distribution situation in system.
9. claim 1,2 or 3 rare-earth complexs coat nano-hollow SiO2As DNA fluorescence probe in research poly-nuclear glycosides
Application in sour conformation change.
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| CN114539341A (en) * | 2022-02-26 | 2022-05-27 | 青岛大学 | Rare earth complex doped DNA crystal for detecting medicine and preparation method and application thereof |
| CN115043420A (en) * | 2022-07-13 | 2022-09-13 | 西安交通大学 | Porous hollow calcium carbonate nanosphere and preparation method and application thereof |
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