CN107619661A - Interface self assembly rare earth compounding supermolecule fluorescence/chiral nano composite material and preparation method thereof - Google Patents
Interface self assembly rare earth compounding supermolecule fluorescence/chiral nano composite material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to nano luminescent material technical field, specially a kind of interface self assembly rare earth compounding supermolecule fluorescence/chiral nano composite material and preparation method thereof.The present invention is first with interface silanization and substitution reaction, in the monofilm that the surface of nano silicon is formed, and passes through with inorganic salt of rare earth Nano Complexes of the coordination generation with fluorescent characteristic of solid liquid interface；Secondly, Nano Complexes and beta diketone class part, double (oxazoline group) pyridine chiral ligands, the solid liquid interface coordination between three pyridine golden pheasant alkali chiral ligands, generation is with the difunctional organic-inorganic nanosized supramolecular material of fluorescence and supermolecule chirality.The fluorescent nano material has the characteristics that the specific surface area of nano material is big, is easy to purify and separates.These nano composite materials can be used for the fields such as the fluorescence imaging of development of new nano-luminescent material/nano fluorescent device, fluorescent marker, drug labelling and tracking, cell tissue and toy biosystem.
Description
Technical field
The invention belongs to nano luminescent material technical field, and in particular to a kind of interface self assembly rare earth compounding supermolecule
Fluorescence/chiral nano composite material and preparation method thereof.
Technical background
Numerator self-assembly technique from bottom to top is structure and the characteristic according to individual molecule or compound, by intermolecular
Noncovalent interaction, design and prepare there is specific or multifunctional supramolecular or nano composite material, and these are compound for utilization
Material assembles molecule（Nanometer）Device, realize miniaturization and the multifunction of product.The technology of molecular self-assembling mainly has：
Langmuir-Blodgett (LB) film, self-assembled film and layer assembly film；The intermolecular active force that they are relied on is usually
Van der Waals force, electrostatic interaction, hydrogen bond and coordination etc..
Nano-meter SiO_22It is not soluble in water, in addition to hydrofluoric acid, insoluble in common acid.Nano-meter SiO_22Be readily synthesized, size/
Shape is easily controllable, nontoxic, cheap, surface is easily modified and the features such as bio-compatible, has to anti-ultraviolet optical
Can, anti-aging other materials, intensity and chemical-resistance can be improved.Especially, Nano-meter SiO_22It is big with specific surface area, surface hydroxyl
Base density is high, is easy to form hybrid material with other functional group reactionses, thus as inorganic carrier material in new supermolecule material
Many fields such as material, optics, medicine, heterocatalysis are respectively provided with the prospect of being widely applied.
The luminous of rare earth compounding absorbs luminous energy by part and is transferred to rare earth ion, by the 4f electronics of metal ion
It is caused in different transitions between energy level, the electromagnetism of the various wavelength from ultraviolet light, visible ray to infrared light district can be launched
Radiation.Rare-earth complexes luminous material has the following advantages that：Photoluminescent band is narrow（Excitation is high）, light absorpting ability is strong, conversion effect
Rate is high, launch wavelength distributed area field width, fluorescence lifetime length, and stability is good.
In the present invention, our design concepts based on molecular self-assembling, first with Silanization reaction by alkyl fatty amine from
It is assembled into Nano-meter SiO_22Surface, form the film modified Nano-meter SiO_2 of fatty amine individual layer2(nanoSiO2NH2), then by double or
The benzyl bromine or benzyl chloride group and Nano-meter SiO_2 of terpyridyl derivative2Substitution reaction between the amino on surface, will double or three pyrroles
Pyridine functional group is grafted onto Nano-meter SiO_22Surface, form the nanoSiO of double/terpyridyl monofilm functionalization2BPy or
nanoSiO2TPy hybrid materials.Again, inorganic salt of rare earth (LnX is utilized3) and Nano-meter SiO_22Double/terpyridyl the film on surface it
Between interfacial coordination act on forming nanoSiO2BPy@LnX3Or nanoSiO2TPy@LnX3Nano Complexes.Finally, using with
The beta-diketon (β-dik) of good optical absorption characteristics and more pyridine ligands and nanoSiO with chiral functional group2BPy@LnX3
Or nanoSiO2TPy@LnX3Coordination between Nano Complexes, formed more with stronger red or green emitting rare earth
First complex nano material；The Nano-meter SiO_2 formed with more pyridine ligands with chirality2@rare earth compoundings nano material except
Stronger rare earth ion characteristic fluorescence transmitting is outer, also the characteristic with supermolecule chirality.
In the supermolecule nano composite ultimately generated, duplex pyridine, terpyridyl, beta-diketon and chiral more pyridines
Part is good light absorption units.They can be by the luminous energy being absorbed to by intersystem crossing process, via part three
Line state is transferred to the excited level of rare earth ion, when the electronics being excited returns to ground state by the excitation state of rare earth ion, swashs
It is to be discharged with the formation of fluorescence to send out state energy, so as to obtain having the fluorescent emission of specific rare earth ion feature.Due to β-
The part such as diketonate ligand, duplex pyridine, terpyridyl and chiral more pyridines is different to the absorbing wavelength of light, and triplet energy state is not
Together, so we by the change of part, can regulate and control the fluorescent emission of rare earth ion to a certain extent.
In the present invention, the design concept based on molecular self-assembling, first with Silanization reaction by alkyl fatty amine self assembly
To Nano-meter SiO_22Surface form the film modified Nano-meter SiO_2 of fatty amine individual layer2(nanoSiO2NH2), then pass through double or three pyrroles
The benzyl bromine or benzyl chloride group and Nano-meter SiO_2 of piperidine derivatives2Substitution reaction between the amino on surface, will double or terpyridyl function
Group is grafted onto Nano-meter SiO_22Surface, form the nanoSiO of double/terpyridyl monofilm functionalization2BPy or nanoSiO2TPy is miscellaneous
Change material.Again, inorganic salt of rare earth (LnX is utilized3) and Nano-meter SiO_22Interfacial coordination between the double/terpyridyl film on surface
Effect forms nanoSiO2BPy@LnX3Or nanoSiO2TPy@LnX3Nano Complexes.Finally, using special with good light absorbs
Property beta-diketon (β-dik) and with chiral functional group more pyridine ligands and nanoSiO2BPy@LnX3Or
nanoSiO2TPy@LnX3Coordination between Nano Complexes, formed with stronger red or green emitting rare earth multicomponent
Complex nano material；The Nano-meter SiO_2 formed with more pyridine ligands with chirality2@rare earth compoundings nano material except compared with
Strong rare earth ion characteristic fluorescence transmitting is outer, also the characteristic with supermolecule chirality.
In the supermolecule nano composite ultimately generated, duplex pyridine, terpyridyl, beta-diketon and chiral more pyridines
Part is good light absorption units.They can be by the luminous energy being absorbed to by intersystem crossing process, via part three
Line state is transferred to the excited level of rare earth ion, when the electronics being excited returns to ground state by the excitation state of rare earth ion, swashs
It is to be discharged with the formation of fluorescence to send out state energy, so as to obtain having the fluorescent emission of specific rare earth ion feature.Due to β-
The part such as diketonate ligand, duplex pyridine, terpyridyl and chiral more pyridines is different to the absorbing wavelength of light, and triplet energy state is not
Together, so we by the change of part, can regulate and control the fluorescent emission of rare earth ion to a certain extent.
The content of the invention
Simple, environment-friendly interface self assembly rare earth compounding supermolecule is prepared it is an object of the invention to provide a kind of
Fluorescence/chiral nano composite material and preparation method thereof.
Interface self assembly rare earth compounding supermolecule fluorescence/chiral nano composite material provided by the invention, is a kind of tool
Have organic and inorganic (chirality) supermolecule nano composite of strong rare-earth fluorescent transmitting, passed through from bottom to top in solid-liquid interface
Silanization reaction and intermolecular coordination and formed；Its precursor material is nano silicon, inorganic salt of rare earth, duplex pyrrole
Pyridine (BPy), terpyridyl (TPy), beta-diketon (β-dik), double (oxazoline group) pyridines (R-pybox, S-pybox) and three
Pyridine-golden pheasant bases (TPyCCD, TPyCCN) derivative.
Rare earth trifluoro sulfonate, duplex pyridine, the following institute of the chemical constitution of terpyridyl and beta-diketon in precursor material
Show：
Chiral more pyridine derivates in precursor material：Three pyridines-golden pheasant alkali (TPyCCD, TPyCCN) and the double (oxazoles of chirality
Quinoline base) pyridine (R-pybox, S-pybox) chemical structural formula it is as follows：
。
Interface self assembly rare earth compounding supermolecule fluorescence/chiral nano composite material preparation method provided by the invention,
Comprise the following steps that：
（One）Using interface self-assembling method, in nano silicon (nanoSiO2) surface graft by duplex pyridine (BPy)
Or the monofilm that terpyridyl (TPy) derivative is formed, the nanometer hybrid inorganic-organic materials of high stability are formed, are designated as
nanoSiO2BPy and nanoSiO2Tpy；Further with inorganic salt of rare earth (LnX3) pass through the coordination generation tool of solid-liquid interface
There is the complex of fluorescent characteristic, be designated as nanoSiO2BPy@LnX3And nanoSiO2TPy@LnX3；
（Two）Pass through Nano Complexes nanoSiO2BPy@LnX3Or nanoSiO2TPy@LnX3With beta-diketonate ligand (β-dik) it
Between interfacial coordination effect, formed rare earth complex supermolecule nano composite, be designated as nanoSiO2BPy@Ln(β-
dik)nAnd nanoSiO2TPy@Ln(β-dik)n；
（Three）Pass through Nano Complexes nanoSiO2BPy@LnX3Or nanoSiO2TPy@LnX3With the double (evils of chiral more pyridine ligands
Oxazoline base) pyridine (i-pybox), the interfacial coordination effect between three pyridines-golden pheasant alkali (i-TPyCCX), form rare earth binary
Complex chirality supermolecule nano composite, is designated as nanoSiO2BPy@Ln (i-pybox) and nanoSiO2TPy@Ln(i-
TPyCCX)。
In the present invention, step（One）Operating process be：
First, by the hydrophilized Nano-meter SiO_2 in surface2It is dispersed in both methanol-DMF mixed solvents (volume ratios 1:0.5-1:
2) in, the 3- TSL 8330s that mass fraction is 5-10% are added, in 60-80 DEG C of water-bath or oil bath reactor
Middle stirring reaction 24-48 hours.Room temperature is cooled to, 3000-6000 rpm are centrifuged, and are fully washed with methanol, are removed not
The 3- TSL 8330s of reaction, obtain amidized Nano-meter SiO_22；
Secondly, amination Nano-meter SiO_22Further with benzyl bromine or double/terpyridyl of benzyl chloride that mass ratio is 5-10% in first
Stirring reaction 5-10 hours in the water-bath of 60-80 DEG C of alcohol-DMF in the mixed solvents or oil bath reactor；It is cooled to room temperature, 3000-
6000 rpm are centrifuged, and are fully washed with methanol, remove unreacted organic matter, and generation pair/terpyridine ligand derives
The film modified Nano-meter SiO_2 of the individual layer of thing2Hybrid inorganic-organic materials, i.e. nanoSiO2BPy and nanoSiO2Tpy；
Finally, nanoSiO2BPy and nanoSiO2TPy hybrid materials and the inorganic salt of rare earth LnX that mass ratio is 5-10%3It is dissolved in
Methanol-DMF in the mixed solvents, reaction 24-72 hours are stirred at room temperature, 3000-6000 rpm are centrifuged, and are fully washed with methanol
Wash, remove unreacted inorganic salt of rare earth, obtain the Nano Complexes nanoSiO with rare-earth fluorescent2BPy@LnX3With
nanoSiO2TPy@LnX3。
Wherein, nanoSiO2BPy or nanoSiO2TPy concentration is 10-50 mg/mL, inorganic salt of rare earth LnX3Concentration
For 15 mg/mL.
In the present invention, step（Two）Operating process be：
By above-mentioned rare earth nano complex nanoSiO2BPy@LnX3Or nanoSiO2TPy@LnX3It is molten to be dispersed in methanol-DMF mixing
In liquid, the methanol solution for the beta-diketon anion i-TPyCCX that mass ratio is 5-10% is added while stirring（That is beta-diketon and KOH
Mol ratio be 1:1-1:1.05 methanol solution）, continue that reaction 24-72 hours, 3000-6000 rpm centrifugations point is stirred at room temperature
From, and fully washed with methanol, unreacted beta-diketon anion is removed, obtains nanoSiO2BPy@Ln(β-dik)nWith
nanoSiO2TPy@Ln(β-dik)nSupermolecule nano composite.
Wherein, nanoSiO2BPy@LnX3And nanoSiO2TPy@LnX3Concentration be 10-50 mg/mL, beta-diketon the moon from
Sub- i-TPyCCX concentration is 15 mg/mL.
In the present invention, step（Three）Operating process be：
By above-mentioned rare earth nano complex nanoSiO2BPy@LnX3Or nanoSiO2TPy@LnX3It is molten to be dispersed in chloroform-DMF mixing
In liquid, the chloroform-DMF solution for chiral more pyridine derivate i-pybox that mass ratio is about 5-10% is added while stirring, is continued
Reaction 24-72 hours are stirred at room temperature, 3000-6000 rpm are centrifuged, and are fully washed with chloroform and methanol, remove unreacted
Chiral more pyridines, obtain the nanoSiO with fluorescence and supermolecule chirality dual-use function2BPy@Ln (i-pybox) and
nanoSiO2TPy@Ln (i-TPyCCX) nano composite material.
Wherein, nanoSiO2BPy@LnX3And nanoSiO2TPy@LnX3Concentration be 10-50 mg/mL, chiral more pyridines
Derivative i-pybox concentration is 15 mg/mL.
The method provided by the invention that rare earth compounding nano-luminescent material is prepared using molecule package technique.Wherein, double/
Terpyridyl monofilm is that the method based on self-assembled film passes through Nano-meter SiO_22One kind " nanometer of the Silanization reaction generation on surface
Level " part, is then reacted with this nanometer of part and rare earth trifluoro sulfonate or nitrate etc. by interfacial coordination, and generation is with glimmering
The nanoSiO of light characteristic2BPy@LnX3Or nanoSiO2TPy@LnX3Nano Complexes.Although these Nano Complexes have had
There is the characteristics of luminescence, but because the ligancy of rare earth ion does not have saturation, less anion X−Easily dissociation, causes these nanometers
The fluorescent emission of complex is easily by some polar groups in solution（Such as-OH）Influence so that fluorescence intensity weaken；Receive
The structure of rice compound also becomes unstable.So the present invention further passes through rare earth ion and beta-diketon or chiral more
Coordination between pyridine ligand, the complexation reaction by both parts by the surface of solids, formation have more strong light absorption
The nanoSiO of ability and hydrophobic property2BPy@Ln(β-dik)nAnd nanoSiO2TPy@Ln(β-dik)nSupermolecule nano composite wood
Material, and the nanoSiO with fluorescence and supermolecule chirality dual-use function2BPy@Ln (i-pybox) and nanoSiO2TPy@Ln
(i-TPyCCX) nano composite material.
This supermolecule fluorescent nano material prepared by the present invention is not only substantially special with rare-earth complexes luminous material
Point, i.e. fluorescent emission are strong, monochromaticjty is good（Half-peak width）, fluorescence lifetime it is long and not by environmental factor interference etc., also with nanometer
The specific surface area of material is big, the features such as being easy to purify and separating.Nano composite material containing chiral ligand is also had concurrently by part
Caused by chiral induction the characteristics of supermolecule chirality material.These nano composite materials can be used for development of new nano fluorescent material
Material/nano fluorescent device, fluorescent marker, drug labelling and tracking, the fluorescence imaging of cell/tissue/toy biosystem
Deng field.
The present invention is based on interfacial molecular self-assembling technique, by rare earth compounding with object（Film）Form be fixed on nanometer
SiO2Surface, have the following advantages that：
（1）Due to this nano-luminescent material be based on high-specific surface area, mechanical strength is good, bio-compatible and cheap receives
Rice SiO2What the coordinate bond between rare earth compounding was formed, thus the composite has higher thermally and chemically stability.
（2）Because the preparation of these nano composite materials is the general principle according to molecular engineering, using from bottom to top
Method progressively generate, thus the composition of composite and distribution controllability and selectivity with molecular level.
（3）Because these composites are with solid nano SiO2Generate for carrier and connected by covalent bond and coordinate bond
Connect, thus be easy to method purifying and separation by centrifugation.
（4）Due to Nano-meter SiO_22The size of carrier is controlled in the range of 10-20 nm, and polynary part is taken with not
With the more pyridines and beta-diketon of absorbing wavelength；The different absorbing wavelengths of these parts provide the possibility of regulation excitation wavelength, more
Add the fluorescence imaging for being suitable for the biosystems such as drug labelling, cell/tissue/toy.
In a word, the preparation process of the inventive method is simple and easy, requires low to equipment, production environment, environmentally friendly, and
The regulation and control of the component and space structure to molecular material can simply be realized.
Except first layer self-assembled monolayer completed in 60 DEG C of water-bath or oil bath in the present invention, other each several parts from
Assembling is to carry out at room temperature.The separation of solid product is carried out by centrifuge, and fully washed with reaction dissolvent, is not required to
Want special consersion unit.
Brief description of the drawings
Fig. 1 be illustrate by taking 2,2 '-bipyridyl and DBM as an example duplex pyridine monofilm formation and its with the fluosulfonic acid of rare earth three
Reactant salt generates nanoSiO2BPy@Ln(CF3SO3)3Nano Complexes and with DBM react generation nanoSiO2BPy@Ln
(DBM)3The process of supermolecule nano composite.
Fig. 2 is formation and its and the rare earth for illustrating terpyridyl monofilm by taking terpyridyl, TPyCCN and R-pybox as an example
Inorganic salt reaction generates nanoSiO2TPy@Ln (i-TPyCCN) and nanoSiO2TPy@Ln (R-pybox) supermolecule chirality nanometer
The process of composite.
Fig. 3 is nano composite material nanoSiO2BPy@Eu(DBM)nBe dispersed in methanol solution centrifuge before (A) and from
The photo of (B) after heart separation；And nanoSiO2BPy@Eu(CF3SO3)3And nanoSiO2BPy@Eu(DBM)nSolid powder is not
With the photo under excitation wavelength, the nm of (C) excitation wavelength 300 and the nm of (D) excitation wavelength 365.
Embodiment
The invention is further illustrated by the following examples.
Embodiment 1：
Take the Nano-meter SiO_2 that 20 g contents are 40%2It is dispersed in 300 mL methanol-DMF mixed solvent (volume ratios 1:1) in, add
Methanol-DMF solution (20 mL) of 1 g 3- TSL 8330s, is stirred in 60 DEG C of water-baths or oil bath reactor
Mix reaction 2 days.Room temperature is cooled to, 4000 rpm are centrifuged, and are fully washed with methanol, remove unreacted 3- aminopropyls
Trimethoxy silane, obtain the amidized Nano-meter SiO_2 of white2, the amidized Nano-meter SiO_22In, surface amino groups content is about
5.3%。
Take 5 g amination Nano-meter SiO_2s2It is dispersed in 150 mL methanol-DMF mixed solvent (volume ratios 1:1) in, matter is added
It is 0.2 g 4,4 '-dimethyl chloride -2 to measure ratio, and 2 '-bipyridyl (is dissolved in 10 mL methanol-DMF in the mixed solvents), 60 DEG C of water
Stirring reaction 10 hours in bath or oil bath reactor.Room temperature is cooled to, 4000 rpm are centrifuged, and are fully washed with methanol,
Generate the film modified Nano-meter SiO_2 of the individual layer of lurid 2,2 '-bipyridine ligand2, i.e. nanoSiO2BPy.The nanometer after modification
SiO2Surface organic matter content is about 8.5%, and the material is not soluble in water and the organic solvent such as methanol, but can be dispersed in DMF
In equal solvent.
Take 2 g nanoSiO2BPy is dispersed in 50 mL methanol-DMF, add the fluosulfonic acid europiums of 0.1 g tri- methanol-
DMF solution (10 mL), reaction 2 days is stirred at room temperature.4000 rpm are centrifuged, and are fully washed with methanol, are obtained milky
Nano Complexes nanoSiO2BPy@Eu(CF3SO3)3.The inorganic and content of organics of material surface modification is about 10.2%, no
The organic solvents such as water and methanol are dissolved in, but can be dispersed in DMF equal solvents, the material has at 285 nm after tested
The characteristic absorption of bipyridyl, there is stronger rare earth Eu in the range of 580-720 nm3+The red fluorescence transmitting of ion, wherein
614 nm are most strong emission peak.
Embodiment 2：
By 2 grams of nanoSiO2BPy@Eu(CF3SO3)3Nano Complexes are dispersed in methanol-DMF mixed solutions, are added while stirring
Enter dibenzoyl methane (DBM) anion methanol solution that mass ratio is about 10%（0.2 gram of DBM and 0.05 gram of KOH mixing is molten
Liquid）.Continue that reaction 2 days is stirred at room temperature, 4000 rpm are centrifuged, and are fully washed with methanol, are removed unreacted DBM, are obtained
To milky nanoSiO2BPy@Eu(DBM)3Nano composite material.The inorganic complexes and organic matter of material surface modification
Content is about 10%, the organic solvent such as not soluble in water and methanol, but can be dispersed in DMF equal solvents, after tested the material
There is the characteristic absorption of bipyridyl at 285 nm, there is stronger rare earth Eu in the range of 580-720 nm3+Ion red is glimmering
Light is launched, wherein 613 nm are most strong emission peak.
Embodiment 3：
By 2 grams of nanoSiO2BPy@Eu(CF3SO3)3Nano Complexes are dispersed in 50 mL chloroform-DMF in the mixed solvent, side
Stirring side adds chloroform-DMF solution that 10 mL contain 0.2 g TPyCCN.Continue to be stirred at room temperature reaction 2 days, 4000 rpm from
The heart separates, and is fully washed with chloroform and methanol, removes unreacted TPyCCN, obtains lurid nanoSiO2BPy@Eu
(TPyCCN) supermolecule chirality nano composite material.The inorganic complexes and content of organics of the composite material surface are about 10%,
The organic solvents such as not soluble in water and methanol, but can be dispersed in DMF equal solvents, the material is in 285-310 nm after tested
Characteristic absorption of the place with bipyridyl and terpyridyl, has stronger rare earth Eu in the range of 570-720 nm3+Ion is red
Fluorescent emission, wherein 614 nm are most strong emission peak.Circular dichroism shows that the supramolecular materials have chiral characteristic.
Embodiment 4：
By 2 grams of nanoSiO2BPy@Eu(CF3SO3)3Nano Complexes are dispersed in 50 mL chloroform-DMF mixed solutions, while stirring
Mix side and add chloroform-DMF solution that 10 mL contain 0.2 g R-pybox.Continue that reaction 2 days, 4000 rpm centrifugations is stirred at room temperature
Separation, and fully washed with methanol, unreacted R-pybox is removed, obtains lurid nanoSiO2BPy@Eu(R-pybox)
Supermolecule chirality nano composite material.The inorganic complexes and content of organics of the composite material surface are about 10%, not soluble in water
With the organic solvent such as methanol, but it can be dispersed in DMF equal solvents, the material has connection at 285-310 nm after tested
The characteristic absorption of pyridine and terpyridyl, there is stronger rare earth Eu in the range of 570-720 nm3+Ion red fluorescence is launched,
Wherein 614 nm are most strong emission peak.Circular dichroism shows that the supramolecular materials have chiral characteristic.
Claims (8)
1. a kind of preparation method of interface self assembly rare earth compounding supermolecule fluorescence/chiral nano composite material, its feature exist
In comprising the following steps that：
（One）Using interface self-assembling method, in nano silicon (nanoSiO2) surface graft by duplex pyridine (BPy) or
The monofilm that terpyridyl (TPy) derivative is formed, forms the nanometer hybrid inorganic-organic materials of high stability, is designated as
nanoSiO2BPy and nanoSiO2TPy；Further with inorganic salt of rare earth (LnX3) pass through the coordination generation tool of solid-liquid interface
There is the complex of fluorescent characteristic, be designated as nanoSiO2BPy@LnX3And nanoSiO2TPy@LnX3；
（Two）Pass through Nano Complexes nanoSiO2BPy@LnX3Or nanoSiO2TPy@LnX3Between beta-diketonate ligand (β-dik)
Interfacial coordination effect, formed rare earth complex supermolecule nano composite, be designated as nanoSiO2BPy@Ln(β-dik)n
And nanoSiO2TPy@Ln(β-dik)n , n=1 3；
（Three）Pass through Nano Complexes nanoSiO2BPy@LnX3Or nanoSiO2TPy@LnX3With the double (oxazoles of chiral more pyridine ligands
Quinoline base) pyridine (i-pybox), the interfacial coordination effect between three pyridines-golden pheasant alkali (i-TPyCCX), form the first wife of rare earth two
Compound chirality supermolecule nano composite, is designated as nanoSiO2BPy@Ln (i-pybox) and nanoSiO2TPy@Ln(i-
TPyCCX)。
2. preparation method according to claim 1, it is characterised in that step（One）Operating process be：
First, by the hydrophilized Nano-meter SiO_2 in surface2Methanol-DMF in the mixed solvents are dispersed in, addition mass fraction is 5-
10% 3- TSL 8330s, the stirring reaction 24-48 hours in 60-80 DEG C of water-bath or oil bath reactor；It is cold
But to room temperature, 3000-6000 rpm are centrifuged, and are fully washed with methanol, remove unreacted 3- aminopropyls trimethoxy
Base silane, obtain amidized Nano-meter SiO_22；
Secondly, amination Nano-meter SiO_22Further with benzyl bromine that mass ratio is 5-10% or double/terpyridyl of benzyl chloride methanol-
Stirring reaction 5-10 hours in the water-bath of 60-80 DEG C of DMF in the mixed solvents or oil bath reactor；It is cooled to room temperature, 3000-6000
Rpm is centrifuged, and is fully washed with methanol, removes unreacted organic matter, the list of generation pair/terpyridine ligand derivative
The Nano-meter SiO_2 of tunic modification2Hybrid inorganic-organic materials, i.e. nanoSiO2BPy and nanoSiO2TPy；
Finally, nanoSiO2BPy and nanoSiO2TPy hybrid materials and the inorganic salt of rare earth LnX that mass ratio is 5-10%3It is dissolved in
Methanol-DMF in the mixed solvents, reaction 24-72 hours are stirred at room temperature, 3000-6000 rpm are centrifuged, and are fully washed with methanol
Wash, remove unreacted inorganic salt of rare earth, obtain the Nano Complexes nanoSiO with rare-earth fluorescent2BPy@LnX3With
nanoSiO2TPy@LnX3。
3. preparation method according to claim 2, it is characterised in that nanoSiO2BPy or nanoSiO2TPy concentration is
10-50 mg/mL, inorganic salt of rare earth LnX3Concentration be 15 mg/mL.
4. the preparation method according to Claims 2 or 3, it is characterised in that step（Two）Operating process be：
By above-mentioned rare earth nano complex nanoSiO2BPy@LnX3Or nanoSiO2TPy@LnX3It is molten to be dispersed in methanol-DMF mixing
In liquid, the methanol solution for the beta-diketon anion that mass ratio is 5-10% is added while stirring, continues that reaction 24-72 is stirred at room temperature
Hour, 3000-6000 rpm are centrifuged, and are fully washed with methanol, are removed unreacted beta-diketon anion, are obtained
nanoSiO2BPy@Ln(β-dik)nAnd nanoSiO2TPy@Ln(β-dik)nSupermolecule nano composite.
5. preparation method according to claim 4, it is characterised in that nanoSiO2BPy@LnX3And nanoSiO2TPy@LnX3
Concentration be 10-50 mg/mL, the concentration of beta-diketon anion is 15 mg/mL.
6. the preparation method according to claim 2 or 5, it is characterised in that step（Three）Operating process be：
By above-mentioned rare earth nano complex nanoSiO2BPy@LnX3Or nanoSiO2TPy@LnX3It is molten to be dispersed in chloroform-DMF mixing
In liquid, the chloroform-DMF solution for chiral more pyridine derivate i-TPyCCX that mass ratio is about 5-10% is added while stirring, is continued
Reaction 24-72 hours are stirred at room temperature, 3000-6000 rpm are centrifuged, and are fully washed with chloroform and methanol, remove unreacted
Chiral more pyridines, obtain the nanoSiO with fluorescence and supermolecule chirality dual-use function2BPy@Ln (i-pybox) and
nanoSiO2TPy@Ln (i-TPyCCX) nano composite material.
7. preparation method according to claim 6, it is characterised in that nanoSiO2BPy@LnX3And nanoSiO2TPy@LnX3
Concentration be 10-50 mg/mL, chiral more pyridine derivate i-TPyCCX concentration is 15 mg/mL.
A kind of 8. interface self assembly rare earth compounding oversubscription being prepared by the preparation method of claim 1,2,3,5 or 7
Sub- fluorescence/chiral nano composite material, is designated as nanoSiO2BPy@Ln(β-dik)nAnd nanoSiO2TPy@Ln(β-dik)n, n=
1-3。
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110330660A (en) * | 2019-06-11 | 2019-10-15 | 河北科技大学 | A kind of preparation method and applications of the rare-earth europium hybrid luminescent materials with aluminium ion sensing capabilities |
| CN111676012A (en) * | 2020-05-15 | 2020-09-18 | 复旦大学 | LB film of luminescent europium complex nano material and preparation method and application thereof |
| CN112047965A (en) * | 2020-09-09 | 2020-12-08 | 黑龙江大学 | Preparation method and application of complex with excited ligand interstitial transfer characteristic |
| CN112198142A (en) * | 2020-09-01 | 2021-01-08 | 浙江工业大学 | Method for distinguishing rare earth ions |
| CN116328746A (en) * | 2023-04-10 | 2023-06-27 | 新特能源股份有限公司 | Terpyridine-silica gel composite material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106939162A (en) * | 2016-01-04 | 2017-07-11 | 内蒙古大学 | SiO2The synthetic method of@Tb (phen-Si) L nuclear shell structure nano luminescent composites |
-
2017
- 2017-09-18 CN CN201710840930.1A patent/CN107619661B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106939162A (en) * | 2016-01-04 | 2017-07-11 | 内蒙古大学 | SiO2The synthetic method of@Tb (phen-Si) L nuclear shell structure nano luminescent composites |
Non-Patent Citations (1)
| Title |
|---|
| M. L. P. REDDY ET AL.: "Visible-light sensitized luminescent europium(III)-β-diketonate complexes: bioprobes for cellular imaging", 《DALTON TRANS.》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110330660A (en) * | 2019-06-11 | 2019-10-15 | 河北科技大学 | A kind of preparation method and applications of the rare-earth europium hybrid luminescent materials with aluminium ion sensing capabilities |
| CN110330660B (en) * | 2019-06-11 | 2021-07-20 | 河北科技大学 | Preparation method and application of rare earth europium hybrid luminescent material with aluminum ion sensing performance |
| CN111676012A (en) * | 2020-05-15 | 2020-09-18 | 复旦大学 | LB film of luminescent europium complex nano material and preparation method and application thereof |
| CN111676012B (en) * | 2020-05-15 | 2022-10-11 | 复旦大学 | LB film of luminescent europium complex nano material and preparation method and application thereof |
| CN112198142A (en) * | 2020-09-01 | 2021-01-08 | 浙江工业大学 | Method for distinguishing rare earth ions |
| CN112198142B (en) * | 2020-09-01 | 2023-03-28 | 浙江工业大学 | Method for distinguishing rare earth ions |
| CN112047965A (en) * | 2020-09-09 | 2020-12-08 | 黑龙江大学 | Preparation method and application of complex with excited ligand interstitial transfer characteristic |
| CN116328746A (en) * | 2023-04-10 | 2023-06-27 | 新特能源股份有限公司 | Terpyridine-silica gel composite material and preparation method thereof |
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