CN108034419A - A kind of water solubility full-inorganic perovskite quantum dot and preparation method thereof - Google Patents

A kind of water solubility full-inorganic perovskite quantum dot and preparation method thereof Download PDF

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CN108034419A
CN108034419A CN201711307716.6A CN201711307716A CN108034419A CN 108034419 A CN108034419 A CN 108034419A CN 201711307716 A CN201711307716 A CN 201711307716A CN 108034419 A CN108034419 A CN 108034419A
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quantum dot
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perovskite quantum
inorganic perovskite
water
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CN108034419B (en
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王著元
杨朝雁
宗慎飞
崔平
崔一平
王春雷
徐淑宏
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Southeast University
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    • B82Y20/00Nanooptics, e.g. quantum optics or photonic crystals
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
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Abstract

The present invention discloses a kind of water-soluble full-inorganic perovskite quantum dot and preparation method thereof, the water-soluble full-inorganic perovskite quantum dot is micelle-like structures, its internal layer is full-inorganic perovskite quantum dot, its outer layer is amphiphilic phosphatide, it is connected between ectonexine by hydrophilic with hydrophobic interaction, its preparation method is as follows:1) full-inorganic perovskite quantum dot toluene solution is prepared, 2) full-inorganic perovskite quantum dot toluene solution is uniformly mixed with amphiphilic phosphatide chloroformic solution, it is dissolved in after removing organic solvent in ultra-pure water, obtains water-soluble full-inorganic perovskite quantum dot.The present invention utilizes the phosphatide of biocompatibility, oil-soluble full-inorganic perovskite quantum dot is dispersed in water, and the realize full-inorganic perovskite quantum dot fluorescent emission of more than 10 days in water, overcome the bio-imaging caused by perovskite quantum dot easily hydrolyzes in water and limit.

Description

A kind of water solubility full-inorganic perovskite quantum dot and preparation method thereof
Technical field
The present invention relates to a kind of water-soluble full-inorganic perovskite quantum dot and preparation method thereof, belong to nanomaterial science and glimmering Light analysis field.
Background technology
Quantum dot (quantum dots, QDs) is also referred to as semiconductor nanocrystal (semiconductor Nanocrystal), refer to reach certain critical dimension (Exciton Bohr Radius) on three dimensions and there is quantum confined effect Semi-conducting material.As a kind of new inorganic fluorescent probe, quantum dot has many unique properties, can be efficiently against Some of organic fluorescent dye and fluorescin deadly defects, are mainly shown as:(1) exciting light spectrum width and continuously distributed;(2) send out It is narrow to penetrate spectrum, usual halfwidth is 25~35nm, and symmetrical;(3) emission spectra is adjustable in the range of 400nm~1350nm; (4) fluorescence quantum efficiency is higher.Compared to traditional fluorescent dye as the difference of material is, it is necessary to a variety of excitations and hair Penetrate spectral width, the features such as overlapping phenomenon is serious, quantum dot can realize the multi-wavelength emission under a kind of excitation wavelength, and launch The overlapping phenomenon unobvious of spectrum, make it have multi-color marking and detect the potential of multicomponent biological sample.
Full-inorganic perovskite quantum dot is as a kind of semi-conducting material, and having that synthesis is simple, emission peak is relatively narrow, (halfwidth is 12~42nm), fluorescence quantum efficiency high (reaching as high as 90%), luminous peak position is adjustable (species and ratio of regulation and control halogens, Regulate and control grain size of the quantum dot synthesis temperature so as to quantum point) the features such as, it possesses huge bio-imaging advantage, but It is the bad application for limiting it on biology of water stability, therefore, there is an urgent need for a kind of water-soluble full-inorganic perovskite quantum dot Preparation method is to solve the above problems.
Phosphatide (phospholipid), is one of constituent of biomembrane, has hydrophilic head and hydrophobic tail, The structures such as liposome, micella can be easily formed, for carrying various hydrophilic, hydrophobic and amphiphilic materials, phosphatide Oil-soluble full-inorganic perovskite quantum dot is effectively dispersed in water by the surface energy that molecule is wrapped in full-inorganic perovskite quantum dot In, prevent full-inorganic perovskite quantum dot hydrolysis, improve its stability and biocompatibility, reduce its bio-toxicity.
The content of the invention
Technical problem:The object of the present invention is to provide a kind of water-soluble full-inorganic perovskite quantum dot and preparation method thereof, The stability of full-inorganic perovskite quantum dot in water is improved, realizes water miscible full-inorganic perovskite quantum dot, and the preparation Method is easy to operate, favorable repeatability, biocompatibility are high.
Technology contents:The present invention provides a kind of water-soluble full-inorganic perovskite quantum dot, the water-soluble full-inorganic Perovskite quantum dot is micelle-like structures, its internal layer is full-inorganic perovskite quantum dot CsPbX3Or full-inorganic perovskite quantum dot CsPb(BrnA1-n)3, X represents one kind in Cl, Br or I, and A represents one kind in Cl or I, and 0 < n < 1, its outer layer is amphiphilic Phosphatide, is connected by hydrophilic with hydrophobic interaction between ectonexine.
Wherein:
The water-soluble full-inorganic perovskite quantum dot is micelle-like structures, its internal layer is full-inorganic perovskite quantum dot CsPbX3With oil-soluble nano particles or full-inorganic perovskite quantum dot CsPb (BrnA1-n)3And oil-soluble nano particles, X are represented One kind in Cl, Br or I, A represent one kind in Cl or I, and 0 < n < 1, its outer layer is amphiphilic phosphatide, is passed through between ectonexine It is hydrophilic to be connected with hydrophobic interaction.
The amphiphilic phosphatide is dipalmitoylphosphatidylcholine, soybean lecithin or distearoyl phosphatidylcholine In one kind.
The full-inorganic perovskite quantum dot CsPbX3Or full-inorganic perovskite quantum dot CsPb (BrnA1-n)3With parents Property phosphatide Mixing ratio by weight example be 1~1.35:54.
The full-inorganic perovskite quantum dot CsPbX3Or full-inorganic perovskite quantum dot CsPb (BrnA1-n)3It is molten with oil Property nano-particle, amphiphilic phosphatide three Mixing ratio by weight example be 1~1.35:1~1.35:54.
Present invention also offers a kind of preparation method of water-soluble full-inorganic perovskite quantum dot, this method includes following step Suddenly:
1) full-inorganic perovskite quantum dot CsPbX3Or full-inorganic perovskite quantum dot CsPb (BrnA1-n)3Preparation:By point Minor CsPbX3The molar ratio of middle each element is by PbX2Powder and CsX powder, which are dissolved in dimethyl sulfoxide (DMSO), obtains mixed solution I, Or by molecular formula CsPb (BrnA1-n)3The molar ratio of middle each element is by PbBr2Powder, PbA2Powder, CsBr powder and CsA powder End, which is dissolved in dimethyl sulfoxide (DMSO), obtains mixed solution II, backward mixed solution I or mixed solution II in add oleic acid and oil Amine, ultrasound to clarification obtain precursor solution, afterwards add in toluene precursor solution, obtain full-inorganic perovskite quantum dot CsPbX3Toluene solution or full-inorganic perovskite quantum dot CsPb (BrnA1-n)3Toluene solution;
2) preparation of water-soluble full-inorganic perovskite quantum dot:In proportion by full-inorganic perovskite quantum dot CsPbX3First Benzole soln or full-inorganic perovskite quantum dot CsPb (BrnA1-n)3Toluene solution received with amphiphilic phosphatide chloroformic solution, oil-soluble Rice corpuscles chloroformic solution after mixing, removes organic solvent and forms uniform film, afterwards by Film Fractionation in ultra-pure water, obtain To water-soluble full-inorganic perovskite quantum dot.
Wherein:
PbX in mixed solution I described in step 1)2Concentration be 0.4mM~1mM, PbA in the mixed solution II2's Concentration is 0.2mM~0.5mM;Oleic acid and oleyl amine are added into mixed solution I or mixed solution II described in step 1), refer to by According to volume ratio mixed solution I or mixed solution II:Oleic acid:Oleyl amine is 10~30:1~6:0.5~0.8 adds oleic acid and oleyl amine Into mixed solution I or mixed solution II;Adding precursor solution in toluene described in step 1), toluene and precursor solution Volume ratio be 1~100:1.
Described in step 1) will precursor solution add toluene in refer to temperature be 10~40 DEG C, stir speed (S.S.) be Under conditions of 1000rpm~1500rpm, precursor solution is added in toluene.
Amphiphilic phosphatide chloroformic solution described in step 2) is added in chloroform by amphiphilic phosphatide powder to be prepared, its concentration is 10~20mg/mL.
Removal organic solvent described in step 2) formed uniform film refer to depressurize on a rotary evaporator remove it is organic molten Agent.
Described in step 2) by Film Fractionation in ultra-pure water, obtaining that water-soluble full-inorganic perovskite quantum dot refers to will be thin After film is dissolved in ultra-pure water, further through centrifuging, being re-dissolved in purify in ultra-pure water, water-soluble full-inorganic perovskite amount is obtained Sub- point.
Beneficial effect:Compared with prior art, the present invention has the advantage that:
1) present invention uses phosphatide technique for packing, coats immobilized artificial membrane in oil-soluble full-inorganic perovskite quantum dot surface, carries The high water stability of full-inorganic perovskite quantum dot, makes it possible biologic applications;
2) present invention improves the biocompatibility of full-inorganic perovskite quantum dot using immobilized artificial membrane, while reduces quantum The release of toxic element in point, reduces the bio-toxicity of quantum dot;
3) present invention is easy to operate, and alternative structure is more, and repeatability is high, to obtain water-soluble full-inorganic perovskite amount The method that son point provides simple and effective.
Brief description of the drawings
Fig. 1 is water-soluble full-inorganic CsPbBr prepared by the present invention3Perovskite quantum dot in 11d fluorescence with the time change Change trend schematic diagram;
Fig. 2 is the water-soluble full-inorganic CsPbBr for having Magnetic Isolation ability3Fluorescence is at any time in 11d for perovskite quantum dot Between variation tendency schematic diagram.
Embodiment
The present invention, as medium, is dispersed in oil-soluble full-inorganic perovskite quantum dot using amphiphilic phospholipid molecule In water, possess the ability of biologic applications, the present invention is further described with reference to the accompanying drawings and examples:
Embodiment 1:
A kind of water solubility full-inorganic perovskite quantum dot, the water-soluble full-inorganic perovskite quantum dot is micellelike knot Structure, its internal layer are full-inorganic perovskite quantum dot CsPbBr3, outer layer is amphiphilic phosphatide dipalmitoylphosphatidylcholine, inside and outside It is connected between layer by hydrophilic with hydrophobic interaction, wherein full-inorganic perovskite quantum dot CsPbBr3, two palmityl phosphatide The part by weight of phatidylcholine is 1:54, its preparation comprises the following steps:
Step 1:In molar ratio 1:1 takes lead bromide powder and cesium bromide powder to be dissolved in 10mL dimethyl sulfoxide (DMSO)s, wherein Bromination lead concentration is 0.4mM;Add 1mL oleic acid and 0.5mL oleyl amines are stablized, ultrasound to solution is clarified, and obtains precursor solution; By the above-mentioned presomas of 0.1mL in the case where 30 DEG C are stirred energetically, it is slowly added in 10mL toluene, obtains full-inorganic CsPbBr3Perovskite Quantum dot.
Step 2:Dipalmitoylphosphatidylcholine powder 200mg is taken, is dissolved in 20mL chloroforms, obtains the two of 10mg/mL Palmitoylphosphatidyl choline chloroformic solution.
Step 3:In 100mL single-necked flasks, by full-inorganic CsPbBr3Perovskite quantum dot toluene solution and two palmityls Phosphatidyl choline chloroformic solution is according to 1:54 ratio is sufficiently mixed, and organic solvent is evaporated under reduced pressure, obtains uniform film.
Step 4:Adding deionized water makes film all after dissolving, and centrifugation, is dispersed in water again, obtain it is water-soluble completely without Machine perovskite quantum dot.
Embodiment 2:
A kind of water solubility full-inorganic perovskite quantum dot, the water-soluble full-inorganic perovskite quantum dot is micellelike knot Structure, its internal layer are full-inorganic perovskite quantum dot CsPbBr1.5Cl1.5, outer layer is amphiphilic phosphatide dipalmitoylphosphatidylcholine, It is connected between ectonexine by hydrophilic with hydrophobic interaction, wherein full-inorganic perovskite quantum dot CsPbBr1.5Cl1.5, two The part by weight of palmitoylphosphatidyl choline is 1.35:54, its preparation comprises the following steps:
Step 1:It is 0.5 according to molar ratio:0.5:1 takes lead bromide powder, lead chloride powder and cesium bromide powder to be dissolved in In 10mL dimethyl sulfoxide (DMSO)s, wherein chlorination lead concentration is 0.2mM;Add 2mL oleic acid and 0.5mL oleyl amines are stablized, it is ultrasonic to molten Liquid is clarified, and obtains precursor solution;By the above-mentioned presomas of 1mL in the case where 30 DEG C are stirred energetically, it is slowly added in 10mL toluene, obtains Full-inorganic perovskite quantum dot CsPbBr1.5Cl1.5Toluene solution.
Step 2:Dipalmitoylphosphatidylcholine powder 200mg is taken, is dissolved in 20mL chloroforms, obtains the two of 10mg/mL Palmitoylphosphatidyl choline chloroformic solution.
Step 3:In 100mL single-necked flasks, by full-inorganic perovskite quantum dot CsPbBr1.5Cl1.5Toluene solution and two Palmitoylphosphatidyl choline chloroformic solution is according to 1.35:54 ratio is sufficiently mixed, and organic solvent is evaporated under reduced pressure, and is obtained uniformly thin Film.
Step 4:After addition deionized water makes film all dissolve, centrifugation, is dispersed in water again.
Embodiment 3:
A kind of water solubility full-inorganic perovskite quantum dot, the water-soluble full-inorganic perovskite quantum dot is micellelike knot Structure, its internal layer are full-inorganic perovskite quantum dot CsPbBr1.5I1.5, outer layer is amphiphilic phosphatide dipalmitoylphosphatidylcholine, It is connected between ectonexine by hydrophilic with hydrophobic interaction, wherein full-inorganic perovskite quantum dot CsPbBr1.5I1.5, two palm fibre The part by weight of palmitic acid phosphatidyl choline is 1.2:54, its preparation comprises the following steps:
Step 1:It is 0.5 according to molar ratio:0.5:1 takes lead bromide powder, lead iodide powder and cesium bromide powder to be dissolved in In 10mL dimethyl sulfoxide (DMSO)s, wherein iodate lead concentration is 0.5mM;Add 2mL oleic acid and 0.5mL oleyl amines are stablized, it is ultrasonic to molten Liquid is clarified, and obtains precursor solution;By the above-mentioned presomas of 1mL in the case where 30 DEG C are stirred energetically, it is slowly added in 10mL toluene, obtains Full-inorganic perovskite quantum dot CsPbBr1.5I1.5Toluene solution.
Step 2:Dipalmitoylphosphatidylcholine powder 200mg is taken, is dissolved in 20mL chloroforms, obtains the two of 10mg/mL Palmitoylphosphatidyl choline chloroformic solution.
Step 3:In 100mL single-necked flasks, by full-inorganic perovskite quantum dot CsPbBr1.5I1.5Toluene solution and two palm fibres Palmitic acid phosphatidyl choline chloroformic solution is according to 1.2:54 ratio is sufficiently mixed, and organic solvent is evaporated under reduced pressure, obtains uniform film.
Step 4:After addition deionized water makes film all dissolve, centrifugation, is dispersed in water again.
Embodiment 4:
A kind of water solubility full-inorganic perovskite quantum dot, the water-soluble full-inorganic perovskite quantum dot is micellelike knot Structure, its internal layer are full-inorganic perovskite quantum dot CsPbBr3, outer layer is amphiphilic soybean lecithin, by hydrophilic between ectonexine It is connected with hydrophobic interaction, wherein full-inorganic perovskite quantum dot CsPbBr3, soybean lecithin part by weight be 1:54, Its preparation comprises the following steps:
Step 1:In molar ratio 1:1 takes lead bromide powder and cesium bromide powder to be dissolved in 10mL dimethyl sulfoxide (DMSO)s, wherein Bromination lead concentration is 0.6mM;Add 1mL oleic acid and 0.5mL oleyl amines are stablized, ultrasound to solution is clarified, and obtains precursor solution; By the above-mentioned presomas of 1mL in the case where 30 DEG C are stirred energetically, it is slowly added in 1mL toluene, obtains full-inorganic CsPbBr3Perovskite quantum Point.
Step 2:Soybean lecithin powder 200mg is taken, is dissolved in 20mL chloroforms, obtains the soybean lecithin chloroform of 10mg/mL Solution.
Step 3:In 100mL single-necked flasks, by full-inorganic CsPbBr3Perovskite quantum dot toluene solution and soybean lecithin Chloroformic solution is according to 1:54 ratio is sufficiently mixed, and organic solvent is evaporated under reduced pressure, obtains uniform film.
Step 4:After addition deionized water makes film all dissolve, centrifugation, is dispersed in water again.
Embodiment 5:
A kind of water solubility full-inorganic perovskite quantum dot, the water-soluble full-inorganic perovskite quantum dot is micellelike knot Structure, its internal layer are full-inorganic perovskite quantum dot CsPbBr3, outer layer is amphiphilic distearoyl phosphatidylcholine, ectonexine Between be connected by hydrophilic with hydrophobic interaction, wherein full-inorganic perovskite quantum dot CsPbBr3, distearyl acyl group phosphatide The part by weight of phatidylcholine is 1:54, its preparation comprises the following steps:
Step 1:In molar ratio 1:1 takes lead bromide powder and cesium bromide powder to be dissolved in 10mL dimethyl sulfoxide (DMSO)s, wherein Bromination lead concentration is 0.8mM;Add 1mL oleic acid and 0.5mL oleyl amines are stablized, ultrasound to solution is clarified, and obtains precursor solution; By the above-mentioned presomas of 0.1mL in the case where 30 DEG C are stirred energetically, it is slowly added in 10mL toluene, obtains full-inorganic CsPbBr3Perovskite Quantum dot.
Step 2:Distearoyl phosphatidylcholine powder 200mg is taken, is dissolved in 20mL chloroforms, obtains 10mg/mL's Distearoyl phosphatidylcholine chloroformic solution.
Step 3:In 100mL single-necked flasks, by full-inorganic CsPbBr3Perovskite quantum dot toluene solution and distearyl Base phosphatidyl choline chloroformic solution is according to 1:54 ratio is sufficiently mixed, and organic solvent is evaporated under reduced pressure, obtains uniform film.
Step 4:After addition deionized water makes film all dissolve, centrifugation, is dispersed in water again.
Embodiment 6:
A kind of water solubility full-inorganic perovskite quantum dot, the water-soluble full-inorganic perovskite quantum dot is micellelike knot Structure, its internal layer are full-inorganic perovskite quantum dot CsPbBr3With oil-soluble ferriferrous oxide nano-particle, outer layer is amphiphilic two Palmitoylphosphatidyl choline, is connected between ectonexine, wherein full-inorganic perovskite quantum by hydrophilic with hydrophobic interaction Point CsPbBr3, oil-soluble ferriferrous oxide nano-particle, dipalmitoylphosphatidylcholine part by weight be 1:1:54, it is made It is standby to comprise the following steps:
Step 1:It is 1 to take the molar ratio of lead bromide powder and cesium bromide powder:1, it is dissolved in 10mL dimethyl sulfoxide (DMSO)s, Wherein bromination lead concentration is 0.4mM;Add 1mL oleic acid and 0.5mL oleyl amines are stablized, ultrasound to solution is clarified, and obtains presoma Solution;By the above-mentioned presomas of 1mL in the case where 30 DEG C are stirred energetically, it is slowly added in 1mL toluene, obtains full-inorganic perovskite quantum dot CsPbBr3Toluene solution.
Step 2:Dipalmitoylphosphatidylcholine powder 200mg is taken, is dissolved in 20mL chloroforms, obtains the two of 10mg/mL Palmitoylphosphatidyl choline chloroformic solution.
Step 3:Oil-soluble ferriferrous oxide nano-particle 200mg is taken, is dissolved in 20mL chloroforms, obtains 10mg/mL's Oil-soluble ferriferrous oxide nano-particle chloroformic solution.
Step 4:In 100mL single-necked flasks, by full-inorganic perovskite quantum dot CsPbBr3:Oil-soluble ferroso-ferric oxide Nano-particle chloroformic solution:Dipalmitoylphosphatidylcholine chloroformic solution is according to 1:1:54 ratio is sufficiently mixed, and is evaporated under reduced pressure Organic solvent, obtains uniform film.
Step 5:After addition deionized water makes film all dissolve, centrifugation, is dispersed in water again.
Embodiment 7:
A kind of water solubility full-inorganic perovskite quantum dot, the water-soluble full-inorganic perovskite quantum dot is micellelike knot Structure, its internal layer are full-inorganic perovskite quantum dot CsPbBr3With oil-soluble ferriferrous oxide nano-particle, outer layer is amphiphilic two Palmitoylphosphatidyl choline, is connected between ectonexine, wherein full-inorganic perovskite quantum by hydrophilic with hydrophobic interaction Point CsPbBr3, oil-soluble ferriferrous oxide nano-particle, dipalmitoylphosphatidylcholine part by weight be 1.35:1:54, its Preparation comprises the following steps:
Step 1:It is 1 to take the molar ratio of lead bromide powder and cesium bromide powder:1, it is dissolved in 10mL dimethyl sulfoxide (DMSO)s, Wherein bromination lead concentration is 0.5mM;Add 1mL oleic acid and 0.5mL oleyl amines are stablized, ultrasound to solution is clarified, and obtains presoma Solution;By the above-mentioned presomas of 1mL in the case where 30 DEG C are stirred energetically, it is slowly added in 1mL toluene, obtains full-inorganic perovskite quantum dot CsPbBr3Toluene solution.
Step 2:Dipalmitoylphosphatidylcholine powder 200mg is taken, is dissolved in 20mL chloroforms, obtains the two of 10mg/mL Palmitoylphosphatidyl choline chloroformic solution.
Step 3:Oil-soluble ferriferrous oxide nano-particle 200mg is taken, is dissolved in 20mL chloroforms, obtains 10mg/mL's Oil-soluble ferriferrous oxide nano-particle chloroformic solution.
Step 4:In 100mL single-necked flasks, by full-inorganic perovskite quantum dot CsPbBr3:Oil-soluble ferroso-ferric oxide Nano-particle chloroformic solution:Dipalmitoylphosphatidylcholine chloroformic solution is according to 1.35:1:54 ratio is sufficiently mixed, and decompression is steamed Organic solvent is sent out, obtains uniform film.
Step 5:After addition deionized water makes film all dissolve, centrifugation, is dispersed in water again.
Embodiment 8:
A kind of water solubility full-inorganic perovskite quantum dot, the water-soluble full-inorganic perovskite quantum dot is micellelike knot Structure, its internal layer are full-inorganic perovskite quantum dot CsPbBr3With oil-soluble gold nanoparticle, outer layer is amphiphilic two palmityls phosphorus Phosphatidylcholine, is connected between ectonexine, wherein full-inorganic perovskite quantum dot by hydrophilic with hydrophobic interaction CsPbBr3, oil-soluble gold nanoparticle, dipalmitoylphosphatidylcholine part by weight be 1:1:54, its preparation includes following Step:
Step 1:It is 1 to take the molar ratio of lead bromide powder and cesium bromide powder:1, it is dissolved in 10mL dimethyl sulfoxide (DMSO)s, Wherein bromination lead concentration is 0.7mM;Add 1mL oleic acid and 0.5mL oleyl amines are stablized, ultrasound to solution is clarified, and obtains presoma Solution;By the above-mentioned presomas of 1mL in the case where 30 DEG C are stirred energetically, it is slowly added in 1mL toluene, obtains full-inorganic perovskite quantum dot CsPbBr3Toluene solution.
Step 2:Dipalmitoylphosphatidylcholine powder 200mg is taken, is dissolved in 20mL chloroforms, obtains the two of 10mg/mL Palmitoylphosphatidyl choline chloroformic solution.
Step 3:Oil-soluble gold nanoparticle 200mg is taken, is dissolved in 20mL chloroforms, obtains the oil-soluble gold of 10mg/mL Nano-particle chloroformic solution.
Step 4:In 100mL single-necked flasks, by full-inorganic perovskite quantum dot CsPbBr3:Oil-soluble gold nanoparticle Chloroformic solution:Dipalmitoylphosphatidylcholine chloroformic solution is according to 1:1:54 ratio is sufficiently mixed, and organic solvent is evaporated under reduced pressure, Obtain uniform film.
Step 5:After addition deionized water makes film all dissolve, centrifugation, is dispersed in water again.
Embodiment 9:
A kind of water solubility full-inorganic perovskite quantum dot, the water-soluble full-inorganic perovskite quantum dot is micellelike knot Structure, its internal layer are full-inorganic perovskite quantum dot CsPbBr3With oil-soluble gold nanoparticle, outer layer is amphiphilic distearyl acyl group Phosphatidyl choline, is connected between ectonexine, wherein full-inorganic perovskite quantum dot by hydrophilic with hydrophobic interaction CsPbBr3, oil-soluble gold nanoparticle, distearoyl phosphatidylcholine part by weight be 1:1.35:54, its preparation includes Following steps:
Step 1:It is 1 to take the molar ratio of lead bromide powder and cesium bromide powder:1, it is dissolved in 10mL dimethyl sulfoxide (DMSO)s, Wherein bromination lead concentration is 0.4mM;Add 1mL oleic acid and 0.5mL oleyl amines are stablized, ultrasound to solution is clarified, and obtains presoma Solution;By the above-mentioned presomas of 1mL in the case where 30 DEG C are stirred energetically, it is slowly added in 1mL toluene, obtains full-inorganic perovskite quantum dot CsPbBr3Toluene solution.
Step 2:Distearoyl phosphatidylcholine powder 200mg is taken, is dissolved in 20mL chloroforms, obtains 10mg/mL's Distearoyl phosphatidylcholine chloroformic solution.
Step 3:Oil-soluble gold nanoparticle 200mg is taken, is dissolved in 20mL chloroforms, obtains the oil-soluble gold of 10mg/mL Nano-particle chloroformic solution.
Step 4:In 100mL single-necked flasks, by full-inorganic perovskite quantum dot CsPbBr3:Oil-soluble gold nanoparticle Chloroformic solution:Distearoyl phosphatidylcholine chloroformic solution is according to 1:1.35:54 ratio is sufficiently mixed, and is evaporated under reduced pressure organic Solvent, obtains uniform film.
Step 5:After addition deionized water makes film all dissolve, centrifugation, is dispersed in water again.
Fig. 1, which can be seen that the full-inorganic perovskite quantum dot coated by phosphatide, can realize more than 10 days glimmering in water Light emitting;Fig. 2, which can be seen that functional nanoparticle, can simply be added into water-soluble full-inorganic perovskite quantum dot In, and there is long-time fluorescent emission ability.
The above is only the preferred embodiment of the present invention, it should be pointed out that:For the ordinary skill people of the art For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications also should It is considered as protection scope of the present invention.

Claims (10)

  1. A kind of 1. water solubility full-inorganic perovskite quantum dot, it is characterised in that:The water-soluble full-inorganic perovskite quantum dot For micelle-like structures, its internal layer is full-inorganic perovskite quantum dot CsPbX3Or full-inorganic perovskite quantum dot CsPb (BrnA1-n)3, X represent Cl, Br or I in one kind, A represent Cl or I in one kind, 0 < n < 1, its outer layer is amphiphilic phosphatide, It is connected between ectonexine by hydrophilic with hydrophobic interaction.
  2. A kind of 2. water-soluble full-inorganic perovskite quantum dot as claimed in claim 1, it is characterised in that:The water solubility is complete Inorganic perovskite quantum dot is micelle-like structures, its internal layer is full-inorganic perovskite quantum dot CsPbX3And oil-soluble nano particles Or full-inorganic perovskite quantum dot CsPb (BrnA1-n)3And oil-soluble nano particles, X represent one kind in Cl, Br or I, A is represented One kind in Cl or I, 0 < n < 1, its outer layer are amphiphilic phosphatide, are connected between ectonexine by hydrophilic with hydrophobic interaction Connect.
  3. A kind of 3. water-soluble full-inorganic perovskite quantum dot as claimed in claim 1 or 2, it is characterised in that:The parents Property phosphatide be dipalmitoylphosphatidylcholine, soybean lecithin or distearoyl phosphatidylcholine in one kind.
  4. A kind of 4. water-soluble full-inorganic perovskite quantum dot as claimed in claim 1, it is characterised in that:The full-inorganic calcium Titanium ore quantum dot CsPbX3Or full-inorganic perovskite quantum dot CsPb (BrnA1-n)3Mixing ratio by weight example with amphiphilic phosphatide is 1 ~1.35:54.
  5. A kind of 5. water-soluble full-inorganic perovskite quantum dot as claimed in claim 2, it is characterised in that:The full-inorganic calcium Titanium ore quantum dot CsPbX3Or full-inorganic perovskite quantum dot CsPb (BrnA1-n)3With oil-soluble nano particles, amphiphilic phosphatide three The Mixing ratio by weight example of person is 1~1.35:1~1.35:54.
  6. 6. a kind of preparation method of full-inorganic perovskite quantum dot water-soluble as described in claim 1 or 2, its feature exist In:This method comprises the following steps:
    1) full-inorganic perovskite quantum dot CsPbX3Or full-inorganic perovskite quantum dot CsPb (BrnA1-n)3Preparation:By molecular formula CsPbX3The molar ratio of middle each element is by PbX2Powder and CsX powder, which are dissolved in dimethyl sulfoxide (DMSO), obtains mixed solution I, or By molecular formula CsPb (BrnA1-n)3The molar ratio of middle each element is by PbBr2Powder, PbA2Powder, CsBr powder and CsA powder are molten Solution obtains mixed solution II in dimethyl sulfoxide (DMSO), backward mixed solution I or mixed solution II in add oleic acid and oleyl amine, surpass Sound to clarification obtains precursor solution, afterwards adds in toluene precursor solution, obtains full-inorganic perovskite quantum dot CsPbX3Toluene solution or full-inorganic perovskite quantum dot CsPb (BrnA1-n)3Toluene solution;
    2) preparation of water-soluble full-inorganic perovskite quantum dot:In proportion by full-inorganic perovskite quantum dot CsPbX3Toluene it is molten Liquid or full-inorganic perovskite quantum dot CsPb (BrnA1-n)3Toluene solution and amphiphilic phosphatide chloroformic solution, oil solubility nanometer grain Sub- chloroformic solution after mixing, removes organic solvent and forms uniform film, afterwards by Film Fractionation in ultra-pure water, obtain water Dissolubility full-inorganic perovskite quantum dot.
  7. A kind of 7. preparation method of water-soluble full-inorganic perovskite quantum dot as claimed in claim 6, it is characterised in that:Step 1) PbX in the mixed solution I described in2Concentration be 0.4mM~1mM, PbA in the mixed solution II2Concentration be 0.2mM ~0.5mM;Oleic acid and oleyl amine are added into mixed solution I or mixed solution II described in step 1), refers to mix according to volume ratio Close solution I or mixed solution II:Oleic acid:Oleyl amine is 10~30:1~6:Oleic acid and oleyl amine are added to mixed solution by 0.5~0.8 I or mixed solution II in;Adding precursor solution in toluene described in step 1), the volume ratio of toluene and precursor solution is 1~100:1.
  8. A kind of 8. preparation method of water-soluble full-inorganic perovskite quantum dot as claimed in claim 6, it is characterised in that:Step 2) the amphiphilic phosphatide chloroformic solution described in is added in chloroform by amphiphilic phosphatide powder to be prepared, its concentration is 10~20mg/mL.
  9. A kind of 9. preparation method of water-soluble full-inorganic perovskite quantum dot as claimed in claim 6, it is characterised in that:Step 2) the removal organic solvent described in forms uniform film and refers to depressurize removal organic solvent on a rotary evaporator.
  10. A kind of 10. preparation method of water-soluble full-inorganic perovskite quantum dot as claimed in claim 6, it is characterised in that:Step It is rapid 2) described in by Film Fractionation in ultra-pure water, obtain water-soluble full-inorganic perovskite quantum dot and refer to Film Fractionation in super After in pure water, further through centrifuging, being re-dissolved in purify in ultra-pure water, water-soluble full-inorganic perovskite quantum dot is obtained.
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107880875A (en) * 2017-12-11 2018-04-06 东南大学 Cell imaging probe based on full-inorganic perovskite quantum dot and preparation method thereof
CN109852372A (en) * 2018-12-10 2019-06-07 吉林大学 A kind of CsPbBr of phospholipid micelles encapsulation3Nanocrystalline composite material and its application
CN109913201A (en) * 2019-04-01 2019-06-21 苏州大学 Two area's fluorescent nano probe of near-infrared and its preparation and application based on black phosphorus
CN111378444A (en) * 2018-12-27 2020-07-07 Tcl集团股份有限公司 Quantum dot film and preparation method thereof
CN114525129A (en) * 2022-01-27 2022-05-24 闽都创新实验室 Preparation method and application of mixed halogen perovskite quantum dot
CN116078427A (en) * 2023-02-07 2023-05-09 无锡市第二人民医院 Nano-enzyme and method for detecting nuclear matrix protein 22 by adopting same
CN116144361A (en) * 2023-02-09 2023-05-23 平顶山学院 Lecithin functionalized high-brightness fluorescent nano probe and preparation method thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103565744A (en) * 2012-07-26 2014-02-12 上海晟纳实业有限公司 Macromolecular phosphatidylglycerol nanoliposome, and preparation methods and applications thereof
CN104388089A (en) * 2014-11-04 2015-03-04 北京理工大学 High-fluorescence-quantum-yield hybridized perovskite quantum dot material and preparation method thereof
CN105331362A (en) * 2015-12-07 2016-02-17 南京理工大学 High-yield preparing method for inorganic halogen perovskite fluorescent quantum dots at room temperature
CN105535996A (en) * 2016-01-08 2016-05-04 贵州医科大学 Novel fluorescence lipidosome nano probe and preparing method thereof
CN105720195A (en) * 2016-04-21 2016-06-29 南京理工大学 Inorganic halogen perovskite resistive random access memory and preparation method
CN106590626A (en) * 2016-12-06 2017-04-26 广东昭信光电科技有限公司 Cation-doped perovskite type quantum dot and preparation method thereof
CN107195741A (en) * 2017-04-06 2017-09-22 南京理工大学 A kind of full-inorganic quantum dot backlight LED preparation method

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103565744A (en) * 2012-07-26 2014-02-12 上海晟纳实业有限公司 Macromolecular phosphatidylglycerol nanoliposome, and preparation methods and applications thereof
CN104388089A (en) * 2014-11-04 2015-03-04 北京理工大学 High-fluorescence-quantum-yield hybridized perovskite quantum dot material and preparation method thereof
CN105331362A (en) * 2015-12-07 2016-02-17 南京理工大学 High-yield preparing method for inorganic halogen perovskite fluorescent quantum dots at room temperature
CN105535996A (en) * 2016-01-08 2016-05-04 贵州医科大学 Novel fluorescence lipidosome nano probe and preparing method thereof
CN105720195A (en) * 2016-04-21 2016-06-29 南京理工大学 Inorganic halogen perovskite resistive random access memory and preparation method
CN106590626A (en) * 2016-12-06 2017-04-26 广东昭信光电科技有限公司 Cation-doped perovskite type quantum dot and preparation method thereof
CN107195741A (en) * 2017-04-06 2017-09-22 南京理工大学 A kind of full-inorganic quantum dot backlight LED preparation method

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107880875A (en) * 2017-12-11 2018-04-06 东南大学 Cell imaging probe based on full-inorganic perovskite quantum dot and preparation method thereof
CN107880875B (en) * 2017-12-11 2020-01-07 东南大学 Cell imaging probe based on all-inorganic perovskite quantum dots and preparation method thereof
CN109852372A (en) * 2018-12-10 2019-06-07 吉林大学 A kind of CsPbBr of phospholipid micelles encapsulation3Nanocrystalline composite material and its application
CN109852372B (en) * 2018-12-10 2021-10-29 吉林大学 Phospholipid micelle encapsulated CsPbBr3Nanocrystalline composite material and application thereof
CN111378444A (en) * 2018-12-27 2020-07-07 Tcl集团股份有限公司 Quantum dot film and preparation method thereof
CN109913201A (en) * 2019-04-01 2019-06-21 苏州大学 Two area's fluorescent nano probe of near-infrared and its preparation and application based on black phosphorus
CN109913201B (en) * 2019-04-01 2022-03-01 苏州大学 Near-infrared two-region fluorescent nano probe based on black phosphorus and preparation and application thereof
CN114525129A (en) * 2022-01-27 2022-05-24 闽都创新实验室 Preparation method and application of mixed halogen perovskite quantum dot
CN114525129B (en) * 2022-01-27 2023-10-03 闽都创新实验室 Preparation method and application of mixed halogen perovskite quantum dot
CN116078427A (en) * 2023-02-07 2023-05-09 无锡市第二人民医院 Nano-enzyme and method for detecting nuclear matrix protein 22 by adopting same
CN116144361A (en) * 2023-02-09 2023-05-23 平顶山学院 Lecithin functionalized high-brightness fluorescent nano probe and preparation method thereof

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