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CN107118773B - Method for preparing light-emitting quantum dots with circular polarization - Google Patents

Method for preparing light-emitting quantum dots with circular polarization Download PDF

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CN107118773B
CN107118773B CN201710486131.9A CN201710486131A CN107118773B CN 107118773 B CN107118773 B CN 107118773B CN 201710486131 A CN201710486131 A CN 201710486131A CN 107118773 B CN107118773 B CN 107118773B
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段鹏飞
霍胜伟
韩建雷
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Beijing Institute of Nanoenergy and Nanosystems
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Abstract

The invention provides a preparation method of gel-supported inorganic achiral quantum dots, which comprises the steps of mixing water with an aqueous solution of achiral quantum dots or achiral quantum dots, adding a solvent, and mixing again to obtain a mixed solution; and mixing the obtained mixed solution with the gel factor, heating and cooling to obtain the gel-loaded inorganic achiral quantum dot. The preparation method enables the achiral quantum dots to have the property of circular polarization luminescence, realizes CPL luminescence with the achiral quantum dots adjustable in full wave band, and realizes CPL luminescence with white light emission.

Description

Method for preparing light-emitting quantum dots with circular polarization
Technical Field
The invention belongs to the technical field of quantum dots, relates to an inorganic achiral quantum dot, and particularly relates to a preparation method of a gel-loaded inorganic achiral quantum dot.
Background
Light is a transverse electromagnetic wave, a ray that vibrates in all directions. The electric field vector E is perpendicular to the magnetic field vector H and perpendicular to the light wave propagation direction. Since the main sensitization effect is the electric field vector, the electric field vector is generally used as the vibration vector of the light wave. The plane formed by the vector of the electric field of the light wave and the propagation direction is called the vibration plane of the light wave. If the plane of vibration does not change with time, the light is called plane polarized light, and the plane of vibration is called plane of polarization. The plane polarized light can be decomposed into two circularly polarized lights with the same amplitude and frequency and opposite rotation directions. The one in which the electric vector rotates in the clockwise direction is called right-handed circularly polarized light, and the one in which the electric vector rotates in the counterclockwise direction is called left-handed circularly polarized light. Two polarized lights with the same amplitude and frequency and opposite rotation directions can be synthesized into one plane polarized light. If the two polarized lights are not the same in amplitude (intensity), the resultant will be one elliptically polarized light. The difference in absorption of the optically active substance with respect to left-handed and right-handed circularly polarized light is called circular dichroism (abbreviated as CD) of the substance. The presence of circular dichroism causes plane-polarized light propagating through the substance to become elliptically polarized and is only observed at wavelengths where absorption occurs. Circular dichroism spectroscopy reveals structural information of the ground state of chiral substances. On the basis of circular dichroism, the intensity of left and right circularly polarized light emitted by certain chiral substances is different, the phenomenon is Circular Polarization Luminescence (CPL), and the structural characteristics of excited states of the substances are expressed. The circular polarization light emission has important application value in the aspects of processing, displaying, storing and the like of optical information.
Quantum dots are quasi-zero-dimensional nanomaterials, consisting of a small number of atoms. Roughly speaking, the quantum dots have three dimensions of less than 100nm, are just like a tiny dot in appearance, and have limited movement of electrons in all directions, so that the quantum confinement effect is particularly remarkable. The main properties of quantum dots are as follows: 1) the emission spectrum of the quantum dots can be controlled by varying the size of the quantum dots. The emission spectrum of a quantum dot can be made to cover the entire visible region by varying its size and its chemical composition. In the case of CdTe quanta, their emission wavelength can be red-shifted from 510nm to 660nm as it grows from 2.5nm to 4.0nm in size; 2) the quantum dots have good light stability. The fluorescence intensity of the quantum dot is 20 times higher than that of the most commonly used organic fluorescent material rhodamine 6G, and the stability of the quantum dot is more than 100 times of that of the rhodamine 6G. Therefore, the quantum dots can observe the marked object for a long time, and a powerful tool is provided for researching the long-term interaction between biomolecules in cells; 3) quantum dots have a broad excitation spectrum and a narrow emission spectrum. The quantum dots with different particle diameters can be synchronously detected by using the same excitation light source, so that the fluorescent label can be used for multicolor labeling, and the application of the fluorescent label in the fluorescent label is greatly promoted. The wavelength range of the excitation light of the conventional organic fluorescent dye is narrow, and different fluorescent dyes usually need excitation light with multiple wavelengths to be excited, which brings much inconvenience to practical research work. In addition, the quantum dots have narrow and symmetrical fluorescence emission peaks and no tailing, and spectral overlapping is not easy to occur when the multicolor quantum dots are used simultaneously. 4) Quantum dots have a large stokes shift. The other optical property of the quantum dot different from that of the organic dye is wide Stokes shift, so that the overlapping of an emission spectrum and an excitation spectrum can be avoided, and the detection of a fluorescence spectrum signal is facilitated. 5) The biocompatibility is good. After being subjected to various chemical modifications, the quantum dots can be subjected to specific connection, have low cytotoxicity and small harm to organisms, and can be used for biological living body marking and detection. 6) The quantum dots have long fluorescence lifetime. The fluorescence lifetime of organic fluorescent dyes is typically only a few nanoseconds (which is comparable to the time for autofluorescence of many biological samples to decay). The fluorescence lifetime of the quantum dots can last for tens of nanoseconds (20 ns-50 ns), so that most of autofluorescence is already decayed after light excitation, and the fluorescence of the quantum dots still exists, and then a fluorescence signal without background interference can be obtained. In conclusion, quantum dots have excellent fluorescence characteristics such as wide and continuous distribution of excitation spectrum, narrow and symmetrical emission spectrum, adjustable color, high photochemical stability, long fluorescence lifetime and the like, and are ideal fluorescent probes.
So far, few reports of realizing circularly polarized light emission, namely realizing full-band adjustable circular polarization luminescence, exist in quantum dots. The universal method is explored to realize the circular polarization luminescence of the achiral quantum dots, the research on inorganic nano materials is expanded, and the realization of the circular polarization luminescence of the achiral quantum dots has great application value in the aspects of 3D imaging technology, molecular switches, optical data storage, optical quantum informatics, chiral recognition, medical imaging enhancement and the like.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides a preparation method of gel-loaded inorganic achiral quantum dots, which is characterized in that the inorganic chiral quantum dots and chiral gel factors are assembled together, so that the inorganic achiral quantum dots show chirality, even if the achiral quantum dots have the property of circular polarization luminescence, CPL luminescence with adjustable achiral quantum dots full wave bands is realized, and CPL luminescence with white light emission is realized.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of gel-supported inorganic achiral quantum dots, which is characterized by comprising the following steps of:
(1) mixing water with an aqueous solution of achiral quantum dots or achiral quantum dots, adding a solvent, and mixing again to obtain a mixed solution;
(2) and (2) mixing the mixed solution obtained in the step (1) with a gel factor, heating, and cooling to obtain the gel-loaded inorganic achiral quantum dot.
As a preferred technical scheme of the invention, the achiral quantum dots in the step (1) comprise any one or a combination of at least two of ZnSe/ZnS, CdS/ZnS, CdSe/ZnS, InP/ZnS, ClS (Se), ClGS (Se) or CZTS (Se), and typical but non-limiting examples of the combination are as follows: combinations of ZnSe/ZnS and CdS/ZnS, CdS/ZnS and CdSe/ZnS, CdSe/ZnS and InP/ZnS, InP/ZnS and ClS (Se), ClS (Se) and ClGS (Se), ClGS (Se) and CZTS (Se), or ZnSe/ZnS, CdS/ZnS and CdSe/ZnS, and the like.
The CdSe/ZnS can be blue light emission CdSe/ZnS quantum dots, cyan light emission CdSe/ZnS quantum dots, green light emission CdSe/ZnS quantum dots, orange-red light emission CdSe/ZnS quantum dots and red light emission CdSe/ZnS quantum dots.
As a preferable technical scheme of the invention, the quantum dots in the step (1) are quantum dots with ligand surface modification.
As a preferred embodiment of the present invention, the ligand comprises any one of 3-mercaptopropionic acid, L-cysteine, N-acetyl-L-cysteine, glutathione or dihydrolipoic acid or a combination of at least two thereof, typical but non-limiting examples of which are: a combination of 3-mercaptopropionic acid and L-cysteine, a combination of L-cysteine and N-acetyl-L-cysteine, a combination of N-acetyl-L-cysteine and glutathione, a combination of glutathione and dihydrolipoic acid, or a combination of 3-mercaptopropionic acid, L-cysteine and N-acetyl-L-cysteine, and the like.
As a preferred embodiment of the present invention, the concentration of the achiral quantum dot aqueous solution in step (1) is 5-20 mg/mL, such as 5mg/mL, 6mg/mL, 7mg/mL, 8mg/mL, 9mg/mL, 10mg/mL, 11mg/mL, 12mg/mL, 13mg/mL, 14mg/mL, 15mg/mL, 16mg/mL, 17mg/mL, 18mg/mL, 19mg/mL or 20mg/mL, but not limited to the values listed, and other values not listed in the range of the values are also applicable.
Preferably, the concentration of the achiral quantum dots after mixing the water with the achiral quantum dots or the achiral quantum dots aqueous solution is 0.5-2 mg/mL, such as 0.5mg/mL, 0.6mg/mL, 0.7mg/mL, 0.8mg/mL, 0.9mg/mL, 1.0mg/mL, 1.1mg/mL, 1.2mg/mL, 1.3mg/mL, 1.4mg/mL, 1.5mg/mL, 1.6mg/mL, 1.7mg/mL, 1.8mg/mL, 1.9mg/mL, or 2.0mg/mL, etc., but not limited to the recited values, and other non-recited values in the range are also applicable.
As a preferred embodiment of the present invention, the solvent in step (1) comprises any one or a combination of at least two of ethanol, tetrahydrofuran, dimethyl sulfoxide, ethylene glycol, methanol, N-dimethylformamide, acetonitrile, aniline, acetone, pyridine, nitromethane or acetic acid, and the combination is typically but not limited to: a combination of ethanol and tetrahydrofuran, a combination of tetrahydrofuran and dimethyl sulfoxide, a combination of dimethyl sulfoxide and ethylene glycol, a combination of ethylene glycol and methanol, a combination of methanol and N, N-dimethylformamide, a combination of N, N-dimethylformamide and acetonitrile, a combination of acetonitrile and aniline, a combination of aniline and acetone, a combination of acetone and pyridine, a combination of pyridine and nitromethane, a combination of nitromethane and acetic acid, or a combination of ethanol, tetrahydrofuran and dimethyl sulfoxide, and the like.
In a preferred embodiment of the present invention, the volume ratio of water to solvent in step (1) is (0.01 to 100):1, for example, 0.01:1, 0.1:1, 0.5:1, 1:1, 2:1, 5:1, 8:1, 10:1, 20:1, 50:1, 80:1 or 100:1, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned value range are also applicable.
As a preferred technical scheme of the invention, the gelator structure of the step (2) is shown as the formula I:
Figure GDA0001469089550000051
wherein n is a positive integer of 2-30, and R is amino, 2-picolinic acid amide, 3-picolinic acid amide, 4-picolinic acid amide or ester.
The gel factors comprise an L configuration and a D configuration, wherein a compound with an amino R is named as LGAm/DGAm, a gel factor with a 4-picolinamide R is named as 4PLG/4PDG, a gel factor with a 3-picolinamide R is named as 3PLG/3PDG, and a gel factor with a 2-picolinamide R is named as 2PLG/2 PDG.
Where n can be 2, 3, 5, 8, 10, 12, 15, 18, 20, 22, 25, 28, 30, etc., but is not limited to the recited values, and other unrecited values within the numerical range are equally applicable.
As a preferred embodiment of the present invention, the mass-to-volume ratio of the gelator and the mixed solution in step (2) is 5 to 20mg/mL, such as 5mg/mL, 6mg/mL, 7mg/mL, 8mg/mL, 9mg/mL, 10mg/mL, 11mg/mL, 12mg/mL, 13mg/mL, 14mg/mL, 15mg/mL, 16mg/mL, 17mg/mL, 18mg/mL, 19mg/mL, or 20mg/mL, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
As a preferred technical scheme of the invention, the heating in the step (2) is carried out until the gelator is completely dissolved.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) the invention provides a preparation method of gel-loaded inorganic achiral quantum dots, which can realize CPL luminescence of achiral quantum dots through molecular self-assembly;
(2) the invention provides a preparation method of gel-loaded inorganic achiral quantum dots, which can realize CPL luminescence of white light emission;
(3) the invention provides a preparation method of gel-loaded inorganic achiral quantum dots, which has the advantages of simple process, room-temperature operation, small environmental influence factors and low cost, and has important significance for researching circular polarization luminescence of inorganic quantum dots.
Drawings
FIG. 1 is an LGAm and DGAm gel-loaded achiral ZnSe/ZnS quantum dot (437nm) CPL luminescence spectrum prepared in example 1;
FIG. 2 is the luminescence spectrum of LGAm and DGAm gel loaded achiral CdS/ZnS quantum dots (441nm) CPL prepared in example 5;
FIG. 3 is the luminescence spectrum of LGAm and DGAm gel-supported achiral CdSe/ZnS quantum dots (450nm) CPL prepared in example 6;
FIG. 4 is the LGAm and DGAm gel-supported achiral CdSe/ZnS quantum dot (500nm) CPL luminescence spectra prepared in example 7;
FIG. 5 is the LGAm and DGAm gel-supported achiral CdSe/ZnS quantum dot (538nm) CPL luminescence spectra obtained from example 8;
FIG. 6 is the luminescence spectrum of LGAm and DGAm gel-supported achiral CdSe/ZnS quantum dots (594nm) CPL prepared in example 9;
FIG. 7 is the luminescence spectrum of LGAm and DGAm gel-supported achiral CdSe/ZnS quantum dots (640nm) CPL prepared in example 10;
FIG. 8 is the luminescence spectrum of 4PLG and 4PDG gel-supported achiral CdSe/ZnS quantum dots (570nm) CPL prepared in example 11;
FIG. 9 is a white light emission CPL luminescence spectrum of CdSe/ZnS quantum dots with mixed maximum emission wavelengths of 450nm, 500nm, 538nm, 594nm and 640nm mixed according to a mass ratio of 4:2:3:3:3 for LGAm and DGAm gel loading prepared in example 12;
FIG. 10 is the luminescence spectrum of the achiral ZnSe/ZnS quantum dot (437nm) CPL prepared in comparative example 1.
Detailed Description
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
example 1
A method for preparing gel-supported inorganic achiral quantum dots, the method comprising the steps of:
(1) mixing 100 mu L of water and 10 mu L of aqueous solution (the concentration is 20mg/mL) of ZnSe/ZnS quantum dots with the maximum emission wavelength of 437nm, adding 1mL of ethanol, and mixing again to obtain mixed solution;
(2) and (2) mixing the mixed solution obtained in the step (1) with 20mg of LGAm, heating until the gel factor is completely dissolved, and cooling to obtain the gel-loaded inorganic achiral quantum dot.
The LGAm gelator was replaced with DGAm gelator and gel-loaded inorganic achiral quantum dots were again prepared using the above conditions.
The light with the wavelength of 360nm is used as the excitation wavelength to excite the two mixed systems, and CPL test is carried out, and the result is shown in figure 1, wherein the maximum emission wavelength is 437nm, the L-type gel factor obtains a positive CPL signal, the maximum intensity is 20, the D-type gel factor obtains a negative CPL signal, the maximum intensity is-20, and the two mixed systems are in mirror symmetry.
Wherein the surface of the quantum dot is modified by 3-mercaptopropionic acid.
Example 2
A method for preparing gel-supported inorganic achiral quantum dots, the method comprising the steps of:
(1) mixing 10 mu L of water with 100 mu L of aqueous solution (the concentration is 10mg/mL) of ZnSe/ZnS quantum dots with the maximum emission wavelength of 437nm, adding 1.8mL of ethanol, and mixing again to obtain mixed solution;
(2) and (2) mixing the mixed solution obtained in the step (1) with 10mg of LGAm, heating until the gel factor is completely dissolved, and cooling to obtain the gel-loaded inorganic achiral quantum dot.
The LGAm gelator was replaced with DGAm gelator and gel-loaded inorganic achiral quantum dots were again prepared using the above conditions.
The CPL test was carried out by exciting the above two mixed systems using light with a wavelength of 360nm as the excitation wavelength, and the results were similar to those of the CPL signal shown in FIG. 1.
Wherein the surface of the quantum dot is modified by 3-mercaptopropionic acid.
Example 3
A method for preparing gel-supported inorganic achiral quantum dots, the method comprising the steps of:
(1) mixing 20 mu L of water with 180 mu L of aqueous solution (the concentration is 5mg/mL) of ZnSe/ZnS quantum dots with the maximum emission wavelength of 437nm, adding 1.8mL of ethanol, and mixing again to obtain mixed solution;
(2) and (2) mixing the mixed solution obtained in the step (1) with 5mg of LGAm, heating until the gel factor is completely dissolved, and cooling to obtain the gel-loaded inorganic achiral quantum dot.
The LGAm gelator was replaced with DGAm gelator and gel-loaded inorganic achiral quantum dots were again prepared using the above conditions.
The CPL test was carried out by exciting the above two mixed systems using light with a wavelength of 360nm as the excitation wavelength, and the results were similar to those of the CPL signal shown in FIG. 1.
Wherein the surface of the quantum dot is modified by 3-mercaptopropionic acid.
Example 4
A method for preparing gel-supported inorganic achiral quantum dots, the method comprising the steps of:
(1) mixing 50 mu L of water with 20 mu L of aqueous solution (the concentration is 12mg/mL) of ZnSe/ZnS quantum dots with the maximum emission wavelength of 437nm, adding 1.3mL of ethanol, and mixing again to obtain mixed solution;
(2) and (2) mixing the mixed solution obtained in the step (1) with 12mg of LGAm, heating until the gel factor is completely dissolved, and cooling to obtain the gel-loaded inorganic achiral quantum dot.
The LGAm gelator was replaced with DGAm gelator and gel-loaded inorganic achiral quantum dots were again prepared using the above conditions.
CPL test was carried out by exciting the above two mixed systems using light having a wavelength of 360nm as an excitation wavelength, and the results were similar to those shown in FIG. 1.
Wherein the surface of the quantum dot is modified by 3-mercaptopropionic acid.
Example 5
A method for preparing gel-supported inorganic achiral quantum dots, the method comprising the steps of:
(1) mixing 80 mu L of water with 120 mu L of CdS/ZnS quantum dot aqueous solution with maximum emission wavelength of 441nm (concentration is 15mg/mL), adding 1mL of ethanol, and mixing again to obtain a mixed solution;
(2) and (2) mixing the mixed solution obtained in the step (1) with 15mg of LGAm, heating until the gel factor is completely dissolved, and cooling to obtain the gel-loaded inorganic achiral quantum dot.
The LGAm gelator was replaced with DGAm gelator and gel-loaded inorganic achiral quantum dots were again prepared using the above conditions.
The light with the wavelength of 360nm is used as the excitation wavelength to excite the two mixed systems, and the CPL test is carried out, and the result is shown in figure 2, wherein the maximum emission wavelength is 441nm, the L-type gel factor obtains a positive CPL signal, the maximum intensity is 9, the D-type gel factor obtains a negative CPL signal, the maximum intensity is-4, and the two mixed systems are in mirror symmetry.
Wherein the surface of the quantum dot is modified by 3-mercaptopropionic acid.
Example 6
A method for preparing gel-supported inorganic achiral quantum dots, the method comprising the steps of:
(1) mixing 100 mu L of water and 50 mu L of CdSe/ZnS quantum dot aqueous solution with the maximum emission wavelength of 450nm (the concentration is 10mg/mL), adding 1.3mL of ethanol, and mixing again to obtain a mixed solution;
(2) and (2) mixing the mixed solution obtained in the step (1) with 10mg of LGAm, heating until the gel factor is completely dissolved, and cooling to obtain the gel-loaded inorganic achiral quantum dot.
The LGAm gelator was replaced with DGAm gelator and gel-loaded inorganic achiral quantum dots were again prepared using the above conditions.
The light with the wavelength of 360nm is used as the excitation wavelength to excite the two mixed systems, and the CPL test is carried out, and the result is shown in figure 3, wherein the maximum emission wavelength is 450nm, the L-type gel factor obtains a positive CPL signal, the maximum intensity is 8, the D-type gel factor obtains a negative CPL signal, the maximum intensity is-8, and the two mixed systems are in mirror symmetry.
Wherein the surface of the quantum dot is modified by 3-mercaptopropionic acid.
Example 7
A method for preparing gel-supported inorganic achiral quantum dots, the method comprising the steps of:
(1) mixing 70 mu L of water with 30 mu L of CdSe/ZnS quantum dot water solution with the maximum emission wavelength of 500nm (the concentration is 10mg/mL), adding 1.4mL of ethanol, and mixing again to obtain a mixed solution;
(2) and (2) mixing the mixed solution obtained in the step (1) with 10mg of LGAm, heating until the gel factor is completely dissolved, and cooling to obtain the gel-loaded inorganic achiral quantum dot.
The LGAm gelator was replaced with DGAm gelator and gel-loaded inorganic achiral quantum dots were again prepared using the above conditions.
The light with the wavelength of 360nm is used as the excitation wavelength to excite the two mixed systems, and the CPL test is carried out, and the result is shown in figure 4, wherein the maximum emission wavelength is 500nm, the L-type gel factor obtains a positive CPL signal, the maximum intensity is 6, the D-type gel factor obtains a negative CPL signal, the maximum intensity is-12, and the two mixed systems are in mirror symmetry.
Wherein the surface of the quantum dot is modified by 3-mercaptopropionic acid.
Example 8
A method for preparing gel-supported inorganic achiral quantum dots, the method comprising the steps of:
(1) mixing 50 mu L of water with 150 mu L of aqueous solution of CdSe/ZnS quantum dots with the maximum emission wavelength of 538nm (the concentration is 5mg/mL), adding 1.3mL of ethanol, and mixing again to obtain mixed solution;
(2) and (2) mixing the mixed solution obtained in the step (1) with 5mg of LGAm, heating until the gel factor is completely dissolved, and cooling to obtain the gel-loaded inorganic achiral quantum dot.
The LGAm gelator was replaced with DGAm gelator and gel-loaded inorganic achiral quantum dots were again prepared using the above conditions.
The light with the wavelength of 360nm is used as the excitation wavelength to excite the two mixed systems, and the CPL test is carried out, and the result is shown in figure 5, wherein the maximum emission wavelength is 538nm, the L-type gel factor obtains a positive CPL signal, the maximum intensity is 12, the D-type gel factor obtains a negative CPL signal, the maximum intensity is-6, and the two mixed systems are in mirror symmetry.
Wherein the surface of the quantum dot is modified by 3-mercaptopropionic acid.
Example 9
A method for preparing gel-supported inorganic achiral quantum dots, the method comprising the steps of:
(1) mixing 80 mu L of water with 120 mu L of CdSe/ZnS quantum dot aqueous solution with maximum emission wavelength of 594nm (the concentration is 15mg/mL), adding 1.2mL of ethanol, and mixing again to obtain a mixed solution;
(2) and (2) mixing the mixed solution obtained in the step (1) with 15mg of LGAm, heating until the gel factor is completely dissolved, and cooling to obtain the gel-loaded inorganic achiral quantum dot.
The LGAm gelator was replaced with DGAm gelator and gel-loaded inorganic achiral quantum dots were again prepared using the above conditions.
The light with the wavelength of 360nm is used as the excitation wavelength to excite the two mixed systems, and the CPL test is carried out, and the result is shown in figure 2, wherein the maximum emission wavelength is 594nm, the L-type gel factor obtains a positive CPL signal, the maximum intensity is 12, the D-type gel factor obtains a negative CPL signal, the maximum intensity is-8, and the two mixed systems are in mirror symmetry.
Wherein the surface of the quantum dot is modified by 3-mercaptopropionic acid.
Example 10
A method for preparing gel-supported inorganic achiral quantum dots, the method comprising the steps of:
(1) mixing 190 mu L of water with 20 mu L of CdSe/ZnS quantum dot water solution with the maximum emission wavelength of 640nm (the concentration is 10mg/mL), adding 1.2mL of ethanol, and mixing again to obtain a mixed solution;
(2) and (2) mixing the mixed solution obtained in the step (1) with 10mg of LGAm, heating until the gel factor is completely dissolved, and cooling to obtain the gel-loaded inorganic achiral quantum dot.
The LGAm gelator was replaced with DGAm gelator and gel-loaded inorganic achiral quantum dots were again prepared using the above conditions.
The light with the wavelength of 360nm is used as the excitation wavelength to excite the two mixed systems, and the CPL test is carried out, and the result is shown in figure 7, wherein the maximum emission wavelength is 640nm, the L-type gel factor obtains a positive CPL signal, the maximum intensity is 6, the D-type gel factor obtains a negative CPL signal, the maximum intensity is-6, and the two mixed systems are in mirror symmetry.
Wherein the surface of the quantum dot is modified by 3-mercaptopropionic acid.
Example 11
A method for preparing gel-supported inorganic achiral quantum dots, the method comprising the steps of:
(1) mixing 50 mu L of water with 50 mu L of CdSe/ZnS quantum dot water solution with the maximum emission wavelength of 570nm (the concentration is 10mg/mL), adding 1.4mL of ethanol, and mixing again to obtain a mixed solution;
(2) and (2) mixing the mixed solution obtained in the step (1) with 10mg of 4PLG, heating until the gel factor is completely dissolved, and cooling to obtain the gel-loaded inorganic achiral quantum dot.
The 4PLG gelator was replaced with 4PDG gelator and gel-loaded inorganic achiral quantum dots were again prepared using the conditions described above.
The light with the wavelength of 360nm is used as the excitation wavelength to excite the two mixed systems, and CPL test is carried out, and the result is shown in figure 2, wherein the maximum emission wavelength is 579nm, the L-type gel factor obtains a positive CPL signal, the maximum intensity is 15, the D-type gel factor obtains a negative CPL signal, the maximum intensity is-5, and the two mixed systems are in mirror symmetry.
Wherein the surface of the quantum dot is modified by 3-mercaptopropionic acid.
Example 12
A method for preparing gel-supported inorganic achiral quantum dots, the method comprising the steps of:
(1) mixing 90 mu L of water and 10 mu L of aqueous solution of CdSe/ZnS quantum dots (the concentration is 20mg/mL), adding 1mL of ethanol, and mixing again to obtain mixed solution;
(2) and (2) mixing the mixed solution obtained in the step (1) with 20mg of LGAm, heating until the gel factor is completely dissolved, and cooling to obtain the gel-loaded inorganic achiral quantum dot.
The LGAm gelator was replaced with DGAm gelator and gel-loaded inorganic achiral quantum dots were again prepared using the above conditions.
Wherein, the mass ratio of CdSe/ZnS quantum dots with maximum emission wavelengths of 450nm, 500nm, 538nm, 594nm and 640nm in the aqueous solution of the CdSe/ZnS quantum dots is 4:2:3:3: 3.
The CPL test is carried out by exciting the two mixed systems by using light with the wavelength of 360nm as the excitation wavelength, and the CPL signal covers the whole visible light area and is in mirror symmetry as shown in figure 9.
Wherein the surface of the quantum dot is modified by 3-mercaptopropionic acid.
Comparative example 1
A preparation method of an inorganic achiral quantum dot without gel loading selects CdSe/ZnS quantum dots with the maximum emission wavelength of 538nm, and the experimental method is the same as that of example 1 except that no gel factor is used.
The light with the wavelength of 360nm is used as the excitation wavelength, and the test result is shown in figure 10, and a CPL signal is not obtained.
Comparative example 2
A preparation method of gel-supported inorganic achiral quantum dots selects CdSe/ZnS quantum dots with the maximum emission wavelength of 538nm, and experiments are the same as example 1 except that the gel factor is (3, 4-dichlorobenzylidene) -D-sorbitol.
Using light with a wavelength of 360nm as the excitation wavelength, the test results were similar to those shown in fig. 10, and no CPL signal was obtained.
Comparative example 3
A preparation method of gel-supported inorganic achiral quantum dots selects CdSe/ZnS quantum dots with the maximum emission wavelength of 538nm, and the experimental method is the same as that of example 1 except that the gel factor is cholesteryl undecylenate.
Using light with a wavelength of 360nm as the excitation wavelength, the test results were similar to those shown in fig. 10, and no CPL signal was obtained.
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (10)

1.一种具有圆偏振发光性能的凝胶负载的无机非手性量子点的制备方法,其特征在于,所述方法包括以下步骤:1. a kind of preparation method of the inorganic achiral quantum dots with the gel load of circularly polarized luminescence property, is characterized in that, described method comprises the following steps: (1)将水与非手性量子点或非手性量子点的水溶液混合,加入溶剂,再次混合得到混合液;(1) mixing water with an aqueous solution of achiral quantum dots or achiral quantum dots, adding a solvent, and mixing again to obtain a mixed solution; (2)将步骤(1)得到的混合液与凝胶因子混合,加热,冷却,得到凝胶负载的无机非手性量子点;(2) mixing the mixture obtained in step (1) with the gelling factor, heating, and cooling to obtain gel-supported inorganic achiral quantum dots; 步骤(2)所述的凝胶因子结构如式I所示:The gel factor structure described in step (2) is shown in formula I:
Figure FDA0002365615620000011
Figure FDA0002365615620000011
其中,n为2~30的正整数,R为氨基、2-吡甲酸酰胺基、3-吡甲酸酰胺基、4-吡甲酸酰胺基或酯基。Wherein, n is a positive integer of 2 to 30, and R is an amino group, a 2-pyrazonic acid amide group, a 3-pyrazic acid amide group, a 4-pyroic acid amide group, or an ester group.
2.根据权利要求1所述的制备方法,其特征在于,步骤(1)所述非手性量子点包括ZnSe/ZnS、CdS/ZnS、CdSe/ZnS或InP/ZnS中任意一种或至少两种的组合。2. preparation method according to claim 1 is characterized in that, the described achiral quantum dot of step (1) comprises any one or at least two in ZnSe/ZnS, CdS/ZnS, CdSe/ZnS or InP/ZnS. combination of species. 3.根据权利要求1所述的制备方法,其特征在于,步骤(1)所述量子点为经配体表面修饰的量子点。3 . The preparation method according to claim 1 , wherein the quantum dots in step (1) are quantum dots modified on the surface of ligands. 4 . 4.根据权利要求3所述的制备方法,其特征在于,所述配体包括3-巯基丙酸、L-半胱氨酸、N-乙酰-L-半胱氨酸、谷胱甘肽或二氢硫辛酸中任意一种或至少两种的组合。4. preparation method according to claim 3 is characterized in that, described part comprises 3-mercaptopropionic acid, L-cysteine, N-acetyl-L-cysteine, glutathione or Any one or a combination of at least two of dihydrolipoic acid. 5.根据权利要求1所述的制备方法,其特征在于,步骤(1)所述非手性量子点水溶液的浓度为5~20mg/mL。5 . The preparation method according to claim 1 , wherein the concentration of the aqueous solution of achiral quantum dots in step (1) is 5-20 mg/mL. 6 . 6.根据权利要求1所述的制备方法,其特征在于,所述水与非手性量子点或非手性量子点水溶液混合后非手性量子点的浓度为0.5~2mg/mL。6 . The preparation method according to claim 1 , wherein the concentration of the achiral quantum dots after the water is mixed with the achiral quantum dots or the achiral quantum dot aqueous solution is 0.5-2 mg/mL. 7 . 7.根据权利要求1所述的制备方法,其特征在于,步骤(1)所述溶剂包括乙醇、四氢呋喃、二甲基亚砜、乙二醇、甲醇、N,N-二甲基甲酰胺、乙腈、苯胺、丙酮、吡啶、硝基甲烷或乙酸中任意一种或至少两种的组合。7. The preparation method according to claim 1, wherein the solvent in step (1) comprises ethanol, tetrahydrofuran, dimethyl sulfoxide, ethylene glycol, methanol, N,N-dimethylformamide, Any one or a combination of at least two of acetonitrile, aniline, acetone, pyridine, nitromethane, or acetic acid. 8.根据权利要求1所述的制备方法,其特征在于,步骤(1)所述水与溶剂的体积比为(0.01~100):1。8 . The preparation method according to claim 1 , wherein the volume ratio of the water to the solvent in step (1) is (0.01-100):1. 9 . 9.根据权利要求1所述的制备方法,其特征在于,步骤(2)所述凝胶因子与混合液的质量体积比为5~20mg/mL。9 . The preparation method according to claim 1 , wherein the mass-volume ratio of the gelling factor to the mixed solution in step (2) is 5-20 mg/mL. 10 . 10.根据权利要求1-9任一项所述的制备方法,其特征在于,步骤(2)所述加热至凝胶因子完全溶解。10. The preparation method according to any one of claims 1-9, wherein the step (2) is heated until the gelling factor is completely dissolved.
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