CN107417632B - Preparation method of inorganic-organic composite titanium dioxide quantum dots and application of inorganic-organic composite titanium dioxide quantum dots in tumor cell imaging detection - Google Patents
Preparation method of inorganic-organic composite titanium dioxide quantum dots and application of inorganic-organic composite titanium dioxide quantum dots in tumor cell imaging detection Download PDFInfo
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- 238000003384 imaging method Methods 0.000 title claims abstract description 13
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- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical class [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 5
- HDZLTCOFYWHPLE-UHFFFAOYSA-N 4-bromo-11,14-diazatetracyclo[7.6.1.05,16.010,15]hexadeca-1(16),2,4,6,8,10,12,14-octaene-12,13-dicarbonitrile Chemical compound C12=NC(C#N)=C(C#N)N=C2C2=CC=CC3=C2C1=CC=C3Br HDZLTCOFYWHPLE-UHFFFAOYSA-N 0.000 claims description 10
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- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical group [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a preparation method of inorganic-organic composite titanium dioxide quantum dots and application of the inorganic-organic composite titanium dioxide quantum dots in tumor cell imaging detection. The technical scheme provided by the invention has the key points that: placing 3- (4-amino) -butyric acid-acenaphthopyrazine-8, 9-dinitrile, tetrabutyl titanate, dimethyl sulfoxide and saturated potassium chloride solution in a reaction vessel, heating and refluxing for 2h, and performing centrifugal separation to obtain the inorganic and organic composite titanium dioxide quantum dot. The invention also specifically discloses application of the inorganic-organic composite titanium dioxide quantum dot in tumor cell imaging detection. The composite titanium dioxide quantum dot prepared by the invention utilizes the characteristic that titanium dioxide has stronger absorbance, so that the absorption energy of the titanium dioxide is transferred to the organic substance 3- (4-amino) -butyric acid-acenaphthopyrazine-8, 9-dinitrile, the total emission intensity of the quantum dot is increased, and a stronger fluorescence signal is obtained.
Description
Technical Field
The invention belongs to the technical field of synthesis and application of quantum dots, and particularly relates to a preparation method of an inorganic-organic composite titanium dioxide quantum dot and application of the inorganic-organic composite titanium dioxide quantum dot in tumor cell imaging detection.
Background
Quantum dots are an important low-dimensional semiconductor material, and the size of each of the three dimensions is not larger than twice the exciton bohr radius of the corresponding semiconductor material. Quantum dots are generally spherical or spheroidal, often with diameters between 2-20 nm. Common quantum dots are composed of IV, II-VI, IV-VI, or III-V elements. Specific examples are silicon quantum dots, germanium quantum dots, cadmium sulfide quantum dots, cadmium selenide quantum dots, cadmium telluride quantum dots, zinc selenide quantum dots, lead sulfide quantum dots, lead selenide quantum dots, indium phosphide quantum dots, indium arsenide quantum dots, and the like. The quantum dots have good application prospects in the fields of electronics, photoelectronics, photovoltaics, biological imaging and the like.
Quantum dots do have a number of advantages over traditional dye molecules in the field of biological imaging. The inorganic crystallites are capable of withstanding multiple excitations and light emissions, while the organic molecules are decomposed, with long-lasting stability allowing researchers to observe cells and tissues for longer periods of time and without difficulty perform interface modification junctions. The quantum dots have the greatest benefit of rich color. The complexity of biological systems often requires the simultaneous observation of several components, which, if stained with dye molecules, require light of different wavelengths for excitation, whereas quantum dots do not present this problem, using nanocrystals of different sizes (and thus different colors) to label different biomolecules. The use of a single light source enables different particles to be monitored in real time. The quantum dots have great application prospect in the research of biochemistry, molecular biology, cell biology, genomics, proteomics, drug screening, biomacromolecule interaction and the like due to the special optical properties of the quantum dots. However, in the aspect of biological imaging, the application of the conventional quantum dots in vivo imaging is limited due to the large biological toxicity of the quantum dots. Therefore, the development of a quantum dot with low biological toxicity becomes a key problem of the quantum dot in the aspect of in vivo tumor imaging.
Disclosure of Invention
The invention solves the technical problem of providing a preparation method of the inorganic-organic composite titanium dioxide quantum dot, and the inorganic-organic composite titanium dioxide quantum dot prepared by the method can be used for imaging detection of tumor cells.
The invention adopts the following technical scheme for solving the technical problems, and the preparation method of the inorganic-organic composite titanium dioxide quantum dot is characterized by comprising the following specific steps: firstly, adding 5-bromoacenaphthenequinone and diaminomaleonitrile into glacial acetic acid, heating, stirring and refluxing for 2h, cooling in an ice water bath, filtering, drying, separating by column chromatography to obtain 3-bromo-acenaphthopyrazine-8, 9-dinitrile, then 3-bromo-acenaphthopyrazine-8, 9-dinitrile and 4-aminobutyric acid are placed in a reaction vessel, adding dimethyl sulfoxide, heating and refluxing for 1h, carrying out reduced pressure distillation to obtain 3- (4-amino) -butyric acid-acenaphthopyrazine-8, 9-dinitrile, finally placing 3- (4-amino) -butyric acid-acenaphthopyrazine-8, 9-dinitrile, tetrabutyl titanate, dimethyl sulfoxide and saturated potassium chloride solution in a reaction container, heating and refluxing for 2h, and carrying out centrifugal separation to obtain the inorganic-organic composite titanium dioxide quantum dot.
Further preferably, the mass ratio of the 5-bromoacenaphthenequinone to the diaminomaleonitrile is 1.5-2; the mass ratio of the 5-bromoacenaphthenequinone to the glacial acetic acid is 0.03-0.1; the mass ratio of the 3-bromo-acenaphthopyrazine-8, 9-dinitrile to the dimethyl sulfoxide is 0.01-0.05; the mass ratio of the 3-bromo-acenaphthopyrazine-8, 9-dinitrile to the 4-aminobutyric acid is 2-3.
Further preferably, the mass ratio of the 3- (4-amino) -butyric acid-acenaphthopyrazine-8, 9-dinitrile to tetrabutyl titanate is 0.002-0.005; the mass ratio of tetrabutyl titanate to saturated potassium chloride solution is 4-5.
The inorganic-organic composite titanium dioxide quantum dot provided by the invention is applied to tumor cell imaging detection, and the inorganic-organic composite titanium dioxide quantum dot presents an obvious fluorescent signal in a cell.
The composite titanium dioxide quantum dot prepared by the invention utilizes the characteristic that titanium dioxide has stronger absorbance, so that the absorption energy of the titanium dioxide is transferred to the organic matter 3- (4-amino) -butyric acid-acenaphthopyrazine-8, 9-dinitrile, the total emission intensity of the quantum dot is increased, and stronger fluorescence signals are obtained. The inorganic-organic composite titanium dioxide quantum dot has low biotoxicity, and the spectral range of the inorganic-organic composite titanium dioxide quantum dot is different from that of a biological sample enough, so that the low-biotoxicity quantum dot which can be used for living tumor imaging is obtained.
Drawings
FIG. 1 is an X-ray diffraction pattern of composite titanium dioxide quantum dots prepared in example 2 of the present invention;
FIG. 2 is a transmission electron microscope image of the composite titanium dioxide quantum dot prepared in example 2 of the present invention;
FIG. 3 is a fluorescence spectrum obtained by the excitation of composite titanium dioxide quantum dots in an aqueous solvent at 550 nm;
fig. 4 is a labeled imaging graph of the composite titanium dioxide quantum dots on tumor cells.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.
Example 1
The synthetic route of 3- (4-amino) -butyric acid-acenaphthopyrazine-8, 9-dinitrile:
the synthesis steps are as follows:
1. adding 200mg of 5-bromoacenaphthenequinone and 125mg of diaminomaleonitrile into a 50mL two-neck flask, then adding 6mL of glacial acetic acid, stirring and heating at 120 ℃, refluxing for 2h, cooling in ice water bath, filtering, drying, and performing column chromatography separation to obtain fresh yellow 3-bromo-acenaphthopyrazine-8, 9-dinitrile;
2. putting 100mg of 3-bromo-acenaphthopyrazine-8, 9-dinitrile and 40mg of 4-aminobutyric acid into a 50mL round-bottom flask, adding 8mL of dimethyl sulfoxide, heating and refluxing at 110 ℃ for 1h to react to generate a red mixture, and carrying out reduced pressure distillation to obtain the 3- (4-amino) -butyric acid-acenaphthopyrazine-8, 9-dinitrile.
Example 2
Adding 6mg of 3- (4-amino) -butyric acid-acenaphthopyrazine-8, 9-dinitrile into a 50mL two-neck flask, adding 25mL of dimethyl sulfoxide, stirring for dissolving, adding 3mL of tetrabutyl titanate, stirring uniformly, adding 0.6mL of saturated potassium chloride solution, heating and refluxing for 2h at 120 ℃, and then carrying out high-speed centrifugal separation to obtain the 3- (4-amino) -butyric acid-acenaphthopyrazine-8, 9-dinitrile composite titanium dioxide quantum dot.
Example 3
X-ray diffraction and transmission electron microscope of the composite titanium dioxide quantum dots and fluorescence spectrum determination of the composite titanium dioxide quantum dots in a water solvent are as follows:
and (3) carrying out diffraction analysis on the dried composite titanium dioxide quantum dot powder on a Bruker D & Advance X-ray diffractometer, wherein the result is shown in figure 1, and the composite titanium dioxide quantum dot is tetragonal anatase titanium dioxide as can be seen from figure 1.
Adding 5mL of water into 1mg of composite titanium dioxide quantum dots, performing ultrasonic dispersion, then dropping the mixture onto a carbon support film, and testing the morphology of the quantum dots on a JEOL2100F super-resolution transmission electron microscope, wherein the prepared composite titanium dioxide quantum dots are nanoparticles with the particle size of 5-10nm, as shown in FIG. 2.
The fluorescence emission diagram of the composite titanium dioxide quantum dots is excited and scanned at 550nm on an Agilent Cary Eclipse fluorescence spectrophotometer, the result is shown in figure 3, and the composite titanium dioxide quantum dots have stronger fluorescence emission signals at 606nm as can be seen from figure 3.
Example 4
And (3) performing label imaging determination on the tumor cells by using the composite titanium dioxide quantum dots:
using the composite titanium dioxide quantum dots prepared in example 2, Hela cells were incubated with the composite titanium dioxide quantum dots at a final concentration of 2.0mg, respectively, at 37 ℃ and 5% CO2Incubate for 30 min. Then, PBS is shaken and rinsed for 5min multiplied by 3, and then cell culture medium is added, and laser confocal imaging is carried out. Representative areas were selected and observed with an oil-glass (100 ×) and repeated three times. The imaging shows that the Hela cell has a strong fluorescence signal, the result is shown in FIG. 4, the acquisition waveband is 580-620nm, and the composite titanium dioxide quantum dot can present an obvious fluorescence signal in the cell.
The foregoing embodiments illustrate the principles, principal features and advantages of the invention, and it will be understood by those skilled in the art that the invention is not limited to the foregoing embodiments, which are merely illustrative of the principles of the invention, and that various changes and modifications may be made therein without departing from the scope of the principles of the invention.
Claims (1)
1. A preparation method of inorganic-organic composite titanium dioxide quantum dots is characterized by comprising the following specific steps: firstly, adding 5-bromoacenaphthoquinone and diaminomaleonitrile into glacial acetic acid, heating, stirring and refluxing for 2h, cooling in an ice-water bath, filtering, drying, separating by column chromatography to obtain 3-bromo-acenaphthopyrazine-8, 9-dinitrile, then placing 3-bromo-acenaphthopyrazine-8, 9-dinitrile and 4-aminobutyric acid into a reaction container, adding dimethyl sulfoxide, heating and refluxing for 1h, carrying out reduced pressure distillation to obtain 3- (4-amino) -butyric acid-acenaphthopyrazine-8, 9-dinitrile, finally placing 3- (4-amino) -butyric acid-acenaphthopyrazine-8, 9-dinitrile, tetrabutyl titanate, dimethyl sulfoxide and saturated potassium chloride solution into the reaction container, heating and refluxing for 2h, and carrying out centrifugal separation to obtain inorganic-organic composite titanium dioxide quantum dots, the inorganic-organic composite titanium dioxide quantum dot is used for tumor cell Hela cell marker imaging, and the inorganic-organic composite titanium dioxide quantum dot presents a fluorescence signal in the tumor cell Hela cell;
the mass ratio of the 5-bromoacenaphthenequinone to the diaminomaleonitrile is 1.5-2: 1; the mass ratio of the 5-bromoacenaphthenequinone to the glacial acetic acid is 0.03-0.1: 1; the mass ratio of the 3-bromo-acenaphthopyrazine-8, 9-dinitrile to the dimethyl sulfoxide is 0.01-0.05: 1; the mass ratio of the 3-bromo-acenaphthopyrazine-8, 9-dinitrile to the 4-aminobutyric acid is 2-3: 1;
the mass ratio of the 3- (4-amino) -butyric acid-acenaphthopyrazine-8, 9-dinitrile to tetrabutyl titanate is 0.002-0.005: 1; the mass ratio of tetrabutyl titanate to saturated potassium chloride solution is 4-5: 1.
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| CN108210939B (en) * | 2018-01-16 | 2021-01-01 | 四川大学 | Active terahertz imaging contrast enhancer and preparation method thereof |
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| CN101723907A (en) * | 2009-07-25 | 2010-06-09 | 大连理工大学 | O-dicyano-acenaphtho pyrazine compound and anti-tumor application thereof |
| CN103739549A (en) * | 2013-09-03 | 2014-04-23 | 河南大学 | Preparation and application of naphthalimide-amino acid compound and modified quantum dot |
| CN109384735A (en) * | 2017-08-11 | 2019-02-26 | 李达 | Application of the composite fluorescence probe in tumour active somatic cell image checking |
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| CN101723907A (en) * | 2009-07-25 | 2010-06-09 | 大连理工大学 | O-dicyano-acenaphtho pyrazine compound and anti-tumor application thereof |
| CN103739549A (en) * | 2013-09-03 | 2014-04-23 | 河南大学 | Preparation and application of naphthalimide-amino acid compound and modified quantum dot |
| CN109384735A (en) * | 2017-08-11 | 2019-02-26 | 李达 | Application of the composite fluorescence probe in tumour active somatic cell image checking |
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