CN110643357A - Preparation method of cadmium sulfide quantum dot modified AIE fluorescent probe molecule - Google Patents
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 16
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 title description 16
- 229910052980 cadmium sulfide Inorganic materials 0.000 title description 16
- 239000002096 quantum dot Substances 0.000 title description 13
- FRLJSGOEGLARCA-UHFFFAOYSA-N cadmium sulfide Chemical class [S-2].[Cd+2] FRLJSGOEGLARCA-UHFFFAOYSA-N 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 229910001868 water Inorganic materials 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 13
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims abstract description 11
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 11
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 43
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 31
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 30
- 238000001816 cooling Methods 0.000 claims description 22
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
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- 238000001035 drying Methods 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 17
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- 229910021641 deionized water Inorganic materials 0.000 claims description 15
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- 238000005406 washing Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 9
- 239000012074 organic phase Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- KEOLYBMGRQYQTN-UHFFFAOYSA-N (4-bromophenyl)-phenylmethanone Chemical compound C1=CC(Br)=CC=C1C(=O)C1=CC=CC=C1 KEOLYBMGRQYQTN-UHFFFAOYSA-N 0.000 claims description 7
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
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- 238000003756 stirring Methods 0.000 claims description 7
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- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- PJANXHGTPQOBST-UHFFFAOYSA-N trans-Stilbene Natural products C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 claims description 6
- PJANXHGTPQOBST-VAWYXSNFSA-N trans-stilbene Chemical group C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 claims description 6
- 238000007605 air drying Methods 0.000 claims description 5
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- 230000008020 evaporation Effects 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
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- 238000010791 quenching Methods 0.000 claims description 5
- 238000010898 silica gel chromatography Methods 0.000 claims description 5
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- 239000012071 phase Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical compound C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 8
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 abstract description 6
- 230000007547 defect Effects 0.000 abstract description 6
- 150000002500 ions Chemical class 0.000 abstract description 6
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- 239000000523 sample Substances 0.000 abstract description 3
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052793 cadmium Inorganic materials 0.000 abstract description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 2
- 239000011593 sulfur Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 4
- 239000004809 Teflon Substances 0.000 description 3
- 229920006362 Teflon® Polymers 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
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- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 206010034972 Photosensitivity reaction Diseases 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005658 halogenation reaction Methods 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 230000036211 photosensitivity Effects 0.000 description 2
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- 239000002994 raw material Substances 0.000 description 2
- PWYVVBKROXXHEB-UHFFFAOYSA-M trimethyl-[3-(1-methyl-2,3,4,5-tetraphenylsilol-1-yl)propyl]azanium;iodide Chemical compound [I-].C[N+](C)(C)CCC[Si]1(C)C(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)C(C=2C=CC=CC=2)=C1C1=CC=CC=C1 PWYVVBKROXXHEB-UHFFFAOYSA-M 0.000 description 2
- 244000248349 Citrus limon Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001661 cadmium Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001917 fluorescence detection Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
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- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- JLZUZNKTTIRERF-UHFFFAOYSA-N tetraphenylethylene Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)=C(C=1C=CC=CC=1)C1=CC=CC=C1 JLZUZNKTTIRERF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000001651 triphenylamine derivatives Chemical class 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/56—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing sulfur
- C09K11/562—Chalcogenides
- C09K11/565—Chalcogenides with zinc cadmium
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention relates to the field of biological probes, and discloses a preparation method of an AIE fluorescent probe molecule modified by cadmium sulfide quantum dots, wherein a sodium sulfide solution is used as a sulfur source, a cadmium acetate solution is used as a cadmium source, the quantum yield of the cadmium sulfide quantum dots synthesized by a hydrothermal method is high, an emission spectrum has narrower half-peak width and good symmetry, no tailing phenomenon exists, the detection and analysis are easy, and the emission wavelength can be controlled by regulating and controlling the size; then reacting to synthesize the 1, 2-bis (4-bromophenyl) -1, 2-stilbene. The electron transfer efficiency is improved by this method. And obtaining the AIE type molecule H by utilizing a displacement reaction and an acidification reaction2BCTPE, and finally preparing the AIE type molecule modified by the cadmium sulfide quantum dots by a simple and efficient hydrothermal method. Aiming at the defects of poor biocompatibility and poor water solubility of the cadmium sulfide quantum dots, the AIE type molecules can make up the defects, and the combination of the two can improve the sensitivity and fluorescence intensity of ion detection.
Description
Technical Field
The invention relates to the field of biological probes, in particular to a preparation method of an AIE fluorescent probe molecule modified by cadmium sulfide quantum dots.
Background
The quantum dot has great potential as a novel fluorescent probe. The quantum dots have been widely applied in many fields of fluorescence detection, such as biological cell labeling and imaging, biological probes, ion determination, drug determination and other fields.
There are two kinds of cadmium sulfide crystal, alpha-type is lemon yellow powder, beta-type is orange red powder. Slightly soluble in water, soluble in acid, slightly soluble in ammonia. Can be used for preparing fireworks, glass glaze, porcelain glaze, luminescent materials and pigments. The high-purity cadmium sulfide is a good semiconductor, has strong photoelectric effect on visible light, and can be used for manufacturing photoelectric tubes and solar cells. Introducing hydrogen sulfide into acid solution of cadmium salt to prepare the cadmium sulfide.
Since the aggregation-induced emission (AIE) phenomenon was discovered by the team of Thanksgiving academists in 2001, research on the light-emitting mechanism and the application prospect of AIE materials was carried out by many scientists at home and abroad. Compared with the traditional organic luminescent dye, the AIE fluorescent dye is a special organic fluorescent material which emits strong light in an aggregation or solid film state and does not emit light or emits weak light in a good solvent. The reported mechanisms of AIE luminescence are broadly classified into intramolecular rotational confinement, intramolecular coplanarity, inhibition of photophysical processes or photochemical reactions, non-close packing, J-aggregate formation, and special excimers, etc. Based on the intensive research on the AIE luminescence mechanism, a large number of luminescent dye systems with AIE properties have been developed, including Tetraphenylethylene (TPE), silole (silole), triphenylamine derivatives, anthracene substitutes, and the like. With the continuous abundance of AIE dye systems, it is necessary to explore the wide application potential. In recent decades, AIE materials have been subject to significant research advances in the fields of biological imaging, chemical/biological sensing, and Organic Light Emitting Diodes (OLEDs).
Disclosure of Invention
In order to solve the technical problem, the invention provides a preparation method of an AIE fluorescent probe molecule modified by cadmium sulfide quantum dotsThe optical fiber has the advantages of high height, good light stability, narrow half-peak width of an emission spectrum, good symmetry, no trailing phenomenon, easy detection and analysis, and controllable emission wavelength by regulating and controlling the size; then 1, 2-bis (4-bromophenyl) -1, 2-stilbene is synthesized through reaction, and only one isomer is generated compared with the traditional halogenation reaction. The electron transfer efficiency is improved by this method. And obtaining the AIE type molecule H by utilizing a displacement reaction and an acidification reaction2BCTPE, and finally preparing the AIE type molecule modified by the cadmium sulfide quantum dots by a simple and efficient hydrothermal method. Aiming at the defects of poor biocompatibility and poor water solubility of the cadmium sulfide quantum dots, the AIE type molecules can well make up the defects, and the combination of the two can improve the sensitivity and fluorescence intensity of ion detection.
The specific technical scheme of the invention is as follows: a preparation method of an AIE fluorescent probe molecule modified by cadmium sulfide quantum dots comprises the following steps:
step 1: preparing cadmium sulfide quantum dots: mixing and stirring a sodium sulfide solution and a cadmium acetate solution, carrying out ultrasonic treatment, standing, centrifuging to obtain a precipitate, washing with deionized water, putting the washed precipitate into a polytetrafluoroethylene reaction kettle, reacting, cooling at room temperature, washing with deionized water and an ethanol solution, drying, and grinding to obtain the cadmium sulfide quantum dot.
Since the size of the quantum dot is smaller than the electron wavelength, the energy of the carrier is quantized, the forbidden band width Eg is 2.42ev, and the forbidden band width at room temperature is about 2.53ev in the visible light range. Therefore, it can be used as a photoelectric converter for a solar cell, a light emitting diode in a flat panel display, a fluorescent probe, etc. And the cadmium sulfide quantum dots are easy to prepare, and the luminous characteristics of the cadmium sulfide quantum dots can be adjusted by changing the composition, size, shape and surface coating of the cadmium sulfide quantum dots.
Step 2: preparation of 2 Br-TPE: adding 4-bromo-benzophenone and zinc powder into a drying container, vacuumizing, and introducing nitrogen for replacement; then injecting tetrahydrofuran, and adding TiCl at low temperature4Then condensing and refluxing for 4-8h at 70-80 ℃ under the condition of introducing nitrogen, separating out an organic phase after the reaction is cooled to room temperature, extracting a water phase by using dichloromethane, and merging the organic phasesDrying with anhydrous sodium sulfate; the crude product was purified by silica gel column chromatography to give 2 Br-TPE.
Compared with anhydrous magnesium sulfate, the anhydrous sodium sulfate has the advantages of large water absorption capacity, low cost, large particles, convenient treatment, slow action, stable property and strong water absorption capacity, and belongs to a neutral desiccant.
And step 3: h2Preparation of BCTPE molecules: adding 2Br-TPE, CuCN and anhydrous tetrahydrofuran into a container, heating the obtained mixture at 150 ℃ and 170 ℃ for 2-4 days, and then cooling to 85-95 ℃; subsequently mixing ethylenediamine with H2Adding O into the mixture, and heating and refluxing for 2-4 hours; after cooling to room temperature, crude 4, 4' - (1, 2-diphenylethylene 1, 2-diyl) benzonitrile was obtained by extraction with dichloromethane and drying with anhydrous magnesium sulfate; after filtration and evaporation of the solvent, the crude 4, 4' - (1, 2-diphenylethylene 1, 2-diyl) benzonitrile is subjected to hydrolysis reaction in ethylene glycol containing NaOH at 190-210 ℃ for 2-4 days; then cooling to room temperature, adding HCl solution to quench the reaction, filtering, washing with water and air drying, grinding to obtain solid powder H2BCTPE molecules.
And 4, step 4: preparing an AIE fluorescent probe molecule modified by cadmium sulfide quantum dots: cadmium sulfide quantum dots dissolved in N, N-dimethylformamide and H dissolved in N, N-dimethylformamide2Carrying out molecular ultrasonic dispersion on BCTPE, and transferring the mixture solution into a Teflon-lined autoclave; putting the autoclave into an environment with the temperature of 70-90 ℃ for reaction for 20-30 hours; and after cooling to room temperature, uniformly pouring the obtained mixture into centrifuge tubes, adding deionized water into each centrifuge tube, then centrifuging, removing supernatant, drying the centrifuge tubes containing precipitates, and grinding to obtain finished products.
The invention adopts a hydrothermal method, is efficient and simple, and can greatly improve the specific surface area, the photosensitivity and the catalytic activity, and the cadmium sulfide quantum dots and H2BCTPE molecules are tightly combined in an N, N-dimethylformamide solvent through pi-pi stacking effect, and can promote electron transfer. The modification of cadmium sulfide can improve the fluorescence quantum efficiency of AIE molecules and enhance the fluorescence intensity.
In conclusion, the cadmium sulfide quantum dot synthesized by a hydrothermal method has high quantum yield, good light stability, narrow half-peak width of an emission spectrum, good symmetry, no tailing phenomenon, easy detection and analysis and controllable emission wavelength by regulating and controlling the size, and takes the sodium sulfide solution as a sulfur source and the cadmium acetate solution as a cadmium source; then 1, 2-bis (4-bromophenyl) -1, 2-stilbene is synthesized through reaction, and only one isomer is generated compared with the traditional halogenation reaction. The electron transfer efficiency is improved by this method. And obtaining the AIE type molecule H by utilizing a displacement reaction and an acidification reaction2BCTPE, and finally preparing the AIE type molecule modified by the cadmium sulfide quantum dots by a simple and efficient hydrothermal method. Aiming at the defects of poor biocompatibility and poor water solubility of the cadmium sulfide quantum dots, the AIE type molecules can well make up the defects, and the combination of the two can improve the sensitivity and fluorescence intensity of ion detection.
Preferably, in the step 1, the concentrations of the sodium sulfide solution and the cadmium acetate solution are 0.8-1.2mg/L respectively; the volume ratio of the sodium sulfide solution to the cadmium acetate solution is (200-400) to (250-400).
Preferably, in the step 1, the stirring time is 2-4h, the ultrasonic treatment is 20-40min, the standing is 20-30h, the centrifugal rotation speed is 4000-.
Preferably, in step 1, the concentration of the ethanol solution is 97 to 99 wt%.
Preferably, in step 2, the amount of 4-bromo-benzophenone is 2.5-7.5g, the amount of zinc powder is 1.24-3.72g, and TiCl is added in g and mL4The amount of the compound (B) is 10-30mL, and the amount of the compound (B) is 30-70 mL.
Preferably, in step 2, the low temperature is from-5 ℃ to-1 ℃.
Preferably, in step 3, the addition amount of 2Br-TPE is 2.5-7.5mmol, the addition amount of CuCN is 6.1-18.3mmol, the addition amount of anhydrous tetrahydrofuran is 15-45mL, the addition amount of ethylenediamine is 2-6mL, and H is calculated by mmol, g and mL2The addition amount of O is 4-8mL, the addition amount of sodium hydroxide is 0.2-0.6g,the addition amount of the ethylene glycol is 20-60mL, and the addition amount of the HCl is 5-15 mL.
Preferably, in step 4, the addition amount of the cadmium sulfide quantum dots dissolved in the N, N-dimethylformamide is 5-10mL in terms of mg and mL, the concentration of the cadmium sulfide quantum dots is 0.8-1.2mg/mL, and the H dissolved in the N, N-dimethylformamide is2The addition amount of BCTPE molecules is 2-6mL, and H2The concentration of BCTPE molecules is 0.8-1.2mg/mL, and the ultrasonic dispersion time is 50-70 min.
Preferably, in step 4, the centrifuge tube containing the precipitate is dried at 50-70 ℃ for 40-50 hours.
Compared with the prior art, the invention has the beneficial effects that:
1. the semiconductor material cadmium sulfide quantum dot modified AIE type molecules are used as fluorescent probes for ion detection, compared with the traditional organic fluorescent dye, the semiconductor material cadmium sulfide quantum dot modified AIE type molecules can have strong fluorescent intensity in an aggregation state, and long-term tracking can be carried out in the process.
2. The AIE type molecule is modified by the cadmium sulfide quantum dots, the intensity of the fluorescence emission peak of the cadmium sulfide is dozens of times of that of the organic fluorescent molecule, the fluorescence intensity of the semiconductor quantum dots cannot be weakened under the condition of long-time continuous emission, and the fluorescence emission is stable. Has the function of mutual promotion with AIE type molecules.
3. The AIE fluorescent probe molecule modified by the cadmium sulfide quantum dots has high fluorescence quantum yield, high fluorescence stability, good biocompatibility and good water solubility, and the prepared AIE fluorescent probe molecule modified by the cadmium sulfide quantum dots has high fluorescence quantum yield, high fluorescence stability, good biocompatibility and good water solubility. Better application in ion detection.
4. The hydrothermal method is efficient and simple, and can greatly improve the specific surface area, the photosensitivity, the catalytic activity, the cadmium sulfide quantum dots and the H2BCTPE molecules are tightly combined in an N, N-dimethylformamide solvent through forming J-aggregates, and can promote the transfer of electrons. The modification of cadmium sulfide can improve the fluorescence quantum efficiency of AIE molecules and enhance the fluorescence intensity.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
1) Preparing cadmium sulfide quantum dots:
mixing 300ml of sodium sulfide solution (1mg/L) and 320ml of cadmium acetate solution (1mg/L), stirring for 3h, carrying out ultrasonic treatment for 30 min, standing for 24h, centrifuging at 5000rpm to obtain a precipitate, washing with deionized water, putting the washed precipitate into a polytetrafluoroethylene reaction kettle, reacting at the reaction temperature of 210 ℃ for 72h, cooling at room temperature, washing with deionized water and 99 wt% ethanol solution, drying at the drying temperature of 90 ℃ for 5h, and grinding to obtain cadmium sulfide quantum dots;
2) preparation of 1, 2-bis (4-bromophenyl) -1, 2-stilbene (2 Br-TPE):
to a dry two-necked round bottom flask was added 5.0g of 4-bromo-benzophenone and 2.48g of zinc powder, and the mixture was evacuated and replaced with nitrogen three times. Then 50ml Tetrahydrofuran (THF) was injected into the round bottom flask with a syringe, and 20ml TiCl was added at-5 deg.C4Then, the mixture is condensed and refluxed at 75 ℃ for 6 hours under the condition of introducing nitrogen, after the reaction is cooled to room temperature, an organic phase is separated, an aqueous phase is extracted by dichloromethane, and the organic phase is combined and dried by anhydrous sodium sulfate. The crude product was purified by silica gel column chromatography to give 2 Br-TPE.
3)H2Preparation of BCTPE molecules:
to a two-necked round bottom flask, 5.0mmol of 2Br-TPE, 12.2mmol of CuCN and 30ml of anhydrous THF were added. The mixture was heated at 160 ℃ for 3 days and then cooled to 90 ℃. Subsequently, 4ml of ethylenediamine and 6ml of H20 was added to the mixture and heated to reflux for 3 hours. After cooling to room temperature, 4' - (1, 2-diphenylethylene 1, 2-diyl) dibenzylnitrile (2CN-TPE) was obtained by extraction with Dichloromethane (DCM) and drying over anhydrous magnesium sulfate. After filtration and evaporation of the solvent, the crude 2CN-TPE was subjected to a hydrolysis reaction in 40ml of ethylene glycol containing 0.4g NaOH at 200 ℃ for 3 days. Then, after cooling to room temperature, 10ml of HCl solution was carefully added to quench the reaction. Filtering, washing with water for three times, air drying, and grinding to obtain solid powder.
4) Preparing an AIE type molecule/cadmium sulfide quantum dot composite material:
the cadmium sulfide quantum dots dissolved in 7.5ml of N, N-dimethylformamide and with the concentration of 1mg/ml are mixed with 1mg/ml H dissolved in 4ml of N, N-dimethylformamide2The BCTPE molecules were ultrasonically dispersed for 1h and the mixture solution was transferred to a Teflon lined autoclave. The autoclave was placed in an oven at 80 ℃ for 24 hours. After cooling to room temperature, the resulting mixture was poured into centrifuge tubes uniformly and an appropriate amount of deionized water was added to each centrifuge tube. The mixture was then centrifuged in a centrifuge and the supernatant discarded. The centrifuge tube containing the precipitate was placed in an oven at 60 ℃ for 48 hours. Finally, the dried precipitate was ground and the powder was collected.
In example 1, for H2Purifying the BCTPE by silica gel column chromatography to obtain H2BCTPE was a brown solid in 43% yield. And supernatant and precipitate can be better separated after hydrothermal reaction and centrifugation.
Example 2
1) Preparing cadmium sulfide quantum dots:
mixing 200ml of sodium sulfide solution (1mg/L) and 250ml of cadmium acetate solution (1mg/L), stirring for 3h, carrying out ultrasonic treatment for 30 min, standing for 24h, centrifuging at 5000rpm to obtain a precipitate, washing with deionized water, putting the washed precipitate into a polytetrafluoroethylene reaction kettle, reacting at the reaction temperature of 200 ℃ for 72h, cooling at room temperature, washing with deionized water and 99 wt% ethanol solution, drying at the drying temperature of 80 ℃ for 5h, and grinding to obtain cadmium sulfide quantum dots;
2) preparation of 1, 2-bis (4-bromophenyl) -1, 2-stilbene (2 Br-TPE):
to a dry two-necked round bottom flask was added 2.5g of 4-bromo-benzophenone and 1.24g of zinc powder, and the mixture was evacuated and replaced with nitrogen three times. Then 30ml Tetrahydrofuran (THF) was injected into the round bottom flask with a syringe, and 10ml TiCl was added at-5 deg.C in a low temperature environment4Then, the mixture is condensed and refluxed at 75 ℃ for 6 hours under the condition of introducing nitrogen, after the reaction is cooled to room temperature, an organic phase is separated, an aqueous phase is extracted by dichloromethane, and the organic phase is combined and dried by anhydrous sodium sulfate. The crude product is passed through a silica gel columnPurifying by chromatography to obtain 2 Br-TPE.
3)H2Preparation of BCTPE molecules:
to a two-necked round bottom flask, 2.5mmol of 2Br-TPE, 6.1mmol of CuCN and 15ml of anhydrous THF were added. The mixture was heated at 160 ℃ for 3 days and then cooled to 90 ℃. Subsequently, 2ml of ethylenediamine and 4ml of H2O was added to the mixture and heated to reflux for 3 hours. After cooling to room temperature, 4' - (1, 2-diphenylethylene 1, 2-diyl) dibenzylnitrile (2CN-TPE) was obtained by extraction with Dichloromethane (DCM) and drying over anhydrous magnesium sulfate. After filtration and evaporation of the solvent, the crude 2CN-TPE was subjected to a hydrolysis reaction in 20ml of ethylene glycol containing 0.2g NaOH at 200 ℃ for 3 days. Then, after cooling to room temperature, 5ml of HCl solution was carefully added to quench the reaction. Filtering, washing with water for three times, air drying, and grinding to obtain solid powder.
4) Preparing an AIE type molecule/cadmium sulfide quantum dot composite material:
cadmium sulfide quantum dots dissolved in 5ml of N, N-dimethylformamide and with the concentration of 1mg/ml and 1mg/ml of H dissolved in 2ml of N, N-dimethylformamide2The BCTPE molecules were ultrasonically dispersed for 1h and the mixture solution was transferred to a Teflon lined autoclave. The autoclave was placed in an oven at 80 ℃ for 24 hours. After cooling to room temperature, the resulting mixture was poured into centrifuge tubes uniformly and an appropriate amount of deionized water was added to each centrifuge tube. The mixture was then centrifuged in a centrifuge and the supernatant discarded. The centrifuge tube containing the precipitate was placed in an oven at 60 ℃ for 48 hours. Finally, the dried precipitate was ground and the powder was collected.
Example 3
1) Preparing cadmium sulfide quantum dots:
mixing 400ml of sodium sulfide solution (1mg/L) and 400ml of cadmium acetate solution (1mg/L), stirring for 3h, carrying out ultrasonic treatment for 30 min, standing for 24h, centrifuging at 5000rpm to obtain a precipitate, washing with deionized water, putting the washed precipitate into a polytetrafluoroethylene reaction kettle, reacting at the reaction temperature of 220 ℃ for 72h, cooling at room temperature, washing with deionized water and 99 wt% ethanol solution, drying at the drying temperature of 100 ℃ for 5h, and grinding to obtain cadmium sulfide quantum dots;
2) preparation of 1, 2-bis (4-bromophenyl) -1, 2-stilbene (2 Br-TPE):
to a dry two-necked round bottom flask was added 4-bromo-benzophenone 7.5g and zinc powder 3.72g, and the mixture was evacuated and replaced with nitrogen three times. Then 70ml Tetrahydrofuran (THF) was injected into the round bottom flask with a syringe, and 30ml TiCl was added under a low temperature environment of-5 deg.C4Then, the mixture is condensed and refluxed at 75 ℃ for 6 hours under the condition of introducing nitrogen, after the reaction is cooled to room temperature, an organic phase is separated, an aqueous phase is extracted by dichloromethane, and the organic phase is combined and dried by anhydrous sodium sulfate. The crude product was purified by silica gel column chromatography to give 2 Br-TPE.
3)H2Preparation of BCTPE molecules:
to a two-necked round bottom flask, 7.5mmol of 2Br-TPE, 18.3mmol of CuCN and 45ml of anhydrous THF were added. The mixture was heated at 160 ℃ for 3 days and then cooled to 90 ℃. Subsequently, 6ml of ethylenediamine and 8ml of H2O was added to the mixture and heated to reflux for 3 hours. After cooling to room temperature, 4' - (1, 2-diphenylethylene 1, 2-diyl) dibenzylnitrile (2CN-TPE) was obtained by extraction with Dichloromethane (DCM) and drying over anhydrous magnesium sulfate. After filtration and evaporation of the solvent, the crude 2CN-TPE was subjected to a hydrolysis reaction in 60ml of ethylene glycol containing 0.6g NaOH at 200 ℃ for 3 days. Then, after cooling to room temperature, 15ml of HCl solution was carefully added to quench the reaction. Filtering, washing with water for three times, air drying, and grinding to obtain solid powder.
4) Preparation of AIE type molecule/cadmium sulfide quantum dot composite material
Cadmium sulfide quantum dots with the concentration of 1mg/ml dissolved in 10ml of N, N-dimethylformamide and 1mg/ml H dissolved in 6ml of N, N-dimethylformamide2The BCTPE molecules were ultrasonically dispersed for 1h and the mixture solution was transferred to a Teflon lined autoclave. The autoclave was placed in an oven at 80 ℃ for 24 hours. After cooling to room temperature, the resulting mixture was poured into centrifuge tubes uniformly and an appropriate amount of deionized water was added to each centrifuge tube. The mixture was then centrifuged in a centrifuge and the supernatant discarded. The centrifuge tube containing the precipitate was placed in an oven at 60 ℃ for 48 hours. Finally, grinding the dried precipitate andthe powder was collected.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (9)
1. A preparation method of an AIE fluorescent probe molecule modified by cadmium sulfide quantum dots is characterized by comprising the following steps:
step 1: preparing cadmium sulfide quantum dots: mixing and stirring a sodium sulfide solution and a cadmium acetate solution, carrying out ultrasonic treatment, standing, centrifuging to obtain a precipitate, washing with deionized water, putting the washed precipitate into a polytetrafluoroethylene reaction kettle, reacting, cooling at room temperature, washing with deionized water and an ethanol solution, drying, and grinding to obtain cadmium sulfide quantum dots;
step 2: preparation of 2 Br-TPE: adding 4-bromo-benzophenone and zinc powder into a drying container, vacuumizing, and introducing nitrogen for replacement; then injecting tetrahydrofuran, and adding TiCl at low temperature4Then condensing and refluxing for 4-8h at 70-80 ℃ under the condition of introducing nitrogen, separating out an organic phase after the reaction is cooled to room temperature, extracting a water phase by using dichloromethane, combining the organic phases, and drying by using anhydrous sodium sulfate; purifying the crude product by silica gel column chromatography to obtain 2 Br-TPE;
and step 3: h2Preparation of BCTPE molecules: adding 2Br-TPE, CuCN and anhydrous tetrahydrofuran into a container, heating the obtained mixture at 150 ℃ and 170 ℃ for 2-4 days, and then cooling to 85-95 ℃; subsequently mixing ethylenediamine with H2Adding O into the mixture, and heating and refluxing for 2-4 hours; after cooling to room temperature, crude 4, 4' - (1, 2-diphenylethylene 1, 2-diyl) benzonitrile was obtained by extraction with dichloromethane and drying with anhydrous magnesium sulfate; after filtration and evaporation of the solvent, the crude 4, 4' - (1, 2-diphenylethane) is filtered offAlkene 1, 2-diyl) dibenzyl nitrile is subjected to hydrolysis reaction in ethylene glycol containing NaOH for 2 to 4 days at the temperature of 190 ℃ and 210 ℃; then cooling to room temperature, adding HCl solution to quench the reaction, filtering, washing with water and air drying, grinding to obtain solid powder H2BCTPE molecules;
and 4, step 4: preparing an AIE fluorescent probe molecule modified by cadmium sulfide quantum dots: cadmium sulfide quantum dots dissolved in N, N-dimethylformamide and H dissolved in N, N-dimethylformamide2Carrying out molecular ultrasonic dispersion on BCTPE, and transferring the mixture solution into a Teflon-lined autoclave; putting the autoclave into an environment with the temperature of 70-90 ℃ for reaction for 20-30 hours; and after cooling to room temperature, uniformly pouring the obtained mixture into centrifuge tubes, adding deionized water into each centrifuge tube, then centrifuging, removing supernatant, drying the centrifuge tubes containing precipitates, and grinding to obtain finished products.
2. The method according to claim 1, wherein in step 1, the concentrations of the sodium sulfide solution and the cadmium acetate solution are 0.8 to 1.2mg/L, respectively; the volume ratio of the sodium sulfide solution to the cadmium acetate solution is (200-400) to (250-400).
3. The preparation method as claimed in claim 1, wherein in step 1, the stirring time is 2-4h, the ultrasonic treatment is 20-40min, the standing is 20-30h, the centrifugal rotation speed is 4000-6000rpm, the reaction temperature is 200-220 ℃, the reaction time is 70-75h, the drying temperature is 80-100 ℃, and the drying time is 3-7 h.
4. The method according to claim 1, wherein the concentration of the ethanol solution in step 1 is 97 to 99 wt%.
5. The method according to claim 1, wherein in the step 2, the amount of 4-bromo-benzophenone is 2.5 to 7.5g, the amount of zinc powder is 1.24 to 3.72g, and TiCl is added in g and mL4The amount of the compound (B) is 10-30mL, and the amount of the compound (B) is 30-70 mL.
6. The method according to claim 1, wherein the low temperature is from-5 ℃ to-1 ℃ in the step 2.
7. The method according to claim 1, wherein in step 3, the amount of 2Br-TPE added is 2.5 to 7.5mmol, the amount of CuCN added is 6.1 to 18.3mmol, the amount of anhydrous tetrahydrofuran added is 15 to 45mL, the amount of ethylenediamine added is 2 to 6mL, H and/or a mixture thereof2The addition amount of O is 4-8mL, the addition amount of sodium hydroxide is 0.2-0.6g, the addition amount of ethylene glycol is 20-60mL, and the addition amount of HCl is 5-15 mL.
8. The method according to claim 1, wherein in step 4, the amount of cadmium sulfide quantum dots dissolved in N, N-dimethylformamide is 5 to 10mL in terms of mg and mL, the concentration of cadmium sulfide quantum dots is 0.8 to 1.2mg/mL, and H dissolved in N, N-dimethylformamide is added2The addition amount of BCTPE molecules is 2-6mL, and H2The concentration of BCTPE molecules is 0.8-1.2mg/mL, and the ultrasonic dispersion time is 50-70 min.
9. The method of claim 1, wherein in step 4, the centrifuge tube containing the precipitate is dried at 50-70 ℃ for 40-50 hours.
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