CN117089341A - Preparation method and application of fluorescence sensor - Google Patents
Preparation method and application of fluorescence sensor Download PDFInfo
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- CN117089341A CN117089341A CN202311071942.4A CN202311071942A CN117089341A CN 117089341 A CN117089341 A CN 117089341A CN 202311071942 A CN202311071942 A CN 202311071942A CN 117089341 A CN117089341 A CN 117089341A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 86
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 43
- 239000002096 quantum dot Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011148 porous material Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- 239000012670 alkaline solution Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 8
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 8
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 8
- 238000001514 detection method Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 25
- 150000002500 ions Chemical class 0.000 description 10
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 7
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- 239000000523 sample Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 5
- 230000005284 excitation Effects 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- 229910002808 Si–O–Si Inorganic materials 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
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- 230000002452 interceptive effect Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000007850 fluorescent dye Substances 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical group NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 229910008051 Si-OH Inorganic materials 0.000 description 2
- 229910006358 Si—OH Inorganic materials 0.000 description 2
- 238000007112 amidation reaction Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
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- 230000003301 hydrolyzing effect Effects 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
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- 229910000077 silane Inorganic materials 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
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- 238000005452 bending Methods 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
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- 206010012601 diabetes mellitus Diseases 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 239000012678 infectious agent Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 230000002438 mitochondrial effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
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- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000035479 physiological effects, processes and functions Effects 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
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- 238000007363 ring formation reaction Methods 0.000 description 1
- 230000019491 signal transduction Effects 0.000 description 1
- 230000011664 signaling Effects 0.000 description 1
- 238000002444 silanisation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
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- 125000000437 thiazol-2-yl group Chemical group [H]C1=C([H])N=C(*)S1 0.000 description 1
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Classifications
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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
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/645—Specially adapted constructive features of fluorimeters
- G01N21/6456—Spatial resolved fluorescence measurements; Imaging
- G01N21/6458—Fluorescence microscopy
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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- C09K2211/1007—Non-condensed systems
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
Abstract
The application discloses a preparation method and application of a fluorescence sensor, and belongs to the technical field of fluorescence sensing materials. The application adopts a physical embedding mode to load organic fluorescent molecules into mesoporous silica pore canals, and then grafts silanized luminous quantum dots onto the surface of mesoporous silica in a covalent bond mode. Not only maintains the fluorescence property and excellent water solubility of the luminous quantum dot, but also effectively prevents the leakage of organic fluorescent molecules, combines the low cytotoxicity and the protection effect of mesoporous silica, and simultaneously plays the role of the organic fluorescent molecules on H 2 O 2 Specificity of (3)The ratio fluorescent nano sensor with good practical application value is obtained.
Description
Technical Field
The application belongs to the technical field of fluorescent sensing materials, and particularly relates to a preparation method and application of a fluorescent sensor.
Background
ROS is a generic term that includes hydrogen peroxide (H 2 O 2 ) Hydroxyl radical (OH), peroxy Radical (ROO) · ) Singlet oxygen 1 O 2 ) Superoxide anion radical (O) 2 ·- ) And hypochlorous acid/hypochlorous acid ion (HOCl/ClO) - ) They are all derived from molecular oxygen in biological life processes. Specifically, oxygen is produced endogenously, primarily by the mitochondrial respiratory process in the body, and also exogenously by exposure to ultraviolet light, xenobiotics, and infectious agents. ROS are therefore vital to physiology as functional signaling entities. Wherein H is 2 O 2 As second messengers, are involved in signal transduction of normal cells and are involved in many physiological processes. At the same time H 2 O 2 Is three types of carcinogens, and its imbalance will lead to various diseases such as cardiovascular disease, neurodegenerative disease, diabetes and cancer. Therefore, a method capable of accurately detecting H in a human body was developed 2 O 2 Horizontal methods are critical to preventing these diseases.
Compared with other methods, the fluorescence sensing technology is used for H due to high sensitivity and strong specificity 2 O 2 Is used in the sensing field of the sensor. In recent years, most of the tests for H 2 O 2 The fluorescent probe of (2) is based on a single-emission fluorescent response, which is achieved for H by varying the fluorescence intensity at the original emission peak 2 O 2 But the method is susceptible to factors such as sample concentration and excitation intensity. Ratio fluorescence technology has recently gained widespread attention and has been able to overcome these drawbacks with a linear response, high sensitivity and low sensitivityDetection limit, etc. The change of the ratio probe signal can be identified by naked eyes, and the ratio probe can eliminate the influence of the environment on probe detection through the ratio of the two peak intensities, and can measure the change of the emission intensity of different wavelengths. Various types of nanomaterials have been used to fabricate ratiometric fluorescence sensors in which mesoporous silica has a large pore volume and an ordered porous structure, thus being capable of loading more molecules; secondly, the mesoporous silica surface has abundant silicon hydroxyl groups, so that the mesoporous silica is easy to functionalize, and the diversified application of the mesoporous silica is ensured; meanwhile, the mesoporous silica has excellent biocompatibility and low cytotoxicity. Thus mesoporous silica provides an excellent support carrier for rate sensing. However, mesoporous silica is in H 2 O 2 The water solubility problem in the field of fluorescence sensing is less studied, which greatly limits the further use of fluorescent probes in biological systems.
Disclosure of Invention
Aiming at the technical defects of low fluorescence efficiency, poor water solubility and the like of the ratio fluorescent probe material in the prior art, the application utilizes carbon points with excellent water dispersibility to carry out surface modification on MSN so as to realize a preparation method and application of the high-performance fluorescent sensor.
In order to achieve the above purpose, the present application provides the following technical solutions:
the technical scheme is as follows: h (H) 2 O 2 Ratio fluorescence sensor, described H 2 O 2 The ratio fluorescent sensor takes mesoporous silica as a carrier, organic fluorescent molecules are loaded in an inner pore canal of the carrier, and the outer surface of the carrier is grafted with silanized luminescent quantum dots.
As a further preference, the mass ratio of mesoporous silica to organic fluorescent molecules is 5:1.
As a further preferred aspect, the method for preparing mesoporous silica comprises the steps of: adding a surfactant and an alkaline solution into water, heating and stirring, then adding a mixed solution of tetraethyl orthosilicate and n-hexane, cooling to room temperature after the reaction is completed, filtering, washing and drying the obtained white powder, and removing a template agent.
The purpose of adding the alkaline solution is to make the reaction conditions alkaline, so that the siloxane is subjected to hydrolytic polycondensation to form white powder, and finally the target product is obtained. The alkaline solution may be sodium hydroxide solution or ammonia water.
Still more preferably, the surfactant is cetyltrimethylammonium bromide. The volume ratio of the water to the alkaline solution to the normal hexane to the tetraethyl orthosilicate is 160:7:2:5. The heating and stirring means stirring for 30min at 35 ℃. The method for removing the template agent (namely the surfactant) comprises the following steps: calcination was carried out at 550℃for 5h.
As a further preferred aspect, the method for preparing the silylated luminescent quantum dot comprises the steps of: adding carbon quantum dots, N-hydroxysuccinimide and 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride into an organic solvent for reaction, then adding 3-aminopropyl triethoxysilane, and stirring. The mass ratio of the carbon quantum dots to the N-hydroxysuccinimide to the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride is 1:1:1. The organic solvent is ethanol.
The second technical scheme is as follows: the H 2 O 2 The preparation method of the ratio fluorescence sensor adopts a physical embedding mode to load organic fluorescent molecules into mesoporous silica pore canals, and then the silanized luminescent quantum dots are grafted onto the surface of the mesoporous silica in a covalent bond mode.
As a further preference, the preparation method specifically comprises the following steps:
dissolving organic fluorescent molecules in chloroform or dichloromethane, then adding mesoporous silica into the solution, and carrying out heating treatment under ultrasonic conditions to obtain MSN-BA; mixing MSN-BA with silanized luminescent quantum dot, and reacting at room temperature for 15H to obtain H 2 O 2 A ratio fluorescence sensor. The steps may further include post-processing, specifically including: washing and drying.
As a further preference, the heat treatment means heating at 38℃for 1-2h. The ultrasonic power is 100W.
As a further preference, the MSN-BA and the silanized luminescent quantum dot are used in a ratio of 1 mg:15. Mu.L.
According to the application, a physical loading method is used, organic fluorescent molecules are loaded into the pore canal of mesoporous silica through ultrasonic heating, and a rear grafting method is used for fixing the silanized luminescent quantum dots on the surface of Yu Jiekong silica. The carbon quantum dot activates carboxyl by N-hydroxysuccinimide and 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, and activated-COOH and-NH of 3-aminopropyl triethoxysilane 2 Amidation reaction is carried out to form amide groups, and meanwhile, the carbon quantum dots contain Si-O-Si bonds which are further condensed with Si-OH on mesoporous silica so as to be fixed on the surface of the mesoporous silica.
The technical scheme is as follows: the H 2 O 2 Ratio fluorescence sensor at H 2 O 2 Application in detection.
The technical scheme is as follows: the H 2 O 2 Use of a ratiometric fluorescence sensor in intracellular sensing and imaging.
Compared with the prior art, the application has the following advantages and technical effects:
the application utilizes chemical bonds to connect the luminescent quantum dots to the surface of mesoporous silica, and simultaneously the mesoporous silica pore canal carries organic fluorescent molecules, thereby not only maintaining the fluorescent property and excellent water solubility of the luminescent quantum dots, but also preventing the organic fluorescent molecules in the pore canal from leaking, combining the low cytotoxicity and the protective effect of the mesoporous silica, and simultaneously playing the role of the organic fluorescent molecules on H 2 O 2 Specific fluorescence property and the like, and the ratio fluorescence nano sensor with good practical application value is obtained.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application. In the drawings:
FIG. 1 is a TEM image of a luminescent quantum dot according to example 1 of the present application;
FIG. 2 is an infrared spectrum of CD and SiCD in example 2 of the present application;
FIG. 3 is an SEM and TEM image of the material of example 3 of the present application; a is a mesoporous silica SEM image, b is an MSN-BA SEM image; c is a TEM image of MSN-BA;
FIG. 4 is an SEM image (a) and a TEM image (b) of the fluorescent nanosensor material of example 4 of the application;
FIG. 5 shows the concentration of H in the fluorescent nanosensor material of example 4 of the application 2 O 2 A fluorescent emission pattern (a) and a linear relationship pattern (b) thereof;
FIG. 6 is a response test result of the fluorescent nano-sensing material in example 4 of the present application; a is a response result graph of fluorescent nano sensing materials under the influence of different ROS and other ions, and b is detection of H by interfering ions on the fluorescent nano sensing materials 2 O 2 Is a graph of the impact results;
FIG. 7 shows the results of a photo-stability test of MSN-BA-SiCD prepared in example 4;
FIG. 8 is a graph showing cell activity data of fluorescent nanosensory material of example 4 of the application;
FIG. 9 is a reaction scheme of the present application.
Detailed Description
Various exemplary embodiments of the application will now be described in detail, which should not be considered as limiting the application, but rather as more detailed descriptions of certain aspects, features and embodiments of the application.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the application. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present application. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the application described herein without departing from the scope or spirit of the application. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present application. The specification and examples of the present application are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The "room temperature" as used herein is calculated as 25.+ -. 2 ℃ unless otherwise indicated.
The raw materials used in the following examples of the present application are all commercially available.
The application provides an H 2 O 2 Ratio fluorescence sensor, described H 2 O 2 The ratio fluorescent sensor takes mesoporous silica as a carrier, organic fluorescent molecules are loaded in an inner pore canal of the carrier, and the outer surface of the carrier is grafted with silanized luminescent quantum dots.
The application provides the H 2 O 2 The preparation method of the ratio fluorescence sensor comprises the following steps:
1) Dissolving organic fluorescent molecules in an organic solvent, adding mesoporous silica into the organic solvent, and performing heating treatment under ultrasonic conditions to obtain MSN-BA;
2) Activating carboxyl of the carbon quantum dot, and then adding silane to obtain a silane modified carbon dot (SiCD), namely a silanized luminescent quantum dot;
3) Adding MSN-BA and SiCD into organic solvent to make reactionWashing and drying to obtain H 2 O 2 A ratio fluorescence sensor.
In some preferred embodiments of the application, step 1), the organic solvent is chloroform or dichloromethane. The organic fluorescent molecules are probe molecules BA. The mass ratio of the mesoporous silica to the organic fluorescent molecules is 5:1. The ultrasonic power is 100W; the heating treatment temperature is 38 ℃ and the time is 1-2h, preferably 2h.
In some preferred embodiments of the present application, step 1), the preparation method of mesoporous silica comprises the steps of: dissolving a surfactant in deionized water, adding an alkaline solution (the purpose of adding the alkaline solution is to make the reaction condition alkaline, so that siloxane is subjected to hydrolytic polycondensation to form white powder, and finally obtaining a target product, wherein the alkaline solution can be sodium hydroxide solution or ammonia water, preferably ammonia water), heating and stirring, then adding a mixed solution of n-hexane and tetraethyl orthosilicate, reacting for 12 hours, and under stirring conditions, cooling to room temperature completely, filtering to obtain a white powder precipitate, washing and drying, and removing a template agent to obtain mesoporous silica. The surfactant is cetyl trimethyl ammonium bromide. The volume ratio of the deionized water to the alkaline solution to the normal hexane to the tetraethyl orthosilicate is 160:7:2:5. The heating and stirring means stirring for 30min at 35 ℃. The drying refers to drying at room temperature for 1 day. The method for removing the template agent comprises the following steps: calcination was carried out at 550℃for 5h.
In some preferred embodiments of the application, step 2), the specific method of silylation is: adding the carbon quantum dots, N-hydroxysuccinimide and 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride into an organic solvent for reaction for 6-12h, then adding 3-aminopropyl triethoxysilane, and stirring for 12h at room temperature to complete silanization. The mass ratio of the carbon quantum dots to the N-hydroxysuccinimide to the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride is 1:1:1. The organic solvent is ethanol.
In some preferred embodiments of the application, step 3), the MSN-BA is used in an amount ratio of 1mg to 15. Mu.L to the silanized luminescent quantum dots. The reaction is carried out at room temperature for 15 hours. The organic solvent refers to ethanol.
According to the application, a physical loading method is used, organic fluorescent molecules are loaded into the pore canal of mesoporous silica through ultrasonic heating, and a rear grafting method is used for fixing the silanized luminescent quantum dots on the surface of Yu Jiekong silica. The carbon quantum dot activates carboxyl by N-hydroxysuccinimide and 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, and activated-COOH and-NH of 3-aminopropyl triethoxysilane 2 Amidation reaction is carried out to form amide groups, and meanwhile, the carbon quantum dots contain Si-O-Si bonds which are further condensed with Si-OH on mesoporous silica so as to be fixed on the surface of the mesoporous silica.
The technical scheme is as follows: the H 2 O 2 Ratio fluorescence sensor at H 2 O 2 Application in detection.
The technical scheme is as follows: the H 2 O 2 Use of a ratiometric fluorescence sensor in intracellular sensing and imaging.
The concentrations of ethanol in the examples below are all absolute ethanol.
The following examples serve as further illustrations of the technical solutions of the application.
Example 1
1g of citric acid and 2g of urea were dissolved in 10mL of deionized water, reacted at 160℃for 4 hours, then cooled to room temperature, the resulting solvent was mixed with 20mL of ethanol, centrifuged at 8000r/min for 10 minutes with a centrifuge, the precipitate was collected and dispersed in ethanol, and ethanol was washed twice to remove residual solvent and organic solvent, to obtain a blue Carbon Dot (CD).
When the microstructure of the obtained CD was observed, as shown in FIG. 1, it was found that the lattice spacing of the carbon dots was 0.21nm.
Example 2
Blue CD (200 mg), N-hydroxysuccinimide (200 mg) and 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride (200 mg) obtained in example 1 above were suspended in 2mL of ethanol, stirred at room temperature for 6 hours, then 150. Mu.L of 3-aminopropyl triethoxysilane was added, stirred at room temperature for 12 hours, and the precipitate was collected by centrifugation and dispersed in 2mL of ethanol to obtain silane-modified CD (SiCD).
The structural characteristics of the obtained SiCD were characterized, the obtained infrared spectrum is shown in FIG. 2, and compared with the infrared spectrum of blue CD, the SiCD is 1082cm -1 The peak at the position is attributed to the antisymmetric stretching vibration of Si-O-Si bond, and is 3400-2500cm at the same time -1 The bending vibration peak of-OH in the carboxyl group was reduced and 3392cm was observed -1 ,1676cm -1 And 1649cm -1 Indicating that the carboxyl group on SiCD reacts with the amino group to form a secondary amide bond.
Example 3
Cetyl trimethylammonium bromide (200 mg) was dissolved in 32mL of deionized water, 1.4mL of ammonia was added with stirring, and the mixture was heated to 35℃and stirred for 30 minutes. Then, 0.4mL of a mixed solution of n-hexane and 1mL of tetraethyl orthosilicate was slowly added to the above aqueous solution of cetyltrimethylammonium bromide, and the mixed solution was stirred at 35℃for 12 hours, and then cooled to room temperature, and suction filtration was performed to obtain silica. The product was then calcined in a muffle furnace at 550 ℃ for 5 hours to remove the template cetyltrimethylammonium bromide, resulting in Mesoporous Silica (MSN).
10mg of mesoporous silica and 2mg of probe molecule BA ((E) -2- (benzo [ d ] thiazol-2-yl) -3- (4- (diethylamino) -2- ((4- (4, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) benzyl) oxy) phenyl) acrylonitrile) were dissolved in 2mL of methylene chloride and reacted at a temperature of 38℃for 2 hours under ultrasound of 100W, ethanol was washed three times to obtain BA-loaded mesoporous silica (MSN-BA).
When the microstructure of the obtained MSN and MSN-BA is observed, as shown in FIG. 3, it can be seen from a and b in FIG. 3 that the mesoporous material has a representative nanosphere structure. As can be seen from c in FIG. 3, MSN-BA has ordered mesoporous channels.
Example 4
MSN-BA (10 mg) obtained in example 3 above was suspended in 3mL of ethanol, sonicated for 20 minutes, then 100. Mu.L of aqueous ammonia was added, stirred at room temperature for 30 minutes, 150. Mu.L of SiCD obtained in example 2 above was added, stirred at room temperature for 15 hours, spin-dried, ethanol washed 2 times, and water washed once to obtain SiCD-modified MSN-BA (MSN-BA-SiCD).
When the microstructure of the obtained MSN-BA-SiCD was observed, as shown in FIG. 4, it was seen that MSN-BA-SiCD had an ordered pore structure and a nanosphere structure.
Test example 1
For the MSN-BA-SiCD pair H obtained in example 4 2 O 2 The response is tested: uniformly dispersing MSN-BA-SiCD in mixed solution of DMSO: PBS=1:99 (v/v), fixing MSN-BA-SiCD concentration to 5×10 -5 g/mL H at a concentration of 0-400. Mu.M 2 O 2 . Fluorescence excitation wavelength of 365nm, research on H by MSN-BA-SiCD 2 O 2 Is a fluorescent emission spectrum of (2).
The fluorescence emission spectrum results are shown in FIG. 5, and with H 2 O 2 The fluorescence intensity is continuously enhanced by increasing the concentration. Shows a macroscopic fluorescence color change from initial blue light to green light, indicating probe molecules BA and H 2 O 2 The inverse cyclization reaction occurs to produce a more highly conjugated compound. Fluorescence emission intensity and H 2 O 2 The concentration is 0-3.5X10 -4 Exhibits good linear relationship in the M range (R 2 = 0.9879), the lowest detection limit of the final assay is 4.78×10 -6 M。
Test example 2
The MSN-BA-SiCD obtained in example 4 was tested for specificity: fixing the concentration of various Reactive Oxygen Species (ROS) and other ions to 4.5X10 -4 M, fluorescence excitation wavelength is 365nm, and fluorescence emission spectra of MSN-BA-SiCD on various ROS and different ions are respectively studied, and the result is shown as a in FIG. 6 (the bar graph in the graph a corresponds to 0-15 in sequence, and 0 is a blank control group, namely no interference ions).
Further testing interference ROS to MSN-BA-SiCD detection H by competition experiments 2 O 2 Is to be added to the following: adding H into the mixed solution containing various ions 2 O 2 The concentration is 4.5X10 -4 M, fluorescence excitation wavelength was 365nm, and the test results are shown as b in FIG. 6.
From FIG. 6, it canIt can be seen that MSN-BA-SiCD is specific to H only 2 O 2 A response is generated, and little or no response to other ions is generated. Meanwhile, as can be seen from the graph, the fluorescence intensity of interfering ions and the addition of H alone 2 O 2 The fluorescence intensity was almost uniform (0 is blank, i.e. no interfering ions; 1 is the addition of H alone) 2 O 2 The method comprises the steps of carrying out a first treatment on the surface of the Others are addition of interfering ions and H 2 O 2 )。
The results indicate that MSN-BA-SiCD is opposite to H 2 O 2 Has specificity, good selectivity and anti-interference performance.
Test example 3
Photostability test of fluorescent molecules BA and MSN-BA-SiCD: the fluorescence emission intensities of fluorescent molecules BA and MSN-BA-SiCD prepared in example 4 were measured within 45 minutes after continuous ultraviolet light (λ=365 nm), and as a result, as shown in fig. 7, it can be seen that the fluorescence intensity of fluorescent molecules was reduced by 52.9% after 45 minutes under strong excitation, while the fluorescence intensity of MSN-BA-SiCD was reduced by only 18.3%. The protection of the Si-O-Si network in MSN may be the main reason for the high photostability of MSN-BA-SiCD materials, which can effectively prevent the oxidation or destruction of fluorescent molecules by other factors, avoiding the photo-bleaching phenomenon.
Test example 4
Cytotoxicity of the ratiometric fluorescent nanosensor prepared in example 4 was measured using MTT method, and cells were incubated with HepG2 cells at different concentrations of MSN-BA-SiCD for 24h, and viability was measured, as shown in fig. 8: with increasing MSN-BA-SiCD concentration, the cell survival rate is maintained above 90%. The fluorescence sensor MSN-BA-SiCD has low toxicity to cells, and has good detection performance and biocompatibility.
The present application is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present application are intended to be included in the scope of the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.
Claims (10)
1. H (H) 2 O 2 A ratio fluorescence sensor characterized in that the H 2 O 2 The ratio fluorescent sensor takes mesoporous silica as a carrier, organic fluorescent molecules are loaded in an inner pore canal of the carrier, and the outer surface of the carrier is grafted with silanized luminescent quantum dots.
2. H according to claim 1 2 O 2 The ratio fluorescence sensor is characterized in that the mass ratio of the mesoporous silica to the organic fluorescent molecules is 5:1.
3. H according to claim 2 2 O 2 The ratio fluorescent sensor is characterized in that the preparation method of the mesoporous silica comprises the following steps: adding a surfactant and an alkaline solution into water, heating and stirring, then adding a mixed solution of tetraethyl orthosilicate and n-hexane, cooling and filtering after the reaction is completed, washing and drying the obtained white powder, and removing a template agent.
4. H according to claim 1 2 O 2 The ratio fluorescence sensor is characterized in that the preparation method of the silanized luminescent quantum dot comprises the following steps: adding carbon quantum dots, N-hydroxysuccinimide and 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride into an organic solvent for reaction, then adding 3-aminopropyl triethoxysilane, and stirring.
5. An H as claimed in any one of claims 1 to 4 2 O 2 The preparation method of the ratio fluorescence sensor is characterized in that organic fluorescent molecules are loaded into mesoporous silica pore channels in a physical embedding mode, and then silanized luminescent quantum dots are fixed on the surface of the mesoporous silica through a post grafting method.
6. H according to claim 5 2 O 2 The preparation method of the ratio fluorescence sensor is characterized in thatThe preparation method specifically comprises the following steps:
adding mesoporous silica into an organic fluorescent molecule solution, and carrying out ultrasonic heating to obtain MSN-BA; mixing MSN-BA with silanized luminous quantum dots, and reacting at room temperature to obtain H 2 O 2 A ratio fluorescence sensor.
7. H according to claim 6 2 O 2 The preparation method of the ratio fluorescence sensor is characterized in that the heating is performed at 38 ℃ for 1-2h.
8. H according to claim 6 2 O 2 The preparation method of the ratiometric fluorescence sensor is characterized in that the dosage ratio of MSN-BA to silanized luminescent quantum dots is 1mg to 15 mu L.
9. An H as claimed in any one of claims 1 to 4 2 O 2 Ratio fluorescence sensor at H 2 O 2 Application in detection.
10. An H as claimed in any one of claims 1 to 4 2 O 2 Use of a ratiometric fluorescence sensor in intracellular sensing and imaging.
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