CN117106444A - Near-infrared chemiluminescent nanoprobe and preparation method and application thereof - Google Patents
Near-infrared chemiluminescent nanoprobe and preparation method and application thereof Download PDFInfo
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- CN117106444A CN117106444A CN202311066891.6A CN202311066891A CN117106444A CN 117106444 A CN117106444 A CN 117106444A CN 202311066891 A CN202311066891 A CN 202311066891A CN 117106444 A CN117106444 A CN 117106444A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 42
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000523 sample Substances 0.000 claims abstract description 17
- 238000001514 detection method Methods 0.000 claims abstract description 8
- 229920000642 polymer Polymers 0.000 claims abstract description 5
- 238000011068 loading method Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims abstract description 3
- 238000012546 transfer Methods 0.000 claims abstract description 3
- -1 nitro, hydroxyl Chemical group 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 125000002252 acyl group Chemical group 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000004414 alkyl thio group Chemical group 0.000 claims description 4
- 125000000304 alkynyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 239000003517 fume Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- OXTSSJOQCJZYLA-UHFFFAOYSA-N bis(2,3,4,5,6-pentachlorophenyl) oxalate Chemical compound ClC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1OC(=O)C(=O)OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl OXTSSJOQCJZYLA-UHFFFAOYSA-N 0.000 claims description 2
- PWZYGWAQEWLCJF-UHFFFAOYSA-N bis(2,4,5-trichlorophenyl) oxalate Chemical compound C1=C(Cl)C(Cl)=CC(Cl)=C1OC(=O)C(=O)OC1=CC(Cl)=C(Cl)C=C1Cl PWZYGWAQEWLCJF-UHFFFAOYSA-N 0.000 claims description 2
- CBZOGAWUNMFXFQ-UHFFFAOYSA-N bis(2,4-dinitrophenyl) oxalate Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC=C1OC(=O)C(=O)OC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O CBZOGAWUNMFXFQ-UHFFFAOYSA-N 0.000 claims description 2
- TZZLVFUOAYMTHA-UHFFFAOYSA-N bis-(2,4,5-trichloro-6-(pentyloxycarbonyl)phenyl)oxalate Chemical compound CCCCCOC(=O)C1=C(Cl)C(Cl)=CC(Cl)=C1OC(=O)C(=O)OC1=C(Cl)C=C(Cl)C(Cl)=C1C(=O)OCCCCC TZZLVFUOAYMTHA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000000000 cycloalkoxy group Chemical group 0.000 claims description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000001072 heteroaryl group Chemical group 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000012074 organic phase Substances 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920001184 polypeptide Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 102000004196 processed proteins & peptides Human genes 0.000 claims description 2
- 108090000765 processed proteins & peptides Proteins 0.000 claims description 2
- 102000004169 proteins and genes Human genes 0.000 claims description 2
- 108090000623 proteins and genes Proteins 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 239000011669 selenium Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 238000003384 imaging method Methods 0.000 abstract description 6
- 238000004020 luminiscence type Methods 0.000 abstract description 6
- 230000005284 excitation Effects 0.000 abstract description 4
- 238000001338 self-assembly Methods 0.000 abstract description 3
- 238000001727 in vivo Methods 0.000 abstract description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000008346 aqueous phase Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 3
- 239000000370 acceptor Substances 0.000 description 3
- 238000000295 emission spectrum Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- ADRVRLIZHFZKFE-UHFFFAOYSA-N ethanediperoxoic acid Chemical compound OOC(=O)C(=O)OO ADRVRLIZHFZKFE-UHFFFAOYSA-N 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 238000011534 incubation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920001992 poloxamer 407 Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000003642 reactive oxygen metabolite Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
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
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
- C09K11/07—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials having chemically interreactive components, e.g. reactive chemiluminescent compositions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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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
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
-
- 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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- Chemical Kinetics & Catalysis (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
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- General Chemical & Material Sciences (AREA)
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Abstract
The invention relates to the technical field of near infrared chemiluminescent probes, in particular to a near infrared chemiluminescent nano probe, a preparation method and application thereof, comprising the following steps: the oxalate is used as an energy transfer donor, the near infrared fluorescent molecule is used as an energy receptor, and the near infrared chemiluminescent nanoprobe is formed through the loading or self-assembly of the water-oil amphiphilic polymer. The near infrared chemiluminescence nano probe prepared by the method has the characteristics of high starting speed, long luminescence half-life, low hydrogen peroxide detection limit and the like, can realize rapid chemiluminescence marking and imaging of hydrogen peroxide, does not need an excitation light source, and provides important technical support for future application in vivo luminescence marking and clinical operation.
Description
Technical Field
The invention relates to the technical field of near infrared chemiluminescent probes, in particular to a near infrared chemiluminescent nano probe and a preparation method and application thereof.
Background
The light emitted by fluorescent molecules after excitation by the energy released by the chemical reaction is called chemiluminescence. Chemiluminescence is a reaction process that converts chemical reaction energy into light energy. Chemiluminescent system with oxalate, hydrogen peroxide and fluorescent agent as main components is generally called as 'peroxyoxalate chemiluminescent system' (Peroxy Oxalate Chemiluminescence, POCL), which has many unique advantages of high luminous efficiency, long service life, green environmental protection and the like.
The mechanism of the general chemiluminescent reaction of oxalate can be divided into the following three stages.
(1) Oxalate + hydrogen peroxide→cyclic oxide DOD (intermediate);
(2) Cyclic oxide (intermediate) +phosphor→excited singlet excited state phosphor;
(3) Excited singlet excited state phosphor → phosphor + radiation.
It is thought that if a system in which oxalate and fluorescent molecules are dissolved in a high concentration is produced in the presence of a catalyst and hydrogen peroxide in an amount sufficient for the chemiluminescent reaction, a chemiluminescent body can be obtained, but it has been found that as the concentration of oxalate increases, part of the energy contributing to chemiluminescence is lost through non-radiative transitions due to extinction of fluorescence by unreacted oxalate, and thus the detection sensitivity of the oxalate luminescent system to hydrogen peroxide is limited. Therefore, by designing novel fluorescent dye small molecules, the better proportion of oxalate and fluorescent molecules is regulated and controlled to improve the detection limit of hydrogen peroxide.
Disclosure of Invention
The invention aims to solve the defects in the prior art, and provides a near infrared chemiluminescence nano probe, a preparation method and application thereof, wherein the prepared near infrared chemiluminescence nano probe has the characteristics of high starting speed, long luminescence half-life, low hydrogen peroxide detection limit and the like, can realize rapid chemiluminescence marking and imaging of hydrogen peroxide, does not need an excitation light source, and provides important technical support for future application in vivo luminescence marking and clinical surgery.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the near infrared chemiluminescence nano probe is formed by taking oxalate as an energy transfer donor and near infrared fluorescent molecules as an energy receptor through water-oil amphiphilic polymer loading or self-assembly, wherein the near infrared fluorescent molecules have the following structures:
wherein the electron withdrawing group QA is selected from any one of the following structural formulas:
electron donating group Ar 1 And Ar is a group 2 Each independently selected from any one of the following structural formulas:
wherein R is 1 Is any one of sulfur, selenium, oxygen, nitrogen and carbon atoms;
R 2 is any one of hydrogen, cyano, nitro, hydroxyl, amino, optionally substituted alkyl, alkoxy, alkylthio, alkenyl, alkynyl, cycloalkyl, acyl and aryl;
R 3 each independently selected from the group consisting of hydrogen, trifluoromethyl, cyano, nitro, halogen, hydroxy, amino, optionally substituted alkyl, alkylamine salt, alkoxy, alkylthio, alkenyl, alkynyl, cycloalkyl, cycloalkyloxy, cycloalkoxythio, acyl, aryl, heterocyclyl, heteroaryl, heterocycloalkyl, mono-or di-substituted amino.
Preferably, the oxalate is any one selected from bis (2, 4, 5-trichloro-6-pentoxycarbonyl phenyl) oxalate, bis (2, 4, 5-trichlorophenyl) oxalate, bis (2, 4-dinitrophenyl) oxalate and bis (pentachlorophenyl) oxalate:
preferably, the water-oil amphiphilic polymer is selected from one or more of polystyrene and derivatives thereof, polyethylene glycol and derivatives thereof, polyacrylic acid and derivatives thereof, polypeptides and proteins:
the invention also provides a preparation method of the near infrared chemiluminescence nano probe, which comprises the following steps:
step 1, carrying out ultrasonic treatment on an organic phase mixture of oxalate, near infrared fluorescent molecules and a water-oil amphiphilic unit to obtain a clear solution;
step 2, rapidly injecting the clarified solution obtained in the step 1 into water, stirring in a fume hood, and removing the organic solvent under vacuum;
and 3, filtering the solution from which the organic solvent is removed in the step 2 through a membrane filter to obtain the corresponding fluorescent nano probe.
The invention also provides application of the near infrared chemiluminescence nano probe obtained by the preparation method in hydrogen peroxide detection.
Compared with the prior art, the invention has the following beneficial effects:
1. the near infrared chemiluminescent nanoprobe prepared by the method has the characteristics of high starting speed, long luminescent half-life, low hydrogen peroxide detection limit and the like, and can realize rapid chemiluminescent marking and imaging of hydrogen peroxide without an excitation light source.
2. The near infrared chemiluminescent nanoprobe prepared by the invention can reach the highest brightness only in 10 minutes at 37 ℃, and reaches the half-life of luminescence after 40 minutes.
3. The detection limit of the near infrared chemiluminescence nano probe prepared by the invention on hydrogen peroxide can reach below 1mM, and the penetration depth of the near infrared chemiluminescence nano probe on tissues is deeper, so that the near infrared chemiluminescence nano probe has excellent performance.
Drawings
FIG. 1 is a graph showing the absorption spectrum of the chemiluminescent nanoprobe TPAHT-BT of the present invention in an aqueous phase;
FIG. 2 is a graph showing the emission spectrum of the chemiluminescent nanoprobe TPAHT-BT of the present invention in an aqueous phase;
FIG. 3 is a graph showing the absorption spectrum of the chemiluminescent nanoprobe TPAHT-BSeT of the present invention in an aqueous phase;
FIG. 4 is a graph showing the emission spectrum of the chemiluminescent nanoprobe TPAHT-BSeT of the present invention in an aqueous phase;
FIG. 5 is a graph showing the change of chemiluminescent intensity of the chemiluminescent nanoprobe TPAHT-BT of the present invention after incubation with different reactive oxygen species;
FIG. 6 is a graph showing the intensity of chemiluminescence of the chemiluminescent nanoprobe TPAHT-BT of the present invention incubated with different active oxygen;
FIG. 7 is a graph showing the linear relationship between the chemiluminescent intensity of the chemiluminescent nanoprobe TPAHT-BT and the concentration of hydrogen peroxide;
FIG. 8 is a graph of normalized fluorescence and chemiluminescence spectra in tetrahydrofuran of the chemiluminescent nanoprobe TPAHT-BT of the present invention;
FIG. 9 is a chemiluminescent image of the chemiluminescent nanoprobe of the present invention after incubation of TPAHT-BT with hydrogen peroxide.
Detailed Description
The following technical solutions in the embodiments of the present invention will be clearly and completely described with reference to the accompanying drawings, so that those skilled in the art can better understand the advantages and features of the present invention, and thus the protection scope of the present invention is more clearly defined. The described embodiments of the present invention are intended to be only a few, but not all embodiments of the present invention, and all other embodiments that may be made by one of ordinary skill in the art without inventive faculty are intended to be within the scope of the present invention.
Example 1: preparation of product 1
The chemical structural formulas of the fluorescent molecules, the oxalate molecules and the amphiphilic molecules used in the near infrared chemiluminescent nanoprobe are as follows:
a mixture of 50. Mu.g of TPAHT-BT, 200. Mu.g of CPPO, 1mg of F-127 and 0.3mL of tetrahydrofuran was sonicated to obtain a clear solution. The clear solution was then quickly poured into 2mL of deionized water, stirred in a fume hood for 2 hours and concentrated under vacuum. The concentrated solution was then filtered through a membrane filter (diameter=0.22 μm) to obtain the corresponding chemiluminescent nanoprobe 1, and the prepared chemiluminescent nanoprobe 1 was stored at 4 ℃ for further use.
Example 2: preparation of product 2
The chemical structural formulas of the fluorescent molecules, the oxalate molecules and the amphiphilic molecules used in the near infrared chemiluminescent nanoprobe are as follows:
a mixture of 50. Mu.g of TPAHT-BSeT, 200. Mu.g of CPPO, 1mg of F-127 and 0.3mL of tetrahydrofuran was sonicated to obtain a clear solution. The clear solution was then quickly poured into 2mL of deionized water, stirred in a fume hood for 2 hours and concentrated under vacuum. The concentrated solution was then filtered through a membrane filter (diameter=0.22 μm) to obtain the corresponding chemiluminescent nanoprobe 2, and the prepared chemiluminescent nanoprobe 2 was stored at 4 ℃ for further use.
Example 3: investigation of optical Properties of products
The absorption and emission spectra of the chemiluminescent nanoprobe are shown in figures 1-4, and the chemiluminescent nanoprobe has the advantages of being beneficial to weakening interference of background signals, improving signal to noise ratio of imaging and the like.
Example 4: product specificity Studies
In the specificity test, different configured free radicals are respectively added into the chemiluminescent nanoprobe, and the chemiluminescent intensities are respectively tested at different time nodes, as shown in fig. 5 and 6, the product prepared by the invention shows excellent specificity to hydrogen peroxide in a medium taking water as an embodiment, and has the potential of being used as the chemiluminescent nanoprobe in a complex system.
Example 5: chemical luminescence linear relation of products
The linear relationship of chemiluminescent intensities of chemiluminescent nanoprobes after different hydrogen peroxide concentrations are added is shown in fig. 7, and the chemiluminescent nanoprobes of the present invention have good linear relationship of response to hydrogen peroxide.
Example 6: chemiluminescent spectrum of product
The intensity of chemiluminescence was measured 1min after adding 30mM hydrogen peroxide to the chemiluminescent nanoprobe of the present invention at 37℃incubation, as shown in FIG. 8, the product exhibited a rapid response and distinct chemiluminescence, and the spectrum of the chemiluminescence in the aqueous phase was substantially indistinguishable from that in tetrahydrofuran.
Example 7: chemiluminescent imaging effect of product
Hydrogen peroxide with different concentrations was added to the chemiluminescent nanoprobe of the present invention at 37 degrees celsius, and the chemiluminescent intensity was photographed at different time nodes, as shown in fig. 9, and the product exhibited rapid chemiluminescent enhancement and slower decay rates.
In conclusion, the chemiluminescent fluorescent nanoprobe product based on the oxalate system can successfully realize in-vitro chemiluminescent imaging. In addition, the invention uses commercial oxalate as the energy donor of chemiluminescence, and the fluorescent micromolecules serving as the energy acceptors have the advantages of simplicity and easiness in material preparation, so that the chemiluminescent nanoprobe has non-negligible competitiveness.
In addition, the invention uses only the oxalate molecules as energy donors, two near infrared dyes as energy acceptors, and a chemiluminescent nanoprobe respectively constructed by taking Pluronic F-127 as an amphiphilic unit as an example, and can be modified or changed according to the description in the related field for a person skilled in the related field, wherein the content comprises the nanoprobe prepared by using oxalate molecules with other structures as energy donors, or using emission units with other wave bands as energy acceptors, or using cladding or self-assembly of other amphiphilic materials and the application thereof in biology.
The description and practice of the invention disclosed herein will be readily apparent to those skilled in the art, and may be modified and adapted in several ways without departing from the principles of the invention. Accordingly, modifications or improvements may be made without departing from the spirit of the invention and are also to be considered within the scope of the invention.
Claims (5)
1. The near infrared chemiluminescence nano probe is characterized in that oxalate is used as an energy transfer donor, a near infrared fluorescent molecule is used as an energy receptor, the near infrared chemiluminescence nano probe is formed by loading or self-assembling a water-oil amphiphilic polymer, and the near infrared fluorescent molecule has the following structure:
wherein the electron withdrawing group QA is selected from any one of the following structural formulas:
electron donating group Ar 1 And Ar is a group 2 Each independently selected from any one of the following structural formulas:
wherein R is 1 Is any one of sulfur, selenium, oxygen, nitrogen and carbon atoms;
R 2 is any one of hydrogen, cyano, nitro, hydroxyl, amino, optionally substituted alkyl, alkoxy, alkylthio, alkenyl, alkynyl, cycloalkyl, acyl and aryl;
R 3 each independently selected from the group consisting of hydrogen, trifluoromethyl, cyano, nitro,Halogen, hydroxy, amino, optionally substituted alkyl, alkylamine salt group, alkoxy, alkylthio, alkenyl, alkynyl, cycloalkyl, cycloalkyloxy, cycloalkoxythio, acyl, aryl, heterocyclyl, heteroaryl, heterocycloalkyl, mono-or di-substituted amino.
2. The near infrared chemiluminescent nanoprobe of claim 1 wherein the oxalate is selected from any of bis (2, 4, 5-trichloro-6-pentoxycarbonyl phenyl) oxalate, bis (2, 4, 5-trichlorophenyl) oxalate, bis (2, 4-dinitrophenyl) oxalate, bis (pentachlorophenyl) oxalate:
3. the near infrared chemiluminescent nanoprobe of claim 1 wherein the water-oil amphiphilic polymer is selected from one or more of polystyrene and its derivatives, polyethylene glycol and its derivatives, polyacrylic acid and its derivatives, polypeptides, proteins:
4. the method for preparing the near infrared chemiluminescent nanoprobe according to claim 1, comprising the following steps:
step 1, carrying out ultrasonic treatment on an organic phase mixture of oxalate, near infrared fluorescent molecules and a water-oil amphiphilic unit to obtain a clear solution;
step 2, rapidly injecting the clarified solution obtained in the step 1 into water, stirring in a fume hood, and removing the organic solvent under vacuum;
and 3, filtering the solution from which the organic solvent is removed in the step 2 through a membrane filter to obtain the corresponding fluorescent nano probe.
5. The use of near infrared chemiluminescent nanoprobe obtained by the preparation method of claim 4 in hydrogen peroxide detection.
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| CN117442269A (en) * | 2023-12-22 | 2024-01-26 | 中日友好医院(中日友好临床医学研究所) | Search system and method for surgical suture needle |
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| CN117442269A (en) * | 2023-12-22 | 2024-01-26 | 中日友好医院(中日友好临床医学研究所) | Search system and method for surgical suture needle |
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