CN112239603B - IR-790 and preparation method thereof, sensitized up-conversion nano probe and preparation method thereof, and peroxynitrite detection method - Google Patents
IR-790 and preparation method thereof, sensitized up-conversion nano probe and preparation method thereof, and peroxynitrite detection method Download PDFInfo
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- CMFNMSMUKZHDEY-UHFFFAOYSA-N peroxynitrous acid Chemical compound OON=O CMFNMSMUKZHDEY-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 48
- 238000001514 detection method Methods 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 239000000523 sample Substances 0.000 title claims abstract description 31
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 claims abstract description 41
- 239000002105 nanoparticle Substances 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 11
- 239000011230 binding agent Substances 0.000 claims abstract description 11
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000001681 protective effect Effects 0.000 claims abstract description 7
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 31
- 229910052691 Erbium Inorganic materials 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 17
- 238000011534 incubation Methods 0.000 claims description 16
- 229910052779 Neodymium Inorganic materials 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 239000007853 buffer solution Substances 0.000 claims description 11
- 229910004064 NOBF4 Inorganic materials 0.000 claims description 10
- WCZAXBXVDLKQGV-UHFFFAOYSA-N n,n-dimethyl-2-(7-oxobenzo[c]fluoren-5-yl)oxyethanamine oxide Chemical compound C12=CC=CC=C2C(OCC[N+](C)([O-])C)=CC2=C1C1=CC=CC=C1C2=O WCZAXBXVDLKQGV-UHFFFAOYSA-N 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- OWFXIOWLTKNBAP-UHFFFAOYSA-N isoamyl nitrite Chemical compound CC(C)CCON=O OWFXIOWLTKNBAP-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 238000004440 column chromatography Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- CIJQGPVMMRXSQW-UHFFFAOYSA-M sodium;2-aminoacetic acid;hydroxide Chemical compound O.[Na+].NCC([O-])=O CIJQGPVMMRXSQW-UHFFFAOYSA-M 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 238000010998 test method Methods 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 13
- 239000000975 dye Substances 0.000 description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- RWSXRVCMGQZWBV-WDSKDSINSA-N glutathione Chemical compound OC(=O)[C@@H](N)CCC(=O)N[C@@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-WDSKDSINSA-N 0.000 description 4
- 238000004020 luminiscence type Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- 206010070834 Sensitisation Diseases 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000011258 core-shell material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 230000008313 sensitization Effects 0.000 description 3
- -1 Er @ OA-NaGdF4 Inorganic materials 0.000 description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229960003180 glutathione Drugs 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229960003330 pentetic acid Drugs 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 108010024636 Glutathione Proteins 0.000 description 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical class O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005558 fluorometry Methods 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 238000000504 luminescence detection Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
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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
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/0066—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain being part of a carbocyclic ring,(e.g. benzene, naphtalene, cyclohexene, cyclobutenene-quadratic acid)
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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
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- B82Y40/00—Manufacture or treatment of nanostructures
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- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
- C09B23/08—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7772—Halogenides
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Abstract
The invention discloses a cyanine dye IR-790 and a preparation method thereof, a sensitized up-conversion nano probe and a preparation method thereof, and a peroxynitrite detection method, wherein the cyanine dye IR-790 comprises the following steps: the cyanine dye IR-783, the p-nitrophenol and the acid-binding agent are subjected to contact reaction under dark conditions and in the presence of protective gas and a solvent to prepare the cyanine dye IR-790. The up-conversion nano particles can form a sensitized nano probe with cyanine dye IR-790, the nano probe has obvious response to peroxynitrite, the nano probe has the advantages of wide detection range, high sensitivity, good selectivity, low cost, high detection speed and the like, and meanwhile, the preparation methods have the advantages of mild conditions and simplicity and convenience in operation.
Description
Technical Field
The invention relates to an up-conversion nano material, in particular to cyanine dye IR-790 and a preparation method thereof, a sensitized up-conversion nano probe and a preparation method thereof, and a peroxynitrite detection method.
Background
Peroxynitrite is a nitric oxide derivative, a very strong biological oxidant, and has high reactivity and instability.
At present, mature methods for detecting peroxynitrite in the prior art include: although the detection method can effectively detect peroxynitrite in a certain range, the detection method still has the defects of complex synthetic method, complex operation, short emission wavelength and the like.
Disclosure of Invention
The invention aims to provide cyanine dye IR-790 and a preparation method thereof, a sensitized up-conversion nano probe and a preparation method thereof, and a peroxynitrite detection method, wherein the up-conversion nano particles can form the nano probe with cyanine dye IR-790, the nano probe is obviously responded to peroxynitrite, the nano probe has the advantages of wide detection range, high sensitivity, good selectivity, low cost, rapid detection and the like, and meanwhile, the preparation methods have the advantages of mild conditions and simplicity and convenience in operation.
In order to achieve the above object, the present invention provides a method for preparing cyanine dye IR-790, the method comprising: the cyanine dye IR-783, the p-nitrophenol and the acid-binding agent are subjected to contact reaction under dark conditions and in the presence of a protective gas and a solvent to prepare the cyanine dye IR-790.
The invention also provides a cyanine dye IR-790 prepared by the preparation method.
The invention also provides a preparation method of the IR-790 sensitized up-conversion nano probe, which comprises the following steps: NOBF is prepared4Modified OA-NaGdF4:Yb,Er@OA-NaGdF4Yb and Nd up-conversion nano particles, the cyanine Dye IR-790 and a buffer solution are incubated under the dark condition to obtain Dye-NOBF4-UCNPs nanoprobes, i.e. sensitized up-conversion nanoprobes.
The invention further provides a sensitized up-conversion nano probe prepared by the preparation method.
The invention further provides a detection method of peroxynitrite, which comprises the following steps:
1) detecting the fluorescence intensity I of the sensitized up-conversion nano probe1；
2) Respectively incubating a series of peroxynitrite solutions with known concentrations with different sensitization up-conversion nanoprobes, detecting the fluorescence intensity I of the system, finally drawing a working curve by taking delta I as a vertical coordinate and taking the concentration C of peroxynitrite in the incubation starting time system as a horizontal coordinate to obtain a working equation, wherein the delta I is I1-I；
3) Incubating a peroxynitrite to-be-detected sample with unknown concentration and Dye-UCNPs nanoprobes, detecting the fluorescence intensity of a system, and calculating through a working equation to obtain the concentration of the peroxynitrite in the to-be-detected sample.
In the above technical solution, the detection principle of peroxynitrite in the present invention is shown in fig. 9: the energy emitted by the light is absorbed by the dye IR-790 and transferred to the NOBF4Modified OA-NaGdF4:Yb,Er@OA-NaGdF4Nd of shell layer of Yb, Nd upconversion nanoparticles3+And Yb3+And further transmitted to Yb in the core3+And finally transferred to luminescence center Er3+Thereby increasing the fluorescence intensity of the system.
When peroxynitrite is added into the system, the energy transfer is hindered due to the high-selectivity reaction of the dye IR-790 and the peroxynitrite, so that the fluorescence intensity of the system is quenched; and the intensity of quenching of the fluorescence intensity and the concentration of the peroxynitrite are in a linear relation, so that the concentration of the peroxynitrite can be detected by utilizing the fluorescence intensity of the system.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a graph showing the absorption spectra of cyanine dyes IR-783 and IR-790 in detection example 1
FIG. 2 is a graph showing fluorescence intensity in detection example 2
FIG. 3A is OA-NaGdF in detection example 34Yb, Er transmission electron microscope images;
FIG. 3B shows OA-NaGdF in detection example 34Yb, Er @ OA-NaGdF4, Yb, Nd transmission mirror image;
FIG. 4 is an elemental analysis chart in detection example 4;
FIG. 5 is an infrared spectrum in detection example 5;
FIG. 6 is a graph showing fluorescence intensities when substances coexist with an upconverting material in the reaction system in application example 1;
FIG. 7A is a graph showing the fluorescence intensity in application example 1;
FIG. 7B is a graph of the fluorescence intensity peroxynitrite content based on FIG. 6;
fig. 8 is a statistical chart of interference detection results of application example 2;
FIG. 9 is a schematic diagram of the detection of peroxynitrite according to the present invention.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, one or more new ranges of values may be obtained from combinations of values between the endpoints of each range, the endpoints of each range and the individual values, and the individual values of the points, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a preparation method of cyanine dye IR-790, which comprises the following steps: the cyanine dye IR-783, the p-nitrophenol and the acid-binding agent are subjected to contact reaction under dark conditions and in the presence of protective gas and a solvent to prepare the cyanine dye IR-790.
In the above-mentioned preparation method, the conditions of the contact reaction can be selected within a wide range, but in order to further improve the detection sensitivity and selectivity of the produced cyanine dye IR-790 for peroxynitrite, it is preferable that the contact reaction satisfies at least the following conditions: the reaction temperature is 10-30 ℃, and the reaction time is 10-24 h.
In the above-mentioned preparation method, the amount of each material can be selected within a wide range, but in order to further improve the sensitivity and selectivity of the prepared cyanine dye IR-790 to peroxynitrite, it is preferable that the ratio of the cyanine dye IR-783 to p-nitrophenol is 20 mg: 20-40 mg;
in the above preparation method, the amount of the acid-binding agent may be selected within a wide range, but in order to further improve the sensitivity and selectivity of the obtained cyanine dye IR-790 to peroxynitrite detection, it is preferable that the ratio of the cyanine dye IR-783 to the acid-binding agent is 20 mg: 2-6 mg.
In the above preparation method, the amount of the solvent may be selected within a wide range, but in order to further improve the sensitivity and selectivity of the obtained cyanine dye IR-790 for peroxynitrite detection, it is preferable that the ratio of the amount of the cyanine dye IR-783 to the amount of the solvent is 20 mg: 10-20 mL.
In the above preparation method, the kind of the acid-binding agent may be selected from a wide range, but in order to further improve the detection sensitivity and selectivity of the produced cyanine dye IR-790 for peroxynitrite, preferably, the acid-binding agent is selected from at least one of triethylamine, pyridine, and sodium acetate.
In the above-mentioned production method, the kind of the solvent may be selected within a wide range, but in order to further improve the detection sensitivity and selectivity of the produced cyanine dye IR-790 for peroxynitrite, it is preferable that the solvent is selected from at least one of DMF, DMSO, and acetonitrile.
In the above production method, the kind of the shielding gas may be selected within a wide range, but in order to further enhance the shielding effect, it is preferable that the shielding gas is selected from at least one of nitrogen, argon and helium.
In the above preparation method, in order to further improve the purity of the produced cyanine dye IR-790, preferably, after the contact reaction, the preparation method further comprises: washing the reaction product for three times by using ether, performing column chromatography by using a methanol/dichloromethane mixed solvent as a mobile phase, and then sequentially evaporating and drying the solvent to finally obtain the cyanine dye IR-790.
The invention also provides a cyanine dye IR-790 prepared by the preparation method.
The invention also provides a preparation method of the sensitization up-conversion nano probe, and the methodThe preparation method comprises the following steps: NOBF is prepared4Modified OA-NaGdF4:Yb,Er@OA-NaGdF4Yb and Nd up-conversion nanoparticles, the cyanine Dye IR-790 and a buffer solution are incubated under the dark condition to obtain Dye-NOBF4-UCNPs nanoprobes, i.e. sensitized up-conversion nanoprobes.
In the above-mentioned preparation method, the amount of each material can be selected within a wide range, but for further improvement of Dye-NOBF4Detection sensitivity and selectivity of UCNPs nanoprobes for peroxynitrite, preferably, NOBF4Modified OA-NaGdF4The dosage ratio of Yb, Er @ OA-NaGdF4 to Yb and Nd up-conversion nano particles, IR-790 and buffer solution is 1.6 mg: 0.002-0.006 mg: 0.2-0.3 mL.
In the above-mentioned preparation method, the conditions for incubation can be selected within a wide range, but Dye-NOBF is further improved4-detection sensitivity and selectivity of UCNPs nanoprobes for peroxynitrite, preferably incubation satisfies the following conditions: incubating at 20-40 deg.C for 20-30 min;
in the above-mentioned preparation method, the kind of the buffer solution and the pH can be selected within a wide range, but the Dye-NOBF is further improved4Sensitivity and selectivity of UCNPs nanoprobes for peroxynitrite detection, preferably the buffer solution is glycine-sodium hydroxide buffer solution, pH 8.4-8.6.
The invention further provides a sensitized up-conversion nano probe prepared by the preparation method.
The invention further provides a detection method of peroxynitrite, which comprises the following steps:
1) detecting the fluorescence intensity I of the sensitized up-conversion nano probe1；
2) Respectively incubating a series of peroxynitrite solutions with known concentrations with different sensitized up-conversion nano probes, detecting the fluorescence intensity I of the system, finally drawing a tool by taking delta I as a vertical coordinate and the concentration C of peroxynitrite in the system at the incubation starting time as a horizontal coordinatePlotting to obtain a working equation, where Δ I ═ I1-I；
3) Incubating a peroxynitrite sample with unknown concentration and Dye-UCNPs nanoprobe, detecting the fluorescence intensity of the system, and calculating to obtain the concentration of the peroxynitrite in the sample to be detected through a working equation.
In the above detection method, the conditions of incubation may be selected within a wide range, and in order to further improve the sensitivity and selectivity of detection, it is preferable that the incubation satisfies at least the following conditions: the incubation temperature is 20-30 deg.C, and the incubation time is 20-25 min.
In the above detection method, the peroxynitrite solution can be selected within a wide range, and in order to further improve the sensitivity and selectivity of the detection, it is preferable that the peroxynitrite solution is prepared by: mixing isoamyl nitrite, hydrogen peroxide and water, wherein the dosage ratio of the isoamyl nitrite to the hydrogen peroxide to the water is 10-20 mg: 10-20 mg: 30-50 mL.
In the above detection method, the working equation may be selected in a wide range, and in order to further improve the sensitivity and selectivity of detection, it is preferable that Δ I be 320.0618+560.3141 logC.
The present invention will be described in detail below by way of examples. In the following examples, cyanine dye IR-783 is commercially available from Sigma-Aldrich.
The peroxynitrite standard solution is prepared by the following method: 2.2-22mL of 30% hydrogen peroxide solution is diluted to 70mL with water, the mixture is cooled to 4 ℃ in ice water, 4-40mL of 5mol/L sodium hydroxide and 5mL of 0.04mol/L diethylenetriaminepentaacetic acid (DTPA) are added to 0.5mol/L sodium hydroxide, after gentle mixing, the pH is adjusted to 12.5-13.0, the mixture is stirred vigorously for 150min, washed with water and then the unreacted hydrogen peroxide is removed with manganese dioxide. The maximum absorption peak at 302nm was observed by recording the absorption band at 220-440nm with an ultraviolet spectrometer.
Preparation example 1
OA-NaGdF4Preparation of Yb, Er upconversion particles
Using the wordW.Wang, M.ZHao, L.Wang and H.Chen, Core-shell-up conversion nanoparticles of type NaGdF4 Yb, Er @ NaGdF4 Nd, Yb and induced with a NIR dye a accessible probe for luminescence determination of the fraction of water in organic solvents, Mikrochim Acta (186 (2019))6H9GdO6·XH2O，0.2 M C6H9YbO6·XH2O，0.2M C6H9ErO6·XH2O was mixed with OA and ODE, heated to 150 ℃ to remove water, then cooled to 50 ℃ and NH was added4F-CH3OH, then heated to 300 ℃ and held for one hour, finally cooled, centrifuged, washed and stored.
Preparation example 2
OA-NaGdF4:Yb,Er@OA-NaGdF4Yb, Nd upconversion nanoparticles
Wang, M.ZHao, L.Wang and H.Chen, Core-shell up conversion nanoparticles of type NaGdF4:Yb,Er@NaGdF4Nd, Yb and doped with a NIR dye are a viable probe for luminescence determination of the fraction of water in organic solvents, Mikrochim Acta 186(9) (2019)6306H9GdO6·XH2O，0.2M C6H9YbO6·XH2O，0.2M C6H9NdO6·XH2O was mixed with OA and ODE, heated to 150 ℃ to remove water, then cooled to 50 ℃ and NH was added4F-CH3OH, then heated to 300 ℃ and held for one hour, finally cooled, centrifuged, washed and stored.
Preparation example 3
NOBF4Modified OA-NaGdF4:Yb,Er@OA-NaGdF4Preparation of Yb, Nd:
wang, M.ZHao, L.Wang and H.Chen, Core-shell up conversion nanoparticles of type NaGdF4:Yb,Er@NaGdF4Nd, Yb and doped with a NIR dye are a viable probe for luminescence determination of the fraction of water in organic solvents, Mikrochim Acta 186(9) (2019)630. 5mL of OA-NaGdF dispersed in cyclohexane were added at 25 deg.C4:Yb,Er@OA-NaGdF4Yb, Nd solution (10mg/mL) and 5mL NOBF4Solution (DMF as solvent, with NOBF)45.84mg) solution was mixed and gently shaken for 15min to extract the nanoparticles from the bottom DMF layer into a centrifuge tube. The nanoparticles dispersed in DMF were purified by adding 1.5mL of a mixed solution of toluene and cyclohexane (1:1 by volume) and centrifuging at 11000rpm for 15 min. Dissolving the nanoparticles in water solution, and evaporating residual cyclohexane and toluene in a water bath kettle at 45 ℃ to obtain NOBF4Modified OA-NaGdF4:Yb,Er@OA-NaGdF4Yb, Nd upconversion nanoparticles.
Example 1
Firstly, carrying out vacuum drying treatment on a reaction vessel, weighing 20mg of dye IR-783 and 40mg of p-nitrophenol in a two-neck flask, taking 15mL of DMF as a solvent, adding 3mg of triethylamine as an acid-binding agent, introducing inert gas as protective gas, and reacting for 12h at 25 ℃ in the dark. After the reaction is finished, washing with diethyl ether for three times to primarily remove impurities, then performing column chromatography purification by taking a dichloromethane/methanol mixed solution (30:1 volume ratio) as a developing agent to obtain a green solution, evaporating and drying to finally obtain a green solid, namely the dye IR-790.
Example 2
The procedure is as in example 1, except that 20mg of p-nitrophenol is used and 1mL of triethylamine is replaced by 2mg of pyridine.
Example 3
The procedure is as in example 1, except that 20mg of p-nitrophenol is used and 1mL of triethylamine is replaced by 6mg of pyridine.
Example 4
To a series of 2.00mL centrifuge tubes was added 400. mu.L of NOBF, respectively4-UCNPs solution (concentration 4mg/mL, NOBF)4-UCNPs, NOBF in preparation 34Modified OA-NaGdF4:Yb,Er@OA-NaGdF4Yb, Nd) and 40. mu.L of Dye IR-790 solution (0.1mg/mL), followed by addition of 200. mu.L of glycine-sodium hydroxide buffer solution (pH 8.6), and dark incubation at 25 ℃ for 25min to give Dye-NOBF4-a UCNPs nanoprobe,
example 5
The procedure was followed as in example 4, except that the IR-790 solution (0.1mg/mL) was used in an amount of 20. mu.L.
Example 6
The procedure was followed as in example 4, except that the IR-790 solution (0.1mg/mL) was used in an amount of 60. mu.L.
Detection example 1
Dye absorption spectra were obtained on a Hitachi U-3900 UV spectrophotometer, and as can be seen from FIG. 1, the curves a and b in the figure correspond to cyanine dyes IR-783 and IR-790, and as can be seen from the figure, IR-790 has been synthesized successfully.
Detection example 2
The OA-NaGdF was measured by a fluorometer with Hitachi F-25004:Yb,Er、OA-NaGdF4:Yb,Er@OA-NaGdF4Yb, Nd upconversion nano-particles are subjected to luminescence detection, the result is shown in figure 2, and the curves a and b in the figure correspond to OA-NaGdF4Yb, Er and OA-NaGdF4:Yb,Er@OA-NaGdF4The fluorescence intensity curve of the Yb and Nd upconversion nanoparticles shows that the core-shell structure can enhance the luminescence intensity of the upconversion nanoparticles.
Detection example 3
Subjecting the OA-NaGdF to transmission electron microscope with Hitachi HT-77004:Yb,Er、OA-NaGdF4:Yb,Er@OA-NaGdF4The morphology of Yb, Nd upconversion nanoparticles is characterized, and the detection results sequentially correspond to the graphs in FIGS. 3A and 3B. As can be seen from FIGS. 3A and 3B, OA-NaGdF4:Yb,Er、OA-NaGdF4:Yb,Er@OA-NaGdF4The Yb and Nd upconversion nanoparticles are in hexagonal phase.
Detection example 4
The OA-NaGdF was subjected to scanning electron microscopy using SEM Regulus 81004:Yb,Er@OA-NaGdF4The Yb and Nd upconversion nanometer particles are subjected to element analysis, and the result is shown in figure 4. As can be seen from the figure, OA-NaGdF was successfully prepared in preparation example 24:Yb,Er@OA-NaGdF4Yb, Nd upconversion nanoparticles.
Detection example 5
Use of IR Prestige-21 Fourier transform Infrared spectrometer to measure OA-NaGdF in preparation example 24:Yb,Er@OA-NaGdF4Yb, Nd, NOBF in preparation example 34Modified OA-NaGdF4:Yb,Er@OA-NaGdF4Yb, Nd upconversion nanoparticles, Dye-NOBF in example 44Analysis of-UCNPs nanoprobes, it can be seen from FIG. 5 that NOBF was successfully prepared in preparation example 34Modified OA-NaGdF4:Yb,Er@OA-NaGdF4Yb, Nd upconversion nanoparticles, example 4 successfully prepared Dye-NOBF4-UCNPs nanoprobes.
Application example 1
Detection of peroxynitrite:
a series of Dye-NOBF at example 44A series of peroxynitrite standard solutions (44 mu mol/L) (the volumes are 0 mu L, 1 mu L, 2 mu L, 3 mu L, 4 mu L, 5 mu L, 10 mu L, 20 mu L, 50 mu L, 100 mu L, 150 mu L and 200 mu L in sequence) are added into the UCNPs nanoprobes, the volume is determined to be 1mL by water, then the UCNPs nanoprobes are placed in a constant temperature oscillator for 10min under the condition of 25 ℃, and the experimental data are recorded by a fluorescence spectrometer.
The fluorescence intensity of each system in the reaction system was recorded by a fluorometer having a Hitachi F-2500 mark, and the results are shown in FIG. 6. In FIG. 6, curve a is NOBF4Modified OA-NaGdF4:Yb,Er@OA-NaGdF4The fluorescence of Yb, Nd up-conversion material and the dye IR-790, the curve b is NOBF4Modified OA-NaGdF4:Yb,Er@OA-NaGdF4The fluorescence curve of Yb, Nd upconversion nanoparticles, curve c is NOBF4Modified OA-NaGdF4:Yb,Er@OA-NaGdF4The fluorescence patterns of Yb, Nd, the dye IR-790 and peroxynitrite in the presence of the system show that the fluorescence intensity is quenched. The intensity of curve a is significantly enhanced relative to curve b, and the fluorescence intensity of curve c is significantly enhanced relative to curve bAnd decreases.
The fluorometry was carried out using a fluorometer with the Hitachi brand F-2500. Working curves were plotted, and the results are shown in FIGS. 7A and 7B, peroxynitrite and fluorescence quenching intensity Δ I (Δ I ═ I)1-I，I1And I is the fluorescence intensity value of the system without peroxynitrite and with peroxynitrite respectively), the working equation is that Δ I is 320.0618+560.3141 logC. From 7A, the fluorescence intensity gradually decreased with increasing concentrations of peroxynitrite. The detection limit of the detection method is 0.0088 mu mol/L.
Application example 2
Interference detection:
a series of Dye-NOBF at example 44To the UCNPs nanoprobes, 50. mu.L of peroxynitrite (10. mu. mol/L) and 50. mu.L of interfering substances (each containing Fe) were added3+、Fe2+、S2-、NO2 -、 H2O2、S2O3 2-50 mu mol/L of interferents, HClO and Glutathione (GSH), adding deionized water to the volume of 1mL, placing the mixture in a constant temperature oscillator for continuous oscillation for 25min at the temperature of 25 ℃, and recording experimental data by using a fluorescence spectrometer.
From the obtained fluorescence intensity values, a histogram (I) was plotted1-I)，I1The fluorescence intensity value after sensitization of the dye is represented, the I point represents the fluorescence intensity value without the dye, the result is shown in figure 8, and the figure shows that various interferents have no obvious influence on the system. The fluorescence intensity is basically unchanged, the last histogram is peroxynitrite, the fluorescence intensity quenching effect is good, and the fluorescence probe is good in selectivity.
The products of examples 2 to 3 and examples 5 to 6 were tested in the same manner as described above, wherein the results of tests of examples 2 to 3 substantially agreed with the results of tests of the product of example 1, and the results of tests of examples 5 to 6 substantially agreed with the results of tests of the product of example 4.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that, in the foregoing embodiments, various technical features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various combinations that are possible in the present invention are not described separately.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. A preparation method of an IR-A sensitized up-conversion nano probe is characterized by comprising the following steps: NOBF is prepared4Modified OA-NaGdF4:Yb,Er@OA-NaGdF4Yb, Nd up-conversion nano particles, cyanine Dye IR-A and buffer solution are incubated under dark condition to obtain Dye-NOBF4-UCNPs nanoprobes, i.e. sensitized up-conversion nanoprobes;
the structural formulA of the cyanine dye IR-A is shown as formulA 1:
2. the method according to claim 1, wherein the cyanine dye IR- A is prepared by A method comprising:
carrying out contact reaction on A cyanine dye IR-783, p-nitrophenol and an acid-binding agent under dark conditions in the presence of A protective gas and A solvent to obtain the cyanine dye IR-A;
wherein the contact reaction at least satisfies the following conditions: the reaction temperature is 10-30 ℃, and the reaction time is 10-24 h; the dosage ratio of the cyanine dye IR-783 to the p-nitrophenol is 20 mg: 20-40 mg; the dosage ratio of the cyanine dye IR-783 to the acid-binding agent is 20 mg: 2-6 mg; the dosage ratio of the cyanine dye IR-783 to the solvent is 20 mg: 10-20 mL; the acid-binding agent is selected from at least one of triethylamine, pyridine and sodium acetate; the solvent is at least one selected from DMF, DMSO and acetonitrile; the protective gas is at least one selected from nitrogen, argon and helium;
wherein, after the contact reaction, the preparation method further comprises: washing the reaction product for three times by using ether, performing column chromatography by using A methanol/dichloromethane mixed solvent as A mobile phase, and then sequentially evaporating and drying the solvent to finally obtain the cyanine dye IR-A.
3. The method of claim 1, wherein the NOBF is prepared by4Modified OA-NaGdF4:Yb,Er@OA-NaGdF4:The dosage ratio of Yb, Nd up-conversion nano particles, IR-A and buffer solution is 1.6 mg: 0.002-0.006 mg: 0.2-0.3 mL.
4. The production method according to claim 1, wherein the incubation satisfies the following condition: the incubation temperature is 20-40 deg.C, and the incubation time is 20-30 min.
5. The method according to claim 1, wherein the buffer solution is a glycine-sodium hydroxide buffer solution having a pH of 8.4 to 8.6.
6. An IR-A sensitized up-conversion nanoprobe, characterized in that the sensitized up-conversion nanoprobe is prepared by the preparation method of any one of claims 1 to 5.
7. A method for detecting peroxynitrite, comprising:
1) detecting the fluorescence intensity I of the sensitized upconversion nanoprobe of claim 61；
2) Respectively incubating a series of peroxynitrite solutions with known concentrations with different sensitized up-conversion nano-probes, and detecting the fluorescence of the systemAnd finally drawing a working curve by taking the delta I as an ordinate and the concentration C of the peroxynitrite in the incubation starting time system as an abscissa to obtain a working equation, wherein the delta I is I1-I；
3) Mixing a peroxynitrite sample with unknown concentration to be tested with the Dye-NOBF4And incubating the UCNPs nano probe, detecting the fluorescence intensity of the system, and calculating the concentration of peroxynitrite in the sample to be detected through the working equation.
8. The detection method according to claim 7, wherein the incubation satisfies at least the following conditions: the incubation temperature is 20-30 deg.C, and the incubation time is 20-25 min.
9. A test method according to claim 7, wherein the peroxynitrite solution is prepared by: mixing isoamyl nitrite, hydrogen peroxide and water, wherein the dosage ratio of the isoamyl nitrite to the hydrogen peroxide to the water is 10-20 mg: 10-20 mg: 30-50 mL.
10. The detection method of claim 7, wherein the working equation is Δ I320.0618 +560.3141 logC.
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