CN113403063A - Near-infrared fluorescent probe for detecting biological mercaptan and preparation method thereof - Google Patents
Near-infrared fluorescent probe for detecting biological mercaptan and preparation method thereof Download PDFInfo
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- CN113403063A CN113403063A CN202110671938.6A CN202110671938A CN113403063A CN 113403063 A CN113403063 A CN 113403063A CN 202110671938 A CN202110671938 A CN 202110671938A CN 113403063 A CN113403063 A CN 113403063A
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- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 38
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 title abstract description 12
- 238000002360 preparation method Methods 0.000 title abstract description 8
- ZLQJVGSVJRBUNL-UHFFFAOYSA-N methylumbelliferone Natural products C1=C(O)C=C2OC(=O)C(C)=CC2=C1 ZLQJVGSVJRBUNL-UHFFFAOYSA-N 0.000 claims abstract description 40
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims abstract description 26
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 claims abstract description 26
- IUNJCFABHJZSKB-UHFFFAOYSA-N 2,4-dihydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C(O)=C1 IUNJCFABHJZSKB-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 24
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 23
- 229960000956 coumarin Drugs 0.000 claims abstract description 21
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 claims abstract description 12
- JXKPEJDQGNYQSM-UHFFFAOYSA-M sodium propionate Chemical compound [Na+].CCC([O-])=O JXKPEJDQGNYQSM-UHFFFAOYSA-M 0.000 claims abstract description 12
- 239000004324 sodium propionate Substances 0.000 claims abstract description 12
- 229960003212 sodium propionate Drugs 0.000 claims abstract description 12
- 235000010334 sodium propionate Nutrition 0.000 claims abstract description 12
- 238000006000 Knoevenagel condensation reaction Methods 0.000 claims abstract description 10
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- 238000000034 method Methods 0.000 claims description 26
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
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- 238000001035 drying Methods 0.000 claims description 14
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 13
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- 238000001914 filtration Methods 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 6
- 239000001632 sodium acetate Substances 0.000 claims description 6
- 235000017281 sodium acetate Nutrition 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 5
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 229960000583 acetic acid Drugs 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000011449 brick Substances 0.000 claims description 4
- 239000012362 glacial acetic acid Substances 0.000 claims description 4
- 239000012074 organic phase Substances 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
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- 125000003396 thiol group Chemical class [H]S* 0.000 claims 7
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- 239000012472 biological sample Substances 0.000 abstract description 4
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 54
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- 239000000543 intermediate Substances 0.000 description 29
- 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 27
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 17
- 230000004044 response Effects 0.000 description 17
- FFFHZYDWPBMWHY-VKHMYHEASA-N L-homocysteine Chemical compound OC(=O)[C@@H](N)CCS FFFHZYDWPBMWHY-VKHMYHEASA-N 0.000 description 14
- 229960003180 glutathione Drugs 0.000 description 13
- 235000001014 amino acid Nutrition 0.000 description 9
- 238000002189 fluorescence spectrum Methods 0.000 description 9
- 238000001514 detection method Methods 0.000 description 8
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- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
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- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 208000024827 Alzheimer disease Diseases 0.000 description 1
- OABOXRPGTFRBFZ-IMJSIDKUSA-N Cys-Cys Chemical compound SC[C@H](N)C(=O)N[C@@H](CS)C(O)=O OABOXRPGTFRBFZ-IMJSIDKUSA-N 0.000 description 1
- 206010058314 Dysplasia Diseases 0.000 description 1
- 108010024636 Glutathione Proteins 0.000 description 1
- 125000000415 L-cysteinyl group Chemical group O=C([*])[C@@](N([H])[H])([H])C([H])([H])S[H] 0.000 description 1
- 206010067125 Liver injury Diseases 0.000 description 1
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- 239000012670 alkaline solution Substances 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000000332 coumarinyl group Chemical group O1C(=O)C(=CC2=CC=CC=C12)* 0.000 description 1
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 1
- 235000018417 cysteine Nutrition 0.000 description 1
- 108010004073 cysteinylcysteine Proteins 0.000 description 1
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- 230000007935 neutral effect Effects 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000004962 physiological condition Effects 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 230000037380 skin damage Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
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- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
- C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
- C07D311/18—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted otherwise than in position 3 or 7
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Abstract
The invention discloses a near-infrared fluorescent probe for detecting biological mercaptan and a preparation method thereof, and the near-infrared fluorescent probe is prepared by synthesizing a TEM (transmission electron microscope) by taking isophorone and malononitrile as raw materials through a Knoevenagel condensation reaction; synthesizing 7-hydroxy-3-methyl-coumarin from 2, 4-dihydroxybenzaldehyde and sodium propionate by cyclization and hydrolysis reaction; then 7-hydroxy-3-methyl-coumarin and N-bromosuccinimide are used as raw materials, and the 7-hydroxy-3-aldehyde-coumarin is synthesized through halogenation and hydrolysis reaction; then TEM and 7-hydroxy-3-aldehyde-coumarin are used as raw materials, and an intermediate TX-OH is synthesized through Knoevenagel condensation reaction; and finally, synthesizing the fluorescent probe by taking TX-OH and acryloyl chloride as raw materials. The fluorescent probe has better selectivity for thiol and is not interfered by other amino acids. Can be used for detecting biological mercaptan in a biological sample and has good application prospect.
Description
Technical Field
The invention belongs to the technical field of analysis and detection, and particularly relates to a near-infrared fluorescent probe for detecting biological thiol and a preparation method of the near-infrared fluorescent probe.
Background
Cysteine (Cys), homocysteine (Hcy), and reduced Glutathione (GSH) are collectively referred to as biological thiols. Being a large number of small molecule sulfhydryl species present in organisms, they play a very important role in balancing redox processes and mitigating damage caused by free radicals and toxins. Studies have shown that fluctuations in biological thiol levels are of great relevance to the development of many human diseases, such as heart disease, dysplasia, skin damage, liver damage, osteoporosis, and alzheimer's disease. Therefore, the detection of Cys/Hcy/GSH in vivo will have a positive and meaningful impact on understanding the development and progression of disease.
Fluorescent probe molecules generally consist of a fluorophore, a linker arm, and a recognition group. Fluorescent probe molecules generally emit at a shorter wavelength and are generally interfered by the background of the biological sample itself, resulting in false positive signals. And the near infrared (650-900 nm) fluorescence emission can effectively reduce the interference factor. Therefore, the development of near-infrared fluorescent probes will greatly promote the accuracy of biological sample detection.
Disclosure of Invention
The invention aims to provide a near-infrared fluorescent probe for detecting biological thiol, and the fluorescent probe molecule has good selectivity and anti-interference capability on detection of the biological thiol.
The invention also aims to provide a preparation method of the near-infrared fluorescent probe for detecting the biological thiol.
The invention adopts the technical scheme that a near-infrared fluorescent probe for detecting biological mercaptan has a structural formula shown as the following formula (I):
the invention adopts another technical scheme that a preparation method of a near-infrared fluorescent probe for detecting biological mercaptan is implemented according to the following steps:
and 5, synthesizing the fluorescent probe by using the intermediate TX-OH obtained in the step 4 and acryloyl chloride as raw materials.
The present invention is also characterized in that,
in the step 1, the method specifically comprises the following steps:
dissolving isophorone, malononitrile and a catalyst in N, N-dimethylformamide, stirring for 6 hours at 120 ℃ by taking argon as a protective gas, cooling to room temperature after the reaction is finished, injecting the reaction mixed solution into ice water, separating out a brown solid, drying, and separating and purifying by using column chromatography to obtain an intermediate TEM;
the catalyst is a viscous liquid formed by mixing acetic anhydride, glacial acetic acid and piperidine; the molar ratio of isophorone to malononitrile is 1: 1.
in the step 2, the method specifically comprises the following steps:
dissolving 2, 4-dihydroxybenzaldehyde, sodium propionate and a catalyst triethylamine in acetic anhydride, heating and refluxing for 12h, injecting water into a reaction liquid, performing suction filtration to obtain a brick red solid, washing, drying, separating and purifying by column chromatography, dissolving the obtained product in dichloromethane, continuously reacting, adding acetic anhydride and pyridine as catalysts, stirring for 24h at room temperature, extracting by using dichloromethane and water, collecting an organic phase, drying by using anhydrous sodium sulfate, filtering, performing reduced pressure rotary evaporation to remove the organic solvent, and separating and purifying by using column chromatography to obtain an intermediate 7-hydroxy-3-methyl-coumarin; the molar ratio of the 2, 4-dihydroxybenzaldehyde to the sodium propionate is 1: 1.
in step 3, the method specifically comprises the following steps:
using azobisisobutyronitrile as a free radical reaction initiator, dissolving the azodiisobutyronitrile, 7-hydroxy-3-methyl-coumarin and N-bromosuccinimide in carbon tetrachloride, heating and refluxing for 8 hours, decompressing and rotary-steaming to remove an organic solvent, adding sodium acetate to dissolve the sodium acetate in acetic anhydride, heating and refluxing for 12 hours, then adding a hydrochloric acid solution, continuously stirring, cooling to room temperature, carrying out suction filtration, and washing with ice water to obtain a brown solid, namely an intermediate 7-hydroxy-3-aldehyde-coumarin; the molar ratio of 7-hydroxy-3-methyl-coumarin to N-bromosuccinimide is 1: 2.
in step 4, the method specifically comprises the following steps:
dissolving TEM, 7-hydroxy-3-aldehyde-coumarin and a catalyst in absolute ethyl alcohol, reacting for 4 hours at 50 ℃, cooling to room temperature after the reaction is finished, filtering to obtain red solid precipitate, and repeatedly washing with absolute ethyl alcohol to obtain an intermediate TX-OH; TEM and 7-hydroxy-3-aldehyde-coumarin in a molar ratio of 1:1, the catalyst is piperidine.
In step 5, the method specifically comprises the following steps:
dissolving TX-OH, acryloyl chloride and a catalyst in dichloromethane, stirring at room temperature, monitoring the reaction process by TLC (thin layer chromatography) until the reaction process is finished, performing reduced pressure spin-drying on the solvent, and performing column chromatography separation and purification to obtain the fluorescent probe; the molar ratio of TX-OH to acryloyl chloride is 1: 2, the catalyst is triethylamine.
The invention has the advantages that the near-infrared fluorescent probe is constructed by a simple organic synthesis means to realize the simultaneous detection of three kinds of biological mercaptan, and an on-off signal response mechanism is presented by the change of the fluorescence intensity. In the detection process, the fluorescent probe molecule shows good selectivity and anti-interference capability, has a proper pH application range, and provides a certain application potential for further detection under physiological conditions.
Drawings
FIG. 1 is a fluorescence emission spectrum of probe molecules (10. mu. mol/L) in a mixed solution of different organic solvents and water (5:5, V: V);
FIG. 2 shows fluorescence emission spectra of probe molecules (10. mu. mol/L) and Cys responses in different organic solvent and water (5:5, V: V) mixed solutions;
FIG. 3 shows DMSO and H2O fluorescence emission spectra of response of probe molecules (10 mu mol/L) and Cys in the solution with different volume ratios;
FIG. 4 is DMSO: H2A graph of the change in fluorescence of probe molecules (10. mu. mol/L) in O (5:5, V: V) solution in response to Cys at different pH;
FIG. 5 is DMSO: H2Fluorescence emission spectra of probe molecules (10. mu. mol/L) in O (5:5, V: V) solution in selective response to biological thiol;
FIG. 6 is DMSO: H2Histogram of fluorescence intensity of competition response of probe molecules (10. mu. mol/L) in O (5:5, V: V) solution with Cys and other different amino acids;
FIG. 7 is DMSO: H2Histogram of fluorescence intensity of competitive responses of probe molecules (10. mu. mol/L) in O (5:5, V: V) solution with Hcy and other different amino acids;
FIG. 8 is DMSO: H2Histogram of fluorescence intensity of competitive responses of probe molecules (10. mu. mol/L) in O (5:5, V: V) solution with GSH and other different amino acids;
FIG. 9 is DMSO: H2Responding to fluorescence emission spectra of probes in O (5:5, V: V) solution and Cys with different concentrations,
FIG. 10 shows the increase in fluorescence intensity before and after the probe response (F-F)0) A linear fit to Cys concentration;
FIG. 11 is DMSO: H2Responding to ultraviolet absorption spectrums by a probe in an O (5:5, V: V) solution and Cys with different concentrations;
FIG. 12 is DMSO: H2Fluorescence emission spectra of probes in O (5:5, V: V) solution and different concentrations of Hcy response;
FIG. 13 shows the increase in fluorescence intensity before and after the probe response (F-F)0) A linear fit to Hcy concentration;
FIG. 14 is DMSO: H2Responding to ultraviolet absorption spectrums by probes in O (5:5, V: V) solution and Hcy with different concentrations;
FIG. 15 is DMSO: H2In O (5:5, V: V) solutionThe probe responds to fluorescence emission spectra with GSH with different concentrations;
FIG. 16 shows the increase in fluorescence intensity before and after the probe response (F-F)0) A linear fit to GSH concentration;
FIG. 17 is DMSO: H2Probes in O (5:5, V: V) solution respond to ultraviolet absorption spectra with GSH of different concentrations.
Detailed Description
The present invention will be described in detail with reference to the following detailed description and accompanying drawings.
The invention relates to a near-infrared fluorescent probe for detecting biological mercaptan, which has a structural formula shown as the following formula (I):
the invention relates to a preparation method of a near-infrared fluorescent probe for detecting biological mercaptan, which is implemented according to the following steps:
the method specifically comprises the following steps: dissolving isophorone, malononitrile and a catalyst in N, N-dimethylformamide, stirring for 6 hours at 120 ℃ by taking argon as a protective gas, cooling to room temperature after the reaction is finished, injecting the reaction mixed solution into ice water, separating out a brown solid, drying, and separating and purifying by using column chromatography to obtain an intermediate TEM;
the catalyst is a viscous liquid formed by mixing acetic anhydride, glacial acetic acid and piperidine; the molar ratio of isophorone to malononitrile is 1: 1;
the method specifically comprises the following steps: dissolving 2, 4-dihydroxybenzaldehyde, sodium propionate and a catalyst triethylamine in acetic anhydride, heating and refluxing for 12h, injecting water into a reaction liquid, separating out a solid, performing suction filtration to obtain a brick red solid, repeatedly washing ice water, drying, performing column chromatography separation and purification, dissolving the obtained product in dichloromethane, continuously reacting, adding acetic anhydride and pyridine as catalysts, stirring for 24h at room temperature, extracting with dichloromethane and water, collecting an organic phase, drying with anhydrous sodium sulfate, filtering, performing reduced pressure rotary evaporation to remove the organic solvent, and performing column chromatography separation and purification to obtain an intermediate 7-hydroxy-3-methyl-coumarin;
the molar ratio of the 2, 4-dihydroxybenzaldehyde to the sodium propionate is 1: 1;
the method specifically comprises the following steps: taking Azobisisobutyronitrile (AIBN) as a free radical reaction initiator, dissolving the Azobisisobutyronitrile (AIBN), 7-hydroxy-3-methyl-coumarin and N-bromosuccinimide in carbon tetrachloride, heating and refluxing for 8 hours, carrying out reduced pressure rotary evaporation to remove an organic solvent, then adding sodium acetate to dissolve the sodium acetate in acetic anhydride, heating and refluxing for 12 hours, then adding a hydrochloric acid solution, continuously stirring, cooling to room temperature, carrying out suction filtration, and repeatedly washing with ice water to obtain a brown solid, namely an intermediate 7-hydroxy-3-aldehyde-coumarin;
the molar ratio of 7-hydroxy-3-methyl-coumarin to N-bromosuccinimide is 1: 2;
the method specifically comprises the following steps: dissolving TEM, 7-hydroxy-3-aldehyde-coumarin and a catalyst in absolute ethyl alcohol, reacting for 4 hours at 50 ℃, cooling to room temperature after the reaction is finished, filtering to obtain red solid precipitate, and repeatedly washing with absolute ethyl alcohol to obtain an intermediate TX-OH;
TEM and 7-hydroxy-3-aldehyde-coumarin in a molar ratio of 1:1, the catalyst is piperidine;
and 5, synthesizing the fluorescent probe TX by taking the intermediate TX-OH obtained in the step 4 and acryloyl chloride as raw materials, wherein the structural formula is shown as the formula (I).
The method specifically comprises the following steps: dissolving TX-OH, acryloyl chloride and a catalyst in dichloromethane, stirring at room temperature, monitoring the reaction process by TLC (thin layer chromatography) until the reaction process is finished, performing reduced pressure spin-drying on the solvent, and performing column chromatography separation and purification to obtain the fluorescent probe;
the molar ratio of TX-OH to acryloyl chloride is 1: 2, the catalyst is triethylamine.
The principle of the fluorescence probe prepared by the method for detecting the biological mercaptan is as follows:
in DMSO, H2In the O (5:5, V: V) mixed solution, the probe solution itself hardly emits a fluorescent signal. When the biological thiol molecules are added into the solution, the fluorescence intensity is obviously improved at 488nm excitation wavelength and 718nm, and an 'on-off' response mechanism of a fluorescence signal is presented. And the color of the solution turned yellow to dark blue under "naked eye" observation.
Examples
The invention relates to a preparation method of a near-infrared fluorescent probe for detecting biological mercaptan, which is implemented according to the following steps:
the synthetic route is as follows:
the method specifically comprises the following steps: in a 250mL three-necked flask, under argon atmosphere, was added 0.2g of acetic anhydride, 0.4mL of glacial acetic acid, and 1.8mL of piperidine, followed by 16.5mL (110mmol) of isophorone, 6.6g (110mmol) of malononitrile, and the mixture was dissolved in 55mL of N, N-dimethylformamide and stirred at 120 ℃ for 6 hours. After the reaction was completed, the reaction mixture was cooled to room temperature. Pouring the reaction mixed solution into ice water, separating out a brown solid, drying, and separating and purifying by using column chromatography, wherein an eluent is petroleum ether and dichloromethane is 1:1(v: v), so as to obtain a yellow solid;
the method specifically comprises the following steps: 6.0g of 2, 4-dihydroxybenzaldehyde and 9.0g of sodium propionate were added to a 100mL round-bottom flask and dissolved in 15mL of propionic anhydride, 6mL of triethylamine was slowly added dropwise to the flask using a dropping funnel, and the mixture was heated under reflux for 12 hours to react, whereby the color of the solution changed from yellow to black. 30mL of water is injected into the reaction solution, and then solid is separated out; and (5) carrying out suction filtration to obtain a brick red solid, repeatedly washing with ice water and drying. Separating and purifying by column chromatography, wherein an eluent is dichloromethane and methanol which are 30:1, and obtaining white solid;
the method specifically comprises the following steps: a50 mL round bottom flask was charged with 0.190g of 7-hydroxy-3-methyl-coumarin dissolved in 20mL of dichloromethane, 2mL of acetic anhydride and 3 drops of pyridine were added, stirred at room temperature for 24h, and the progress of the reaction was monitored by TLC until the reaction was complete. Extraction was performed using dichloromethane and water, and the organic phase was collected and dried using anhydrous sodium sulfate. Filtering, performing reduced pressure rotary evaporation to remove the organic solvent, and separating and purifying by using column chromatography, wherein an eluent is pure dichloromethane, so as to obtain a white solid product, namely 7-acetoxyl-3-aldehyde-coumarin;
the method specifically comprises the following steps: under argon, 0.30g (1.6mmol) of 7-hydroxy-3-aldehyde-coumarin and 0.372g (2.0mmol) of TEM were dissolved in 10mL of absolute ethanol, 100. mu.L of piperidine was then added, and the reaction mixture was reacted overnight at 50 ℃. After the reaction was completed, the reaction mixture was cooled to room temperature. Filtering to obtain red solid precipitate, and repeatedly washing with anhydrous ethanol;
the method specifically comprises the following steps: in N2Under protection, 0.10g (0.28mmol) of TX-OH and 0.045mg (0.50mmol) of acryloyl chloride were dissolved in 5mL of anhydrous dichloromethane, and 100. mu.L of anhydrous triethylamine was added. Stir at rt and monitor the progress to completion by TLC. Removing the organic solvent by a rotary evaporator under reduced pressure, and separating and purifying by column chromatography, wherein an eluent is n-hexane and ethyl acetate which are 3:1 to obtain an orange-yellow solid;
wherein the product is characterized as follows:
1H NMR(400MHz,DMSO-d6)δ8.38(s,1H),7.64(d,J＝8.5Hz,1H),7.49(d,J＝16.2Hz,1H),7.28(d,J＝1.9Hz,1H),7.20-7.00(m,2H),6.73(s,1H),6.53-6.38(m,1H),6.31(dd,J＝17.2,10.3Hz,1H),6.14-6.02(m,1H),2.36(s,4H),0.89(s,6H).
13C NMR(400MHz,DMSO-d6)δ170.54,164.15,159.65,155.24,153.93,153.60,140.88,135.00,133.47,130.83,130.37,127.79,124.71,122.89,119.66,117.87,114.13,113.34,110.49,78.31,42.77,38.43,32.22,27.90.
MS:([M+Na]+)；Calcd for C25H20N2O4:435.1315；Found:435.1268.
probe test solvent screening
Based on the examples, the fluorescence emission performance of the probe TX (10 μmol/L) in different mixed solutions of organic solvent and water was tested. As shown in fig. 1, by comparing the fluorescence emission intensity in different organic solvents. It was found that when the organic solvent was chosen to be DMSO, the probe itself had a small background fluorescence emission. Further, as shown in fig. 2, the fluorescence emission performance of probe TX (10 μmol/L) after responding to Cys (5.0equiv.) in various organic solvent and water mixed solutions was tested. When the organic solvent was DNSO, a significant increase in fluorescence signal was exhibited.
CysCys (5.0equiv.) responses were tested for probe TX (10. mu. mol/L) in the presence of mixed solvents DMSO and water at different volume ratios, as shown in FIG. 3. It was found that when the probe TX was in DMSO: H2The fluorescent material has better fluorescence emission under a mixed solvent system with the O ratio of 1: 1.
pH range test for probe application
In DMSO, H2The effect of probes on Cys response in O (5:5, V: V) solution at different pH (3-11) ranges was tested, as shown in FIG. 4. The following are found: the fluorescence of the probe per se can obviously increase in a strong alkaline solvent, but the fluorescence intensity value tends to be in a stable state in neutral and alkaline solutions after response. Therefore, the probe is suitable for testing with a pH value ranging from 7 to 9.
Selective testing of probes
In DMSO, H2O (5:5, V: V) solution, the fluorescence emission spectra of each amino acid added to probe TX (10. mu. mol/L) were compared, including: 100 μmol/L, 1) Thr; 2) ser; 3) phe; 4) met; 5) lys; 6) leu; 7) ile; 8) his; 9) arg; 10) ala; 11) val; 12) tyr, and 20. mu. mol/L, 13) Cys; 14) hcy; 15) GSH. As shown in FIG. 5, in addition to the three thiol analytes, no significant increase in fluorescence intensity was observed at 488nm for the other amino acids. The result shows that the probe TX shows a good selective detection effect on the three biological thiols.
Anti-interference capability test of probe
The interfering atmosphere was created by adding 100. mu. mol/L of each amino acid of the above examples to 10. mu. mol/L of probe TX. Thereafter, the change in the fluorescence spectrum was measured after adding 20. mu. mol/LCys, Hcy and GSH as analytes. As shown in FIGS. 6, 7 and 8, the fluorescence responses of the other various amino acids (100. mu. mol/L, bars in the grid) and the fluorescence intensities after addition of Cys, Hcy and GSH (20. mu. mol/L, bars in the black) were compared, respectively. The fluorescence emission intensity of the probe TX shows obvious change at 718nm under the excitation wavelength of 488nm, and the result shows that the recognition of the three biological thiols by the probe TX in the presence of other various amino acids is hardly influenced.
Titration experiment of the Probe
As shown in FIG. 9, the probe TX solution itself had no significant fluorescence emission signal under 488nm wavelength excitation. However, when Cys is present, the solution color is shifted. And, it showed a great increase in the value of fluorescence intensity at 710 nm. In addition, when the analyte reached 20. mu. mol/L, the fluorescence intensity was increased by about 5 times. Meanwhile, from the ultraviolet-visible absorption spectrum 10, there was a tendency similar to the increase of fluorescence at 525 nm. As shown in FIGS. 11-14, the probe showed Cys-like behavior for Hcy and GSH.
Further, as shown in FIGS. 15-17, probes TX respond with Cys with a net increase in fluorescence intensity (F-F)0) Shows better linear correlation with Cys concentration of 0-10 mu mol/L (wherein, F0And F are fluorescence intensity values before and after the probe reacts with Cys, Hcy, and GSH, respectively). Regression equation for probe TX is y-30.17 +79.58x(R20.9810). At the same time, probes TX and Hcy (GSH) respond to net increase in fluorescence intensity (F-F)0) Has better linear correlation with the concentration of Hcy (GSH) between 0 and 4 mu mol/L, and the regression equation is that y is 48.14+205.51x (R)2＝0.9772)(y＝53.36+192.51x(R2＝0.9734))。
The fluorescent probe disclosed by the invention is used for detecting biological thiol by constructing a probe TX based on a dicyan isophorone framework with strong electron pulling capability, and the fluorescence emission wavelength of the fluorescent probe is red-shifted to an NIR region by conjugated connection of a coumarin group. At the excitation wavelength of 488nm, the probe has almost no fluorescence. After the biological thiol reacts with the probe molecules, the fluorescence intensity at 718nm is obviously enhanced. And, the net increase in fluorescence intensity before and after the reaction (F-F)0) And the concentration of the biological thiol shows better linear correlation in a certain range. The probe TX has good selectivity to thiol and is not interfered by other amino acids. Can be used for detecting biological mercaptan in a biological sample and has good application prospect.
Claims (7)
1. A near-infrared fluorescent probe for detecting biological thiol is characterized in that the fluorescent probe has a structural formula shown as the following formula (I):
2. the method for preparing the near-infrared fluorescent probe for detecting the biological thiol as claimed in claim 1, which is implemented by the following steps:
step 1, synthesizing an intermediate TEM by taking isophorone and malononitrile as raw materials through a Knoevenagel condensation reaction;
step 2, synthesizing an intermediate 7-hydroxy-3-methyl-coumarin by cyclization and hydrolysis reaction by taking 2, 4-dihydroxybenzaldehyde and sodium propionate as raw materials;
step 3, synthesizing an intermediate 7-hydroxy-3-aldehyde-coumarin by taking the intermediate 7-hydroxy-3-methyl-coumarin and N-bromosuccinimide obtained in the step 2 as raw materials through halogenation and hydrolysis reactions;
step 4, synthesizing an intermediate TX-OH by taking the intermediate TEM obtained in the step 1 and the step 3 and 7-hydroxy-3-aldehyde-coumarin as raw materials through a Knoevenagel condensation reaction;
and 5, synthesizing the fluorescent probe by using the intermediate TX-OH obtained in the step 4 and acryloyl chloride as raw materials.
3. The method for preparing a near-infrared fluorescent probe for detecting biological thiol according to claim 2, wherein the step 1 specifically comprises:
dissolving isophorone, malononitrile and a catalyst in N, N-dimethylformamide, stirring for 6 hours at 120 ℃ by taking argon as a protective gas, cooling to room temperature after the reaction is finished, injecting the reaction mixed solution into ice water, separating out a brown solid, drying, and separating and purifying by using column chromatography to obtain an intermediate TEM;
the catalyst is a viscous liquid formed by mixing acetic anhydride, glacial acetic acid and piperidine; the molar ratio of isophorone to malononitrile is 1: 1.
4. the method for preparing a near-infrared fluorescent probe for detecting biological thiol according to claim 2, wherein the step 2 specifically comprises:
dissolving 2, 4-dihydroxybenzaldehyde, sodium propionate and a catalyst triethylamine in acetic anhydride, heating and refluxing for 12h, injecting water into a reaction liquid, performing suction filtration to obtain a brick red solid, washing, drying, separating and purifying by column chromatography, dissolving the obtained product in dichloromethane, continuously reacting, adding acetic anhydride and pyridine as catalysts, stirring for 24h at room temperature, extracting by using dichloromethane and water, collecting an organic phase, drying by using anhydrous sodium sulfate, filtering, performing reduced pressure rotary evaporation to remove the organic solvent, and separating and purifying by using column chromatography to obtain an intermediate 7-hydroxy-3-methyl-coumarin; the molar ratio of the 2, 4-dihydroxybenzaldehyde to the sodium propionate is 1: 1.
5. the method for preparing a near-infrared fluorescent probe for detecting biological thiol according to claim 2, wherein the step 3 specifically comprises:
using azobisisobutyronitrile as a free radical reaction initiator, dissolving the azodiisobutyronitrile, 7-hydroxy-3-methyl-coumarin and N-bromosuccinimide in carbon tetrachloride, heating and refluxing for 8 hours, decompressing and rotary-steaming to remove an organic solvent, adding sodium acetate to dissolve the sodium acetate in acetic anhydride, heating and refluxing for 12 hours, then adding a hydrochloric acid solution, continuously stirring, cooling to room temperature, carrying out suction filtration, and washing with ice water to obtain a brown solid, namely an intermediate 7-hydroxy-3-aldehyde-coumarin; the molar ratio of 7-hydroxy-3-methyl-coumarin to N-bromosuccinimide is 1: 2.
6. the method for preparing a near-infrared fluorescent probe for detecting biological thiol according to claim 2, wherein in the step 4, the method specifically comprises:
dissolving TEM, 7-hydroxy-3-aldehyde-coumarin and a catalyst in absolute ethyl alcohol, reacting for 4 hours at 50 ℃, cooling to room temperature after the reaction is finished, filtering to obtain red solid precipitate, and repeatedly washing with absolute ethyl alcohol to obtain an intermediate TX-OH; TEM and 7-hydroxy-3-aldehyde-coumarin in a molar ratio of 1:1, the catalyst is piperidine.
7. The method for preparing a near-infrared fluorescent probe for detecting biological thiol according to claim 2, wherein in the step 5, the method specifically comprises:
dissolving TX-OH, acryloyl chloride and a catalyst in dichloromethane, stirring at room temperature, monitoring the reaction process by TLC (thin layer chromatography) until the reaction process is finished, performing reduced pressure spin-drying on the solvent, and performing column chromatography separation and purification to obtain the fluorescent probe; the molar ratio of TX-OH to acryloyl chloride is 1: 2, the catalyst is triethylamine.
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| CN114933555A (en) * | 2022-06-24 | 2022-08-23 | 西北大学 | Near-infrared fluorescent probe for detecting micromolecular mercaptan and preparation method thereof |
| CN116041301A (en) * | 2023-02-27 | 2023-05-02 | 新乡医学院 | Organic small molecular probe for detecting amino acid and preparation method and application thereof |
| CN116970116A (en) * | 2023-09-22 | 2023-10-31 | 南昌大学 | Polymer copolymer containing coumarin-Tb complex, and preparation method and application thereof |
| CN116970116B (en) * | 2023-09-22 | 2024-01-02 | 南昌大学 | Polymer copolymer containing coumarin-Tb complex, and preparation method and application thereof |
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