CN114213357A - 7-nitro-1, 2, 3-benzooxadiazole derivative and synthetic method and application thereof - Google Patents
7-nitro-1, 2, 3-benzooxadiazole derivative and synthetic method and application thereof Download PDFInfo
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- WCUXXCKIUMXCIB-UHFFFAOYSA-N 7-nitro-1,2,3-benzoxadiazole Chemical class [O-][N+](=O)C1=CC=CC2=C1ON=N2 WCUXXCKIUMXCIB-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000010189 synthetic method Methods 0.000 title description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000010949 copper Substances 0.000 claims abstract description 37
- 238000012360 testing method Methods 0.000 claims abstract description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001514 detection method Methods 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000000523 sample Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229940125904 compound 1 Drugs 0.000 claims abstract description 7
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims abstract description 6
- NTCCNERMXRIPTR-UHFFFAOYSA-N 2-hydroxy-1-naphthaldehyde Chemical compound C1=CC=CC2=C(C=O)C(O)=CC=C21 NTCCNERMXRIPTR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000010992 reflux Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 5
- WREUYJHLZYIWOF-UHFFFAOYSA-N 4-chloro-7-nitrobenzo[g][1,2,3]benzoxadiazole Chemical compound ClC1=CC2=C(C3=C1N=NO3)C=CC(=C2)[N+](=O)[O-] WREUYJHLZYIWOF-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims abstract 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 12
- 239000011550 stock solution Substances 0.000 claims description 12
- 238000010521 absorption reaction Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- IGHBXJSNZCFXNK-UHFFFAOYSA-N 4-chloro-7-nitrobenzofurazan Chemical compound [O-][N+](=O)C1=CC=C(Cl)C2=NON=C12 IGHBXJSNZCFXNK-UHFFFAOYSA-N 0.000 claims description 5
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 230000009977 dual effect Effects 0.000 claims description 2
- 239000007850 fluorescent dye Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 239000012488 sample solution Substances 0.000 claims description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 claims description 2
- 238000001308 synthesis method Methods 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 150000001768 cations Chemical class 0.000 description 5
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- 239000000872 buffer Substances 0.000 description 4
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- JKMHFZQWWAIEOD-UHFFFAOYSA-N 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethanesulfonic acid Chemical compound OCC[NH+]1CCN(CCS([O-])(=O)=O)CC1 JKMHFZQWWAIEOD-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000007995 HEPES buffer Substances 0.000 description 2
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- 208000008948 Menkes Kinky Hair Syndrome Diseases 0.000 description 1
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- 208000024777 Prion disease Diseases 0.000 description 1
- 206010039966 Senile dementia Diseases 0.000 description 1
- 102000019197 Superoxide Dismutase Human genes 0.000 description 1
- 108010012715 Superoxide dismutase Proteins 0.000 description 1
- 102000003425 Tyrosinase Human genes 0.000 description 1
- 108060008724 Tyrosinase Proteins 0.000 description 1
- 208000018839 Wilson disease Diseases 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
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- 239000007787 solid Substances 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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Abstract
The invention provides a 7-nitro-1, 2, 3-benzooxadiazole derivative and a synthesis method and application thereof. The synthesis method of the 7-nitro-1, 2, 3-benzooxadiazole derivative comprises the following steps: firstly, heating 4-chloro-7-nitrobenzo-1, 2, 3-benzooxadiazole and o-phenylenediamine in ethanol for refluxing, filtering and washing to obtain a compound 1; then, the compound 1 and 2-hydroxy-1-naphthaldehyde are heated and refluxed in methanol, filtered and washed to obtain the target compound, namely 7-nitro-1, 2, 3-benzooxadiazole (NBD) derivative. The invention also provides a method for colorimetric and fluorescent dual-mode detection of divalent copper ions, which comprises the following steps: using NBD derivative as probe in acetonitrile-H2Quantitative determination of Cu in O (pH 7.4) solution2+The content of (a). The detection method can detect the water solution with high selectivity and high sensitivityThe copper ions are simple, convenient and quick to operate. Simultaneously provides test paper for detecting divalent copper ions so as to detect Cu2+Is more convenient and fast.
Description
Technical Field
The invention relates to a 7-nitro-1, 2, 3-benzooxadiazole derivative, in particular to a 7-nitro-1, 2, 3-benzoxadiazole derivativeAzole derivative, synthesis method thereof and method for detecting Cu2+The use of (1).
Background
Copper, one of the essential elements of the human body, participates in many basic physiological processes. Due to its unique redox properties, copper becomes a catalyst cofactor for a variety of metalloenzymes, such as cytochrome oxidase, tyrosinase, and Cu/Zn superoxide dismutase. However, excessive copper ions in the human body stimulate the production of reactive oxygen species, which damage the central nervous system, resulting in a number of neurodegenerative diseases, such as Menkes ' disease, Wilson's disease, senile dementia, Parkinson's disease and prion diseases. However, the method is used for detecting Cu with high selectivity and high sensitivity in an aqueous system2+The number of probes of (a) is currently very small. Therefore, Cu can be detected and monitored quickly and reliably2+Has important significance in environmental science and biological toxicology.
Among many analytical detection methods, optical (colorimetric and fluorescent) probes have attracted much attention because of their advantages of high sensitivity, high accuracy, simple and rapid operation, little damage to analytes, and "naked eye" detection.
The test paper colorimetric method is simple, convenient and quick to operate, does not need special instruments and equipment or professional training, is easy to popularize, has clear and easily distinguished results, and is widely applied to a plurality of fields such as environmental analysis, life science and the like. It is very important to find a test paper for detecting copper ions.
Disclosure of Invention
The invention aims to provide a 7-nitro-1, 2, 3-benzooxadiazole (NBD) derivative, a synthetic method thereof and a method for detecting Cu2+The use of (1). The NBD derivative can avoid the interference of various metal ions, can detect the copper ions in the aqueous solution with high selectivity and high sensitivity, is simple, convenient and quick to operate, does not need special instruments and special training, is easy to popularize, and has clear and easily distinguished results.
In order to achieve the purpose, the technical solution of the invention is as follows:
an NBD derivative of the formula:
a method for synthesizing NBD derivatives comprises the following steps:
the first step is as follows: heating and refluxing reactants 4-chloro-7-nitrobenzo-1, 2, 3-benzooxadiazole (NBD-Cl) and o-phenylenediamine in ethanol for 5-8 h, and after the reaction is finished, performing suction filtration and washing to obtain a compound 1.
The second step is that: heating and refluxing the compound 1 and 2-hydroxy-1-naphthaldehyde in methanol for 8-10h, after the reaction is finished, carrying out suction filtration, and washing to obtain the target compound NBD derivative.
The reaction formula is as follows:
preferably, in the steps, the molar ratio of the NBD-Cl to the o-phenylenediamine in the first step is 1:1, the heating time is 6 hours, and the heating temperature is 80 ℃; in the second step, the molar ratio of the compound 1, 2-hydroxy-1-naphthaldehyde is 1:1, the heating time is 9 hours, and the heating temperature is 75 ℃.
A method for detecting copper ions by using NBD derivatives comprises the following steps:
(1) arrangement 10-3DMSO stock solutions of M NBD derivatives, configuration 10-2M Cu2+An aqueous solution of (a);
(2) 150 μ L of NBD derivative stock solution was added to a clean cuvette with Cu2+Gradually changing the solution from orange to grey green, gradually weakening the absorption peak at 473nm, gradually increasing the absorption peak at 600nm, and appearing an isoabsorption point at 550 nm.
(3) Add 12. mu.L of NBD derivative stock solution to clean colorimetric tube with Cu2+The concentration is increased, the fluorescence intensity at 540nm is measured on a fluorescence photometer to be gradually enhanced, and the fluorescence intensity I of the system at 540nm540nmAnd [ Cu ]2+]The concentration is 9-72X 10-6Exhibits a good linear relationship (R) in the range of M20.996), with Cu2+Concentration is plotted on the abscissa as fluorescence intensity I540nmPlotting for ordinate to obtain Cu2+Linear equation of concentration versus fluorescence intensity: f-164.66864 +24.86483[ Cu ]2 +]；
(4) Adding 12 mu L of NBD derivative fluorescent probe stock solution into a clean colorimetric tube, adding x mu L of sample solution to be detected, fixing the volume to 5mL by using secondary water, detecting on a fluorescence spectrophotometer, and substituting the measured fluorescence intensity into the linear equation in the step (2) to obtain [ Cu ]2+]Sample to be tested [ Cu ]2+]To be measured＝5000μL×[Cu2+]×10-6X mu L, then Cu can be obtained2+The concentration of (c).
Detect Cu2+The test paper of (1), which contains an NBD derivative.
The detection Cu2+The preparation method of the test paper comprises the following steps: the NBD derivative is dissolved in DMSO solvent, and then the filter paper strip is soaked in DMSO solution of the NBD derivative and dried to obtain NBD derivative test paper (orange color).
In order to ensure that the color of the test paper changes obviously before and after detection, the DMSO concentration of the NBD derivative in the step is preferably 1X 10-3M。
Soaking the test paper in the solution with the concentration of 1 × 10-3M,5×10-3M,1×10-2After the aqueous solution of M copper ions, the test paper gradually changed from orange to gray-green.
Compared with the prior art, the detection method has the following advantages and effects:
(1) the method is economical: the needed reagent has low price, simple synthesis, high product yield and low detection cost.
(2) The specificity is high: the method can be used for detecting divalent copper ions in a dual mode with high selectivity and is not interfered by other coexisting cations.
(3) And (3) shortcut: the detection time is only 30-60s, and the detection requirement of emergency can be completely met.
(4) The operation is simple and convenient: the detection is carried out only by a fluorescence spectrophotometer, the detection means is simple and convenient, and the result is clear and distinguishable.
(5) The invention can be used for detecting Cu by test paper2+And no special instrument and equipment and professional training are needed, and any person can operate the device.
Drawings
FIG. 1 shows the use of NBD derivatives of the invention for Cu determination2+A fluorescence selectivity map of;
FIG. 2 shows the use of NBD derivatives of the invention for Cu determination2+A fluorescence spectrum of (a);
FIG. 3 shows the determination of Cu by NBD derivatives of the invention2+The working curve of (2);
FIG. 4 shows the use of NBD derivatives of the invention for Cu determination2+Ultraviolet absorption spectrum of (1);
FIG. 5 shows the NBD derivative-Cu of the present invention2+Impact of the system is compared to the figure.
FIG. 6 is a color change chart of the test paper for detecting copper ions of different concentrations in an aqueous solution by using NBD derivative test paper according to the present invention.
The specific implementation mode is as follows:
the invention is explained in more detail below with reference to the figures and examples. Wherein L in the figure is NBD derivative.
Example 1 Synthesis and characterization of NBD derivatives
In the first step, 0.1g (0.5mmol) of NBD-Cl and 0.054g (0.5mmol) of o-phenylenediamine are dissolved in 7ml of absolute ethanol, heated and refluxed for 6 hours, and after the reaction is finished, suction filtration is carried out to obtain a compound 1.1H NMR(DMSO-d6)δ(ppm):10.701(s,1H,-NH),8.533(d,1H,ArH),7.119(m,2H,ArH),6.829(d,1H,ArH),6.635(t,1H,ArH),5.915(d,1H,ArH),5.279(s,2H,-NH2)..
In the second step, 0.36g (0.5mmol) of Compound 1 and 0.086g (0.5mmol) of 2-hydroxy-1-naphthaldehyde were dissolved in 20mL of methanol solution and heated under reflux for 9 hours. After the reaction is finished, suction filtration is carried out, impurities are washed away by methanol, and vacuum drying is carried out to obtain orange solid, namely the NBD derivative.1H NMR(DMSO-d6)δ(ppm):15.22(d,1H,-OH),11.14(s,1H,-NH),9.72(d,1H,-C＝NH),8.52(d,1H,ArH),8.47(d,1H,ArH),8.09(d,1H,ArH),7.87(d,1H,ArH),7.77(d,1H,ArH),7.61(t,1H,ArH),7.55(m,2H,ArH),7.48(t,1H,ArH),7.36(t,1H,ArH),6.84(d,1H,ArH),6.19(d,1H,ArH).
EXAMPLE 2 NBD derivatives for Cu2+Fluorescence selective assay of
Stock solutions of NBD derivatives at 1mM were prepared in DMSO, 0.01M Cu in distilled water2+Preparing a HEPES buffer solution with the pH value of 7.4 and the concentration of 0.025M; 60 mu L of NBD derivative stock solution is added into a clean colorimetric tube, and 60 mu L of Cu is respectively added2+，K+,Ca2+,Na+,Mg2+,Al3+,Zn2+,Hg2+,Ag+,Pb2+,Co2+,Ni2+,Cr3+,Cd3+,Fe3+0.15mLHEPES buffer, make volume to 5mL with acetonitrile and water mixed solution (v/v is 1:1), shake, add 2.5mL into clean cuvette, detect only Cu on fluorescence spectrophotometer2+The fluorescence intensity at 545nm is obviously enhanced by adding (1). Fluorescence selectivity is shown in FIG. 1.
EXAMPLE 3 NBD derivatives determination of Cu2+Linear relation of (1)
60 mu L of NBD derivative stock solution is added into a clean colorimetric tube, and Cu with different volumes is added respectively2+(4.5. mu.L, 9. mu.L, 12. mu.L, 15. mu.L, 18. mu.L, 21. mu.L, 24. mu.L, 27. mu.L, 30. mu.L, 33. mu.L, 36. mu.L), 0.15mLHEPES buffer, 5mL of a mixed solution of acetonitrile and water (v/v 1:1), shake up, add 2.5mL of the resulting solution to a clean cuvette, detect the concentration on a fluorescence spectrophotometer, and detect the concentration with Cu in accordance with the concentration of Cu in the sample2+With the addition of (2), the fluorescence intensity at 540nm gradually increased (see FIG. 2). Fluorescence intensity of System at 540nm I540nmAnd [ Cu ]2+]The concentration is 9-72X 10-6Exhibits a good linear relationship (R) in the range of M20.996), with Cu2+Concentration is plotted on the abscissa as fluorescence intensity I540nmPlotting for ordinate to obtain Cu2+Linear equation of concentration versus fluorescence intensity: f-164.66864 +24.86483[ Cu ]2+]，[Cu2+]Has a unit of 10-6mol/L; the working linearity diagram is shown in fig. 3.
Example 4 NBD derivatives for Cu2+Ultraviolet absorption measurement of
150 μ L of NBD derivative stock solution was addedAdding Cu with different volumes into a clean colorimetric tube respectively2+(6. mu.L, 12. mu.L, 18. mu.L, 24. mu.L, 30. mu.L, 36. mu.L, 42. mu.L, 48. mu.L), 0.15mL of HEPES buffer was added, 5mL of the buffer was made up with a mixed solution of acetonitrile and water (v/v ═ 1:1), 2.5mL of the buffer was shaken and added to a clean cuvette, followed by detection with Cu on an ultraviolet-visible spectrophotometer2+Gradually changing the solution from orange to grey green, gradually weakening the absorption peak at 473nm, gradually increasing the absorption peak at 600nm, and appearing an isoabsorption point at 550 nm. The ultraviolet absorption spectrum is shown in FIG. 4.
Example 5 coexisting cation pair Cu2+Interference fluorescence measurement of
60 μ L of NBD derivative stock solution was added to a clean colorimetric tube, and 60 μ L of Cu was added to each sample2+And 60. mu.L of various other cations (K)+,Ca2+,Na+,Mg2+,Al3+,Zn2+,Hg2+,Ag+,Pb2+,Co2+,Ni2+,Cr3+,Cd3+,Fe3+) 0.15mL of buffered epes was added to a mixed solution of acetonitrile and water (v/v ═ 1:1) to 5mL, and the mixture was shaken up to 2.5mL and then added to a clean cuvette and examined with a fluorescence spectrophotometer. Coexisting cation pair NBD derivative-Cu2+The interference of the fluorescence intensity of (2) is shown in FIG. 5.
Experiments prove that other common cations do not interfere the system to Cu2+The measurement of (1).
EXAMPLE 6 preparation of test paper
A2X 1cm strip of filter paper was soaked in 0.1mol/L HCl for one hour, then washed to neutrality with distilled water, and then dried for use, the NBD derivative synthesized in example 1 was dissolved in DMSO solvent, and then the prepared strip was soaked in a prepared NBD derivative solution (wherein the concentration of the NBD derivative was 10%-3M)1h, drying to obtain the test paper containing the NBD derivative.
EXAMPLE 7 NBD derivative test paper for Cu at various concentrations2+Aqueous solution
The test strips containing NBD derivatives prepared in example 6 were immersed in 1X 10 samples of each test strip-3M，5×10-3M，1×10-2Cu of M2+In the aqueous solution, after 1min, the test paper is taken out, and the color of the test paper gradually changes from orange to grey-green. (see FIG. 6).
Claims (8)
1. A7-nitro-1, 2, 3-benzooxadiazole (NBD) derivative is characterized in that the structural formula is as follows:
2. the method for synthesizing NBD derivatives according to claim 1, comprising the steps of:
firstly, heating and refluxing reactants 4-chloro-7-nitrobenzo-1, 2, 3-benzooxadiazole (NBD-Cl) and o-phenylenediamine in ethanol for 5-8 h, and after the reaction is finished, performing suction filtration and washing to obtain a compound 1.
And secondly, heating and refluxing the compound 1 and the 2-hydroxy-1-naphthaldehyde in methanol for 8-10h, performing suction filtration, and washing to obtain a target compound, namely the 7-nitro-1, 2, 3-benzooxadiazole (NBD) derivative.
3. The method for synthesizing NBD derivative according to claim 2, wherein the molar ratio of NBD-Cl to o-phenylenediamine is 1:1 in the first step, the heating time is 6 hours, and the heating temperature is 80 ℃; in the second step, the molar ratio of the compound 1 to the 2-hydroxy-1-naphthaldehyde is 1:1, the heating time is 9 hours, and the heating temperature is 75 ℃.
4. Use of the NBD derivative according to claim 1 for the detection of copper ions.
5. A method for detecting copper ions in a dual mode by using NBD derivatives is characterized by comprising the following steps:
(1) arrangement 10-3M DMSO stock of NBD derivatives as described in claim 1, configuration 10-2M Cu2+An aqueous solution of (a);
(2) 150 μ L of NBD derivative stock solution was added to a clean cuvette with Cu2+The solution is gradually changed from orange to grayish green, and the solution is detected on an ultraviolet visible spectrophotometer, the absorption peak at 473nm is gradually weakened, the absorption peak at 600nm is gradually strengthened, and equal absorption points appear at 550 nm;
(3) add 12. mu.L of NBD derivative stock solution to clean colorimetric tube with Cu2+The concentration is increased, the fluorescence intensity at 545nm measured on a fluorescence photometer is gradually enhanced, and the fluorescence intensity I of the system at 540nm is increased540nmAnd [ Cu ]2+]The concentration is 9-72X 10-6Exhibits a good linear relationship (R) in the range of M20.996), with Cu2+Concentration is plotted on the abscissa as fluorescence intensity I540nmPlotting for ordinate to obtain Cu2+Linear equation of concentration versus fluorescence intensity: f-164.66864 +24.86483[ Cu ]2+]；
(4) Adding 12 mu L of NBD derivative fluorescent probe stock solution into a clean colorimetric tube, adding x mu L of sample solution to be detected, fixing the volume to 5mL by using secondary water, detecting on a fluorescence spectrophotometer, and substituting the measured fluorescence intensity into the linear equation in the step (2) to obtain [ Cu ]2+]Sample to be tested [ Cu ]2+]To be measured＝5000μL×[Cu2+]×10-6The Cu in the sample to be measured can be obtained by x mu L2 +The concentration of (c).
6. Detect Cu2+A test strip comprising the NBD derivative according to claim 1.
7. Detecting Cu as claimed in claim 62+The preparation method of the test paper comprises the following steps: the NBD derivative of claim 1 dissolved in DMSO, followed by immersing the filter strip in DMSO solution of NBD derivative and drying to obtain Cu test2+The test paper of (1).
8. The method for preparing a strip according to claim 7, wherein the DMSO concentration of the NBD derivative is 1X 10-3M。
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