CN111518026A - Fluorescent molecular probe for identifying and detecting oxalic acid and preparation method and application thereof - Google Patents

Fluorescent molecular probe for identifying and detecting oxalic acid and preparation method and application thereof Download PDF

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CN111518026A
CN111518026A CN202010371955.3A CN202010371955A CN111518026A CN 111518026 A CN111518026 A CN 111518026A CN 202010371955 A CN202010371955 A CN 202010371955A CN 111518026 A CN111518026 A CN 111518026A
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oxalic acid
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贾丽华
郭祥峰
高昕
杨瑞
赵振龙
张宇
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Qiqihar University
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Abstract

A fluorescent molecular probe for identifying and detecting oxalic acid and a preparation method and application thereof relate to a probe for identifying and detecting oxalic acid and a preparation method and application thereof. The invention aims to solve the technical problems that the existing fluorescent probe for identifying and detecting oxalic acid by using a fluorescence method cannot realize quantitative detection, has poor selectivity and is easy to be interfered by other organic acids. The structural formula of the fluorescent molecular probe is as follows:
Figure DDA0002478475100000011
the preparation method comprises the following steps: firstly, salicylic acid, concentrated sulfuric acid and methanol react to prepare an intermediate I; secondly, preparing an intermediate II by the intermediate I and hydrazine hydrate; reacting the tri-8-hydroxyquinaldine, selenium dioxide and 1, 4-dioxane to prepare an intermediate III; IV, intermediate III and IIIReacting the intermediate II to obtain an intermediate IV; fifthly, adding intermediate IV and Fe3+The oxalic acid is identified and detected through fluorescence enhancement, the selectivity is high, the oxalic acid is not interfered by other organic acids, and the detection limit is 1.3 × 10‑7mol/L. Can be used in the fields of environment and food.

Description

Fluorescent molecular probe for identifying and detecting oxalic acid and preparation method and application thereof
Technical Field
The invention relates to a probe for identifying and detecting oxalic acid, a preparation method and application thereof.
Background
Oxalic acid is a common organic dicarboxylic acid, widely exists in plants, and is particularly high in content in vegetables such as spinach, amaranth and Chinese chives. Oxalic acid taken into a body through diet can form calcium oxalate which is insoluble in water with calcium ions, thereby not only influencing the absorption of calcium in a human body, but also increasing the risk of diseases such as renal calculus and the like. At present, the methods for detecting oxalic acid mainly comprise a titration method, a colorimetric method, a chromatography method and the like. These conventional methods are not only complicated in operation but also have disadvantages such as low sensitivity or high instrument price. As a new detection means, the fluorescent molecular probe has the advantages of high sensitivity, low cost, simple and convenient operation and the like, and is widely concerned. Therefore, it is important to develop a method for detecting oxalic acid using a fluorescent molecular probe. An article entitled oxalate proportional fluorescent probes and living cells imaging based on alkyne conjugated carboxamidoquinoline (aromatic fluorescent probes for oxalate based on alkyl-conjugated carboxamidoquinoline) published by Chunsheng, Qianhong et al in Dalton journal (Dalton Transactions) at 2011, volume 40, page 1034 and 1037 discloses a method for detecting oxalate by using fluorescent molecular probes. However, the molecular probe recognizes and detects oxalic acid through fluorescence quenching, can only detect the oxalic acid qualitatively, and has poor selectivity and is easy to be interfered by other organic acids.
Disclosure of Invention
The invention provides a fluorescent molecular probe for identifying and detecting oxalic acid and a preparation method and application thereof, aiming at solving the technical problems that the existing fluorescent probe for identifying and detecting oxalic acid by using a fluorescence method cannot realize quantitative detection, has poor selectivity and is easily interfered by other organic acids.
The invention relates to a fluorescent molecular probe for identifying and detecting oxalic acid, which has a structural formula as follows:
Figure BDA0002478475080000011
the fluorescent molecular probe can identify and detect oxalic acid and the content thereof through fluorescence enhancement.
The preparation method of the fluorescent molecular probe for identifying and detecting oxalic acid comprises the following steps:
firstly, salicylic acid and concentrated sulfuric acid are mixed according to a molar ratio of 1: (0.9-1.5), adding the mixture into methanol, stirring the mixture under the protection of nitrogen, heating the mixture to boiling reflux, and keeping the mixture for 12-18 hours; cooling to room temperature, removing methanol by rotary evaporation, and washing with water for multiple times; extracting with dichloromethane, drying with anhydrous sodium sulfate, and separating with silica gel column chromatography to obtain intermediate I;
secondly, mixing the intermediate I obtained in the first step with hydrazine hydrate in a molar ratio of 1: (2.5-4.5), adding the mixture into ethanol, stirring and heating until boiling and refluxing for reaction for 10.5-13.5 h; spin-drying the reaction solution, and recrystallizing with deionized water to obtain an intermediate II;
thirdly, mixing 8-hydroxyquinaldine and selenium dioxide in a molar ratio of 1: (1.5-2.5) adding the mixture into 1, 4-dioxane, reacting for 6-18 h at the temperature of 95-100 ℃ under the protection of nitrogen, and cooling and standing; filtering, spin-drying the filtrate, and separating by silica gel column chromatography to obtain an intermediate III;
fourthly, mixing the intermediate III obtained in the third step with the intermediate II obtained in the second step in a molar ratio of 1: (1.2-2.5), adding the mixture into ethanol, stirring, heating to boiling, performing reflux reaction for 3.5-4.5 hours, separating out a yellow solid, and washing with ethanol to obtain an intermediate IV;
fifthly, adding the intermediate IV obtained in the fourth step into an organic solvent, and adding Fe with the same molar quantity as the intermediate IV at room temperature3+And obtaining the fluorescent molecular probe for identifying and detecting the oxalic acid.
The fluorescent molecular probe for identifying and detecting oxalic acid is applied to identifying and detecting oxalic acid by fluorescence enhancement.
The composite fluorescent probe for identifying and detecting oxalic acid can detect the oxalic acid and the content thereof in rainwater, wastewater and plants through fluorescence enhancement, is not interfered by other organic acids, has higher selectivity and sensitivity, and has a detection Limit (LOD) of the probe to the oxalic acid of 1.3 × 10-7mol/L. The fluorescent probe can be used for detecting the oxalic acid content in environmental samples, foods and other fields, and has wide potential application value.
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FIG. 1 is a graph showing the change of fluorescence spectrum of the fluorescent molecular probe for identifying and detecting oxalic acid prepared in example 1 before and after the addition of organic acid and amino acid;
FIG. 2 is a bar graph showing the interference between the fluorescence intensity of the fluorescent molecular probe for identifying and detecting oxalic acid prepared in example 1 before and after the addition of organic acid and amino acid and the identification of oxalic acid by other organic acid or amino acid; (in the figure, the letter code numbers correspond to organic acids or amino acids, respectively, (A) blank, (B) L-methionine, (C) L-tryptophan, (D) L-proline, (E) L-arginine, (F) L-aspartic acid, (G) L-phenylalanine, (H) L-threonine, (I) L-serine, (J) L-lysine, (K) L-valine, (L) L-histidine, (M) L-tyrosine, (N) L-leucine, (O) L-cysteine, (P) L-glutamic acid, (Q) citric acid, (R) formic acid, (S) acetic acid, (T) benzoic acid, (U) salicylic acid, (V) tartaric acid, (W) succinic acid, and (X) mandelic acid;
FIG. 3 is a graph showing the change of fluorescence spectra of the fluorescent molecular probe for identifying and detecting oxalic acid prepared in example 1 for different concentrations of oxalic acid;
FIG. 4 is a graph showing the change in fluorescence intensity of the fluorescent molecular probe for identifying and detecting oxalic acid prepared in example 1 for different concentrations of oxalic acid.
Detailed Description
The first embodiment is as follows: the structural formula of the fluorescent molecular probe for identifying and detecting oxalic acid is as follows:
Figure BDA0002478475080000031
the fluorescent molecular probe can identify and detect the oxalic acid content through fluorescence enhancement.
The second embodiment is as follows: the preparation method of the fluorescent molecular probe for identifying and detecting oxalic acid comprises the following steps:
firstly, salicylic acid and concentrated sulfuric acid are mixed according to a molar ratio of 1: (0.9-1.5), adding the mixture into methanol, stirring the mixture under the protection of nitrogen, heating the mixture to boiling reflux, and keeping the mixture for 12-18 hours; cooling to room temperature, removing methanol by rotary evaporation, and washing with water for multiple times; extracting with dichloromethane, drying with anhydrous sodium sulfate, and separating with silica gel column chromatography to obtain intermediate I;
secondly, mixing the intermediate I obtained in the first step with hydrazine hydrate in a molar ratio of 1: (2.5-4.5), adding the mixture into ethanol, stirring and heating until boiling and refluxing for reaction for 10.5-13.5 h; spin-drying the reaction solution, and recrystallizing with deionized water to obtain an intermediate II;
thirdly, mixing 8-hydroxyquinaldine and selenium dioxide in a molar ratio of 1: (1.5-2.5) adding the mixture into 1, 4-dioxane, reacting for 6-18 h at the temperature of 95-100 ℃ under the protection of nitrogen, and cooling and standing; filtering, spin-drying the filtrate, and separating by silica gel column chromatography to obtain an intermediate III;
fourthly, mixing the intermediate III obtained in the third step with the intermediate II obtained in the second step in a molar ratio of 1: (1.2-2.5), adding the mixture into ethanol, stirring, heating to boiling, performing reflux reaction for 3.5-4.5 hours, separating out a yellow solid, and washing with ethanol to obtain an intermediate IV;
fifthly, adding the intermediate IV obtained in the fourth step into an organic solvent, and adding Fe with the same molar quantity as the intermediate IV at room temperature3+And obtaining the fluorescent molecular probe for identifying and detecting the oxalic acid.
The third concrete implementation mode: the second embodiment is different from the first embodiment in that: the mass percentage concentration of the concentrated sulfuric acid in the step one is more than or equal to 98 percent; the rest is the same as the second embodiment.
The fourth concrete implementation mode: the second or third embodiment is different from the first or second embodiment in that: in the first step, the molar ratio of the salicylic acid to the concentrated sulfuric acid is 1: 1; the other is the same as the second or third embodiment.
The fifth concrete implementation mode: this embodiment is different from one of the second to fourth embodiments in that: stirring and heating to boiling reflux for 13h under the protection of nitrogen in the first step, and the rest is the same as one of the second to fourth embodiments.
The sixth specific implementation mode: the present embodiment is different from one of the second to fifth embodiments in that: washing with water for multiple times in the first step; the other is the same as one of the second to fifth embodiments.
The seventh embodiment: the present embodiment is different from one of the second to sixth embodiments in that: in the second step, the intermediate I and hydrazine hydrate are mixed according to a molar ratio of 1: 3; the other is the same as one of the second to sixth embodiments.
The specific implementation mode is eight: the present embodiment is different from one of the second to seventh embodiments in that: in the third step, the molar ratio of the 8-hydroxyquinaldine to the selenium dioxide is 1: 2; the rest is the same as one of the second to seventh embodiments.
The specific implementation method nine: the present embodiment differs from the second to eighth embodiments in that: reacting for 7 hours at the temperature of 97 ℃ under the protection of nitrogen in the third step; the rest is the same as the second to eighth embodiments.
The detailed implementation mode is ten: the present embodiment differs from one of the second to ninth embodiments in that: in the fourth step, the molar ratio of the intermediate III to the intermediate II is 1: 2; the other is the same as in one of the second to ninth embodiments.
The concrete implementation mode eleven: this embodiment is different from one of the second to tenth embodiments in that: in the fifth step, the organic solvent is DMSO (dimethyl sulfoxide), DMF (dimethylformamide), THF (tetrahydrofuran), acetonitrile or a combination of a plurality of the DMSO and the THF; the rest is the same as in one of the second to tenth embodiments.
The specific implementation mode twelve: the application of the fluorescent molecular probe for identifying and detecting oxalic acid in the first embodiment is to identify and detect oxalic acid by fluorescence enhancement by using the fluorescent molecular probe.
The specific implementation mode is thirteen: the twelfth difference between this embodiment and the specific embodiment is that the oxalic acid is oxalic acid in rainwater, waste water, plants or food. The rest is the same as the embodiment twelve.
The beneficial effects of the present invention are verified by the following examples:
example 1: the preparation method of the fluorescent molecular probe for identifying and detecting oxalic acid in the embodiment comprises the following steps:
firstly, 15.0g (0.11mol) of salicylic acid, 100mL of methanol and 10mL of concentrated sulfuric acid with the mass percent concentration of 98 percent are sequentially added into a 250mL round-bottom flask, stirred under the protection of nitrogen and heated to boiling reflux for 13 hours. Cooling to room temperature, removing methanol by rotary evaporation, and washing with water for multiple times; extracting with dichloromethane, drying with anhydrous sodium sulfate overnight, eluting with dichloromethane, and separating with silica gel column chromatography to obtain intermediate I; yield of intermediate I7.623 g, 46%. The intermediate I is liquid in character and is directly used for the next synthesis. In the first step, the intermediate I is synthesized by directly utilizing salicylic acid, namely
Figure BDA0002478475080000051
Secondly, 7.436g (48.9mmol) of intermediate I, 50mL of absolute ethyl alcohol and 15.02g (150mmol) of hydrazine hydrate with the mass percent concentration of 50% are sequentially added into a 250mL round-bottom flask, and then the mixture is stirred and heated to boiling reflux for reaction for 13 hours. Removing ethanol by rotary evaporation, and recrystallizing with deionized water to obtain 3.266g of an intermediate II; yield of intermediate ii was 45%, melting point: and analyzing the intermediate II at 144.5-145.6 ℃, wherein the result is as follows: FTIR (KBr) v (cm)-1):3647,3320, 3262,3060,2773,2669,2584,1965,1926,1886,1809,1659,1587,1535,1495,1437,1359. In the second step, the intermediate I and 50% hydrazine hydrate are utilized to synthesize an intermediate II, namely
Figure BDA0002478475080000052
Three, 25 directionsAdding 150mL of 1, 4-dioxane into a 0mL round-bottom flask, heating to 60 ℃, and adding 4.177g (37.6mmol) of selenium dioxide; 3.097g (19.5mmol) of 8-hydroxyquinaldine was weighed out and dissolved in 10mL of 1, 4-dioxane, and the reaction solution was slowly dropped dropwise. Continuously reacting for 18 hours at the temperature of 95 ℃ under the protection of nitrogen, cooling and standing; filtering, spin-drying the filtrate, leaching the product with dichloromethane, and separating by silica gel column chromatography to obtain an intermediate III; the yield of intermediate III was 1.281g, 40% yield, melting point: and analyzing the intermediate III at 96.5-98.2 ℃, wherein the result is as follows: FTIR (KBr) v (cm)-1):3425,3372,3060,2838,1952,1704,1626,1594,1561,1495,1463. In the step III, 8-hydroxy quinaldine and selenium dioxide are utilized to synthesize an intermediate III, namely
Figure BDA0002478475080000053
Fourthly, adding 0.090g (0.50mmol) of the intermediate III, 15mL of absolute ethyl alcohol and 0.104g (0.68mmol) of the intermediate II into a reaction bottle, stirring, heating to boiling, refluxing and reacting for 4 hours, cooling and standing the reaction mixture, separating out light yellow solid, washing with absolute ethyl alcohol, and drying to obtain an intermediate IV; yield of intermediate iv was 0.092g, yield 60%, melting point: 258.2 to 261.5 ℃. The intermediate IV is subjected to structural analysis, and the result is as follows:1H NMR(600MHz,DMSO-d6) (ppm):12.173(s,1H),11.615(s,1H),9.863(s,1H),8.636(s,1H),8.371(d,J＝4.5Hz,1H), 8.113(d,J＝4.2Hz,1H),7.886(d,J＝3.6Hz,1H),7.474(dd,J＝3.9Hz,3.3Hz,2H),7.430 (d,J＝3.9Hz,1H),7.145(d,J＝3.9Hz,1H),6.996(dd,J＝3.9Hz,3.6Hz,2H).13C NMR (150MHz,DMSO-d6)(ppm):165.50,159.19,153.93,152.02,148.99,138.63,137.14,134.36, 129.37,129.33,128.91,119.51,118.32,118.22,117.71,117.00,112.67.FTIR(KBr)v(cm-1): 3743,3467,3407,3251,3052,2730,2588,1947,1646,1600,1535,1503,1463.ESI-MS m/z [M+H]+308.1035 Calcd, and 308.1022 Found by Foundation. From the analysis results, the structural formula of the intermediate IV is shown in
Figure BDA0002478475080000061
Fifthly, 100mL of the solution is prepared, the concentration is 1.0 × 10-5A DMSO solution of intermediate IV in mol/L, then 100. mu.L of Fe with a concentration of 0.010mol/L is added3+Performing ultrasonic treatment on the aqueous solution for 30min, and standing to obtain a fluorescent molecular probe for identifying and detecting the oxalic acid; the compound oxalic acid fluorescent molecular probe is uniformly distributed in DMSO (dimethyl sulfoxide), and can be used for directly detecting the oxalic acid content. The compound oxalic acid fluorescent molecular probe is analyzed, and the results are as follows: MS (ESI) m/z calcd for C17H17FeN3O4S+(M+Fe3+)439.0289 found from found 439.0267 found by analysis, intermediate IV and Fe3+Stable 1: 1 Complex, namely fluorescent molecular probe for identifying and detecting oxalic acid, and the structure is
Figure BDA0002478475080000062
The concentration of the fluorescent molecular probe for identifying and detecting oxalic acid prepared in example 1 was 1.0 × 10-5mol/L, in the DMSO solution, adding common organic acid or amino acid: formic acid, acetic acid, benzoic acid, salicylic acid, tartaric acid, succinic acid, mandelic acid, citric acid, oxalic acid, L-methionine, L-tryptophan, L-proline, L-arginine, L-aspartic acid, L-phenylalanine, L-threonine, L-serine, L-lysine, L-valine, L-histidine, L-tyrosine, L-leucine, L-cysteine, L-glutamic acid. The concentration of the organic acid or amino acid solution is 5 times of the concentration of the probe, the fluorescence spectrum of the organic acid or amino acid solution is measured, the obtained fluorescence spectrum is shown in figure 1, as can be seen from figure 1, the oxalic acid has a remarkable influence on the fluorescence spectrum of the probe, and other common organic acids and amino acids have no obvious influence on the spectrum. In the blank solution, the fluorescence intensity of the probe is weak, and when oxalic acid is added, the fluorescence of the probe at 500nm of the fluorescence spectrum is enhanced. Rarely is the high selectivity of the fluorescence response, and the single fluorescence of the probe enhances the recognition of oxalic acid in common organic acids and amino acids.
The concentration of the fluorescent molecular probe for identifying and detecting oxalic acid prepared in example 1 was 1.0 × 10-5mol/L of DMS thereinAdding oxalic acid into the solution O, performing ultrasonic treatment, standing, wherein the concentration of the oxalic acid aqueous solution is 5 times of that of the probe, and then respectively adding other common organic acids or amino acids: formic acid, acetic acid, benzoic acid, salicylic acid, tartaric acid, succinic acid, mandelic acid, citric acid, L-methionine, L-tryptophan, L-proline, L-arginine, L-aspartic acid, L-phenylalanine, L-threonine, L-serine, L-lysine, L-valine, L-histidine, L-tyrosine, L-leucine, L-cysteine, L-glutamic acid. The concentration of the organic acid or amino acid solution is 5 times of the concentration of the probe, the fluorescence spectrum of the solution is measured, and the obtained fluorescence intensity graph is shown in figure 2, and as can be seen from figure 2, when other organic acids or amino acids and oxalic acid coexist, the emission wavelength and the fluorescence intensity of the probe are not obviously changed basically, and the recognition and detection capability is not obviously influenced. The result shows that the probe has good selectivity and strong anti-interference capability to the response of oxalic acid, and is an ideal fluorescent molecular probe for identifying oxalic acid by fluorescence enhancement with high selectivity.
The concentration of the fluorescent molecular probe for identifying and detecting oxalic acid prepared in example 1 was 1.0 × 10-5Adding oxalic acid into DMSO solution under the condition of continuously stirring, wherein the adding concentration of the oxalic acid is 0-38 mu mol/L, researching the influence of different oxalic acid concentrations on a probe fluorescence spectrum, and obtaining a fluorescence spectrum as shown in figure 3. from figure 3, with the increase of the oxalic acid concentration, the probe has an emission wavelength of 500nm and a gradually increased fluorescence intensity in the fluorescence spectrum, when the oxalic acid concentration is about 28 mu mol/L, the absorption intensity and the fluorescence intensity both tend to be stable and do not have significant changes any more, a relation curve of the probe fluorescence intensity and the oxalic acid concentration is shown in figure 4. when the oxalic acid concentration is within the range of 0-28 mu mol/L, the fluorescence intensity and the oxalic acid concentration show a good linear relation, and according to the standard linear relation, the detection Limit (LOD) of the probe to the oxalic acid can be calculated to be 1.3 × 10- 7mol/L, therefore, the fluorescent probe prepared in the embodiment can quantitatively detect oxalic acid.
The concentration of the fluorescent molecular probe for identifying and detecting oxalic acid prepared in example 1 was 1.0 × 10-5mol/L, oxalic acid labeling is carried out on ultrapure waterRecovery experiments. 0, 0.3, 0.5 and 0.7 mu L of oxalic acid aqueous solution with the concentration of 0.050mol/L are respectively transferred and taken as standard samples, 3 mu L of ultrapure water is respectively added into the standard samples, and finally, a probe DMSO solution is added to test the fluorescence spectrum. Recovery was calculated from fluorescence intensity in combination with the standard curve. The experimental results are shown in table 1, and the recovery rate of oxalic acid in ultrapure water is 99.7-100.4%. The probe has good effect on the quantitative detection of the oxalic acid, and can be applied to the quantitative detection of the oxalic acid in the actual sample solution.
Table 1 shows the recovery rate of oxalic acid from ultrapure water sample by probe detection
Figure BDA0002478475080000071
Figure BDA0002478475080000081
a mean value (n ═ 3)
Example 2: the preparation method of the fluorescent molecular probe for identifying and detecting oxalic acid in the embodiment comprises the following steps:
firstly, 14.8g (0.11mol) of salicylic acid, 90mL of methanol and 11mL of concentrated sulfuric acid with the mass percent concentration of 98 percent are sequentially added into a 250mL round-bottom flask, stirred under the protection of nitrogen, heated to boiling reflux and kept for 15 h. Cooling to room temperature, removing methanol by rotary evaporation, and washing with water for multiple times; extracting with dichloromethane, drying with anhydrous sodium sulfate overnight, eluting with dichloromethane, and separating with silica gel column chromatography to obtain intermediate I; yield of intermediate I7.954 g, 48%. The intermediate I is liquid in character and is directly used for the next synthesis. In the first step, the intermediate I is synthesized by directly utilizing salicylic acid, namely
Figure BDA0002478475080000082
Secondly, 7.428g (48.8mmol) of intermediate I, 50mL of absolute ethyl alcohol and 17.78g (178mmol) of hydrazine hydrate with the mass percent concentration of 50% are sequentially added into a 250mL round-bottom flask, and then the mixture is stirred and heated to boiling reflux reaction 12h. Removing ethanol by rotary evaporation, and recrystallizing with deionized water to obtain 3.411g of an intermediate II; yield of intermediate ii was 47%, melting point: and analyzing the intermediate II at 144.5-145.6 ℃, wherein the result is as follows: FTIR (KBr) v (cm)-1):3647,3320, 3262,3060,2773,2669,2584,1965,1926,1886,1809,1659,1587,1535,1495,1437,1359. In the second step, the intermediate I and 50% hydrazine hydrate are utilized to synthesize an intermediate II, namely
Figure BDA0002478475080000083
Adding 145mL of 1, 4-dioxane into a 250mL round-bottom flask, heating to 60 ℃, and then adding 3.130g (28.2mmol) of selenium dioxide; 3.094g (19.4mmol) of 8-hydroxyquinaldine was dissolved in 10mL of 1, 4-dioxane, and the solution was slowly dropped. Continuously reacting for about 12 hours at the temperature of 97 ℃ under the protection of nitrogen, cooling and standing; filtering, spin-drying the filtrate, leaching the product with dichloromethane, and separating by silica gel column chromatography to obtain an intermediate III; the yield of intermediate III was 1.217g, yield 38%, melting point: and analyzing the intermediate III at 96.5-98.2 ℃, wherein the result is as follows: FTIR (KBr) v (cm)-1):3425,3372,3060,2838,1952,1704,1626,1594,1561,1495,1463. In the step III, 8-hydroxy quinaldine and selenium dioxide are utilized to synthesize an intermediate III, namely
Figure BDA0002478475080000084
Fourthly, adding 0.095g (0.55mmol) of the intermediate III, 15mL of absolute ethyl alcohol and 0.119g (0.78mmol) of the intermediate II into a reaction bottle, stirring and heating until boiling, refluxing and reacting for 4.5 hours, cooling and standing the reaction mixture, separating out light yellow solid, washing with absolute ethyl alcohol, and drying to obtain an intermediate IV; yield of intermediate iv 0.095g, yield 62%, melting point: 258.2 to 261.5 ℃. The intermediate IV is subjected to structural analysis, and the result is as follows:1H NMR(600MHz,DMSO-d6) (ppm):12.173(s,1H),11.615(s,1H),9.863(s,1H),8.636(s,1H),8.371(d,J＝4.5Hz,1H), 8.113(d,J＝4.2Hz,1H),7.886(d,J＝3.6Hz,1H),7.474(dd,J＝3.9Hz,3.3Hz,2H),7.430 (d,J＝3.9Hz,1H),7.145(d,J＝3.9Hz,1H),6.996(dd,J＝3.9Hz,3.6Hz,2H).13CNMR (150MHz,DMSO-d6)(ppm):165.50,159.19,153.93,152.02,148.99,138.63,137.14,134.36, 129.37,129.33,128.91,119.51,118.32,118.22,117.71,117.00,112.67.FTIR(KBr)v(cm-1): 3743,3467,3407,3251,3052,2730,2588,1947,1646,1600,1535,1503,1463.ESI-MS m/z [M+H]+308.1035 Calcd, and 308.1022 Found by Foundation. From the analysis results, the structural formula of the intermediate IV is shown in
Figure BDA0002478475080000091
Fifthly, 100mL of the solution is prepared, the concentration is 1.0 × 10-5mol/L of DMF solution of intermediate IV, then 100. mu.L of Fe with a concentration of 0.010mol/L3+Performing ultrasonic treatment on the aqueous solution for 30min, and standing to obtain a fluorescent molecular probe for identifying and detecting the oxalic acid; the composite oxalic acid fluorescent molecular probe is uniformly distributed in DMF (dimethyl formamide), and can be used for directly detecting the oxalic acid content. Intermediates IV and Fe3+Stable 1: 1 Complex, namely fluorescent molecular probe for identifying and detecting oxalic acid, and the structure is
Figure BDA0002478475080000092
The concentration of the fluorescent molecular probe for identifying and detecting oxalic acid prepared in example 2 was 1.0 × 10-5And (3) mol/L, adding common organic acid or amino acid into the DMF solution: formic acid, acetic acid, benzoic acid, salicylic acid, tartaric acid, succinic acid, mandelic acid, citric acid, oxalic acid, L-methionine, L-tryptophan, L-proline, L-arginine, L-aspartic acid, L-phenylalanine, L-threonine, L-serine, L-lysine, L-valine, L-histidine, L-tyrosine, L-leucine, L-cysteine, L-glutamic acid. The concentration of the organic acid or amino acid solution is 5 times of that of the probe, and the fluorescence spectrum of the probe is measured, wherein the oxalic acid has obvious influence on the fluorescence spectrum of the probe, and other common organic acids and amino acids have no obvious influence on the spectrum. In the blank solution, the fluorescence intensity of the probe is very weak, and when oxalic acid is added, the probe fluorescesFluorescence enhancement at 500nm of spectrum. The single fluorescence of the probe in common organic acid and amino acid enhances the recognition of oxalic acid.
The concentration of the fluorescent molecular probe for identifying and detecting oxalic acid prepared in example 2 was 1.0 × 10-5Adding oxalic acid into a DMF solution of the probe, performing ultrasonic treatment, standing, wherein the concentration of the oxalic acid aqueous solution is 5 times of that of the probe, and then respectively adding other common organic acids or amino acids: formic acid, acetic acid, benzoic acid, salicylic acid, tartaric acid, succinic acid, mandelic acid, citric acid, L-methionine, L-tryptophan, L-proline, L-arginine, L-aspartic acid, L-phenylalanine, L-threonine, L-serine, L-lysine, L-valine, L-histidine, L-tyrosine, L-leucine, L-cysteine, L-glutamic acid. The concentration of the organic acid or amino acid solution is 5 times of that of the probe, the fluorescence spectrum of the probe is measured, when other organic acids or amino acids and oxalic acid coexist, the emission wavelength and the fluorescence intensity of the probe are not obviously changed basically, and the identification and detection capability is not obviously influenced. The result shows that the probe has good selectivity and strong anti-interference capability to the response of oxalic acid, and is an ideal fluorescent molecular probe for identifying oxalic acid by fluorescence enhancement with high selectivity.
The concentration of the fluorescent molecular probe for identifying and detecting oxalic acid prepared in example 2 was 1.0 × 10-5Adding oxalic acid into DMF solution at a concentration of 0-38 mu mol/L under the condition of continuous stirring, and testing fluorescence spectra of the probe under different oxalic acid concentrations, wherein the results show that the probe has an emission wavelength of 500nm and gradually enhanced fluorescence intensity in the fluorescence spectra along with the increase of the oxalic acid concentration, when the oxalic acid concentration is about 29 mu mol/L, the absorption intensity and the fluorescence intensity tend to be stable and do not have significant change, the fluorescence intensity of the probe and the oxalic acid concentration present a good linear relationship, and according to the standard linear relationship, the detection Limit (LOD) of the probe to the oxalic acid can be calculated to be 1.32 × 10-7mol/L, therefore, the fluorescent probe prepared in the embodiment can quantitatively detect oxalic acid.
The concentration of the fluorescent molecular probe for identifying and detecting oxalic acid prepared in example 2 was 1.0 × 10-5mol/L for tap waterThe water was subjected to oxalic acid spiking recovery experiments. Transferring 0, 0.3, 0.5 and 0.7 mu L of oxalic acid water solution with the concentration of 0.050mol/L respectively as a standard sample, adding 3 mu L of tap water into the standard sample, finally adding a probe DMF solution, and testing the fluorescence spectrum. Recovery was calculated from fluorescence intensity in combination with the standard curve. The experimental results are shown in table 2, and the recovery rate of oxalic acid in tap water is 98.2-99.3%. The probe has good effect on the quantitative detection of the oxalic acid, and can be applied to the quantitative detection of the oxalic acid in the actual sample solution.
Table 2 shows the recovery rate of oxalic acid from the tap water sample by the probe
Figure BDA0002478475080000101
Figure BDA0002478475080000111
a mean value (n ═ 3)
Example 3: the preparation method of the fluorescent molecular probe for identifying and detecting oxalic acid in the embodiment comprises the following steps:
firstly, 15.3g (0.11mol) of salicylic acid, 80mL of methanol and 12mL of concentrated sulfuric acid with the mass percent concentration of 98 percent are sequentially added into a 250mL round-bottom flask, stirred under the protection of nitrogen, heated to boiling reflux and kept for 13 hours. Cooling to room temperature, removing methanol by rotary evaporation, and washing with water for multiple times; extracting with dichloromethane, drying with anhydrous sodium sulfate overnight, eluting with dichloromethane, and separating with silica gel column chromatography to obtain intermediate I; yield of intermediate I8.120 g, 49% yield. The intermediate I is liquid in character and is directly used for the next synthesis. In the first step, the intermediate I is synthesized by directly utilizing salicylic acid, namely
Figure BDA0002478475080000112
Secondly, 7.430g (48.8mmol) of intermediate I, 50mL of absolute ethyl alcohol and 20.38g (204mmol) of hydrazine hydrate with the mass percent concentration of 50% are added into a 250mL round-bottom flask in sequence, and then the mixture is stirred and heatedThe reaction is carried out for 11 h under boiling reflux. Removing ethanol by rotary evaporation, and recrystallizing with deionized water to obtain 3.484g of an intermediate II; yield of intermediate ii was 48%, melting point: and analyzing the intermediate II at 144.5-145.6 ℃, wherein the result is as follows: FTIR (KBr) v (cm)-1):3647,3320, 3262,3060,2773,2669,2584,1965,1926,1886,1809,1659,1587,1535,1495,1437,1359. In the second step, the intermediate I and 50% hydrazine hydrate are utilized to synthesize an intermediate II, namely
Figure BDA0002478475080000113
Adding 160mL of 1, 4-dioxane into a 250mL round-bottom flask, heating to 60 ℃, and adding 5.217g (47.0mmol) of selenium dioxide; 3.090g (19.4mmol) of 8-hydroxyquinaldine was weighed out and dissolved in 10mL of 1, 4-dioxane, and the reaction solution was slowly dropped. Continuously reacting for about 8 hours at the temperature of 98 ℃ under the protection of nitrogen, cooling and standing; filtering, spin-drying the filtrate, leaching the product with dichloromethane, and separating by silica gel column chromatography to obtain an intermediate III; the yield of intermediate III was 1.345g, yield 42%, melting point: and analyzing the intermediate III at 96.5-98.2 ℃, wherein the result is as follows: FTIR (KBr) v (cm)-1):3425,3372,3060,2838,1952,1704,1626,1594,1561,1495,1463. In the step III, 8-hydroxy quinaldine and selenium dioxide are utilized to synthesize an intermediate III, namely
Figure BDA0002478475080000114
Fourthly, adding 0.093g (0.54mmol) of the intermediate III, 15mL of absolute ethyl alcohol and 0.159g (1.05mmol) of the intermediate II into a reaction bottle, stirring and heating until boiling, refluxing and reacting for 3.5 hours, cooling and standing the reaction mixture, separating out light yellow solid, washing with absolute ethyl alcohol and drying to obtain an intermediate IV; yield of intermediate iv 0.098g, yield 64%, melting point: 258.2 to 261.5 ℃. The intermediate IV is subjected to structural analysis, and the result is as follows:1H NMR(600MHz,DMSO-d6) (ppm):12.173(s,1H),11.615(s,1H),9.863(s,1H),8.636(s,1H),8.371(d,J＝4.5Hz,1H), 8.113(d,J＝4.2Hz,1H),7.886(d,J＝3.6Hz,1H),7.474(dd,J＝3.9Hz,3.3Hz,2H),7.430 (d,J＝3.9Hz,1H),7.145(d,J＝3.9Hz,1H),6.996(dd,J＝3.9Hz,3.6Hz,2H).13C NMR (150MHz,DMSO-d6)(ppm):165.50,159.19,153.93,152.02,148.99,138.63,137.14,134.36, 129.37,129.33,128.91,119.51,118.32,118.22,117.71,117.00,112.67.FTIR(KBr)v(cm-1): 3743,3467,3407,3251,3052,2730,2588,1947,1646,1600,1535,1503,1463.ESI-MS m/z [M+H]+308.1035 Calcd, and 308.1022 Found by Foundation. From the analysis results, the structural formula of the intermediate IV is shown in
Figure BDA0002478475080000121
Fifthly, 100mL of the solution is prepared, the concentration is 1.0 × 10-5A solution of intermediate IV in mol/L of T, to which 100. mu.L of Fe with a concentration of 0.010mol/L are then added3+Performing ultrasonic treatment on the aqueous solution for 30min, and standing to obtain a fluorescent molecular probe for identifying and detecting the oxalic acid; the composite oxalic acid fluorescent molecular probe is uniformly distributed in THF, and can be used for directly detecting the oxalic acid content. Intermediates IV and Fe3+Stable 1: 1 Complex, namely fluorescent molecular probe for identifying and detecting oxalic acid, and the structure is
Figure BDA0002478475080000122
The concentration of the fluorescent molecular probe for identifying and detecting oxalic acid prepared in example 3 was 1.0 × 10-5mol/L, in its THF solution, respectively adding a common organic acid or amino acid: formic acid, acetic acid, benzoic acid, salicylic acid, tartaric acid, succinic acid, mandelic acid, citric acid, oxalic acid, L-methionine, L-tryptophan, L-proline, L-arginine, L-aspartic acid, L-phenylalanine, L-threonine, L-serine, L-lysine, L-valine, L-histidine, L-tyrosine, L-leucine, L-cysteine, L-glutamic acid. The concentration of the organic acid or amino acid solution is 5 times of that of the probe, and the fluorescence spectrum of the probe is measured, wherein the oxalic acid has obvious influence on the fluorescence spectrum of the probe, and other common organic acids and amino acids have no obvious influence on the spectrum. In the blank solution, the fluorescence intensity of the probe is very weak when oxalic acid is usedThe addition results in an increase in fluorescence at 500nm of the probe fluorescence spectrum. The fluorescence response has high selectivity, and the single fluorescence of the probe in common organic acid and amino acid enhances the recognition of oxalic acid.
The concentration of the fluorescent molecular probe for identifying and detecting oxalic acid prepared in example 3 was 1.0 × 10-5Adding oxalic acid into THF solution of the probe, performing ultrasonic treatment, standing, wherein the concentration of the oxalic acid aqueous solution is 5 times of that of the probe, and then respectively adding other common organic acids or amino acids: formic acid, acetic acid, benzoic acid, salicylic acid, tartaric acid, succinic acid, mandelic acid, citric acid, L-methionine, L-tryptophan, L-proline, L-arginine, L-aspartic acid, L-phenylalanine, L-threonine, L-serine, L-lysine, L-valine, L-histidine, L-tyrosine, L-leucine, L-cysteine, L-glutamic acid. The concentration of the organic acid or amino acid solution is 5 times of that of the probe, the fluorescence spectrum of the probe is measured, when other organic acids or amino acids and oxalic acid coexist, the emission wavelength and the fluorescence intensity of the probe are not obviously changed basically, and the identification and detection capability is not obviously influenced. The result shows that the probe has good selectivity and strong anti-interference capability to the response of oxalic acid, and is an ideal fluorescent molecular probe for identifying oxalic acid by fluorescence enhancement with high selectivity.
The concentration of the fluorescent molecular probe for identifying and detecting oxalic acid prepared in example 3 was 1.0 × 10-5Adding oxalic acid into THF solution of the probe at the concentration of 0-38 mu mol/L under the condition of continuous stirring, testing fluorescence spectra of the probe under different oxalic acid concentrations, wherein the results show that the probe has an emission wavelength of 500nm and gradually enhanced fluorescence intensity in the fluorescence spectra along with the increase of the oxalic acid concentration, and when the oxalic acid concentration is about 30 mu mol/L, the absorption intensity and the fluorescence intensity tend to be stable and do not have significant change-7mol/L, therefore, the fluorescent probe prepared in the embodiment can quantitatively detect oxalic acid.
Fluorescent molecular probes for the identification and detection of oxalic acid prepared in example 3The concentration of needles was 1.0 × 10-5And (3) performing an oxalic acid standard-adding recovery experiment on the spinach extracting solution at mol/L. Transferring 0, 0.3, 0.5 and 0.7 microliter of oxalic acid water solution with the concentration of 0.050mol/L respectively as a standard sample, adding 3 microliter of spinach extract into the standard sample, adding a probe THF solution, and testing the fluorescence spectrum. Recovery was calculated from fluorescence intensity in combination with the standard curve. The experimental results are shown in Table 3, and the recovery rate of oxalic acid in spinach extract is 96.7-98.6%. The probe has good effect on the quantitative detection of the oxalic acid, and can be applied to the quantitative detection of the oxalic acid in the actual sample solution.
Table 3 shows the recovery rate of oxalic acid from spinach extract sample by probe detection
Figure BDA0002478475080000131
Figure BDA0002478475080000141
a, an average value (n-3) was measured.

Claims (10)

1. A fluorescent molecular probe for identifying and detecting oxalic acid is characterized in that the structural formula of the fluorescent molecular probe is as follows:
Figure FDA0002478475070000011
2. the method for synthesizing the fluorescent molecular probe for identifying and detecting oxalic acid as claimed in claim 1, which is characterized by comprising the following steps:
firstly, salicylic acid and concentrated sulfuric acid are mixed according to a molar ratio of 1: (0.9-1.5), adding the mixture into methanol, stirring the mixture under the protection of nitrogen, heating the mixture to boiling reflux, and keeping the mixture for 12-18 hours; cooling to room temperature, removing methanol by rotary evaporation, and washing with water for multiple times; extracting with dichloromethane, drying with anhydrous sodium sulfate, and separating with silica gel column chromatography to obtain intermediate I;
secondly, mixing the intermediate I obtained in the first step with hydrazine hydrate in a molar ratio of 1: (2.5-4.5), adding the mixture into ethanol, stirring and heating until boiling and refluxing for reaction for 10.5-13.5 h; spin-drying the reaction solution, and recrystallizing with deionized water to obtain an intermediate II;
thirdly, mixing 8-hydroxyquinaldine and selenium dioxide in a molar ratio of 1: (1.5-2.5) adding the mixture into 1, 4-dioxane, reacting for 6-18 h at the temperature of 95-100 ℃ under the protection of nitrogen, and cooling and standing; filtering, spin-drying the filtrate, and separating by silica gel column chromatography to obtain an intermediate III;
fourthly, mixing the intermediate III obtained in the third step with the intermediate II obtained in the second step in a molar ratio of 1: (1.2-2.5), adding the mixture into ethanol, stirring, heating to boiling, performing reflux reaction for 3.5-4.5 hours, separating out a yellow solid, and washing with ethanol to obtain an intermediate IV;
fifthly, adding the intermediate IV obtained in the fourth step into an organic solvent, and adding Fe with the same molar quantity as the intermediate IV at room temperature3+And obtaining the fluorescent molecular probe for identifying and detecting the oxalic acid.
3. The method for synthesizing a fluorescent molecular probe for identifying and detecting oxalic acid according to claim 2, wherein the molar ratio of salicylic acid to concentrated sulfuric acid in the step one is 1: 1.
4. the method for synthesizing a fluorescent molecular probe for identifying and detecting oxalic acid as claimed in claim 2 or 3, wherein in the first step, stirring and heating to boiling reflux are carried out for 13h under the protection of nitrogen.
5. The method for synthesizing a fluorescent molecular probe for identifying and detecting oxalic acid as claimed in claim 2 or 3, wherein the molar ratio of the intermediate I to hydrazine hydrate in the second step is 1: 3.
6. the method for synthesizing a fluorescent molecular probe for identifying and detecting oxalic acid as claimed in claim 2 or 3, wherein the molar ratio of 8-hydroxyquinaldine to selenium dioxide in the step III is 1: 2.
7. the method for synthesizing a fluorescent molecular probe for identifying and detecting oxalic acid as claimed in claim 2 or 3, wherein the molar ratio of the intermediate III to the intermediate II in the fourth step is 1: 2.
8. the method for synthesizing a fluorescent molecular probe for identifying and detecting oxalic acid as claimed in claim 2 or 3, wherein the organic solvent in step five is DMSO, DMF, THF, acetonitrile or a combination of several of the above.
9. The use of the fluorescent molecular probe for the identification and detection of oxalic acid as claimed in claim 1, wherein the fluorescent molecular probe is used for the identification and detection of oxalic acid by fluorescence enhancement.
10. The use of a fluorescent molecular probe for the identification and detection of oxalic acid as claimed in claim 9, wherein the oxalic acid is oxalic acid in rainwater, wastewater, plants or food.
CN202010371955.3A 2020-05-06 2020-05-06 Fluorescent molecular probe for identifying and detecting oxalic acid and preparation method and application thereof Pending CN111518026A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114836201A (en) * 2022-04-04 2022-08-02 哈尔滨理工大学 Zinc ion mediated fluorescence sensor and preparation method and application thereof
CN114836201B (en) * 2022-04-04 2024-01-26 哈尔滨理工大学 Zinc ion-mediated fluorescence sensor and preparation method and application thereof

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