Method for colorimetrically detecting amphetamine and methyamphetamine in drugs based on furyl probe

Abstract

The invention provides a method for colorimetrically detecting amphetamine and methyamphetamine in drugs based on furyl probes. The furyl probes in the method are furan-indanone, furan-indene dicyanide and furan-indene cyanide respectively. Wherein before and after amphetamine or methyl amphetamine is added into the probe furan-indanone, the color of the solution is changed from faint yellow to rose red; before and after amphetamine or methyl amphetamine is added into the probe furan-indene dicyanide, the color of the solution is changed from brown yellow to blue; the color of the solution is changed from yellow to orange before and after amphetamine is added into the probe furan-indene cyanogen, and the color of the solution is changed from yellow to green before and after methylamphetamine is added into the probe furan-indene cyanogen. Rapid colorimetric distinguishing of single amphetamine or methyamphetamine and qualitative detection of a mixture of amphetamine and methyamphetamine are achieved. The method has no special limitation in use, can quickly complete qualitative detection without pretreatment of an object to be detected, is simple to operate, economical, practical, high in specificity and sensitivity, stable and repeatable in result, and can be practically applied and popularized.

Description

Technical Field

[0001] The invention belongs to the field of drug detection and provides a method for colorimetrically detecting amphetamine and methamphetamine in drugs based on furanyl probes. Background Art

[0002] Drug abuse poses a huge threat to personal physical and mental health, family harmony, and social stability. In actual drug production, trafficking, and abuse scenarios, its complex and changeable components and forms as well as its highly camouflaged appearance pose great challenges to on-site detection.

[0003] Typical amphetamine drugs, represented by amphetamine and methamphetamine, are highly addictive, mainly by preventing the release of dopamine inhibitors to produce euphoria. Their increasingly serious smuggling and abuse trends have made them the representatives of the second generation of synthetic drugs. Achieving highly sensitive, highly specific, and rapid on-site detection of amphetamine and methamphetamine is of great significance for strictly controlling their abuse, transportation, and sale, thereby effectively reducing related crimes.

[0004] Compared with other methods of on-site drug detection, such as chromatography-mass spectrometry, infrared spectroscopy, Raman spectroscopy, ion mobility spectrometry, etc., colorimetric technology based on the selective interaction between recognition elements and target molecules to output visual signals has become one of the important solutions for on-site drug detection because of its many excellent characteristics such as intuitive results, adjustable structure, high specificity, fast response speed, and high device modularity.

[0005] The present invention develops a method for colorimetrically detecting amphetamine and methamphetamine in drugs based on furanyl probes. The method uses 1,3-indanedione, 1,3-bis(dicyanomethylidene)indane and 3-(dicyanomethylidene)indone as electron-withdrawing groups and furanyl as a recognition group to achieve a highly specific and highly sensitive rapid differentiation response to amphetamine and methamphetamine in the form of a detection reagent or a functionalized sponge group. Summary of the invention

[0006] The object of the present invention is to provide a method for colorimetric detection of amphetamine and methamphetamine in drugs based on a furyl probe. The furyl probes in this method use 1,3-indanedione, 1,3-bis(dicyanomethylene) indane, and 3-(dicyanomethylene) indole-2-one as electron-withdrawing groups and furyl as the recognition group, and are obtained through the Knoevenagel condensation reaction. Among them, the furyl probe with 1,3-indanedione as the electron-withdrawing group (furan-indanone) changes the solution color from light yellow to rose red before and after adding amphetamine or methamphetamine; the furyl probe with 1,3-bis(dicyanomethylene) indane as the electron-withdrawing group (furan-indanedinitrile) changes the solution color from brownish yellow to blue before and after adding amphetamine or methamphetamine; the furyl probe with 3-(dicyanomethylene) indole-2-one as the electron-withdrawing group (furan-indanonitrile) changes the solution color from yellow to orange after adding amphetamine and from yellow to green after adding methamphetamine; all three probes can achieve colorimetric responses to amphetamine and methamphetamine. Among them, the probe furan-indanonitrile can achieve colorimetric differentiation between amphetamine and methamphetamine. The different colorimetric responses are due to the differences in the aggregation states of different products. The reaction product of the probe furan-indanonitrile with amphetamine shows a more aggregated state compared to the reaction product of the probe furan-indanonitrile with methamphetamine, and thus shows a more blue-shifted absorption. Based on this innovative detection mechanism, the rapid colorimetric differentiation of amphetamine and methamphetamine and the qualitative detection of a mixture of amphetamine and methamphetamine are realized for the first time.

[0007] The method for colorimetric detection of amphetamine and methamphetamine in drugs based on a furyl probe according to the present invention is carried out according to the following steps:

[0008] Preparation of the detection reagent:

[0009] a. Weigh 1,3-indanedione and furfural in a molar ratio of 1:1, place them in a 100 mL three-necked flask, add 10 mL of H2O, and stir at room temperature for 24 h; after the reaction is completed, filter, collect the precipitated solid and wash it with ice water, then dissolve the precipitated solid in dichloromethane, extract it with saturated brine, dry the obtained organic layer with anhydrous magnesium sulfate, filter and rotary evaporate to obtain the crude product, and then dissolve the crude product in a 500 mL mixed solution of dichloromethane and ethanol with a volume ratio of 1:9 for recrystallization, filter, and dry in vacuo to obtain a yellow solid, which is the furan-indanone probe;

[0010] b. Weigh 1,3-bis(dicyanomethylene)indan and furfural in a molar ratio of 1:1, place them in a 100 mL three-necked flask, add 15 mL of acetic anhydride, control the reaction temperature at 80 °C and stir for 3 h. After the reaction is completed and cooled to room temperature, perform recrystallization with ether, filter to obtain an orange solid, wash the obtained orange solid successively with 300 mL of ether and n-hexane, then dissolve the orange solid in dichloromethane, extract with saturated brine, dry the extracted organic layer with anhydrous magnesium sulfate, filter and rotary evaporate to obtain an orange solid, which is the furan-indene dicyano probe;

[0011] c. Weigh 3-(dicyanomethylene)indanone and furfural in a molar ratio of 1:1, place them in a 100 mL three-necked flask, add 10 mL of ethanol, control the reaction temperature at 80 °C and stir for 15 min. After the reaction is completed and cooled to room temperature, filter, collect the precipitated solid, wash the obtained solid successively with 300 mL of ether and n-hexane, then dry it under vacuum to obtain an orange solid, which is the furan-indene cyano probe;

[0012] d. Dissolve the furan-indanone, furan-indene dicyano, and furan-indene cyano probes obtained in steps a, b, and c respectively in dichloromethane, prepare solutions with a concentration of 10 mmol / L, and then dilute them with ethanol to 0.5 mmol / L to obtain detection reagents, namely the furan-indanone probe solution, the furan-indene dicyano probe solution, and the furan-indene cyano probe solution;

[0013] e. Dissolve the furan-indene cyano probe obtained in step c in dichloromethane, prepare a solution with a concentration of 1 mmol / L, then soak the polyurethane sponge in this solution, and after complete soaking, take it out and dry it in an oven at 40 °C to obtain a sensing unit, namely the furan-indene cyano probe-functionalized sponge matrix;

[0014] Detection of amphetamine and methamphetamine by the furan-indanone probe solution:

[0015] f. Take 180 μL of the furan-indanone probe solution obtained in step d and place it in test tubes respectively. Add 20 μL of a 5 mmol / L amphetamine ethanol solution and 20 μL of a 5 mmol / L methamphetamine ethanol solution to the test tubes respectively, observe the color change before and after the reaction, and record the absorption spectrum and optical photograph;

[0016] Detection of amphetamine and methamphetamine by the furan-indene dicyano probe solution:

[0017] g. Take 180 μL of the furan-indene dicyanide probe solution obtained in step d and place it in test tubes respectively. Add 20 μL of amphetamine ethanol solution with a concentration of 5 mmol / L and 20 μL of methamphetamine ethanol solution with a concentration of 5 mmol / L to the test tubes respectively. Observe the colorimetric change before and after the reaction, and record the absorption spectrum and optical photo;

[0018] Detection of amphetamine and methamphetamine by furan-indene cyanide probe solution:

[0019] h. Take 180 μL of the furan-indene cyanide probe solution obtained in step d and place it in test tubes respectively. Add 20 μL of amphetamine ethanol solution with a concentration of 5 mmol / L and 20 μL of methamphetamine ethanol solution with a concentration of 5 mmol / L to the test tubes respectively. Observe the colorimetric change before and after the reaction, and record the absorption spectrum and optical photo;

[0020] Detection of amphetamine and methamphetamine by furan-indene cyanide probe-functionalized sponge base:

[0021] i. Take two pieces of the furan-indene cyanide probe-functionalized sponge base obtained in step e, and respectively suck 20 μL of amphetamine ethanol solution with a concentration of 5 mmol / L and 20 μL of methamphetamine ethanol solution with a concentration of 5 mmol / L and drop them onto the sponge base. Observe the colorimetric change before and after the reaction;

[0022] Detection of amphetamine and methamphetamine mixture by furan-indene cyanide probe-functionalized sponge base:

[0023] j. Take the furan-indene cyanide probe-functionalized sponge base obtained in step e, suck 20 μL of the mixed solution of amphetamine and methamphetamine with a total concentration of 2 mmol / L and drop it onto the sponge base. Observe the colorimetric change before and after the reaction.

[0024] The present invention provides a method for colorimetric detection of amphetamine and methamphetamine in drugs based on a furan-based probe. The chemical names of the probes furan-indanone, furan-indene dicyanide and furan-indene cyanide are 2-(furan-2-ylmethylene)-1H-indene-1,3(2H)-dione, 2,2'-(2-(furan-2-ylmethylene)-1H-indene-1,3(2H)-dimethylene)dipropanedinitrile and (Z)-2-(2-(furan-2-ylmethylene)-3-oxo-2,3-dihydro-1H-indene-1-ylidene)propanedinitrile respectively, which can be obtained by Knoevenagel condensation reaction. The corresponding chemical structural formulas (Ⅰ), (Ⅱ), (Ⅲ) of the probes furan-indanone, furan-indene dicyanide and furan-indene cyanide are respectively:

[0025]

[0026] The present invention provides a method for colorimetric detection of amphetamine and methamphetamine in drugs based on a furyl probe. The detection principle of this method is that the primary / secondary amino group of the analyte amphetamine or methamphetamine attacks the double bond on the furyl group of the probe, thereby causing a ring-opening reaction, and the transformation of the probe to the molecular structure of the product corresponds to a color change.

[0027] The present invention provides a method for colorimetric detection of amphetamine and methamphetamine in drugs based on a furyl probe. The furyl probes in this method can all achieve colorimetric responses to the drugs amphetamine and methamphetamine. Among them, for the probe furan-indanone, the solution color changes from light yellow to rose red before and after adding amphetamine or methamphetamine; for the probe furan-indanedicarbonitrile, the solution color changes from brownish yellow to blue before and after adding amphetamine or methamphetamine; and for the probe furan-indanonitrile, the solution color changes from yellow to orange after adding amphetamine, and the solution color changes from yellow to green after adding methamphetamine. For the convenience of on-site actual detection applications, the probe furan-indanonitrile is loaded on a sponge substrate. After dropping an amphetamine solution, the color of the probe-functionalized sponge substrate changes from yellow to red, and after dropping a methamphetamine solution, the color of the probe-functionalized sponge substrate changes from yellow to green. Its detection is not interfered by other common drugs, amine substances, etc., and can achieve qualitative discrimination of a mixture of amphetamine and methamphetamine. The present invention has no special restrictions in use. At room temperature, the analyte does not need to be pretreated to quickly complete qualitative detection. The operation is simple, economical and practical, with high specificity and sensitivity, and the results are stable and repeatable. The above advantages make the present invention easy to be practically applied and promoted in the field of on-site rapid detection.

[0028] The method of the present invention can achieve qualitative detection of amphetamine or methamphetamine alone, and the colorimetric response effects to amphetamine and methamphetamine can be distinguished by the naked eye, with high sensitivity, strong specificity, short reaction time, and can achieve qualitative detection of a mixture of amphetamine and methamphetamine through a probe-functionalized sponge substrate. Brief Description of the Drawings

[0029] Figure 1 Shows the detection effects of the probes furan-indanone, furan-indanedicarbonitrile and furan-indanonitrile in ethanol on amphetamine or methamphetamine in Example 1 of the present invention. Among them, a shows the detection effect of the probe furan-indanone in ethanol on amphetamine or methamphetamine, b shows the detection effect of furan-indanedicarbonitrile in ethanol on amphetamine or methamphetamine, and c shows the detection effect of furan-indanonitrile in ethanol on amphetamine or methamphetamine;

[0030] Figure 2The detection effects of the probes furan-indanone, furan-indanedinitrile, and furan-indanonitrile in Example 2 of the present invention on amphetamine or methamphetamine in methanol, acetonitrile, ethyl acetate, tetrahydrofuran, and dichloromethane, where a is the detection effect of the probe furan-indanone on amphetamine or methamphetamine in methanol, acetonitrile, ethyl acetate, tetrahydrofuran, and dichloromethane, b is the detection effect of the probe furan-indanedinitrile on amphetamine or methamphetamine in methanol, acetonitrile, ethyl acetate, tetrahydrofuran, and dichloromethane, and c is the detection effect of the probe furan-indanonitrile on amphetamine or methamphetamine in methanol, acetonitrile, ethyl acetate, tetrahydrofuran, and dichloromethane;

[0031] Figure 3 The detection effects of the furan-indanonitrile probe solutions with concentrations of 0.01, 0.05, 0.1, 0.3, and 0.5 mmol / L in Example 3 of the present invention on amphetamine or methamphetamine, where a are the corresponding optical pictures of the furan-indanonitrile probe solutions with concentrations of 0.01, 0.05, 0.1, 0.3, and 0.5 mmol / L before and after detecting amphetamine or methamphetamine, b are the corresponding absorption spectra of the furan-indanonitrile probe solutions with concentrations of 0.01, 0.05, 0.1, 0.3, and 0.5 mmol / L before and after detecting amphetamine, and c are the corresponding absorption spectra of the furan-indanonitrile probe solutions with concentrations of 0.01, 0.05, 0.1, 0.3, and 0.5 mmol / L before and after detecting methamphetamine;

[0032] Figure 4 The detection effects of the furan-indanonitrile probe-functionalized sponge matrix with concentrations of 0.05, 0.1, 0.5, 1.0, 2.0, 3.0, and 5.0 mmol / L in Example 4 of the present invention on amphetamine or methamphetamine;

[0033] Figure 5 The time responses of the furan-indanonitrile probe-functionalized sponge matrix to amphetamine or methamphetamine in Example 5 of the present invention, where a is the time response of the furan-indanonitrile probe-functionalized sponge matrix to amphetamine, and b is the time response of the furan-indanonitrile probe-functionalized sponge matrix to methamphetamine;

[0034] Figure 6 The detection effects of the furan-indanonitrile probe-functionalized sponge matrix on amphetamine or methamphetamine with concentrations of 0, 0.2, 0.4, 0.6, 0.8, 1.0, 2.0, 3.0, 4.0, and 5.0 mmol / L in Example 6 of the present invention;

[0035] Figure 7 The detection effects of the furan-indanonitrile probe-functionalized sponge matrix on amphetamine, methamphetamine, or 16 other interfering substances in Example 7 of the present invention;

[0036] Figure 8Detection effect of the furan-indene cyanide probe-functionalized sponge matrix in Example 8 of the present invention on mixtures of amphetamine and methamphetamine with concentration ratios of 0:5, 1:4, 2:3, 3:2, 4:1, and 5:0. Detailed implementation mode

[0037] The present invention will be further described below through specific examples, but the invention is not limited to these examples.

[0038] Example 1

[0039] Preparation of the probe furan-indanone:

[0040] a. Weigh 1,3-indanedione and furfural at a molar ratio of 1:1, place them in a 100 mL three-necked flask, add 10 mL of H2O, and stir at room temperature for 24 h; after the reaction is completed, filter, collect the precipitated solid, wash it with ice water, then dissolve the precipitated solid in dichloromethane, extract with saturated brine, dry the obtained organic layer with anhydrous magnesium sulfate, filter and rotary evaporate to obtain the crude product, and then dissolve the crude product in a 500 mL mixed solution of dichloromethane and ethanol with a volume ratio of 1:9 for recrystallization. Obtain a yellow solid through filtration and vacuum drying, which is the furan-indanone probe;

[0041] Preparation of the probe furan-indanedinitrile:

[0042] b. Weigh 1,3-bis(dicyanomethylene)indane and furfural at a molar ratio of 1:1, place them in a 100 mL three-necked flask, add 15 mL of acetic anhydride, control the reaction temperature at 80 °C and stir for 3 h; after the reaction is completed and cooled to room temperature, perform recrystallization with ether, filter to obtain an orange solid, wash the obtained orange solid successively with 300 mL of ether and n-hexane, then dissolve the orange solid in dichloromethane, extract with saturated brine, dry the obtained organic layer with anhydrous magnesium sulfate, filter and rotary evaporate to obtain an orange solid, which is the furan-indanedinitrile probe;

[0043] Preparation of the probe furan-indene cyanide:

[0044] c. Weigh 3-(dicyanomethylene)indanone and furfural at a molar ratio of 1:1, place them in a 100 mL three-necked flask, add 10 mL of ethanol, control the reaction temperature at 80 °C and stir for 15 min; after the reaction is completed and cooled to room temperature, filter, collect the precipitated solid, wash the obtained solid successively with 300 mL of ether and n-hexane, and then vacuum dry to obtain an orange solid, which is the furan-indene cyanide probe;

[0045] Preparation of the detection reagent:

[0046] d. Dissolve the furan-indanone, furan-indanedinitrile, and furan-indanonitrile probes obtained in steps a, b, and c in dichloromethane respectively to prepare a solution with a concentration of 10 mmol / L, and then dilute it with ethanol to 0.5 mmol / L to obtain the detection reagents, namely the furan-indanone probe solution, the furan-indanedinitrile probe solution, and the furan-indanonitrile probe solution;

[0047] Detection effect of the furan-indanone probe on amphetamine and methamphetamine in ethanol:

[0048] e. Take 180 μL of the 0.5 mmol / L furan-indanone probe solution obtained in step d and place it in test tubes respectively. Then add 20 μL of a 5 mmol / L amphetamine solution and 20 μL of a 5 mmol / L methamphetamine solution to the test tubes respectively. After full reaction, record the optical photos and spectra; The detection effects of the furan-indanone probe molecule on amphetamine and methamphetamine in an ethanol solvent are as Figure 1 shown in a. After adding amphetamine or methamphetamine, the color of the reagent changes from yellow to red. In addition, measured with a UV-visible absorption spectrometer, a product absorption characteristic peak appears at 525 nm, and this color change is obvious;

[0049] Detection effect of the furan-indanedinitrile probe on amphetamine and methamphetamine in ethanol:

[0050] f. Take 180 μL of the 0.5 mmol / L furan-indanedinitrile probe solution obtained in step d and place it in test tubes respectively. Then add 20 μL of a 5 mmol / L amphetamine solution and 20 μL of a 5 mmol / L methamphetamine solution to the test tubes respectively. After full reaction, record the optical photos and spectra; The detection effects of the furan-indanedinitrile probe molecule on amphetamine and methamphetamine in an ethanol solvent are as Figure 1 shown in b. After adding amphetamine and methamphetamine, the color of the reagent changes from brown-yellow to blue. In addition, measured with a UV-visible absorption spectrometer, a product characteristic peak appears at 615 nm, and this color change is obvious;

[0051] Detection effect of the furan-indanonitrile probe on amphetamine and methamphetamine in ethanol:

[0052] g. Take 180 μL of the 0.5 mmol / L furan-indanonitrile probe solution obtained in step d and place it in test tubes respectively. Then add 20 μL of a 5 mmol / L amphetamine solution and 5 mmol / L methamphetamine solution to the test tubes. After full reaction, record the optical photos and spectra; The detection effects of the furan-indanonitrile probe molecule on amphetamine and methamphetamine in an ethanol solvent are as Figure 1As shown in c, after adding amphetamine, the color of the reagent changed from yellow to orange, and a characteristic shoulder peak of the product appeared at 510 nm in the corresponding absorption spectrum; while after adding methamphetamine, the color of the reagent changed from yellow to green, and a characteristic peak of the product appeared at 595 nm in the corresponding absorption spectrum.

[0053] Example 2

[0054] Detection effects of the probes furan-indanone, furan-indanedinitrile and furan-indanecarbonitrile on amphetamine or methamphetamine in methanol, acetonitrile, ethyl acetate, tetrahydrofuran and dichloromethane:

[0055] The probes furan-indanone, furan-indanedinitrile and furan-indanecarbonitrile prepared in steps a, b, and c of Example 1 were respectively dissolved in methanol, acetonitrile, ethyl acetate, tetrahydrofuran and dichloromethane to prepare probe solutions with concentrations of 0.5 mmol / L. Then, 180 μL of the probe solution of the corresponding solvent was taken into a test tube to obtain a detection reagent; then, 20 μL of a 5 mmol / L amphetamine solution and a 5 mmol / L methamphetamine solution were respectively added to the detection reagent. After sufficient reaction, optical photos were recorded.

[0056] The detection effects of the molecules of the probes furan-indanone, furan-indanedinitrile and furan-indanecarbonitrile on amphetamine or methamphetamine in solvents of methanol, acetonitrile, ethyl acetate, tetrahydrofuran and dichloromethane are as Figure 2 shown. After adding amphetamine or methamphetamine, the color of the reagent changed significantly, proving that the molecules of the probes furan-indanone, furan-indanedinitrile and furan-indanecarbonitrile are effective in detecting amphetamine or methamphetamine in methanol, acetonitrile, ethyl acetate, tetrahydrofuran and dichloromethane; among them, the ethyl acetate solution and dichloromethane solution of the probe furan-indanone, and the methanol solution of the probe furan-indanecarbonitrile can all achieve the differential colorimetric response of amphetamine and methamphetamine.

[0057] Example 3

[0058] Detection effects of furan-indanecarbonitrile probe solutions with concentrations of 0.01, 0.05, 0.1, 0.3 and 0.5 mmol / L on amphetamine or methamphetamine:

[0059] The 10 mmol / L furan-indene cyanide probe dichloromethane solution prepared in step d of Example 1 was diluted with ethanol to prepare furan-indene cyanide probe solutions with concentrations of 0.01, 0.05, 0.1, 0.3, and 0.5 mmol / L. 180 μL of the furan-indene cyanide probe solution with the corresponding concentration was pipetted into a test tube to obtain a detection reagent; then, 20 μL of a 5 mmol / L amphetamine solution or methamphetamine solution was added to the detection reagents with concentrations of 0.01, 0.05, 0.1, 0.3, and 0.5 mmol / L respectively. After full reaction, optical photos and absorption spectra were recorded;

[0060] The detection effects of furan-indene cyanide probe molecules with concentrations of 0.01, 0.05, 0.1, 0.3, and 0.5 mmol / L on amphetamine or methamphetamine are as follows Figure 3 shown. After adding amphetamine or methamphetamine, both the color and absorption spectrum of the furan-indene cyanide probe solution with concentrations of 0.05, 0.1, 0.3, and 0.5 mmol / L changed significantly, proving that the furan-indene cyanide probes with concentrations of 0.01, 0.05, 0.1, 0.3, and 0.5 mmol / L are all effective in detecting amphetamine or methamphetamine.

[0061] Example 4

[0062] The detection effects of furan-indene cyanide probe-functionalized sponge substrates with concentrations of 0.05, 0.1, 0.5, 1.0, 2.0, 3.0, and 5.0 mmol / L on amphetamine or methamphetamine:

[0063] The furan-indene cyanide probe obtained in step c of Example 1 was dissolved in dichloromethane to prepare solutions with concentrations of 0.05, 0.1, 0.5, 1, 2, 3, and 5 mmol / L. Then, the polyurethane sponge was soaked in this solution. After complete soaking, it was taken out and dried in an oven at a temperature of 40 °C to obtain furan-indene cyanide probe-functionalized sponge substrates with concentrations of 0.05, 0.1, 0.5, 1.0, 2.0, 3.0, and 5.0 mmol / L; then, 20 μL of a 5 mmol / L amphetamine solution or methamphetamine solution was dropped onto the furan-indene cyanide probe-functionalized sponge substrates with concentrations of 0.05, 0.1, 0.5, 1.0, 2.0, 3.0, and 5.0 mmol / L respectively. After the reaction was complete, optical photos were recorded, as shown in Figure 4As shown, after dropping amphetamine, the furan-indocyanine probe-functionalized sponge bases with concentrations of 0.05, 0.1, 0.5, 1.0, 2.0, 3.0, and 5.0 mmol / L all turned red; while after dropping methamphetamine, the furan-indocyanine probe-functionalized sponge bases with concentrations of 0.05, 0.1, 0.5, 1.0, 2.0, 3.0, and 5.0 mmol / L all turned green; the colorimetric changes of the furan-indocyanine probe-functionalized sponge bases with concentrations of 0.05, 0.1, 0.5, 1.0, 2.0, 3.0, and 5.0 mmol / L before and after detecting amphetamine or methamphetamine were all relatively obvious, proving that the furan-indocyanine probe-functionalized sponge bases with concentrations of 0.05, 0.1, 0.5, 1.0, 2.0, 3.0, and 5.0 mmol / L were all effective in detecting amphetamine or methamphetamine.

[0064] Example 5

[0065] Time response of the furan-indocyanine probe-functionalized sponge base to amphetamine or methamphetamine:

[0066] Dissolve the furan-indocyanine probe obtained in step c of Example 1 in dichloromethane to prepare a solution with a concentration of 1 mmol / L, then soak the polyurethane sponge in this solution, and after complete soaking, take it out and dry it in an oven at a temperature of 40 °C to obtain the furan-indocyanine probe-functionalized sponge base; then drop 20 μL of amphetamine solution or methamphetamine solution with a concentration of 5 mmol / L onto the furan-indocyanine probe-functionalized sponge base respectively, and record the optical photos at times 0, 5, 10, 30, 60, 120, and 180 s respectively. As Figure 5 shown, after dropping amphetamine, the furan-indocyanine probe-functionalized sponge base changed from yellow to orange-red within 5 s and to bright red at 60 s; while after dropping methamphetamine, the furan-indocyanine probe-functionalized sponge base changed from yellow to yellow-green within 5 s and to gray-green at 60 s; at times 0, 5, 10, 30, 60, 120, and 180 s, the colorimetric changes of the furan-indocyanine probe-functionalized sponge base for detecting amphetamine or methamphetamine were all relatively obvious, proving that the furan-indocyanine probe-functionalized sponge base was effective in detecting amphetamine or methamphetamine at times 0, 5, 10, 30, 60, 120, and 180 s.

[0067] Example 6

[0068] Detection effect of the furan-indocyanine probe-functionalized sponge base on amphetamine or methamphetamine with concentrations of 0, 0.2, 0.4, 0.6, 0.8, 1.0, 2.0, 3.0, 4.0, and 5.0 mmol / L:

[0069] The furan-indene cyanide probe obtained in step c of Example 1 was dissolved in dichloromethane to prepare a solution with a concentration of 1 mmol / L. Then, the polyurethane sponge was immersed in this solution. After complete immersion, it was taken out and dried in an oven at a temperature of 40 °C to obtain a furan-indene cyanide probe-functionalized sponge substrate. Then, 20 μL of amphetamine solutions, methamphetamine solutions, or blank ethanol solutions with concentrations of 0.2, 0.4, 0.6, 0.8, 1.0, 2.0, 3.0, 4.0, and 5.0 mmol / L were respectively dropped onto the furan-indene cyanide probe-functionalized sponge substrate. After the reaction was complete, optical photos were recorded. As Figure 6 shown, as the concentration of the dropped amphetamine solution increased, the furan-indene cyanide probe-functionalized sponge substrate gradually changed from orange to red; and as the concentration of the dropped methamphetamine solution increased, the furan-indene cyanide probe-functionalized sponge substrate gradually changed from yellowish green to green. The colorimetric changes of the furan-indene cyanide probe-functionalized sponge substrate before and after detecting amphetamine or methamphetamine with concentrations of 0.2, 0.4, 0.6, 0.8, 1.0, 2.0, 3.0, 4.0, and 5.0 mmol / L were all relatively obvious, proving that the furan-indene cyanide probe-functionalized sponge substrate was effective in detecting amphetamine or methamphetamine with concentrations of 0.2, 0.4, 0.6, 0.8, 1.0, 2.0, 3.0, 4.0, and 5.0 mmol / L.

[0070] Example 7

[0071] Detection effects of the furan-indene cyanide probe-functionalized sponge substrate on amphetamine, methamphetamine, or other 16 interfering substances:

[0072] The furan-indene cyanide probe obtained in step c of Example 1 was dissolved in dichloromethane to prepare a solution with a concentration of 1 mmol / L. Then, the polyurethane sponge was immersed in this solution. After complete immersion, it was taken out and dried in an oven at a temperature of 40 °C to obtain a furan-indene cyanide probe-functionalized sponge substrate;

[0073] Using ethanol as the solvent, cocaine, ketamine, morphine, heroin, barbital, methadone, etomidate, γ-hydroxybutyric acid, N-(1-carbamoyl-2,2-dimethylpropyl)-1-(4-pentenyl)indazole-3-carboxamide (synthetic cannabinoid-0749), fentanyl common drugs, and aniline, sulfanilamide, L-glutamine, N-hydroxybenzamide, diphenylamine, or N-ethyl-N-hydroxyaniline other amines were used as interfering substances to prepare interfering substance ethanol solutions with corresponding concentrations of 0.5 mg / mL, as well as amphetamine and methamphetamine ethanol solutions;

[0074] Then, 20 μL of the prepared blank ethanol and ethanol solutions of amphetamine, methamphetamine, cocaine, ketamine, morphine, heroin, barbital, methadone, etomidate, γ-hydroxybutyric acid, N-(1-carbamoyl-2,2-dimethylpropyl)-1-(4-pentenyl)-1H-indazole-3-carboxamide (synthetic cannabinoid-0749), fentanyl, aniline, sulfanilamide, L-glutamine, N-hydroxybenzamide, diphenylamine or N-ethyl-N-hydroxyaniline with a concentration of 0.5 mg / mL were respectively dropped onto the furan-indocyanine probe-functionalized sponge substrate. After the reaction was complete, optical photos were recorded. As Figure 7 shown, after dropping amphetamine onto the furan-indocyanine probe-functionalized sponge substrate, the color changed from yellow to red, while after dropping methamphetamine, the color changed from yellow to green. The other drugs and amines dropped did not cause obvious colorimetric changes, indicating that the furan-indocyanine probe molecule has good specificity for amphetamine and methamphetamine.

[0075] Example 8

[0076] Detection effect of the furan-indocyanine probe-functionalized sponge substrate on mixtures of amphetamine and methamphetamine with concentration ratios of 0:5, 1:4, 2:3, 3:2, 4:1, and 5:0:

[0077] The furan-indocyanine probe obtained in step c of Example 1 was dissolved in dichloromethane to prepare a solution with a concentration of 1 mmol / L. Then, the polyurethane sponge was immersed in this solution. After complete immersion, it was taken out and dried in an oven at a temperature of 40 °C to obtain the furan-indocyanine probe-functionalized sponge substrate;

[0078] Using ethanol as the solvent and keeping the total concentration of amphetamine and methamphetamine at 2 mmol / L unchanged, ethanol solutions with concentration ratios of amphetamine to methamphetamine of 0:5, 1:4, 2:3, 3:2, 4:1, and 5:0 were prepared;

[0079] Then, the prepared ethanol solutions with various concentration ratios of amphetamine and methamphetamine were respectively dropped onto the furan-indocyanine probe-functionalized sponge substrate. After the reaction was complete, optical photos were recorded. As Figure 8 shown, as the proportion of amphetamine in the dropped mixture solution increased, the colorimetric response of the furan-indocyanine probe-functionalized sponge substrate gradually changed from green to red; for mixtures of amphetamine and methamphetamine with various ratios, the furan-indocyanine probe-functionalized sponge substrate could produce obvious colorimetric responses to them, proving that the furan-indocyanine probe-functionalized sponge substrate can achieve qualitative discrimination of mixtures of amphetamine and methamphetamine.

Claims

1. A method for colorimetric detection of amphetamine and methamphetamine in drugs based on furanyl probes, characterized in that: Follow these steps: Preparation of detection reagents: a. Weigh 1,3-indandione and furfural in a molar ratio of 1:1, place in a 100 mL three-necked flask, add 10 mL of H2O, and stir at room temperature for 24 h; after the reaction is completed, filter, collect the precipitated solid and wash it with ice water, then dissolve the precipitated solid in dichloromethane, extract it with saturated brine, dry the organic layer obtained by the extraction with anhydrous magnesium sulfate, filter and spin-dry to obtain a crude product, then dissolve the crude product in 500 mL of a mixed solution of dichloromethane and ethanol in a volume ratio of 1:9 for recrystallization, filter, and vacuum dry to obtain a yellow solid, which is the furan-indanone probe; b. Weigh 1,3-bis(dicyanomethylene)indane and furfural in a molar ratio of 1:1, place in a 100 mL three-necked flask, add 15 mL of acetic anhydride, control the reaction temperature to 80°C and stir for 3 h; after the reaction is completed and cooled to room temperature, recrystallize with ether, filter to obtain an orange solid, wash the obtained orange solid with 300 mL of ether and n-hexane in sequence, then dissolve the orange solid in dichloromethane, extract with saturated brine, dry the extracted organic layer with anhydrous magnesium sulfate, filter and spin-dry to obtain an orange solid, which is the furan-indane dicyano probe; c. Weigh 3-(dicyanomethylene)indone and furfural in a molar ratio of 1:1, place in a 100 mL three-necked flask, add 10 mL of ethanol, control the reaction temperature to 80°C and stir for 15 min; after the reaction is completed and cooled to room temperature, filter and collect the precipitated solid, wash the obtained solid with 300 mL of ether and n-hexane in turn, and then vacuum dry to obtain an orange solid, which is the furan-indene cyanide probe; d. Dissolve the furan-indanone, furan-indane dicyanide, and furan-indane cyanide probes obtained in steps a, b, and c in dichloromethane to prepare solutions with a concentration of 10 mmol / L, and then dilute them with ethanol to 0.5 mmol / L to obtain detection reagents, namely, furan-indanone probe solution, furan-indane dicyanide probe solution, and furan-indane cyanide probe solution; e. Dissolve the furan-indene cyanide probe obtained in step c in dichloromethane to prepare a solution with a concentration of 1 mmol / L, and then soak the polyurethane sponge in the solution. After the immersion is complete, take it out and place it in an oven to dry at 40° C. to obtain a sensing unit, i.e., a furan-indene cyanide probe functionalized sponge base; Furan-indone probe solution for detection of amphetamine and methamphetamine: f. Take 180 μL of the furan-indanone probe solution obtained in step d and place them in test tubes, add 20 μL of a 5 mmol / L amphetamine ethanol solution and 20 μL of a 5 mmol / L methamphetamine ethanol solution to the test tubes, observe the colorimetric changes before and after the reaction, and record the absorption spectrum and optical photographs; Detection of amphetamine and methamphetamine using furan-indane dicyandiamide probe solution: g. Take 180 μL of the furan-indane dicyanide probe solution obtained in step d and place them in test tubes, add 20 μL of a 5 mmol / L amphetamine ethanol solution and 20 μL of a 5 mmol / L methamphetamine ethanol solution to the test tubes, observe the colorimetric changes before and after the reaction, and record the absorption spectrum and optical photographs; Detection of amphetamine and methamphetamine using furan-indane cyanide probe solution: h. Take 180 μL of the furan-indene cyanide probe solution obtained in step d and place them in test tubes, add 20 μL of 5 mmol / L amphetamine ethanol solution and 20 μL of 5 mmol / L methamphetamine ethanol solution to the test tubes, observe the colorimetric changes before and after the reaction, and record the absorption spectrum and optical photographs; Detection of amphetamine and methamphetamine using furan-indene cyanide probe functionalized sponge: i. Take two sponge bases functionalized with furan-indene cyanide probes obtained in step e, and respectively pipette 20 μL of 5 mmol / L amphetamine ethanol solution and 20 μL of 5 mmol / L methamphetamine ethanol solution onto the sponge bases, and observe the colorimetric changes before and after the reaction; Detection of amphetamine and methamphetamine mixture using furan-indene cyanide probe functionalized sponge: j. Take the furan-indene cyanide probe functionalized sponge base obtained in step e, pipette 20 μL of a mixed solution of amphetamine and methamphetamine with a total concentration of 2 mmol / L and drop it onto the sponge base, and observe the colorimetric changes before and after the reaction.

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