CN116217438A - Molecular sensor with three switching responses of on and off for alkaline environment and application - Google Patents

Molecular sensor with three switching responses of on and off for alkaline environment and application Download PDF

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CN116217438A
CN116217438A CN202310126913.7A CN202310126913A CN116217438A CN 116217438 A CN116217438 A CN 116217438A CN 202310126913 A CN202310126913 A CN 202310126913A CN 116217438 A CN116217438 A CN 116217438A
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molecular sensor
alkaline environment
molecular
maleonitrile
dihydroxybenzene
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李春辉
陈玉婷
王晓倩
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Dezhou University
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Abstract

The invention provides an on-off three-conversion response molecular sensor for an alkaline environment and application thereof, belonging to the technical field of detection of organic functional materials. The invention discloses a dihydroxybenzene-maleonitrile molecular sensor, which is prepared by taking diaminomaleonitrile and 2, 4-dihydroxybenzaldehyde as reaction raw materials through one-step polymerization reaction. Because the molecular sensor acceptor unit contains two types of deprotonated hydroxyl sites and electron-withdrawing cyano groups, the molecular sensor acceptor unit shows fluorescence on-off-on-off three-conversion detection signals for alkaline environment, has high sensitivity and good selectivity, and has important application value; the preparation method has the advantages of low cost, simple preparation process and the like, is suitable for industrial popularization, and creates favorable conditions for popularization and application of the dihydroxybenzene-maleonitrile molecular sensor.

Description

Molecular sensor with three switching responses of on and off for alkaline environment and application
Technical Field
The invention relates to the technical field of detection of organic functional materials, in particular to a dihydroxybenzene-maleonitrile molecular sensor with sensitive fluorescence on-off-on-off three-conversion response to alkaline environment change and application thereof.
Background
At present, a pH meter or pH test paper is adopted for pH detection, and the accuracy of the pH meter or pH test paper on the change of an acid-base environment is slightly lower. The fluorescent molecular sensor realizes qualitative and visual detection of the object to be detected on the molecular level, has accurate and rapid result, and becomes an important method for detecting pH change in various fields. Based on different detection requirements, numerous pH fluorescence molecular sensors with different functions have been prepared. However, most of the fluorescence detection signals of the pH molecular sensors reported at present are single-direction change, namely, along with the change of acid/alkaline environment, fluorescence is single conversion signals of 'off-on' or 'on-off'; the molecular sensor with the fluorescence signal having 'off-on' multi-conversion response along with the change of the acid-base environment of the solution has fewer reports, and particularly has fewer three-conversion 'on-off' responses which are sensitive along with the enhancement of the fluorescence signal in the alkaline environment; and the demand for sensitive detection of alkaline pH dynamic changes in industrial production is increasing.
The diaminomaleonitrile contains an amino electron donating group and a cyano electron withdrawing group, and is a common intramolecular charge transfer sensor construction unit; the imine-C=N-group generated by the condensation of the amino group and the aldehyde not only has stronger proton complexing capability, but also can increase the conjugation of fluorescent molecules by the p-pi conjugation after being connected with the fluorescent group, and can induce sensitive spectral signal change. A series of fluorescent molecular sensors with different detection properties were developed by chemical modification of the maleonitrile group [ A.B. Rani, S. Swami, A. Agarwala, D. Behera,and R. Shrivastava, RSC Adv., 2019, 9, 30599-30614]. However, a molecular sensor constructed by a maleonitrile unit and having a sensitive fluorescent "on-off-on-off" three-transition detection response to an alkaline environment has not been reported yet.
Disclosure of Invention
The technical aim of the invention is to provide a molecular sensor which has sensitive fluorescence 'on-off-on-off' three-conversion detection response to alkaline environment and is easy to prepare.
The invention further aims to provide a method capable of dynamically detecting the pH value of the alkaline environment in the industrial production process, and the method has the advantages of being quick, sensitive, simple and the like.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a dihydroxybenzene-maleonitrile molecular sensor with fluorescence 'on-off-on-off' three-conversion detection response to alkaline environment has the molecular structure as follows:
Figure SMS_1
a dihydroxybenzene-maleonitrile molecular sensor with fluorescence 'on-off-on-off' three-conversion detection response to alkaline environment is prepared by the following steps:
at N 2 Under the protection condition, sequentially placing alpha mmol of 2, 4-dihydroxybenzaldehyde and beta mmol of diaminomaleonitrile into a round-bottom flask containing gamma mL of absolute ethyl alcohol, adding delta [ mu ] L of glacial acetic acid, heating to 75 ℃, and continuing to react for 4-6 hours; filtering the mixture obtained by the reaction, washing with absolute ethyl alcohol for three times, and drying to obtain a reddish brown dihydroxybenzene-maleonitrile molecular sensor; alpha, beta, gamma and delta are 2:1:20:100.
The dihydroxybenzene-maleonitrile sensor is prepared by the following reaction formula:
Figure SMS_2
the invention has the following technical effects: the dihydroxybenzene-maleonitrile molecular sensor acceptor unit contains two types of four hydroxyl deprotonation sites, and enol tautomerism balance exists between ortho-phenolic hydroxyl and imino; with the continuous enhancement of the alkaline environment of the solution, the maximum fluorescence emission of the molecule shows three-step change: with the increase of the added sodium oxide, the maximum fluorescence emission of the molecular sensor is blue-shifted to 547 nm and reduced at 627 nm, then red-shifted to 649 nm and obviously enhanced, and finally the intensity of the fluorescence emission position is unchanged and obviously reduced, so that a sensitive 'on-off-on-off' three-conversion fluorescence detection signal is presented for alkaline environment change, and the molecular sensor has higher application value; the dihydroxybenzene-maleonitrile molecular sensor provided by the invention has the advantages of high yield, low cost, mild preparation condition, simple preparation process and the like, is suitable for industrial implementation, and creates favorable conditions for popularization and application in the industrial field.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of the compound obtained in examples 1 to 3.
FIG. 2 shows fluorescence emission spectra of dihydroxybenzene-maleonitrile molecular sensors after adding NaOH of different concentrations to 90% DMSO distilled water solution.
FIG. 3 shows fluorescence emission spectra of dihydroxybenzene-maleonitrile molecular sensors after adding NaOH of different concentrations to 90% DMSO tap water solution.
Detailed Description
The invention discloses a dihydroxybenzene-maleonitrile molecular sensor with fluorescence on-off-on-off three-conversion detection response to alkaline environment, which has the molecular structure as follows:
Figure SMS_3
；
the preparation method can be prepared by taking diaminomaleonitrile and 2, 4-dihydroxybenzaldehyde as reaction raw materials through one-step polymerization reaction, and the preparation reaction formula is as follows:
Figure SMS_4
。
example 1
At N 2 Under the protection condition, sequentially placing 2 mmol of 2, 4-dihydroxybenzaldehyde and 1 mmol of diaminomaleonitrile into a round-bottomed flask containing 20 mL absolute ethyl alcohol, adding 100 mu L of glacial acetic acid, heating to 75 ℃, and continuing to react for 4 hours; filtering the mixture obtained by the reaction, washing with absolute ethanol for three times, and drying to obtain a reddish brown powdery compound A,1706, mg, yield 49%.
Example 2
At N 2 Under the protection condition, sequentially placing 2 mmol of 2, 4-dihydroxybenzaldehyde and 1 mmol of diaminomaleonitrile into a round-bottomed flask containing 20 mL absolute ethyl alcohol, adding 100 mu L of glacial acetic acid, heating to 75 ℃, and continuing to react for 6 hours; the reaction mixture was filtered, washed with absolute ethanol three times and dried to give compound B as a reddish brown powder, 177.5. 177.5 mg, in 51% yield.
Example 3
At N 2 Under the protection condition, sequentially placing 2 mmol of 2, 4-dihydroxybenzaldehyde and 1 mmol of diaminomaleonitrile into a round bottom flask containing 20 mL absolute ethyl alcohol, heating to 75 ℃, and continuously reacting for 4 hours; the reaction mixture was filtered, washed with absolute ethanol three times and dried to give compound C as a reddish brown powder, 139.2. 139.2 mg, in 40% yield.
The nuclear magnetic resonance hydrogen spectra of the compounds A, B and C obtained in examples 1 to 3 were analyzed and measured to be identical, and the data were as follows: at the position of 1 H NMR (CDCl 3 400 MHz), comprising 4 OH proton signal peaks: 12.24 (s, 2H), 10.85 (s, 2H); proton signal peak on 2 c=n-carbon atoms: 8.80 (s, 2H); 6 aromatic ring proton signal peaks: 7.74 (d, 2H), 6.48 (m, 2H), 6.40 (d, 2H), which is substantially in accordance with the theoretical values of the dihydroxybenzene-maleonitrile compound. From this, it was confirmed that the molecular structure of compound A, B and C was:
Figure SMS_5
i.e. dihydroxybenzaldehyde-maleonitrile molecules.
Example 4
Fluorescence detection performance of dihydroxybenzene-maleonitrile molecular sensor on NaOH with different concentrations in 90% DMSO distilled water solution: at a concentration of 2X 10 -5 NaOH with different concentrations is respectively added into 90% DMSO distilled water solution of dihydroxybenzene-maleonitrile compound with mol/L, and the molar equivalent ratio of the NaOH to the distilled water solution is respectively 1:0, 1:0.2, 1:0.4, 1:0.6, 1:0.8, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:15, 1:20, 1:25, 1:30, 1:35, 1:40 and 1:50. 1:60, 1:70, 1:80, 1:90, 1:100, 1:200, 1:300, 1:400, 1:500, and after 3 minutes of mixing, spectroscopy testing was performed. Detailed fluorescence emission spectroscopy property studies indicate that: as the amount of NaOH material in the solution increases from 0→0.6→10→500 times, the maximum emission of the molecular sensor first disappears at 627 nm, while the 547 nm emission increases slightly; the maximum emission of 547 nm then red shifted to 649 nm, 29.7 fold enhancement; it then showed a 5.6-fold decrease in emission at 649 nm without a change in emission peak position, indicating that the dihydroxybenzene-maleonitrile molecular sensor has the sensitive "on-off-on-off three-switch fluorescence signal detection potential for alkaline environments in 90% dmso distilled water.
Example 5
Fluorescence detection performance of dihydroxybenzene-maleonitrile molecular sensor on NaOH with different concentrations in 90% DMSO tap water solution: at a concentration of 2X 10 -5 NaOH with different concentrations is respectively added into 90% DMSO tap water solution of a mol/L dihydroxybenzene-maleonitrile compound, the molar equivalent ratio of the NaOH to the dihydroxybenzene-maleonitrile compound is respectively 1:0, 1:0.2, 1:0.4, 1:0.6, 1:0.8, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:15, 1:20, 1:25, 1:30, 1:35, 1:40, 1:50, 1:60, 1:70, 1:80, 1:90, 1:100, 1:200, 1:300, 1:400 and 1:500, and the mixture is subjected to spectroscopic test after 2 hours of mixing. Detailed fluorescence emission spectroscopy property studies indicate that: as the amount of NaOH substances in the solution is continuously increased, the maximum emission of the molecular sensor is blue-shifted and reduced at 627 nm, the fluorescence emission is red-shifted and obviously enhanced, and finally the emission is reduced, consistent with the change trend of the spectroscopy after the molecular sensor is mixed with the distilled water solution of 90% DMSO for 3 minutes, the molecular sensor has rapid three-conversion fluorescence detection potential of 'on-off-on-off' in the 90% DMSO tap water solution.
Example 6
Dihydroxybenzene-maleonitrile molecular sensor is prepared into distilled water solution with concentration of 2 multiplied by 10 in 90 percent DMSO -5 The spectroscopic properties of the mol/L solution were unchanged after two hours of rest.

Claims (3)

1. A molecular sensor with on-off three-conversion response to alkaline environment has the molecular structure as follows:
Figure QLYQS_1
。
2. a method of preparing a molecular sensor having an on-off three-switch response to an alkaline environment as claimed in claim 1, comprising the steps of:
at N 2 Under the protection condition, sequentially placing alpha mmol of 2, 4-dihydroxybenzaldehyde and beta mmol of diaminomaleonitrile into a round-bottom flask containing gamma mL of absolute ethyl alcohol, adding delta [ mu ] L of glacial acetic acid, heating to 75 ℃, and continuing to react for 4-6 hours; filtering the mixture obtained by the reaction, washing with absolute ethyl alcohol for three times, and drying to obtain a reddish brown dihydroxybenzene-maleonitrile molecular sensor; alpha, beta, gamma and delta are 2:1:20:100.
3. A molecular sensor application in which the maximum fluorescence emission signal of the molecular sensor is changed in three steps with increasing alkaline environment of the solution, wherein the molecular sensor has an on-off three-switching response to alkaline environment as claimed in claim 1: the maximum fluorescence emission is firstly reduced in blue shift, then is increased in red shift and is obviously enhanced, and finally the intensity of the fluorescence emission position is unchanged and is obviously reduced, so that the device presents sensitive on-off-on-off three-conversion fluorescence detection signals for different alkaline water environment changes, and has the performance of dynamically detecting the pH value of an alkaline environment.
CN202310126913.7A 2023-01-07 2023-02-15 Molecular sensor with three switching responses of on and off for alkaline environment and application Pending CN116217438A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117024308A (en) * 2023-10-10 2023-11-10 德州学院 Molecular probe with four-detection function and preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117024308A (en) * 2023-10-10 2023-11-10 德州学院 Molecular probe with four-detection function and preparation method and application thereof
CN117024308B (en) * 2023-10-10 2023-12-08 德州学院 Molecular probe with four-detection function and preparation method and application thereof

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