CN102967596A - Detection of preparation of manganese ions probe based on naked eye visual colorimetry and application - Google Patents

Abstract

The invention discloses a probe-N,N-bis(4-diethylaminosalicylidene)ethylenediamine and a probe based on the naked-eye visual colorimetry for detecting manganese ions in water quality. Manganese ion detection kits and test strips. The manganese ion probe can be synthesized by one-step reaction, the detection mechanism is based on coordination reaction, and the manganese ion in the liquid to be tested can be detected by naked-eye visual colorimetry. The manganese ion detection kit provided by the present invention contains a reagent stock solution 1 and a reagent stock solution 2 . Wherein, reagent stock solution 1 is HEPES buffer solution; reagent stock solution 2 is a solution of N,N-bis(4-diethylaminosalicylidene)ethylenediamine. The manganese ion detection test paper provided by the invention is composed of N,N-bis(4-diethylaminosalicylidene)ethylenediamine and a solid carrier. The invention can realize rapid quantitative or semi-quantitative detection of trace manganese ions in water quality with high sensitivity and high selectivity. The probe of the invention has a simple synthetic route and low cost, and has great application prospects in the field of environmental protection.

Description

Preparation and application of a probe for detecting manganese ions based on naked-eye visual colorimetry

technical field

The present invention relates to the preparation and application of a probe for detecting manganese ions based on naked-eye visual colorimetry, in particular to the synthesis of N,N-bis(4-diethylaminosalicylidene)ethylenediamine The preparation and application of a manganese ion detection kit and test paper based on the probe belong to the technical field of analytical chemistry detection.

technical background

Manganese is one of the essential trace elements for the human body, but excessive intake of manganese can easily cause manganese poisoning. Especially in fields such as electric welding, mining, and dry battery production, it is easy to inhale manganese for a long time and cause chronic manganese poisoning. Manganese poisoning has the manifestations of neurasthenia syndrome such as dizziness, headache, easy fatigue, sleep disturbance and forgetfulness, as well as symptoms such as limb pain, weakness and heaviness of lower limbs. In severe cases, it is prone to emotional instability and significant mental and emotional changes, such as apathy, unresponsiveness, involuntary crying and laughing, obsessive-compulsive ideas, impulsive behavior and other neurological disorders. Therefore, the selective recognition of manganese ions, especially the real-time on-line detection of manganese ions, is of great significance to medicine, biology and environmental science.

At present, the detection methods of manganese in water mainly include: flameless atomic absorption spectrophotometry; formaldehyde oxime spectrophotometry; coprecipitation-flame atomic absorption spectrophotometry. However, these analytical methods are expensive and cumbersome in practical application, and often require special experimental instruments. Therefore, it is imperative to develop a simple, fast and real-time field detection manganese ion sensor.

The invention adopts the effective cooperation between the probe and the manganese ions to change the absorption wavelength of the probe's absorption spectroscopic spectrum, and realizes the highly sensitive selective identification and detection of the manganese ions in the water quality. The manganese ion detection test paper of the present invention is simple to prepare, low in cost, can detect the manganese ion concentration rapidly on the spot in real time, is easy to produce and use on a large scale, and has great application prospects in the field of environmental protection.

Contents of the invention

The present invention aims to provide a kind of manganese ion detection probe——N, N-bis(4-diethylamino salicylidene) ethylenediamine preparation method and application thereof, which can be selectively detected by changing the color Manganese ions in water quality were detected. The present invention further provides a manganese ion detection kit and a manganese ion detection test paper based on the detection probe.

The synthetic manganese ion water-soluble probe of the present invention---N, the chemical structure of N-two (4-diethylamino salicylidene) ethylenediamine is

The synthetic route is as follows:

Add the ethanol solution of ethylenediamine dropwise into the ethanol solution of 4-diethylamino salicylaldehyde, stir at room temperature for 15 minutes and then reflux for 1 hour. The solvent was removed and recrystallized from ethanol to obtain N,N-bis(4-diethylaminosalicylidene)ethylenediamine product.

The manganese ion probe disclosed by the present invention—N, N-bis(4-diethylaminosalicylidene)ethylenediamine can be used to prepare a manganese ion detection kit, and the kit includes reagent stock solution 1 And reagent stock solution 2, wherein reagent stock solution 1 is HEPES buffer solution, buffer solution pH value is 7.5-10, the solvent of buffer solution is deionized water; Reagent stock solution 2 is manganese ion probe——N, N-double The solution of (4-diethylaminosalicylidene)ethylenediamine has a concentration of (10-100)×10 ^-6 M, and its solvent is deionized water or absolute ethanol. During application, the concentration of manganese ions can be detected quantitatively or semi-quantitatively by visual colorimetry with naked eyes. At the same time, in order to obtain more accurate results, UV-visible spectrophotometry can be used for detection.

The manganese ion probe disclosed by the invention—N,N-bis(4-diethylaminosalicylidene)ethylenediamine can be used to prepare test paper for detecting manganese ions. The test paper is composed of N,N-bis(4-diethylaminosalicylidene)ethylenediamine and a solid carrier. The solution of N,N-bis(4-diethylaminosalicylidene)ethylenediamine (solvent can be deionized water or absolute ethanol) is directly coated on the surface of the substrate by soaking to prepare Test strips. During detection, the detection of manganese ions is achieved by directly inserting the test paper into the liquid to be tested, and observing the color change, and the concentration of manganese ions can be detected semi-quantitatively according to the color change results of the test paper.

The solid carrier used in the present invention can be qualitative filter paper, A4 paper, non-woven fabric, polymer film, cellulose film or starch film.

Compared with other existing detection methods, the present invention has the following advantages:

1. The manganese ion probe involved in the present invention has good selectivity, and the probe only has a color response to manganese ions, and other common metal ions (such as lead, cadmium, mercury, copper, etc.) do not cause interference;

2. The manganese ion probe involved in the present invention has a simple synthesis route, convenient post-processing, low cost, and is suitable for actual production and application;

3. The manganese ion probe involved in the present invention has a fast response speed, can change color within 1 minute, and has high sensitivity;

4. The manganese ion detection test paper involved in the present invention has a slightly light yellow color, and turns brown or brown-red after the coordination reaction with divalent manganese ions, which is obvious and can be distinguished with the naked eye.

5. The manganese ion probe involved in the present invention is easy to use and can be directly used to detect manganese ions in water samples, avoiding the need for large-scale instruments or experiments in the detection process of traditional detection methods, and the lower limit of determination can reach 1×10 ^-6 M;

Description of drawings

Fig. 1 is the ultraviolet spectrogram (detection working curve) of the absorbance change at 535nm place of adding different concentrations of manganese ions to the stock solution in the embodiment.

Figure 2 is a digital photo of the color change of the solution after adding different concentrations of manganese ions to the stock solution in the embodiment.

Fig. 3 is the ultraviolet spectrogram of the absorbance change at 535 nm when different metal cations are added to the stock solution in the embodiment.

Figure 4 is a digital photograph of the color change of the solution after adding different metal cations to the stock solution in the embodiment.

Detailed ways

The present invention will be further described below in conjunction with embodiment, but the present invention is not limited thereto.

Example:

(1) Add dropwise the ethanol solution (100ml) of 1.2g ethylenediamine to 7.73g while stirring, in the absolute ethanol solution (80ml) of 4-diethylamino salicylaldehyde, reflux after stirring at room temperature for 15 minutes Hour. The solvent was removed, and recrystallized from ethanol three times to obtain N,N-bis(4-diethylaminosalicylidene)ethylenediamine product.

(2) Dissolve the probes in (1) in HEPES buffer solution with a pH of 8, prepare a solution with a concentration of 20×10 ^-6 M, and use it as a stock solution. Take 15 parts of the stock solution with a volume of 3ml, add an equal volume to them respectively, and the concentrations are (1) 1×10 ^-6 M; (2) 2×10 ^-6 M; (3) 3×10 ^-6 M (4)4×10 ^-6 M; (5)5×10 ^-6 M; (6)6×10 ^-6 M; (7)7×10 ^-6 M; (8)8×10 ^-6 M (9)9×10 ^-6 M; (10)10×10 ^-6 M; (11)11×10 ^-6 M; (12)12×10 ^-6 M; (13)13×10 ^-6 M ; (14) 14×10 ^-6 M; (15) 15×10 ^-6 M; (16) 0×10 ^-6 M manganese ion solution. The change of its ultraviolet absorbance at 535nm was measured (Figure 1), and the ultraviolet spectrum was used as a manganese ion detection working curve.

(3) Taking the detection working curve prepared in (2) as a reference, take 3ml of the stock solution in (2), and add the sample to be tested (the volume is the same as that of the manganese ion solution added in (2)) in the stock solution , Measure the intensity of the absorption spectrum at 535nm, and calculate the content of divalent manganese ions from the detection working curve. The lower detection limit of manganese ions is 1×10 ^-6 M and the upper detection limit is 10×10 ^-6 M

(4) Pipette 4 parts of 3ml of the stock solution described in step (2) respectively, add the same volume as that of the manganese ion solution added in (2) and the concentrations are (a) 1×10 ^-6 M; (b) )5×10 ^-6 M; (c) 1×10 ^-6 M; (d) 0×10 ^-6 M manganese ion solution. The color change results of the stock solution are shown in Figure 2, and manganese ions were successfully detected.

(5) Pipette 15 parts of the 3ml stock solution described in step (2) respectively, and add Fe ³⁺ , Cu ²⁺ , Al ³⁺ , Mn ²⁺ , Co ²⁺ , Ag ⁺ , Ba ²⁺ , Ca ²⁺ , Cd ²⁺ , Zn ²⁺ , Hg ²⁺ , Cr ³⁺ , Mg ²⁺ , Pb ²⁺ and Ni ²⁺ solutions, the concentration of the added metal ion solution is 1×10 ^-6 M, the same volume as that of the manganese ion solution added in (2). The color change results of the final stock solution are shown in Figure 4, and the UV absorbance changes at 535nm are shown in Figure 3.

(6) Take the stock solution described in step (2), soak the qualitative filter paper therein, cut it into long strips after drying, and obtain the manganese ion detection test paper. The prepared manganese ion detection test paper was respectively immersed in the concentrations of (a) 1×10 ^-6 M; (b) 1×10 ^-5 M; (c) 1×10 ^-4 M; (d) 1×10 ^{- 3} M; (e) 0×10 ^-6 M manganese ion solution for 30 seconds, take it out. Test paper can detect manganese ions in water very well.

The above-mentioned embodiments are used to illustrate the present invention, rather than to limit the present invention. Within the spirit of the present invention and the protection scope of the claims, any modification and change made to the present invention will fall into the protection scope of the present invention.

Claims (10)

1. one kind is detected the probe of manganese ion based on the bore hole visual colorimetry, and its structural formula is as follows:

Its called after N, two (4-diethylin salicylidene) the inferior ethylenediamines of N-.

2. probe---N who detects manganese ion based on the bore hole visual colorimetry, the inferior ethylenediamine of N-(4-diethylin salicylidene), its preparation method is as follows: the ethanolic solution of ethylenediamine is added drop-wise in the ethanolic solution of 4-diethylin salicylide, and stirring at room refluxed 1 hour after 15 minutes.Remove solvent, use ethyl alcohol recrystallization, obtain N, two (4-diethylin salicylidene) the inferior ethylenediamine products of N-.

3. one kind is detected the kit of manganese ion based on the bore hole visual colorimetry, comprises:

Reagent storing solution 1:HEPES damping fluid;

Reagent storing solution 2:N, the solution of two (4-diethylin salicylidene) the inferior ethylenediamines of N-.

4. the kit described in according to claim 3, its reagent storing solution 1 is the HEPES damping fluid, and pH value is 7.5-10, and the solvent of damping fluid is deionized water; The concentration of reagent storing solution 2 is (10-100) * 10 ^-6M, its solvent are deionized water or absolute ethyl alcohol.

According to claim 4 described in method, it is characterized in that: the identification of manganese ion is to realize according to the variation of observing directly that solution colour changes and indirectly measure wavelength 535nm place absorbance by the ultraviolet-visible absorption spectrophotometer with detecting.

6. one kind is detected the Test paper of manganese ion based on the bore hole visual colorimetry, is by N in the claim 1, and two (4-diethylin salicylidene) the inferior ethylenediamine wiring solution-formings of N-are coated on solid carrier surface in the mode of direct immersion and form; Wherein said N, the structural formula of two (4-diethylin salicylidene) the inferior ethylenediamines of N-is as follows:

7. according to claim 6, N, the concentration of two (4-diethylin salicylidene) the inferior ethylenediamine solutions of N-is (10-100) * 10 ^-6M, solvent are deionized water or absolute ethyl alcohol.

8. described method according to claim 6, solid carrier can be qualitative filter paper, A4 paper, nonwoven fabrics, thin polymer film, cellulose membrane or starch film.

9. the method described in according to claim 6, the detection that it is characterized in that manganese ion and identification are that the change color by test paper realizes.

10. one kind is detected the probe of manganese ion in the water quality and relevant detection kit and test paper based on the bore hole visual colorimetry, it is characterized in that only divalent manganesetion being had developing response, change into brown or brownish red by colourless or faint yellow, and be obvious color range graded with divalent manganesetion (in the detectability) the colour developing situation of variable concentrations.

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