CN102863725A - Preparations and applications of polymer probes for detecting copper ions on basis of naked eye visual colorimetry - Google Patents

Abstract

The invention discloses a polymer probe-P(NVP-co-GMA-g-H)(P1) for detecting copper ions in water on the basis of the naked eye visual colorimetry, a gel probe-P(NVP-co-bis-(GMA-g-H)(P2) for detecting copper ions in water on basis of the naked eye visual colorimetry, which is prepared by improving the P1, and a P2-based gel colorimetric sensor for detecting copper ions. The copper ion polymer probes are synthesized easily, the detection mechanism is based on the coordination reaction and the naked eye visual colorimetry is adopted to detect the copper ions in a solution to be detected. By adopting the probes, the high-sensitivity and high-selectivity rapid quantitative or semi-quantitative detection of trace copper ions in water can be realized. The synthetic routes of the probes are simple, the costs are low and the probes have great application prospect in the environmental protection field.

Description

A kind of preparation and application thereof that detects the polymer probe of cupric ion based on the bore hole visual colorimetry

Technical field

This patent has related to a kind of polymer probe---P (NVP-co-GMA-g-H) preparation and application thereof (P1) that detects cupric ion based on the bore hole visual colorimetry, be specifically related to polymer probe P1 and based on (P2) synthetic of the gel probe P (NVP-co-Bis-(GMA-g-H)) of P1 and the preparation and the application that detect the gel colorimetric sensor based on the cupric ion of P2, belong to analytical chemistry detection technique field.

Technical background

Copper is one of necessary trace element of human body, but the intoxicating phenomenons such as the copper intake too highly easily causes nausea, vomiting, Upper abdominal pain, acute haemolysis and uriniferous tubules distortion, threat to life when serious.Therefore, identifying especially to the selectivity of cupric ion, the real-time on-site of cupric ion detects all significant for medical science, biology and environmental science.

The copper detection method mainly contains in the water at present: flameless atomic absorption spectrometry; Co-precipitation-atomic absorption spectrophotometry, but these analysis means not only costliness but also loaded down with trivial details in actual applications, and usually need special laboratory apparatus.Therefore, develop a kind of simply, the copper ion sensor of rapid detection is imperative.

This patent adopts polymer probe and cupric ion effective mating reaction to occur so that the absorption spectrophotometric spectra absorbing wavelength of polymer probe changes, and has realized highly sensitive selectivity identification and detection to cupric ion in the water quality.It is simple, with low cost that the cupric ion of this patent detects the preparation of gel colorimetric sensor, can detect rapidly copper ion concentration by real-time on-site, and be easy to use of large-scale production, at field of Environment Protection huge application prospect arranged.

Patent content

This patent aims to provide a kind of polymer probe that detects cupric ion---and preparation method and the gel colorimetric sensor of P (NVP-co-GMA-g-H), the variation by the gel color can optionally detect the cupric ion in the water quality.

The cupric ion water-soluble polymers probe that this patent synthesized---the chemical structure of P (NVP-co-GMA-g-H) is

Synthetic line is as follows:

Take by weighing monomer GMA, NVP, initiator A IBN 70 ℃ of reactions 24 hours, uses petroleum ether precipitation three times after reaction finishes, and obtains polymer P (VP-co-GMA) white powder.Get P (VP-co-GMA) in the 50mL round-bottomed flask, add excess hydrazine hydrate, round-bottomed flask is placed the thermostatical oil bath, temperature arranges 70 ℃, reaction 4h, and petroleum ether precipitation obtains white powder P (NVP-co-GMA-g-H).

The synthetic line of the gel probe that this patent synthesized is as follows:

Take by weighing respectively monomer GMA, NVP, crosslinking agent B IS, initiator A PS, and SP; Weighed object is poured in 30 5mL centrifuge tubes after the deionized water for stirring dissolving; Centrifuge tube places the thermostatical oil bath, and temperature arranges 35 ℃, reaction 24h.Gel was given birth in taking-up after reaction was finished, and soaked with deionized water, regularly changed water and took out after one week, got product GMA and NVP gel copolymer P (VP-co-GMA-Bis).Get an amount of gel P (VP-co-GMA-Bis) in the 100mL round-bottomed flask, add excess hydrazine hydrate and deionized water, round-bottomed flask is placed the thermostatical oil bath, temperature arranges 70 ℃, takes out gel behind the reaction 4h, soaks with deionized water, regularly changes water.Take out when guaranteeing the noresidue hydrazine hydrate, make P (NVP-co-Bis-(GMA-g-H)), get final graft product.

The disclosed cupric ion polymer probe of this patent---P (NVP-co-GMA-g-H) can be used for preparing cupric ion and detects the gel colorimetric sensor.During application by can be quantitatively with the bore hole visual colorimetry or sxemiquantitative detect copper ion concentration.In order to obtain more accurately result, can adopt the ultraviolet-visible spectrophotometry to detect simultaneously.

This patent is compared with existing other detection meanss, has the following advantages:

1. the cupric ion polymer probe selectivity that relates to of this patent is good, and this probe only has developing response to cupric ion, and other common metal ion are (such as Fe ³⁺, Cu ²⁺, Mg ²⁺, Ca ²⁺, Mn ²⁺, Co ²⁺, Pb ²⁺, Al ³⁺, Cr ³⁺, K ⁺, Ba ²⁺, Zn ²⁺, Ni ²⁺Deng) do not cause interference;

2. the cupric ion polymer probe synthetic route that relates to of this patent is simple, post-processed convenient, cost is low, be fit to production application;

3. the cupric ion polymer probe response speed that relates to of this patent is very fast, highly sensitive;

The cupric ion that relates to of this patent detect gel this as oyster white, with overstrike or red-brown after the bivalent cupric ion coordination reaction, phenomenon is obvious, bore hole can be distinguished;

5. the cupric ion polymer probe that the present invention relates to is easy to use, can be directly used in the cupric ion that detects in the water sample, has avoided the traditional detection method need to be by the process of large-scale instrument or experiment in testing process;

6. it is easy to use that the cupric ion that relates to of this patent detects the gel colorimetric sensor, water insoluble, water body to be measured need not be taken a sample, and directly adds the gel colorimetric sensor and can detect cupric ion in the water body, sensor can take out after detecting, and has avoided the problem of the secondary pollution of traditional detection method.

Description of drawings

Fig. 1 is that polymers soln adds the ultraviolet spectrogram (testing curve) that the absorbancy of different concns cupric ion at the 420nm place changes among the embodiment.

Fig. 2 is that polymers soln adds the number that solution colour changes behind the different metal positively charged ion of same concentrations and shines among the embodiment.

Fig. 3 is that polymers soln adds the different metal positively charged ion of same concentrations at the ultraviolet spectrogram of the absorbancy variation at 420nm place among the embodiment.

Fig. 4 is that the gel colorimetric sensor adds that the number of colour-change shines behind the different metal positively charged ion of same concentrations among the embodiment.

Fig. 5 is that the gel colorimetric sensor adds that the number of colour-change shines behind the different concns cupric ion among the embodiment.

Fig. 6 is that the gel colorimetric sensor adds that the number of different time colour-change shines behind the same concentrations copper ion solution among the embodiment.

Embodiment

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

Embodiment:

(1) takes by weighing respectively monomer GMA2.8g, NVP 11.2g (GMA and NVP1: 5 reactions, NVP1mol wherein, GMA0.2mol), initiator A IBN 0.5%, 70 ℃ of reactions 24 hours, after finishing, reaction uses petroleum ether precipitation three times, obtain polymer P (VP-co-GMA) white powder 12.7g.Get in 8g P (VP-co-GMA) and the 50mL round-bottomed flask, add excess hydrazine hydrate, round-bottomed flask is placed the thermostatical oil bath, temperature arranges 70 ℃, reaction 4h, and petroleum ether precipitation obtains white powder P (NVP-co-GMA-g-H).

(2) get the polymers soln that institute's polymer probe that closes dissolving preparation in (1) becomes 5mg/mL, adding Cu ²⁺Concentration is respectively 0,10,20,30,60,70,80,90,100,110 μ M.Measure its variation at the ultraviolet absorptivity at 420nm place (Fig. 1), this UV spectrum is as cupric ion testing curve.

(3) pipette respectively polymers soln described in 14 parts of 3ml steps (2), add the different ions (Fe of same concentrations ³⁺, Cu ²⁺, Mg ²⁺, Ca ²⁺, Mn ²⁺, Co ²⁺, Pb ²⁺, Al ³⁺, Cr ³⁺, K ⁺, Ba ²⁺, Zn ²⁺, Ni ²⁺) solution, institute adds the identical of copper ion solution in volume and (2), and final solution colour-change result is (wherein first is blank assay, reacts with deionized water) as shown in Figure 2, and 420nm place ultraviolet absorptivity changes as shown in Figure 3.

(4) take by weighing respectively monomer GMA28.4829g, (GMA and NVP mol ratio are reaction in 1: 5 to NVP 111.2783g, NVP 1mol wherein, GMA 0.2mol), linking agent 1% (massfraction) BIS 13.9974g, initiator 0.5% (molar fraction) APS 1.3694g, and 0.5% (molar fraction) SP 1.1423g; Weighed object is poured in 30 5mL centrifuge tubes after the dissolving of 150mL deionized water for stirring; Centrifuge tube places the thermostatical oil bath, and temperature arranges 35 ℃, reaction 24h.Gel was given birth in taking-up after reaction was finished, and soaked with deionized water, regularly changed water and took out after one week, got product GMA and NVP gel copolymer P (VP-co-GMA-Bis).Get an amount of gel P (VP-co-GMA-Bis) in the 100mL round-bottomed flask, add excess hydrazine hydrate and 50mL deionized water, round-bottomed flask is placed the thermostatical oil bath, temperature arranges 70 ℃, takes out gel behind the reaction 4h, soaks with deionized water, regularly changes water.Take out when guaranteeing the noresidue hydrazine hydrate, make P (NVP-co-Bis-(GMA-g-H)), get final graft product.

(5) the circle thickness sheet such as P (NVP-co-Bis-(GMA-g-H)) hydrogel is cut into, respectively with 1 * 10 ^-3The different metal ion of M: Fe ³⁺, Cu ²⁺, Mg ²⁺, Ca ²⁺, Mn ²⁺, Co ²⁺, Pb ²⁺, Al ³⁺, Cr ³⁺, K ⁺, Ba ²⁺, Zn ²⁺, Ni ²⁺The result as shown in Figure 4 to react at normal temperatures 5min (wherein first is blank assay, with the deionized water reaction).

(6) pipette respectively described in 4 parts of steps (5) and to wait circle thickness sheet, add respectively the identical and concentration of volume and be followed successively by (a) 0 * 10 ^-4M; (b) 1 * 10 ^-4M; (c) 1 * 10 ^-3M; (d) 1 * 10 ^-2The copper ion solution of M.Gel slice colour-change result is (wherein first is blank assay) as shown in Figure 5.

(7) pipette respectively described in 3 parts of steps (5) and to wait circle thickness sheet, adding the identical and concentration of volume all is 1 * 10 ^-3In the copper ion solution of M, react respectively 0min, 5min, 60min, the result is as shown in Figure 6.

Above-described embodiment is used for this patent of explaining, rather than this patent is limited, and in the protection domain of the spirit of this patent and claim, to any modification and the change that this patent is made, all falls into the protection domain of this patent.

Claims (8)

1. polymer probe---P (NVP-co-GMA-g-H) who detects cupric ion based on the bore hole visual colorimetry, its structural formula is as follows:

2. polymer probe---P (NVP-co-GMA-g-H) who detects cupric ion based on the bore hole visual colorimetry, its preparation method is as follows: get monomer GMA, NVP, initiator A IBN, 70 ℃ of reactions 24 hours, use petroleum ether precipitation three times after reaction finishes, obtain polymer P (VP-co-GMA) white powder.Add excess hydrazine hydrate at P (VP-co-GMA), 70 ℃ of isothermal reaction 4h, petroleum ether precipitation obtain polymer P (NVP-co-GMA-g-H).

3. gel probe---P (NVP-co-Bis-(GMA-g-H)) who detects cupric ion based on the bore hole visual colorimetry, its preparation method is as follows: take by weighing monomer GMA, NVP, crosslinking agent B IS, initiator A PS and SP; Stirring and dissolving, 35 ℃ of constant temperature oil bath 24h.Gel was given birth in taking-up after reaction was finished, and washed a week, got product GMA and NVP gel copolymer P (VP-co-GMA-Bis).In gel P (VP-co-GMA-Bis), add excess hydrazine hydrate and deionized water, take out gel behind 70 ℃ of constant temperature oil bath 4h, take out when being washed to the noresidue hydrazine hydrate, make P (NVP-co-Bis-(GMA-g-H)).

4. the reagent proportioning described in according to claim 3, wherein GMA and NVP mol ratio are 1: 5, and linking agent is 1% (massfraction) BIS, and initiator is 0.5% (molar fraction) APS and 0.5% (molar fraction) SP.

According to claim 4 described in method, it is characterized in that: the identification of cupric ion is to realize according to direct viewing gel colour-change and the variation of indirectly measuring wavelength 420nm place absorbancy by the ultraviolet-visible absorption spectrophotometer with detecting.

6. gel colorimetric sensor that detects cupric ion based on the bore hole visual colorimetry is that P (NVP-co-GMA-g-H) polymer probe is made gel and cut into slices with prior art by method in the claim 3 and form for the basis in the claim 1; The structural formula of wherein said P (NVP-co-GMA-g-H) is as follows:

7. the method described in according to claim 6, the detection that it is characterized in that cupric ion and identification are that the colour-change by the gel colorimetric sensor realizes.

8. one kind is detected the polymer probe of cupric ion in the water quality and relevant gel colorimetric sensor based on the bore hole visual colorimetry, it is characterized in that only bivalent cupric ion being had developing response, change brown or red-brown into by oyster white, and be obvious color range graded with bivalent cupric ion (in the detectability) the colour developing situation of different concns.

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