CN111499773A - Functional polymer material with functions of specific recognition and rapid chromium ion detection, and preparation and application thereof - Google Patents
Functional polymer material with functions of specific recognition and rapid chromium ion detection, and preparation and application thereof Download PDFInfo
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- CN111499773A CN111499773A CN202010320165.2A CN202010320165A CN111499773A CN 111499773 A CN111499773 A CN 111499773A CN 202010320165 A CN202010320165 A CN 202010320165A CN 111499773 A CN111499773 A CN 111499773A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
Abstract
The invention discloses a functional polymer material with the functions of specific recognition and rapid chromium ion detection, and preparation and application thereof. The functional polymer material with the functions of specific identification and rapid chromium ion detection is obtained by performing carboxyl and sulfhydrylation on the aldehyde chitosan. The functional polymer material and heavy metal chromium ions can form a complex with a stable structure, so that the chromium ions can be accurately and quickly detected. Compared with the traditional detection equipment, the material has high sensitivity and good selectivity, does not need to adopt expensive and complex-operation precise instruments, can realize the on-site detection and the division of the pollution degree only by using a detection reagent, has observable detection result, simple and convenient operation and low cost, and has no toxic or side effect on the used reagent and the operation process.
Description
Technical Field
The invention belongs to the technical field of detection, and particularly relates to a functional polymer material with functions of specific identification and rapid chromium ion detection, and preparation and application thereof.
Background
Heavy metals involved in environmental pollution are generally referred to as having a density of greater than 5.0g/cm3And the metals with obvious biotoxicity mainly comprise heavy metals such as cadmium, mercury, arsenic, copper, lead, zinc, chromium, nickel and the like. With the rapid development of industrialization, more and more heavy metals are released into the surrounding environment, such as: water environment, farming field. The pollution of heavy metals to agricultural lands and environmental water bodies finally affects human health. Because heavy metal ions have strong chelation, the generated chelate is difficult to biodegrade, is easy to enrich through a food chain and finally transfers into a human body, and can form serious threats to human health, such as: affecting the human central nervous system (Hg)2+，Pb2+，As3+An equiheavy metal); causing kidney or liver cancer (Cu)2+，Cd2+， Hg2+，Pb2+An equiheavy metal); or pathological changes of skin, bone and teeth (Ni)2+，Cu2+，Cd2+，Cr3+An equiheavy metal). In view of the serious harm brought by heavy metal ions, the detection of the content of heavy metals in various farming areas and the surrounding water environment, the confirmation of the heavy metal pollution distribution condition and the restoration of the heavy metal pollution distribution condition are urgently needed to prevent the health harm brought by heavy metal enrichment.
At present, the detection method of heavy metal ions at home and abroad is mainly an instrumental analysis method. The traditional standard trace heavy metal analysis technology (in ppm and ppb range), such as Atomic Absorption Spectrometry (AAS) inductively coupled plasma mass spectrometry (ICP), Mass Spectrometry (MS), X-ray fluorescence spectrometry (R-FS) and the like, has higher sensitivity and selectivity and accurate analysis result, but the used instruments and equipment are precise, the operation process is complicated and fussy, the technical requirement on detection personnel is high, and the method is not suitable for rapid detection of heavy metal ions on the spot.
Therefore, for the detection of heavy metals, a heavy metal detection technology with the characteristics of convenience, rapidness, high sensitivity and high selectivity is urgently needed. Based on the detection, the invention provides a technical method for rapidly detecting heavy metal chromium by using a detection agent prepared by modified aldehyde chitosan. The technical method has simple operation and low requirement, does not need professional personnel and equipment, and can carry out on-site detection at any time; the sensitivity is high, the response is fast, the anti-interference performance is strong, the complicated sample pretreatment is not needed, the treatment result can be obtained only through color change, and the secondary pollution can not be generated in the detection process; small volume, convenient carrying and low detection cost. The function can be similar to that of wide pH test paper, and the heavy metal pollution type can be judged and the pollution degree can be divided according to the displayed color type and color gradient.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide a preparation method of a functional polymer material with the functions of specific identification and rapid detection of chromium ions. Natural high molecular chitosan is subjected to hydroformylation, carboxylation and sulfhydrylation treatment to prepare the detection agent which can specifically identify heavy metal chromium ions and the detection result of which can be seen by naked eyes.
The invention also aims to provide the functional polymer material which is prepared by the method and has the functions of specific recognition and rapid detection of chromium ions.
The invention further aims to provide application of the functional polymer material with the functions of specific identification and rapid chromium ion detection in heavy metal chromium ion detection. The pollution degree of the heavy metal chromium ions is accurately divided and applied through macroscopic and color gradient division.
The purpose of the invention is realized by the following technical scheme:
a method for preparing a functional polymer material with specific recognition and rapid chromium ion detection functions comprises the following steps:
(1) adding the aldehyde chitosan into a PBS (phosphate buffer solution), adding a grafting compound containing carboxyl, reacting for 4-6h under the conditions of stirring and 30-40 ℃, centrifuging, washing and drying to obtain carboxyl functionalized aldehyde chitosan;
(2) adding carboxyl functionalized formylated chitosan into an organic solvent, adding a grafting compound containing sulfydryl, reacting for 6-8h under the conditions of stirring and 40-60 ℃, centrifuging, washing and drying to obtain the chitosan simultaneously containing sulfydryl, carboxyl and aldehyde groups, namely the functional polymer material with the functions of specific recognition and rapid chromium ion detection.
Preferably, the aldehyde chitosan in the step (1) is prepared by the following method:
adding chitosan into mixed acid of nitric acid and phosphoric acid, adding nitrite, reacting for 8-10 hours, and drying to obtain aldehyde chitosan.
The molecular weight of the chitosan is 50000-100000; the mass volume ratio of the chitosan to the mixed acid is 1: 14-15; the volume ratio of the nitric acid to the phosphoric acid is 4: 1-5: 1, wherein the concentration of the nitric acid is 65-68 percent, and the concentration of the phosphoric acid is 85 percent.
The nitrite is NaNO2And KNO2At least one of; the dosage of the nitrite is 1/4-1/5 of chitosan.
And adding deionized water for precipitation after the reaction is finished to obtain a product.
The drying temperature is 50-60 ℃ and the drying time is 24-36 hours.
Preferably, the pH range of the PBS buffer in the step (1) is 7.1-7.4.
Preferably, the mass-to-volume ratio of the aldehyde-functionalized chitosan to the PBS buffer solution in the step (1) is 1 g: 20 ml.
Preferably, the grafting compound containing carboxyl in the step (1) is at least one of 2-aminoethanesulfonic acid, glycine, glutamic acid and lysine, and the amino group of the grafting compound containing carboxyl can react with the aldehyde chitosan by Schiff base reaction.
Preferably, the mass ratio of the carboxyl-containing grafting compound to the aldehyde chitosan in the step (1) is 1: 1-1: 2.
preferably, the rotation speed of the stirring in the step (1) is 3000-5000 rpm; the rotation speed of the centrifugation is 4000-6000 rpm; the washing is to wash with PBS buffer solution and deionized water in sequence; the drying temperature is-70 ℃ to-90 ℃ and the drying time is 8-12 h.
Preferably, the ratio of the carboxyl-functionalized aldehydized chitosan to the organic solvent in the step (2) is 1 g: 20 ml.
Preferably, the organic solvent in step (2) is at least one of n-hexane and cyclohexane.
Preferably, the thiol-group-containing graft compound of step (2) is at least one of thioglycolic acid, 3-mercaptopropionic acid, and GSH (glutathione); the using amount of the grafting compound containing the sulfydryl is 1/5-1/10 of carboxyl functionalized hydroformylation chitosan.
Preferably, the rotation speed of the stirring in the step (2) is 3000-5000 rpm; the rotation speed of the centrifugation is 4000-6000 rpm; the drying temperature is-70 ℃ to-90 ℃, and the drying time is 8-12 h; the washing refers to washing with methanol and deionized water in sequence.
The functional polymer material prepared by the method has the functions of specific recognition and rapid detection of chromium ions.
The functional polymer material with the functions of specific recognition and rapid chromium ion detection is applied to detection of heavy metal chromium ions.
The sample for detecting the heavy metal chromium ions is in a liquid state, and the pH value of the sample is 5-9.
The invention adopts natural high molecular chitosan as raw material, and introduces carboxyl by Schiff base reaction and introduces sulfydryl by reactions such as dehydration condensation, esterification and the like through modified grafting of active groups such as amino, hydroxyl and the like carried by the chitosan; by combining the structural characteristics of chitosan, the introduced functional group compound is grafted on the outer side of the chitosan group to form a dynamic 'claw' which has stronger adsorption and chelation effects on heavy metals; as the sulfydryl and the carboxyl have specificity to the chelating coordination of the metal chromium ions, a specific orange-red complex can be generated, the color change generated by the reaction can be seen by naked eyes, and in the concentration range of 0-100ppm, the color of the chelate presents an obvious gradient change along with the increase of the concentration of the chromium ions, and the ultraviolet spectrophotometry is combined to know that the chromium ion solutions with different concentrations have different absorbances in the ultraviolet spectrophotometer, and the change of the absorbances presents a certain linear relation with the solution concentration along with the increase of the solution concentration. The upper detection limit can reach 10ppm, and effective detection of chromium ions can be realized in a macroscopic mode.
Meanwhile, the modified natural polymer chitosan-based detection agent is used for carrying out specific identification on chromium ions in a macroscopic mode, and the selectivity of the detection agent on the chromium ions needs to be considered. Under the same conditions, appropriate amounts of metal copper, metal nickel, metal lead, metal iron, metal cadmium and metal chromium ion solutions with the concentration of 100ppm are respectively prepared, and 1ml of each solution is placed in a centrifugal tube to be used as a liquid to be detected. The prepared modified chitosan-based detection agent is used for detecting the ionic solutions, and the obvious color change of the chromium ionic solutions can be found, which shows that the detection agent has excellent selectivity on the chromium ions.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the modified chitosan detection agent provided by the invention has the advantages of high sensitivity, good selectivity and low detection limit.
(2) The modified chitosan detection agent provided by the invention can be used for detecting metal chromium ions, and the pollution degree grade of the metal chromium ions can be judged through macroscopic color change, so that the rapid field detection is realized.
(3) The raw material adopted by the invention is the functional polymer obtained by taking the natural polymer chitosan as the main base material through modification treatment, the preparation method is simple, the cost is low, and a convenient and replaceable consumable reagent is provided for the field metal chromium ion detection.
Drawings
FIG. 1 shows the responses of the detection reagents to different ions in step (1) of example 4, in which Pb is shown from left to right2+、Ni2+、Cu2+、Fe2+、Cd2+And Cr6+The upper graph shows the metal ion solution before the detection agent is added, and the lower graph shows the metal ion solution after the detection agent is added.
FIG. 2 is a graph showing the color response of the detection agent to a chromium ion solution in the concentration range of 10-100ppm in step (2) of example 4.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
Those who do not specify specific conditions in the examples of the present invention follow conventional conditions or conditions recommended by the manufacturer. The raw materials, reagents and the like which are not indicated for manufacturers are all conventional products which can be obtained by commercial purchase.
Example 1
(1) Preparing aldehyde chitosan: taking 10g of chitosan with the molecular weight of 50000, placing the chitosan into a reaction container of 65-68% of nitric acid and 85% of phosphoric acid mixed acid, wherein the addition amount of the mixed acid is 140ml, and the volume ratio of the nitric acid to the phosphoric acid is 4: 1, subsequently adding sodium nitrite, wherein the mass ratio of the addition amount to the chitosan amount is 1: 5. and (3) carrying out a closed reaction for 8h, adding 500ml of deionized water into the reaction vessel after the reaction is finished, and carrying out forced air drying on the prepared aldehyde chitosan at 50 ℃ for 24h for later use.
(2) Introducing a carboxyl functional group. Placing 1g of prepared aldehyde chitosan into a reaction container, adding 20ml of PBS buffer solution into the container in advance, wherein the pH of the buffer solution is 7.2, adding glutamic acid, and the mass ratio of the addition amount to the aldehyde chitosan is 1: 1, magnetically stirring and reacting for 4 hours at 30 ℃ and 3000rpm, centrifuging at 4000rpm, washing 3 times by PBS buffer solution and deionized water respectively, and freeze-drying for 12 hours at-80 ℃ for later use.
(3) Introducing a mercapto functional group. Placing 1g of carboxylation modified chitosan-based product into a reaction vessel containing 20ml of normal hexane, adding GSH (glutathione) with the addition amount of 1/10 (mass ratio) of the substrate dosage, stirring and heating at 40 ℃, 3000rpm for 6h, centrifuging at 4000rpm, washing for 3 times by methanol and water respectively, and freeze-drying at-80 ℃ for 12h to prepare the natural polymer reagent with specific recognition and rapid naked eye detection of metal chromium ions.
Example 2
(1) Preparing aldehyde chitosan: taking 10g of chitosan with the molecular weight of 50000, placing the chitosan into a reaction container of 65-68% of nitric acid and 85% of phosphoric acid mixed acid, wherein the addition amount of the mixed acid is 150ml, and the volume ratio of the nitric acid to the phosphoric acid is 5: 1, subsequently adding sodium nitrite, wherein the mass ratio of the addition amount to the chitosan amount is 1: 4. And (3) carrying out a closed reaction for 8h, adding 500ml of deionized water into the reaction vessel after the reaction is finished, and drying the prepared aldehyde chitosan in forced air drying at 50 ℃ for 24h for later use.
(2) Introducing a carboxyl functional group. Placing 1g of prepared aldehyde chitosan into a reaction container, adding 20ml of PBS buffer solution into the container in advance, wherein the pH of the buffer solution is 7.4, adding glutamic acid, and the mass ratio of the addition amount to the aldehyde chitosan is 1: 2, reacting for 4 hours at 30 ℃ and 3000rpm under magnetic stirring, centrifuging at 4000rpm, washing 3 times by PBS buffer solution and deionized water respectively, and freeze-drying for 12 hours at-80 ℃ for later use.
(3) Introducing a mercapto functional group. Placing 1g of carboxylation modified chitosan-based product into a reaction container filled with 20ml of normal hexane, adding GSH (glutathione) with the addition amount of 1/5 (mass ratio) of the substrate dosage, stirring and heating at 40 ℃, 3000rpm for 6h, centrifuging at 4000rpm, washing for 3 times by methanol and water respectively, and freeze-drying at-80 ℃ for 12h to prepare the natural polymer reagent with specific recognition and rapid naked eye detection of metal chromium ions.
Example 3
(1) Preparing aldehyde chitosan: taking 10g of chitosan with the molecular weight of 50000 and placing the chitosan into a reaction container of 65-68% of nitric acid and 85% of phosphoric acid mixed acid, wherein the dosage of the mixed acid is 140ml, and the volume ratio of the nitric acid to the phosphoric acid is 4: 1, subsequently adding potassium nitrite, wherein the mass ratio of the addition amount to the chitosan amount is 1: 5. and (3) carrying out a closed reaction for 8h, adding 500ml of deionized water into the reaction vessel after the reaction is finished, and drying the prepared aldehyde chitosan in forced air drying at 50 ℃ for 24h for later use.
(2) Introducing a carboxyl functional group. Placing 1g of prepared aldehyde chitosan into a reaction container, adding 20ml of PBS buffer solution into the container in advance, wherein the pH of the buffer solution is 7.2, adding 2-aminoethanesulfonic acid, and the addition amount of the 2-aminoethanesulfonic acid is 1: 1, reacting for 4 hours at 30 ℃ and 3000rpm under magnetic stirring, centrifuging at 4000rpm, washing 3 times by PBS buffer solution and deionized water respectively, and freeze-drying for 12 hours at-80 ℃ for later use.
(3) Introducing a mercapto functional group. Placing 1g of carboxylation modified chitosan-based product into a reaction vessel containing 20ml of n-hexane, adding 3-mercaptopropionic acid, wherein the addition amount is 1/10 (mass ratio) of the substrate dosage, stirring and heating at 40 ℃, 3000rpm for 6 hours, centrifuging at 4000rpm, washing for 3 times by methanol and water respectively, and freeze-drying at-80 ℃ for 12 hours to prepare the natural polymer reagent with specific recognition and rapid naked eye detection of metal chromium ions.
Example 4
(1) Respectively preparing 100ppm of chromium ion standard solution, copper ion standard solution, iron ion standard solution, nickel ion standard solution, lead ion standard solution and cadmium ion standard solution, and adjusting the pH value of the solutions to be within the range of 5.7-6.3. Each 1ml of the reagent solution was placed in a 2.5ml centrifuge tube and labeled, and then 0.005g of the detection reagent prepared in example 1 (natural polymer reagent) was added thereto. After 30s, the color of the centrifuge tube filled with the chromium ion standard solution is obviously changed from yellow to orange-red. The results of this example are shown in FIG. 1.
(2) 10ppm, 20ppm, 30ppm, 40ppm, 50ppm, 60ppm, 70ppm, 80ppm, 90ppm, 100ppm of chromium ion solutions were prepared, 1ml of each solution was placed in a 2.5ml centrifuge tube and labeled, and then 0.005g of the detection reagent (natural polymer reagent) prepared in example 1 was added thereto. After 30s, the solution containing chromium ions with different concentrations has obvious color change, and the color changes from light yellow to orange red in a gradient way along with the concentration of the chromium ions from 10ppm to 100 ppm. After spectral scanning is carried out by an ultraviolet spectrophotometer, the chromium standard solution without the detection reagent (natural polymer reagent) has obvious absorption peaks at 260nm and 380nm, after the detection reagent (natural polymer reagent) is added, the peak at 380nm disappears, the peak at 260nm undergoes blue shift, and the change of the peak size along with the change of concentration shows that the change has certain regularity. The results of this example are shown in FIG. 2.
(3) And (3) combining the chromium ions with different concentrations in the step (2), adding a detection reagent, generating different color changes to divide the pollution degree: 10 grades such as 10ppm, 20ppm, 30ppm, 40ppm, 50ppm, 60ppm, 70ppm, 80ppm, 90ppm, 100ppm, etc.
Comparative example 1
The conditions in step (2) of example 1 were: the addition amount of the chitosan is 1: 1 is changed into 2: 1, the other conditions are not changed, and the natural polymer reagent is prepared.
When 0.005g of the natural polymer agent obtained in comparative example was added to 1ml of each of the chromium ion solutions having concentrations of 10ppm, 20ppm, 30ppm, 40ppm, 50ppm, 60ppm, 70ppm, 80ppm, 90ppm and 100ppm, respectively, no discoloration was observed in the chromium ion solutions, and thus, the mass ratio of the carboxyl group-modified substance to the aldehyde-modified chitosan was changed, and the resultant was remarkably reduced in the chromium ion.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a functional polymer material with specific recognition and rapid chromium ion detection functions is characterized by comprising the following steps:
(1) adding the aldehyde chitosan into PBS buffer solution, adding a grafting compound containing carboxyl, reacting for 4-6h under the conditions of stirring and 30-40 ℃, centrifuging, washing and drying to obtain carboxyl functionalized aldehyde chitosan;
(2) adding carboxyl functionalized formylated chitosan into an organic solvent, adding a grafting compound containing sulfydryl, reacting for 6-8h under the conditions of stirring and 40-60 ℃, centrifuging, washing and drying to obtain the chitosan simultaneously containing sulfydryl, carboxyl and aldehyde groups, namely the functional polymer material with the functions of specific recognition and rapid chromium ion detection.
2. The method for preparing a functional polymer material with specific recognition and rapid detection of chromium ions according to claim 1, wherein the mass ratio of the carboxyl-containing graft compound to the aldehyde chitosan in the step (1) is 1: 1-1: 2; the using amount of the grafting compound containing the sulfydryl is 1/5-1/10 of carboxyl functionalized hydroformylation chitosan.
3. The method for preparing a functional polymer material with specific recognition and rapid detection of chromium ions according to claim 1 or 2, wherein the grafting compound containing carboxyl in the step (1) is at least one of 2-aminoethanesulfonic acid, glycine, glutamic acid and lysine; the grafting compound containing the sulfydryl in the step (2) is at least one of thioglycolic acid, 3-mercaptopropionic acid and glutathione.
4. The method for preparing a functional polymer material with specific recognition and rapid chromium ion detection functions as claimed in claim 1 or 2, wherein the mass-to-volume ratio of the aldehyde chitosan in step (1) to the PBS buffer is 1 g: 20ml of the solution; the ratio of the carboxyl functionalized formylated chitosan to the organic solvent in the step (2) is 1 g: 20ml of the solution; the pH range of the PBS buffer solution in the step (1) is 7.1-7.4.
5. The method for preparing a functional polymer material with specific recognition and rapid chromium ion detection functions as claimed in claim 1 or 2, wherein the aldehyde chitosan in step (1) is prepared by the following method:
adding chitosan into mixed acid of nitric acid and phosphoric acid, adding nitrite, reacting for 8-10 hours, and drying to obtain aldehyde chitosan; the molecular weight of the chitosan is 50000-100000; the mass volume ratio of the chitosan to the mixed acid is 1: 14-15; the volume ratio of the nitric acid to the phosphoric acid is 4: 1-5: 1, wherein the concentration of the nitric acid is 65-68 percent, and the concentration of the phosphoric acid is 85 percent.
6. The method for preparing functional polymer material with specific recognition and rapid chromium ion detection functions as claimed in claim 5, wherein the nitrite is NaNO2And KNO2At least one of; the dosage of the nitrite is 1/4-1/5 of chitosan.
7. The method for preparing functional polymer material with specific recognition and rapid detection of chromium ions as claimed in claim 1 or 2, wherein the stirring speed in step (1) is 3000-5000 rpm; the rotation speed of the centrifugation is 4000-6000 rpm; the washing is to wash with PBS buffer solution and deionized water in sequence; the drying temperature is-70 ℃ to-90 ℃, and the drying time is 8-12 h;
the organic solvent in the step (2) is at least one of n-hexane and cyclohexane; the stirring speed in the step (2) is 3000-5000 rpm; the rotation speed of the centrifugation is 4000-6000 rpm; the drying temperature is-70 ℃ to-90 ℃, and the drying time is 8-12 h; the washing refers to washing with methanol and deionized water in sequence.
8. A functional polymer material with specific recognition and rapid chromium ion detection prepared by the method of any one of claims 1 to 7.
9. The functional polymer material with the functions of specific recognition and rapid chromium ion detection as claimed in claim 8 is applied to detection of heavy metal chromium ions.
10. The application of the functional polymer material with the functions of specific recognition and rapid detection of chromium ions in the detection of heavy metal chromium ions according to claim 9, wherein a sample for the detection of heavy metal chromium ions is in a liquid state, and the pH value of the sample is 5-9.
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| CN114080959A (en) * | 2021-10-21 | 2022-02-25 | 舒城县农业科学研究所 | Organic selenium-rich rice cultivation method |
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