CN113070050A - Chitosan-based hydrogel adsorbent capable of visually identifying and removing mercury ions and preparation method and application thereof - Google Patents

Chitosan-based hydrogel adsorbent capable of visually identifying and removing mercury ions and preparation method and application thereof Download PDF

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CN113070050A
CN113070050A CN202110467500.6A CN202110467500A CN113070050A CN 113070050 A CN113070050 A CN 113070050A CN 202110467500 A CN202110467500 A CN 202110467500A CN 113070050 A CN113070050 A CN 113070050A
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polyethylene glycol
chitosan
rhodamine
hydrazide
mercury ions
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CN113070050B (en
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邱晓勇
郝京诚
崔基炜
黄�俊
甄曰菊
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Shandong University
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Abstract

The invention provides a chitosan-based hydrogel adsorbent capable of visually identifying and removing mercury ions, and a preparation method and application thereof. The preparation method comprises the following steps: reacting polyethylene glycol with 4-aldehyde benzoic acid to prepare benzaldehyde-terminated polyethylene glycol; preparing the rhodamine 6G hydrazide modified by polyethylene glycol through the reaction of the rhodamine 6G hydrazide and benzaldehyde terminated polyethylene glycol; benzaldehyde-terminated polyethylene glycol is used as a cross-linking agent, and rhodamine 6G hydrazide modified by the polyethylene glycol is covalently cross-linked to chitosan, so that the hydrogel adsorbent which is environment-friendly and high in biosafety is prepared. The hydrogel adsorbent disclosed by the invention has excellent adsorption selectivity and removal capacity on mercury ions, and shows specific color change, so that the hydrogel adsorbent can be used for visual identification in an aqueous solution and efficiently removing the mercury ions; in addition, the adsorbent is in a block shape, so that the adsorbent is easy to remove after adsorption is finished, and is convenient to operate in practical application.

Description

Chitosan-based hydrogel adsorbent capable of visually identifying and removing mercury ions and preparation method and application thereof
Technical Field
The invention relates to a chitosan-based hydrogel adsorbent capable of visually identifying and removing mercury ions, and a preparation method and application thereof, and belongs to the technical field of functional materials.
Background
The heavy metal pollution of the water environment poses great threat to both ecological environment and human health, wherein mercury ions are one of the widely existing heavy metal ions with the highest toxicity, and the mercury ions can enter organisms through food chains, penetrate through blood brain barriers, are enriched in parts such as brain tissues, kidneys and the like, and are extremely harmful to the organisms. The mercury ion pollution of the water body can be treated by methods such as chemical precipitation, electrochemical reduction, coagulation, membrane separation, adsorption, permeation and the like, wherein the adsorption method is widely concerned by people due to the characteristics of low price, high efficiency, easy operation and the like.
Chitosan is a deacetylated product of chitin, mainly exists in shells of arthropods such as shrimps, crabs and insects, and is the second most abundant biopolymer existing in nature. Because of a large amount of amino and hydroxyl groups in chitosan molecules, the chitosan has strong chelation effect on heavy metal ions, is nontoxic and easy to degrade, and is an excellent material for preparing the heavy metal ion adsorbent. However, chitosan has poor water solubility and low specific surface area, and cannot be directly used as an adsorbent, so it is required to modify it and impart functionality thereto by physical or chemical methods, most commonly grafting or crosslinking methods. For example, chinese patent document CN110586045A discloses a preparation method and application of an amphoteric magnetic chitosan adsorbent, which comprises synthesizing magnetic chitosan by solvothermal "one-pot method", and preparing thiourea modified magnetic chitosan by schiff base reaction under the action of glutaraldehyde; and grafting carboxyl on the surface of the magnetic chitosan through amidation reaction under the action of a catalyst to obtain the amphoteric magnetic chitosan adsorbent. The magnetic powder material prepared by the invention is used for adsorbing Cr (VI) and Cd (II). Chinese patent document CN104607152A discloses a rhodamine derivative modified fluorescent magnetic adsorbent. The synthetic method of the fluorescent magnetic adsorbent comprises the following steps: glutaraldehyde is used as a cross-linking agent, the chitosan is coated with ferroferric oxide nano particles to prepare magnetic chitosan microspheres, and under the action of epoxy chloropropane, rhodamine derivative molecules with amino groups are adhered to the surfaces of the magnetic chitosan to obtain fluorescent magnetic composite adsorbent powder; the adsorbent is used for mercury ion adsorption and identification. Chinese patent document CN105817208A discloses a rhodamine B grafted chitosan adsorbent and preparation and application thereof. Firstly, reacting rhodamine B with hydrazine hydrate to prepare rhodamine B hydrazide; then, glyoxal is used as a cross-linking agent, and rhodamine B hydrazide is grafted to chitosan to obtain the adsorbent. The adsorbent can be used for adsorbing and detecting mercury ions in an environmental water sample. However, the prepared adsorbent is in a powder form, and the adsorbent is difficult to separate from a solution at the later stage or can be separated only by an external magnetic field, so that the adsorbent has great defects in practical application; in addition, glyoxal, glutaraldehyde and the like are usually used as cross-linking agents in the preparation of the chitosan adsorbent at present, and the aldehyde small-molecule cross-linking agents have obvious biotoxicity and can cause secondary pollution in the water treatment process. In terms of adsorption performance, the chitosan adsorbent used for removing mercury ions at present is less, and the adsorption performance is not high (the removal rate of mercury ions is not more than 90%).
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a chitosan-based hydrogel adsorbent capable of visually identifying and removing mercury ions, and a preparation method and application thereof. The preparation method is simple, low-toxicity benzaldehyde-terminated polyethylene glycol is used as a cross-linking agent, and the polyethylene glycol-modified rhodamine 6G hydrazide obtained by reacting with the rhodamine 6G hydrazide has the characteristics of environmental friendliness and high biological safety; then covalently crosslinking the chitosan-based hydrogel adsorbent to chitosan to prepare the chitosan-based hydrogel adsorbent. The adsorbent prepared by the method is non-toxic, high in biological safety, good in adsorption selectivity and adsorptivity and capable of effectively removing mercury ions in water, and has a color recognition function on the mercury ions, and the later-stage separation is easy.
The technical scheme of the invention is as follows:
a chitosan-based hydrogel adsorbent capable of visually identifying and removing mercury ions is a block-shaped material with a three-dimensional porous structure, and the pore diameter of the adsorbent is 100-200 mu m.
The preparation method of the chitosan-based hydrogel adsorbent capable of visually identifying and removing mercury ions comprises the following steps:
(1) in a solvent A, under the action of a catalyst, reacting polyethylene glycol with p-formaldehyde benzoic acid to prepare benzaldehyde-terminated polyethylene glycol (DF-PEG);
(2) in a solvent B, reacting benzaldehyde-terminated polyethylene glycol with rhodamine 6G hydrazide through Schiff base to prepare polyethylene glycol-modified rhodamine 6G hydrazide (RF); the molar ratio of the benzaldehyde-terminated polyethylene glycol to rhodamine 6G hydrazide is 1: 0.95-1: 1.05;
(3) dissolving chitosan in a dilute acid solution to obtain a chitosan solution; dissolving polyethylene glycol-modified rhodamine 6G hydrazide and benzaldehyde-terminated polyethylene glycol in water to obtain a mixed solution; mixing the chitosan solution and the mixed solution, reacting, and then carrying out freeze drying to obtain the chitosan-based hydrogel adsorbent.
Preferably, in step (1), the solvent a is methanol, ethanol, acetone or tetrahydrofuran; preferably, the solvent A is tetrahydrofuran; the volume ratio of the mass of the p-formaldehyde benzoic acid to the solvent A is 0.005-0.1 g/mL.
Preferably, in the step (1), the catalyst is a combination of dicyclohexyl diimine and 4-dimethylamino pyridine, and the mass ratio of the dicyclohexyl diimine to the 4-dimethylamino pyridine is 1: 15-20; the mass of the catalyst is 1-3 times of that of p-formaldehyde benzoic acid. Preferably, the catalyst dicyclohexyl diimine is added into the reaction system in a dropwise manner.
Preferably, in step (1), the molar ratio of the hydroxyl groups of the polyethylene glycol to the carboxyl groups of p-formaldehyde benzoic acid is 1: 1-1: 3.
preferably, in step (1), the polyethylene glycol may be linear polyethylene glycol or hyperbranched polyethylene glycol; preferably, the polyethylene glycol is a linear polyethylene glycol, a four-arm polyethylene glycol or an eight-arm polyethylene glycol.
Preferably, according to the present invention, in step (1), the number average molecular weight of the polyethylene glycol is 200-; preferably, the number average molecular weight of the polyethylene glycol is 2000-.
Preferably, according to the invention, in step (1), the reaction temperature is between 15 and 50 ℃. The reaction time is 10-60 hours; preferably, the reaction time is 40-55 h.
Preferably, in step (1), the reaction is carried out under the protection of inert gas; the inert gas is nitrogen, argon or helium; preferably, the inert gas is nitrogen.
According to the invention, the post-treatment of the reaction solution obtained in step (1) by reacting polyethylene glycol with p-formaldehyde benzoic acid can be carried out according to the prior art. Preferably, the post-treatment steps are as follows: and filtering the reaction solution to remove precipitates, carrying out rotary evaporation to obtain a solid intermediate product, washing with dichloromethane, and drying to obtain the benzaldehyde-terminated polyethylene glycol.
Preferably, in step (2), the solvent B is methanol, ethanol or acetone; preferably, the solvent B is acetone; the mass ratio of the rhodamine 6G hydrazide to the solvent B is 0.001-0.01G/mL.
Preferably, in step (2), the reaction of rhodamine 6G hydrazide and benzaldehyde-terminated polyethylene glycol can be carried out under the action of a catalyst; the catalyst is boric acid, benzenesulfonic acid or glacial acetic acid; preferably, the catalyst is glacial acetic acid. The amount of the catalyst is determined by the prior art.
Preferably, according to the invention, in step (2), the reaction temperature is 10-58 ℃; preferably, the reaction temperature is 55-58 ℃. The reaction time is 2 to 96 hours, preferably 2 to 8 hours.
According to the invention, in the step (2), the benzaldehyde-terminated polyethylene glycol is added into a system containing the solvent B and the rhodamine 6G hydrazide in a dropwise manner.
According to the invention, in the step (2), the molar ratio of the benzaldehyde-terminated polyethylene glycol to the rhodamine 6G hydrazide is 1: 0.95-1: 1.05, only one end of a polyethylene glycol chain in the benzaldehyde-terminated polyethylene glycol is modified by rhodamine 6G hydrazide, the other end of the polyethylene glycol chain is still a benzaldehyde group with reactivity, the benzaldehyde group can generate Schiff base reaction with amino in chitosan molecules, and RF molecules are firmly grafted in the adsorbent in a chemical bond form.
According to the invention, in the step (2), the reaction solution obtained by the reaction of benzaldehyde-terminated polyethylene glycol and rhodamine 6G hydrazide can be subjected to post-treatment according to the prior art. Preferably, the post-treatment steps are as follows: and filtering the reaction solution to remove precipitates, and performing rotary evaporation and vacuum drying to obtain the polyethylene glycol modified rhodamine 6G hydrazide.
According to the invention, in the step (2), rhodamine 6G hydrazide can be prepared according to the existing method. Preferably, the preparation of the rhodamine 6G hydrazide comprises the following steps: in a solvent C, rhodamine 6G and hydrazine hydrate react to prepare rhodamine 6G hydrazide.
Preferably, the solvent C is methanol or ethanol; the volume ratio of the mass of the rhodamine 6G to the volume of the solvent C is 0.01-0.1G/mL.
Preferably, the molar ratio of the rhodamine 6G to the hydrazine hydrate is 1: 5-1: 60, adding a solvent to the mixture; further preferably, the molar ratio of rhodamine 6G to hydrazine hydrate is 1: 20-1: 55.
preferably, the hydrazine hydrate is aqueous solution of hydrazine hydrate with the mass concentration of 40-90%.
Preferably, the reaction temperature is 30-80 ℃; further preferably, the reaction temperature is 70 to 80 ℃. The reaction time is 2 to 24 hours, preferably 10 to 20 hours.
Preferably, the hydrazine hydrate is added to the system in a dropwise manner.
Preferably, the post-treatment of the reaction solution obtained by the reaction of rhodamine 6G and hydrazine hydrate can be carried out according to the prior art. Further preferably, the post-treatment steps are as follows: and filtering the reaction liquid to obtain a solid intermediate product, washing the obtained solid intermediate product by using a mixed solvent of ethanol and diethyl ether, and then drying in vacuum to obtain the rhodamine 6G hydrazide.
Preferably, in step (3), the weight average molecular weight of the chitosan is 50,000-500,000Da, and the deacetylation degree is more than or equal to 85%; preferably, the chitosan has a weight average molecular weight of 150,000 Da.
Preferably, in step (3), the diluted acid solution is acetic acid aqueous solution, hydrochloric acid aqueous solution or citric acid aqueous solution; the mass concentration of the dilute acid solution is 1-5%.
According to the invention, in the step (3), the mass concentration of the chitosan solution is 1-10%; preferably, the chitosan solution has a mass concentration of 2-3%.
According to the invention, in the step (3), the mass ratio of the polyethylene glycol modified rhodamine 6G hydrazide to the benzaldehyde terminated polyethylene glycol is 2-8: 1. The benzaldehyde-terminated polyethylene glycol is added in the step (3) of the invention to serve as a cross-linking agent for chitosan molecule reaction, so that chemical reaction occurs between chitosan molecules to form a three-dimensional macromolecular network structure, namely, a block adsorbent in a hydrogel form is formed. If the crosslinking agent is not added, a hydrogel type bulk adsorbent cannot be formed.
According to the invention, the concentration of the polyethylene glycol modified rhodamine 6G hydrazide in the mixed solution in the step (3) is preferably 0.1-2G/mL.
According to the invention, in the step (3), the mass ratio of the chitosan to the polyethylene glycol modified rhodamine 6G hydrazide is 1: 3-20.
Preferably, in step (3), the reaction temperature after mixing the chitosan solution and the mixed solution is room temperature, and the reaction is carried out until hydrogel is formed. The room temperature has the meaning well known in the art, i.e. 25 ± 5 ℃.
The application of the chitosan-based hydrogel adsorbent capable of visually identifying and removing mercury ions is applied to adsorbing mercury ions in an aqueous solution.
The invention has the technical characteristics and beneficial effects that:
(1) environment-friendly and high biological safety. Polyethylene glycol modified rhodamine 6G hydrazide (RF) and mouse fibroblasts (3T3 cells) are cultured for 24h, and the survival rate of the cells is tested through an MTT experiment. The results show that: even in the case of high concentration (400mg/mL) of RF co-culture, 3T3 cells still had high cell viability, indicating that RF cytotoxicity was low. The invention uses low-toxicity benzaldehyde-terminated polyethylene glycol (DF-PEG) to replace the traditional micromolecule aldehyde compounds with biological toxicity such as glyoxal, glutaraldehyde and the like as the cross-linking agent for chitosan reaction; the fluorescent polymer molecule RF with low toxicity replaces micromolecule rhodamine B hydrazide in the prior art to be used as the recognition agent of mercury ions, so that the biological safety of the adsorbent is obviously improved, the environmental protection is facilitated, and the secondary pollution of the water body caused by the adsorbent can not be caused.
(2) The adsorption performance is good. The chitosan molecules in the adsorbent prepared by the invention contain abundant amino and hydroxyl, the DF-PEG cross-linking agent contains a large amount of ethylene glycol repeating units, and N, O atoms on the functional groups have stronger coordination effect on mercury ions, so that the adsorbent can be used for adsorbing the mercury ions. The adsorbent was placed in aqueous solutions each containing mercury ions, and the concentration of mercury ions was measured by a flame atomic absorption method. The results show that: the adsorbent has high adsorption capacity to mercury ions, and the removal rate of the mercury ions can reach 96.5%.
(3) The selectivity is high. The adsorbent synthesized by the invention can selectively identify and adsorb mercury ions, and is accompanied with obvious fluorescence response and color change. The results show that: the adsorbent changes color to red only after adsorbing mercury ions and is accompanied by obvious fluorescence emission enhancement; the color changes to blue upon exposure to copper ions, whereas cadmium and lead ions do not cause significant color changes and fluorescence emissions. The color change is determined by the specific recognition capability of the rhodamine group in the grafted RF to the mercury ions; when mercury ions do not exist, the five-membered spiro structure in the rhodamine group is in a closed ring state, and no fluorescence emission or color exists; when mercury ions exist, a five-membered spiro ring structure in the rhodamine group is opened, and due to intramolecular charge transfer, fluorescence emission is enhanced and color change occurs. The modification and grafting of rhodamine 6G hydrazide by the method do not affect the specific recognition of rhodamine groups to mercury ions, but fully play the roles of good water solubility and high biological safety, and are beneficial to the specific recognition of the rhodamine groups to the mercury ions. In addition, since RF is grafted on the adsorbent through covalent bond, RF leakage can not occur during the use process, or the fluorescence sensing performance can not be reduced or disappeared, namely, the selection and identification performance of the adsorbent has stability.
(4) And the later separation is simple. The hydrogel adsorbent prepared by the invention is in a block shape and is not easy to diffuse into a water body, so that the secondary pollution of the adsorbent to the water body is not caused in the water treatment process; after adsorption is finished, the adsorbent is easy to remove, does not need to be separated from the water body by means of magnetic fields, filtration and the like, and is convenient to operate in practical application.
(5) The adsorbent is prepared by cross-linking agent, aldehyde group (-CHO) of RF and amino group (-NH) of chitosan2) The Schiff base can be prepared by mixing the raw materials at room temperature within a few seconds, the reaction condition is mild, and the operation process is simple. The benzaldehyde-terminated polyethylene glycol (DF-PEG) plays a role of a cross-linking agent, so that chitosan molecules form a macromolecular network structure through a cross-linking reaction, namely a hydrogel structure is formed; the rhodamine 6G hydrazide modified polyethylene glycol (RF) plays a role of an indicator in the adsorbent, and color indication is performed by utilizing the specific binding effect of rhodamine groups in RF molecules on mercury ions.
(6) In the step (2), the mole ratio of the benzaldehyde-terminated polyethylene glycol to the rhodamine 6G hydrazide is controlled to obtain the RF molecules with only one end modified by the rhodamine group, and the other end still has a benzaldehyde group with reactivity, so that the RF molecules can be subjected to Schiff base reaction with the chitosan molecules. If the ratio of rhodamine 6G hydrazide is too high, and both ends of the RF molecules are modified by rhodamine groups, the RF molecules cannot be covalently bonded on the adsorbent, so that the color rendering performance of the adsorbent is poor.
In the step (3), the proportion of DF-PEG and chitosan needs to be controlled, if the addition amount of DF-PEG is too small and the crosslinking density of chitosan molecules is too low, a hydrogel network structure cannot be formed, namely a block-shaped hydrogel adsorbent cannot be formed; if DF-PEG is added too much, the crosslinking density of chitosan molecules is too high, and the formed hydrogel has higher brittleness and is easy to crack.
Description of the drawings:
fig. 1 is a scanning electron micrograph of a chitosan-based hydrogel adsorbent prepared in example 1;
FIG. 2 shows chitosan-based hydrogel adsorbents prepared in example 1 for different metal ions (Cu)2+,Hg2+,Cd2+,Pb2 +) A comparison graph of removal rates of;
FIG. 3 shows chitosan-based hydrogel adsorbents prepared in example 1 for different metal ions (Cu)2+,Hg2+,Cd2+,Pb2 +) (ii) a fluorescence response profile of;
FIG. 4 is a graph showing the test of the adsorption capacity of the chitosan-based hydrogel adsorbent prepared in example 1 for mercury ions;
FIG. 5 is a time kinetics test of mercury ion adsorption by the chitosan-based hydrogel adsorbent prepared in example 1;
FIG. 6 is a graph showing the comparison of the cell viability of mouse fibroblasts after 24 hours of culture in Rh solutions prepared in example 1 at different concentrations.
The specific implementation mode is as follows:
the present invention will be further described with reference to the following examples, but is not limited thereto.
Meanwhile, the experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
In the examples, the rhodamine 6G hydrazide used was prepared as follows:
dissolving 0.958G of rhodamine 6G in 30mL of absolute ethanol, dripping 3.0G of hydrazine hydrate aqueous solution (the mass concentration is 85%) at room temperature, then stirring and refluxing at 78 ℃ for reaction for 12h, cooling and filtering to obtain a solid crude product, washing by using an ethanol/diethyl ether mixed solvent, and drying to obtain the rhodamine 6G hydrazide.
Example 1
A preparation method of a chitosan hydrogel adsorbent capable of visually identifying and removing mercury ions comprises the following steps:
(1) preparation of benzaldehyde-terminated polyethylene glycol (DF-PEG): 8g of polyethylene glycol 4000 and 0.9g of p-formaldehyde benzoic acid were dissolved in 50mL of tetrahydrofuran, and 0.09g of DMAP (4-dimethylaminopyridine) was added; a50 mL tetrahydrofuran solution in which 1.65g of DCC (dicyclohexylcarbodiimide) was dissolved was dropwise added under a nitrogen atmosphere, and the mixture was stirred at room temperature for 48 hours. And then filtering to remove the precipitate, carrying out rotary evaporation on the filtrate to obtain a crude product, precipitating for three times by using dichloromethane, and drying to obtain a white paraffin-shaped product, namely the benzaldehyde-terminated polyethylene glycol.
(2) Preparation of polyethylene glycol modified rhodamine 6G hydrazide (RF): dripping 30mL of acetone solution in which 1.00G of DF-PEG is dissolved into 30mL of acetone solution containing 0.10G of rhodamine 6G hydrazide dropwise, wherein the molar ratio of DF-PEG to rhodamine 6G hydrazide is 1:1.05, adding 2 drops of glacial acetic acid as a catalyst, heating and refluxing for 4h at 58 ℃, cooling and filtering, and carrying out rotary evaporation and vacuum drying on the filtrate to obtain a light purple product, namely the polyethylene glycol modified rhodamine 6G hydrazide.
(3) Preparation of chitosan-based hydrogel adsorbent: 0.3g of chitosan (the deacetylation degree is more than or equal to 85%) with the weight-average molecular weight of 150,000Da is dissolved in 10mL of 2 wt% acetic acid aqueous solution to prepare a chitosan solution with the mass concentration of 3%. 250mgDF-PEG was dissolved in 1.0mL of water to prepare a 20 wt% DF-PEG aqueous solution. 400mg of RF was dissolved in 250. mu.L of 20 wt% DF-PEG aqueous solution, the solution was dropped into 0.7g of chitosan solution in a vortex state to form hydrogel within several seconds, and the chitosan hydrogel adsorbent having an RF content of 30% was obtained by freeze-drying.
The adsorbent prepared in this example was subjected to scanning electron microscopy and the results are shown in FIG. 1. As can be seen from FIG. 1, the adsorbent has a three-dimensional porous structure with a pore size of 100-200 μm.
Example 2
A preparation method of a chitosan hydrogel adsorbent capable of visually identifying and removing mercury ions comprises the following steps:
(1) preparation of benzaldehyde-terminated polyethylene glycol (DF-PEG): dissolving 4g of polyethylene glycol 2000 and 0.9g of p-formaldehyde benzoic acid in 50mL of tetrahydrofuran, and adding 0.09g of DMAP; a50 mL tetrahydrofuran solution in which 1.65g of DCC was dissolved was dropwise added under a nitrogen atmosphere, and the mixture was stirred at room temperature for 48 hours. And then filtering to remove the precipitate, carrying out rotary evaporation on the filtrate to obtain a crude product, precipitating for three times by using dichloromethane, and drying to obtain a white paraffin-shaped product, namely the benzaldehyde-terminated polyethylene glycol.
(2) Preparation of polyethylene glycol modified rhodamine 6G hydrazide (RF): dripping 30mL of acetone solution in which 1.00G of DF-PEG is dissolved into 30mL of acetone solution containing 0.10G of rhodamine 6G hydrazide dropwise, wherein the molar ratio of DF-PEG to rhodamine 6G hydrazide is 1:1.05, adding 2 drops of glacial acetic acid as a catalyst, heating and refluxing for 4h at 58 ℃, cooling and filtering, and carrying out rotary evaporation and vacuum drying on the filtrate to obtain a light purple product, namely the polyethylene glycol modified rhodamine 6G hydrazide.
(3) Preparation of chitosan-based hydrogel adsorbent: 0.2g of chitosan (deacetylation degree is more than or equal to 85%) with weight-average molecular weight of 50,000Da is dissolved in 10mL of 2 wt% citric acid aqueous solution to prepare chitosan solution with mass concentration of 2%. 250mgDF-PEG was dissolved in 1.0mL of water to prepare a 20 wt% DF-PEG aqueous solution. 50mg of RF is dissolved in 250 mu L of 10 wt% DF-PEG aqueous solution, the solution is dropped into 0.7g of chitosan solution in a vortex state to form hydrogel within a few seconds, and the chitosan hydrogel adsorbent with the RF content of 5% is obtained by freeze drying.
Example 3
A preparation method of a chitosan hydrogel adsorbent capable of visually identifying and removing mercury ions comprises the following steps:
(1) preparation of benzaldehyde-terminated polyethylene glycol (DF-PEG): 10g of four-armed polyethylene glycol 5000 and 0.9g of p-formaldehyde benzoic acid were dissolved in 50mL of tetrahydrofuran, and 0.09g of DMAP was added; a50 mL tetrahydrofuran solution in which 1.65g of DCC was dissolved was dropwise added under a nitrogen atmosphere, and the mixture was stirred at room temperature for 48 hours. And then filtering to remove the precipitate, carrying out rotary evaporation on the filtrate to obtain a crude product, precipitating for three times by using dichloromethane, and drying to obtain a white paraffin-shaped product, namely the benzaldehyde-terminated polyethylene glycol.
(2) Preparation of polyethylene glycol modified rhodamine 6G hydrazide (RF): dripping 30mL of acetone solution in which 1.00G of DF-PEG is dissolved into 30mL of acetone solution containing 0.10G of rhodamine 6G hydrazide dropwise, wherein the molar ratio of DF-PEG to rhodamine 6G hydrazide is 1:1.05, adding 2 drops of boric acid as a catalyst, heating and refluxing for 8h at 58 ℃, cooling and filtering, and carrying out rotary evaporation and vacuum drying on the filtrate to obtain a light purple product, namely the polyethylene glycol modified rhodamine 6G hydrazide.
(3) Preparation of chitosan-based hydrogel adsorbent: 0.3g of chitosan (degree of deacetylation: 85% or more) with a weight-average molecular weight of 500,000Da was dissolved in 10mL of a 1 wt% aqueous solution of acetic acid to prepare a chitosan solution with a mass concentration of 3%. 250mgDF-PEG was dissolved in 1.0mL of water to prepare a 20 wt% DF-PEG aqueous solution. 150mg of RF is dissolved in 250 mu L of 20 wt% DF-PEG aqueous solution, the solution is dropped into 0.7g of chitosan solution in a vortex state to form hydrogel within a few seconds, and the chitosan hydrogel adsorbent with 14% of RF content is obtained by freeze drying.
Example 4
A preparation method of a chitosan hydrogel adsorbent capable of visually identifying and removing mercury ions comprises the following steps:
(1) preparation of benzaldehyde-terminated polyethylene glycol (DF-PEG): dissolving 8g of polyethylene glycol 4000 and 0.9g of p-formaldehyde benzoic acid in 50mL of tetrahydrofuran, and adding 0.09g of DMAP; a50 mL tetrahydrofuran solution in which 1.65g of DCC was dissolved was dropwise added under a nitrogen atmosphere, and the mixture was stirred at room temperature for 48 hours. And then filtering to remove the precipitate, carrying out rotary evaporation on the filtrate to obtain a crude product, precipitating for three times by using dichloromethane, and drying to obtain a white paraffin-shaped product, namely the benzaldehyde-terminated polyethylene glycol.
(2) Preparation of polyethylene glycol modified rhodamine 6G hydrazide (RF): dripping 30mL of acetone solution in which 1.00G of DF-PEG is dissolved into 30mL of acetone solution containing 0.10G of rhodamine 6G hydrazide dropwise, wherein the molar ratio of DF-PEG to rhodamine 6G hydrazide is 1:1.05), heating and refluxing for 8h at 58 ℃, cooling and filtering, and carrying out rotary evaporation and vacuum drying on the filtrate to obtain a light purple product, namely the polyethylene glycol modified rhodamine 6G hydrazide.
(3) Preparation of chitosan-based hydrogel adsorbent: 0.3g of chitosan (the degree of deacetylation is more than or equal to 85%) with the weight-average molecular weight of 150,000Da is dissolved in 10mL of 1 wt% acetic acid aqueous solution to prepare a chitosan solution with the mass concentration of 3%. 250mgDF-PEG was dissolved in 1.0mL of water to prepare a 20 wt% DF-PEG aqueous solution. 250mg of RF is dissolved in 250 mu L of 20 wt% DF-PEG aqueous solution, the solution is dropped into 0.7g of chitosan solution in a vortex state to form hydrogel within a few seconds, and the chitosan hydrogel adsorbent with 20% of RF content is obtained by freeze drying.
Comparative example 1
A method of making a chitosan hydrogel adsorbent, as described in example 1, except that:
in the step (3), no RF is added, and the specific steps are as follows: 0.3g of chitosan (the deacetylation degree is more than or equal to 85%) with the weight-average molecular weight of 150,000Da is dissolved in 10mL of 2 wt% acetic acid aqueous solution to prepare a chitosan solution with the mass concentration of 3%. DF-PEG was dissolved in 1.0mL of water in an amount of 250mg to obtain a 20 wt% DF-PEG aqueous solution. Taking 250 mu L of 20 wt% DF-PEG aqueous solution, dripping the solution into 0.7g of chitosan solution in a vortex state to form hydrogel within a period of several seconds, and freeze-drying to obtain the chitosan hydrogel adsorbent.
The other steps and conditions were identical to those of example 1.
The results show that the chitosan adsorbent prepared in the comparative example is white, and the color of the adsorbent is not changed after adsorbing mercury ions. Thus, RF acts as a mercury ion indicator in the hydrogel adsorbent.
Comparative example 2
A method of making a chitosan hydrogel adsorbent, as described in example 1, except that:
in the step (3), rhodamine 6G hydrazide is used for replacing RF to prepare the chitosan hydrogel adsorbent, and other steps and conditions are consistent with those in the example 1.
The result shows that the chitosan adsorbent prepared by the comparative example has no obvious change in the color of the adsorbent after adsorbing mercury ions. Rhodamine 6G hydrazide cannot be dissolved in water, aggregation is easy to occur in the hydrogel preparation process, fluorescence quenching is caused, and therefore the obtained hydrogel adsorbent is poor in mercury ion recognition capability. The RF molecule used in the invention contains polyethylene glycol group, and RF shows good water solubility and stability, which is beneficial to preparing the adsorbent with good indication performance.
Comparative example 3
A method of making a chitosan hydrogel adsorbent, as described in example 1, except that:
the weight average molecular weight of the chitosan used in the step (3) is 20,000Da, and the deacetylation degree is more than or equal to 85 percent.
The other steps and conditions were identical to those of example 1.
The results show that the adsorbent prepared in the comparative example has no obvious color change after adsorbing mercury ions. The preparation method of the invention needs to select chitosan with molecular weight more than 50,000Da to prepare the adsorbent with obvious color change indication.
Test example:
testing the performance of the chitosan hydrogel adsorbent:
(1) the adsorption selectivity and the color indication effect of the adsorbent on mercury ions.
The adsorbents prepared in inventive example 1 were placed in a container containing 488mg/L Cu2+,413mg/L Hg2+,456mg/L Cd2+,577mg/L Pb2+The water solution is placed for 2 hours, the adsorbent is taken out for photographing, the concentration of the residual metal ions in the solution is tested through flame atomic absorption spectroscopy, the removal rate of the adsorbent to the metal ions is calculated, and the test result is shown in figure 2.
As can be seen from FIG. 2, the mercury ion removal rate of the adsorbent is obviously higher than that of Cu2+,Cd2+And Pb2+And the sorbent turns red only after adsorbing mercury ions.
(2) Fluorescence selectivity of adsorbents to mercury ions
The adsorbents prepared in example 1 of the present invention were each placed at the same concentration (10)-4M) of Cu2+,Hg2+,Cd2+And Pb2+The fluorescence emission spectrum of the solution was tested with water as a blank and the results are shown in fig. 3.
As can be seen from FIG. 3, the fluorescence emission intensity of the adsorbent in the mercury ion solution is the strongest and is higher than Hg2+,Cd2+And Pb2+。
(3) Adsorption capacity of adsorbent to mercury ions
The adsorbents prepared in example 1 of the present invention were placed in each of 0-800mg/L Hg2+The dosage of the adsorbent in the aqueous solution is 5mg/mL, the aqueous solution is placed at room temperature for 2 hours, the adsorbent is taken out for photographing, the concentration of mercury ions in the solution after the adsorption balance is achieved through a flame atomic absorption spectrum test, an adsorption isotherm is drawn, and the test result is shown in figure 4.
The adsorption curve was fitted using a Lanmguir adsorption isotherm (correction factor R) over the range of concentration tested20.9832); calculating to obtain the maximum adsorption capacity of the adsorbent to mercury ions to be 115 mg/L; when Hg is contained2+At an initial concentration of 158mg/L, Hg after adsorption2+The equilibrium concentration of (A) is 5.6mg/L, and the removal rate of the mercury ions by the adsorbent is calculated to be 96.5%.
(4) Testing of adsorption equilibration time
The adsorbent prepared in example 1 of the present invention was placed in 200mg/L Hg2+The concentration of mercury ions remaining in the solution was measured at intervals in the aqueous solution of (1) by flame atomic absorption spectroscopy, and a time kinetic curve of the adsorbent was plotted, and the test results are shown in fig. 5.
As can be seen from FIG. 5, the mercury ions adsorbed by the adsorbent can reach equilibrium within 30 min.
(5) Cytotoxicity testing of RF
Mouse fibroblasts (3T3 cells) were cultured in high-glucose DMEM medium, then different concentrations of RF aqueous solution were added, and the survival rate of 3T3 cells in the case of co-culture at different concentrations of RF (prepared in example 1) was tested by the MTT method. The concentrations of the RF aqueous solutions were 500, 1000, 2000, 5000. mu.g/mL, respectively, and the test results are shown in FIG. 6.
As can be seen from FIG. 6, even though the RF concentration was 5000. mu.g/mL, the cell survival rate was still over 70%, thus demonstrating that the cytotoxicity of RF was low.

Claims (10)

1. The chitosan-based hydrogel adsorbent capable of visually identifying and removing mercury ions is characterized in that the adsorbent is a block-shaped material with a three-dimensional porous structure, and the pore diameter is 100-200 mu m.
2. The method for preparing the chitosan-based hydrogel adsorbent capable of visually recognizing and removing mercury ions according to claim 1, comprising the steps of:
(1) in a solvent A, under the action of a catalyst, reacting polyethylene glycol with p-formaldehyde benzoic acid to prepare benzaldehyde-terminated polyethylene glycol (DF-PEG);
(2) in a solvent B, reacting benzaldehyde-terminated polyethylene glycol with rhodamine 6G hydrazide through Schiff base to prepare polyethylene glycol-modified rhodamine 6G hydrazide (RF); the molar ratio of the benzaldehyde-terminated polyethylene glycol to rhodamine 6G hydrazide is 1: 0.95-1: 1.05;
(3) dissolving chitosan in a dilute acid solution to obtain a chitosan solution; dissolving polyethylene glycol-modified rhodamine 6G hydrazide and benzaldehyde-terminated polyethylene glycol in water to obtain a mixed solution; mixing the chitosan solution and the mixed solution, reacting, and then carrying out freeze drying to obtain the chitosan-based hydrogel adsorbent.
3. The method for preparing a chitosan-based hydrogel adsorbent capable of visually recognizing and removing mercury ions according to claim 2, wherein the step (1) comprises one or more of the following conditions:
i. the solvent A is methanol, ethanol, acetone or tetrahydrofuran; preferably, the solvent A is tetrahydrofuran; the volume ratio of the mass of the p-formaldehyde benzoic acid to the solvent A is 0.005-0.1 g/mL;
ii. The catalyst is a combination of dicyclohexyl diimine and 4-dimethylamino pyridine, and the mass ratio of the dicyclohexyl diimine to the 4-dimethylamino pyridine is 1: 15-20; the mass of the catalyst is 1-3 times of that of p-formaldehyde benzoic acid; preferably, the catalyst dicyclohexyl diimine is added into a reaction system in a dropwise manner;
iii, the molar ratio of the hydroxyl of the polyethylene glycol to the carboxyl in the p-formaldehyde benzoic acid is 1: 1-1: 3;
iv, the polyethylene glycol can be linear polyethylene glycol or hyperbranched polyethylene glycol; preferably, the polyethylene glycol is linear polyethylene glycol, four-arm polyethylene glycol or eight-arm polyethylene glycol;
v, the number average molecular weight of the polyethylene glycol is 200-; preferably, the number average molecular weight of the polyethylene glycol is 2000-;
vi, the reaction temperature is 15-50 ℃; the reaction time is 10-60 hours; preferably, the reaction time is 40-55 h;
vii, the reaction is carried out under the protection of inert atmosphere; the inert gas is nitrogen, argon or helium; preferably, the inert gas is nitrogen.
4. The method for preparing a chitosan-based hydrogel adsorbent capable of visually recognizing and removing mercury ions according to claim 2, wherein the step (2) comprises one or more of the following conditions:
i. the solvent B is methanol, ethanol or acetone; preferably, the solvent B is acetone; the mass ratio of the rhodamine 6G hydrazide to the solvent B is 0.001-0.01G/mL;
ii. The reaction of rhodamine 6G hydrazide and benzaldehyde-terminated polyethylene glycol can also be carried out under the action of a catalyst; the catalyst is boric acid, benzenesulfonic acid or glacial acetic acid; preferably, the catalyst is glacial acetic acid;
iii, the reaction temperature is 10-58 ℃; preferably, the reaction temperature is 55-58 ℃; the reaction time is 2 to 96 hours, preferably 2 to 8 hours;
iv, adding the benzaldehyde-terminated polyethylene glycol into a system containing a solvent B and rhodamine 6G hydrazide in a dropwise manner.
5. The method for preparing a chitosan-based hydrogel adsorbent capable of visually identifying and removing mercury ions according to claim 2, wherein in the step (2), the preparation of the rhodamine 6G hydrazide comprises the steps of: in a solvent C, rhodamine 6G and hydrazine hydrate react to prepare rhodamine 6G hydrazide.
6. The method for preparing chitosan-based hydrogel adsorbent capable of visually recognizing and removing mercury ions according to claim 5, wherein one or more of the following conditions are included:
i. the solvent C is methanol or ethanol; the volume ratio of the mass of the rhodamine 6G to the volume of the solvent C is 0.01-0.1G/mL;
ii. The molar ratio of rhodamine 6G to hydrazine hydrate is 1: 5-1: 60, adding a solvent to the mixture; further preferably, the molar ratio of rhodamine 6G to hydrazine hydrate is 1: 20-1: 55;
iii, the hydrazine hydrate is aqueous solution of hydrazine hydrate with the mass concentration of 40-90%;
iv, the reaction temperature is 30-80 ℃; further preferably, the reaction temperature is 70-80 ℃; the reaction time is 2-24 hours, preferably 10-20 hours;
and v, adding the hydrazine hydrate into the system in a dropwise manner.
7. The method for preparing a chitosan-based hydrogel adsorbent capable of visually identifying and removing mercury ions according to claim 2, wherein in the step (3), the weight average molecular weight of the chitosan is 50,000-500,000Da, and the deacetylation degree is greater than or equal to 85%; preferably, the chitosan has a weight average molecular weight of 150,000 Da.
8. A method for preparing chitosan-based hydrogel adsorbent capable of visually recognizing and removing mercury ions according to claim 2, wherein step (3) comprises one or more of the following conditions:
i. the dilute acid solution is acetic acid aqueous solution, hydrochloric acid aqueous solution or citric acid aqueous solution; the mass concentration of the dilute acid solution is 1-5%;
ii. The mass concentration of the chitosan solution is 1-10%; preferably, the mass concentration of the chitosan solution is 2-3%;
iii, the mass ratio of the polyethylene glycol modified rhodamine 6G hydrazide to the benzaldehyde terminated polyethylene glycol is 2-8: 1;
iv, in the mixed solution, the concentration of the polyethylene glycol modified rhodamine 6G hydrazide is 0.1-2G/mL;
v, the reaction temperature of the mixed solution of the chitosan solution and the mixed solution is room temperature, and the reaction is carried out until hydrogel is formed.
9. The method for preparing a chitosan-based hydrogel adsorbent capable of visually identifying and removing mercury ions according to claim 2, wherein in the step (3), the mass ratio of the chitosan to the polyethylene glycol modified rhodamine 6G hydrazide is 1: 3-20.
10. The application of the chitosan-based hydrogel adsorbent capable of visually identifying and removing mercury ions according to claim 1 in adsorbing mercury ions in an aqueous solution.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113845655A (en) * 2021-10-20 2021-12-28 山东大学 Water-soluble fluorescein polymer probe for mercury ion detection and preparation and application thereof
CN114933706A (en) * 2022-05-12 2022-08-23 华南理工大学 Biomass dynamic gel polymer based on Schiff base reaction, lithium metal negative electrode, and preparation method and application of biomass dynamic gel polymer
CN115753933A (en) * 2022-12-22 2023-03-07 中国热带农业科学院南亚热带作物研究所 Preparation method and application of carboxymethyl chitosan-based hydrogel modified electrode
CN116535669A (en) * 2023-05-10 2023-08-04 北京盈合微纳科技有限公司 Degradable heavy metal chelating agent and preparation method thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102153700A (en) * 2011-03-16 2011-08-17 江南大学 Preparation of hydrophilic polymer and application thereof in detecting mercury ions based on change of fluorescence and color
CN104614369A (en) * 2014-12-29 2015-05-13 同济大学 Preparation method of high-selectivity Hg<2+> color indicator based on Rhodamine B thiohydrazine derivative
CN104607152A (en) * 2014-12-16 2015-05-13 天津工业大学 Rhodamine derivative modified magnetic chitosan adsorbent used for Hg (II) inspection and adsorption
CN105385439A (en) * 2015-12-01 2016-03-09 东华大学 Reaction type Rhodamine-class fluorescence probe for mercury ion detection and preparation as well as application thereof
CN105817208A (en) * 2016-05-06 2016-08-03 福州大学 Rhodamine B-grafted chitosan adsorbent and preparation and application thereof
US9914111B1 (en) * 2017-01-20 2018-03-13 Wuhu Gefeng Green Technology Research Center Co., Ltd. Solid-phase synthetic procedure for attapulgite-crosslinked chitosan composite adsorbent
CN112159522A (en) * 2020-10-09 2021-01-01 山东大学 Water-soluble rhodamine-based fluorescent/colorimetric dual-mode probe and preparation method and application thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102153700A (en) * 2011-03-16 2011-08-17 江南大学 Preparation of hydrophilic polymer and application thereof in detecting mercury ions based on change of fluorescence and color
CN104607152A (en) * 2014-12-16 2015-05-13 天津工业大学 Rhodamine derivative modified magnetic chitosan adsorbent used for Hg (II) inspection and adsorption
CN104614369A (en) * 2014-12-29 2015-05-13 同济大学 Preparation method of high-selectivity Hg<2+> color indicator based on Rhodamine B thiohydrazine derivative
CN105385439A (en) * 2015-12-01 2016-03-09 东华大学 Reaction type Rhodamine-class fluorescence probe for mercury ion detection and preparation as well as application thereof
CN105817208A (en) * 2016-05-06 2016-08-03 福州大学 Rhodamine B-grafted chitosan adsorbent and preparation and application thereof
US9914111B1 (en) * 2017-01-20 2018-03-13 Wuhu Gefeng Green Technology Research Center Co., Ltd. Solid-phase synthetic procedure for attapulgite-crosslinked chitosan composite adsorbent
CN112159522A (en) * 2020-10-09 2021-01-01 山东大学 Water-soluble rhodamine-based fluorescent/colorimetric dual-mode probe and preparation method and application thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
MENG,QINGTAO ET AL.: "A new rhodamine–chitosan fluorescent material for the selective detection of Hg2+ in living cells and efficient adsorption of Hg2+ in natural water", 《SENSORS AND ACTUATORS B: CHEMICAL》 *
刘伟: "《生物高分子材料及其应用研究》", 30 November 2017, 电子科技大学出版社 *
段久芳: "《天然高分子材料》", 30 September 2016, 华中科技大学出版社 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113845655A (en) * 2021-10-20 2021-12-28 山东大学 Water-soluble fluorescein polymer probe for mercury ion detection and preparation and application thereof
CN113845655B (en) * 2021-10-20 2022-06-24 山东大学 Water-soluble fluorescein polymer probe for mercury ion detection and preparation and application thereof
CN114933706A (en) * 2022-05-12 2022-08-23 华南理工大学 Biomass dynamic gel polymer based on Schiff base reaction, lithium metal negative electrode, and preparation method and application of biomass dynamic gel polymer
CN115753933A (en) * 2022-12-22 2023-03-07 中国热带农业科学院南亚热带作物研究所 Preparation method and application of carboxymethyl chitosan-based hydrogel modified electrode
CN115753933B (en) * 2022-12-22 2023-08-11 中国热带农业科学院南亚热带作物研究所 Preparation method and application of carboxymethyl chitosan-based hydrogel modified electrode
CN116535669A (en) * 2023-05-10 2023-08-04 北京盈合微纳科技有限公司 Degradable heavy metal chelating agent and preparation method thereof
CN116535669B (en) * 2023-05-10 2023-12-08 北京盈合微纳科技有限公司 Degradable heavy metal chelating agent and preparation method thereof

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