Lead-cadmium ion double-template magnetic molecularly imprinted polymer and preparation method thereof
Technical Field
The invention relates to the field of heavy metal ion enrichment, in particular to a lead-cadmium ion double-template magnetic molecularly imprinted polymer and a preparation method thereof.
Background
Cadmium and lead are heavy metal elements which are seriously polluted and have strong toxicity at present, and even if the concentration of cadmium and lead is extremely low in the natural environment, the cadmium and lead can cause serious harm to human beings. Excessive lead intake by people can inhibit the development of the brain, resulting in chronic nephritis; the food polluted by lead can be enriched to human body through food chain, thus causing harm to human body, when the content of blood lead reaches 2.9-3.86 mu mol.L-1Lead poisoning may occur; whileCadmium has carcinogenicity, and in addition, the accumulation of cadmium in a human body can cause the damage of renal function and the damage of the regulation function of calcium and phosphorus, thereby causing bone decalcification, bone softening and pathological fracture; therefore, monitoring the content of lead and cadmium ions in environmental and food samples is of great significance.
The magnetic molecular imprinting technology not only has stronger adsorption capacity on heavy metals, but also has the characteristic of controllable magnetic separation, avoids complex concentration and classification processes such as centrifugation and filtration, and is widely concerned in the field of heavy metals. The existing magnetic cadmium ion imprinted polymer only selectively adsorbs cadmium ions, and has the defects of small adsorption capacity and low adsorption enrichment efficiency, and lead and cadmium heavy metal pollutants in water environment, soil or agricultural products often exist at the same time; in addition, in the prior art, methacrylic acid, salicylaldoxime, acrylamide, vinylpyridine and the like are generally used as functional monomers, and the chemicals have certain toxicity to human bodies and are easy to have certain risks in detection of food samples.
Disclosure of Invention
Aiming at the problems, the invention provides a preparation method of a lead-cadmium ion double-template magnetic molecularly imprinted polymer.
The purpose of the invention is realized by adopting the following technical scheme:
a preparation method of a lead-cadmium ion double-template magnetic molecularly imprinted polymer comprises the following steps:
(1)Fe3O4@mSiO2preparation of
(2) Synthesis of double-template magnetic molecularly imprinted polymer
Fe3O4@mSiO2Ultrasonically dispersing in solvent, adding silane coupling agent, regulating pH to 10 with alkali solution, adding papain as functional monomer and carbodiimide as dehydrating agent to react with the coupling agent, adding soluble lead salt and cadmium salt as template molecules, stirring for reaction, magnetically separating, and adding Pb2+、Cd2+Eluting, cleaning and vacuum drying to prepare the double-template magnetic molecularly imprinted polymer;
preferably, the solvent is a mixed solution of ethanol and water in a volume ratio of 1:4 and Fe3O4@mSiO2The solid-to-liquid ratio of (A) is 0.3-0.5g/100 mL;
preferably, the silane coupling agent is one of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, and Fe3O4@mSiO2The mixing ratio of (A) to (B) is 8 mL/g;
preferably, the alkali liquor is diethanolamine or triethanolamine or tetrabutylammonium;
preferably, the papain is commercial papain, CAS No. 9001-73-4, casein is used as a substrate, the enzyme activity is more than or equal to 2000units/mg, and the enzyme activity is Fe3O4@mSiO2The mass ratio of (A) is 1-1.5 g/g;
preferably, the carbodiimide is one or more of N, N '-dicyclohexylcarbodiimide, N' -bis (2, 6-diisopropylphenyl) carbodiimide, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, 1-cyclohexyl-2-morpholinoethylcarbodiimide p-toluenesulfonate, and Fe3O4@mSiO2The mass ratio of (A) is 0.5-1.5 g/g.
Preferably, the concentrations of the soluble lead salt and the soluble cadmium salt added in the reaction system are respectively 1-2 mmol/L;
preferably, the elution in step (2) is first washed with deionized water and ethanol, respectively, and then washed with 0.1mol · L under ultrasonic conditions-1Washing with EDTA solution until the washing solution can not detect the heavy metal ions in the template, and washing with methanol for three times.
The second purpose of the application is to provide a lead-cadmium ion dual-template magnetic molecularly imprinted polymer, which is prepared by any one of the preparation methods.
The application also aims to provide an application of the lead-cadmium ion dual-template magnetic molecularly imprinted polymer, which comprises the detection, enrichment and/or separation of lead and/or cadmium in a sample to be detected.
The invention has the beneficial effects that:
(1) the invention uses Pb2+、Cd2+Preparing a papain magnetic molecularly imprinted polymer for the double templates; the magnetic molecularly imprinted polymer can simultaneously adsorb two heavy metal ions of lead and cadmium with high selectivity and high adsorption capacity, has good recycling performance and wide application range, and can be used for Pb in biological samples, environmental samples, food and agricultural products2+、Cd2+Has wide application prospect in rapid magnetic separation, enrichment and analysis.
(2) The papain contains sulfydryl, can be better complexed with lead and cadmium ions, can provide more binding sites simultaneously, so as to coordinate with a large amount of metal ions, is nontoxic, is derived from plants, has good thermal stability, and is natural, sanitary and safe.
(3) The obtained magnetic molecularly imprinted polymer has the advantages of simple preparation, low cost, low operation requirement, high selectivity on template ions and the like, and the magnetic molecularly imprinted polymer prepared by combining the magnetic nanoparticles and the imprinting technology not only has the advantage of high selectivity of the imprinted polymer, but also can realize rapid separation under the action of an external magnetic field, thereby avoiding complex operations such as centrifugation, filtration and the like and improving the enrichment and separation efficiency.
Drawings
The invention is further illustrated by means of the attached drawings, but the embodiments in the drawings do not constitute any limitation to the invention, and for a person skilled in the art, other drawings can be obtained on the basis of the following drawings without inventive effort.
FIG. 1 is a schematic diagram of a preparation process of the lead-cadmium ion dual-template magnetic molecularly imprinted polymer.
Detailed Description
The invention is further described with reference to the following examples.
Example 1
A preparation method of a lead-cadmium ion double-template magnetic molecularly imprinted polymer comprises the following steps:
(1)Fe3O4@mSiO2preparation of
In N25.838g FeCl under protection3·6H2O and 3.003g FeSO4·7H2Dissolving O in 100mL distilled water, heating to 80 deg.C, dripping 13mL concentrated ammonia water while mechanically stirring, stirring at 80 deg.C for 30min, adding sodium pyrophosphate 1g, heating the solution to 90 deg.C, stirring for 1.5h, magnetically separating, washing with distilled water, drying in 50 deg.C vacuum drier for 6h to obtain magnetic nanometer Fe3O4(ii) a 0.5g of hexadecyl trimethyl ammonium bromide (CTAB) and 0.01 mol.L are taken-150mL of NaOH and 50mL of deionized water are put in a 250mL flask, ultrasonic treatment is carried out for 15min, and the prepared magnetic nano Fe is added3O40.7g, mechanically stirring for 10min under the condition of 80 ℃ water bath, slowly dropwise adding 10mL of ethanol solution of TEOS, reacting for 2h, cleaning with ethanol after the reaction is finished, dispersing the cleaned compound particles in 20mL of ethanol containing 60mg of ammonium nitrate, heating to 60 ℃, keeping for 30min, centrifuging, repeating the cleaning for 2 times to remove CTAB, and vacuum drying at 60 ℃ for 5h to obtain Fe3O4@mSiO2;
(2) Synthesis of double-template magnetic molecularly imprinted polymer
1.0g of prepared Fe3O4@mSiO2Adding into a mixed solution of 160mL of deionized water and 40mL of ethanol, performing ultrasonic dispersion for 30min, dropwise adding 8mL of LAPTES (3-aminopropyltriethoxysilane), dropwise adding diethanolamine to pH 10, reacting for 1h under the conditions of 90 ℃ water bath and mechanical stirring, sequentially adding 1.2g of papain and 1.0g of carbodiimide into the mixed solution, reacting for 6h, and finally adding 1.2mmol of Pb (NO) (NO is 1.2 mmol)3)2、Cd(NO3)2Stirring for 1 hr, magnetically separating, washing with deionized water and ethanol, and repeatedly treating with 0.1 mol/L under ultrasonic action-1EDTA washing until no Pb could be detected2+、Cd2+Washing with methanol for 3 times, and vacuum drying at 50 deg.C for 6 hr to obtain double-template magnetic molecularly imprinted polymer (DMIIP).
Example 2
Air drying or oven drying soil, rice and rice hull, pulverizing, and sieving with 200 mesh sieve; accurately weighing 0.2500g of the crude product in a digestion tube, adding 10mL of nitric acid, performing microwave digestion, wherein the microwave digestion procedure comprises the steps of firstly performing temperature programming to 250 ℃ in 20min, digesting for 20min, then cooling to room temperature, dispelling acid, cooling, then performing constant volume to 50mL by using a buffer solution with pH of 6.0, and performing magnetic solid-phase extraction and graphite furnace atomic absorption spectrophotometer determination.
Adding 30mg of lead-cadmium ion double-template magnetic imprinting molecular polymer into an 80mL beaker, adding 5.0mL of methanol, carrying out ultrasonic treatment for 5min, carrying out activation and magnetic separation, washing twice with 10.0mL of deionized water, adding a treated sample solution, oscillating for 30min at normal temperature, carrying out magnetic separation, and decanting; the adsorbent was washed twice with 5.0mL of methanol and finally with 3.0mL of 0.6 mol. L-1Ultrasonically washing with HCl for 10min, blowing nitrogen to evaporate the obtained solution to dryness, and fixing the volume of the concentrate to 50mL by using 0.1% nitric acid; determination of Pb in solution by graphite furnace atomic absorption spectrophotometer2+、Cd2+The standard recovery experiment was performed at the same time.
The results of the experiment are shown in table 1. Pb in the sample2+And Cd2+The measured recovery rate ranges are 85.3% -100% and 89.7% -104% respectively, and the relative standard deviation is less than 4.3%, which shows that the result is accurate and reliable. All samples were tested for lead and cadmium. The national standard requires that the Pb content of soil is less than or equal to 80 mg/kg-1,Cd≤0.3mg·kg-1(ii) a Pb of rice is less than or equal to 0.2 mg/kg-1,Cd≤0.1mg·kg-1(ii) a The Pb content of the feed is less than or equal to 5.0 mg/kg-1,Cd≤1.0mg·kg-1(ii) a The lead content in the rice hull 1 reaches the standard and the cadmium exceeds the standard; the lead and cadmium contents in the rice hull 2 reach the standard; while lead of soil and rice does not exceed the standard, cadmium seriously exceeds the standard. This indicates that the land has been heavily contaminated with cadmium.
TABLE 1 measurement results and recovery of lead and cadmium in soil, rice hulls
Experimental example 1
Accurately weighing 30mg of lead-cadmium ion dual-template magnetic molecularly imprinted polymer (DMIIP) to 10mL of Pb-containing polymer2+、Cd2+、Cu2+、Mg2+、Zn2+And the concentrations are all 1.0 mg/mL-1In the solution (pH 6), adsorbing at 25 deg.C for 1h with shaking, separating the adsorbent with a magnet, collecting the supernatant, and measuring Pb in the solution with a graphite furnace atomic absorption spectrophotometer2+、Cd2+、Cu2+、Mg2+、Zn2+The concentration of (A) is determined by preparing a magnetic non-molecularly imprinted polymer (DMNIP) as a control without adding Pb (NO)3)2、Cd(NO3)2The steps other than template molecule are the same as the preparation method of DMIIP.
The distribution coefficient K is calculated as followsdSelecting coefficient k and imprinting factor alpha.
Kd=Qbm/c0
k=Kd(Pb2+、Cd2+、Cu2+、Mg2+、Zn2+)/Kd(Mg2+)
α=kDMIIP/kDMNIP
QbmIs a lead-cadmium ion double-template magnetic molecularly imprinted polymer pair Pb2+、Cd2+、Cu2+、Mg2+、Zn2+Binding concentration (mmol. g)-1),c0Is the initial concentration of the solution.
Table 2 shows Pb pairs of lead-cadmium ion dual-template magnetic molecularly imprinted polymers2+、Cd2+And its analog Cu2+,Zn2+And Mg2 +Adsorption capacity (Q) and partition coefficient (K)d) The selection coefficient (k) and the imprinting factor (α). From Table 2, it can be seen that the Pb-Cd ion dual-template magnetic molecularly imprinted polymer is aligned with Pb2+、Cd2+Adsorption capacity (Q) and partition coefficient (K) ofd) The selection coefficient (k) and the imprinting factor (alpha) are greater than Cu2+、Zn2+、Mg2+The marked lead-cadmium ion double-template magnetic molecularly imprinted polymer microsphere can specifically adsorb imprinted ion Pb2+、Cd2+。
TABLE 2 adsorption and imprinting selectivity of lead-cadmium ion double-template magnetic molecularly imprinted polymers
Experimental example 2
30mg of lead-cadmium ion double-template magnetic molecularly imprinted polymer is weighed and added into 10mL of Pb-containing polymer2+、Cd2+The concentration is 1.0 mg/mL-1The solution was mixed (pH 6) with 0.6 mol. L each time in 8 adsorption cycles-1Hydrochloric acid for ultrasonic elution of Pb2+、Cd2+Then washing the mixture to be neutral by using secondary distilled water, NaOH solution and secondary distilled water in sequence, drying the mixture in vacuum at 50 ℃ for 6 hours, and adsorbing Pb again by using a regenerated adsorbent2+、Cd2+This cycle was repeated to calculate the amount of adsorption, and the results are shown in Table 3.
TABLE 3 Effect of the number of reuses on the adsorption Performance
Number of times of use
|
1
|
2
|
3
|
4
|
5
|
6
|
7
|
8
|
QPb(mg·g-1)
|
75.6
|
75.2
|
74.6
|
73.7
|
73.0
|
72.3
|
71.5
|
70.9
|
QCd(mg·g-1)
|
41.2
|
40.9
|
40.5
|
40.2
|
39.8
|
39.4
|
39.1
|
38.7 |
In practical applications, the recycling rate is a very important parameter of the adsorbent. As can be seen from Table 3, the double-template magnetic molecularly imprinted polymer containing the same lead and cadmium ions can be used for treating Pb after being repeatedly used for 8 times2+、Cd2+The adsorption capacity is respectively 75.6mg g-1Reduced to 70.9mg g-1,41.2mg·g-1Reduced to 38.7mg g-1Approximately 6.3% and 6.1% respectively. The reason is that the adsorption amount of the lead-cadmium ion double-template magnetic molecularly imprinted polymer is slightly reduced because a small amount of adsorbed heavy metal on the adsorbent cannot be completely eluted in the using process; experimental results show that the lead-cadmium ion double-template magnetic molecularly imprinted polymer has good reusability.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.