CN109632985B - Method for detecting bisphenol compounds and derivatives thereof based on extraction technology of metal organic framework nano materials - Google Patents
Method for detecting bisphenol compounds and derivatives thereof based on extraction technology of metal organic framework nano materials Download PDFInfo
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Abstract
The invention provides a method for detecting bisphenol compounds and derivatives thereof based on an extraction technology of a metal organic framework nano material. The nano material is NH2MIL-101(Fe) material, bisphenolic compounds and derivatives thereof log KowBisphenols and derivatives thereof in the range of 1.17 to 3.96 are referred to as BPs. The method comprises the following steps: s1: adsorbing agent NH2Adding MIL-101(Fe) into a sample containing BPs, adjusting the pH of the sample to be within the range of 2.0-7.0, and performing ultrasonic treatment for 1.0-5.0min to obtain liquid after ultrasonic treatment; s2: centrifuging the liquid obtained in the step S1 after ultrasonic treatment to obtain liquid A, and removing a supernatant M of the liquid A to obtain liquid B; s3: carrying out vortex elution on the liquid B obtained in the S2 for 1.0-5.0min by using an eluent, then carrying out centrifugal treatment to obtain a liquid C, and collecting a supernatant N of the liquid C, wherein the eluent is one of methanol, acetonitrile and acetone; s4: after the volume of the supernatant N in step S3 was fixed, quantitative analysis was performed by chromatography.
Description
Technical Field
The invention relates to the technical field of detection, in particular to a method for dispersing micro-solid phase extraction technology based on metal organic framework materials and using bisphenol compounds and derivatives thereof
Background
Metal Organic Frameworks (MOFs), also known as Porous Coordination Polymers (PCPs), are a network-like framework structure with highly ordered three-dimensional structure crystals formed by self-assembly of Metal ions (clusters or secondary building blocks (SBUs)) and Organic ligands (linkers) through Coordination bonds. The MOFs have ultra-high specific surface area up to 10400m2g-1And the specific surface area of the general nano material is far lower than the value. In addition, MOFs have uniformly structured cavities with specific pore sizes (about 0.3-10 nm), and ultra-low densities (as low as 0.13g cm)-3) And thermal stability (about 300 to 600 ℃) and strong adsorption affinity. Furthermore, the central metal, coordinately unsaturated metal sites (CUS or open metal sites), functional linkers, and active loading species can be used for synthesis, modification, and post-modification of MOF materials. The above outstanding characteristics of MOFs make these hybrid organic-inorganic materials ideal as sample pretreatment adsorbents in separation science.
In the dispersed micro solid phase extraction, the hydrogen bond action between the adsorbent and the target molecule and the coordination with the open metal site play important roles in the extraction process. Generally speaking, for the same type of organic matters, compared with the organic matters with small polarity, the adsorption effect between the traditional nano material and the polar organic compound is weaker, so that the traditional adsorbent cannot meet the analysis requirement.
Although there is no report at present, the inventors have studied to obtain: the hydrogen bond acting force generated by the amino group on the MOFs surface and bisphenol compounds and derivatives (BPs) thereof can greatly improve the analysis and extraction performance, and the scheme of the invention is made on the basis of the hydrogen bond acting force.
Disclosure of Invention
The invention provides a method for detecting bisphenol compounds and derivatives thereof based on an extraction technology of a metal organic framework nano material, which has the advantages of high precision, low detection limit and simple and convenient operation, and is very suitable for analyzing and detecting trace BPs in environmental samples.
A method for detecting bisphenol compounds and derivatives thereof based on an extraction technology of metal organic framework nano materials. The nano material is NH2-MIL-101(Fe) material; the bisphenol compound and the derivative thereof are log KowBisphenols and derivatives thereof in the range of 1.17 to 3.96, referred to as BPs, the process comprising the steps of:
s1: adsorbing agent NH2Adding MIL-101(Fe) into a sample containing BPs, adjusting the pH of the sample to be within the range of 2.0-7.0, and performing ultrasonic treatment for 1.0-5.0min to obtain liquid after ultrasonic treatment;
s2: centrifuging the liquid obtained in the step S1 after ultrasonic treatment to obtain liquid A, and removing a supernatant M of the liquid A to obtain liquid B;
s3: carrying out vortex elution on the liquid B obtained in the S2 for 1.0-5.0min by using an eluent, then carrying out centrifugal treatment to obtain a liquid C, and collecting a supernatant N of the liquid C, wherein the eluent is one of methanol, acetonitrile and acetone;
s4: after the volume of the supernatant N in step S3 was fixed, quantitative analysis was performed by chromatography.
Further setting, in step S1, adjusting the pH value of the sample to be within the range of 2.0-6.0.
On the basis, in step S2, corresponding to 5ml of sample, the NH is further set2MIL-101(Fe) was used in an amount of 30 mg.
Still further, in step S2, the ultrasound time is 2 min.
Further, in step S3, the eluent is methanol.
Preferably, in step S3, the eluent is 0.4mL of methanol corresponding to 5mL of sample.
On this basis, in step S3, the vortex elution time was 1 min.
MIL-101(Fe) (Material Institute Lavoisier, MIL) is an acid stable and hydrophilic MOFs with a zeolite-type crystal structure with high tolerance to air, water and common organic solvents. Therefore, MIL-101(Fe) can be used as a good adsorbent material for dispersed micro solid phase extraction, and the derivative NH thereof2-MIL101(Fe) has similar properties.
NH-based as established by the inventors2Micro-dispersed solid phase extraction method of MIL-101(Fe) to detect traces of BPs in the environment. Under the optimal extraction condition, the relative recovery rate of the BPs in the environment water matrix ranges from 90.8 to 117.78 percent, and the minimum detection limit is 0.0161 to 0.131 mu g L-1The in-day precision is 0.93-4.86%, and the in-day precision is 1.30-7.63%, which shows that the method has the advantages of wide linear range, high precision, low detection limit, good reproducibility and stability, simple synthetic method of the adsorbent material, simple and convenient pretreatment operation, and common analysis and detection instruments, and is very suitable for the analysis and detection of trace BPs in environmental samples.
Comparing the performance of the method with that of the prior analysis method, the developed method has lower LOD value, higher recovery rate and high precision. Furthermore, based on NH2The dispersed solid phase extraction method of MIL-101(Fe) can complete the extraction and elution processes within 3min, and the use amount of organic solvent in the whole extraction process is far lower than that of other methods. It is worth mentioning that as an adsorbent in the environmental analysis enrichment process, NH2The MIL-101(Fe) has higher recovery rate for low-polarity BPs, and the extraction performance for high-polarity BPs is greatly improved compared with that of the MIL-101 (Fe).
The present invention will be described in further detail with reference to the accompanying drawings.
Drawings
FIG. 1 is a schematic diagram of the crystal structure of MIL-101 (Fe);
FIG. 2 is NH2N of MIL-101(Fe)2Adsorption and desorption isotherms and particle size distribution maps;
FIG. 3 shows an extracting agent NH2Effect of MIL-101(Fe) dosage on BPs recovery;
FIG. 4 is a graph of the effect of sample pH on the efficiency of BPs extraction;
FIG. 5 is a graph of the effect of sonication time on recovery of BPs;
FIG. 6 is a graph showing the effect of elution solvent species on the efficiency of BPs extraction;
FIG. 7 Effect of eluent volume on the efficiency of extraction of BPs;
FIG. 8 is a chromatogram of an actual sample of bisphenol compound and its derivatives;
FIG. 9 is a schematic diagram of the steps of the method of the present invention.
Detailed Description
The invention is described in detail below by way of exemplary embodiments. The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Examples
First synthesis of NH2MIL-101 (Fe). FeCl was added to 60mL of DMF solution3·6H2O (19.75mmol, 5.338g) and NH2BDC (10.0mmol, 1.812g), the mixture was magnetically stirred for 10min and transferred to a 100mL stainless steel autoclave with a Teflon liner and heated at 110 ℃ for 24 h. After cooling to room temperature, the suspension was transferred to a 100mL plastic centrifuge tube, centrifuged at 7000rpm for 5min and the product collected as a dark brown solid, which was washed thoroughly with DMF to remove unreacted NH2BDC, washed three times with ultrapure water and ethanol each, and finally dried under vacuum at 60 ℃ for 6h to give activated NH2-MIL-101(Fe)。
At 77K liquid nitrogen temperature, by N2Adsorption and desorption experiments, analysis of NH2Surface area and pore structure of MIL-101 (Fe). NH (NH)2N of MIL-101(Fe)2The adsorption/desorption isotherm results are shown in figure 2. Porous NH calculated by fitting of BET and BJH methods2SBET of MIL-101(Fe) nanomaterial is 2914.35m2g-1Average pore volume of 1.46m3g-1The pore diameter is 2.19 nm. The large pore size and high specific surface area of the nano materials can greatly improve the adsorption efficiency of the nano materials.
Chromatographic conditions are as follows:
analytical quantification was performed using HPLC-FLD system, mobile phases B and C were acetonitrile and pH 3.0 phosphoric acid ultrapure water, respectively. Elution was performed using a 22min binary gradient, with the following specific conditions: 30% C at 0.0-3.0 min; 31-4.0min, 30% -40% C; 4.1-17.0min, 40% C,17.1-18min, 40% -30% C,18-22min, 30% C. Flow rate 1.0mL min-1The column temperature was 30 ℃ and the sample injection volume was 10. mu.L. The fluorescence excitation wavelength and the emission wavelength were 233nm and 303nm, respectively.
And (3) extraction and detection steps:
the method comprises the following steps: placing 5mL sample solution containing BPs into a 15mL conical centrifuge tube, and then adding 10-50 mg NH2-MIL-101(Fe) nanomaterial, adjusting the pH to 2.0-7.0, and subjecting it to ultrasonic treatment for 1.0-5.0 min.
As shown in FIG. 3, 30mg NH was added due to the large specific surface area and high adsorption efficiency of the nanomaterial2MIL-101(Fe) is already sufficient to obtain satisfactory results. Therefore, preferably, 30mg of NH is selectively added to 5ml of the liquid to be tested2-MIL-101(Fe) nanomaterial.
It can be seen from FIG. 4 that the recovery rate is not very different at pH values in the range of 2.0 to 7.0, but drops sharply to zero when the pH value is increased from 7.0 to 11.0. This is because of NH2MIL-101(Fe) is relatively stable under acidic and neutral conditions, and is easily hydrolyzed under alkaline conditions, even resulting in the collapse of MOFs frameworks. Further, NH increased from pH 6.0 to pH 7.02Recovery of polar BPs (e.g., BFDGE2H2O, BPF) from MIL-101(Fe) is slightly reduced (. DELTA.ERs about 2.1-9.0%). This is because NH is present at a solution pH of 2.0 to 6.02The surface of the MIL-101(Fe) material is positively charged and has stable structure; when the pH value is 6-7, the zeta potential begins to become negative, the surface of the material is slightly negatively charged, the hydrogen bond interaction is no longer stable, and therefore the polar BPs (such as BFDGE 2H)2O, BPF) recovery decreased slightly; when the pH value exceeds 7, the MOFs structural skeleton is broken, and thus the recovery rate is sharply reduced. Therefore, the pH is preferably 2.0 to 6.0. After the addition of the adsorbent, the pH values of the three aqueous solutions of seawater, river water and tap water were 5.58, 4.03 and 3.15, respectively, so that it was not necessary to adjust the pH values of the sample solutions.
As shown in FIG. 5, the recovery rate of BPs gradually increases to the maximum value when the ultrasound time is 1.0-2.0 min, and then gradually decreases from 2min to 5min, but generally speaking, the recovery rate is objective when the ultrasound time is 1.0-5.0 min. After the ultrasonic time exceeds 2min, the recovery rate of the BPs is in a downward trend, because the reaction balance is shifted to the left by the ultrasonic for too long time, and the energy is strong in the ultrasonic process, a part of adsorbed target substances can fall off, and the MOF framework structure can collapse, thereby affecting the recovery rate of the sample. Therefore, it is preferable that the extraction time is set to 2.0 min.
Step two: and centrifuging the sample obtained in the step (i) at 5000rpm for 10min to obtain liquid A. The supernatant M of the obtained liquid A was removed to obtain a liquid B.
Step three: eluting liquid B with 0.1-0.8mL of eluting solvent by vortex for 1.0-5.0min, centrifuging at 5000rpm for 3min to obtain solution C, and collecting supernatant N of solution C. Eluting solvent: methanol, acetonitrile and acetone.
There was little significant increase in extraction efficiency when the vortex time was extended from 1.0min to 5.0 min. Therefore, the elution time is preferably 1.0 min.
As shown in fig. 6, the elution recovery capacities of BPs for different eluents are ranked as: methanol > acetone > acetonitrile, indicating that methanol is most suitable as eluent. Preferably, the eluent is methanol.
The volume of elution solvent used in elution should be sufficient to completely elute the analyte from the adsorbent, but as little elution solvent as possible should be used to avoid over-diluting the sample. As can be seen from FIG. 7, the recovery of BPs is highest when the methanol volume is 400. mu.L. When the volume is less than 400. mu.L, BPs cannot be completely eluted; whereas when the elution volume was increased from 400. mu.L to 800. mu.L, the concentration of the target analyte was significantly reduced and the fold enrichment decreased due to dilution, although the recovery remained essentially unchanged. It is therefore preferred that for 5ml of sample, 400. mu.L of methanol is used as the elution solvent.
Step IV: and (4) carrying out constant volume on the supernatant N and then carrying out chromatographic analysis.
Example 2:
the experimental procedure is as shown in example 1, with the following differences: the amount of the extracting agent is 30mg, the ultrasonic extraction time is 2.0min, the elution solvent is 400 mu L of methanol, the elution time is 1.0min, and the pH value of the sample is within the range of 2.0-6.0.
The experimental results are as follows:
correlation coefficient R of linear equation of BPs2Between 0.9986 and 0.9997; when the S/N ratio is 3, the lowest detection limit is 0.016-0.131 mu g L-1(ii) a The limit of quantitation is 0.05-0.44 mu g L when the S/N ratio is 10-1. The linear ranges of the bisphenol compound and the bisphenol derivative are respectively 0.5-200 mu g L-1，0.25～200μg L-1。
To test the stability of the process, the inventors measured daytime and daytime recovery data for the process, with a high setting for each test (50 μ g L)-1) Zhong (20 mu g L)-1) And low (5 μ g L)-1) Detecting the same batch of samples once every 2h when the recovery rate in the day is measured at three concentration levels, and measuring 6 times in total to obtain an average value; when the daytime recovery rate is measured, the sample injection detection is carried out at 8:00 am every day, the continuous detection is carried out for 6 times, and the average value is taken. At three concentration levels, the in-day precision range of the target analyte is 0.93-4.86%; the daytime precision is 1.30-7.63%. The method has good reproducibility and completely meets the requirement of actual detection.
Experimental example:
experimental reagent: water samples were collected from different regions of wenzhou china. Wherein the river water sample is from Wenzea river, the seawater sample is from coastal region near Yangtze town of Hannan county, and the tap water sample is directly collected from laboratory of Wenzhou medical university. Each water sample was filtered through a 0.45 μm PES filter and stored in a clean glass vial at 4 ℃. The above samples were used after being left to room temperature during testing.
After the water samples of each kind are divided into groups, BPs with known quantity are respectively added into the water samples, and the concentrations of the added BPs standard substances are respectively 0 and 5 mu g L-1，20μg L-1And 50 μ g L-1。
The experimental process comprises the following steps: the experimental procedure is as shown in example 1, with the following differences: the amount of the extracting agent is 30mg, the ultrasonic extraction time is 2.0min, the elution solvent is 400 mu L of methanol, the elution time is 1.0min, and the pH value of the sample is within the range of 2.0-6.0.
The actual detection effect was evaluated by the Relative Recovery (RR), also called method recovery. The relative recovery is obtained by the following formula:
RR(％)＝ni/n0×100％
in this formula, niRepresenting the response value, n, of the target analyte recovered from the actual sample matrix0Representing the response value generated by a known amount of standard added to the matrix.
BADGE.2H was detected in river water without addition of BPs2O, concentration 4.33 +/-0.93 mu g L-1And no BPs and derivatives thereof were detected in the blank samples without BPs added in both tap water and seawater;
when the actual sample is added with the standard substance with high, medium and low detection concentrations, the recovery rate range of the BPs in the environmental water sample is 90.78-117.8%. FIG. 8 is a chromatogram of an actual sample, in which the sample concentration in the environmental water sample is 20 μ g L-1. The data show that the established processing and detecting method is simple, efficient and reproducible, and is very suitable for log KowAnalytical detection of trace amounts of broad polarity BPs and their derivatives ranging from 1.17 to 3.96.
Comparing the performance of the method with that of the prior analysis method, the developed method has lower LOD value, higher recovery rate and high precision. Furthermore, based on NH2The dispersed solid phase extraction method of MIL-101(Fe) can complete the extraction and elution processes within 3min, and the use amount of organic solvent in the whole extraction process is far lower than that of other methods. It is worth mentioning that as an adsorbent in the environmental analysis enrichment process, NH2The MIL-101(Fe) has higher recovery rate for low-polarity BPs, and the extraction performance for high-polarity BPs is greatly improved compared with that of the MIL-101 (Fe).
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (4)
1. A method for detecting bisphenol compounds and derivatives thereof based on an extraction technology of metal organic framework nano materials is characterized by comprising the following steps: the nano material is NH2-MIL-101(Fe) material; the bisphenol compound and the derivative thereof are log KowBisphenols and derivatives thereof in the range of 1.17 to 3.96, referred to as BPs, the process comprising the steps of:
s1: adding 10-50 mg NH into 5mL sample solution containing BPs2MIL-101(Fe) nano material, adjusting the pH value of a sample to be within the range of 2.0-7.0, and performing ultrasonic treatment for 1.0-5.0min to obtain liquid after ultrasonic treatment;
s2: centrifuging the liquid obtained in the step S1 after ultrasonic treatment to obtain liquid A, and removing a supernatant M of the liquid A to obtain liquid B;
s3: carrying out vortex elution on the liquid B obtained in the S2 for 1.0-5.0min by using an eluent, then carrying out centrifugal treatment to obtain a liquid C, and collecting a supernatant N of the liquid C, wherein the eluent is one of methanol, acetonitrile and acetone;
s4: carrying out constant volume on the supernatant N in the step S3, and then carrying out chromatographic analysis and quantification;
in step S3, the eluent is 0.4mL of methanol corresponding to 5mL of the sample;
analytical quantification was performed using HPLC-FLD system, mobile phases B and C are acetonitrile and pH =3.0 phosphoric acid ultrapure water, respectively; elution was performed using a 22min binary gradient, with the following specific conditions: 0.0-3.0min 30% C, 3.1-4.0 min 30-40% C, 4.1-17.0min 40% C,17.1-18min 40-30% C,18-22min 30% C; the flow rate is 1.0mL min-1, the column temperature is 30 ℃, and the sample injection volume is 10 mu L; the fluorescence excitation wavelength and the emission wavelength were 233nm and 303nm, respectively.
2. The method for detecting bisphenol compounds and derivatives thereof based on the extraction technology of metal organic framework nano materials as claimed in claim 1, wherein the method comprises the following steps: in step S1, the pH value of the sample is adjusted to be within the range of 2.0-6.0.
3. The method for detecting bisphenol compounds and their derivatives based on the extraction technology of metal organic framework nanomaterials as claimed in any one of claims 1 to 2, wherein: in step S2, the ultrasound time is 2 min.
4. The method for detecting bisphenol compounds and derivatives thereof based on the extraction technology of metal organic framework nano materials as claimed in claim 1, wherein the method comprises the following steps: in step S3, the vortex elution time was 1 min.
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