CN109632985A - A method of abstraction technique detection bisphenol compound and its derivative based on metal organic frame nano material - Google Patents
A method of abstraction technique detection bisphenol compound and its derivative based on metal organic frame nano material Download PDFInfo
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- CN109632985A CN109632985A CN201811527247.3A CN201811527247A CN109632985A CN 109632985 A CN109632985 A CN 109632985A CN 201811527247 A CN201811527247 A CN 201811527247A CN 109632985 A CN109632985 A CN 109632985A
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Abstract
The present invention provides a kind of method of abstraction technique detection bisphenol compound and its derivative based on metal organic frame nano material.The nano material is NH2- MIL-101 (Fe) material, bisphenol compound and its derivative are log KowBisphenol compound and its derivative of the range in 1.17~3.96, referred to as BPs.The method includes the steps of: S1: by adsorbent NH2- MIL-101 (Fe) is added in the sample containing BPs and adjusts sample P H in the range of 2.0~7.0, then carries out 1.0~5.0min of ultrasonic treatment, obtains liquid after ultrasound；S2: centrifugal treating is carried out to liquid after ultrasound obtained in step S1 and obtains liquid A, obtains liquid B after removing the supernatant M of the liquid A；S3: progress centrifugal treating obtains liquid C after carrying out 1.0~5.0min of vortex elution to liquid B obtained in S2 using eluant, eluent, collects the supernatant N of the liquid C, and the eluant, eluent is one of methanol, acetonitrile and acetone；S4: after carrying out constant volume to the supernatant N in step S3, it is quantitative to carry out chromatography.
Description
Technical field
The present invention relates to detection technique fields, more particularly to the micro- Solid Phase Extraction skill of the dispersion based on metal-organic framework material
Art is in the method for bisphenol compound and its derivative
Background technique
Metal organic frame (Metal Organic Frameworks, MOFs), also referred to as Porous coordination polymer (Porous
Coordination Polymers, PCPs), it is with high-sequential three-dimensional structure crystal, by metal ion (cluster or second level knot
Structure unit (SBUs)) and the mesh skeleton structure that is self-assembly of by coordinate bond of organic ligand (connexon).MOFs has super
High specific surface area, reaches as high as 10400m2g-1, and the specific surface area of general nano material will be well below this value.In addition,
MOFs also has the homogeneous texture cavity of special pore size distribution (about 0.3~10nm), and extremely-low density is (down to 0.13g cm-3) and heat it is steady
Qualitative (about 300~600 DEG C) and strong absorption affinity etc..Moreover, central metal, (CUS is opened in unsatuated metal ligand site
Put metallic site), functionalization connector and active cargo matter can be used for the synthesis, modification and rear modification of MOF material.MOFs's
Protruded above feature makes these hybrid organic-inorganic materials become ideal sample pre-treatments adsorbent in separation science.
In dispersing micro- Solid Phase Extraction, the hydrogen bond action between adsorbent and target molecule and the coordination with open metallic site
It plays an important role in extraction process.In general for same type of organic matter, the organic matter small compared to polarity is passed
Suction-operated between nano material of uniting and polar organic compound is weaker, therefore conventional adsorbent is unable to satisfy analysis and requires.
Though inventor studies to obtain at present also without report: the amino and bisphenol compound and its derivative on the surface MOFs
The Hyarogen-bonding that object (BPs) generates will greatly improve analytical extraction performance, and formulate the present invention program based on this.
Summary of the invention
The abstraction technique detection bisphenol compound that the present invention provides a kind of based on metal organic frame nano material and
The method of its derivative, not only precision is high, detection limit is low and easy to operate, is very suitable to point of trace BPs in environmental sample
Analysis detection.
A kind of side of abstraction technique detection bisphenol compound and its derivative based on metal organic frame nano material
Method.The nano material is NH2- MIL-101 (Fe) material；Bisphenol compound and its derivative are log KowRange 1.17~
Bisphenol compound and its derivative in 3.96, referred to as BPs, the method includes the steps of:
S1: by adsorbent NH2- MIL-101 (Fe) is added in the sample containing BPs and adjusts sample P H in 2.0~7.0
In range, then 1.0~5.0min of ultrasonic treatment is carried out, obtains liquid after ultrasound；
S2: centrifugal treating is carried out to liquid after ultrasound obtained in step S1 and obtains liquid A, removes the supernatant of the liquid A
Liquid B is obtained after liquid M；
S3: progress centrifugal treating obtains after carrying out 1.0~5.0min of vortex elution to liquid B obtained in S2 using eluant, eluent
To liquid C, the supernatant N of the liquid C is collected, the eluant, eluent is one of methanol, acetonitrile and acetone；
S4: after carrying out constant volume to the supernatant N in step S3, it is quantitative to carry out chromatography.
Further it is arranged, in step S1, adjusts the sample pH in the range of 2.0~6.0.
Further it is arranged on this basis, in step S2, corresponding 5ml sample, the NH2- MIL-101 (Fe) usage amount is
30mg。
Further, in step S2, the ultrasonic time is 2min.
Further, in step S3, the eluant, eluent is methanol.
Preferably, in step S3, corresponding 5ml sample, the eluant, eluent is 0.4mL methanol.
On this basis, in step S3, vortex elution time is 1min.
MIL-101 (Fe) (Material Institute Lavoisier, MIL) is a kind of absolute acid stability and hydrophily
MOFs has zeolite type crystal structure, has very high tolerance to empty gas and water and common organic solvent.Therefore, MIL-101
(Fe) it can be used as in a kind of micro- Solid Phase Extraction of good sorbent material dispersion, derivative NH2- MIL-101 (Fe) has phase
Like property.
Inventor established based on NH2The micro disperse solid phase extraction method of-MIL-101 (Fe) is to detect the trace in environment
Measure BPs.Under optimum extraction condition, relative recovery range of the BPs in environment water-based is 90.8~117.78%, minimum
Detection is limited to 0.0161~0.131 μ g L-1, withinday precision is 0.93~4.86%, and day to day precision is 1.30~7.63%,
Illustrate that the range of linearity of this method is wider, precision is high, and detection limit is low, reproducibility and has good stability, and sorbent material conjunction
Simple at method, pre-treatment is easy to operate, and analysis and detecting instrument is common, therefore is very suitable to point of trace BPs in environmental sample
Analysis detection.
The performance of this method is compared with the analysis method of forefathers, the method developed has lower LOD value, compared with
High-recovery and high precision.In addition, being based on NH2The dispersion solid-phase extraction method of-MIL-101 (Fe) can complete extraction in 3min
It takes and elution process, the usage amount of organic solvent is well below other methods in entire extraction process.It is noted that conduct
Adsorbent in environmental analysis enrichment process, NH2- MIL-101 (Fe) not only has higher recovery to low pole BPs, to polarity
There has also been be substantially improved compared to MIL-101 (Fe) for the extraction ability of big BPs.
The present invention is further described in detail below in conjunction with attached drawing.
Detailed description of the invention
Fig. 1 is the crystal structure schematic diagram of MIL-101 (Fe)；
Fig. 2 is NH2The N of-MIL-101 (Fe)2Adsorption/desorption isotherms and grain size distribution；
Fig. 3 is extractant NH2Influence of-MIL-101 (Fe) dosage to the BPs rate of recovery；
Fig. 4 is influence of the sample pH value to BPs extraction efficiency；
Fig. 5 is influence of the ultrasonic time to the BPs rate of recovery；
Fig. 6 is influence of the eluting solvent type to BPs extraction efficiency；
Influence of the position Fig. 7 eluant, eluent volume to BPs extraction efficiency；
Fig. 8 is the actual sample chromatogram of bisphenol compound and its derivative；
Fig. 9 is the method for the present invention step schematic diagram.
Specific embodiment
In the following, being specifically described by exemplary embodiment to the present invention.This specific embodiment is only to of the invention
It explains, is not limitation of the present invention, those skilled in the art are can according to need after reading this specification to this
Embodiment makes the modification of not creative contribution, but as long as all by the guarantor of Patent Law in scope of the presently claimed invention
Shield.
Embodiment
First synthesize NH2-MIL-101(Fe).FeCl is added in 60mL DMF solution3·6H2O (19.75mmol,
5.338g) and NH2- BDC (10.0mmol, 1.812g) will be transferred to 100mL polytetrafluoro after mixture magnetic agitation 10min
In the stainless steel autoclave of ethylene liner, and heated for 24 hours under the conditions of 110 DEG C.After being cooled to room temperature, suspension is moved to
In 100mL plastic centrifuge tube, it is collected into brownish black solid product after being centrifuged 5min with 7000rpm, sufficiently washs removing not with DMF
The NH of reaction2- BDC, then respectively washed three times with ultrapure water and ethyl alcohol, it finally is dried in vacuo 6h at 60 DEG C, the NH activated2-
MIL-101(Fe)。
Under 77K liquid nitrogen temperature, pass through N2Adsorption/desorption experiment, analyzes NH2The surface area of-MIL-101 (Fe) and hole knot
Structure.NH2The N of-MIL-101 (Fe)2Absorption/desorption isotherm result is as shown in Figure 2.It is porous through BET and BJH method the Fitting Calculation
NH2The SBET of-MIL-101 (Fe) nano material is 2914.35m2g-1, average pore sizes are 1.46m3g-1, aperture 2.19nm.
The large aperture of nano material and high-specific surface area can substantially increase their adsorption efficiency.
Chromatographic condition:
Analyze using HPLC-FLD system quantitative, Mobile phase B and C are that the phosphoric acid of acetonitrile and pH=3.0 are ultrapure respectively
Water.It is eluted using the binary gradient of 22min, actual conditions are as follows: 0.0-3.0min30%C；3.1-4.0min, 30%-
40%C；4.1-17.0min, 40%C, 17.1-18min, 40%-30%C, 18-22min, 30%C.Flow velocity is 1.0mL min-1, column temperature is 30 DEG C, and sample feeding volume is 10 μ L.Fluorescence exciting wavelength and launch wavelength are respectively 233nm and 303nm.
Extraction and detecting step:
Step is 1.: the 5mL sample solution for containing BPs being placed in 15mL conical centrifuge tube, 10~50mg is then added
NH2- MIL-101 (Fe) nano material adjusts PH to 2.0~7.0, and is ultrasonically treated 1.0~5.0min.
As shown in figure 3, the large specific surface area and adsorption efficiency due to nano material are high, 30mg NH2- MIL-101 (Fe) is
Through being enough to obtain satisfied result.It is therefore preferred that 30mg NH is added in the liquid to be checked of corresponding 5ml, selection2-MIL-101
(Fe) nano material.
It can be seen from figure 4 that pH value, within the scope of 2.0-7.0, the rate of recovery is not much different, but when pH value increases from 7.0
When to 11.0, the rate of recovery sharply declines until being zero.This is because NH2- MIL-101 (Fe) compares under acid and neutrallty condition
Stablize, and be easy hydrolysis under alkaline condition, even results in MOFs structure collapse.In addition, pH from 6.0 increase to 7.0 when, NH2-
MIL-101 (Fe) slightly reduces (Δ ERs about 2.1-9.0%) to the rate of recovery of polarity BPs (such as BFDGE2H2O, BPF).This is
Since when solution ph is 2.0-6.0, NH2- MIL-101 (Fe) material surface is positively charged, and stable structure；When pH value is
When 6-7, zeta current potential begins to change into negative value, and material surface has a small amount of negative electrical charge, and interaction of hydrogen bond is no longer stable, therefore pole
Property BPs (such as BFDGE 2H2O, BPF) the rate of recovery slightly reduce；When pH value is more than 7, MOFs structural framework is destroyed, therefore is returned
Yield sharply declines.It is therefore preferred that pH is 2.0~6.0.After adsorbent is added, three kinds of seawater, river water and tap water aqueous solutions
PH value be respectively 5.58,4.03 and 3.15, therefore do not need adjust sample solution pH value.
As shown in figure 5, in 1.0~2.0min of ultrasonic time, the rate of recovery of BPs is gradually increased to maximum value, then from
When ultrasonic time is 2min to 5min, the rate of recovery of BPs is gradually decreased, but ultrasonic time is located at 1.0~5.0min in general
When the rate of recovery it is all very objective.After ultrasonic time is more than 2min, the rate of recovery of BPs is on a declining curve, this is because excessively prolonged
Ultrasound can be such that reaction balance moves to left, and energy is very strong in ultrasonic procedure, and the object of a part absorption may fall off, MOF
Frame structure may also can collapse, to influence the rate of recovery of sample.It is therefore preferred that extraction time is set as 2.0min.
Step is 2.: then to step 1. in obtain sample and carry out 5000rpm centrifugation 10min obtaining liquid A.Removal obtains liquid
Liquid B is obtained after the supernatant M of body A.
Step is 3.: after carrying out elution processing to liquid B using 0.1-0.8mL eluting solvent and by vortex 1.0-5.0min
Solution C is obtained with 5000rpm centrifugation 3min again, collects the supernatant N of solution C.Eluting solvent: methanol, acetonitrile and acetone.
When vortex time is extended to 5.0min from 1.0min, extraction efficiency is almost without obviously increasing.Therefore, it elutes
Time is preferably 1.0min.
Shown in Fig. 6, the BPs of different eluant, eluents elutes recycling ability ranking are as follows: methanol > acetone > acetonitrile shows that methanol is most suitable
Cooperation is eluent.Preferably, eluant, eluent is methanol.
When elution, the volume of eluting solvent should be enough from adsorbent complete elution analysis object, but should also use few as far as possible
Eluting solvent to avoid exceedingly dilute sample.From figure 7 it can be seen that the BPs rate of recovery reaches when methanol volume is 400 μ L
To highest.When volume is less than 400 μ L, BPs cannot be eluted completely；And working as elution volume increases to 800 μ L from 400 μ L, although
The rate of recovery is held essentially constant, but the significant reduction of concentration of target analytes, and due to diluting effect, enrichment times are reduced.
It is therefore preferred that for the sample of 5ml, using 400 μ L methanol as eluting solvent.
Step is 4.: carrying out chromatography again after carrying out constant volume to supernatant N.
Embodiment 2:
Experimentation is as described in Example 1, and difference is: the amount 30mg of extractant, and ultrasonic extraction time 2.0min is washed
400 μ L methanol of desolventizing, elution time 1.0min, in the range of sample pH value is 2.0-6.0.
Experimental result:
The relative coefficient R of the linear equation of BPs2Between 0.9986 to 0.9997；It is minimum in signal-to-noise ratio S/N=3
Detection limit is 0.016~0.131 μ g L-1；In signal-to-noise ratio S/N=10, quantitative limit is 0.05~0.44 μ g L-1.Bisphenols
The range of linearity for closing object and bis-phenol analog derivative is 0.5~200 μ g L respectively-1, 0.25~200 μ g L-1。
For the stability of detection method, inventor determines the in the daytime and in a few days rate of recovery data of method, detects every time
Height (50 μ g L are set-1), in (20 μ g L-1) and low (5 μ g L-1) three concentration levels, same batch of sample when surveying the in a few days rate of recovery
It is primary every 2h detection, it surveys 6 times be averaged in total；Every morning 8:00 sample detection when measuring the rate of recovery in the daytime, it is continuous to examine
It surveys 6 times, is averaged.In three concentration levels, the withinday precision range of target analytes is 0.93~4.86%；In the daytime smart
Density is 1.30~7.63%.Illustrate that the reproducibility of the method is good, complies fully with actually detected requirement.
Experimental example:
Experiment reagent: water sample is acquired from the different regions in Chinese Wenzhou.Wherein, river water sample comes from Wenruitang river, seawater
Sample is from coastal area near Cangnan county Yanting town, and originally water sample is directly acquired from Wenzhou Medical University laboratory.It will be every
A water sample is stored in clean vial under the conditions of 4 DEG C after 0.45 μm of PES membrane filtration.It is first when the above sample detection
It places to room temperature and reuses.
After the water sample of each type is grouped, it is separately added into the BPs of known quantity in water sample, BPs standard concentration is added
To be respectively 0,5 μ g L-1, 20 μ g L-1With 50 μ g L-1。
Experimentation: experimentation is as described in Example 1, and difference is: the amount 30mg of extractant, ultrasonic extraction time
2.0min, 400 μ L methanol of eluting solvent, elution time 1.0min, in the range of sample pH value is 2.0-6.0.
With relative recovery (Relative recovery, RR), also known as the method rate of recovery, to evaluate actually detected effect.
Relative recovery is acquired by following formula:
RR (%)=ni/n0× 100%
In this formula, niIt represents the recycling from actual sample matrix and obtains the response of target analytes, n0Represent addition
The response that the standard items of known quantity generate into matrix.
BADGE2H is detected in the river water for being not added with BPs2O, concentration are 4.33 ± 0.93 μ g L-1, and be not added with
BPs and its derivative residual are not all detected in the blank sample of BPs tap water and seawater；
When actual sample adds the standard items of high, medium and low three detectable concentrations, the rate of recovery of the BPs in environmental water sample
Range is 90.78~117.8%.Fig. 8 is the chromatogram of actual sample, and the loading concentrations in this chromatogram in environmental water sample are
20μg L-1.Statistics indicate that the processing detection method of our foundation is simple, efficient, reproducibility, it is very suitable to log KowRange from
The analysis detection of the wide polarity BPs of 1.17 to 3.96 trace and its derivative.
The performance of this method is compared with the analysis method of forefathers, the method developed has lower LOD value, compared with
High-recovery and high precision.In addition, being based on NH2The dispersion solid-phase extraction method of-MIL-101 (Fe) can complete extraction in 3min
It takes and elution process, the usage amount of organic solvent is well below other methods in entire extraction process.It is noted that conduct
Adsorbent in environmental analysis enrichment process, NH2- MIL-101 (Fe) not only has higher recovery to low pole BPs, to polarity
There has also been be substantially improved compared to MIL-101 (Fe) for the extraction ability of big BPs.
This specific embodiment is only explanation of the invention, is not limitation of the present invention, those skilled in the art
Member can according to need the modification that not creative contribution is made to the present embodiment after reading this specification, but as long as at this
All by the protection of Patent Law in the scope of the claims of invention.
Claims (7)
1. a kind of method of abstraction technique detection bisphenol compound and its derivative based on metal organic frame nano material,
It is characterized by: the nano material is NH2- MIL-101 (Fe) material；Bisphenol compound and its derivative are log KowRange
Bisphenol compound and its derivative in 1.17~3.96, referred to as BPs, the method includes the steps of:
S1: by adsorbent NH2- MIL-101 (Fe) is added in the sample containing BPs and adjusts sample P H in 2.0~7.0 range
It is interior, then 1.0~5.0min of ultrasonic treatment is carried out, obtain liquid after ultrasound；
S2: centrifugal treating is carried out to liquid after ultrasound obtained in step S1 and obtains liquid A, after the supernatant M for removing the liquid A
Obtain liquid B；
S3: progress centrifugal treating obtains liquid after carrying out 1.0~5.0min of vortex elution to liquid B obtained in S2 using eluant, eluent
Body C, collects the supernatant N of the liquid C, and the eluant, eluent is one of methanol, acetonitrile and acetone；
S4: after carrying out constant volume to the supernatant N in step S3, it is quantitative to carry out chromatography.
2. it is according to claim 1 based on metal organic frame nano material abstraction technique detection bisphenol compound and
The method of its derivative, it is characterised in that: in step S1, adjust the sample P H value in the range of 2.0~6.0.
3. it is according to claim 2 based on metal organic frame nano material abstraction technique detection bisphenol compound and
The method of its derivative, it is characterised in that: in step S2, correspond to 5ml sample, NH2-MIL-101 (Fe) usage amount is
30mg。
4. the abstraction technique according to any one of claims 1 to 3 based on metal organic frame nano material detects bis-phenol
The method of class compound and its derivative, it is characterised in that: in step S2, the ultrasonic time is 2min.
5. it is according to claim 4 based on metal organic frame nano material abstraction technique detection bisphenol compound and
The method of its derivative, it is characterised in that: in step S3, the eluant, eluent is methanol.
6. it is according to claim 4 based on metal organic frame nano material abstraction technique detection bisphenol compound and
The method of its derivative, it is characterised in that: in step S3, corresponding 5ml sample, the eluant, eluent is 0.4mL methanol.
7. it is according to claim 6 based on metal organic frame nano material abstraction technique detection bisphenol compound and
The method of its derivative, it is characterised in that: in step S3, vortex elution time is 1min.
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