CN103558305B - A kind of method detecting trace phenols environmental estrogens - Google Patents
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Abstract
The invention discloses a kind of method detecting trace phenols environmental estrogens, belong to biological sample and environment inspection (prison) survey technology field.Extract in the method and comprise the following steps: the pH value regulating solution to be measured is 2.5 ~ 3.5, adds surfactant and extractant, and ultrasonic mixing, then low-temperature centrifugation, discard upper strata, adopt high performance liquid chromatography quantitatively to detect.The present invention adopts ultrasonic wave added surfactant emulsifies micro-extraction technique, the toxicity spreading agents such as acetone, methyl alcohol, acetonitrile are substituted with the surfactant of low toxicity, quantitatively detect in conjunction with high performance liquid chromatography (HPLC) again, the advantage such as there is efficient, low toxicity, easy and simple to handle, expense is low, enrichment times reaches more than 200 times, sensing range is 0.01 ~ 0.10 μ g/L, can be widely used in inspection (prison) cls analysis of the middle phenols environmental estrogens of spirulina biological sample, environment, food and medicine.
Description
Technical field
The present invention is specifically related to a kind of method detecting trace phenols environmental estrogens, belongs to biological sample and environment inspection (prison) survey technology field.
Background technology
Phenols environmental estrogens is the pollutant that in environment, a modal class has estrogen active.A large amount of environmental surveys result and laboratory study show phenols environmental estrogens as bisphenol-A, pentachloro-phenol and estradiol etc. to the increase of the minimizing of the rising of male testical cancer and prostate-cancer incidence in recent years, sperm quantity, women with breast cancer, the cancer of the uterus incidence of disease, buck feminize and the change etc. of immunologic function all has the effect that can not be ignored.Therefore phenols environmental estrogens (PEs) has become the focus pollutant of primary study and monitoring in recent years.At present, the U.S., Japan and the country such as European have made regulation to the maximum residue limit of part phenols environmental estrogens in water body, generally in the level that 0.1 μ g/L is even lower.But current result of study shows: this pollutant at a lower level, still can produce estrogen effect to biology.Therefore, set up this compounds dosage-response curve in vivo, and determine that the threshold value of its performance estrogen active is most important.For this reason, must set up as early as possible there is high sensitivity and optionally qualitative and quantitative analysis method.
The current existing abstraction technique overwhelming majority still depends on liquid-liquid extraction or Solid-Phase Extraction carries out being separated and enrichment, and operating process is more loaded down with trivial details, and organic solvent volatilization is seriously polluted, and testing cost is higher.And still there is certain toxicity and pollution problem in the extractant that uses of existing micro-extraction technique and spreading agent.
Summary of the invention
The object of this invention is to provide a kind of method detecting trace phenols environmental estrogens.
In order to realize above object, the technical solution adopted in the present invention is:
A kind of method detecting trace phenols environmental estrogens, mainly comprise and extract and detect two steps, described extraction comprises the following steps: regulate the pH value of solution to be measured to be that 2.5 ~ 3.5(is beneficial to improve the micro-extraction recovery), add surfactant and extractant, ultrasonic mixing, low-temperature centrifugation again, discards upper strata.
Described phenols environmental estrogens is bisphenol-A (BPA), 17 alpha-estradiols (17 α-Estradiol), 4-tert-butyl phenol (4-BP), 4 bromine bisphenol-As (4-Br-BPA) and/or the tertiary octyl phenol of 4-(4-t-OP).
Described surfactant is lauryl sodium sulfate (SDS), cetyl trimethyl ammonium bromide (CTAB) or tween, as polysorbas20.Preferably sodium dodecyl sulfate.
Described extractant is chlorobenzene (C
6h
5cl), tetrachloromethane (CCl
4) or methenyl choloride (CHCl
3).Preferred methenyl choloride.
Described ultrasonic power is 350 ~ 450W, and switch gap is that namely 5s:3s(opens 5s pass 3s), amount to 40 ~ 60 times.Preferably 50 times.
The temperature of described low-temperature centrifugation is 0 ~ 4 DEG C, and rotating speed is 4000 ~ 6000rpm, and the time is 2 ~ 5min.Preferably, the ultracentrifugal temperature of low temperature is 4 DEG C, and rotating speed is 5000rpm, and the time is 2min.
Described detection comprises the steps: quantitatively to detect extracting the solution high performance liquid chromatograph obtained, and mobile phase is acetonitrile and deionized water, and condition of gradient elution is: 0 ~ 6min, acetonitrile: water=45:55; 6 ~ 20min, acetonitrile: water=70:30; Column temperature is 25 DEG C, and ultraviolet wavelength is 270nm, and flow velocity is 0.8mL/min, and sample size is 20 μ L.
General, before the extraction step, there are differences for its pre-treatment step of different samples, such as biological sample, environmental sample, food or medicine etc.
When during detected object is biological sample (as spirulina cells), phenols environmental estrogens remains, need to clean biological sample, broken and purified treatment, specifically comprise the steps: that (1) cleaning biological sample removes nutrient culture media and part metabolic product, ultrasonication; (2) add concentrated sulfuric acid purification in the sample after ultrasonication, leave standstill, centrifugal, get supernatant for subsequent use.Namely adopt as the macromolecular substances such as protein, lipid in concentrated acid sulfonation method purification spirulina smudge cells, after ultrasonication, the volume ratio of sample and the concentrated sulphuric acid is 100:3.This supernatant is solution to be measured.
Centrifuge method cleaning biological sample is adopted in described step (1), by biological sample centrifuging and taking precipitation (biological sample after adding water centrifugal or biological sample itself be suspending liquid), add water in precipitation again centrifugal, repeat above-mentioned steps, last abandoning supernatant.
First in precipitation, appropriate water is added before ultrasonication in described step (1), for subsequent use after mixing.For spirulina cells suspending liquid, preferably, the power of ultrasonication is 350 ~ 450W, and switch gap is 5s:3s, and switch gap number of times is 30 times, amounts to 50 ~ 60 times.
The time that described step (2) leaves standstill is 2 ~ 5min, preferred 2min.Ultracentrifugal rotating speed is 4000 ~ 6000rpm, and the time is 2 ~ 5min, and preferred rotating speed is 5000rpm, and the time is 2min.
When the phenols environmental estrogens of trace during detected object is environmental sample (as water sample), need to carry out filtering and impurity removing operation (as crossed the filter membrane removal of impurities of 0.22 μm) to water sample, filtrate is solution to be measured; Or add concentrated sulfuric acid purification in filtrate, leave standstill, centrifugal, get supernatant for subsequent use, this supernatant is solution to be measured.
When phenols environmental estrogens remains during detected object is food or medicine (as spirulina tablet, granule etc.), need to grind food or medicine, digest and sulfonation process, specifically comprise the steps: food or medicine to grind, add HNO
3-HClO
4the acid mixture of (4:1, V/V) digests, and is heated to solution and becomes limpid look and with white cigarette, continue to be heated to digestion completely, add water centrifugal or directly centrifugal, add the excessive concentrated sulphuric acid in supernatant, leave standstill, centrifugal, gets supernatant for subsequent use.The supernatant that final step obtains is solution to be measured.
Beneficial effect of the present invention:
The present invention adopts ultrasonic wave added surfactant emulsifies micro-extraction technique, compared with the dispersive liquid-liquid microextraction technology of routine, instead of the toxicity spreading agents such as acetone, methyl alcohol and acetonitrile, replace with the surfactant of low toxicity, there is the advantages such as efficient, low toxicity, easy and simple to handle and low expense, can be applicable to the how residual extraction of trace of complex biological matrix sample.
When during detected object is for biology, environmental sample or food, medicine etc., phenols environmental estrogens remains, first adopt in concentrated acid sulfonation method purification sample as macromolecular substances such as fat, protein, create the good matrix condition that is conducive to micro-extraction, again in conjunction with ultrasonic wave added surfactant emulsifies micro-extraction technique, namely can be used for the analysis of complex biological matrix sample, is that one is easy and simple to handle, quick, cost is low, bioaccumulation efficiency is high and environment amenable sample pre-treatments new technology.This technology centralized procurement extraction, concentrated and purify in one, trace phenols environmental estrogens in sample can be detected fast in conjunction with high performance liquid chromatography (HPLC), and enrichment times high (> 200 times), efficiently, sensitive, sensing range reaches 0.01 ~ 0.10 μ g/L, can be widely used in inspection (prison) cls analysis of the middle phenols environmental estrogens of spirulina biological sample, environment, food and medicine.
Accompanying drawing explanation
Fig. 1 is the influential effect figure of extractant to phenols environmental estrogens extraction efficiency;
Fig. 2 is the influential effect figure of extractant volume to phenols environmental estrogens extraction efficiency;
Fig. 3 is the influential effect figure of surfactant to phenols environmental estrogens extraction efficiency;
Fig. 4 is the influential effect figure of ultrasonic extraction time to phenols environmental estrogens extraction efficiency;
Fig. 5 is the influential effect figure of pH value to phenols environmental estrogens extraction efficiency;
Fig. 6 is the chromatogram of phenols environmental estrogens in water sample and spirulina sample.
Embodiment
Following embodiment is only described in further detail the present invention, but does not form any limitation of the invention.
Embodiment 1
The detection of phenols environmental estrogens in tap water:
Take from water 15mL, cross the filter membrane of 0.22 μm; Get the tap water after 10mL filtration in 15mL centrifuge tube, add the 0.3mL concentrated sulphuric acid and regulate solution ph to be 3, then add 500 μ L SDS and 50 μ L CHCl
3, mixed liquor concussion shaken up, ultrasonic mixing, ultrasonic power is 400W, switch gap 5s:3s, amounts to 50 times, centrifugal 2min under 5000rpm rotating speed, and droplet is formed on bottom; With microsyringe suction foot droplet 40 μ L, adopt the high-efficient liquid phase chromatogram condition optimized quantitatively to detect the content of phenols environmental estrogens, mobile phase is acetonitrile and deionized water, and condition of gradient elution is: 0 ~ 6min, acetonitrile: water=45:55; 6 ~ 20min, acetonitrile: water=70:30; Column temperature is 25 DEG C, and ultraviolet wavelength is 270nm, and flow velocity is 0.8mL/min, and sample size is 20 μ L.
Embodiment 2
Spirulina-350(ASP-350) in the detection of phenols environmental estrogens:
Get the spirulina ASP-350 water sample that 10mL is in exponential phase, be placed in 15mL centrifuge tube, add deionized water to 15mL, centrifugal 2min, removes supernatant; The ASP-350 of precipitation at the bottom of pipe is added deionized water to 10mL, centrifugal 2min, then precipitate A SP-350 cell is added water to 10mL; Ultrasonication, power is 400W, and switch gap is 5s:3s, and switch gap number of times is 50 times, and total break process time is 400s; Add the 0.3mL concentrated sulphuric acid and place 2min in centrifuge tube, centrifugal 2min under the condition of 5000rpm; Getting supernatant adjust ph is 3, adds 500 μ L surfactant SDS and 50 μ L extractant CHCl
3, ultrasonic mixing, ultrasonic power is 400W, switch gap 5s:3s, and amount to 50 times, high-speed low temperature is centrifugal, and rotating speed is 5000rpm, and temperature is 4 DEG C, and centrifugation time is 2min; Get the droplet 40 μ L at the bottom of centrifuge tube with micro-sampling pin, adopt the high-efficient liquid phase chromatogram condition optimized quantitatively to detect the content of phenols environmental estrogens, mobile phase is acetonitrile and deionized water, and condition of gradient elution is: 0 ~ 6min, acetonitrile: water=45:55; 6 ~ 20min, acetonitrile: water=70:30; Column temperature is 25 DEG C, and ultraviolet wavelength is 270nm, and flow velocity is 0.8mL/min, and sample size is 20 μ L.
Embodiment 3
Spirulina-834(ASP-834) in the detection of phenols environmental estrogens:
Get the spirulina ASP-834 water sample that 10mL is in exponential phase, be placed in 15mL centrifuge tube, add deionized water to 15mL, centrifugal 2min, removes supernatant; The ASP-834 of precipitation at the bottom of pipe is added deionized water to 10mL, centrifugal 2min, then precipitate A SP-834 cell is added water to 10mL; Ultrasonication, power is 400W, and switch gap is 5s:3s, and switch gap number of times is 50 times, and total break process time is 400s; Add the 0.3mL concentrated sulphuric acid and place 2min in centrifuge tube, centrifugal 2min under the condition of 5000rpm; Getting supernatant adjust ph is 3, adds 500 μ L surfactant SDS and 50 μ L extractant CHCl
3, ultrasonic mixing, ultrasonic power is 400W, switch gap 5s:3s, and amount to 50 times, high-speed low temperature is centrifugal, and rotating speed is 5000rpm, and temperature is 4 DEG C, and centrifugation time is 2min; Get the droplet 35 μ L at the bottom of centrifuge tube with micro-sampling pin, adopt the high-efficient liquid phase chromatogram condition optimized quantitatively to detect the content of phenols environmental estrogens, mobile phase is acetonitrile and deionized water, and condition of gradient elution is: 0 ~ 6min, acetonitrile: water=45:55; 6 ~ 20min, acetonitrile: water=70:30; Column temperature is 25 DEG C, and ultraviolet wavelength is 270nm, and flow velocity is 0.8mL/min, and sample size is 20 μ L.
Embodiment 4
The detection of phenols environmental estrogens in spiral algae sheet:
Accurately take spiral algae sheet (the biological board of Nanning Fu Laixin, spirulina chewing tablets) sample 2.0g, grind and be placed in 50mL conical flask; Add 15mLHNO
3-HClO
4the mixed acid digestion of (4:1, V/V), heats on electric hot plate, when solution becomes Clear colourless and with Bai Yanshi, then continues heating (catching up with acid) to residual volume and is about 2mL; Digestive juice is transferred in 15mL centrifuge tube, add pure water and be settled to 15mL, add 0.3mL concentrated acid sulfonation, leave standstill 2min, centrifugal 2min under 5000rpm rotating speed; Get supernatant 10mL, then add 500 μ LSDS and 50 μ L CHCl
3, the ultrasonic mixing of mixed liquor, ultrasonic power is 400W, switch gap 5s:3s, amount to 50 times, then under 5000rpm condition centrifugal 2min; With the droplet 35 μ L got with micro-sampling pin at the bottom of centrifuge tube, adopt the high-efficient liquid phase chromatogram condition optimized quantitatively to detect the content of phenols environmental estrogens, mobile phase is acetonitrile and deionized water, and condition of gradient elution is: 0 ~ 6min, acetonitrile: water=45:55; 6 ~ 20min, acetonitrile: water=70:30; Column temperature is 25 DEG C, and ultraviolet wavelength is 270nm, and flow velocity is 0.8mL/min, and sample size is 20 μ L.
Test example
1, the optimization of ultrasonic wave added surfactant emulsifies micro-extraction condition
(1) different extractant is on the impact of phenols environmental estrogens extraction efficiency
Test method: adopt identical testing sample, extractant adopts chlorobenzene (C respectively
6h
5cl), tetrachloromethane (CCl
4) and methenyl choloride (CHCl
3), volume is 50 μ L, surfactant adopts 500 μ L SDS, the power of ultrasonic mixing is 400W, switch gap 5s:3s, amount to 50 times, adopt high performance liquid chromatography to detect the content of bisphenol-A (BPA), 17 alpha-estradiols (17 α-Estradiol), 4-tert-butyl phenol (4-BP), 4 bromine bisphenol-As (4-Br-BPA) and the tertiary octyl phenol of 4-(4-t-OP), measurement result as shown in Figure 1.
As can be seen from Figure 1, micro-extraction best results when extractant is methenyl choloride.
(2) different extractant volume is on the impact of phenols environmental estrogens extraction efficiency
Test method: adopt identical testing sample, extractant adopts methenyl choloride, volume is respectively 20 μ L, 30 μ L, 40 μ L, 50 μ and 60 μ L, surfactant adopts 500 μ L SDS, the power of ultrasonic mixing is 400W, switch gap 5s:3s, amounts to 50 times, adopt high performance liquid chromatography to detect the content of 5 kinds of phenols environmental estrogens, measurement result as shown in Figure 2.
As can be seen from Figure 2, micro-extraction best results when extractant volume is 50 μ L.
(3) different surfaces activating agent is on the impact of phenols environmental estrogens extraction efficiency
Test method: surfactant adopts lauryl sodium sulfate (SDS), cetyl trimethyl ammonium bromide (CTAB) and polysorbas20 (Tween-20) respectively, and other test conditions are with above-mentioned.The content of 5 kinds of phenols environmental estrogens, measurement result as shown in Figure 3.
As can be seen from Figure 3, when surfactant is SDS, effect of extracting is best.
(4) the ultrasonic extraction time is on the impact of phenols environmental estrogens extraction efficiency
Test method: adopt identical testing sample, the ultrasonic extraction time, extractant adopted methenyl choloride (CHCl as shown in Fig. 4 horizontal ordinate
3), volume is 50 μ L, and surfactant adopts 500 μ L SDS, and the power of ultrasonic mixing is 400W, switch gap 5s:3s, amounts to 50 times, and adopt high performance liquid chromatography to detect the content of 5 kinds of phenols environmental estrogens, measurement result is as shown in Figure 4.
(5) pH value is on the impact of phenols environmental estrogens extraction efficiency
Test method: adopt identical testing sample, pH value is respectively 2,3,4,5,6,7, and extractant adopts methenyl choloride (CHCl
3), volume is 50 μ L, and surfactant adopts 500 μ L SDS, and the power of ultrasonic mixing is 400W, switch gap 5s:3s, amounts to 50 times, and adopt high performance liquid chromatography to detect the content of 5 kinds of phenols environmental estrogens, measurement result is as shown in Figure 5.
(6) chromatogram of phenols environmental estrogens in different sample
Test method: remove ionized water, warm auspicious pool water sample and spirulina-350, spirulina-793, spirulina-834 water sample respectively, adopt the phenols environmental estrogens in ultrasonic wave added surfactant emulsifies micro-extraction technique extraction sample after pre-treatment, extractant adopts methenyl choloride (CHCl
3), volume is 50 μ L, and surfactant adopts 500 μ L SDS, and the power of ultrasonic mixing is 400W, switch gap 5s:3s, amounts to 50 times, and adopt high performance liquid chromatography to detect, chromatogram is as shown in Figure 6.
2, the mensuration of the analytical technology parameter of ultrasonic wave added surfactant emulsifies micro-extraction
Test condition: test specimen is spirulina-834, volume 10mL; Concentrated sulphuric acid consumption 0.3mL; 50 μ L CHCl
3extractant; 500 μ L SDS surfactants; Ultrasonic power is 400W, switch gap 5s:3s, amounts to 50 times.Analytical technology parametric results is as shown in table 1 below.
Table 1 analytical technology parametric results
Note: (1) enrichment times: the ratio of micro-extraction after stain substrate concentration and actual sample pollutant levels.
(2) detection limit: the actual sample based on 3 times of signal to noise ratio (S/N ratio)s is minimum detects concentration.
(3) range of linearity: the pollutant levels gradient scope presenting remarkable linear relationship.
(4) related coefficient: the linear relationship between different pollutant levels respective peaks area.
3, ultrasonic emulsification micro-extraction and disperse the analytical performance of micro-extraction to contrast in ultrasonic wave added surfactant emulsifies micro-extraction and prior art
Test condition: test specimen is spirulina-834, volume 10mL; Concentrated sulphuric acid consumption 0.3mL; 50 μ L CHCl
3extractant; 500 μ L SDS surfactants; Ultrasonic power is 400W, switch gap 5s:3s, amounts to 50 times.Analytical performance comparing result is as shown in table 2 below.
Table 2 analytical performance comparing result
4, actual water sample analysis result
Test condition: test specimen is water sample, volume 10mL; Concentrated sulphuric acid consumption 0.3mL; 50 μ L CHCl
3extractant; (C) 500 μ L SDS surfactants; Ultrasonic power is 400W, switch gap 5s:3s, amounts to 50 times.Water sample analysis result is as shown in table 3 below.
Table 3 actual water sample analysis result
Note: " ND " refers to not detect.
5, the analysis result of actual blunt top spirulina sample
Test condition: test specimen is three kinds of spirulinas, volume 10mL; Concentrated sulphuric acid consumption 0.3mL; 50 μ L CHCl
3extractant; 500 μ L SDS surfactants; Ultrasonic power is 400W, switch gap 5s:3s, amounts to 50 times.The analysis result of blunt top spirulina sample is as shown in table 4 below.
The analysis result of the actual blunt top spirulina sample of table 4
Note: " ND " refers to not detect.
Claims (6)
1. one kind is detected the method for trace phenols environmental estrogens, it is characterized in that: mainly comprise and extract and detect two steps, described extraction comprises the following steps: regulate the pH value of solution to be measured to be 2.5 ~ 3.5, add surfactant and extractant, ultrasonic mixing, low-temperature centrifugation again, discards upper strata; Described extractant is chlorobenzene, tetrachloromethane or methenyl choloride; Described surfactant is lauryl sodium sulfate; Described phenols environmental estrogens is bisphenol-A, 17 alpha-estradiols, 4-tert-butyl phenol, 4 bromine bisphenol-As and/or the tertiary octyl phenol of 4-.
2. the method for detection trace phenols environmental estrogens according to claim 1, is characterized in that: described extractant is methenyl choloride.
3. the method for detection trace phenols environmental estrogens according to claim 1, it is characterized in that: described ultrasonic power is 350 ~ 450W, switch gap is 5s:3s, amounts to 40 ~ 60 times.
4. the method for detection trace phenols environmental estrogens according to claim 1, it is characterized in that: described detection comprises the steps: quantitatively to detect extracting the solution high performance liquid chromatograph obtained, mobile phase is acetonitrile and deionized water, condition of gradient elution is: 0 ~ 6min, acetonitrile: water=45:55; 6 ~ 20min, acetonitrile: water=70:30; Column temperature is 25 DEG C, and ultraviolet wavelength is 270nm, and flow velocity is 0.8mL/min, and sample size is 20 μ L.
5. the method for detection trace phenols environmental estrogens according to claim 1, it is characterized in that: when detected object is when in biological sample, phenols environmental estrogens remains, described solution to be measured prepares primarily of following steps: (1) cleaning biological sample, ultrasonication; (2) add the concentrated sulphuric acid in the sample after ultrasonication, leave standstill, centrifugal, get supernatant and get final product.
6. the method for detection trace phenols environmental estrogens according to claim 1, it is characterized in that: when during detected object is food or medicine, phenols environmental estrogens remains, described solution to be measured prepares primarily of following steps: food or medicine are ground, add HNO
3-HClO
4acid mixture digest, add water after digestion completely centrifugal or directly centrifugal, in supernatant, add the excessive concentrated sulphuric acid, leave standstill, centrifugal, get supernatant and get final product.
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| Determination of bisphenol A and naphthols in river water samples by capillary zone electrophoresis after cloud point extraction;Shuxian Zhong等;《Talanta》;20110412;第85卷;第488页摘要，第486页第2.3.1节和第3.1.1节 * |
| Determination of estrogens in water by HPLC–UV using cloud point extraction;Ling Wang等;《Talanta》;20060217;第70卷;第47页摘要，第48页第2.2节 * |
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