CN109060864A - The non-extraction rapid detection method of long-life organic free radical in Atmospheric particulates - Google Patents
The non-extraction rapid detection method of long-life organic free radical in Atmospheric particulates Download PDFInfo
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Abstract
This method is related to long-life organic free radical in detection airborne fine particulate matter rapidly and efficiently, and atmospheric aerosol samples are not necessarily to solvent extraction.This method is the conventional method low efficiency in order to solve the problems, such as persistence organic free radical in detection airborne fine particulate matter.This method includes: one, filter membrane is weighed before and after acquiring Atmospheric particulates, to obtain the quality of the Atmospheric particulates of acquisition；Two, the filter membrane for collecting Atmospheric particulates is cut out to the slice of a 2-3mm wide, and is weighed；Three, the filter membrane cut folding EPR detection is placed directly within to be detected in quartz ampoule.Four, data are recorded, number of free radical is calculated.This method is not necessarily to solvent extraction, the aerosol sample being adsorbed on quartz fibre filter membrane is removed without from filter membrane, directly adopt EPR detection, the reset condition of Atmospheric particulates is not destroyed, avoid the interference of experimentation, it ensure that the accuracy of the detection of long-life organic free radical in the Atmospheric particulates of detection, method are easy quickly.
Description
Technical field
The invention belongs to Environment Oriented analysis technical fields, and in particular to long-life organic freedom in a kind of Atmospheric particulates
The non-extraction rapid detection method of base.
Background technique
Long-life organic free radical is there is time longer freedom in the environment for short life free radical
Base.Long-life organic free radical can generate reactive oxygen species in environment, thus break the balance of people's interior free yl, and to human body
It causes to damage.Atmospheric particulates are to the harm of human body by extensive concern, and its ingredient is sufficiently complex, the dirt to Atmospheric particulates
Contaminating Mechanism Study, there are still difficulties.Existing research detects the presence of long-life organic free radical in Atmospheric particulates, but
It is that organic free radical mostly uses solution extraction method in current detection Atmospheric particulates, it is incomplete that this inevitably will lead to extraction
Either particulate matter component reacts with extracting solution and the generation of free radical or part is caused to be quenched, to influence free radical inspection
It is accurate and comprehensive to survey.
Summary of the invention
To solve the above-mentioned problems, the present invention provides long-life organic free radicals in a kind of quickly detection Atmospheric particulates
Method.
The method of long-life organic free radical in quick detection Atmospheric particulates provided by the present invention, including walk as follows
It is rapid:
1) it weighs before acquiring Atmospheric particulates to filter membrane, is denoted as m0, Atmospheric particulates are acquired using the filter membrane,
Filter membrane after acquisition is weighed, m is denoted ast, the quality m of the Atmospheric particulates acquiredt-m0；
2) filter membrane for collecting Atmospheric particulates is cut into slice, and weighed, be denoted as mu；
3) filter membrane cut is folded and placed in quartz ampoule and carries out electron paramagnetic resonance spectrum (EPR) (EPR) detection, obtain EPR letter
Number map；
4) according to epr signal map, the concentration of long-life organic free radical in Atmospheric particulates is calculated.
In above method step 1), the filter membrane can be quartz fibre filter membrane；
It further include drying the filter membrane under the conditions of 450 DEG C before weighing to the filter membrane before acquisition Atmospheric particulates
12h is placed in the operation saved in drying box to remove the impurity such as organic matter；
Aerosol sample is acquired using mass flow atmospheric particles sampler, the acquisition of big flow andersen sampler can also be used
The atmospheric aerosol samples of different-grain diameter, such as kinetic diameter (aerodynamic diameters, dae) less than 1.0 μm, 1.0-
2.5 μm, 2.5-10 μm, the particulate matter of the different dynamic diameter greater than 10 μm.Different-grain diameter is adsorbed using quartz fibre filter membrane
Atmospheric particulates.
Further include operations described below before weighing to the filter membrane after acquisition: by the filter membrane doubling after acquisition, using Aluminium Foil Package
It covers, is placed in and is saved with the drying box under acquisition front filter the same terms.
In above method step 2), the width of the slice can be 2-3mm.
In above method step 3), the quartz ampoule is that quartz ampoule is used in EPR detection.
In step 3), the free radical in sample is detected using the electronic paramagnetic resonance spectrometer of X-band, passes through tune
Whole central magnetic field, microwave frequency, microwave power, modulating frequency, modulation amplitude, field sweep width, gain acceptance in, sweep time etc.,
Obtain to obtain the instrument parameter of optimal peak type.
Wherein, the instrument parameter of use is as follows: central magnetic field: 3500G；Microwave frequency: 9.36GHz；Microwave power:
0.63mW；Modulating frequency: 100kHz；Modulation amplitude: 1.0G；Field sweep width: 100G；Gain acceptance in: 30dB；Sweep time:
100s。
Sample is detected under above-mentioned instrument parameter, obtains epr signal map.
In above method step 4), according to the g value in epr signal map, peak width (Δ Hp-p) etc. information sample is determined
Property analysis；According to spin quantitative theory, quantitative analysis is carried out to the free radical in sample using Bruker ' s Xenon software, is obtained
The absolute magnitude for obtaining free radical in institute's sample, is denoted as Spins,
The calculation formula of the concentration (Spins/g) of free radical in surveyed Atmospheric particulates are as follows:
This method is related to long-life organic free radical in detection airborne fine particulate matter rapidly and efficiently, atmospheric aerosol samples
Without solvent extraction, the problem of being able to solve long-life organic free radical detection method low efficiency in traditional airborne fine particulate matter.
The aerosol sample being adsorbed on quartz fibre filter membrane directlys adopt EPR detection, method is easy to be fast without removing from filter membrane
Speed.To sum up, this non-solvent extraction and the method without removing from absorption filter membrane, do not destroy the original shape of Atmospheric particulates
State ensure that the accuracy of the detection of long-life organic free radical in the Atmospheric particulates of detection.With the use of mass flow atmospheric
Particulate cascade sampling device, can the long-life organic free radical in the atmospheric aerosol samples to different dynamic partial size carry out it is same
Sample acquisition and EPR detection are walked, has weight to the distribution characteristics for illustrating long-life organic free radical on different-grain diameter Atmospheric particulates
Want meaning.
The method for thering is document report to survey Atmospheric particulates long-life free radical using quartzy tissue pool method, compared to document
Report using quartzy tissue pool method, this method is succinct, quickly, it is accurate, easily operated, device therefor is few and easy acquisition.Tool
Body advantage is as follows:
A, test sample are cut: this method directly cuts out the quartz fibre film of absorption aerosol sample using ceramic scissors
It cuts, equipment is easy to get, and avoids the secondary pollution in cutting process；And require to be cut to specified area to sample film in document, it needs
Specific to cut instrument, operating process may cause pollution.
B, the placement of test sample: this method will fold after the samples weighing sheared and be placed directly within detection quartz ampoule
In, it is easy to operate；And particularly customized glass slide and coverslip are needed in document, sample is placed in one, sample cell is subsequently placed in
In, operation is relatively cumbersome, and needs particularly customized a variety of equipment.
C, sample quantify: this method directly has the long-life in sample on the basis of using Bruker ' Xenon software
Machine free radical is quantified, and the absolute spin population of sample is obtained, without another purchase standard items.Document needs another purchase Cr3+The standards such as mark
Product are calculated response coefficient, measure sample later, the dense of the middle EPFRs of sample is finally calculated after measuring standard items
Degree, method are related to plurality of reagents, and quantitative approach is more complex.
Detailed description of the invention
Fig. 1 is the example of the EPR spectrogram of the Atmospheric particulates without measuring when careful optimization.
Fig. 2 is the epr signal map of long-life organic free radical in the Atmospheric particulates detected in the embodiment of the present invention.
Specific embodiment
The present invention will be described below by way of specific embodiments, but the present invention is not limited thereto.
Experimental method used in following embodiments is conventional method unless otherwise specified；Institute in following embodiments
Reagent, biomaterial etc., are commercially available unless otherwise specified.
Atmospheric particulates are acquired using low discharge particle sampler, it is big to calculate acquisition for the film weighing of acquisition front and back
Aerated particle amount of substance.Using Bruker EMX-plus X-band EPR wave spectrum (Bruker Instruments, Billerica)
Directly the long-life organic free radical in Atmospheric particulates is detected.
It is as follows that case is embodied:
One, before sample acquisition, quartz fibre filter membrane dries 12h under the conditions of 450 DEG C, to remove the impurity such as organic matter.So
It is placed in drying box and saves, weigh (m before sampling0=0.1472g).Quartz fibre filter membrane doubling after acquisition, uses Aluminium Foil Package
It covers, is placed in and is saved for 24 hours with the drying box under acquisition the same terms, weigh (mt=0.1563g).
Two, use when the strip filter membrane of the quartz fibre filter membrane for finishing weighing, cutting 2-3m wide is placed in detection to facilitate
Quartz ampoule in, weigh to the strip filter membrane for cutting lower, note mu=0.0101g.
Three, in the quartz ampoule when quartz fibre filter membrane cut to be directly placed in detection, in case detection.
Four, right using Bruker EMX-plus X-band EPR wave spectrum (Bruker Instruments, Billerica)
Long-life organic free radical in sample is detected, by adjusting central magnetic field, microwave frequency, microwave power, modulating frequency,
The parameters such as modulation amplitude, field sweep width, gain acceptance in, sweep time, the maximum signal-to-noise ratio under the premise of acquisition epr signal is undistorted
Detection effect.
Epr signal intensity strong depend-ence microwave power, however be not the selectively bigger epr signal amplitude of microwave power just
Stronger, when microwave power increases to certain numerical value, epr signal rate of rise is closely zero, and sample signal reaches saturation at this time, spectrum
Line widens distortion.Therefore, microwave power when unsaturation should be selected to carry out sample measurement.Modulation amplitude also directly affects EPR letter
Number amplitude and shape select lesser modulation amplitude that can accurately measure the spectrum of sample under conditions of meeting sensitivity
Shape realizes high-resolution detection, therefore the modulation amplitude of this experimental selection is 1.0G.Survey when such as Fig. 1 being without careful optimization
The EPR spectrogram example (central magnetic field: 3500G of the Atmospheric particulates obtained；Microwave frequency: 9.81GHz；Modulating frequency: 100kHz；
Modulation amplitude: 1.0G；Field sweep width: 100G；Microwave power: 20mW；Sweep time: 50s；Time constant 40.96ms).
The instrument parameter for the optimization that this patent uses is as follows: central magnetic field: 3500G；Microwave frequency: 9.36GHz；Microwave function
Rate: 0.63mW；Modulating frequency: 100kHz；Modulation amplitude: 1.0G；Field sweep width: 100G；Gain acceptance in: 30dB；Sweep time:
100s.Spectrogram such as Fig. 2 under the conditions of the instrument parameter of optimization.
Five, surveyed Free Radical Signal: g-factor 2.00318, Δ H is obtained according to optimal peak typep-pThe list of=6.6G
Peak, thus it is speculated that be semiquinone type free base.According to spin quantitative theory, using Bruker ' s Xenon software to the free radical in sample
Quantitative analysis is carried out, the absolute magnitude of free radical in institute's sample is obtained, is denoted as Spins.
Then, in surveyed Atmospheric particulates long-life organic free radical concentration (Spins/g) are as follows:
Claims (6)
1. the method for long-life organic free radical, includes the following steps: in a kind of detection Atmospheric particulates
1) it weighs before acquiring Atmospheric particulates to filter membrane, is denoted as m0, Atmospheric particulates are acquired using the filter membrane, will be adopted
Filter membrane after collection is weighed, and m is denoted ast, the quality of the Atmospheric particulates acquired, mt-m0；
2) filter membrane for collecting Atmospheric particulates is cut into slice, and weighed, be denoted as mu；
3) filter membrane cut is folded and placed to progress electron paramagnetic resonance detection in quartz ampoule, obtains epr signal map；
4) according to epr signal map, the concentration of long-life organic free radical in Atmospheric particulates is calculated.
2. according to the method described in claim 1, it is characterized by: the filter membrane is quartz fibre filter membrane in step 1).
3. method according to claim 1 or 2, it is characterised in that: in step 2), the width of the slice is 2-3mm.
4. method according to any one of claim 1-3, it is characterised in that: in step 3), the quartz ampoule is electronics
Quartz ampoule is used in paramagnetic resonance EPR detection；
The free radical in sample is detected using the electronic paramagnetic resonance spectrometer of X-band, by adjusting central magnetic field, micro-
Wave frequency rate, microwave power, modulating frequency, modulation amplitude, field sweep width, gain acceptance in, sweep time etc. obtain to obtain most
The instrument parameter of excellent peak type.
5. according to the method described in claim 4, it is characterized by: the instrument parameter used is as follows: central magnetic field: 3500G；It is micro-
Wave frequency rate: 9.36GHz；Microwave power: 0.63mW；Modulating frequency: 100kHz；Modulation amplitude: 1.0G；Field sweep width: 100G；It connects
By gain: 30dB；Sweep time: 100s.
6. method according to any one of claims 1-5, it is characterised in that: in step 4), according in epr signal map
G value, peak width information to sample carry out qualitative analysis；According to spin quantitative theory, using Bruker ' s Xenon software to sample
Free radical in product carries out quantitative analysis, obtains the absolute magnitude of free radical in institute's sample, is denoted as Spins,
The calculation formula of the concentration (Spins/g) of free radical in surveyed Atmospheric particulates are as follows:
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Cited By (1)
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| CN109961223A (en) * | 2019-03-21 | 2019-07-02 | 中国科学院生态环境研究中心 | A kind of exposure appraisal procedure exposing long-life free radical in the airborne fine particulate matter of monitor based on individual |
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| CN101936930A (en) * | 2010-08-11 | 2011-01-05 | 南京大学 | Method for measuring superoxide anion radicals in tape grass leaves |
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| CN109961223A (en) * | 2019-03-21 | 2019-07-02 | 中国科学院生态环境研究中心 | A kind of exposure appraisal procedure exposing long-life free radical in the airborne fine particulate matter of monitor based on individual |
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