CN105628728B - A kind of method that hydroxy free radical concentration changes in solution in detection course of reaction - Google Patents
A kind of method that hydroxy free radical concentration changes in solution in detection course of reaction Download PDFInfo
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Abstract
The method that hydroxy free radical concentration changes in solution in course of reaction is detected the invention discloses a kind of.This method comprises the following steps：1）Prepare hydroxyl radical free radical chelating agent solution；2）The reaction system of structure generation hydroxyl radical free radical, determines sampling time point, after question response starts, is sampled by identified sampling time point, the sample solution of acquirement is added in hydroxyl radical free radical chelating agent solution, be well mixed, obtain mixed solution；3）By step 2）Mixed solution be placed in electron paramagnetic resonance and tested, obtain hydroxyl radical free radical characteristic absorption spectrogram；4）Each hydroxyl radical free radical characteristic absorption spectrogram is contrasted, determines the change in concentration of the hydroxyl radical free radical in reaction system.The method of the present invention both during detectable response differential responses moment hydroxyl radical free radical concentration, and the situation of change of hydroxy free radical concentration during detectable response, reaction process is tracked, the detection efficiency height of this method, cost is low, result is accurate, reproducible.
Description
Technical field
The method that hydroxy free radical concentration changes in solution in course of reaction is detected the present invention relates to a kind of, belongs to chemistry point
Analysis field.
Background technology
Many chemical reactions can generate substantial amounts of hydroxyl radical free radical during the course of the reaction, such as Fenton's reaction, class Fenton's reaction,
This kind of reaction is widely used in the fields such as environmental protection, chemical industry, pharmacy.However, because hydroxyl radical free radical is extremely active, detection
It is difficult, it is difficult to which that this kind of reaction is furtherd investigate.
At present, there are two kinds using the more method that can detect hydroxy free radical concentration in solution both at home and abroad：Fluorescence point
Light photometry and electron paramagnetic resonance method（EPR）.
Fluorescence spectrophotometry is that chemical reaction occurs with developer using hydroxyl radical free radical to produce color change, passes through face
Color change measures the concentration of hydroxyl radical free radical indirectly, such as patent a kind of " method for detecting hydroxy free radical concentration in solution（China
Patent publication No. CN103983592A）" it is exactly to catch hydroxyl radical free radical first with dimethyl sulfoxide (DMSO), then occur with organic dyestuff
The diazo-reaction of colour developing, the absorbance for finally determining solution detect the hydroxy free radical concentration in solution.Such method
Testing result accuracy is poor, and data redundancy is poor.
EPR is the method for the detection hydroxyl radical free radical just developed in recent years, such as a kind of patent " hydroxyl free radical in plant body
Assay method "（China Patent Publication No. CN102297875A）, made first using hydroxyl radical free radical chelating agent extremely unstable
Hydroxyl radical free radical is of short duration to be stabilized, during this period the single electron signal intensity in quick detection sample solution come characterize hydroxyl from
By the concentration of base.Such method detection data are relatively stable, and testing result reappearance is higher, but needs in advance by hydroxyl radical free radical chela
Mixture adds in the solution, i.e., before hydroxyl radical free radical does not generate also, hydroxyl radical free radical chelating agent has just been added in solution, this
Every part of testing sample of sample can only detect the concentration of a hydroxyl radical free radical.It can only namely detect and react the hydroxyl being initially generated certainly
By the concentration of base, the hydroxy free radical concentration in can not detect testing sample solution each stage during the course of the reaction.
The present invention develops a kind of new hydroxyl radical free radical detection method, and this method, which can be detected in same course of reaction, appoints
Meaning moment reaction system（Reaction solution）The concentration of middle hydroxyl radical free radical, the change of hydroxy free radical concentration in course of reaction can be detected
Change situation, reaction process can be tracked.
The content of the invention
The method that hydroxy free radical concentration changes in solution in course of reaction is detected it is an object of the invention to provide a kind of.
The technical solution used in the present invention is：
A kind of method that hydroxy free radical concentration changes in solution in detection course of reaction, comprises the following steps：
1) hydroxyl radical free radical chelating agent is dissolved in cushioning liquid, obtains hydroxyl radical free radical chelating agent solution；
2) reaction system of structure generation hydroxyl radical free radical, determines sampling time point, after question response starts, by being determined
Sampling time point sampling, the sample solution of acquirement is added in hydroxyl radical free radical chelating agent solution, be well mixed, mixed
Close solution；
3) by step 2）Mixed solution be placed in electron paramagnetic resonance and tested, obtain the suction of hydroxyl radical free radical feature
Receive spectrogram；
4) the hydroxyl radical free radical characteristic absorption spectrogram that each sample point measures is contrasted, is determined according to peak intensity in reaction system
The change in concentration of hydroxyl radical free radical.
Step 1）Described hydroxyl radical free radical chelating agent is one in 5,5- dimethyl pyridine N-oxides, dimethyl sulfoxide (DMSO)
Kind.
Step 1）Described cushioning liquid be used for by the pH stable of hydroxyl radical free radical chelating agent solution 7.0~8.0 it
Between.
Described cushioning liquid is potassium dihydrogen phosphate-sodium hydroxide buffer solution.
Step 1）The substance withdrawl syndrome of described hydroxyl radical free radical chelating agent solution is 0.05~0.10mol/L.
The reaction system of described generation hydroxyl radical free radical is Fenton's reaction system, one kind in class Fenton's reaction system.
Step 2）To, per sub-sampling 0.5~1.5mL, being added to 100~200 μ L hydroxyl radical free radical chela during sampling time point
In mixture solution.
The beneficial effects of the invention are as follows：
（1）The method of the present invention can detect differential responses moment hydroxy free radical concentration in course of reaction；
（2）The method of the present invention can detect the situation of change of hydroxy free radical concentration in course of reaction, tracking react into
Journey；
（3）The method detection efficiency of the present invention is high, cost is low, result is accurate, reproducible.
Brief description of the drawings
Fig. 1 is the hydroxyl radical free radical characteristic absorption spectrogram in the Fenton's reaction 5s systems of embodiment 1；
Fig. 2 is the hydroxyl radical free radical characteristic absorption spectrogram in the Fenton's reaction 30s systems of embodiment 1；
Fig. 3 is the hydroxyl radical free radical characteristic absorption spectrogram in the Fenton's reaction 1min systems of embodiment 1；
Fig. 4 is the hydroxyl radical free radical characteristic absorption spectrogram in the Fenton's reaction 5min systems of embodiment 1；
Fig. 5 is the hydroxyl radical free radical characteristic absorption spectrogram in the Fenton's reaction 15min systems of embodiment 1；
Fig. 6 is the hydroxyl radical free radical characteristic absorption spectrogram in the Fenton's reaction 30min systems of embodiment 1.
Embodiment
A kind of method that hydroxy free radical concentration changes in solution in detection course of reaction, comprises the following steps：
1) hydroxyl radical free radical chelating agent is dissolved in cushioning liquid, obtains hydroxyl radical free radical chelating agent solution；
2) reaction system of structure generation hydroxyl radical free radical, determines sampling time point, after question response starts, by being determined
Sampling time point sampling, the sample solution of acquirement is added in hydroxyl radical free radical chelating agent solution, be well mixed, mixed
Close solution；
3) by step 2）Mixed solution be placed in electron paramagnetic resonance and tested, obtain the suction of hydroxyl radical free radical feature
Receive spectrogram；
4) the hydroxyl radical free radical characteristic absorption spectrogram that each sample point measures is contrasted, is determined according to peak intensity in reaction system
The change in concentration of hydroxyl radical free radical.
Preferably, step 1）Described hydroxyl radical free radical chelating agent is 5,5- dimethyl pyridine N-oxides, dimethyl Asia
One kind in sulfone.
Preferably, step 1）Described cushioning liquid is used for the pH stable of hydroxyl radical free radical chelating agent solution 7.0
Between~8.0.
Preferably, described cushioning liquid is potassium dihydrogen phosphate-sodium hydroxide buffer solution.
Preferably, step 1）The substance withdrawl syndrome of described hydroxyl radical free radical chelating agent solution is 0.05~0.10mol/
L。
Preferably, the reaction system of described generation hydroxyl radical free radical is Fenton's reaction system, in class Fenton's reaction system
One kind.
Preferably, step 2）To, per sub-sampling 0.5~1.5mL, being added to 100~200 μ L hydroxyl during sampling time point
In free radical chelating agent solution.
The present invention is made further explanation and description with reference to specific embodiment.
Embodiment 1：
1）The phosphate buffer solution for being 7.4 according to national standard configuration pH value：1.36g potassium dihydrogen phosphates are weighed, add 79mL
Substance withdrawl syndrome is 0.1mol/L sodium hydroxide solution, is diluted with water to 200mL；
2）Weigh 1.97g 5,5- dimethyl pyridine N-oxides（DMPO）It is added to step 1）Cushioning liquid in, obtain
Substance withdrawl syndrome is 0.08mol/L DMPO solution；
3）The configuration of Fenton's reaction liquid to be measured：Measure the phthalic acid diformazan that 200mL mass-volume concentrations are 250mg/L
Ester（DMP）The aqueous solution, 0.061g green vitriol solids are added, it is 30% that 90 μ L mass fractions are added after stirring and dissolving
Hydrogenperoxide steam generator, that is, start Fenton's reaction；
4）Fenton's reaction timing, 1mL Fenton's reaction liquid is drawn respectively at 5s, 30s, 1min, 5min, 15min and 30min,
It is added to 120 μ L steps 2）In obtained DMPO solution, rocking uniformly, DMPO catches the hydroxyl radical free radical in Fenton's reaction liquid,
Generate stable DMPO-OH；
5）Semicanal step 4 is drawn with internal diameter 0.5mm capillaries）The DMPO-OH solution of the stabilization of middle generation, is burnt with lighter
Burning seals capillary bottom of the tube, inserts ERP（Kepler-16）Resonator in detect hydroxyl radical free radical signal intensity, hydroxyl from
It is 1 by the characteristic absorption peak of base:2:2:1 four peaks.Fig. 1~Fig. 6 be respectively Fenton's reaction start 5s, 30s, 1min, 5min,
Hydroxyl radical free radical characteristic absorption spectrogram in 15min and 30min systems；
6）According to the peak intensity of above-mentioned hydroxyl radical free radical characteristic absorption peak, pass through contrast, you can the measure differential responses moment
Hydroxy free radical concentration change, analysis judge reaction process.
As shown in Figure 1：Reaction time 5s, peak intensity 28000；
As shown in Figure 2：Reaction time 30s, peak intensity 3100；
As shown in Figure 3：Reaction time 1min, peak intensity 2100；
As shown in Figure 4：Reaction time 5min, peak intensity 1400；
As shown in Figure 5：Reaction time 15min, peak intensity 1250；
As shown in Figure 6：Reaction time 30min, peak intensity 1700.
1~Fig. 6 of complex chart is understood：Four spikes, and peak is presented in curve in hydroxyl radical free radical characteristic absorption spectrogram
At high proportion substantially 1:2:2:1, it is the characteristic absorption spectrogram of hydroxyl radical free radical in an epr, can assert and contain hydroxyl in solution certainly
By base.Due to the proportional relation that the peak intensity of absworption peak is into strict with hydroxy free radical concentration, therefore according to every characteristic absorption
The peak strength of absworption peak is that can obtain the relative concentration of hydroxyl radical free radical in different solutions in spectrogram, also can be different by contrasting
Trace analysis hydroxy free radical concentration size.
Embodiment 2：
1）The phosphate buffer solution 200mL for being 7.0 according to national standard configuration pH value；
2）Weigh 2.34g dimethyl sulfoxide (DMSO)s（DMSO）It is added to step 1）Cushioning liquid in, obtain substance withdrawl syndrome
For 0.15mol/L DMSO solution；
3）The configuration of class Fenton's reaction liquid to be measured：The DMP aqueous solution that 200mL mass-volume concentrations are 250mg/L is measured, is added
Enter 0.081g green vitriol solids, add the copper-bath that 1mL mass-volume concentrations are 4g/L, add after stirring and dissolving
Enter the hydrogenperoxide steam generator that 120 μ L mass fractions are 30%, that is, start class Fenton's reaction；
4）Class Fenton's reaction timing, during the course of the reaction at the time of any desired test, draw 1.5mL class Fenton's reactions
Liquid, it is added to 100 μ L steps 2）DMSO solution in, be well mixed, DMSO catch class Fenton's reaction liquid in hydroxyl radical free radical,
Generate stable DMSO-OH；
5）Semicanal step 4 is drawn with internal diameter 0.5mm capillaries）The DMSO-OH of the stabilization of middle generation solution, uses lighter
Calcination seals capillary bottom of the tube, inserts ERP（Kepler-16）Resonator in detect hydroxyl radical free radical characteristic absorption peak peak value
Intensity；
6）The peak intensity for the characteristic absorption peak of hydroxyl radical free radical at different moments that comparative determination obtains, you can determine course of reaction
The change of the hydroxy free radical concentration of middle generation, so as to track reaction process.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (4)
1. a kind of detect the method that hydroxy free radical concentration changes in solution in course of reaction, it is characterised in that：Including following step
Suddenly：
1）Hydroxyl radical free radical chelating agent is dissolved in cushioning liquid, obtains hydroxyl radical free radical chelating agent solution；
2）The reaction system of structure generation hydroxyl radical free radical, determines sampling time point, after question response starts, is taken by identified
Sample point in time sampling, the sample solution of acquirement is added in hydroxyl radical free radical chelating agent solution, be well mixed, obtain mixing molten
Liquid；
3）By step 2）Mixed solution be placed in electron paramagnetic resonance and tested, obtain hydroxyl radical free radical characteristic absorpting spectrum
Figure；
4）The hydroxyl radical free radical characteristic absorption spectrogram that each sample point measures is contrasted, the hydroxyl in reaction system is determined according to peak intensity
The change in concentration of free radical；
Step 1）Described cushioning liquid is used for the pH stable of hydroxyl radical free radical chelating agent solution between 7.0~8.0；Step
Rapid 2）The reaction system of described generation hydroxyl radical free radical is Fenton's reaction system, one kind in class Fenton's reaction system；Step
2）To 0.5~1.5mL of every sub-sampling during sampling time point, it is added in 100~200 μ L hydroxyl radical free radical chelating agent solution.
2. according to the method for claim 1, it is characterised in that：Step 1）Described hydroxyl radical free radical chelating agent is 5,5- bis-
One kind in PICOLINE N-OXIDES, dimethyl sulfoxide (DMSO).
3. according to the method for claim 1, it is characterised in that：Step 1）Described cushioning liquid is potassium dihydrogen phosphate-hydrogen
Sodium oxide molybdena cushioning liquid.
4. according to the method for claim 1, it is characterised in that：Step 1）The thing of described hydroxyl radical free radical chelating agent solution
The amount concentration of matter is 0.05~0.10mol/L.
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| CN110988010A (en) * | 2019-12-27 | 2020-04-10 | 桂林电子科技大学 | Method for detecting free radicals in polymerization reaction process on line |
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| CN102297875B (en) * | 2010-06-23 | 2014-04-23 | 中国科学院生态环境研究中心 | Method for measuring hydroxyl free radical in plant body |
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Inventor after: Sun Zhimin Inventor after: Li Junyi Inventor before: Sun Zhimin |
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Address after: 510060 No. 348, East Ring Road, Yuexiu District, Guangzhou, Guangdong. Patentee after: Guangzhou municipal engineering design and Research Institute Co., Ltd. Address before: 510060 No. 348, East Ring Road, Yuexiu District, Guangzhou, Guangdong. Patentee before: Guangzhou City Engineering Design studies total institute |