CN108508056A - A kind of method of accurate quantification trace solid free-radical contents - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000007787 solid Substances 0.000 title claims abstract description 15
- 238000011002 quantification Methods 0.000 title claims abstract description 9
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims description 14
- 238000011088 calibration curve Methods 0.000 claims 1
- 238000000280 densification Methods 0.000 claims 1
- 238000012360 testing method Methods 0.000 abstract description 24
- 238000009825 accumulation Methods 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- 150000003254 radicals Chemical class 0.000 description 22
- 238000005259 measurement Methods 0.000 description 9
- 238000000804 electron spin resonance spectroscopy Methods 0.000 description 6
- 238000001514 detection method Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000003245 coal Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000004435 EPR spectroscopy Methods 0.000 description 1
- UGQYFBCIIFQWTF-UHFFFAOYSA-L [Br+].[Cl-].[K+].[Cl-] Chemical compound [Br+].[Cl-].[K+].[Cl-] UGQYFBCIIFQWTF-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N24/00—Investigating or analyzing materials by the use of nuclear magnetic resonance, electron paramagnetic resonance or other spin effects
- G01N24/10—Investigating or analyzing materials by the use of nuclear magnetic resonance, electron paramagnetic resonance or other spin effects by using electron paramagnetic resonance
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Abstract
Description
技术领域technical field
本发明涉及自由基定量检测技术领域，尤其涉及一种精确定量微量固体自由基含量的方法。The invention relates to the technical field of free radical quantitative detection, in particular to a method for accurately quantifying the content of trace solid free radicals.
背景技术Background technique
含有不配对电子的物质均可用电子顺磁共振波谱仪(EPR)来检测。电子顺磁共振技术至今已在物理学、半导体、有机化学、络合物化学、辐射化学、化工、海洋化学、催化剂、生物学、生物化学、医学、环境科学、地质探矿等许多领域内得到广泛的应用。自由基的准确定量，是该技术深入利用的关键。如专利CN103105409A中的一种煤焦油自由基定量检测的方法，采用了已知自由基含量的标样建立了标准曲线进行定量。然而，EPR检测十分灵敏，测试条件的细微改变，都会对结果产生较大的影响，即使建立了标准曲线，也会存在较大的测量误差。EPR定量测试的关键在于灵敏度、稳定性和重复性。All substances containing unpaired electrons can be detected by electron paramagnetic resonance spectroscopy (EPR). Electron paramagnetic resonance technology has been widely used in many fields such as physics, semiconductor, organic chemistry, complex chemistry, radiation chemistry, chemical industry, marine chemistry, catalyst, biology, biochemistry, medicine, environmental science, geological prospecting, etc. Applications. The accurate quantification of free radicals is the key to the further utilization of this technology. For example, in the method for quantitative detection of coal tar free radicals in the patent CN103105409A, a standard sample with known free radical content is used to establish a standard curve for quantification. However, EPR detection is very sensitive, and slight changes in test conditions will have a great impact on the results. Even if a standard curve is established, there will be large measurement errors. The key points of EPR quantitative testing are sensitivity, stability and repeatability.
在对样品自由基含量进行定量时，几何形状，温度，谐振腔质量(Q-因子)，微波功率，调制幅度等参数均对结果有直接的影响。通过对测试仪器的控制及维护和对测试环境的精确控制，温度，谐振腔质量(Q-因子)，微波功率，调制幅度等参数都可以在多次测量中保持良好的一致性。然而，当检测样品量较少时，由于样品管尺寸相对较大，导致样品自身的几何形状以及测试时的堆积形状在多次测量中难以保持完全一致，甚至导致谐振腔质量(Q-因子)也发生变化，进一步导致最终的测量结果重复性较差，导致测量的误差。When quantifying the free radical content of a sample, parameters such as geometry, temperature, resonant cavity quality (Q-factor), microwave power, and modulation amplitude all have a direct impact on the result. Through the control and maintenance of the test equipment and the precise control of the test environment, parameters such as temperature, resonant cavity quality (Q-factor), microwave power, and modulation amplitude can maintain good consistency in multiple measurements. However, when the amount of detected sample is small, due to the relatively large size of the sample tube, it is difficult to keep the geometric shape of the sample itself and the stacked shape during the test completely consistent in multiple measurements, and even cause the quality of the resonant cavity (Q-factor) Changes also occur, which further lead to poor repeatability of the final measurement results, resulting in measurement errors.
如果能避免测试过程样品自身的几何形状和堆积现状对测试结果的影响，将会极大的提高EPR定量检测的稳定性和重复性，提高测量的准确度。因此，建立一套完善的针对微量样品的自由基准确定量方法是十分必要的。If the influence of the geometric shape and stacking status of the sample itself on the test results during the test process can be avoided, the stability and repeatability of the EPR quantitative detection will be greatly improved, and the accuracy of the measurement will be improved. Therefore, it is very necessary to establish a complete set of free reference determination methods for trace samples.
发明内容Contents of the invention
针对现有的微量样品测试存在的上述问题，现提供一种重复性好的精确定量微量固体自由基含量的方法。Aiming at the above-mentioned problems existing in the existing micro-sample test, a method for accurately quantifying the content of micro-solid free radicals with good repeatability is now provided.
具体技术方案如下：The specific technical scheme is as follows:
一种精确定量微量固体自由基含量的方法，具有这样的特征，包括如下步骤：A method for accurately quantifying the content of trace solid free radicals is characterized in that it comprises the steps of:
1)、取少量待测样品，称量，记录其质量为m1；1), take a small amount of sample to be tested, weigh it, and record its mass as m 1 ;
2)、取少量完全干燥的光谱纯溴化钾，称量，记录其质量为m2；2), take a small amount of completely dry spectrally pure potassium bromide, weigh it, and record its mass as m 2 ;
3)、将待测样品与溴化钾混合并研磨形成混合均匀的细粉末；3), the sample to be tested is mixed with potassium bromide and ground to form a uniformly mixed fine powder;
4)、取一定量细粉末，称量，记录其质量为m3，将细粉末装入样品管中，并使其致密分布于样品管的底部；4) Take a certain amount of fine powder, weigh it, record its mass as m 3 , put the fine powder into the sample tube, and make it densely distributed at the bottom of the sample tube;
5)、将样品管放入谐振器中测量，根据标准曲线法，得其自由基含量f(S1)，计算得待测样品中自由基含量f(S2)为：5), put the sample tube into the resonator for measurement, and obtain the free radical content f(S 1 ) according to the standard curve method, and calculate the free radical content f(S 2 ) in the sample to be tested as:
上述的精确定量微量固体自由基含量的方法，还具有这样的特征，步骤1)中2mg≤m1≤10mg。The above-mentioned method for accurately quantifying the content of trace solid free radicals also has the feature that in step 1), 2 mg≤m 1 ≤10 mg.
上述的精确定量微量固体自由基含量的方法，还具有这样的特征，步骤2)中20mg≤m2≤100mg。The above-mentioned method for accurately quantifying the content of trace solid free radicals also has the feature that in step 2), 20mg≤m 2 ≤100mg.
上述的精确定量微量固体自由基含量的方法，还具有这样的特征，步骤4)中20mg≤m3≤50mg。The above-mentioned method for accurately quantifying the content of trace solid free radicals also has the feature that in step 4), 20mg≤m 3 ≤50mg.
上述的精确定量微量固体自由基含量的方法，还具有这样的特征，步骤4)中将细粉末装入样品管中，并将样品管离心处理，使细粉末致密分布于样品管的底部。The above-mentioned method for accurately quantifying the content of trace solid free radicals also has the feature that in step 4), the fine powder is loaded into the sample tube, and the sample tube is centrifuged so that the fine powder is densely distributed at the bottom of the sample tube.
本发明中可通过待测样品与多个不同自由基含量的标准样品的测试结果对比，根据标样的测试结果与其自由基含量，绘制标准曲线，即可获得自由基含量与EPR测试结果的函数关系f(S)。In the present invention, by comparing the test results of the sample to be tested with a plurality of standard samples with different free radical contents, and drawing a standard curve according to the test results of the standard samples and their free radical content, the function of free radical content and EPR test results can be obtained relation f(S).
上述方案的有益效果是：The beneficial effect of said scheme is:
(1)本发明提供的方法中测试所需样品仅为2～10mg，样品消耗量小，可适用于样品量极少的测试；(1) The sample required for the test in the method provided by the present invention is only 2-10 mg, the sample consumption is small, and it can be applied to the test with a very small amount of sample;
(2)本方法将待测样品与溴化钾混合后研磨均匀，使样品粉碎成细微的颗粒均匀分散于溴化钾中，增加待测样品量，也避免了同一样品在重复测试过程因每次测试时样品几何形状和堆积形状(谐振腔质量Q因子)的不同导致的测试误差，提高了测试精度。(2) In this method, the sample to be tested is mixed with potassium bromide and ground evenly, so that the sample is pulverized into fine particles and evenly dispersed in potassium bromide, increasing the amount of sample to be tested, and avoiding the repeated testing process of the same sample due to each The test error caused by the difference in sample geometry and stacking shape (resonator quality Q factor) during the first test improves the test accuracy.
附图说明Description of drawings
图1-图4为本发明实施例中4个不同煤焦样品的重复性测试结果示意图；Fig. 1-Fig. 4 is the repeatability test result schematic diagram of 4 different coal char samples in the embodiment of the present invention;
图5为现有常规技术中重复性测试结果示意图。Fig. 5 is a schematic diagram of repeatability test results in the prior art.
具体实施方式Detailed ways
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动的前提下所获得的所有其他实施例，都属于本发明保护的范围。The following will clearly and completely describe the technical solutions in the embodiments of the present invention with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only some, not all, embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without creative efforts fall within the protection scope of the present invention.
需要说明的是，在不冲突的情况下，本发明中的实施例及实施例中的特征可以相互组合。It should be noted that, in the case of no conflict, the embodiments of the present invention and the features in the embodiments can be combined with each other.
下面结合附图和具体实施例对本发明作进一步说明，但不作为本发明的限定。The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments, but not as a limitation of the present invention.
本实施例提供的确定量微量固体自由基含量的方法中包括如下步骤：取少量待测样品，称量，记录其质量为m1，2mg≤m1≤10mg；取少量完全干燥的光谱纯溴化钾，称量，记录其质量为m2，20mg≤m2≤100mg；将待测样品与溴化钾混合并研磨形成混合均匀的细粉末；取一定量细粉末，称量，记录其质量为m3，20mg≤m3≤50mg，将细粉末装入样品管中，并将样品管离心处理，使细粉末致密分布于样品管的底部；将样品管放入谐振器中测量，并将其自由基信号S1代入自由基含量标准曲线，得其自由基含量f(S1)，计算得待测样品中自由基含量f(S2)为：The method for determining the amount of trace solid free radicals provided in this example includes the following steps: take a small amount of sample to be tested, weigh it, and record its mass as m 1 , 2 mg≤m 1 ≤10 mg; take a small amount of completely dried spectrally pure bromine Potassium chloride, weigh, record its mass as m 2 , 20mg≤m 2 ≤100mg; mix and grind the sample to be tested with potassium bromide to form a uniformly mixed fine powder; take a certain amount of fine powder, weigh it, and record its mass m 3 , 20mg≤m 3 ≤50mg, put the fine powder into the sample tube, and centrifuge the sample tube to make the fine powder densely distributed at the bottom of the sample tube; put the sample tube into the resonator for measurement, and The free radical signal S 1 is substituted into the free radical content standard curve to obtain the free radical content f(S 1 ), and the free radical content f(S 2 ) in the sample to be tested is calculated as:
图1-图4为本发明实施例中4个不同煤焦样品的重复性测试结果示意图；图5为现有常规技术中重复性测试结果示意图。由图1-图4所示，采用本发明中提供的测试方法进行4个不同的样品组的平行测试时，两次实验测量曲线均高度吻合，说明本发明中提供的测试方法相对于图5中采用常规技术进行测量时具有更为优异的重复性。Figures 1 to 4 are schematic diagrams of the repeatability test results of four different coal char samples in the embodiment of the present invention; Figure 5 is a schematic diagram of the repeatability test results in the prior conventional technology. Shown in Fig. 1-Fig. 4, when adopting the test method provided in the present invention to carry out the parallel test of 4 different sample groups, two experimental measurement curves are highly consistent, illustrate that the test method provided in the present invention is relative to Fig. 5 It has more excellent repeatability when measured by conventional techniques.
以上仅为本发明较佳的实施例，并非因此限制本发明的实施方式及保护范围，对于本领域技术人员而言，应当能够意识到凡运用本发明说明书及图示内容所作出的等同替换和显而易见的变化所得到的方案，均应当包含在本发明的保护范围内。The above are only preferred embodiments of the present invention, and are not intended to limit the implementation and protection scope of the present invention. For those skilled in the art, they should be able to realize the equivalent replacement and The solutions obtained by obvious changes shall all be included in the protection scope of the present invention.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112630252A (en) * | 2020-11-05 | 2021-04-09 | 浙江大学 | Nondestructive testing method for stability of tablet containing antioxidant butyl hydroxy anisole |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4668714A (en) * | 1984-08-30 | 1987-05-26 | Japan Atomic Energy Research Institute | Molded dosimeter containing a rubber and powdered crystalline alanine |
| SU1603266A1 (en) * | 1988-12-13 | 1990-10-30 | Институт Торфа Ан Бсср | Calibration specimen for epr-spectroscopy |
| CN103105409A (en) * | 2013-01-16 | 2013-05-15 | 华东理工大学 | Method for detecting free radical ration in coal tar |
| CN103472083A (en) * | 2013-09-17 | 2013-12-25 | 上海大学 | Method for detecting influence of electron beam irradiation on free radical concentration of coal by virtue of electron paramagnetic resonance |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4668714A (en) * | 1984-08-30 | 1987-05-26 | Japan Atomic Energy Research Institute | Molded dosimeter containing a rubber and powdered crystalline alanine |
| SU1603266A1 (en) * | 1988-12-13 | 1990-10-30 | Институт Торфа Ан Бсср | Calibration specimen for epr-spectroscopy |
| CN103105409A (en) * | 2013-01-16 | 2013-05-15 | 华东理工大学 | Method for detecting free radical ration in coal tar |
| CN103472083A (en) * | 2013-09-17 | 2013-12-25 | 上海大学 | Method for detecting influence of electron beam irradiation on free radical concentration of coal by virtue of electron paramagnetic resonance |
Non-Patent Citations (2)
| Title |
|---|
| 李佃平 等: "《矿井综放工作面自然发火的早期预控技术及应用》", 31 May 2011, 煤炭工业出版社 * |
| 郑榕萍 等: "标准曲线法测定煤中自由基含量", 《波谱学杂志》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112630252A (en) * | 2020-11-05 | 2021-04-09 | 浙江大学 | Nondestructive testing method for stability of tablet containing antioxidant butyl hydroxy anisole |
| CN112630252B (en) * | 2020-11-05 | 2022-04-01 | 浙江大学 | Nondestructive testing method for stability of tablet containing antioxidant butyl hydroxy anisole |
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