CN104965042A - Detection method for various kinds of trace glucocorticoid and derivate thereof in surface water body - Google Patents
Detection method for various kinds of trace glucocorticoid and derivate thereof in surface water body Download PDFInfo
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Abstract
The invention discloses a detection method for various kinds of trace glucocorticoid and a derivate thereof in a surface water body. The detection method comprises the steps that 1, a water body sample is preprocessed, wherein solid phase extraction is carried out on the water body sample after the water body sample is filtered; 2, an ultra-high performance liquid chromatography-mass spectrometry series method is adopted for analyzing the content of trace glucocorticoid and the derivate thereof in the water body sample; 3, a standard curve is drawn, an external standard method is used for quantitative determination, and the concentration of the trace glucocorticoid and the derivate thereof in the water body sample through conversion. The detection method has the advantages of being easy and convenient to operate, environmentally friendly and low in detection limit.
Description
Technical field
The present invention relates to the detection method of chemical substance, particularly relate to a kind of Ultra Performance Liquid Chromatography mass spectrum series process that adopts to the detection method of glucocorticoid in the water sample of earth's surface and derivant (comprising natural glucocorticoid, esterified saccharides cortin and halogeno-sugar cortin) thereof.
Background technology
The a kind of of endocrine disruptor is the nearly emphasis that decades, environmental science was paid close attention to, it can interference body internal system thus impact the endocrine disruption system of human body and animal, nearly decades womb cancer morbidity rise, children's sexal maturity in advance, neonatal immunity power declines and is all proved to be relevant to endocrine disruptor.Glucocorticoid and derivant thereof are as a class of endocrine disruptor, it is novel endocrine disruptor extensively concerned at present, research finds that glucocorticoid and derivant thereof just can cause damage to the immunity of biology, reproduction and immune system under the concentration level of ng/L, the problems such as the impaired and developmental defect of serious caused reproduction, the situations such as the fish be under the exposure of glucocorticoid may cause that organism immune response suppresses, growth inhibition and physiological situation deterioration.In view of the similarity of glucocorticoid and estrogen, androgen and progestational hormone structure, its biological effect may be intersected, as there are some researches show two kinds of glucocorticoids: hydrocortisone and metacortandracin may cause the masculine phenomenon of female mosquito fish, be therefore necessary to launch research to the glucocorticoid in surface water body and derivant thereof.
Glucocorticoid in surface water body and derivant thereof are originated more, mainly contain: the mankind's daily secretion discharge and unemployed medical glucocorticoid and derivant medicine thereof, it should be noted that, China's glucocorticoid medicine reaches the degree of abuse, in the hospital of investigation, utilization rate is more than 20%, and Individual hospitals is more than 50%.In addition animal husbandry due to size of animal huge, daily secretion discharge capacity is also very considerable, and some glucocorticoid medicines such as dexamethasone is widely used in livestock breed aquatics, its glucocorticoid amount entered in water body produced is very huge, and the waste water and dregs of other hormone sensitive lipase gene industry is also the pollution source that can not be ignored.
Harm human and animal's body produced in view of glucocorticoid and derivant thereof and its extensive existence in the surface water body that human contact is close, earth's surface water body example has complicated matrix feature in addition, larger interference can be produced to detection sensitivity, and glucocorticoid content can reach extremely low ng/L rank in water body, make the glucocorticoid detection method in surface water body comparatively deficient.The detection method of current environmental hormone mainly contains gas chromatography tandem mass spectrum series process, Liquid Chromatography-Tandem Mass Spectrometry series process and immunoassay etc., but all also exists that sensitivity is low, derivatization is difficult, be not suitable for the drawbacks such as large-scale operation.Therefore the present invention utilizes Solid-Phase Extraction hormone to set up highly sensitive, easy easy-to-use, the glucocorticoid that can detect many kinds of substance and derivant detection method thereof in conjunction with Ultra Performance Liquid Chromatography mass spectrum serial connection technology.
Summary of the invention
In order to solve the difficulty that prior art exists, the present invention is directed to water environment mesostroma complicated, glucocorticoid and derivative content thereof are extremely low, the problems such as detection difficulty is large, provide a kind of efficient, easy, economic analytical approach, realize the mensuration of glucocorticoid to common in the water body example of earth's surface and derivant thereof.
In surface water body, a detection method for several trace glucocorticoid and derivant thereof, comprises the steps:
(1) pre-service of water body example: carry out Solid-Phase Extraction after being filtered by water body example;
(2) Ultra Performance Liquid Chromatography-extract of mass spectrum series connection method to water body example is adopted to detect;
(3) drawing standard curve, and carry out quantitative measurement with external standard method, by the concentration obtaining trace glucocorticoid and derivant thereof in water body example that converts.
The detection method of several trace glucocorticoid and derivant thereof in surface water body of the present invention, wherein, the chromatographic condition in Ultra Performance Liquid Chromatography-mass spectrum series connection method described in step (2) is:
ACQUITY
tMsuperelevation liquid chromatograph, Agilent Zorbax SB-C18 post (100mm × 3mm, 1.8 μm) and Micromass-Quattro Premier XE mass spectrometer, use MassLynxV4.1 software, column temperature: 40 DEG C; Sample temperature: 4 DEG C; Sampling volume: 3 μ L; Mobile phase A: methyl alcohol, Mobile phase B: containing 0.1% (volume fraction) second aqueous acid, elution program is as follows: 0 ~ 6min, A:35% → 45%; 6 ~ 12min, A:45% → 80%; 12 ~ 15min, A:80% → 95%; 15 ~ 15.1min, A:95% → 35%.
The detection method of several trace glucocorticoid and derivant thereof in surface water body of the present invention, wherein, the Mass Spectrometry Conditions in Ultra Performance Liquid Chromatography-mass spectrum series connection method described in step (2) is:
Ion gun is that electron spray ionisation adopts ESI (-) pattern, capillary voltage: 3.00kV, radio-frequency lens 1 voltage: 27.0V, radio-frequency lens 2 voltage: 0.0V, ion source temperature: 99 DEG C, desolventizing temperature: 450 DEG C, desolventizing airshed: 600L/h, collision gradient: 1.9, adopts more options reaction monitoring translative mode MRM.
The detection method of several trace glucocorticoid and derivant thereof in surface water body of the present invention, wherein, the pre-service of described water body example comprises the steps:
Gather the surface water body sample needing to detect, be placed in Brown Glass Brown glass bottles and jars only and transport laboratory back, for avoiding the blocking of solid-phase extraction column, the Whatman company GF/C glass fiber filter paper of 1.5L water body example first through 1.2 μm of apertures is filtered, then pass through to use 6mL ethyl acetate in advance with the flow velocity of 3 ~ 5mL/min, the HLB solid-phase extraction column of 6mL acetonitrile and the activation of 6mL ultrapure water, water body example is all by after solid-phase extraction column, with 12mL ultrapure water drip washing solid-phase extraction column, and the moisture eliminated in extraction column is dried up with nitrogen, be the ethylacetate/acetonitrile wash-out HLB solid-phase extraction column of 1:1 again by 6mL volume ratio, collecting eluent utilizes faint nitrogen to dry up, again constant volume is dissolved to be measured with 100 μ L methyl alcohol, all extracting and enriching processes complete in 6h.
The detection method of several trace glucocorticoid and derivant thereof in surface water body of the present invention, wherein, described glucocorticoid and derivant thereof are metacortandracin, cortisone, hydrocortisone, prednisolone, flumethasone, dexamethasone, fluoxyprednisolone, fludrocortisone acetate, Triamcinolone acetonide, methylprednisolone, beclomethasone, cortisone acetate, hydrocortisone acetate, fluorometholone, dexamethasone acetate, budesonide and clobetasol propionate.
The detection method of several trace glucocorticoid and derivant thereof in surface water body of the present invention, wherein, the mass spectrum acquisition parameter in described Mass Spectrometry Conditions is as shown in table 1:
The mass spectrum acquisition parameter of table 1 target glucocorticoid and derivant thereof
1)
1)
arepresent that this fragmention is quota ion
The detection method of several trace glucocorticoid and derivant thereof in surface water body of the present invention, wherein, described method also comprises: the isotope standard cortisol-d using glucocorticoid
4the loss of actual sample in pre-treatment and testing process is corrected as marking in process.
In surface water body of the present invention, the detection method difference from prior art of several trace glucocorticoid and derivant thereof is:
In surface water body of the present invention, the detection method of several trace glucocorticoid and derivant thereof is for the extremely low concentration of the matrix characteristic sum target substance of the complexity of water body example, process simple and effective hydrophilic-lipophilic balance (HLB) solid-phase extraction column is adopted to extract targetedly, select the MRM conversion ions pair of high specificity, adopt highly sensitive Ultra Performance Liquid Chromatography tandem mass spectrometry quantitatively to detect, and utilize isotope standard cortisol-d
4correct the loss of issuable target substance in experimentation.The invention provides that a kind of detection limit is low, recovering effect good, can detect the analytical approach of many kinds of substance, can common glucocorticoid in express-analysis water body and derivative content thereof.
Be described further below in conjunction with the detection method of accompanying drawing to trace glucocorticoid several in surface water body of the present invention and derivant thereof.
Accompanying drawing explanation
The chromatogram of Fig. 1 to be addition be metacortandracin solution of 10ug/L;
Fig. 2 is addition is the cortisone of 10ug/L and the chromatogram of prednisolone (the quantitative conversion ions of two kinds of materials is to identical) solution;
The chromatogram of Fig. 3 to be addition be hydrocortisone solution of 10ug/L;
The chromatogram of Fig. 4 to be addition be flumethasone solution of 10ug/L;
The chromatogram of Fig. 5 to be addition be dexamethasone solution of 10ug/L;
The chromatogram of Fig. 6 to be addition be fluoxyprednisolone solution of 10ug/L;
The chromatogram of Fig. 7 to be addition be fludrocortisone acetate solution of 10ug/L;
The chromatogram of Fig. 8 to be addition be Triamcinolone acetonide solution of 10ug/L;
The chromatogram of Fig. 9 to be addition be methylprednisolone solution of 10ug/L;
The chromatogram of Figure 10 to be addition be beclomethasone solution of 10ug/L;
The chromatogram of Figure 11 to be addition be cortisone acetate solution of 10ug/L;
The chromatogram of Figure 12 to be addition be hydrocortisone acetate solution of 10ug/L;
The chromatogram of Figure 13 to be addition be fluorometholone solution of 10ug/L;
The chromatogram of Figure 14 to be addition be dexamethasone acetate solution of 10ug/L;
The chromatogram of Figure 15 to be addition be budesonide solution of 10ug/L;
The chromatogram of Figure 16 to be addition be clobetasol propionate solution of 10ug/L;
Figure 17 is the chromatogram of glucocorticoid and the derivant thereof detected in embodiment 2; Wherein chromatogram is followed successively by from top to bottom: cortisone (cortisone) and prednisolone (prednisolone), hydrocortisone (Hydrocortisone), dexamethasone (Dexamethasone), fluoxyprednisolone (Triamcinolone), Triamcinolone acetonide (Triamcinolone acetonide), hydrocortisone acetate (Hydrocortisone acetate).
Embodiment
Embodiment 1
A detection method for trace glucocorticoid and derivative content thereof in surface water body, the method comprises the steps:
(1) pre-service of surface water body sample
The Whatman company GF/C glass fiber filter paper of surface water body sample through 1.2 μm of apertures gathering 1.5L is filtered, then pass through to use 6mL ethyl acetate in advance with the flow velocity of 3 ~ 5mL/min, hydrophilic-lipophilic balance (HLB) solid-phase extraction column of 6mL acetonitrile and the activation of 6mL ultrapure water, water sample is all by after Solid-Phase Extraction (SPE) post, with 12mL ultrapure water drip washing SPE post, and the moisture eliminated in extraction column is dried up with faint nitrogen, finally use 6mL ethylacetate/acetonitrile (1:1, V/V) wash-out HLB solid-phase extraction column, collecting eluent utilizes faint nitrogen to dry up, again to be measured after dissolving constant volume with 100 μ L methyl alcohol, all extracting and enriching processes must complete in 6h.
(2) extract of Ultra Performance Liquid Chromatography mass spectrum serial connection technology to surface water is utilized to detect
Experimental apparatus of the present invention and condition are: ACQUITY
tMsuperelevation liquid chromatograph, Agilent Zorbax SB-C18 post (100mm × 3mm, 1.8 μm) and Micromass-Quattro Premier XE mass spectrometer, use MassLynx V4.1 software, chromatographic elution conditions: column temperature: 40 DEG C; Sample temperature: 4 DEG C; Sampling volume: 3 μ L; Mobile phase A: methyl alcohol, Mobile phase B: containing 0.1% (volume fraction) second aqueous acid, elution program is as shown in table 1:
The superelevation liquid-phase chromatographic analysis condition of table 2 17 kinds of target glucocorticoids and derivant thereof
Mass Spectrometry Conditions: ion gun is that electron spray ionisation adopts ESI (-) pattern, adopt more options reaction monitoring translative mode (MRM), capillary voltage: 3.00kV, radio-frequency lens 1 (RF lens 1) voltage: 27.0V, radio-frequency lens 2 (RF lens 2) voltage: 0.0V, ion source temperature: 99 DEG C, desolventizing temperature: 450 DEG C, desolventizing airshed: 600L/h, collision gradient: 1.9, Mass Spectrometry Conditions is as shown in table 1.
The mass spectrum acquisition parameter of table 1 target glucocorticoid and derivant thereof
1)
1)
arepresent that this fragmention is quota ion
(3) drafting of typical curve, and carry out quantitative measurement with external standard method
The drafting of described external standard method typical curve: utilize analytical balance to take standard sugar cortin and derivant sample is dissolved in Chromatographic Pure Methanol, be mixed with the standard solution of series concentration, adopt Ultra Performance Liquid Chromatography mass spectrum serial connection technology to carry out analysis to detect, be horizontal ordinate respectively with concentration, be that ordinate carries out regretional analysis with peak area, obtain typical curve, for the content of glucocorticoid in working sample and derivant thereof.
(4) sample and the recovery mensuration
Gather earth's surface water body example, according to step (1), pre-treatment operation is carried out to water sample, carry out Ultra Performance Liquid Chromatography mass spectrum serial connection technology by step (2) again to detect, and compare with the typical curve that step (3) obtains, in order to correct the loss of actual sample in pre-treatment and testing process, this research uses the isotope standard cortisol-d of glucocorticoid and derivant thereof
4mark as in process.Eventually through the concentration obtaining trace glucocorticoid and derivant thereof in water sample to be measured that converts.
Gather identical water body example, add glucocorticoid and the derivant standard solution thereof of 50ng/L, measure glucocorticoid and derivatives concentration content thereof according to above-mentioned pre-treatment and detection method, calculate the recovery according to the following formula:
The R-recovery, %;
C-adds glucocorticoid and derivative content thereof in the water sample of standard solution, ng/L;
C
0-do not add glucocorticoid and derivative content thereof in the water sample of standard solution, ng/L;
Wherein said glucocorticoid and derivant thereof comprise: metacortandracin, cortisone, hydrocortisone, prednisolone, flumethasone, dexamethasone, fluoxyprednisolone, fludrocortisone acetate, Triamcinolone acetonide, methylprednisolone, beclomethasone, cortisone acetate, hydrocortisone acetate, fluorometholone, dexamethasone acetate, budesonide and clobetasol propionate.Standard model chromatogram is shown in Fig. 1-Figure 16.
The present invention adopts interpolation standard sugar cortin and derivant biased sample thereof in order to calculate the recovery, and addition is 50ng/L.Calculate the signal intensity of target glucocorticoid and derivant thereof in addition according to 3 times of detection limit signal to noise ratio (S/N ratio)s (S/N), calculate the detection limit of each target glucocorticoid and derivant thereof according to the working curve of concentration-peak area.The recovery and the minimum detectability of this method are as shown in table 3.
The method recovery of table 3 17 kinds of target glucocorticoids and derivant thereof and detection limit
The invention has the beneficial effects as follows the extremely low concentration of the matrix characteristic sum target substance of the complexity for surface water body sample, process simple and effective hydrophilic-lipophilic balance (HLB) solid-phase extraction column is adopted to extract targetedly, and adopting highly sensitive, the Ultra Performance Liquid Chromatography tandem mass spectrometry that specificity is good quantitatively detects.The invention provides that a kind of detection limit is low, recovering effect good, can detect the analytical approach of many kinds of substance, can common glucocorticoid in express-analysis surface water body and derivative content thereof.The inventive method also comprises the isotope standard cortisol-d using glucocorticoid
4the loss of actual sample in pre-treatment and testing process is corrected as marking in process.
Embodiment 2
A detection method for trace glucocorticoid and derivative content thereof in surface water body, the method comprises the steps:
(1) pre-service of surface water body sample
Gather 5 each 1.5L of water body example of parts of Beijing urban river, be placed in Brown Glass Brown glass bottles and jars only, first water sample filters through the GF/C glass fiber filter paper in 1.2 μm of apertures to remove impurity, HLB solid-phase extraction column uses 6mL ethyl acetate in advance, 6mL acetonitrile and the activation of 6mL ultrapure water, then the water sample after filtering passes through solid-phase extraction column with the flow velocity of 3 ~ 5mL/min, water sample is all by after HLB post, with 12mL ultrapure water drip washing solid-phase extraction column, and the moisture eliminated in extraction column is dried up with nitrogen, finally use 6mL ethylacetate/acetonitrile (1:1, V/V) wash-out HLB solid-phase extraction column, collect eluent and dry up with faint nitrogen, again dissolve constant volume with 100 μ L methyl alcohol to detect for UPLC-MS/MS, all pretreatment process complete in 6h.
(2) Ultra Performance Liquid Chromatography-mass spectrum serial connection technology is utilized to detect water body example extract
The experimental apparatus that Ultra Performance Liquid Chromatography-mass spectrum series process is selected and condition are: ACQUITY
tMsuperelevation liquid chromatograph, Agilent Zorbax SB-C18 post (100mm × 3mm, 1.8 μm) and Micromass-Quattro Premier XE mass spectrometer, use MassLynxV4.1 software, column temperature: 40 DEG C; Sample temperature: 4 DEG C; Sampling volume: 3 μ L.
Experiment proves: when methyl alcohol is as mobile phase, elute effect for target substance is better than common eluting solvent as acetonitrile, relatively 0.1% formic acid/aqueous solution and 0.1% acetic acid/water solution are for the impact of target substance Ionization Efficiency, result shows, the effect of 0.1% acetic acid/water solution is better, therefore selective flow phase A: methyl alcohol and Mobile phase B: containing 0.1% (volume fraction) second aqueous acid as final mobile phase solvent, elution program is as follows: 0 ~ 6min, A:35% → 45%; 6 ~ 12min, A:45% → 80%; 12 ~ 15min, A:80% → 95%; 15 ~ 15.1min, A:95% → 35%.Electron spray ionisation adopts ESI (-) pattern, capillary voltage: 3.00kV, radio-frequency lens 1 (RF lens 1) voltage: 27.0V, radio-frequency lens 2 (RF lens2) voltage: 0.0V, ion source temperature: 99 DEG C, desolventizing temperature: 450 DEG C, desolventizing airshed: 600L/h, collision gradient: 1.9, adopts more options reaction monitoring translative mode (MRM), adopts the Mass Spectrometry Conditions of table 1.
The mass spectrum acquisition parameter of table 1 target glucocorticoid and derivant thereof
1)
1)
arepresent that this fragmention is quota ion
(3) drafting of typical curve, and carry out quantitative measurement with external standard method
Analytical balance is utilized to take standard sugar cortin and derivant biased sample is dissolved in Chromatographic Pure Methanol, be mixed with the standard solution of series concentration gradient, adopt Ultra Performance Liquid Chromatography mass spectrum series process to carry out analysis to detect, be horizontal ordinate respectively with concentration, be that ordinate carries out regretional analysis with peak area, drawing standard curve, for measuring the content of trace glucocorticoid and derivant thereof in water sample.
(4) sample tests
In step (1), pre-treatment operation is carried out to 5 parts of water samples, the detection of Ultra Performance Liquid Chromatography tandem mass spectrometry is carried out with step (2), and compare with the typical curve that step (3) obtains, consider the loss of pre-treatment and testing process, eventually through the concentration obtaining trace glucocorticoid and derivant thereof in water sample to be measured that converts.Net result is as shown in table 4:
Concentration level/the ngL of 17 kinds of glucocorticoids and derivant thereof in table 4 sampling point
-1
1) n.d. represents and does not detect
Chromatogram is shown in Figure 17.
Above-described embodiment is only be described the preferred embodiment of the present invention; not scope of the present invention is limited; under not departing from the present invention and designing the prerequisite of spirit; the various distortion that those of ordinary skill in the art make technical scheme of the present invention and improvement, all should fall in protection domain that claims of the present invention determines.
Claims (7)
1. the detection method of several trace glucocorticoid and derivant thereof in surface water body, is characterized in that: comprise the steps:
(1) pre-service of water body example: carry out Solid-Phase Extraction after being filtered by water body example;
(2) Ultra Performance Liquid Chromatography-extract of mass spectrum series connection method to water body example is adopted to detect;
(3) drawing standard curve, and carry out quantitative measurement with external standard method, by the concentration obtaining trace glucocorticoid and derivant thereof in water body example that converts.
2. the detection method of several trace glucocorticoid and derivant thereof in surface water body according to claim 1, is characterized in that: the instrument in Ultra Performance Liquid Chromatography-mass spectrum series connection method described in step (2) and chromatographic condition are:
ACQUITY
tMsuperelevation liquid chromatograph, Agilent Zorbax SB-C18 post (100mm × 3mm, 1.8 μm) and Micromass-Quattro Premier XE mass spectrometer, use MassLynxV4.1 software, column temperature: 40 DEG C; Sample temperature: 4 DEG C; Sampling volume: 3 μ L; Mobile phase A: methyl alcohol, Mobile phase B: containing 0.1% (volume fraction) second aqueous acid, elution program is as follows: 0 ~ 6min, A:35% → 45%; 6 ~ 12min, A:45% → 80%; 12 ~ 15min, A:80% → 95%; 15 ~ 15.1min, A:95% → 35%.
3. the detection method of several trace glucocorticoid and derivant thereof in surface water body according to claim 2, is characterized in that: the Mass Spectrometry Conditions in Ultra Performance Liquid Chromatography-mass spectrum series connection method described in step (2) is:
Ion gun is that electron spray ionisation adopts ESI (-) pattern, capillary voltage: 3.00kV, radio-frequency lens 1 voltage: 27.0V, radio-frequency lens 2 voltage: 0.0V, ion source temperature: 99 DEG C, desolventizing temperature: 450 DEG C, desolventizing airshed: 600L/h, collision gradient: 1.9, adopts more options reaction monitoring translative mode MRM.
4. the detection method of several trace glucocorticoid and derivant thereof in surface water body according to claim 3, is characterized in that: the pre-service of described water body example comprises the steps:
Gather the water body example needing to detect, be placed in Brown Glass Brown glass bottles and jars only and transport laboratory back, for avoiding the blocking of solid-phase extraction column, the Whatman company GF/C glass fiber filter paper of 1.5L water body example first through 1.2 μm of apertures is filtered, then pass through to use 6mL ethyl acetate in advance with the flow velocity of 3 ~ 5mL/min, the HLB solid-phase extraction column of 6mL acetonitrile and the activation of 6mL ultrapure water, water body example is all by after solid-phase extraction column, with 12mL ultrapure water drip washing solid-phase extraction column, and the moisture eliminated in extraction column is dried up with nitrogen, be the ethylacetate/acetonitrile wash-out HLB solid-phase extraction column of 1:1 again by 6mL volume ratio, collecting eluent utilizes faint nitrogen to dry up, again constant volume is dissolved to be measured with 100 μ L methyl alcohol, all extracting and enriching processes complete in 6h.
5. the detection method of several trace glucocorticoid and derivant thereof in surface water body according to claim 4, is characterized in that: described glucocorticoid and derivant thereof are metacortandracin, cortisone, hydrocortisone, prednisolone, flumethasone, dexamethasone, fluoxyprednisolone, fludrocortisone acetate, Triamcinolone acetonide, methylprednisolone, beclomethasone, cortisone acetate, hydrocortisone acetate, fluorometholone, dexamethasone acetate, budesonide and clobetasol propionate.
6. the detection method of several trace glucocorticoid and derivant thereof in surface water body according to claim 5, is characterized in that: the mass spectrum acquisition parameter in described Mass Spectrometry Conditions is as shown in table 1:
The mass spectrum acquisition parameter of table 1 target glucocorticoid and derivant thereof
1)
1)
arepresent that this fragmention is quota ion
7. the detection method of several trace glucocorticoid and derivant thereof in surface water body according to claim 6, is characterized in that: described method also comprises: the isotope standard cortisol-d using glucocorticoid
4the loss of actual sample in pre-treatment and testing process is corrected as marking in process.
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| CN105784902A (en) * | 2016-03-11 | 2016-07-20 | 重庆华邦制药有限公司 | Detection method for low-concentration clobetasone butyrate |
| CN108226340A (en) * | 2017-12-29 | 2018-06-29 | 重庆华邦制药有限公司 | A kind of separation determination diflucortolone and its method of 6 β diflucortolones and 16 β diflucortolones |
| CN108226340B (en) * | 2017-12-29 | 2020-08-11 | 重庆华邦制药有限公司 | Method for separating and measuring diflucortolone and 6 beta diflucortolone and 16 beta diflucortolone thereof |
| CN109856266A (en) * | 2019-01-22 | 2019-06-07 | 广州大学 | Simultaneously in determination of the environment water sample a variety of trace salt sugar cortins analysis method |
| CN112162043A (en) * | 2020-09-22 | 2021-01-01 | 上海药明奥测医疗科技有限公司 | Liquid chromatography tandem mass spectrometry detection method for glucocorticoid in biological body fluid |
| CN112394131A (en) * | 2020-11-02 | 2021-02-23 | 泉州南京大学环保产业研究院 | Ecological risk evaluation method for corticoids in sediments |
| CN115290778A (en) * | 2022-07-27 | 2022-11-04 | 山东省分析测试中心 | Method for analyzing and identifying trace glucocorticoid in environmental water body |
| CN115290778B (en) * | 2022-07-27 | 2024-05-31 | 山东省分析测试中心 | Analysis and identification method for trace glucocorticoid in environmental water body |
| CN117030904A (en) * | 2023-10-07 | 2023-11-10 | 北京林业大学 | Method for measuring 144 steroid hormones in environmental sample by liquid chromatography-mass spectrometry |
| CN117030904B (en) * | 2023-10-07 | 2023-12-19 | 北京林业大学 | Method for measuring 144 steroid hormones in environmental sample by liquid chromatography-mass spectrometry |
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