CN103792314B - The common detection technique of ten kinds of estrogen in a kind of water environment - Google Patents
The common detection technique of ten kinds of estrogen in a kind of water environment Download PDFInfo
- Publication number
- CN103792314B CN103792314B CN201410031449.4A CN201410031449A CN103792314B CN 103792314 B CN103792314 B CN 103792314B CN 201410031449 A CN201410031449 A CN 201410031449A CN 103792314 B CN103792314 B CN 103792314B
- Authority
- CN
- China
- Prior art keywords
- estrogen
- water sample
- sample
- water
- kinds
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The present invention relates to the technology of ten kinds of estrogen in a kind of water environment of detection simultaneously.After water sample being carried out pre-treatment by solid phase extraction techniques, Liquid Chromatography-Tandem Mass Spectrometry instrument is used to detect its content.Water sample after this method will gather removes the impurity particle suspended in water by miillpore filter, and by solid-phase extraction device by the estrogen enrichment method in water sample to solid-phase extraction column, then with ethyl acetate, the estrogen being enriched in solid-phase extraction column is eluted, dry up with nitrogen, constant volume, finally with the content of Liquid Chromatography-Tandem Mass Spectrometry instrument detection estrogen.The method is easy and simple to handle, and the rate of recovery is higher, the lowest, can detect the estrogen of relatively multiple types simultaneously.
Description
Technical field
The present invention relates to a kind of use Liquid Chromatography-Tandem Mass Spectrometry instrument to measure oestrone in water environment, 17 beta estradiols simultaneously, female
Triol, ethinylestradiol, nonyl phenol, octyl phenol, Estradiol Valerate, hexestrol, diethylstilbestrol, bisphenol-A etc. ten kinds
The method of estrogen.
Background technology
Environmental estrogens is a kind of exogenous material, it is possible to simulate and disturb human or animal body inner estrogen normal synthesis,
The processes such as transport, combination, can be to the reproductive system of body, and immune system and reproductive system impact.Present in environment female
Hormone mainly includes natural estrogen such as oestrone (Estrone, E1), 17 beta estradiols (17 β-Estradiol, E2) and female three
Alcohol (Estriol, E3) and Prof. Du Yucang estrogen such as ethinylestradiol (17 α-Ethynylestradiol, EE2), nonyl phenol
(4-n-Nonylphenol, NP), octyl phenol (4-tert-Octylphenol, OP), Estradiol Valerate (17-beta-Estradiol
17-valerate, EV), diethylstilbestrol (Diethylstibestrol, DES), hexestrol (Hexestrol, HEX), bis-phenol
A (Bisphenol A) etc., abundant species.The every day of humans and animals all can discharge natural estrogen, it was reported that adult male
Discharge oestrone 5 μ g every day, and 17 beta estradiols that women discharges every day and oestrone are respectively 2-12 μ g and 3-20 μ g.People
Work synthetic estrogen such as ethinylestradiol is used as contraceptive and is widely used, and also can impact water body when being discharged in water body.
Research shows, even if in extremely low concentration, these estrogen also can be to bio life Sexual interferences such as the fish in water body, such as hero
Fish feminizes, and can cause human diseases.
The phenomenon that estrogen causes water body Mesichthyes to feminize in recent years increasingly causes the concern of people, and uses the modern times
The detection of the trace estrogen of water body is particularly important by detection technique.The method of detection estrogen has a lot, but can be simultaneously
The estrogen kind of detection is the most less.Main flow detection means has gas-chromatography (GC) and a liquid chromatogram (LC), particularly it
With mass spectrometry Liquid Chromatography-Tandem Mass Spectrometry (LC-MS/MS) compared with gas-chromatography (GC/MS), it is not necessary to derivatization,
Time-consuming few.Setting up favorable reproducibility, the rate of recovery and highly sensitive, the detection method that multiple estrogen detects simultaneously is particularly significant.
Summary of the invention
The present invention be directed to the content of estrogen in natural water, intend a kind of rate of recovery of exploitation high, quickly, exactly with
Time measure oestrone, 17 beta estradiols, estriol, ethinylestradiol, nonyl phenol, octyl phenol, Estradiol Valerate, hexane is female
Phenol, diethylstilbestrol, the technology of ten kinds of estrogen such as bisphenol-A.
Technical scheme is as follows:
One measures oestrone, 17 beta estradiols, estriol, ethinylestradiol, nonyl phenol, octyl phenol, valeric acid female two simultaneously
Alcohol, hexestrol, diethylstilbestrol, ten kinds of estrogen official methods of bisphenol-A, the step following steps of the method:
(1) water sample pre-treatment
PH value with the membrane filtration in 0.45 μm aperture and is adjusted to 3.0 by the water sample of collection.Measure the water sample of 1.0L, use
The specification of Waters company is that water sample is enriched with by the C18 solid phase extraction column of 6mL, 200mg, and speeds control exists
10ml/min.Solid phase extraction column activates before using, and condition is, successively uses 6mL ethyl acetate, 6mL methyl alcohol and 6
The aqueous hydrochloric acid solution pretreatment of mL pH=3.After enrichment terminates, wash post with the methanol aqueous solution that 6mL volume ratio is 10%
Except other impurity, then vacuumize dry 20min to remove moisture removal.After drying, with the ethyl acetate of 6mL by target chemical combination
Thing is eluted in nitrogen blowpipe, is dried up with gentle nitrogen stream.Sample is transferred in sample bottle and is saved in the refrigerator of 4 DEG C
In to be measured；
(2) Liquid Chromatography-Tandem Mass Spectrometry instrument detection estrogen concentrations is used
Chromatographic column: Thermo Accucore C18,100 × 2.1mm, particle diameter 2.6 μm；
Flowing phase and condition of gradient elution: flowing is made up of mobile phase A and Mobile phase B, and mobile phase A is the ammoniacal liquor of 0.5%, stream
Dynamic phase B is pure methyl alcohol, and condition of gradient elution is, the ratio of Mobile phase B is maintained at 20% in front 2min, in 2-8min from
20% is raised to 60%, continues to increase to 90% from 60% in 8-13min, maintains 90% in 13-16min, 16-16.1min from
90% is down to 20%, maintains 20% constant in 16.1-20min；
(3) drafting of calibration curve, draws calibration curve with external standard method；
(4) mensuration of sample size:
By the water sample gathered according to 1) method carry out pre-treatment, according to 2) described in condition carry out the mensuration of estrogen, and
With 3) in method calculate estrogen content.
Method of the present invention also includes using Milli-Q ultra-pure water, and adding concentration is 200 μ g/L, the ten of 500 μ g/L
Plant target mixed sample, the content assaying method described in (4) is installed, measures the concentration of each estrogen.
Estrogen of the present invention is oestrone, 17 beta estradiols, estriol, ethinylestradiol, nonyl phenol, octyl phenol,
Estradiol Valerate, hexestrol, diethylstilbestrol, bisphenol-A.
The invention has the beneficial effects as follows that the organic solvent needed for using solid phase extraction techniques is less, reduce the pollution to environment,
And enrichment times is high, and Liquid Chromatography-Tandem Mass Spectrometry instrument used is highly sensitive, easy and simple to handle, detection limit is low, with gas-chromatography
Compare and more save the time.The present invention provides a kind of rate of recovery high, favorable reproducibility, and highly sensitive co-detection method can be surveyed simultaneously
The content of fixed more multiple (ten kinds) estrogen.
Accompanying drawing explanation
Fig. 1 is the spectrogram of 100 μ g/L standard specimens, and peak sequence is EE2:10.06min, NP:14.58min, OP:
13.07min, EV:14.20min, HEX:10.53min, E3:6.46min, DES:9.79min, BPA:8.44min, E1:9.92min,
E2:9.90min。
Fig. 2 is the spectrogram of the standard specimen of the NP of 100 μ g/L, and appearance time is: 14.58min；
Fig. 3 is the spectrogram of the standard specimen of the OP of 100 μ g/L, and appearance time is: 13.07min；
Fig. 4 is the spectrogram of the standard specimen of the EV of 100 μ g/L, and appearance time is: 14.20min；
Fig. 5 is the spectrogram of the standard specimen of the HEX of 100 μ g/L, and appearance time is 10.53min；
Fig. 6 is the spectrogram of the standard specimen of the E3 of 100 μ g/L, and appearance time is: 6.46min；
Fig. 7 is the spectrogram of the standard specimen of the DES of 100 μ g/L, and appearance time is: 9.79min；
Fig. 8 is the spectrogram of the standard specimen of the BPA of 100 μ g/L, and appearance time is: 8.44min；
Fig. 9 is the spectrogram of the standard specimen of the E1 of 100 μ g/L, and appearance time is 9.92min；
Figure 10 is the spectrogram of the standard specimen of the E2 of 100 μ g/L, and appearance time is 9.90min.
Detailed description of the invention
Below in conjunction with example and accompanying drawing, the present invention will be further described:
(1) water sample pre-treatment
PH value with the membrane filtration in 0.45 μm aperture and is adjusted to 3.0 by the water sample of collection.Measure the water sample of 1.0L, use
The specification of Waters company is that water sample is enriched with by the C18 solid phase extraction column of 6mL, 200mg, and speeds control exists
10ml/min.Solid phase extraction column activates before using, and condition is priority 6mL ethyl acetate, 6mL methyl alcohol and 6
The aqueous hydrochloric acid solution pretreatment of mL pH=3.After enrichment terminates, wash post with the methanol aqueous solution that 6mL volume ratio is 10%
Except other impurity, then vacuumize dry 20min to remove moisture removal.After drying, with the ethyl acetate of 6mL by target chemical combination
Thing is eluted in nitrogen blowpipe, is dried up with gentle nitrogen stream.Sample is transferred in sample bottle and is saved in the refrigerator of 4 DEG C
In to be measured；
(2) use Liquid Chromatography-Tandem Mass Spectrometry instrument detection estrogen concentrations:
The condition of Liquid Chromatography-Tandem Mass Spectrometry instrument: liquid phase is Shimadzu LC-20A, band automatic sampler, Shimadzu Corporation of Japan, matter
Spectrometer is the 3200QTRAP linear ion trap mass spectrometer of AB, charged spray ion gun (ESI), U.S. Applied
Biosystem company；
Chromatographic column: Thermo Accucore C18,100 × 2.1mm, particle diameter 2.6 μm.Ion gun: electric spray ion source (ESI),
Detection pattern: anionic textiles pattern, ion spray voltage :-4500V, temperature: 450 DEG C, ion source gas 1 pressure is
35psi, ion source gas 2 pressure is 40psi, curtain gas (N2) pressure is 12psi, collides gas (N2) pressure: High.
Flowing uses pure methyl alcohol and 0.5% ammoniacal liquor mutually, condition of gradient elution such as table 1；
By measured by Liquid Chromatography-Tandem Mass Spectrometry instrument oestrone, 17 beta estradiols, estriol, ethinylestradiol, nonyl
Phenol, octyl phenol, Estradiol Valerate, hexestrol, diethylstilbestrol, the quantitative limit of bisphenol-A is respectively 0.4 μ g/L, 8 μ g/L,
8 μ g/L, 8 μ g/L, 2 μ g/L, 4 μ g/L, 8 μ g/L, 0.8 μ g/L, 0.8 μ g/L and 8 μ g/L；
Table 1 flows phase elution requirement；
| Time | The concentration (%) of methyl alcohol | |
| 1 | 0.01 | 20 |
| 2 | 1.00 | 20 |
| 3 | 8.00 | 60 |
| 4 | 13.00 | 90 |
| 5 | 16.00 | 60 |
| 6 | 16.10 | 20 |
| 7 | 20.00 | 20 |
(3) drafting of calibration curve
Draw calibration curve with external standard method, methyl alcohol will be dissolved in by estrogen standard items, be configured to the storing solution of high concentration, then with each
The storing solution of individual estrogen is made into mixed mark, and is diluted to, from seven kinds of different series of 5-500 μ g/L mixed mark concentration, pass through liquid phase
The detection of chromatographic tandem mass spectrograph is analyzed, and with mixed mark concentration as abscissa, corresponding peak area is ordinate, the straight line that matching obtains
It is calibration curve.The present invention is all higher than 0.99 by the coefficient correlation that this external standard method obtains, and Fig. 1 is various when being 100 μ g/L
The spectrogram of estrogen；
(4) mensuration of the rate of recovery:
Using Milli-Q ultra-pure water, adding concentration is 200 μ g/L, and ten kinds of target mixed samples of 500 μ g/L are installed (4)
Described content assaying method, measures the concentration of each estrogen, and calculates by equation below.
Rate of recovery R=(C-C0)/C1×100%.
C: the actual concentrations recorded in water sample after adding standard specimen, μ g/L.
C0: do not add the concentration recorded in standard specimen water, μ g/L.
C1: the concentration of the standard specimen of interpolation.
The estrogen rate of recovery is as shown in table 2.
Table 2 rate of recovery.
| The estrogen rate of recovery (%) | 200μg/L | 500μg/L |
| Ethinylestradiol | 100.4±0.6 | 70.1±6.5 |
| Nonyl phenol | 52.6±3.0 | 45.9±4.0 |
| Octyl phenol | 69.4±8.9 | 81.2±1.5 |
| Estradiol Valerate | 42.3±18.1 | 47.2±0.5 |
| Hexestrol | 83.0±9.5 | 97.9±2.1 |
| Estriol | 89.1±9.1 | 108.2±0.2 |
| Bisphenol-A | 70.6±32.5 | 96.9±7.0 |
| Oestrone | 98.2±7.0 | 80.5±8.0 |
| 17 beta estradiols | 93.7±5.7 | 71.3±11.9 |
| Diethylstilbestrol | 78.1±2.9 | 83.9±2.6 |
Claims (1)
1. the method simultaneously measuring ten kinds of estrogen in water environment, comprises following ten kinds: oestrone, 17 beta estradiols, estriol,
Ethinylestradiol, nonyl phenol, octyl phenol, Estradiol Valerate, hexestrol, diethylstilbestrol, bisphenol-A；Specifically comprise the following steps that
(1) water sample pre-treatment
By the water sample of collection with the membrane filtration in 0.45 μm aperture and by pH tone pitch to 3.0, measure the water sample of 1.0L, use
The specification of Waters company is that water sample is enriched with by the C18 solid phase extraction column of 6mL, 200mg, and speeds control exists
10ml/min, solid phase extraction column activates before using, and condition is priority 6mL ethyl acetate, 6mL methyl alcohol and 6
The aqueous hydrochloric acid solution pretreatment of mL pH=3, after enrichment terminates, washes post with the methanol aqueous solution that 6mL volume ratio is 10%
Except other impurity, then vacuumize dry 20min to remove moisture removal, after drying, with the ethyl acetate of 6mL by target chemical combination
Thing is eluted in nitrogen blowpipe, is dried up with gentle nitrogen stream, sample is transferred in sample bottle and is saved in the refrigerator of 4 DEG C
In to be measured；
(2) use Liquid Chromatography-Tandem Mass Spectrometry instrument detection estrogen concentrations:
Chromatographic column: Thermo Accucore C18,100 × 2.1mm, particle diameter 2.6 μm；
Flowing phase and condition of gradient elution: flowing is made up of mobile phase A and Mobile phase B, and mobile phase A is the ammoniacal liquor of 0.5%, stream
Dynamic phase B is pure methyl alcohol, and condition of gradient elution is, the ratio of Mobile phase B is maintained at 20% in front 2min, in 2-8min from
20% is raised to 60%, continues to increase to 90% from 60% in 8-13min, maintains 90% in 13-16min, 16-16.1min from
90% is down to 20%, maintains 20% constant in 16.1-20min；
(3) drafting of calibration curve
Calibration curve is drawn with external standard method；
(4) mensuration of sample size
By the water sample gathered according to 1) method carry out pre-treatment, according to 2) described in condition carry out the mensuration of estrogen, and
With 3) in method calculate estrogen content.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410031449.4A CN103792314B (en) | 2014-01-23 | 2014-01-23 | The common detection technique of ten kinds of estrogen in a kind of water environment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410031449.4A CN103792314B (en) | 2014-01-23 | 2014-01-23 | The common detection technique of ten kinds of estrogen in a kind of water environment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103792314A CN103792314A (en) | 2014-05-14 |
| CN103792314B true CN103792314B (en) | 2016-09-07 |
Family
ID=50668183
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410031449.4A Active CN103792314B (en) | 2014-01-23 | 2014-01-23 | The common detection technique of ten kinds of estrogen in a kind of water environment |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103792314B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105319286A (en) * | 2014-07-25 | 2016-02-10 | 江苏维赛科技生物发展有限公司 | Ultra high performance liquid chromatography-tandem mass spectrometry used for detecting diethylstilbestrol in sludge |
| CN105334282B (en) * | 2015-10-27 | 2017-05-03 | 哈尔滨工业大学 | Co-detecting method for environmental estrogens in surface water body |
| CN107543876A (en) * | 2017-06-09 | 2018-01-05 | 上海市环境科学研究院 | A kind of method that SPE liquid chromatography tandem mass spectrometry detects 9 kinds of estrogenic chemicalses in water body simultaneously |
| CN107121518B (en) * | 2017-06-30 | 2019-08-23 | 华东理工大学 | A kind of method that Sync enrichment detects phenols, estrogens and androgens incretion interferent in drinking water |
| CN110882515B (en) * | 2019-11-07 | 2021-07-06 | 桂林理工大学 | Method for improving degradation rate of diethylstilbestrol degraded by laccase by using acetosyringone and application |
| CN110935129B (en) * | 2019-11-07 | 2021-07-09 | 桂林理工大学 | Application of syringaldehyde as redox mediator for degrading stilbestrol by laccase and method for improving degradation rate of stilbestrol degraded by laccase |
| CN111302499B (en) * | 2019-11-07 | 2022-04-08 | 桂林理工大学 | Method for rapidly catalyzing and degrading diethylstilbestrol |
| CN113702558A (en) * | 2021-04-02 | 2021-11-26 | 华东理工大学 | Method for detecting trace estrogen substances in water environment |
| CN114324627A (en) * | 2021-11-24 | 2022-04-12 | 贵阳学院 | Method for detecting pollution of trace estrogen endocrine disrupting compounds in reclaimed water by biological-chemical combination |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000180428A (en) * | 1998-12-11 | 2000-06-30 | Sumika Chemical Analysis Service Ltd | Method for analysis of estrogen |
| US6898533B1 (en) * | 2000-02-01 | 2005-05-24 | The United States Of America As Represented By The Department Of Health And Human Services | Methods for predicting the biological, chemical, and physical properties of molecules from their spectral properties |
| JP2011163944A (en) * | 2010-02-10 | 2011-08-25 | Kao Corp | Method for quantifying estrogen |
| CN102175792A (en) * | 2010-12-24 | 2011-09-07 | 北京师范大学 | Method for detecting estrogen, nonyl phenol, octylphenol and bisphenol A together in water environment |
| CN102183606A (en) * | 2011-03-02 | 2011-09-14 | 北京师范大学 | Method for detecting estrogen, nonyl phenol, octyl phenol and bisphenol A in water body sediment together |
| CN103185762A (en) * | 2011-12-29 | 2013-07-03 | 复旦大学 | Method for analyzing and detecting a plurality of endocrine disruptors in food |
-
2014
- 2014-01-23 CN CN201410031449.4A patent/CN103792314B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000180428A (en) * | 1998-12-11 | 2000-06-30 | Sumika Chemical Analysis Service Ltd | Method for analysis of estrogen |
| US6898533B1 (en) * | 2000-02-01 | 2005-05-24 | The United States Of America As Represented By The Department Of Health And Human Services | Methods for predicting the biological, chemical, and physical properties of molecules from their spectral properties |
| JP2011163944A (en) * | 2010-02-10 | 2011-08-25 | Kao Corp | Method for quantifying estrogen |
| CN102175792A (en) * | 2010-12-24 | 2011-09-07 | 北京师范大学 | Method for detecting estrogen, nonyl phenol, octylphenol and bisphenol A together in water environment |
| CN102183606A (en) * | 2011-03-02 | 2011-09-14 | 北京师范大学 | Method for detecting estrogen, nonyl phenol, octyl phenol and bisphenol A in water body sediment together |
| CN103185762A (en) * | 2011-12-29 | 2013-07-03 | 复旦大学 | Method for analyzing and detecting a plurality of endocrine disruptors in food |
Non-Patent Citations (8)
| Title |
|---|
| Assessment of source water contamination by estrogenic disrupting compounds in China.;Jiang Weiwei 等;《Journal of Environmental Sciences》;20120229;第24卷(第2期);320-328 * |
| Derivatisation and gas chromatography–chemical ionisation mass spectrometry of selected synthetic and natural endocrine disruptive chemicals;Oliver Lerch 等;《Journal of Chromatography A》;20030328;第991卷(第1期);77-97 * |
| High-sensitivity analysis of female-steroid hormones in environmental samples;Helena Tomšíková 等;《TrAC Trends in Analytical Chemistry》;20120430;第34卷;35-58 * |
| 固相萃取-气相色谱/质谱联用法同时检测水体中 9 种环境雌激素;廖涛 等;《分析化学》;20130331;第41卷(第3期);422-426 * |
| 固相萃取－超高效液相色谱-三重四极杆质谱法同时测定不同水体中的6种雌激素;曾玉珠 等;《色谱》;20131231;第31卷(第12期);1176-1181 * |
| 超高效液相色谱－串联质谱法测定肉制品中８种雌激素残留量;耿金培 等;《理化检验（化学分册）》;20121231;第48卷(第12期);1398-1402 * |
| 雌激素对水生生物的影响及其检测方法研究进展;张秀珍 等;《海洋湖沼通报》;20100930(第3期);79-90 * |
| 饮用水水源及水厂内分泌干扰物污染分析;朗朗 等;《环境工程》;20081231;第26卷;60-63 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103792314A (en) | 2014-05-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103792314B (en) | The common detection technique of ten kinds of estrogen in a kind of water environment | |
| CN102636611B (en) | Method for jointly detecting estrogen, nonyl phenol, octylphenol and bisphenol A in complex substrate water sample | |
| Zhang et al. | MCX based solid phase extraction combined with liquid chromatography tandem mass spectrometry for the simultaneous determination of 31 endocrine-disrupting compounds in surface water of Shanghai | |
| CN107543876A (en) | A kind of method that SPE liquid chromatography tandem mass spectrometry detects 9 kinds of estrogenic chemicalses in water body simultaneously | |
| CN104215716B (en) | A kind of detect the method for total testosterone in human serum | |
| CN106053638A (en) | Method for detecting aminoglycoside antibiotic residue amount in animal-derived food | |
| CN102636604B (en) | Quantitative detecting method for estrogen in milk | |
| CN105203654A (en) | Method for measuring content of 11 illegally added medicaments in veterinary drug powder | |
| CN105675788B (en) | The method of progesterone and testosterone in high performance liquid chromatography tandem mass spectrum technology for detection saliva | |
| CN103983707B (en) | A kind of method for detecting meat drug residue and pretreatment reagent kit thereof | |
| CN102636610B (en) | Co-detection method for estrogen coalition in water environment | |
| CN101701943A (en) | Method for measuring dimethyl fumarate in product by gas chromatography-mass spectrometry | |
| CN102866225A (en) | Method for quantitatively detecting perfluorooctane sulfonate isomeride in water sample | |
| CN106706826A (en) | Analysis method of plant hormones in milligram-grade plants | |
| CN103267820A (en) | Method for simultaneously detecting multiple estrogens in sludge | |
| CN106645518B (en) | The measuring method of chloramphenicol residue in a kind of propolis virgin rubber | |
| Jing-Xi et al. | Determination of lead species in algae by capillary electrophoresis-inductively coupled plasma-mass spectrometry | |
| CN106645477B (en) | A kind of remaining method of detection florfenicol amine and application | |
| CN106872588A (en) | The detection method of TCs in a kind of water sample | |
| CN105628837A (en) | Detecting method for mesotrione and metabolite thereof in soil | |
| CN103293268B (en) | A kind of people urinates the detection method of hydrocortisone | |
| CN105628826A (en) | Ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) used for detecting residual quantity of adamantanamine in seawater and ocean sediments | |
| CN104569191A (en) | Detection method for ornithine in plasma | |
| CN109283272B (en) | Detection method of 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and sodium salt thereof | |
| CN102901778A (en) | Pretreatment method for detecting chloramphenicol in milk or mild products and method for detecting chloramphenicol in milk or mild products |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210913 Address after: 361000 unit 401-11, No. 3, xishanwei Road, phase III, software park, Xiamen, Fujian Patentee after: Xiamen Zhongke Yucheng Center Management Co.,Ltd. Address before: 361021 No. 1799, Jimei Avenue, Xiamen, Fujian Patentee before: INSTITUTE OF URBAN ENVIRONMENT, CHINESE ACADEMY OF SCIENCES |
|
| TR01 | Transfer of patent right |