CN103012199A - Method for preparing hydrogen sulphide fast and highly selectively colorimetric probe - Google Patents
Method for preparing hydrogen sulphide fast and highly selectively colorimetric probe Download PDFInfo
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- CN103012199A CN103012199A CN2012105125678A CN201210512567A CN103012199A CN 103012199 A CN103012199 A CN 103012199A CN 2012105125678 A CN2012105125678 A CN 2012105125678A CN 201210512567 A CN201210512567 A CN 201210512567A CN 103012199 A CN103012199 A CN 103012199A
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- XIKHTCQHDCGMQI-UHFFFAOYSA-N N#CC(c(cc1)ccc1N(CCO)CCO)=C(C#N)C#N Chemical compound N#CC(c(cc1)ccc1N(CCO)CCO)=C(C#N)C#N XIKHTCQHDCGMQI-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a method for preparing a hydrogen sulphide fast and highly selectively colorimetric probe and particularly relates to a method for preparing a tri-cyano vinyl nitrogen phenyl compound as a hydrogen sulphide fast and highly selectively colorimetric probe and the application of the colorimetric probe. The probe can be used for identifying the hydrogen sulphide highly selectively and analyzing the hydrogen sulphide qualitatively and quantitatively through the observation of naked eyes. The probe is synthesized easily by adopting the heating method through one-step reaction.
Description
Technical field
The present invention relates to the preparation method of quick highly selective hydrogen sulfide colorimetric probe.
Background technology
Hydrogen sulfide is with typical rotten egg smell and toxicity and famous, yet nearest research finds, the hydrogen sulfide in the life entity has a lot of physiological functions.Hydrogen sulfide has become after nitrogen protoxide and carbon monoxide, and found the third has bioactive gaseous signal molecule.Hydrogen sulfide in the life entity has participated in many physiological processs, has vasodilator, regulates the physiological functions such as blood pressure, myocardial contraction, adjusting respiratory system, inhibited apoptosis, neurotransmission.In case the hydrogen sulfide content in the life entity can not maintain in the normal physiological level scope, many pathologies just can occur in life entity, comprise artery and pulmonary hypertension, heart trouble, senile dementia, the diseases such as gastric mucosa injury and liver cirrhosis.In addition, hydrogen sulfide can also be removed intracellular active nitrogen and active oxygen species.And many studies show that as the third found gaseous signal molecule, exists between hydrogen sulfide and other two kinds of gaseous signal molecule nitrogen protoxides and the carbon monoxide to interact.Therefore, hydrogen sulfide is relevant life entity health whether important molecule.
Given this, can effectively to detect the analytical procedure that particularly can detect hydrogen sulfide under the physiological level condition be of crucial importance and significant in development.The analytical procedure of the detection hydrogen sulfide of nowadays having reported comprises the methods such as electrochemical methods, vapor-phase chromatography, metal inducement sulfurization-precipitation method, fluorescent probe detection.In these numerous detection methods, fluorescent probe is owing to its distinctive advantage becomes the focus that the researchist pays close attention to, but at present still there are some problems in the fluorescent probe of report, comprises that selectivity is good not, response speed is fast not, synthetic complicated and water-soluble good not etc.Hydrogen sulfide katabolism speed in the organism is very fast, cause the continual fluctuation of content of hydrogen sulfide in the organism, bring very large difficulty for the detection of hydrogen sulfide in the life entity, therefore development can the rapid detection life entity in the analytical procedure of hydrogen sulfide be necessary.Mercaptan and hydrogen sulfide in the life entity have similar structures, and it can consist of potential interference to the detection of hydrogen sulfide, and therefore, development highly selective probe becomes the problem that urgent need solves.In addition, the colorimetric probe is observed owing to need to not carrying out by advanced person's expensive instrument " bore hole ", thereby reaches the purpose of quantitative and qualitative analysis, therefore is subject to extensive concern.In a word, the development selectivity high, colorimetric probe synthetic simple, good water solubility is those skilled in the art's urgent problems.
Summary of the invention
A kind of quick highly selective hydrogen sulfide colorimetric probe simple, good water solubility for preparing is badly in need of in this area, can detect hydrogen sulfide under the physiological level condition thereby can effectively detect particularly.For this reason, the present invention has synthesized the colorimetric probe of the hydrogen sulfide of a class novelty, and it is synthetic simple, good water solubility, stability is high and/or selectivity is high, and/or can identify fast hydrogen sulfide.Probe of the present invention can carry out the mensuration of hydrogen sulfide under the physiological level condition.
Particularly, the invention provides a kind of hydrogen sulfide colorimetric probe, it is tricyano ethene pyridyl compounds, and its structure is as follows:
Preferably, colorimetric probe of the present invention is:
The present invention also provides the preparation method of above-mentioned hydrogen sulfide colorimetric probe, and it is to make by synthesizing by heating corresponding to the corresponding pyridyl compounds of probe of the present invention and TCNE.Preferably, the corresponding pyridyl compounds corresponding to probe of the present invention of the present invention is the pyridyl diethanolamine.
In the preparation method of hydrogen sulfide colorimetric probe of the present invention, temperature of reaction is 40-100 ℃; Reaction times is 4h-10h; And/or the mol ratio of pyridyl compounds and TCNE is about 1:1 to 1:5, is preferably 1:1.5 or 1:2.
The present invention also provides detection preparation or the test kit for detection of concentration of hydrogen sulfide in the sample (for example blood sample), and it comprises probe of the present invention.Preferably, detection preparation of the present invention or test kit also comprise the working instructions of product.Also preferably, test kit of the present invention also comprises the buffer reagent for the concentration of hydrogen sulfide of measuring sample.
The present invention also provides the method for concentration of hydrogen sulfide in the detection sample (for example blood sample), and it comprises the step that probe of the present invention is contacted with sample to be tested.
Hydrogen sulfide colorimetric probe of the present invention can with the hydrogen sulfide effect, the variation (variations of simultaneous distinct colors) that produces absorption spectrum, thus realization is to the detection by quantitative of hydrogen sulfide.
Particularly, hydrogen sulfide colorimetric probe of the present invention all can not cause respectively the obvious change of absorption spectrum with mercaptan amino acid, non-mercaptan amino acid and other ion effects, thereby realize the selectivity identification to hydrogen sulfide, and then optionally be used for getting rid of the existence of these mercaptan amino acid, non-mercaptan amino acid and other ions to the interference of the quantitative assay of hydrogen sulfide.
It should be noted that as everyone knows, sodium sulphite and Sodium sulfhydrate can produce hydrogen sulfide in the aqueous solution, and namely sodium sulphite and Sodium sulfhydrate are the supply bodies of hydrogen sulfide, and sodium hydrosulfide is extremely unstable, so be difficult to accurately prepare sodium hydrosulfide.So the overwhelming majority finishes by measuring sodium sulphite at present, namely measures sodium sulphite and is equal to mensuration hydrogen sulfide.Therefore, the mensuration of relevant hydrogen sulfide colorimetric probe is all finished for sodium sulphite among the present invention, but it will be apparent to those skilled in the art that probe of the present invention can be directly used in qualitative or measures quantitatively the concentration of the hydrogen sulfide in the sample (for example blood sample sample).
The good water solubility of hydrogen sulfide colorimetric probe of the present invention, thus can be conducive under the physiological level condition detection to hydrogen sulfide.
Selectively, the good stability of hydrogen sulfide colorimetric probe of the present invention, and then can prolonged preservation use.
Further, hydrogen sulfide colorimetric probe of the present invention is quick highly selective hydrogen sulfide colorimetric probe, and synthetic simple, is conducive to business-like applying.
Description of drawings
Fig. 1 a, Fig. 1 b and Fig. 1 c are different concns Na
2S (0-200 μ M) is on impact and the Na of probe (5 μ M) absorption spectrum
2S (from left to right: 0,50,100,200,300,400, the 500 μ M) variation of the lower probe solution colour of existence.
Fig. 2 is that different analytes (150 μ M) are on the impact of probe (5 μ M) absorption spectrum.
Fig. 3 is that different analytes (150 μ M) are to probe (5 μ M) absorption spectrum quantitative analysis Na
2The impact of S (150 μ M).
Fig. 4 is that probe (5 μ M) is to different concns Na
2S (400 μ M, 800 μ M), Cys (300 μ M, 400 μ M) and the test result of GSH (600 μ M, 10mM) time of response.
Embodiment:
The invention provides synthetic route, method and the spectrum property thereof of above-mentioned quick highly selective hydrogen sulfide colorimetric probe.
Hydrogen sulfide colorimetric probe of the present invention is a class tricyano ethene pyridyl compounds, and it has following general structure
In the following formula: R
1, R
2, R
3, R
4, R
5, R
6Be hydrogen atom, straight or branched alkyl, straight or branched alkoxyl group, sulfonic group, ester group, carboxyl; R
1, R
2, R
3, R
4, R
5, R
6Can be identical or different.
Synthetic route and the method for such hydrogen sulfide colorimetric fluorescence probe are as follows:
Particularly, colorimetric probe of the present invention can prepare by the following method, pyridyl compounds (for example pyridyl diethanolamine) and the TCNE of certain mol proportion (for example 1:1-1:5) are dissolved in N, in the dinethylformamide (DMF), then the lower thermostatically heating of high temperature (for example 80 ℃) refluxes for some time (for example 4h), then use organism (for example ethyl acetate) extraction, then revolve the steaming organic phase, obtain thick product.If obtain purer product, thick product can be used the mixed system (for example v/v, 100:1) of methylene dichloride and anhydrous methanol carry out column chromatography and separate.
Therefore, the present invention also provides TCNE for the preparation of the purposes in the colorimetric probe that detects hydrogen sulfide.
The present invention also provides pyridyl compounds (for example pyridyl diethanolamine) for the preparation of the purposes in the colorimetric probe that detects hydrogen sulfide.
The notable feature of quick highly selective identification hydrogen sulfide colorimetric probe of the present invention is that highly selective is identified hydrogen sulfide/sodium sulphite fast, and/or can accurately carry out quantitative analysis to hydrogen sulfide/sodium sulphite in the presence of other high densitys nature amino acid and other ions.Importantly, hydrogen sulfide colorimetric probe of the present invention can also carry out qualitative and quantitative analysis with the mode that " bore hole " observes.
The below will be by illustrating in greater detail the present invention by following examples.Following examples only are illustrative, should be understood that the present invention is not subjected to the restriction of following embodiment.
Embodiment 1
(scheme 1) is dissolved in 20mL N with 377.3mg (1mmol) pyridyl diethanolamine and 128mg (1.0mmol) TCNE, dinethylformamide (DMF), then with 80 ℃ of thermostatically heating backflow 4h, then use ethyl acetate extraction, get the ethyl acetate phase, then revolve steaming and obtain thick product, then use the mixed system (v/v of methylene dichloride and anhydrous methanol, 100:1) carry out column chromatography and separate, obtain red pure product 298mg, productive rate is 59 ﹪.
(scheme 2) is dissolved in 20mL N with 377.3mg (1mmol) pyridyl diethanolamine and 192mg (1.5mmol) TCNE, dinethylformamide (DMF), then with 80 ℃ of thermostatically heating backflow 4h, then use ethyl acetate extraction, get the ethyl acetate phase, then revolve steaming and obtain thick product, then use the mixed system (v/v of methylene dichloride and anhydrous methanol, 100:1) carry out column chromatography and separate, obtain red pure product 415mg, productive rate is 82 ﹪.
(scheme 3) is dissolved in 20mL N with 377.3mg (1mmol) pyridyl diethanolamine and 256mg (2.0mmol) TCNE, dinethylformamide (DMF), then with 80 ℃ of thermostatically heating backflow 4h, then use ethyl acetate extraction, get the ethyl acetate phase, then revolve steaming and obtain thick product, then use the mixed system (v/v of methylene dichloride and anhydrous methanol, 100:1) carry out column chromatography and separate, obtain red pure product 450mg, productive rate is 89 ﹪.
(scheme 4) is dissolved in 20mL N with 377.3mg (1mmol) pyridyl diethanolamine and 192mg (1.5mmol) TCNE, dinethylformamide (DMF), then with 60 ℃ of thermostatically heating backflow 6h, then use ethyl acetate extraction, get the ethyl acetate phase, then revolve steaming and obtain thick product, then use the mixed system (v/v of methylene dichloride and anhydrous methanol, 100:1) carry out column chromatography and separate, obtain red pure product 359mg, productive rate is 71 ﹪.
(scheme 5) is dissolved in 20mL N with 377.3mg (1mmol) pyridyl diethanolamine and 192mg (1.5mmol) TCNE, dinethylformamide (DMF), then with 100 ℃ of thermostatically heating backflow 3h, then use ethyl acetate extraction, get the ethyl acetate phase, then revolve steaming and obtain thick product, then use the mixed system (v/v of methylene dichloride and anhydrous methanol, 100:1) carry out column chromatography and separate, obtain red pure product 243mg, productive rate is 48 ﹪.
1(* 10 for H NMR (400MHz, DMSO) δ
-6): 3.63-3.69 (m, 8H, J=24Hz), 4.92 (t, 2H, J=5.2Hz), 7.06 (d, 2H, J=9.6Hz), 7.90 (d, 2H, J=9.2Hz);
13(* 10 for C NMR (100MHz, DMSO) δ
-6): 53.37,58.25,74.49,113.26,114.63,114.69,114.83,116.68,132.26,135.61,154.70; ESI-MS calculated value C
15H
15N
4O
2[M+H]
+283; Measured value 283.
Embodiment 2
The present inventor has carried out following test: (a) different concns Na
2S (0-200 μ M) is on the impact of probe (5 μ M) absorption spectrum; (b) Na of the absorption intensity at 527nm place and adding
2Linear relationship between the S concentration (0-130 μ M); (c) different concns Na
2S (from left to right: 0,50,100,200,300,400,500 μ M) exist the color of lower probe solution (5 μ M) to become gradually colourless by pink.Said determination is to carry out in water (20mM PBS, pH 7.4), and employed probe is probe prepared among the embodiment 1, and all spectrum tests all are at 25 ℃ of lower Na
2Record behind the S adding effect 10min.The result is referring to Fig. 1.
As can be seen from Figure 1, be accompanied by Na in the probe solution
2The increase of S concentration, absorption spectrum descends gradually, and 0
-The Na of 130 μ M
2In the S concentration range, Na
2Concentration and the absorption intensity of S are linear.At present, the content of hydrogen sulfide is 10 in most of life entity blood of having reported
-100 μ M just in time fall in the sensing range of probe of the present invention.Therefore, probe of the present invention can more accurately be determined the content of hydrogen sulfide in the blood sample to be measured.
Embodiment 3
Different analytes (150 μ M) are on the impact of probe (5 μ M) absorption spectrum.Analyte comprises: halfcystine Cys, gsh GSH, leucine Leu, proline(Pro) Pro, Threonine Thr, L-glutamic acid Glu, glycine Gly, potassium ion K
+, calcium ion Ca
2+, zine ion Zn
2+, sulfate ion SO
4 2-, nitrate ion NO
3 -, perchlorate ClO
4 -, sodium sulphite Na
2S, their concentration is 150 μ M.All test conditions are to finish in water (20mM PBS, pH 7.4), and employed probe is probe prepared among the embodiment 1, and all spectrum all record behind 25 ℃ of lower analyte adding effect 10min.Particularly, the probe storing solution (1mM) that pipettes 25 μ L is put in the 5mL colorimetric cylinder, then adds the 3mL ultrapure water, pipetting the above-mentioned analyte storing solutions of 75 μ L (10mM) adds in the colorimetric cylinder again, then (pH 7.4,200mM), are settled to 5mL with ultrapure water at last to pipette the PBS solution of 0.5mL.Shake up, leave standstill 10min, can measure.The result as shown in Figure 2.
As can be seen from Figure 2, probe has very high selectivity to hydrogen sulfide, can react with hydrogen sulfide in specific manner, before and after the reaction, absorption spectrum has considerable change, and considerable change does not occur absorption intensity after the common mercaptan that exists in the organism and ion and the probe effect.
Embodiment 4
Different analytes (150 μ M) are on the impact of probe (5 μ M) absorption spectrum quantitative analysis hydrogen sulfide (150 μ M).Analyte comprises: halfcystine Cys, gsh GSH, leucine Leu, proline(Pro) Pro, Threonine Thr, L-glutamic acid Glu, glycine Gly, potassium ion K
+, calcium ion Ca
2+, zine ion Zn
2+, sulfate ion SO
4 2-, nitrate ion NO
3 -, perchloric acid is with ion ClO
4 -, their concentration is 150 μ M.All test conditions are to finish in water (20mM PBS, pH 7.4), and employed probe is probe prepared among the embodiment 1, and all spectrum all record behind 25 ℃ of lower analyte adding effect 10min.The result as shown in Figure 3, A wherein
0The measured value that represents pure probe solution, A represents to add the measured value behind the target analytes.
As can be seen from Figure 3, the common mercaptan that exists in the organism and ion can obviously not disturb probe that the qualitative and quantitative of hydrogen sulfide is detected.
Embodiment 5
Probe (5 μ M) is to different concns Na
2S (400 μ M, 800 μ M), halfcystine Cys (300 μ M, 400 μ M) and the test result of GSH (600 μ M, 10mM) time of response.At first, the probe storing solution (1mM) that pipettes 25 μ L is put in the 5mL colorimetric cylinder, (pH 7.4 to its PBS solution that adds 0.5mL, 200mM), pipette again the storing solution (10mM) of the above-mentioned analyte of respective volume, be settled to 5mL with ultrapure water at last, shake up fast, timing is measured, and wherein employed probe is probe prepared among the embodiment 1.The result as shown in Figure 4.
As can be seen from Figure 4, Na
2Considerable change namely occurs in absorption intensity behind S and the probe reaction 1mi n, and absorption intensity tends towards stability behind the 7min.The rapidity that this absorption intensity weakens and palpability illustrate that this probe can be used for the instant detection of hydrogen sulfide fully.
Although described the present invention with above-mentioned embodiment, should be understood that, under the prerequisite that does not deviate from spirit of the present invention, the present invention can further modify and change, and these modifications and the change all belong within protection scope of the present invention.
Claims (10)
1. the method for preparing compound, comprising heating pyridyl compounds and TCNE, wherein said compound has following structure
Wherein: R
1, R
2, R
3, R
4, R
5, R
6For being independently selected from the group that is formed by hydrogen atom, straight or branched alkyl, straight or branched alkoxyl group, sulfonic group, ester group and hydroxyl; And R wherein
1, R
2, R
3, R
4, R
5And R
6Can be identical or different.
2. 1 method as requested, wherein temperature of reaction is 40 ℃～100 ℃.
3. 1 method as requested, wherein temperature of reaction is 80 ℃.
4. according to claim 3 method, the reaction times wherein is 4h～10h.
5. according to claim 4 method, wherein the mol ratio of pyridyl compounds and TCNE is 1:1 to 1:1.5, or is 1:5 to 1:2, or is 1:2 to 1:5.
6. each method according to claim 1-5, wherein said pyridyl compounds is the pyridyl diethanolamine.
7. according to claim 6 method, wherein prepared compound is:
8. according to claim 7 method, wherein pyridyl diethanolamine and the TCNE with 1:1 to 1:5 is dissolved in N, dinethylformamide, then with 80 ℃ of thermostatically heating backflow 4h, then use ethyl acetate extraction, the ethyl acetate phase, then revolve to steam and obtain thick product, then use the mixed system of methylene dichloride and anhydrous methanol to carry out column chromatography and separate the described compound of acquisition.
9. pyridyl diethanolamine or the TCNE purposes in preparation hydrogen sulfide colorimetric probe.
10. purposes according to claim 9, wherein said hydrogen sulfide colorimetric probe is defined compound in the claim 7.
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| CN201210362405 | 2012-09-19 | ||
| CN201210512567.8A CN103012199B (en) | 2012-09-19 | 2012-12-04 | Method for preparing hydrogen sulphide fast and highly selectively colorimetric probe |
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| CN201210512345.6A Expired - Fee Related CN102993047B (en) | 2012-09-19 | 2012-12-04 | Quick high-selectivity hydrogen sulfide colorimetric probe |
| CN201210513802.3A Expired - Fee Related CN103018237B (en) | 2012-09-19 | 2012-12-04 | Application of fast and high-selective hydrogen sulphide colorimetric probe |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10196343B2 (en) | 2013-01-30 | 2019-02-05 | Ecolab Usa Inc. | Hydrogen sulfide scavengers |
| US10308886B2 (en) | 2015-04-22 | 2019-06-04 | Ecolab Usa Inc. | Development of a novel high temperature stable scavenger for removal of hydrogen sulfide |
| US10336950B2 (en) | 2016-07-29 | 2019-07-02 | Ecolab Usa Inc. | Antifouling and hydrogen sulfide scavenging compositions and methods |
| US10407626B2 (en) | 2015-09-08 | 2019-09-10 | Ecolab Usa Inc. | Hydrocarbon soluble/dispersible hemiformals as hydrogen sulfide scavengers |
| US10538710B2 (en) | 2017-07-13 | 2020-01-21 | Ecolab Usa Inc. | Hydrogen sulfide scavengers |
| US10584286B2 (en) | 2015-09-08 | 2020-03-10 | Ecolab Usa Inc. | Hydrogen sulfide scavengers |
| US11499108B2 (en) | 2019-01-23 | 2022-11-15 | Championx Usa Inc. | Complete removal of solids during hydrogen sulfide scavenging operations using a scavenger and a Michael acceptor |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104419401A (en) * | 2013-08-28 | 2015-03-18 | 苏州罗兰生物科技有限公司 | Fluorescent probe for detecting hydrogen sulfide by virtue of fluorescence enhancement as well as synthetic method and application of fluorescent probe |
| CN104910054B (en) * | 2015-04-20 | 2017-01-11 | 济南大学 | High-selectivity colorimetric ratio method for determining Hg2+ in pure water system |
| CN112002105B (en) * | 2020-08-17 | 2022-06-10 | 江苏省电力试验研究院有限公司 | Electrochemical energy storage power station safety early warning and fault positioning system based on molecular probe |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996028757A1 (en) * | 1995-03-13 | 1996-09-19 | Akzo Nobel N.V. | Non-linear optical polycarbonates |
| WO2012013563A1 (en) * | 2010-07-29 | 2012-02-02 | Basf Se | Dmapn having low dgn content and method for producing dmapa from dmapn having low dgn content |
| CN102603567A (en) * | 2012-01-18 | 2012-07-25 | 浙江工业大学 | Stilbene nitrile derivatives, and preparation method and application thereof |
-
2012
- 2012-12-04 CN CN201210512567.8A patent/CN103012199B/en not_active Expired - Fee Related
- 2012-12-04 CN CN201210512345.6A patent/CN102993047B/en not_active Expired - Fee Related
- 2012-12-04 CN CN201210513802.3A patent/CN103018237B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996028757A1 (en) * | 1995-03-13 | 1996-09-19 | Akzo Nobel N.V. | Non-linear optical polycarbonates |
| WO2012013563A1 (en) * | 2010-07-29 | 2012-02-02 | Basf Se | Dmapn having low dgn content and method for producing dmapa from dmapn having low dgn content |
| CN102603567A (en) * | 2012-01-18 | 2012-07-25 | 浙江工业大学 | Stilbene nitrile derivatives, and preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| CHUNRONG LIU等: "Reaction Based Fluorescent Probes for Hydrogen Sulfide", 《ORG LETT.》 * |
| ELKE GUBBELMANS等: "Poly(phenylquinoxalines) for second-order nonlinear optical applications", 《POLYMER》 * |
| P. KITIPICHAI等: "In-Situ Poling and Synthesis of NLO Chromophore-Bearing Polyurethanes for Second Harmonic Generation", 《JOUMALOF POLYMER SCIENCE: PART A POLYMER CHEMISTRY》 * |
| YONG QIAN等: "Selective fluorescent probes for live-cell monitoring of sulphide", 《NATURE COMMUNICATIONS》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10196343B2 (en) | 2013-01-30 | 2019-02-05 | Ecolab Usa Inc. | Hydrogen sulfide scavengers |
| US10703710B2 (en) | 2013-01-30 | 2020-07-07 | Ecolab Usa Inc. | Hydrogen sulfide scavengers |
| US11339118B2 (en) | 2013-01-30 | 2022-05-24 | Ecolab Usa Inc. | Hydrogen sulfide scavengers |
| US10308886B2 (en) | 2015-04-22 | 2019-06-04 | Ecolab Usa Inc. | Development of a novel high temperature stable scavenger for removal of hydrogen sulfide |
| US11085002B2 (en) | 2015-04-22 | 2021-08-10 | Championx Usa Inc. | Development of a novel high temperature stable scavenger for removal of hydrogen sulfide |
| US10407626B2 (en) | 2015-09-08 | 2019-09-10 | Ecolab Usa Inc. | Hydrocarbon soluble/dispersible hemiformals as hydrogen sulfide scavengers |
| US10584286B2 (en) | 2015-09-08 | 2020-03-10 | Ecolab Usa Inc. | Hydrogen sulfide scavengers |
| US10336950B2 (en) | 2016-07-29 | 2019-07-02 | Ecolab Usa Inc. | Antifouling and hydrogen sulfide scavenging compositions and methods |
| US10538710B2 (en) | 2017-07-13 | 2020-01-21 | Ecolab Usa Inc. | Hydrogen sulfide scavengers |
| US11499108B2 (en) | 2019-01-23 | 2022-11-15 | Championx Usa Inc. | Complete removal of solids during hydrogen sulfide scavenging operations using a scavenger and a Michael acceptor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103012199B (en) | 2014-11-26 |
| CN102993047B (en) | 2014-09-24 |
| CN103018237B (en) | 2014-09-24 |
| CN103018237A (en) | 2013-04-03 |
| CN102993047A (en) | 2013-03-27 |
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