CN102830098A - Fluorescent sensor for measuring picric acid content and preparation method thereof - Google Patents
Fluorescent sensor for measuring picric acid content and preparation method thereof Download PDFInfo
- Publication number
- CN102830098A CN102830098A CN2012102523813A CN201210252381A CN102830098A CN 102830098 A CN102830098 A CN 102830098A CN 2012102523813 A CN2012102523813 A CN 2012102523813A CN 201210252381 A CN201210252381 A CN 201210252381A CN 102830098 A CN102830098 A CN 102830098A
- Authority
- CN
- China
- Prior art keywords
- picric acid
- acid content
- preparation
- slide
- fluorescence
- 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.)
- Pending
Links
Images
Landscapes
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention discloses a fluorescent sensor for measuring the picric acid content. A fluorescent carrier in a film substrate monomer is an allyl four iodine fluorescein. 15mg of fluorescent carrier allyl four iodine fluorescein is dissolved in 0.2ml of N, N-dimethylformamide for sufficient dissolution, 200mg of acrylamide, 0.4ml of hydroxyethyl methylacrylate, 0.15ml of cross-linking agent triethoxy trimethyl acrylate and 0.2ml of triethanolamine are added, finally 0.25ml of 1-oxhydryl cyclohexyl phenyl ketone is added for even mixing; and a solution is removed to drop on a Teflon plate, a quartz slide subjected to silanization is covered on the Teflon plate, an ultraviolet lamp is used for irradiating for 20 minutes, and drying is carried out at a room temperature. The sensor has the advantages of simple preparation, good stability, short response time, good reproducibility and the like, and can continuously and timely measure the picric acid content on line.
Description
Technical field
The present invention relates to a kind of fluorescent optical sensor, be specifically related to a kind of fluorescent optical sensor of measuring picric acid content and preparation method thereof.
Background technology
Picric acid, formal name used at school 2,4, the 6-trinitrophenol belongs to nitro-phenolic compound, is faint yellow crystalline solid, odorless, bitter.Main manufacturing, the germifuge on the agricultural and mildew removing agent, the germifuge on the medical treatment and the manufacturing of astringent etc. as explosive.Eyes, skin, respiratory tract and alimentary canal are produced harm, and the words that suck human body can cause symptoms such as headache, dizziness, nauseating, vomiting, anorexia, diarrhoea and heating, and damage red blood cell, the nephritis that causes bleeding, hepatitis, jaundice etc.Be strong oxidizer, can be with combustible, reductive agent vigorous reaction and combustion explosion takes place.Can corroding metal, and the slaine that generates to vibrations or thermoae be sensitivity.If the excessive water body that enters will cause pollution of waterhead, so picric acid has been one of important indicator of environmental monitoring.
Picric detection method is used the classical chemical method that nitrophenols is reduced into azo dyes always, ultraviolet spectrophotometry, at present higher vapor-phase chromatography and high performance liquid chromatographies of sensitivity that adopt more.The AAS detectability is than higher, but operation steps is more.Liquid phase chromatography need extract concentrated, operates also comparatively loaded down with trivial detailsly, and the picric WS of gc analysis, moisture can cause shorten the serviceable life of chromatographic column, and serious meeting was lost efficacy chromatographic column.Along with the development of sensing technology, particularly fluorescence chemical sensor show simple and rapid analytical characteristic, and in field widespread uses such as Pharmaceutical Analysis, biologicall tests.In the design and development of various fluorescent optical sensors, the fluorescent optical sensor that changes based on fluorescence intensity has simple to operate, advantages such as response speed fast, good reversibility, life-span length.
Therefore, developing a kind of new picric acid fluorescent optical sensor is highly significant.
Summary of the invention
The present invention is intended to develop a kind of new fluorescent optical sensor, makes it can measure picric content.
For achieving the above object; The present invention provides a kind of fluorescence chemical sensor that detects picric acid content; The quartzy slide, the membrane matrix monomer that comprise silanization are attached to the auroral poles film on the slide through photopolymerization, and the fluorescence carrier in the said membrane matrix monomer is the propenyl tetraiodofluorescein.
The allyl tetraiodofluorescein, structural formula is following:
A kind of preparation method who detects the fluorescence chemical sensor of picric acid content comprises the silanization of slide, the preparation of auroral poles film, and the preparation method of said auroral poles film is following: 15mg fluorescence carrier propenyl tetraiodofluorescein is dissolved in 0.2ml N; In the N-NMF; Fully dissolving adds the 200mg acrylic amide, the 0.4ml hydroxyethyl methacrylate; 0.15ml crosslinking chemical triethoxy trimethyl acrylic ester; 0.2ml triethanolamine adds 0.25ml1-hydroxy-cyclohexyl phenyl ketone at last, mixes; Pipette above-mentioned drips of solution on polyfluortetraethylene plate, cover on it, used ultra violet lamp again 20 minutes, take out the good slide of photocuring successively water and alcohol flushing with the quartzy slide that silanization is good, till the loss that does not observe carrier, drying at room temperature.
To be pack into the top of teflon flow cell of auroral poles film that fluorescence carrier is processed with the propenyl tetraiodofluorescein; Testing sample is with the speed input flow cell of 1.3ml/min; The maximum excitation wavelength of fluorescence carrier and transmitted wave strong point are measured fluorescence intensity in the variable concentrations picric acid solution, and measure picric content in the unknown appearance according to correction equation.
Beneficial effect: the fluorescence molecule of the present invention's design is easy to synthesize, and has effectively stoped the loss of fluorescence carrier through the method for Covalent Immobilization; And this sensor construction is simple, has shown good stability, reappearance and reversibility (Fig. 2); Realized continuous, real-time, online mensuration (Fig. 3) to picric acid content in the WS.
Description of drawings
Fig. 1 is the fluorescence spectrum figure of sensitive membrane in the variable concentrations picric acid solution, is respectively from top to bottom: blank solution, 1 * 10
-7Moll
-1, 1 * 10
-6Moll
-1, 1 * 10
-5Moll
-1, 1 * 10
-4Mol l
-1, 1 * 10
-3Mol l
-1, 1 * 10
-2Mol l
-1, 0.5 * 10
-1Moll
-1, 1 * 10
-1Moll
-1The result shows the increase along with picric acid concentration, and the fluorescence intensity of sensitive membrane obviously weakens.We can measure picric concentration through the variation of fluorescence intensity.
Fig. 2 is a fluorescence intensity situation over time when circulation feeds the picric WS of variable concentrations.Wherein horizontal ordinate is the time, and ordinate is a fluorescence intensity.Picric acid content is followed successively by from low to high: 0mol l
-1, 1 * 10
-5Mol l
-1, 1 * 10
-2Moll
-1, 1 * 10
-1Mol l
-1From finding out the variation from a kind of solution to another kind of fluorescence intensity of solution on scheming, 7 times repetitive cycling is measured fluorescence intensity, and reappearance and reversibility are all more satisfactory, and release time and change in concentration order are also irrelevant.This sensor sheet has revealed good stability, reappearance and reversibility.
Fig. 3 is the graph of a relation of picric acid concentration (C) and fluorescence intensity (I).When picric acid concentration 1 * 10
-7～0.5 * 10
-1Moll
-1Between the time, presented good linear relationship between-lnC and the fluorescence intensity, correction equation is: I=7.43 (lnC)+353.05 (R=0.9940).Picric acid concentration is 1 * 10
-7～0.5 * 10
-1Mol l
-1Between the time, can be used as the picric quantitative relationship of sensor determination.
Embodiment
Embodiment 1:
Synthetic route in the synthesis step list of references of allyl tetraiodofluorescein (Anal.Chim.Acta, 1997:V342 207-213), concrete steps are as follows:
With mol ratio is that easin (compd A) and the bromopropene (compd B) of 1:3 is at N; In the dinethylformamide, under 80 ℃ of conditions, stirred 3 hours, it is fully reacted; Rotary evaporation was removed N after reaction finished; Dinethylformamide, 0.2mol l is used in the dissolving of gained solid water
-1Hydrochloric acid be adjusted to acidity, produce red precipitate, filter, drying is used ethyl alcohol recrystallization.Obtain the tetraiodofluorescein derivant (Compound C) of the two keys of band edge base, productive rate is 65%, MS: (M+H)
+877.
Nitryl group in the picric acid on the aromatic ring is a strong electron-withdrawing group, has formed fluorescent composition with tetraiodofluorescein, causes the fluorescent quenching of tetraiodofluorescein.Therefore, during the picric acid changes of contents, fluorescence intensity changes thereupon, sees Fig. 1.The above-mentioned fluorescence intensity response that this tetraiodofluorescein derivant produces in containing the picric acid solution of variable concentrations can be used as fluorescent optical sensor, to realize a small amount of picric acid original position, detection in real time in the solution.
Embodiment 2:
The preparation and the mensuration of fluorescent optical sensor may further comprise the steps:
1, the silanization of slide: with soaking 40 minutes in quartzy slide (diameter 12.5mm) the immersion chromic acid lotion; Putting into 3% hydrofluorite successively soaked 30 minutes; Totally make with distilled water flushing then and fully no longer speckle with 3% hydrofluorite, add again in 10% the oxydol and soaked 30 minutes.Clean with distilled water flushing again.Transfer pipet with dry is measured the 0.2ml propyl methacrylate, 2ml 0.2mol l
-1PH be that 3.6 acetic acid-sodium-acetate buffer and 8ml distilled water mix, stirs propyl methacrylate is melted to prepare silanization solution fully.Slide immersed in this solution 2～3 hours, cleaned with distilled water then, and drying at room temperature is subsequent use.
2, the preparation of auroral poles film: 15mg allyl tetraiodofluorescein is dissolved in 0.2ml N, in the dinethylformamide, fully dissolving.Add the 200mg acrylic amide successively, 0.4ml hydroxyethyl methacrylate, 0.15ml crosslinking chemical triethoxy trimethyl acrylic ester, 0.15ml triethanolamine and 0.2ml 1-hydroxy-cyclohexyl phenyl ketone.Get the above-mentioned solution of 0.1～0.2ml on polyfluortetraethylene plate; With the slide lid of silanization on it, (the good slide of photocuring successively water and alcohol flushing are taken out in the irradiation of wavelength=254nm) 20 minutes to use uviol lamp again; Till the loss that does not observe carrier, drying at room temperature.
Fluorescence measurement carries out on the PerkingElmer LS55 phosphorescence spectrophotometer of band computer data processing system.The quartzy slide that will adhere to the auroral poles film is fixed in the homemade teflon flow cell by nut, and face makes the auroral poles film contact with sample solution down.A both arms optical fiber one terminates on the spectrophotometer; The other end inserts flow cell and is close to the slide reverse side; The end of the radiation that excitation source sends through both arms optical fiber is transferred to and shines surface of glass slide in the flow cell; And exciting the fluorescent material in the auroral poles film, emitted fluorescence turns back to detecting device by other end transmission again, measures.Sample solution is by the speed input flow cell of peristaltic pump with 1.3ml/min, and auroral poles film and sample solution just can obtain a stable fluorescence intensity level after reaching balance.Fluorescence chemical sensor of the present invention can be applicable to picric acid Determination on content in the WS.
Embodiment 3: the mensuration of correction equation
Picric acid solution (0mol l with variable concentrations
-1, 1 * 10
-7Mol l
-1, 1 * 10
-6Mol l
-1, 1 * 10
-5Mol l
-1, 1 * 10
-4Moll
-1, 1 * 10
-3Mol l
-1, 1 * 10
-2Mol l
-1, 0.5 * 10
-1Moll
-1, 1 * 10
-1Moll
-1) respectively by the speed input flow cell of peristaltic pump with 1.3ml/min, auroral poles film and solution just can obtain a stable fluorescence intensity (I) after reaching balance.Make fitting a straight line with Sigmaplot software, when picric acid concentration 1 * 10
-7～0.5 * 10
-1Mol l
-1Between the time, presented good linear relationship between-lnC and the fluorescence intensity, as shown in Figure 3, obtain correction equation and be: I=7.43 (ln C)+353.05 (R=0.9940).Picric acid concentration is 1 * 10
-7～0.5 * 10
-1Mol l
-1Between the time, can be used as the picric quantitative relationship of sensor determination.
The sample of the unknown concentration that needs are measured by the speed input flow cell of peristaltic pump with 1.3ml/min, after auroral poles film and solution reach balance, is read the numerical value of stable fluorescence intensity after the same method, according to correction equation, obtains picric content.
Embodiment 4:
With the excessive picric acid of (greater than reacting dose) and quantitatively quinine reaction, quinine and picric acid generate deposition.To precipitate and solution separating, consider the picric content that does not consume in the liquid, the concentration of indirect determination quinine through measuring.The component of compound quinine parenteral solution is a quinine sulfate, caffeine and urethane (urethane), and back two kinds of compositions are interference measurement not.Concrete determination step is following:
Get 100ml 1 * 10
-2Mol/L picric acid standard solution adds the compound quinine parenteral solution of selling on a certain amount of market in a beaker, fully stir; Make it deposition fully, suction filtration is with low amounts of water washing precipitation 2 times; Filtrating is transferred in the 250ml volumetric flask, adds water to scale mark, shakes up; Get this liquid 0.25ml and measure, the result is as shown in the table:
Embodiment 5:
With the sanitary sewage is research object, investigates the application of this sensor in actual water sample with standard addition method.Sanitary sewage after the usefulness process simple filtration is respectively 1.0 * 10 through the method configuration concentration of stepwise dilution
-5Mol l
-1, 5.0 * 10
-5Mol l
-1, 1.0 * 10
-4Mol l
-1Picric acid solution, by above-mentioned experimental procedure, water sample is directly measured, the result is as shown in the table:
A: three measured mean values
B: standard deviation
Claims (2)
1. a fluorescence chemical sensor that detects picric acid content comprises that the quartzy slide of silanization, membrane matrix monomer are attached to the auroral poles film on the slide through photopolymerization, and it is characterized in that: the fluorescence carrier in the said membrane matrix monomer is the propenyl tetraiodofluorescein.
2. a preparation method who detects the fluorescence chemical sensor of picric acid content comprises the silanization of slide, the preparation of auroral poles film, it is characterized in that the preparation method of said auroral poles film is following: 15 mg fluorescence carrier propenyl tetraiodofluoresceins are dissolved in 0.2 ml N; In the dinethylformamide; Fully dissolving adds 200 mg acrylic amides, 0.4 ml hydroxyethyl methacrylate; 0.15 ml crosslinking chemical triethoxy trimethyl acrylic ester; 0.2 the ml triethanolamine adds 0.25 ml 1-hydroxy-cyclohexyl phenyl ketone at last, mixes; Pipette above-mentioned drips of solution on polyfluortetraethylene plate, cover on it, used ultra violet lamp again 20 minutes, drying at room temperature with the quartzy slide that silanization is good.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102523813A CN102830098A (en) | 2012-07-20 | 2012-07-20 | Fluorescent sensor for measuring picric acid content and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102523813A CN102830098A (en) | 2012-07-20 | 2012-07-20 | Fluorescent sensor for measuring picric acid content and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102830098A true CN102830098A (en) | 2012-12-19 |
Family
ID=47333309
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012102523813A Pending CN102830098A (en) | 2012-07-20 | 2012-07-20 | Fluorescent sensor for measuring picric acid content and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102830098A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105203509A (en) * | 2015-09-07 | 2015-12-30 | 南京邮电大学 | Detection method for picric acid by using crocodile-skin-shaped fluorescent nano fibers |
| CN105295042A (en) * | 2015-12-08 | 2016-02-03 | 齐鲁工业大学 | Preparation method of nitrogen-containing polymer quantum dot used for detecting picric acid |
| CN106525779A (en) * | 2015-09-15 | 2017-03-22 | 南京邮电大学 | Method for detecting picric acid by using pill-like film |
| CN109900665A (en) * | 2019-02-27 | 2019-06-18 | 山东省科学院海洋仪器仪表研究所 | A kind of method that molecular engram selection fluorescence quenching method measures DDT in water body |
| CN110790706A (en) * | 2019-10-25 | 2020-02-14 | 西北师范大学 | Molecular sensor capable of singly and selectively identifying picric acid molecules and synthesis and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1990014591A1 (en) * | 1989-05-17 | 1990-11-29 | Isoline A/S | Method for simultaneous control of cleaning and hygiene and agent for use when carrying out the method |
| CN1884431A (en) * | 2006-05-19 | 2006-12-27 | 湖南大学 | Method for fixing fluorescent carrier |
| CN101108795A (en) * | 2007-07-22 | 2008-01-23 | 中北大学 | 1-propylene oxygen basis-4-hydroxyanthraquinone-9, 10-diketone and method of preparing the same and application thereof |
| CN101410756A (en) * | 2006-03-28 | 2009-04-15 | Az电子材料美国公司 | Negative photoresist compositions |
| CN101864097A (en) * | 2010-05-31 | 2010-10-20 | 陕西师范大学 | Preparation method of polycyclopentadiene silicane fluorescence sense film doped with chitosan and application thereof |
-
2012
- 2012-07-20 CN CN2012102523813A patent/CN102830098A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1990014591A1 (en) * | 1989-05-17 | 1990-11-29 | Isoline A/S | Method for simultaneous control of cleaning and hygiene and agent for use when carrying out the method |
| CN101410756A (en) * | 2006-03-28 | 2009-04-15 | Az电子材料美国公司 | Negative photoresist compositions |
| CN1884431A (en) * | 2006-05-19 | 2006-12-27 | 湖南大学 | Method for fixing fluorescent carrier |
| CN101108795A (en) * | 2007-07-22 | 2008-01-23 | 中北大学 | 1-propylene oxygen basis-4-hydroxyanthraquinone-9, 10-diketone and method of preparing the same and application thereof |
| CN101864097A (en) * | 2010-05-31 | 2010-10-20 | 陕西师范大学 | Preparation method of polycyclopentadiene silicane fluorescence sense film doped with chitosan and application thereof |
Non-Patent Citations (5)
| Title |
|---|
| ALBERT H. ADELMAN ET AL: "Long-lived States in Photochemical Reactions. II. Photoreduction of Fluorescein and its Halogenated Derivatives", 《PHOTOREDUCTION OF FLUORESCEIN AND ITS HALOGENATED DERIVATIVES》, vol. 78, 20 August 1956 (1956-08-20), pages 3977 - 3980 * |
| CLAUDIA PREININGER ET AL: "Fluorosensors for ammonia using rhodamines immobilizd in plasticized poly(vinyl chloride) and in sol-gel; a comparative study", 《ANALYTICA CHIMICA ACTA》, vol. 342, 31 December 1997 (1997-12-31), pages 207 - 213 * |
| XIN YANG ET AL.: "Picric acid sensitive optode based on a fluorescence carrier covalently bound to membrane", 《THE ANALYST》, vol. 126, 15 February 2001 (2001-02-15), pages 349 - 352 * |
| 高攀峰: "新型荧光化学传感器研制及其在环境分析中的应用", 《中国优秀博硕士学位论文全文数据库（硕士）》, no. 11, 15 November 2006 (2006-11-15) * |
| 龙立平等: "荧光熄灭的苦味酸光化学传感器", 《分析化学》, vol. 31, 30 April 2003 (2003-04-30), pages 414 - 419 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105203509A (en) * | 2015-09-07 | 2015-12-30 | 南京邮电大学 | Detection method for picric acid by using crocodile-skin-shaped fluorescent nano fibers |
| CN106525779A (en) * | 2015-09-15 | 2017-03-22 | 南京邮电大学 | Method for detecting picric acid by using pill-like film |
| CN106525779B (en) * | 2015-09-15 | 2019-05-28 | 南京邮电大学 | " pill shape " fluorescence membrane is to picric detection method |
| CN105295042A (en) * | 2015-12-08 | 2016-02-03 | 齐鲁工业大学 | Preparation method of nitrogen-containing polymer quantum dot used for detecting picric acid |
| CN105295042B (en) * | 2015-12-08 | 2017-08-04 | 齐鲁工业大学 | A kind of preparation method for being used to detect picric polymer with nitrogen quantum dot |
| CN109900665A (en) * | 2019-02-27 | 2019-06-18 | 山东省科学院海洋仪器仪表研究所 | A kind of method that molecular engram selection fluorescence quenching method measures DDT in water body |
| CN109900665B (en) * | 2019-02-27 | 2021-04-30 | 山东省科学院海洋仪器仪表研究所 | Method for measuring DDT in water body by molecular imprinting selective fluorescence quenching method |
| CN110790706A (en) * | 2019-10-25 | 2020-02-14 | 西北师范大学 | Molecular sensor capable of singly and selectively identifying picric acid molecules and synthesis and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Aksuner | Development of a new fluorescent sensor based on a triazolo-thiadiazin derivative immobilized in polyvinyl chloride membrane for sensitive detection of lead (II) ions | |
| Li et al. | A novel fluorescence ratiometric pH sensor based on covalently immobilized piperazinyl-1, 8-napthalimide and benzothioxanthene | |
| JP6258355B2 (en) | Novel aza-BODIPY compound for selective detection of nitrite ion in water and its preparation method | |
| Chao et al. | A ratiometric fluorescence probe for monitoring cyanide ion in live cells | |
| Aksuner et al. | Selective optical sensing of copper (II) ions based on a novel cyclobutane-substituted Schiff base ligand embedded in polymer films | |
| CN102830098A (en) | Fluorescent sensor for measuring picric acid content and preparation method thereof | |
| CN111687408B (en) | Fluorescent copper nanocluster, preparation method and application thereof | |
| JP2700165B2 (en) | Compounds, reagents and methods for cation measurement | |
| CN110229147A (en) | A kind of cumarin-benzothiazolyl hydrazone compounds and its preparation method and application | |
| Razak et al. | Reflectance chemosensor based on bis-thiourea derivative as ionophore for copper (II) ion detection | |
| CN107417681B (en) | Fluorescent probe compound containing coumarin-thiadiazole Schiff base and preparation method and application thereof | |
| CN109651249A (en) | A kind of fluorescence probe detecting endocytoplasmic reticulum cysteine and its synthesis and application | |
| Gavrilenko et al. | A colorimetric sensor based on a polymethacrylate matrix with immobilized 1-(2-pyridylazo)-2-naphthol for the determination of cobalt | |
| Zhang et al. | Combination of imine bond and samarium emitter enables turn-off fluorescence detection of hydrazine in vapor and water samples | |
| Abdel Aziz et al. | A Novel Fluorimetric Bulk Optode Membrane Based on NOS Tridentate Schiff Base for Selective Optical Sensing of Al 3+ Ions | |
| CN110878085A (en) | Rapid high-selectivity hypobromous acid fluorescent probe, preparation method and application | |
| Niu et al. | A ratiometric fluorescence halide sensor based on covalently immobilization of quinine and benzothioxanthene | |
| Wang et al. | A three-in-one versatile sensor for concise detecting biogenic amines and beef freshness | |
| Sheta et al. | Smart prototype for an electronic color sensor device for visual simultaneous detection of macrofuran based on a coated paper strip | |
| Amin | Application of a triacetylcellulose membrane with immobilizated of 5-(2′, 4′-dimethylphenylazo)-6-hydroxypyrimidine-2, 4-dione for mercury determination in real samples | |
| CN109370573A (en) | A kind of fluorescence probe, the preparation method and applications of dimercurion and temperature detection | |
| CN114394986B (en) | Ratio type peroxynitrosyl fluorescent probe, preparation method and application | |
| CN110003175A (en) | A kind of compound and its application for detecting underwater gold category ion concentration | |
| Zhang et al. | A Dual Spectroscopic Probe Based on Benzothiazole for Detection of Hydrazine | |
| CN108169196B (en) | Method for rapidly detecting fluorine ions in environment |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C05 | Deemed withdrawal (patent law before 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20121219 |