CN106117098B - A kind of fluorescent optical sensor and preparation method thereof of detection chloride ion in cement - Google Patents
A kind of fluorescent optical sensor and preparation method thereof of detection chloride ion in cement Download PDFInfo
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- CN106117098B CN106117098B CN201610510282.9A CN201610510282A CN106117098B CN 106117098 B CN106117098 B CN 106117098B CN 201610510282 A CN201610510282 A CN 201610510282A CN 106117098 B CN106117098 B CN 106117098B
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- 230000003287 optical effect Effects 0.000 title claims abstract description 38
- 239000004568 cement Substances 0.000 title claims abstract description 21
- 238000001514 detection method Methods 0.000 title claims abstract description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical class SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 11
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical compound C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 241000370738 Chlorion Species 0.000 abstract description 10
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 4
- 150000001450 anions Chemical class 0.000 abstract description 2
- 238000010791 quenching Methods 0.000 abstract description 2
- 125000004429 atom Chemical group 0.000 description 4
- 238000002189 fluorescence spectrum Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000011398 Portland cement Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- YGCXFEFXVBLUKJ-UHFFFAOYSA-N 3-[(3,5-dicarboxyphenyl)disulfanyl]phthalic acid Chemical group C(=O)(O)C=1C=C(C=C(C=1)C(=O)O)SSC1=C(C(C(=O)O)=CC=C1)C(=O)O YGCXFEFXVBLUKJ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002730 mercury Chemical class 0.000 description 1
- VRJVVIKEWDDYOG-UHFFFAOYSA-N mercury;nitric acid Chemical compound [Hg].O[N+]([O-])=O VRJVVIKEWDDYOG-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
- C07C323/62—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/22—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/187—Metal complexes of the iron group metals, i.e. Fe, Co or Ni
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Immunology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Molecular Biology (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Optics & Photonics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The present invention relates to cement detection field, more particularly to a kind of fluorescent optical sensor and preparation method thereof of detection chloride ion in cement.A kind of fluorescent optical sensor of detection chloride ion in cement, the chemical formula of the fluorescent optical sensor is C16H6O8S2Co.The fluorescent optical sensor of the present invention is easily prepared, and the experimental results showed that Fluorescence-quenching occurs after the fluorescent optical sensor adsorbing chloride ions, and other anion will not interfere fluorescence property, therefore it can be used for qualitative and quantitatively detect chlorion, and the sensibility of the fluorescent optical sensor is high, detected value is accurate, and make after detection reagent has extraordinary potential application prospect as when detecting chlorion in cement field.
Description
Technical field
The present invention relates to cement detection field, more particularly to a kind of the fluorescent optical sensor and its system of detection chloride ion in cement
Preparation Method.
Background technology
Chlorion is a kind of harmful components in cement and cement raw material, directly to pre- in New Type Dry-process Cement Production
Hot device and kiln calcining have an impact, and cause the accidents such as ring formation and putty, influence operation rate and cement clinker quality；In cement
In to be more than certain content can also will produce expansion to the reinforcing bars rusting in concrete, while so that reinforced steel bar strength is reduced and make
It at the destruction of concrete, causes concrete to burst apart when serious, hides some dangers for construction quality, so must be strictly controlled.Therefore,
Some technologically advanced national standards all define the limitation and detection method of the chlorion in cement in the world, only in this way
It can ensure that the quality and long-time stability of engineering.There is corresponding detection chlorine in the GB/T 176-2008 of domestic current national standard
The method of ion；Wherein the ammonium thiocyanate volumetric method operating time is long, for quickly detecting inconvenience；Although and mercury salt titration
It is fast and convenient, but it will use the nitric acid mercury reagent of severe toxicity, be easy to pollute the environment.Therefore, there is an urgent need for develop now
A kind of method of novel quick detection chlorion.
Invention content
Technical problem to be solved by the invention is to provide a kind of fluorescent optical sensors of detection chloride ion in cement.
It is another object of the present invention to provide the preparation methods of above-mentioned fluorescent optical sensor.
A kind of fluorescent optical sensor of detection chloride ion in cement, the chemical formula of the fluorescent optical sensor is C16H6O8S2Co,
In, C16H6O8S2For 3- ((3,5- dicarboxyphenyi) disulphanes base) phthalandione root, the fluorescent optical sensor is anorthic system,P-1It is empty
Between group, cell parameter isa=12.262 (1),b=9.816 (1),c=13.418 (3),α=79.526 (1) o,β=
81.236 (8) o,γ=75.522 (3) o, V=1615.04 (1)3。
The method of the fluorescent optical sensor of above-mentioned detection chloride ion in cement is：By 3- ((3,5- dicarboxyphenyis) disulphanes
Base) phthalandione and cobalt nitrate be dissolved in the mixed solvent of acetonitrile and dimethylacetylamide, be stirred at room temperature after dissolving formed it is mixed
Liquid A is closed, the mixed liquor A is then stood 72 hours at 40 DEG C and obtains mixed liquid B, mixed liquid B is then transferred to poly- four
In vinyl fluoride autoclave, places it in and reacted in 155 DEG C of baking ovens 24 hours, be down to room temperature with 5 DEG C/h later and filter
To the fluorescent optical sensor.
Further, the molar ratio of 3- ((3, the 5- dicarboxyphenyi) disulphanes base) phthalandiones and cobalt nitrate is 1:1.
Further, the volume ratio of the acetonitrile and dimethylacetylamide is 1:2.
Wherein, the English name of the 3- ((3,5- dicarboxyphenyi) disulphanes base) phthalandione is 3- ((3,5-
Dicarboxyphenyl) disulfanyl) phthalic acid, chemical constitution is as follows：
。
The method that the preparation method of fluorescent optical sensor used in the present invention uses solvent heat after first standing, first by 40 DEG C
Under 72 hours stand form small crystal nucleus so that solvent thermal process later can obtain our desired fluorescent optical sensors.Such as
The method of solvent heat is directly used to will be unable to for fruit so that fluorescent optical sensor crystallization, will cannot get fluorescent optical sensor of the invention,
What is obtained is a kind of unformed compound.
The present invention has the advantages that：
The fluorescent optical sensor of the present invention is easily prepared, and the experimental results showed that is sent out after the fluorescent optical sensor adsorbing chloride ions
Raw Fluorescence-quenching, and other anion will not interfere fluorescence property, therefore it can be used for qualitative and quantify
Chlorion is detected, and the sensibility of the fluorescent optical sensor is high, detected value is accurate, made after detection reagent as in cement field
There is extraordinary potential application prospect when detecting chlorion.
Description of the drawings
Fig. 1 is the coordination schematic diagram of the fluorescent optical sensor of the present invention.
Fig. 2 is the fluorescence spectra after the fluorescent optical sensor adsorbing chloride ions of the present invention.
Specific implementation mode
With reference to embodiment, the present invention will be described in detail, and embodiment is only the preferred embodiment of the present invention,
It is not limitation of the invention.
Wherein, the fluorescent optical sensor used in the present invention is synthesized using the following method：
Embodiment 1
By 0.3mmol3- ((3,5- dicarboxyphenyis) disulphanes base) phthalandiones and 0.3mmol cobalt nitrates be dissolved in 6mL acetonitriles and
In the mixed solvent of 12mL dimethylacetylamides, mixed liquor A is formed after dissolving is stirred at room temperature, then by the mixed liquor
A stands 72 hours at 40 DEG C and obtains mixed liquid B, and then mixed liquid B is transferred in polytetrafluoroethylene (PTFE) autoclave, by it
It is placed in 155 DEG C of baking ovens and reacts 24 hours, be down to room temperature with 5 DEG C/h later and the fluorescent optical sensor is obtained by filtration.
Then the fluorescent optical sensor of gained is subjected to monocrystalline characterization.
The X ray diffracting data of the fluorescent optical sensor is visited on diffractometer in the faces Bruker Smart Apex CCD, is used
MoKαIt radiates (λ=0.71073), Lp factor corrections is collected and carried out with ω scan modes, absorption correction uses SADABS journeys
Sequence.With direct method solution structure, whole non-hydrogen atom coordinates then are found out with difference Fourier method, theoretical hydrogenation method is used in combination to obtain hydrogen
Atom site (C H 1.083), is modified structure with least square method.Evaluation work uses SHELXTL journeys in PC machine
Sequence packet is completed.
Parsing is it is found that the chemical formula of the fluorescent optical sensor is C after tested16H6O8S2Co, wherein C16H6O8S2For 3- ((3,
5- dicarboxyphenyis) disulphanes base) phthalandione root, the fluorescent optical sensor is anorthic system,P-1Space group, cell parameter area=
12.262 (1),b=9.816 (1),c=13.418 (3),α=79.526 (1) o,β=81.236 (8) o,γ=75.522
(3) o, V=1615.04 (1)3, Z=2.
It is coordinated schematic diagram as shown in Figure 1, Co atoms take the pattern of 6 coordinations, wherein each Co atoms respectively with 3 3-
6 O atoms coordination on ((3,5- dicarboxyphenyi) disulphanes base) phthalandione molecule, wherein two 3- ((3,5- dicarboxyl benzene
Base) disulphanes base) two carboxyls of phthalandione are respectively adopted bidentate chelating pattern and are connected with Co atoms, and another 3- ((3,5- bis-
Carboxyl phenyl) disulphanes base) on two carboxyls be then connected with Co atoms with monodentate pattern.
By fluorescent optical sensor in embodiment 1 pulverize it is last be dispersed in water, then pass through add various concentration chlorine
Ion carries out fluorescence spectrum test, excitation wavelength 325nm.Fluorescence spectra as shown in Fig. 2, from figure it will be seen that
Increase to 0.006mol/L from 0 with the concentration of chlorion, fluorescence intensity continuously decreases, moreover, if addition be nitrate anion,
Sensor of the invention fluorescence intensity is not influenced if sulfate radical or acetate（It is not shown in the diagram）, fluorescence intensity is basic
It is similar when with a concentration of 0mM, therefore qualitative and quantitative detection can be carried out to chlorion using the variation of fluorescence intensity.
The common portland cement of 0.3g acid is dissolved, 100mL is settled to；Then the embodiment of the present invention 1 is added
Fluorescent optical sensor carries out fluorescence spectrum test after stirring evenly.Intensity contrast obtained by measured fluorescence intensity and Fig. 1, such as
Fruit intensity is less than the fluorescence intensity of 0.005mol/L, then can know that the chlorine ion concentration of the common portland cement is less than by calculating
The 0.06% of the requirement of standard.Therefore, detection reagent of the invention is extraordinary latent as having when detecting chlorion in cement field
Application prospect.
Embodiments of the present invention above described embodiment only expresses, the description thereof is more specific and detailed, but can not
Therefore it is interpreted as the limitation to the scope of the claims of the present invention, as long as skill obtained in the form of equivalent substitutions or equivalent transformations
Art scheme should all be fallen within the scope and spirit of the invention.
Claims (1)
1. a kind of fluorescent optical sensor of detection chloride ion in cement, it is characterised in that the chemical formula of the fluorescent optical sensor is
C16H6O8S2Co, wherein C16H6O8S2For 3- ((3,5- dicarboxyphenyis) disulphanes base) phthalandione root；
The fluorescent optical sensor is anorthic system,P-1Space group, cell parameter area=12.262 (1),b=9.816 (1),c
=13.418 (3),α=79.526 (1) o,β=81.236 (8) o,γ=75.522 (3) o, V=1615.04 (1)3
The fluorescent optical sensor of the detection chloride ion in cement synthesizes in accordance with the following methods：By 3- ((3,5- dicarboxyphenyis)
Disulphanes base) phthalandione and cobalt nitrate be dissolved in the mixed solvent of acetonitrile and dimethylacetylamide, after dissolving is stirred at room temperature
Mixed liquor A is formed, the mixed liquor A is then stood 72 hours at 40 DEG C and obtains mixed liquid B, then shifts mixed liquid B
Into polytetrafluoroethylene (PTFE) autoclave, places it in 155 DEG C of baking ovens and react 24 hours, be down to room temperature later with 5 DEG C/h
The fluorescent optical sensor is obtained by filtration；
The molar ratio of 3- ((3,5- dicarboxyphenyis) disulphanes base) phthalandiones and cobalt nitrate is 1:1；
The volume ratio of the acetonitrile and dimethylacetylamide is 1:2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610510282.9A CN106117098B (en) | 2016-06-30 | 2016-06-30 | A kind of fluorescent optical sensor and preparation method thereof of detection chloride ion in cement |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610510282.9A CN106117098B (en) | 2016-06-30 | 2016-06-30 | A kind of fluorescent optical sensor and preparation method thereof of detection chloride ion in cement |
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| Publication Number | Publication Date |
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| CN106117098A CN106117098A (en) | 2016-11-16 |
| CN106117098B true CN106117098B (en) | 2018-07-13 |
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| CN102495032A (en) * | 2011-11-15 | 2012-06-13 | 深圳大学 | Chloride ion fluorescence detection method, device thereof and application thereof |
| CN104418875A (en) * | 2013-08-28 | 2015-03-18 | 苏州罗兰生物科技有限公司 | Fluorescent molecular probe for detecting fluoride ions as well as synthesis method and application thereof |
| CN104418874A (en) * | 2013-08-28 | 2015-03-18 | 苏州罗兰生物科技有限公司 | Fluorescent molecular probe for detecting fluoride ions in aqueous solutions as well as synthesis method and application thereof |
-
2016
- 2016-06-30 CN CN201610510282.9A patent/CN106117098B/en not_active Expired - Fee Related
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| CN1732173A (en) * | 2002-10-29 | 2006-02-08 | 辛斯－伊诺瓦实验室 | High pure phthalein derivative and process for preparing the same |
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