CN111579542B - Application of derivative - Google Patents
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- CN111579542B CN111579542B CN202010589147.4A CN202010589147A CN111579542B CN 111579542 B CN111579542 B CN 111579542B CN 202010589147 A CN202010589147 A CN 202010589147A CN 111579542 B CN111579542 B CN 111579542B
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- C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
- C07C237/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton
- C07C237/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
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- 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
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- 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"
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- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
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- 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"
- G01N2021/6443—Fluorimetric titration
Abstract
The invention discloses application of a derivative, and belongs to the field of compounds. The method comprises the first step of reacting 2-aminoanthraquinone with chloroacetyl chloride in the presence of an alkaline reagent to obtain a compound II; and secondly, reacting the compound II with m-phenylenediamine in the presence of an alkaline reagent to obtain a compound III. The anthraquinone derivative provided by the invention is simple in preparation method, and the anthraquinone derivative is high in sensitivity when being used as a fluorescence chemical sensor.
Description
The application is as follows: 2019-12-20, with the application number: 201911328105.9, the name is: a novel anthraquinone derivative, a synthetic method and a divisional application of an invention patent of application.
Technical Field
The invention relates to the field of compounds, in particular to application of anthraquinone derivatives.
Background
Copper is the third most abundant transition metal element in the human body after iron and zinc. Cu2+The proper amount of the composition in human body is beneficial to maintaining the normal work of the body. Cu2+Can participate in enzyme reaction, enzyme transcription and some redox processes in vivo, and is also closely related to physiological reaction of human under stress and panic. But if Cu is present in vivo2+The abnormal metabolism of (a) may induce a series of diseases such as Menkes ' syndrome, Wilsom ' syndrome, familial muscular atrophy, Alzheimer's disease, etc. Therefore, a method for detecting Cu with high sensitivity and high selectivity is designed and developed2+The method has important significance.
Disclosure of Invention
The invention provides an anthraquinone derivative, a synthesis method and application aiming at the existing technical problems.
The purpose of the invention can be realized by the following technical scheme:
an anthraquinone derivative, wherein the structure of the anthraquinone derivative is shown as a compound III:
the reaction route of the preparation method of the anthraquinone derivative is as follows:
in some specific embodiments, the method comprises the steps of:
firstly, 2-aminoanthraquinone reacts with chloroacetyl chloride in the presence of an alkaline reagent to obtain a compound II;
and secondly, reacting the compound II with m-phenylenediamine in the presence of an alkaline reagent to obtain a compound III.
The method comprises the following steps: in the first reaction step: the reaction solvent is at least one of dichloromethane, chloroform and tetrahydrofuran.
The method comprises the following steps: the first step of reaction is carried out under the condition of alkaline reagent, and the alkaline reagent is at least one of 4-dimethylamino pyridine, pyridine and triethylamine.
The method comprises the following steps: the mol ratio of the 2-aminoanthraquinone to the chloracetyl chloride is 1: 1-1.5, wherein the molar ratio of the 2-aminoanthraquinone to the alkaline reagent is 1:1 to 10.
The method comprises the following steps: in the second reaction step: the molar ratio of the compound II to the m-phenylenediamine is 2-3: 1, and the molar ratio of the m-phenylenediamine to the alkaline reagent is 1:1 to 5.
The method comprises the following steps: in the second reaction step: the reaction solvent is at least one of acetonitrile, dichloromethane and ethanol; the alkaline reagent is at least one of potassium iodide, N-diisopropylethylamine, anhydrous potassium carbonate, 4-dimethylaminopyridine, pyridine and triethylamine.
The technical scheme of the invention is as follows: the anthraquinone derivative is used as a fluorescent chemical sensor for detecting Cu2+The use of (1).
The technical scheme of the invention is as follows: the anthraquinone derivative is used as a photochemical sensor for detecting Cu2+The use of (1).
The invention has the beneficial effects that:
the anthraquinone derivative provided by the invention is simple in preparation method, and the anthraquinone derivative is high in sensitivity when being used as a fluorescence chemical sensor.
Drawings
FIG. 1 shows probe molecules PNDA (example 1) vs Cu2+Selective absorption spectrum identification.
FIG. 2 is Cu2+Absorbance spectrum titration plot for probe molecule PNDA (example 1).
FIG. 3 is a graph of probe molecules PNDA (example 1) vs. Cu2+Selective fluorescence spectrum identification.
FIG. 4 is Cu2+Fluorescence spectrum titration plot for probe molecule PNDA (example 1).
FIG. 5 shows Cu2+Graph of the effect of reaction time with probe molecule PNDA (example 1) on the fluorescence intensity of the solution.
FIG. 6 shows the selective recognition of Cu for probe PNDA (example 1) in the presence of other coexisting metal ions in solution2+Influence graph of (c).
FIG. 7 shows the selective recognition of Cu by probe PNDA (example 1) at different pH values2+Influence graph of (c).
FIG. 8 shows the probe PNDA in different Cu2+Linear plot of fluorescence intensity at concentration.
Detailed Description
The invention is further illustrated by the following examples, without limiting the scope of the invention:
example 1
1. Synthesis of Compound II
2-aminoanthraquinone (2.23g, 10mmol), 150mL of dichloromethane and 4-dimethylaminopyridine (1.22g, 10mmol) were added in this order to a 500mL three-necked flask, and the mixture was sufficiently cooled in an ice-salt water bath, and then 50mL of a dichloromethane solution containing chloroacetyl chloride (0.8mL, 10mmol) was slowly dropped into the well-stirred three-necked flask using a constant pressure funnel, the temperature of the reaction solution in the three-necked flask was controlled so as not to exceed 0 ℃, and after completion of the dropping, the reaction was continued in an ice-salt water bath for 6 hours. After the reaction, the pH of the reaction solution was adjusted to about 9 with 0.1mol/L NaOH solution. The reaction was then extracted with dichloromethane (3X 25mL), the organic phases combined and washed with water (3X 25mL) and then anhydrous Na2SO4Dry overnight. After filtration, the filtrate was rotary evaporated to remove the organic solvent to give the product ii 2.8g, yield: 93.6%, purity: 99.36 percent.
Elemental analysis: (%) for C16H10NO3Cl calculated: c64.12; h3.36; n4.67, found: c64.87; h3.33; and (4) N4.59.
1H NMR(500MHz,CDCl3,TMS):δ=10.41(s,1H),8.31(t,J=7.0,2H),8.16(s,1H),7.96-7.92(m,2H),7.84(d,J=7.2,2H),4.37(s,2H)ppm.
In a 250mL flask, m-phenylenediamine (1.08g, 10mmol), potassium iodide (3.32mg, 0.02mmol) and N, N-diisopropylethylamine (20mmol) were dissolved in 100mL of acetonitrile and N was passed through2Under reflux and stirring, a 50mL acetonitrile solution containing compound II (5.98g, 20mmol) was slowly added dropwise over 1h using a constant pressure funnel. And after the dropwise addition is finished, continuing the reflux reaction for 20 hours, cooling the reaction liquid to room temperature after the reaction is finished, and pouring the reaction liquid into water. Then extracted with dichloromethane (3X 25mL) and the organic phases were combined and washed with saturated NaCl solution (3X 25 mL). Anhydrous Na for organic phase2SO4Dry overnight. After filtration, the filtrate was rotary evaporated to remove the organic solvent to give 5.88g of product iii (PNDA), yield: 92.7%, purity: 99.28 percent.
Elemental analysis: (%) for C38H26N4O6 calculated: c71.92; h4.13; n8.83, found: c71.79; h4.08; and (8) N8.97.
1H NMR(500MHz,CDCl3,TMS):δ=10.25(s,2H),8.30(t,J=7.2,4H),8.14(s,2H),7.94-7.89(m,4H),7.85(d,J=7.2,4H),7.05(t,J=7.0,1H),6.27(d,J=7.2,2H),5.77(s,1H),4.81(t,J=7.0,2H),3.92(d,J=7.2,4H)ppm.
Example 2
2-aminoanthraquinone (2.23g, 10mmol), 150mL chloroform and pyridine (5mL, 62mmol) were added sequentially to a 250mL three-necked flask, cooled well in an ice-salt bath, and then 50mL of a chloroform solution dissolved with chloroacetyl chloride (0.8mL, 10mmol) was added slowly dropwise to the well-stirred three-necked flask using a constant pressure funnel, the temperature of the reaction solution in the three-necked flask was controlled not to exceed 0 ℃, and after completion of the dropwise addition, the reaction was continued for 6 hours in an ice-salt bath. After the reaction, the pH of the reaction solution was adjusted to about 9 with 0.1mol/L NaOH solution. The reaction was then extracted with dichloromethane (3X 25mL), the organic phases combined and washed with water (3X 25mL) and then anhydrous Na2SO4Dry overnight. After filtration, the filtrate was rotary evaporated to remove the organic solvent to give the product ii 2.73g, yield: 91.3%, purity: 99.12 percent.
In a 250mL flask, m-phenylenediamine (1.08g, 10mmol), potassium iodide (3.32mg, 0.02mmol) and triethylamine (20mmol) were dissolved in 100mL of dichloromethane, and N was passed through2Under reflux and stirring, a 50mL dichloromethane solution containing compound II (5.98g, 20mmol) was added slowly dropwise over 1h using a constant pressure funnel. And after the dropwise addition is finished, continuing the reflux reaction for 20 hours, cooling the reaction liquid to room temperature after the reaction is finished, and pouring the reaction liquid into water. Then extracted with dichloromethane (3X 25mL) and the organic phases were combined and washed with saturated NaCl solution (3X 25 mL). Anhydrous Na for organic phase2SO4Dry overnight. After filtration, the filtrate was rotary evaporated to remove the organic solvent to give 5.71g of product iii (PNDA), yield: 90.1%, purity: 99.21 percent.
Example 3
A250 mL three-necked flask was charged with 2-aminoanthraquinone (2.23g, 10mmol), 150mL of tetrahydrofuran, and triethylamine (5mL, 46mmol) in this order, sufficiently cooled in an ice-brine bath, and then 50mL of ethyl chloride-dissolved solution was introduced into the flask through a constant pressure funnelA tetrahydrofuran solution of acid chloride (0.8ml, 10mmol) was slowly added dropwise to a well-stirred three-necked flask, the temperature of the reaction solution in the three-necked flask was controlled not to exceed 0 ℃, and after completion of the addition, the reaction was continued in an ice-salt water bath for 6 hours. After the reaction, the pH of the reaction solution was adjusted to about 9 with 0.1mol/L NaOH solution. The reaction was then extracted with dichloromethane (3X 25mL), the organic phases combined and washed with water (3X 25mL) and then anhydrous Na2SO4Dry overnight. After filtration, the filtrate was rotary evaporated to remove the organic solvent to give the product ii 2.65g, yield: 88.6%, purity: 99.15 percent.
In a 250mL flask, m-phenylenediamine (1.08g, 10mmol), potassium iodide (3.32mg, 0.02mmol) and anhydrous potassium carbonate (20mmol) were dissolved in 100mL of ethanol, and N was introduced thereinto2Under reflux and stirring, 50mL of ethanol solution containing compound II (5.98g, 20mmol) was slowly added dropwise over 1h using a constant pressure funnel. And after the dropwise addition is finished, continuing the reflux reaction for 20 hours, cooling the reaction liquid to room temperature after the reaction is finished, and pouring the reaction liquid into water. Then extracted with dichloromethane (3X 25mL) and the organic phases were combined and washed with saturated NaCl solution (3X 25 mL). Anhydrous Na for organic phase2SO4 was dried overnight. After filtration, the filtrate was rotary evaporated to remove the organic solvent to give 5.62g of product iii (PNDA), yield: 88.6%, purity: 99.07 percent.
Property test
1. Absorption spectrum experiment
Anthraquinone derivative PNDA vs Cu2+Identification of absorption spectra
FIG. 1 is a diagram of probe molecules PNDA (example 1) vs. Cu2+Selective absorption spectrum identification. 10. mu.L of a metal ion solution (Ca) having a concentration of 0.1mol/L (1-fold molar mass) was added to 10mL of a probe molecule PNDA solution having a concentration of 0.1mmol/L, respectively2+、Na+、Ag+、Mg2+、Co2+、Al3+、Hg2+、Ni2+、K+、Cd2+、Pb2+、Zn2+、Cu2+). The solution system used in the experiment is a mixed solution of acetonitrile/water (3:1, v: v), and the absorption spectrum of the mixed solution is in Shimadzu UV-2450 type ultraviolet spectrophotometryAnd (4) measuring.
From FIG. 1, it can be seen that the absorption of the probe molecule PNDA (example 1) in the mixed solution of acetonitrile/water (3:1, v: v) is about 373nm, and when we add excessive metal ions into the probe molecule solution, we find that only after adding Cu2+Then, the absorption red of the solution is shifted to about 425nm, the color of the solution is changed from yellow green to orange yellow, and when other metal ions are added into the probe molecule solution, the phenomenon does not occur, which shows that the absorption spectrum of the probe molecule to Cu2+Has unique response.
FIG. 2 is Cu2+Absorbance spectrum titration plot for probe molecule PNDA (example 1). 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.2, 1.5, 2.0 times the molar amount of Cu is added to 10mL of probe PNDA solution with the concentration of 0.1mmol/L in sequence2+. The solution system used in the experiment was a mixed solution of acetonitrile/water (3:1, v: v), and the absorption spectrum was measured on an Shimadzu UV-2450 ultraviolet spectrophotometer. As can be seen from FIG. 2, with Cu2+The absorption wavelength of the solution is gradually red-shifted from 373nm to 425nm when Cu is added2+After the addition amount reaches 1 time of the molar amount of the probe molecules, the absorption wavelength of the solution does not move any more, and the intensity of the peak is basically unchanged. This indicates that the probe molecules PNDA and Cu2+Is 1:1 coordinated.
2. Fluorescence spectrum experiment
Anthraquinone derivative PNDA vs Cu2+Fluorescent identification of
FIG. 3 is a graph of probe molecules PNDA (example 1) vs. Cu2+Selective fluorescence spectrum identification. Probe molecule PNDA is dissolved in acetonitrile/water (3:1, v: v) mixed solution to prepare solution with concentration of 10 μmol/L, and metal ions (Ca) with 1 time of molar weight are added into the solution respectively2+、Na+、Ag+、Mg2+、Co2+、Al3+、Hg2+、Ni2+、K+、Cd2+、Pb2+、Zn2+、Cu2+). The excitation wavelength was 420nm, and the fluorescence spectrum of the solution was measured. As can be seen from FIG. 3, the probe molecule solution has only one at 550nmWeak fluorescence emission peak when Cu is added2+Then, a strong fluorescence emission peak appears at 490nm in the solution, but the phenomenon does not occur when other metal ions are added, which indicates that the probe molecule is applied to Cu2+Exhibits very strong fluorescent selective recognition. The solution system used in the experiment was a mixed solution of acetonitrile/water (3:1, v: v), and the fluorescence spectra were measured on an AMINCO Bowman Series 2 fluorescence spectrometer.
FIG. 4 is Cu2+Fluorescence spectrum titration plot for probe molecule PNDA (example 1). To a 10. mu. mol/L acetonitrile/water (3:1, v: v) mixed solution of the probe molecule PNDA, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.2, 1.5, 2.0 times the molar amount of Cu was added2+. Excitation at 420nm, the emission spectrum of the solution was measured, as shown with Cu2+Is increased, a new fluorescence emission peak appears at 490nm, and the intensity of the fluorescence emission peak is changed with Cu2+When Cu is added, the strength is increased continuously2+When the amount of the probe molecules is 1-fold molar weight, the emission peak intensity at 490nm is not substantially increased.
FIG. 5 shows Cu2+Graph of the effect of reaction time with probe molecule PNDA (example 1) on the fluorescence intensity of the solution. To a 10. mu. mol/L acetonitrile/water (3:1, v: v) mixed solution of probe molecules PNDA, 1-fold molar amount of Cu was added2+. The fluorescence intensity of the solution was recorded at 0, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0 minutes at an excitation wavelength of 420nm and an emission wavelength of 490nm, respectively. As shown in the figure, Cu is added into a probe molecule PNDA solution2+After 2 minutes, the fluorescence intensity reached a maximum and remained essentially constant over time.
FIG. 6 shows the selective recognition of Cu for probe PNDA (example 1) in the presence of other coexisting metal ions in solution2+Influence graph of (c). To a 10. mu. mol/L acetonitrile/water (3:1, v: v) mixed solution of probe molecules PNDA, metal ions (Ca) in an amount of 10 times the molar amount were added2+、Na+、Ag+、Mg2+、Co2+、Al3+、Hg2+、Ni2+、K+、Cd2+、Pb2+、Zn2+) Measuring the fluorescence intensity of the solution at an excitation wavelength of 420nm and an emission wavelength of 490nm, and adding 1-fold molar amount of Cu into the solution2 +The fluorescence intensity of the solution was measured at an excitation wavelength of 420nm and an emission wavelength of 490nm, and it can be seen from FIG. 6 that when other metal ions are present in large amounts in the solution, the probe molecules PNDA are paired with Cu2+Is not affected.
FIG. 7 shows the selective recognition of Cu by probe PNDA (example 1) at different pH values2+Influence graph of (c). Adjusting the pH value of a mixed solution of 10 mu mol/L acetonitrile/water (3:1, v: v) of the probe molecule PNDA by using hydrochloric acid or sodium hydroxide solutions with different concentrations respectively, and measuring the fluorescence intensity of the probe solution under the conditions of an excitation wavelength of 420nm and an emission wavelength of 490 nm; then adding 1 time of molar weight of Cu into the solution2+And measuring the fluorescence intensity of the solution under the conditions of excitation wavelength of 420nm and emission wavelength of 490 nm. As can be seen from FIG. 7, the probe molecule pairs Cu in the pH range of 5-102+All have good fluorescence response and are relatively stable, which shows that the probe can detect Cu in wider environment2+。
FIG. 8 shows the probe PNDA (example 1) in different Cu2+Concentration versus fluorescence intensity. It can be seen from the figure that when Cu is added2+The concentration showed good linear relationship in the range of 0.05-0.6mmol/L (R2 ═ 0.9983), and the ordinate I is the probe solution added with Cu2+The fluorescence intensity measured thereafter, I0For probe solution without adding Cu2+The fluorescence intensity measured thereafter, the detection limit calculated using the 3. sigma. IUPAC standard was 2.37X 10-7mol/L。
Claims (3)
1. Anthraquinone derivative used as non-disease diagnosis fluorescent chemical sensor for detecting Cu2+The non-disease diagnostic use of (a), characterized by: the anthraquinone derivative is prepared by the following method:
firstly, 2-aminoanthraquinone reacts with chloroacetyl chloride in the presence of an alkaline reagent to obtain a compound II;
secondly, reacting the compound II with m-phenylenediamine in the presence of an alkaline reagent to obtain a compound III;
wherein: the reaction solvent in the first step is at least one of dichloromethane, chloroform and tetrahydrofuran;
in the first step, the mol ratio of the 2-aminoanthraquinone to the chloracetyl chloride is 1: 1-1.5, wherein the molar ratio of the 2-aminoanthraquinone to the alkaline reagent in the first step is 1: 1-10;
in the second reaction step: the molar ratio of the compound II to the m-phenylenediamine is 2-3: 1, and the molar ratio of the m-phenylenediamine to the alkaline reagent in the second step is 1:1 to 5.
2. Use according to claim 1, characterized in that: the first step reaction is carried out under the condition of an alkaline reagent, and the alkaline reagent in the first step is at least one of 4-dimethylaminopyridine, pyridine and triethylamine.
3. Use according to claim 1, characterized in that: in the second reaction step: the reaction solvent is at least one of acetonitrile, dichloromethane and ethanol; the alkaline reagent in the second step is at least one of N, N-diisopropylethylamine, anhydrous potassium carbonate, 4-dimethylaminopyridine, pyridine and triethylamine.
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AU4679985A (en) * | 1984-08-01 | 1986-02-25 | Biber Rudolf | Neue immunwirksame verbindungen |
JP3127163B2 (en) * | 1991-05-15 | 2001-01-22 | コニカ株式会社 | Melt-type thermal transfer recording ink sheet and image recording medium |
RU2246495C1 (en) * | 2003-11-04 | 2005-02-20 | Государственное образовательное учреждение высшего профессионального образования "Ивановский государственный химико-технологический университет" (ГОУВПО "ИГХТУ") | Tetra-6-(para-sulfophenylene)-anthraquinone porphyrazine metal chelates |
US7635596B2 (en) * | 2004-12-15 | 2009-12-22 | Rohm And Haas Company | Method for monitoring degradation of lubricating oils |
KR100957058B1 (en) * | 2008-04-23 | 2010-05-13 | 고려대학교 산학협력단 | Derivative of Anthraquinone capable of using Cu II selectively and manufacturing method thereof |
WO2012121973A1 (en) * | 2011-03-04 | 2012-09-13 | Life Technologies Corporation | Compounds and methods for conjugation of biomolecules |
FR2990852A1 (en) * | 2012-05-24 | 2013-11-29 | Oreal | ANIONIC DYE OR ANONIUM DYE AGAINST AMMONIUM OR PHOSPHONIUM ION, DYE COMPOSITION COMPRISING SAME, AND PROCESS FOR COLORING KERATINIC FIBERS FROM THESE DYES |
CN105352920A (en) * | 2015-10-08 | 2016-02-24 | 河南师范大学 | Method using 1,4-dihydroxy-9,10-anthraquinone thiosemicarbazone compound as fluorescent probe to detect copper ions |
CN105223176A (en) * | 2015-10-08 | 2016-01-06 | 河南师范大学 | One utilizes Isosorbide-5-Nitrae-dihydroxy-9,10-anthraquinone shrink poplar hydrazide compound to detect the method for copper ion as fluorescence probe |
CN105820811B (en) * | 2016-04-28 | 2017-03-08 | 南京晓庄学院 | A kind of fluorescence probe and synthetic method and its application |
CN106045878B (en) * | 2016-05-12 | 2017-11-03 | 山西大学 | A kind of anthraquinone derivative and its synthetic method and detection Cu2+In application |
CN109975254B (en) * | 2017-12-27 | 2021-05-04 | 南京晓庄学院 | Preparation method of anthraquinone derivative |
CN108863975B (en) * | 2018-01-31 | 2019-05-21 | 南京晓庄学院 | A kind of preparation method of zinc ion probe |
CN108250198B (en) * | 2018-03-20 | 2019-01-22 | 南京晓庄学院 | A kind of julolidine derivative and its preparation method and application |
CN108358815A (en) * | 2018-03-30 | 2018-08-03 | 南京晓庄学院 | A kind of Cu2+The preparation method and application of fluorescence probe |
CN109232394A (en) * | 2018-10-30 | 2019-01-18 | 四川中科微纳科技有限公司 | A kind of fluorescent molecule, preparation method and application identifying copper ion |
CN111579542B (en) * | 2019-12-20 | 2021-02-02 | 南京晓庄学院 | Application of derivative |
-
2019
- 2019-12-20 CN CN202010589147.4A patent/CN111579542B/en not_active Expired - Fee Related
- 2019-12-20 CN CN202010589139.XA patent/CN111718276B/en not_active Expired - Fee Related
- 2019-12-20 CN CN201911328105.9A patent/CN110922338B/en not_active Expired - Fee Related
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CN110922338A (en) | 2020-03-27 |
CN111718276B (en) | 2021-03-30 |
CN111704557B (en) | 2021-02-02 |
CN111704557A (en) | 2020-09-25 |
CN111579542A (en) | 2020-08-25 |
CN111718276A (en) | 2020-09-29 |
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