CN115093433A - Hydrophilic organic near-infrared absorption dye and preparation method and application thereof - Google Patents
Hydrophilic organic near-infrared absorption dye and preparation method and application thereof Download PDFInfo
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- C09D11/50—Sympathetic, colour changing or similar inks
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Abstract
The invention discloses a hydrophilic organic near-infrared absorption dye and a preparation method and application thereof. The dye is 4,4' - ((6, 7-bis (4- (2- (2- (2-methoxyethoxy) ethoxy) phenyl) - [1,2,5] thiadiazolo [3,4-g ] quinoxaline-4, 9-diyl) bis (thiophene-5, 2-diyl)) diphenylamine, 4, 9-bis (5-bromothien-2-yl) -6, 7-bis (4- (2- (2- (2-methoxyethoxy) ethoxy) phenyl) - [1,2,5] thiadiazolo [3,4-g ] quinoxaline, 4-aminobenzeneboronic acid pinacol ester, dissolving palladium tetrakis (triphenylphosphine) and potassium carbonate in tetrahydrofuran and water, and carrying out reflux reaction under an inert atmosphere to obtain the palladium-tetrakis (triphenylphosphine) and potassium carbonate. The dye has good hydrophilicity and light stability, and a wide absorption band of 600-1000 nm; can be applied to near infrared absorption anti-counterfeiting ink.
Description
Technical Field
The invention belongs to the technical field of preparation of organic near-infrared absorption dyes, and particularly relates to a hydrophilic organic near-infrared absorption dye as well as a preparation method and application thereof.
Background
The problem of counterfeit of value documents, securities, trademarks, etc. by lawless persons has become a hazard to today's social order. The existing printing anti-counterfeiting ink mainly comprises ultraviolet fluorescent anti-counterfeiting ink, infrared fluorescent anti-counterfeiting ink, magnetic anti-counterfeiting ink, thermosensitive anti-counterfeiting ink, photochromic anti-counterfeiting ink and the like. The anti-counterfeiting ink has the problems of low technical content and easy imitation. Therefore, recently developed near-infrared absorbing anti-counterfeiting inks have been produced. The near infrared absorption anti-counterfeiting ink is mainly prepared by adding a material with near infrared absorption into the ink, wherein the requirement of the near infrared absorption material is that the maximum absorption wavelength falls within the range of 700-1100 nm. The anti-counterfeiting ink is characterized by no trace in sunlight, and corresponding signals or dark pictures and texts can be observed under a specific detection instrument. The requirements for the near-infrared absorption anti-counterfeiting material are good illumination resistance stability, proper hydrophilicity for being suitable for water-based ink, good anti-counterfeiting effect and high counterfeiting difficulty. Therefore, it is very important to select suitable pigments for near infrared absorption anti-counterfeiting ink.
At present, relevant researchers have achieved certain achievements in the research of near-infrared absorption anti-counterfeiting ink materials. For example, an infrared absorption anti-counterfeiting ink synthesized in the Chinese patent of infrared absorption anti-counterfeiting ink is convenient for detecting anti-counterfeiting characteristics, but the pigment used in the ink is an inorganic pigment containing copper ions, phosphate ions, carbonate ions and the like, so that the introduction and accumulation of the heavy metal ions in the environment can cause harm to the environment. The Chinese patent 'a water-based near-infrared absorption ink-jet ink and a preparation method thereof' synthesizes the water-based near-infrared absorption ink-jet ink, and compared with the traditional solvent-based ink, the ink has the advantages of environmental friendliness, simple and feasible printing mode, convenient inspection and the like; however, the aqueous near-infrared absorbing material used by the ink is a phthalocyanine dye with a sulfonate group, and the dye has poor stability, so that the defect of insufficient durability of the anti-counterfeiting ink is caused. The Chinese patent 'alcohol-soluble dye type infrared anti-counterfeiting ink and a manufacturing method thereof' invents the alcohol-soluble dye type infrared anti-counterfeiting ink, the ink has obvious infrared absorption characteristics, and can realize light-color or even colorless printing; however, the methine cyanine dye used in the anti-counterfeiting ink has poor stability and poor hydrophilicity, and has the defects of durability and environmental friendliness.
Therefore, it is imperative to develop a near infrared absorption anti-counterfeiting material which has good hydrophilicity and stability and is harmless to the environment.
Disclosure of Invention
In order to solve the defects and shortcomings of the prior art, the invention introduces two neutral hydrophilic groups triethylene glycol on the middle core of a donor-acceptor-donor molecular structure taking benzothiadiazoloquinoxaline as an acceptor core, and introduces two anilino groups on two sides as basic hydrophilic modified groups, thereby synergistically promoting the hydrophilicity of the dye and being beneficial to the application of the dye in water-based ink. In addition, the long-chain structure of the two triethylene glycols on the middle core can effectively avoid large planarity caused by large conjugation, and avoid stacking between molecules, thereby improving the light stability of the dye. The absorption of the dye can be expanded to a near infrared region, and the near infrared absorption dye has high stability and can not be deteriorated under the continuous irradiation of near infrared light. In addition, the amino group may also serve as a site for further modification. The dye can be applied as a near-infrared absorption material in near-infrared absorption anti-counterfeiting ink.
The invention aims to provide a hydrophilic organic near-infrared absorption dye, a preparation method of the dye and application of the dye as a near-infrared absorption material in near-infrared absorption anti-counterfeiting ink.
The purpose of the invention is realized by the following technical scheme:
the invention provides a hydrophilic organic near-infrared absorption dye. The organic near-infrared absorbing dye is 4,4' - ((6, 7-bis (4- (2- (2- (2-methoxyethoxy) ethoxy) phenyl) - [1,2,5] thiadiazolo [3,4-g ] quinoxaline-4, 9-diyl) bis (thiophene-5, 2-diyl)) diphenylamine, and has the following structural formula:
the invention provides a preparation method of a hydrophilic organic near-infrared absorption dye, which comprises the following steps:
dissolving 4, 9-bis (5-bromothiophene-2-yl) -6, 7-bis (4- (2- (2- (2-methoxyethoxy) ethoxy) phenyl) - [1,2,5] thiadiazolo [3,4-g ] quinoxaline, 4-aminobenzeneboronic acid pinacol ester, tetrakis (triphenylphosphine) palladium and potassium carbonate in tetrahydrofuran and water, introducing inert gas to enable the reaction system to be in an inert atmosphere, carrying out reflux reaction, and purifying to obtain the dye.
Preferably, the molar ratio of 4, 9-bis (5-bromothien-2-yl) -6, 7-bis (4- (2- (2- (2-methoxyethoxy) ethoxy) phenyl) - [1,2,5] thiadiazolo [3,4-g ] quinoxaline to 4-aminophenylboronic acid pinacol ester is 1: 2-4.
Preferably, the molar ratio of 4, 9-bis (5-bromothien-2-yl) -6, 7-bis (4- (2- (2- (2-methoxyethoxy) ethoxy) phenyl) - [1,2,5] thiadiazolo [3,4-g ] quinoxaline to tetrakis (triphenylphosphine) palladium is 1: 0.1-0.2.
Preferably, the molar ratio of 4, 9-bis (5-bromothien-2-yl) -6, 7-bis (4- (2- (2- (2-methoxyethoxy) ethoxy) phenyl) - [1,2,5] thiadiazolo [3,4-g ] quinoxaline to potassium carbonate is 1: 4-6.
Preferably, the molar volume ratio of the 4, 9-bis (5-bromothien-2-yl) -6, 7-bis (4- (2- (2- (2-methoxyethoxy) ethoxy) phenyl) - [1,2,5] thiadiazolo [3,4-g ] quinoxaline to tetrahydrofuran is 1 mmol: 100 and 120 mL.
Preferably, the molar volume ratio of the 4, 9-bis (5-bromothien-2-yl) -6, 7-bis (4- (2- (2- (2-methoxyethoxy) ethoxy) phenyl) - [1,2,5] thiadiazolo [3,4-g ] quinoxaline to water is 1 mmol: 20-30 mL.
Preferably, the temperature of the reflux reaction is 70 to 80 ℃.
Preferably, the reflux reaction time is 12 to 18 hours.
Preferably, the inert atmosphere is nitrogen.
Preferably, the purification is silica gel chromatography.
Further preferably, the eluent for silica gel chromatography is dichloromethane/methanol.
The invention also provides application of the hydrophilic organic near-infrared absorption dye as a near-infrared absorption material in near-infrared absorption anti-counterfeiting ink.
The product synthesized by the preparation method is 4,4' - ((6, 7-bis (4- (2- (2- (2-methoxyethoxy) ethoxy) phenyl) - [1,2,5]]Thiadiazolo [3,4-g]Quinoxaline-4, 9-diyl) bis (thiophene-5, 2-diyl) diphenylamine (TQGY-NH) 2 ) Molecular formula is C 54 H 54 N 6 O 8 S 3 The relative molecular mass was 1010.3165. TQGY-NH 2 Is green solid powder; is easily dissolved in organic solvents such as dichloromethane, tetrahydrofuran, N-dimethylformamide and dimethyl sulfoxide, and mixed solvents of water and organic solvents. The synthetic route is as follows:
compared with the prior art, the invention has the following beneficial effects:
(1) the hydrophilic organic near-infrared absorption dye is simple to prepare, good in stability, non-toxic, environment-friendly and good in hydrophilicity. Two neutral hydrophilic groups triethylene glycol are introduced to the middle core of the molecular structure, and two anilino groups are introduced to two sides to serve as basic hydrophilic modified groups, so that the hydrophilicity of the dye is synergistically promoted, and the application of the dye in the water-based ink is facilitated. In addition, the long-chain structure of the two triethylene glycols on the middle core can effectively avoid large planarity caused by large conjugation, and avoid stacking between molecules, thereby improving the light stability of the dye.
(2) The absorption band of the hydrophilic organic near-infrared absorption dye extends to a near-infrared absorption region, and the absorption wavelength in the water-based ink covers 600-1000nm, so that the prepared hydrophilic organic near-infrared absorption dye can be applied to the field of near-infrared absorption anti-counterfeiting ink and has a wide application prospect.
Drawings
FIG. 1 is a scheme showing the synthesis of the organic near infrared absorbing dye of the present invention.
FIG. 2 is a NMR spectrum of 4,4' - ((6, 7-bis (4- (2- (2- (2-methoxyethoxy) ethoxy) phenyl) - [1,2,5] thiadiazolo [3,4-g ] quinoxalin-4, 9-diyl) bis (thiophene-5, 2-diyl)) diphenylamine in example 1.
FIG. 3 is a mass spectrum of the matrix-assisted laser desorption ionization time-of-flight of 4,4' - ((6, 7-bis (4- (2- (2- (2-methoxyethoxy) ethoxy) phenyl) - [1,2,5] thiadiazolo [3,4-g ] quinoxalin-4, 9-diyl) bis (thiophene-5, 2-diyl) diphenylamine in example 1.
FIG. 4 is a graph of the absorption spectrum of 4,4' - ((6, 7-bis (4- (2- (2- (2-methoxyethoxy) ethoxy) phenyl) - [1,2,5] thiadiazolo [3,4-g ] quinoxalin-4, 9-diyl) bis (thiophene-5, 2-diyl) diphenylamine in example 4 in aqueous ink.
FIG. 5 is a graph showing the change in absorbance of 4,4' - ((6, 7-bis (4- (2- (2- (2-methoxyethoxy) ethoxy) phenyl) - [1,2,5] thiadiazolo [3,4-g ] quinoxaline-4, 9-diyl) bis (thiophene-5, 2-diyl) diphenylamine at 808nm laser irradiation in example 4.
Detailed Description
The following description of the embodiments of the present invention is provided in connection with the accompanying drawings and examples, but the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available commercially.
The 4, 9-bis (5-bromothien-2-yl) -6, 7-bis (4- (2- (2- (2-methoxyethoxy) ethoxy) phenyl) - [1,2,5] thiadiazolo [3,4-g ] quinoxaline used in the following examples was prepared by the method reported with reference to U.S. Pat. No. 3, 1, US 2012/0322944A. The method comprises the following specific steps: dissolving 6, 7-bis (4- (2- (2- (2-methoxyethoxy) ethoxy) phenyl) -4, 9-bis (thien-2-yl) - [1,2,5] thiadiazolo [3,4-g ] quinoxaline and N-bromosuccinimide in a mixed solvent of chloroform and acetic acid at a volume ratio of 1:1, followed by stirring the reaction solution in the dark for 3 hours; after completion of the reaction, the reaction product was extracted with ethyl acetate and water, and the organic phase was dried over anhydrous magnesium sulfate and separated by silica gel column chromatography to give 4, 9-bis (5-bromothien-2-yl) -6, 7-bis (4- (2- (2- (2-methoxyethoxy) ethoxy) phenyl) - [1,2,5] thiadiazole [3,4-g ] and [3,4-g ] quinoxaline.
Example 1
The organic near infrared absorbing dye of this example, 4' - ((6, 7-bis (4- (2- (2- (2-methoxyethoxy) ethoxy) phenyl) - [1,2,5]]Thiadiazolo [3,4-g]Quinoxaline-4, 9-diyl) bis (thiophene-5, 2-diyl) diphenylamine (TQGY-NH) 2 ) The synthesis route of (2) is shown in figure 1, and the specific steps are as follows:
49mg (0.05mmol) of 4, 9-bis (5-bromothien-2-yl) -6, 7-bis (4- (2- (2- (2-methoxyethoxy) ethoxy) phenyl) - [1,2,5]Thiadiazolo [3,4-g]Quinoxaline, 21.82mg (0.10mmol) of 4-aminophenylboronic acid pinacol ester, 5.75mg (0.005mmol) of tetrakis (triphenylphosphine) palladium and 27.53mg (0.2mmol) of potassium carbonate in 5mL of tetrahydrofuran and 1mL of water, followed by introduction of nitrogen into the system, reflux reaction at 70 ℃ for 12 hours, and purification by chromatography on silica gel (the eluent used is dichloromethane/methanol, v/v ═ 20: 1) give the dye 4,4' - ((6, 7-bis (4- (2- (2- (2-methoxyethoxy) ethoxy) phenyl) - [1,2,5] of]Thiadiazolo [3,4-g]Quinoxaline-4, 9-diyl) bis (thiophene-5, 2-diyl) diphenylamine (TQGY-NH) 2 )35mg, yield 74%.
The prepared compound was characterized by nuclear magnetic resonance hydrogen spectroscopy: 1 H NMR(600MHz,DMSO-d 6 ) δ 8.64(s,2H),7.50(s,4H),7.44-7.39(d, J ═ 7.9Hz,4H),7.22(s,2H),6.85-6.84(d, J ═ 5.3Hz,4H),6.70-6.69(d, J ═ 7.6Hz,4H),5.47(s,4H),4.09(s,4H),3.78(s,4H),3.63(s,4H),3.58(s,4H),3.55(s,4H),3.45(s,4H),3.25(s, 6H). The NMR spectrum of the compound is shown in FIG. 2, and the compound is confirmed to be 4,4' - ((6, 7-bis (4- (2- (2- (2-methoxyethoxy) ethoxy) phenyl) - [1,2,5]]Thiadiazolo [3,4-g]Quinoxaline-4, 9-diyl) bis (thiophene-5, 2-diyl)) diphenylamine.
In addition, the prepared compound is further verified by matrix-assisted laser desorption ionization time-of-flight mass spectrometry: MALDITOF-MS (ESI, M/z) theoretically calculated molecular mass to charge ratio of [ M + H] + C 54 H 55 N 6 O 8 S 3 1011.3243, the actual measured molecular mass-to-charge ratio is: 1011.3275, respectively; the matrix-assisted laser desorption ionization time-of-flight mass spectrum is shown in fig. 3. Illustrative of the compound 4,4' - ((6, 7-bis (4- (2- (2- (2-methoxyethoxy) ethoxy) phenyl) - [1,2,5] is prepared]Thiadiazolo [3,4-g]The structure of quinoxaline-4, 9-diyl) bis (thiophene-5, 2-diyl)) diphenylamine is expected.
Example 2
The organic near-infrared absorbing dye of this example, 4' - ((6, 7-bis (4- (2- (2- (2-methoxyethoxy) ethoxy) phenyl) - [1,2,5]]Thiadiazolo [3,4-g]Quinoxaline-4, 9-diyl) bis (thiophene-5, 2-diyl) diphenylamine (TQGY-NH) 2 ) The synthesis route of (A) is shown in figure 1, and the specific steps are as follows:
118mg (0.12mmol) of 4, 9-bis (5-bromothien-2-yl) -6, 7-bis (4- (2- (2- (2-methoxyethoxy) ethoxy) phenyl) - [1,2,5]Thiadiazolo [3,4-g]Quinoxaline, 78.83mg (0.36mmol) of 4-aminophenylboronic acid pinacol ester, 20.79mg (0.018mmol) of tetrakis (triphenylphosphine) palladium and 82.87mg (0.60mmol) of potassium carbonate are dissolved in 13mL of tetrahydrofuran and 3mL of water, and the system is then purged with nitrogen, refluxed at 75 ℃ for 15 hours, and then purified by chromatography on silica gel (the eluent used is dichloromethane/methanol, v/v ═ 20: 1) to give the dye 4,4' - ((6, 7-bis (4- (2- (2- (2-methoxyethoxy) ethoxy) phenyl) - [1,2,5] of the formula]Thiadiazolo [3,4-g]Quinoxaline-4, 9-diyl) bis (thiophene-5, 2-diyl) diphenylamine (TQGY-NH) 2 )90mg, yield 79%.
The compound TQGY-NH obtained in this example 2 The characterization of (2) was the same as the characterization result in example 1.
Example 3
The organic near infrared absorbing dye of this example, 4' - ((6, 7-bis (4- (2- (2- (2-methoxyethoxy) ethoxy) phenyl) - [1,2,5]]Thiadiazolo [3,4-g]Quinoxaline-4, 9-diyl) bis (thiophene-5, 2-diyl) diphenylamine (TQGY-NH) 2 ) The synthesis route of (A) is shown in figure 1, and the specific steps are as follows:
248mg (0.25mmol) of 4, 9-bis (5-bromothien-2-yl) -6, 7-bis (4- (2- (2- (2-methoxyethoxy) ethoxy) phenyl) - [1,2,5]Thiadiazolo [3,4-g]Quinoxaline, 220.90mg (1.0mmol) of 4-aminophenylboronic acid pinacolThe alcohol ester, 58.25mg (0.05mmol) tetrakis (triphenylphosphine) palladium and 208.99mg (1.5mmol) potassium carbonate were dissolved in 30mL tetrahydrofuran and 7.5mL water, and then the system was purged with nitrogen and refluxed at 80 ℃ for 18 hours, followed by purification by silica gel chromatography (the eluent used was dichloromethane/methanol, v/v ═ 20: 1) to give the dye 4,4' - ((6, 7-bis (4- (2- (2-methoxyethoxy) ethoxy) phenyl) - [1,2,5] as a crude product]Thiadiazolo [3,4-g]Quinoxaline-4, 9-diyl) bis (thiophene-5, 2-diyl) diphenylamine (TQGY-NH) 2 )195mg, 81% yield.
The compound TQGY-NH obtained in this example 2 The characterization of (2) was the same as the characterization result in example 1.
Example 4
Organic near infrared absorbing dye TQGY-NH 2 Absorption spectrum test in resin for aqueous ink.
5.05mg of the dye 4,4' - ((6, 7-bis (4- (2- (2- (2-methoxyethoxy) ethoxy) phenyl) - [1,2,5] prepared in example 1 are added]Thiadiazolo [3,4-g]Quinoxaline-4, 9-diyl) bis (thiophene-5, 2-diyl) diphenylamine (TQGY-NH) 2 ) Dissolved in 5mL of a resin for aqueous ink. When tested, the test temperature was 25 ℃ and the results are shown in FIG. 4. As can be seen from FIG. 4, the dye prepared by the present invention has a strong absorption band (the wavelength corresponding to the maximum absorbance is 800nm) in the range of 600-1000nm in the resin for aqueous ink. The dye is hydrophilic, has strong near infrared absorption capacity and is suitable for being used as a near infrared absorption dye in water-based ink.
Organic near infrared absorbing dye TQGY-NH 2 Stability test of (2).
The dye 4,4' - ((6, 7-bis (4- (2- (2- (2-methoxyethoxy) ethoxy) phenyl) - [1,2,5] prepared in example 1 was used]Thiadiazolo [3,4-g]Quinoxaline-4, 9-diyl) bis (thiophene-5, 2-diyl) diphenylamine (TQGY-NH) 2 ) Compound stock solution prepared at 1mM in dimethylsulfoxide. The mother liquor was diluted with dimethyl sulfoxide to a final concentration of 20 μ M in a total test volume of 3mL at a test temperature of 25 ℃. 808nm is used as excitation wavelength, and the power is 80mW/cm 2 The dye was continuously irradiated and subsequently irradiated at a rate of 0, 10, 20, 30, 40,the absorption spectra were measured at 50, 60 minutes and plotted as absorbance at 800 nm. The change of the measured absorbance along with the laser irradiation time is shown in fig. 5, and it can be seen from fig. 5 that the absorbance of the dye molecule at the wavelength of 800nm is almost unchanged under the continuous radiation of 808nm laser, which shows that the organic near-infrared dye molecule prepared by the invention has good light stability and is suitable for the application in the field of near-infrared absorption anti-counterfeiting ink.
The above examples are preferred embodiments of the present invention, but the present invention is not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A hydrophilic organic near-infrared absorbing dye, wherein the organic near-infrared absorbing dye is 4,4' - ((6, 7-bis (4- (2- (2- (2-methoxyethoxy) ethoxy) phenyl) - [1,2,5] thiadiazolo [3,4-g ] quinoxaline-4, 9-diyl) bis (thiophene-5, 2-diyl)) diphenylamine having the following structural formula:
2. the method of claim 1, comprising the steps of:
dissolving 4, 9-bis (5-bromothiophene-2-yl) -6, 7-bis (4- (2- (2- (2-methoxyethoxy) ethoxy) phenyl) - [1,2,5] thiadiazolo [3,4-g ] quinoxaline, 4-aminobenzeneboronic acid pinacol ester, tetrakis (triphenylphosphine) palladium and potassium carbonate in tetrahydrofuran and water, introducing inert gas to enable the reaction system to be in an inert atmosphere, carrying out reflux reaction, and purifying to obtain the dye.
3. The method of claim 2, wherein the molar ratio of 4, 9-bis (5-bromothien-2-yl) -6, 7-bis (4- (2- (2- (2-methoxyethoxy) ethoxy) phenyl) - [1,2,5] thiadiazolo [3,4-g ] quinoxaline to 4-aminophenylboronic acid pinacol ester is 1: 2-4.
4. The method of claim 2, wherein the molar ratio of 4, 9-bis (5-bromothien-2-yl) -6, 7-bis (4- (2- (2- (2-methoxyethoxy) ethoxy) phenyl) - [1,2,5] thiadiazolo [3,4-g ] quinoxaline to tetrakis (triphenylphosphine) palladium is 1: 0.1-0.2.
5. The method of claim 2, wherein the molar ratio of 4, 9-bis (5-bromothien-2-yl) -6, 7-bis (4- (2- (2- (2-methoxyethoxy) ethoxy) phenyl) - [1,2,5] thiadiazolo [3,4-g ] quinoxaline to potassium carbonate is 1: 4-6.
6. The method of claim 2, wherein the molar volume ratio of 4, 9-bis (5-bromothien-2-yl) -6, 7-bis (4- (2- (2- (2-methoxyethoxy) ethoxy) phenyl) - [1,2,5] thiadiazolo [3,4-g ] quinoxaline to tetrahydrofuran is 1 mmol: 100 and 120 mL.
7. The method of claim 2, wherein the molar volume ratio of 4, 9-bis (5-bromothien-2-yl) -6, 7-bis (4- (2- (2- (2-methoxyethoxy) ethoxy) phenyl) - [1,2,5] thiadiazolo [3,4-g ] quinoxaline to water is 1 mmol: 20-30 mL.
8. The method of claim 2, wherein the inert atmosphere is nitrogen; the temperature of the reflux reaction is 70-80 ℃; the time is 12-18 hours.
9. The method of claim 2, wherein the purification is silica gel chromatography; the eluent for silica gel chromatography is dichloromethane/methanol.
10. Use of a hydrophilic organic near-infrared absorbing dye according to claim 1 as a near-infrared absorbing material in a near-infrared absorbing security ink.
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