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WO2020258510A1 - Agent fluorescent à petites molécules et son procédé de préparation - Google Patents

Agent fluorescent à petites molécules et son procédé de préparation Download PDF

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Publication number
WO2020258510A1
WO2020258510A1 PCT/CN2019/103709 CN2019103709W WO2020258510A1 WO 2020258510 A1 WO2020258510 A1 WO 2020258510A1 CN 2019103709 W CN2019103709 W CN 2019103709W WO 2020258510 A1 WO2020258510 A1 WO 2020258510A1
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WIPO (PCT)
Prior art keywords
chlorophyll
fluorescent agent
small molecule
molecule fluorescent
aqueous solution
Prior art date
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Ceased
Application number
PCT/CN2019/103709
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English (en)
Chinese (zh)
Inventor
刘意
刘耿
孙福强
张林秀
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ankangdemei (zhongshan) Nano Technology Co Ltd
Guangdong Pharmaceutical University
Original Assignee
Ankangdemei (zhongshan) Nano Technology Co Ltd
Guangdong Pharmaceutical University
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Publication of WO2020258510A1 publication Critical patent/WO2020258510A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D207/33—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D207/333—Radicals substituted by oxygen or sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/13—Crystalline forms, e.g. polymorphs
    • 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
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom

Definitions

  • the invention relates to the field of chemical materials, in particular to a small molecule fluorescent agent and a preparation method thereof.
  • organic luminescent materials have received extensive attention and applications in the fields of optoelectronics and biology due to their strong luminous efficiency, adjustable luminous color and better biocompatibility.
  • Traditional fluorescent molecules generally have a large ⁇ -conjugated rigid structure, which makes them have higher luminous efficiency in dilute solutions.
  • the luminescence weakens or even disappears, and the quantum yield is reduced. Produces the phenomenon of aggregation quenching fluorescence in the field of photophysics.
  • small-molecule fluorescent agents usually exhibit fluorescence quenching when encountering certain substances (such as amines).
  • Most blue-light small-molecule fluorescent agents are anthracene, such as 2-chloro-bis(4-methoxy)anthracene.
  • the synthesis method of conventional small molecule fluorescent agent needs to follow a specific synthesis route, through complicated synthesis steps, processes and post-processing, etc., in order to achieve the synthesis goal; and conventional small molecule fluorescent agent achieves the required concentration of effective color development is usually
  • the ⁇ g/mL level is mainly used for analysis and imaging in the field of biomedicine by using its fluorescence quenching phenomenon.
  • the purpose of the present invention is to provide a small molecule fluorescent agent with high luminous efficiency and capable of enhancing fluorescence intensity at a lower concentration in view of the technical problem to be solved.
  • the present invention provides a small molecule fluorescent agent (named: Rb-Cp-S 01), the structure of the small molecule fluorescent agent is shown in the following formula (I):
  • M is any one of Au, Mg or Cu.
  • the chemical formula of the small molecule fluorescent agent is [C 8 H 9 O 2 N 2 S] 2 M, where M is any one of Au, Mg or Cu.
  • the group M is Au (gold), and the structure of the small molecule fluorescent agent is shown in the following formula (II):
  • the chemical formula of the small molecule fluorescent agent is [C 8 H 9 O 2 N 2 S] 2 Au, and it is a white needle-like crystal at room temperature.
  • the small molecule fluorescent agent is a blue fluorescent agent.
  • the present invention also provides a method for preparing the small molecule fluorescent agent.
  • the method includes the following steps: adding citric acid, chlorophyll, and mercaptoethylamine to the ethanol aqueous solution in sequence, stirring and dissolving, and then adding gold chloride or magnesium chloride or chlorination Any one of copper (preferably in the form of a solution) is used as a nucleation inducer, and after continued stirring (preferably 5-15 min), the resulting mixture undergoes a hydrothermal reaction to obtain a product.
  • the weight ratio of citric acid, chlorophyll, mercaptoethylamine and nucleation inducer is 2-8 parts by weight of citric acid, 4-16 parts by weight of chlorophyll, and 1-4 parts by weight Mercaptoethylamine and 0.1 to 0.6 parts by weight of nucleation inducer (for example, gold chloride).
  • gold chloride is used as a nucleation inducer based on strong complexation.
  • the chlorophyll includes but is not limited to one or more of chlorophyll A, chlorophyll B, chlorophyll C, and chlorophyll D, most preferably chlorophyll A.
  • the chlorophyll is a crude chlorophyll extract of a plant.
  • the concentration of the ethanol aqueous solution is an aqueous solution containing 1% to 10% (more preferably 2% to 6%, most preferably 3% to 5%, especially 3%) ethanol by weight percentage.
  • the amount of the ethanol aqueous solution is 100-150 mL.
  • the temperature of the hydrothermal reaction is 150°C to 200°C, more preferably 160°C to 180°C, most preferably 180°C.
  • the hydrothermal reaction time is 2 hours to 5 hours. More preferably, it is 2 hours to 3 hours.
  • the porphyrin nucleus in the chlorophyll (the crude extract is a mixture of multiple components containing the porphyrin ring nucleus) can form a complex with Au 3+ or Mg 2+ or Cu 2+ Due to the strong complexation of gold chloride or magnesium chloride or copper chloride, the porphyrin macrocyclic ring is selectively cracked and opened, and the pyrrole ring unit is mainly generated; in the system, mercaptoethylamine first interacts with Au 3+ or Mg 2 + Or Cu 2+ react for 5-15 minutes to form a complex containing S-Au-S or S-Mg-S or S-Cu-S structure; the double bond oxidation ketone of the side group on the I ring in the porphyrin Acid, the resulting carboxyl group reacts with a complex containing S-Au-S or S-Mg-S or S-Cu-S structure to form an amide structure.
  • the preparation method of the present invention adopts a one-step method, has simple process, strong reaction selectivity, and a yield higher than 60%.
  • the small molecule fluorescent agent of the present invention When the small molecule fluorescent agent of the present invention is a high-efficiency blue fluorescent agent with a new structure, it has high-efficiency fluorescence characteristics and emits blue fluorescence under the action of excitation light at a wavelength of 365 nm.
  • the small molecule fluorescent agent (preferably formulated as an aqueous solution) encounters In the case of small molecules containing -NH 2 compounds such as mercaptoethylamine, cysteine, and glutathione, these compounds will increase the fluorescence intensity of the small molecule fluorescent agent of the present invention by about 3 to 5 times, and its fluorescence intensity will show " The changing law of “enhance first and then quench” can be developed into a specific biosensor for early detection of certain “lesions”.
  • the ultraviolet light with a wavelength of 200-400nm which is unfavorable to the growth and development of crops in natural light, can excite the small molecule fluorescent agent of the present invention, so the latter can absorb less ultraviolet light contained in natural light and emit It produces blue light with a wavelength of 410-470nm, combined with its excellent low cytotoxicity, and can be used as a functional "green" brightener for textiles.
  • the effective dyeing concentration of conventional small molecule fluorescent agents is usually ⁇ g/mL, and the use concentration of the small molecule fluorescent agent of the present invention is ⁇ 30ng/mL to achieve the ideal fluorescent dyeing effect, which is significantly better than conventional small molecules Fluorescent agent.
  • the small molecule fluorescent agent of the present invention uses chlorophyll and citric acid as main raw materials, and chlorophyll is mainly derived from plant extracts, which can reduce dependence on the petrochemical industry and is more environmentally friendly.
  • Figure 1 is the infrared spectrum of the small molecule fluorescent agent of the present invention.
  • Figure 2 shows the fluorescence spectra (sample concentration 200 mg/mL) of the mother liquor of the small molecule fluorescent agent of the present invention prepared under different conditions.
  • Figure 3 is a fluorescence spectrum (sample concentration 300ng/mL) of the mother liquor of the small molecule fluorescent agent of the present invention when gold chloride is used as the nucleating agent.
  • Fig. 4 is the change rule of the fluorescence intensity of the small molecule fluorescent agent of the present invention with the amount of cysteine solution dropped.
  • Fig. 5 is the change rule of the fluorescence intensity of the small molecule fluorescent agent of the present invention with the amount of glutathione solution dropped.
  • the chlorophyll used in the present invention can be a commercially available chlorophyll product, or it can be chlorophyll directly extracted from plants. Those skilled in the art know the extraction method of chlorophyll.
  • torn plant leaves such as masson pine leaves, bauhinia leaves, citrus leaves, spinach leaves, etc.
  • crude plant chlorophyll extract such as masson pine chlorophyll crude extract, bauhinia leaf chlorophyll crude extract, citrus leaf chlorophyll crude extract.
  • the IR in Figure 1 shows that when different nucleation inducers (gold chloride or magnesium chloride or copper chloride) are used, the basic structure of the obtained product is the same, but because the target product has different "S-Au-S" and "S- Mg-S” and "S-Cu-S” structure, so the corresponding information of the map has a small difference.
  • nucleation inducers gold chloride or magnesium chloride or copper chloride
  • each inner lining 20mL put the inner lining into a stainless steel reactor, and react at 180°C for 300 minutes; then naturally cool, filter and recrystallize to obtain the product.
  • the results show that the ethanol content of 1wt%-10wt% is equal It can increase the fluorescence intensity of the product. When the ethanol content is 3wt%, the obtained product is the best.
  • the chlorophyll used in the present invention includes but is not limited to one or more of chlorophyll A, chlorophyll B, chlorophyll C, and chlorophyll D, most preferably chlorophyll A.
  • the following examples 7-11 are based on the dosage ratio of 2-8g citric acid, 4-16g crude masson pine chlorophyll extract, 1-4g mercaptoethanol, 0.1-0.6g gold chloride solution, 100-150mL 1wt%-10wt % Ethanol aqueous solution is hydrothermally reacted at 150°C ⁇ 200°C for 2 ⁇ 5 hours (citric acid, masson pine chlorophyll crude extract, mercaptoethanol are sequentially added to the ethanol aqueous solution, stirred and dissolved, and then added the gold chloride solution, continue After stirring for 5 to 15 minutes, the mixture is subjected to a hydrothermal reaction at 150 to 200°C for 2 to 5 hours, and then cooled, filtered, and recrystallized.
  • the prepared small molecule fluorescent agent (named Rb-Cp-S 01) has a fluorescence enhancement effect Determination.
  • the experimental data is the average result of multiple repetitions.
  • test solution a Weigh 0.05g of cysteine hydrochloride, dissolve it in an appropriate amount of pure water, and then make the volume 10mL (test solution a); weigh the crystal Rb-Cp-S 01 0.001g, dissolve it in 10mL DMSO, and reuse Dilute DMSO and make the volume 100mL (test solution b); take 3mL of test solution a in a quartz cuvette, then add test solution b dropwise to it, and observe the PL and appearance changes of the sample in the quartz cuvette.
  • test solution b Weigh 0.05g of cysteine hydrochloride, dissolve it in an appropriate amount of pure water, and then make the volume 10mL (test solution a); weigh the crystal Rb-Cp-S 01 0.001g, dissolve it in 10mL DMSO, and reuse Dilute DMSO and make the volume 100mL (test solution b); take 3mL of test solution a in a quartz cuvette, then add test solution b dropwise to it, and observe the PL
  • the PL test result in Figure 4 shows that when the drop of cysteine aqueous solution reaches 3 drops (1 drop is 10 ⁇ L, the same below), the fluorescence intensity of the sample begins to increase significantly, and the peak value is reached when 4 or 5 drops are added. The value is more than 3 times stronger than the initial value, and when it is added to a total of 6 drops, the fluorescence intensity drops rapidly, close to the original value.
  • the appearance photos of the corresponding samples under 365nm ultraviolet light also show corresponding changes.
  • test solution c1 mercaptoethylamine
  • Example 9 Weigh 0.01 mL of ethylenediamine, dissolve it in an appropriate amount of pure water, and then dilute to 100 mL (test solution c2); weigh crystal Rb-Cp-S 01 0.001 g, dissolve it in 10 mL DMSO, and then use DMSO Dilute and dilute to 100mL (test solution b); take 3mL of test solution c2 in a quartz cuvette, then add test solution b dropwise to it, and observe the PL and appearance of the sample in the quartz cuvette as follows Figure 4 is similar.
  • test solution d weigh 0.05g of glutathione, dissolve it in an appropriate amount of pure water, and then make the volume 10mL (test solution d); weigh the crystal Rb-Cp-S 01 0.001g, dissolve it in 10mL DMSO, and then dilute with DMSO.
  • the constant volume is 100mL (test solution b); take 3mL of test solution d in a quartz cuvette, then add test solution b dropwise to it, and observe the PL and appearance changes of the sample in the quartz cuvette. The results are shown in Figure 5. Show.
  • the PL test result in Figure 5 shows that the fluorescence intensity of the sample starts to increase significantly when the added cysteine aqueous solution reaches 2 drops; the peak is reached when a total of 4 drops are added, and the intensity value is about 7 times stronger than the initial value.
  • the fluorescence intensity When added to a total of 5 drops or a total of 6 drops, the fluorescence intensity only slightly decreases.
  • the appearance photos of the corresponding samples under 365nm ultraviolet light also show corresponding changes.
  • test solution e Weigh 0.1mL of 25wt% ammonia water, dissolve it in an appropriate amount of pure water, and then make the volume 10mL (test solution e); Weigh the crystal Rb-Cp-S 01 0.001g, dissolve it in 10mL DMSO, then dilute with DMSO and set The volume is 100 mL (test solution b); take 3 mL of test solution e in a quartz cuvette, then add test solution b dropwise to it, and observe the appearance and PL of the sample in the quartz cuvette. The result is the fluorescence characteristics of the sample No significant changes.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un agent fluorescent à petites molécules. La structure de l'agent fluorescent à petites molécules est représentée par la formule I. La présente invention concerne en outre un procédé de préparation de l'agent fluorescent à petites molécules, qui comprend les étapes suivantes consistant à : ajouter de l'acide citrique, de la chlorophylle et de la mercaptoéthylamine dans une solution aqueuse d'éthanol en séquence, agiter pour dissoudre et ajouter ensuite un inducteur de nucléation, continuer à agiter de manière uniforme, et faire subir une réaction hydrothermique au mélange afin d'obtenir un produit. L'agent fluorescent à petite molécule selon la présente invention est un agent fluorescent à lumière bleue à haut rendement ayant une toute nouvelle structure, présente des caractéristiques de fluorescence à haut rendement et émet une fluorescence bleue sous l'action d'une lumière d'excitation ayant une longueur d'onde de 365 nm. De plus, le procédé de préparation selon la présente invention adopte un procédé en une étape, de telle sorte que le procédé est simple, la sélectivité de réaction est élevée, le rendement est haut, et les coûts de production sont faibles.
PCT/CN2019/103709 2019-06-28 2019-08-30 Agent fluorescent à petites molécules et son procédé de préparation Ceased WO2020258510A1 (fr)

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CN201910575232.2A CN110407731A (zh) 2019-06-28 2019-06-28 一种小分子荧光剂及其制备方法
CN201910575232.2 2019-06-28

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009037325A2 (fr) * 2007-09-21 2009-03-26 L'oreal Colorant styryle dérivé d'indole thiol/disulfure, composition colorante comprenant ledit colorant, procédé d'éclaircissement de matériaux à base de kératine au moyen de ce colorant
CN106566540A (zh) * 2016-10-21 2017-04-19 中国科学院长春光学精密机械与物理研究所 一种氮、硫、铜共掺杂碳纳米点及其制备方法与应用
CN109385274A (zh) * 2018-11-13 2019-02-26 广东药科大学 生物质基高效硫氮掺杂碳量子点及其制法与应用

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109674676B (zh) * 2018-11-20 2021-07-09 安康德美（中山）纳米科技有限公司 一种绿色环保发用定型整理剂及制备方法和应用

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009037325A2 (fr) * 2007-09-21 2009-03-26 L'oreal Colorant styryle dérivé d'indole thiol/disulfure, composition colorante comprenant ledit colorant, procédé d'éclaircissement de matériaux à base de kératine au moyen de ce colorant
CN106566540A (zh) * 2016-10-21 2017-04-19 中国科学院长春光学精密机械与物理研究所 一种氮、硫、铜共掺杂碳纳米点及其制备方法与应用
CN109385274A (zh) * 2018-11-13 2019-02-26 广东药科大学 生物质基高效硫氮掺杂碳量子点及其制法与应用

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