WO2023217124A1 - 一种荧光分子、多色体系及其制备方法与应用 - Google Patents

一种荧光分子、多色体系及其制备方法与应用 Download PDF

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WO2023217124A1
WO2023217124A1 PCT/CN2023/092957 CN2023092957W WO2023217124A1 WO 2023217124 A1 WO2023217124 A1 WO 2023217124A1 CN 2023092957 W CN2023092957 W CN 2023092957W WO 2023217124 A1 WO2023217124 A1 WO 2023217124A1
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solution
assembly
fluorescent molecule
hierarchical self
cucurbit
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French (fr)
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陈旭漫
陈晓
刘子豪
李全
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Southeast University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three 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 materials, e.g. electroluminescent or chemiluminescent
    • C09K11/06—Luminescent materials, e.g. electroluminescent or chemiluminescent 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
    • 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
    • G01N21/6447—Fluorescence; Phosphorescence by visual observation
    • G—PHYSICS
    • G06—COMPUTING OR CALCULATING; COUNTING
    • G06Q—INFORMATION AND COMMUNICATION TECHNOLOGY [ICT] SPECIALLY ADAPTED FOR ADMINISTRATIVE, COMMERCIAL, FINANCIAL, MANAGERIAL OR SUPERVISORY PURPOSES; SYSTEMS OR METHODS SPECIALLY ADAPTED FOR ADMINISTRATIVE, COMMERCIAL, FINANCIAL, MANAGERIAL OR SUPERVISORY PURPOSES, NOT OTHERWISE PROVIDED FOR
    • G06Q30/00—Commerce
    • G06Q30/018—Certifying business or products
    • G06Q30/0185—Product, service or business identity fraud
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the invention relates to a fluorescent molecule and a preparation method thereof, a multi-color system containing the fluorescent molecule and the application of the multi-color system in anti-counterfeiting, and belongs to the technical field of organic luminescent materials.
  • Anti-counterfeiting technology is an important means of information protection in human society's social production activities, and is of great significance in solving social problems such as technological plagiarism.
  • the anti-counterfeiting cycle of some traditional anti-counterfeiting technologies is coming to an end.
  • this has promoted the upgrading of traditional anti-counterfeiting technology, and on the other hand, it has also promoted the emergence and development of various new and efficient anti-counterfeiting methods.
  • the use of responsive multi-color luminescent systems to develop anti-counterfeiting technology is one of the many popular research directions in anti-counterfeiting technology.
  • the excitation light-controlled luminescence system is used as a guest molecule to perform host-guest interaction and hierarchical self-assembly with macrocyclic molecules such as cucurbituril. Not only can the luminescence be adjusted by changing the excitation wavelength, but the ratio between the host and guest molecules can also be changed to luminescence. Adjustment greatly enriches the luminous color changes of the multi-color luminescent system. Therefore, studying self-assembled luminescent systems with multi-stimulus responsiveness is of great significance to the development of new anti-counterfeiting technologies.
  • the first purpose of the present invention is to provide a fluorescent molecule.
  • the second purpose of the present invention is to provide a preparation method for the fluorescent molecule.
  • the third purpose of the present invention is Provide a multi-color system containing the fluorescent molecule.
  • the fourth object of the present invention is to provide a preparation method for the multi-color system containing the fluorescent molecule.
  • the fifth object of the present invention is to provide the multi-color system containing the fluorescent molecule. The application of the system in anti-counterfeiting technology.
  • a fluorescent molecule of the present invention which is formed by coupling a carbazolyl structural unit and an alkylpyridinium salt structural unit.
  • the structure of the fluorescent molecule is as follows:
  • n is an integer from 0 to 12.
  • n 1, 3 or 7.
  • a method for preparing fluorescent molecules according to the present invention including the following steps:
  • step (1) the molar ratio of 2,7-dibromocarbazole, 4-pyridineboronic acid and potassium carbonate is 1:1.2-1.5:2-3.
  • the temperature of the heating reaction is 70-120°C, and the time of the heating reaction is 12-18 hours.
  • the halogenated hydrocarbon is bromoethane, 1-bromobutane and 1-bromooctane.
  • the molar ratio of 2,7-bis(4-pyridyl)carbazole and halogenated hydrocarbon is 1:20-30.
  • the reaction temperature is 80-110°C
  • the reaction time is 12-48 hours.
  • the present invention also includes a multi-color luminescent system, which contains the fluorescent molecule of the present invention and cucurbituril.
  • the cucurbituril is cucurbit [7] urea or cucurbit [8] urea.
  • the preparation method of the multi-color luminescent system of the present invention includes the following steps: configuring the fluorescent molecules of the present invention into an aqueous solution with water to obtain solution I, adding cucurbituril to part of the solution I to configure a cucurbituril-luminescent molecule solution , to obtain solution II, which is a multi-color luminescent system.
  • solution I and solution II are mixed according to different proportions to obtain mixed solutions with different proportions, that is, multiple multi-color luminescent systems are obtained.
  • the ratios of solution I and solution II are different, the colors of the multi-color luminescent system that can be obtained are different due to the different ratios between fluorescent molecules and cucurbituril.
  • the ratio of solution I to solution II in the multicolor luminescence system is 1:0.2-3.0.
  • the ratio of solution I to solution II in the multicolor luminescence system is 1:0.1-1.5.
  • the pH of the water is 0-7.
  • the pH of the water is 5.
  • the multi-stimulus-responsive multi-color luminescence system designed by the present invention is a hierarchical self-assembly formed by the interaction between excitation light-regulated fluorescent molecules and excitation light-regulated fluorescent molecules and cucurbituril molecules.
  • the multi-color glow The luminescence behavior of the system can be adjusted by changing the wavelength of the excitation light and adjusting the ratio of host and guest molecules.
  • this multi-luminescent system has rich fluorescent colors and significant effects. It is expected to become a new material in the field of anti-counterfeiting technology.
  • the present invention also includes the application of the multi-color luminescent system in anti-counterfeiting technology.
  • the responsiveness of some components in the multi-color luminescent system to excitation light can be used to develop multi-layer encryption technology.
  • Anti-counterfeiting mechanism of the present invention is achieved by displaying different patterns under different excitation lights in a multi-color luminescent system.
  • the multi-color luminescent system of the present invention consists of background color luminescent molecules, light-controlled luminescent molecules and luminescent hierarchical self-assemblies. Background color luminescent molecules serve as the background, and their luminescent color does not change with the change of the wavelength of the excitation light.
  • Light-controlled luminescent molecules and luminescent hierarchical self-assemblies are used to design specific patterns and display the patterns under fixed excitation wavelengths. When the excitation wavelength is changed to a specific wavelength, some parts of the specific pattern match the background color, and the meaning of the pattern changes. Double-layer anti-counterfeiting is achieved through this principle.
  • the fluorescent molecule of the present invention is formed by coupling a carbazolyl structural unit and an alkylpyridinium salt structural unit. It has excitation light wavelength responsiveness and emits different colors under different excitation lights. Based on this fluorescent molecule, the present invention proposes a new multi-color luminescent system, which is composed of a type of excitation light-regulated fluorescent molecule and a hierarchical self-assembly formed by this type of molecule and cucurbituril molecules.
  • the multi-color luminescent system has the advantages of simple synthesis route, cheap and easily available synthetic raw materials, and simple assembly preparation process. At the same time, the system has dual stimulus responsiveness and significant luminescence effect, and can be used to develop information encryption technology.
  • Figure 1 shows the fluorescence spectra of CPDE, CPDB and CPDO when the excitation light is 330nm and 400nm;
  • Figure 2 is a photo of the fluorescence colors of CPDE, CPDB and CPDO under different excitation lights
  • Figure 3 is the fluorescence spectrum of CPDB under different excitation lights
  • Figure 4 is the fluorescence spectra of CPDB and cucurbit[8]uril in different molar ratios under excitation light of 330nm, 365nm and 400nm;
  • Figure 5 is a photo of the fluorescence colors of CPDB and cucurbit[8]uril at different molar ratios under different excitation lights;
  • Figure 6 is the fluorescence spectra of CPDB and cucurbit[7]urea at 330nm, 365nm and 400nm with different molar ratios;
  • Figure 7 is a photo of the fluorescence colors of CPDB and cucurbit[7]uril at different molar ratios under different excitation lights;
  • Figure 8 is a CIE diagram of the fluorescence colors of CPDB and different molar ratios of cucurbit[8]uril and cucurbit[7]uril under different excitations;
  • Figure 9 is a rendering of the multi-color luminescent system applied to anti-counterfeiting.
  • Figure 1 shows the fluorescence spectra of CPDE, CPDB and CPDO under excitation light of 330nm and 400nm. Among them, (a) is 330nm, and (b) is 400nm. It can be seen from Figure 1 that the fluorescence spectra of CPDE and CPDB are different under the excitation light of 330nm and 400nm. The maximum emission peak wavelengths are approximately 440nm (330nm excitation) and 540nm (400nm excitation) respectively; while the CPDO excitation light is 330nm and 400nm. Under the excitation, there is no obvious difference in the fluorescence spectrum, and the maximum emission peak wavelength is 540nm. Note: CPDE and CPDB have the phenomenon of excitation light regulation and can be used as photoresponsive components. CPDO has no excitation light regulation phenomenon and can be used as background for information camouflage.
  • Figure 2 is a photo of the fluorescence colors of CPDE, CPDB and CPDO under different excitation lights.
  • CPDE and CPDB exhibit blue fluorescence under 330nm excitation light, white fluorescence under 365nm excitation light, and yellow-green fluorescence under 400nm excitation light;
  • CPDO exhibits both 330nm and 400nm excitation light. Shows yellow-green fluorescence.
  • Figure 3 is the fluorescence spectra of CPDB under different excitation lights. It can be seen from Figure 3 that as the excitation wavelength changes from 400nm to 330nm, the maximum emission wavelength of the fluorescent molecule CPDB changes from 540nm to 440nm.
  • Figure 4 is the fluorescence spectra of CPDB and cucurbit[8]uril at different molar ratios under the excitation wavelengths of 330nm, 365nm and 400nm, where (a) is 330nm, (b) is 365nm, and (c) is 400nm. It can be seen from Figure 4 that as the concentration of cucurbit[8]uril increases, the maximum emission wavelength of CPDB finally changes from 540nm and 440nm to 580nm.
  • Figure 5 is a photo of the fluorescence colors of CPDB and cucurbit[8]uril at different molar ratios under different excitation lights.
  • the fluorescent color of CPDB changes from blue to orange under the excitation light of 330nm.
  • the fluorescent color of CPDB changes under the excitation light of 365nm. It shows a white to orange transition.
  • the concentration of cucurbit[8]uril increases, the CPDB fluorescence color exhibits a yellow-green to orange transition under 400nm excitation light.
  • Figure 6 is the fluorescence spectra of CPDB and cucurbit[7]uril at different molar ratios under the excitation wavelengths of 330nm, 365nm and 400nm, where (a) is 330nm, (b) is 365nm, and (c) is 400nm. It can be seen from Figure 6 that as the concentration of cucurbit[7]uril increases, the maximum emission wavelength of CPDB From 540nm and 440nm to 530nm.
  • Figure 7 is a photo of the fluorescence colors of CPDB and cucurbit[7]uril at different molar ratios under different excitation lights. It can be seen from Figure 7 that as the concentration of cucurbit[7]uril increases, the fluorescent color of CPDB changes from blue to green under the excitation light of 330nm. As the concentration of cucurbit[7]uril increases, the fluorescent color of CPDB changes under the excitation light of 365nm. It shows a white to green transition. As the concentration of cucurbit[7]uril increases, the CPDB fluorescence color shows a yellow-green to green transition under 400nm excitation light.
  • the mold is a 248mm ⁇ 248mm ⁇ 5mm rectangular PVE plastic plate.
  • the plastic plate is processed with 31 ⁇ 31 5mm ⁇ 5mm ⁇ 3mm rectangular small slots, and the interval between each small slot is 3mm;
  • the hierarchical self-assembly solution A with a ratio of 1:1 and 1.5:1, and the hierarchical self-assembly solution B with a ratio of 1:1 and 2:1 in Example 6 are prepared for subsequent experiments.
  • step (3) According to the set pattern "IAMSEUer", on the mold of step (1), drop the CPDB solution in the above step (2) into the small groove with the pattern of lowercase English words "e” and "r", step
  • the dripping patterns of the CPDE solution in (2) are capital English letters "S”, “E” and “U”, and the dripping patterns of the hierarchical self-assembly liquid with a ratio of 1:1.0 in step (2) are English letters.
  • step (2) In the small tank of "A”, add the dripping pattern of the level self-assembly liquid with the ratio of 1:1.5 in step (2) to the small tank of the English letter "M”, and mix the ratio of step (2) with 1:
  • the dripping pattern of the 2.0 level self-assembly fluid is in the small groove with the capital letter "I”.
  • Figure 9 is a rendering of the multi-color luminescent system applied to anti-counterfeiting.
  • CPDE and CPDB are used as responsive encryption inks to express misleading information
  • CPDO is used as background ink to hide information
  • hierarchical self-assembly solution A and hierarchical self-assembly solution B are used as non-responsive responsive encryption inks to express true information.
  • Depend on Figure 9 shows that under 365nm light excitation, the displayed information is "IAMSEUer". When switching to 400nm light, "SEUer" and the background are both yellow-green, and the final displayed information is "IAM", which can be used for double anti-counterfeiting.

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Abstract

提供了一种荧光分子、多色体系及其制备方法与应用，该荧光分子的结构如（I）所示，其中，n为0到12的整数。该体系包括该荧光分子葫芦脲之间的相互作用。这种咔唑衍生物是一类烷基吡啶盐取代的咔唑基衍生化合物，其发光性质具有激发光波长依赖性，在室温下酸性水溶液中，通过改变激发光波长实现多色发光。同时，该咔唑衍生物可通过与葫芦脲分子(如葫芦[8]脲和葫芦[7]脲)的主客体作用及自组装行为改变荧光颜色，通过控制咔唑衍生物可通过与葫芦脲分子的比例可以调节荧光变化，进一步丰富本多色发光体系的颜色变化。本多色发光体系合成路线简单，发光调节仅需通过改变激发光波长或组分比例，在防伪和生物成像等领域中具有巨大的应用潜力。

Description

一种荧光分子、多色体系及其制备方法与应用 技术领域
本发明涉及一种荧光分子及其制备方法与包含该荧光分子的多色体系及多色体系在防伪方面的应用，属于有机发光材料技术领域。
背景技术
防伪技术是人类社会进行社会生产活动中用于信息保护的一种重要手段，对解决技术剽窃等社会问题具有重要意义。目前随着社会发展和科学进步，一些传统防伪技术的防伪周期正走向尽头。这一方面促使了传统防伪技术的升级换代，另一方面也促进了各种新型、高效防伪手段的产生和发展。具有响应性的多色发光体系用于开发防伪技术是防伪技术众多热门研究方向之一。
为解决这个问题，各种响应性发光技术，或者说智能发光材料应运而生。目前，pH值、蒸汽、电场、温度、机械力和溶剂等作为控制方法被用于控制发光材料的发光变化。其中之一是具有激发光调控的发光体系，其发光行为可通过改变激发波长进行调控。同时该发光体系制备简单，调控手段简单高效，无需复杂设备，可以有效降低防伪技术的应用成本。
然而，大多数激发光调控发光体系存在发光颜色变化单一的缺点。因此将激发光调控发光体系作为客体分子与大环分子如葫芦脲等进行主客体相互作用和层级自组装，不仅可以通过进行改变激发波长进行发光调节，同时可以改变主客体分子间的比例进行发光调节，极大的丰富了多色发光体系的发光颜色变化。所以，研究具有多刺激响应性的自组装发光体系，对新型防伪技术的发展具有重要意义。
发明内容
发明目的：为了解决现有技术所存在的问题，本发明的第一目的是提供一种荧光分子，本发明的第二目的是提供一种该荧光分子的制备方法，本发明的第三目的是提供一种包含该荧光分子的多色体系，本发明的第四目的是提供一种包含该荧光分子的多色体系的制备方法，本发明的第五目的是提供该包含该荧光分子的多色体系在防伪技术方面的应用。
技术方案：本发明所述的一种荧光分子，所述荧光分子为咔唑基结构单元与烷基吡啶盐结构单元偶联形成，所述荧光分子的结构如下：
其中，n为0到12的整数。
优选地，所述n为1、3或7。
一种本发明所述荧光分子的制备方法，包括如下步骤：
(1)将2，7-二溴咔唑，4-吡啶硼酸和碳酸钾加入到去除溶解氧的DMF与水的混合溶液中，再加入四(三苯基膦)钯，加热反应，反应完成后收集有机层，对有机层纯化得到产物2，7-二(4-吡啶基)咔唑；
(2)将2，7-二(4-吡啶基)咔唑和卤代烃加入到DMF中，氮气保护下反应；反应完成后向反应液中加入丙酮并过滤，滤饼依次用丙酮，二氯甲烷和正己烷多次洗涤得到荧光分子。
优选地，步骤(1)中，所述2，7-二溴咔唑，4-吡啶硼酸和碳酸钾按摩尔比1：1.2～1.5：2～3。
优选地，步骤(1)中，所述加热反应的温度为70～120℃，加热反应的时间为12～18小时。
优选地，步骤(2)中，所述卤代烃为溴乙烷、1-溴丁烷和1-溴辛烷。
优选地，步骤(2)中，所述2，7-二(4-吡啶基)咔唑和卤代烃按摩尔比1：20～30。
优选地，步骤(2)中，所述反应的温度为80～110℃，反应的时间为12～48小时。
本发明还包括一种多色发光体系，所述多色发光体系中包含本发明所述的荧光分子及葫芦脲。
优选地，所述葫芦脲为葫芦[7]脲或葫芦[8]脲。
本发明所述多色发光体系的制备方法，包括如下步骤：将本发明所述荧光分子用水配置成水溶液，得到溶液I，将葫芦脲加入到部分溶液I中，配置为葫芦脲-发光分子溶液，得到溶液II，即为多色发光体系。
优选地，将溶液I和溶液II按照不同配比进行混合，得到不同配比的混合溶液，即得到多个多色发光体系。溶液溶液I和溶液II的配比不同时，因其中荧光分子与葫芦脲之间的比例不同，可以得到的多色发光体系的颜色不同。
优选地，采用葫芦[7]脲时，多色发光体系中溶液I与溶液II的配比1：0.2-3.0。
优选地，采用葫芦[8]脲时，多色发光体系中溶液I与溶液II的配比1：0.1-1.5。
优选地，所述水的pH为0-7。
更优选地，所述水的pH为5。
本发明所设计的多刺激响应性的多色发光体系是包括激发光调控荧光分子及激发光调控荧光分子与葫芦脲分子相互作用形成的层级自组装体。该多色发光 体系的发光行为可以通过改变激发光波长和调节主客体分子比例来调节。同时，该多发光体系，荧光色彩丰富色且效果显著，它有望成为防伪技术领域的新型材料。
本发明还包括所述多色发光体系在防伪技术中的应用。利用多色发光体系中部分组分对激发光的响应性，可用于开发多层加密技术。
本发明防伪机理：本发明的防伪是通过在多色发光体系在激发光不同下显示的图案不同实现防伪目的的。本发明的多色发光体系由背景色发光分子，光控发光分子及发光层级自组装体组成。背景色发光分子作为背景，其发光颜色不随激发光波长改变而改变。光控发光分子及发光层级自组装体用于设计特定图案，并在固定激发波长下显示该图案。当改变激发波长至某一特定波长时，特定图案中某些部分与背景颜色一至，该图案所表达含义发生变化。通过该原理实现双层防伪。
有益效果：本发明和现有技术相比，具有如下显著性优点：
本发明荧光分子是咔唑基结构单元与烷基吡啶盐结构单元偶联形成，具有激发光波长响应性，在不同激发光下，发光颜色不同。基于该荧光分子，本发明所提出了一种新的多色发光体系，该体系是由一类激发光调控荧光分子和该类分子与葫芦脲分子形成的层级自组装体组成。该多色发光体系具有合成路线简单，合成原料廉价易得，组装体制备工艺简单等优点。同时该体系具有双重刺激响应性，发光效果显著，可以用于开发信息加密技术。
附图说明
图1是CPDE、CPDB和CPDO在激发光为330nm和400nm的荧光光谱图；
图2是CPDE、CPDB和CPDO在不同激发光下的荧光色照片；
图3是CPDB在不同激发光下的荧光光谱图；
图4是CPDB和不同摩尔比例葫芦[8]脲在激发光为330nm，365nm和400nm的荧光光谱图；
图5是CPDB和不同摩尔比例葫芦[8]脲在不同激发光下的荧光色照片；
图6是CPDB和不同摩尔比例葫芦[7]脲330nm，365nm和400nm的荧光光谱图；
图7是CPDB和不同摩尔比例葫芦[7]脲在不同激发光下的荧光色照片；
图8是CPDB和不同摩尔比例葫芦[8]脲和葫芦[7]脲在不同激发下荧光色的CIE图；
图9是多色发光体系应用于防伪的效果图。
具体实施方式
下面结合附图对本发明的技术方案作进一步说明。
实施例1荧光分子的制备
(1)将3g 2，7-二溴咔唑，4-吡啶硼酸和碳酸钾按摩尔比1：1.5：3投入到经鼓氮气预处理除去溶解氧的DMF与水的混合溶液中，以四(三苯基膦)钯为催化剂，反应温度为95℃，反应时间为12小时；反应完成后收集有机层并通过柱色谱纯化得到产物1.5g 2，7-二(4-吡啶基)咔唑。
对产物2，7-二(4-吡啶基)咔唑进行1H-NMR分析，结果如下：1H-NMR(DMSO-d6，600MHz)：δ11.77(s，1H)，8.78(d，J＝5.4Hz，4H)，8.38(d，J＝8.1Hz，2H)，8.07(d，J＝5.5Hz，4H)，8.03(s，2H)，7.73(d，J＝7.8Hz，2H)。
(2)0.2g 2，7-二(4-吡啶基)咔唑和溴乙烷按摩尔比1：20投入到DMF中，氮气保护，反应温度为95℃，反应时间为48小时；反应完成后向反应液中加入大量丙酮并过滤，滤饼依次用丙酮，二氯甲烷和正己烷多次洗涤得到最终产物0.2g的4，4'-咔唑-2，7-二基双(1-乙基吡啶-1-溴盐)(简称CPDE)。
对产物4，4'-咔唑-2，7-二基双(1-乙基吡啶-1-溴盐)进行核磁共振氢谱(1H-NMR)分析，结果如下：1H-NMR(DMSO-d6，600MHz)：δ：12.06(s，1H)，9.15-9.13(d，J＝6.9Hz，4H)，8.64-8.63(d，J＝7.0Hz，4H)，8.53-8.51(d，J＝8.3Hz，2H)，8.25(s，2H)，7.96-7.93(dd，2H)，4.67-4.63(t，J＝7.2Hz，4H)，1.61-1.58(t，J＝7.3Hz 6H)。
对产物4，4'-咔唑-2，7-二基双(1-乙基吡啶-1-溴盐)进行核磁共振碳谱(13C-NMR)分析，结果如下：13C-NMR(DMSO-d6)δ：155.81，144.90，141.84，132.45，125.20，122.90，119.65，111.85，55.83，16.82。
对产物4，4'-咔唑-2，7-二基双(1-乙基吡啶-1-溴盐)进行高分辨质谱分析，结果如下：ESI-MS m/z：C26H25N3Br2，[M-2Br]2+：189.60185。
实施例2荧光分子的制备
(1)制备过程同实施例1，所选溴代烃改为1-溴丁烷，得到最终产物0.25g的4，4'-咔唑-2，7-二基双(1-丁基吡啶-1-溴盐)(简称CPDB)。
对产物4，4'-咔唑-2，7-二基双(1-丁基吡啶-1-溴盐)进行1H-NMR分析，结果如下：1H-NMR(DMSO-d6)δ：12.06(s，1H)，9.13-9.12(d，J＝6.6Hz，4H)，8.64-8.63(d，J＝6.8Hz，4H)，8.53-8.51(d，J＝8.3Hz，2H)，8.24(s，2H)，7.95-7.94(dd，J＝1.7Hz，2H)，4.63-4.60(t，J＝7.4Hz，4H)，1.98-1.93(m，J＝7.5Hz，4H)，1.39-1.32(m，J＝7.5Hz，4H)，0.97-0.94(t，J＝7.4Hz，6H)。
对产物4，4'-咔唑-2，7-二基双(1-丁基吡啶-1-溴盐)进行13C-NMR分析，结果如下：13C-NMR(DMSO-d6)δ：155.80，145.08，141.83，132.38，125.18，124.96，122.89，119.66，60.01，33.13，19.29，13.85。
对产物4，4'-咔唑-2，7-二基双(1-丁基吡啶-1-溴盐)进行高分辨质谱分析，结果如下：ESI-MS m/z：C30H33N3Br2，[M-2Br]2+：217.63306。
实施例3荧光分子的制备
(1)制备过程同实施例1，所选溴代烃改为1-溴辛烷，得到最终产物0.25g4，4'-咔唑-2，7-二基双(1-辛基吡啶-1-溴盐)(简称CPDO)。
对产物4，4'-咔唑-2，7-二基双(1-辛基吡啶-1-溴盐)进行1H-NMR分析，结果如下：1H-NMR(DMSO-d6)δ:12.07(s，1H)，9.14-9.13(d，J＝5.2Hz，4H)，8.64-8.63(d，J＝7.0Hz，4H)8.52-8.51(d，J＝8.3Hz，2H)，8.25(s，2H)，7.96-7.94(dd，J＝8.3，1.7Hz，2H)，4.62-4.60(t，J＝7.5Hz，4H)，1.99-1.94(m，4H)，1.34-1.26(m，20H)，0.87-0.85(t，6H)。
对产物4，4'-咔唑-2，7-二基双(1-辛基吡啶-1-溴盐)进行13C-NMR分析，结果如下：13C-NMR(DMSO-d6)δ：155.81，145.07，141.84，132.42，125.18，124.98，122.91，119.67，111.87，60.24，31.63，31.18，28.95，28.88，25.95，22.53，14.42。
对产物4，4'-咔唑-2，7-二基双(1-辛基吡啶-1-溴盐)进行高分辨质谱分析，结果如下：ESI-MS m/z：C38H49N3bBr2：[M-2Br]2+：273.69504。
实施例4CPDE、CPDB和CPDO的荧光测试
通过荧光光谱对CPDE、CPDB和CPDO在激发光为330nm和400nm的进行荧光测试，结果如图1-3所示。
图1是CPDE、CPDB和CPDO在激发光为330nm和400nm的荧光光谱图。其中，(a)为330nm，(b)为400nm。由图1可知CPDE和CPDB在激发光为330nm和400nm的激发下，荧光光谱出现不同，最大发射峰波长分别约为440nm(330nm激发)和540nm(400nm激发)；而CPDO激发光为330nm和400nm的激发下，荧光光谱无明显差别，且最大发射峰波长为540nm。说明：CPDE和CPDB具有激发光调控现象，可作为光响应组分，CPDO无激发光调控现象，可作为背景，用于信息伪装。
图2是CPDE、CPDB和CPDO在不同激发光下的荧光色照片。由图2可知，CPDE和CPDB在330nm激发光照射下呈现蓝色荧光，在365nm激发光照射下呈现白色荧光，在400nm激发光照射下呈现黄绿色荧光；CPDO在330nm和400nm激发光照射下均呈现黄绿色荧光。
图3是CPDB在不同激发光下的荧光光谱图。由图3可知，随着激发波长由400nm转变至330nm，荧光分子CPDB最大发射波长由540nm转变为440nm。
实施例5多色发光体系的制备
(1)将实施例2制备的1.79mg荧光分子4，4'-咔唑-2，7-二基双-(1-丁基吡啶-1-溴盐)(CPDB)溶于3mL水(pH＝5)中配置为浓度为1mM的溶液得到溶液I
(2)将1.33mg葫芦[8]脲分子加入到1mL溶液I中，经超声配置为葫芦[8]脲-发光分子(发光分子与葫芦[8]脲与浓度比为1：2)，分散液得到溶液II，取一定量溶液I和溶液II进行混合，得到溶液I和溶液II的配比为1：0、1：0.1、1：0.2、1：0.3、1：0.4、1：0.5、1：0.6、1：0.7、1：1.0、1：1.3和1：1.5，并用水将溶液中CPDB的浓度均稀释至4×10-5M，得到不同配比的层级自组装液A，即11个多色发光体系。
通过荧光光谱对本实施例制得的多色发光体系进行发光效果的测试，结果如图4-5所示。图4是CPDB和不同摩尔比例葫芦[8]脲在激发光波长为330nm，365nm和400nm下的荧光光谱图，其中，(a)为330nm，(b)为365nm，(c)为400nm。由图4可知，随着葫芦[8]脲浓度的增加，CPDB最大发射波长由540nm和440nm最终转变为580nm。
图5是CPDB和不同摩尔比例葫芦[8]脲在不同激发光下的荧光色照片。由图5可知，随着葫芦[8]脲浓度的增加，CPDB荧光色在330nm激发光下呈现蓝色到橙色转变，随着葫芦[8]脲浓度的增加，CPDB荧光色在365nm激发光下呈现白色到橙色转变，随着葫芦[8]脲浓度的增加，CPDB荧光色在400nm激发光下呈现黄绿色到橙色转变。
实施例6多色发光体系的制备
制备过程同实施例5，其中将3.49mg葫芦[7]脲分子溶于3mL水(pH＝5)中，配置为浓度为1mM的溶液得到溶液II，取一定量溶液I和溶液II进行混合，得到配比为1：0、1：0.2、1：0.4、1：0.6、1：0.8、1：1.0、1：1.6、1：2.0、1：2.6和1：3.0，并用水将溶液中CPDB的浓度均稀释至4×10-5M，得到不同配比的层级自组装液B，即10个多色发光体系。
通过荧光光谱对本实施例制得的11个多色发光体系进行发光效果的测试，结果如图6-7所示。图6是CPDB和不同摩尔比例葫芦[7]脲在激发光波长为330nm，365nm和400nm下的荧光光谱图，其中，(a)为330nm，(b)为365nm，(c)为400nm。由图6可知，随着葫芦[7]脲浓度的增加，CPDB最大发射波长 由540nm和440nm最终转变为530nm。
图7是CPDB和不同摩尔比例葫芦[7]脲在不同激发光下的荧光色照片。由图7可知，随着葫芦[7]脲浓度的增加，CPDB荧光色在330nm激发光下呈现蓝色到绿色转变，随着葫芦[7]脲浓度的增加，CPDB荧光色在365nm激发光下呈现白色到绿色转变，随着葫芦[7]脲浓度的增加，CPDB荧光色在400nm激发光下呈现黄绿色到绿色转变。
CPDB和不同摩尔比例葫芦[8]脲和葫芦[7]脲在不同激发下荧光色的CIE色谱图如图8所示，其中，(a)为实施例5得到的多色发光体系，(b)为实施例6得到的多色发光体系。由图8可知，通过调整激发光和CPDB与葫芦脲之间的比例，可以获得蓝色，黄色，橙色和绿色等不同发射光。
实施例7多色发光体系在防伪技术上的应用
(1)准备模具，模具是248mm×248mm×5mm的长方体PVE塑料板，该塑料板加工出31×31个5mm×5mm×3mm长方体小槽，每个小槽间隔为3mm；
(2)选取实施例1-3分别得到的荧光分子CPDE，CPDB和CPDO，用水(pH＝5)配置成4×10-5M的溶液；再分别取实施例5中的配比为1：1和1.5：1的层级自组装体溶液A，实施例6中配比为1：1和2：1的层级自组装体溶液B准备用于后面的实验。
(3)按照设定的图案“IAMSEUer”，在步骤(1)模具上，将上述步骤(2)中的CPDB溶液滴加图案为小写英文单词“e”和“r”的小槽里，步骤(2)中的CPDE溶液滴加图案为大写英文字母“S”、“E”和“U”，将步骤(2)中配比为1：1.0的层级自组装液的滴加图案为英文字母“A”的小槽里，将步骤(2)中配比为1：1.5层级自组装液的滴加图案为英文字母“M”的小槽里，将步骤(2)中配比为1：2.0层级自组装液的滴加图案为大写英文字母“I”的小槽里。将步骤(2)中的CPDO溶液滴加图案为背景，即滴加在没有设定字母的其他部分的小槽里。
(4)选取波长为365nm和400nm的光源作为激发光源。在365nm激发光源下，CPDE和CPDB与CPDO荧光色不同，因此可与层级自组装体溶液A和B共同展示第一种信息，而当激发光源波长为400nm时，CPDE和CPDB与CPDO荧光色相同，层级自组装体溶液A和层级自组装体溶液B荧光不变，显示第二种信息，结果如图9所示。
图9是多色发光体系应用于防伪的效果图。CPDE和CPDB作为响应性加密墨水用于表达误导信息，CPDO作为背景墨水用于隐藏信息，层级自组装体溶液A和层级自组装体溶液B作为非响应性响应性加密墨水用于表达真实信息。由 图9可知，在365nm光激发下，显示信息为“IAMSEUer”，切换至400nm光时，“SEUer”与背景同为黄绿色，最终显示信息为“IAM”，能够用于双重防伪。

Claims (10)

  1. 一种荧光分子，其特征在于，所述荧光分子为咔唑基结构单元与烷基吡啶盐结构单元偶联形成，所述荧光分子的结构如下：
    其中，n为0到12的整数。
  2. 根据权利要求1所述的荧光分子，其特征在于，所述n为1、3或7。
  3. 一种权利要求1或2所述荧光分子的制备方法，其特征在于，包括如下步骤：
    (1)将2，7-二溴咔唑，4-吡啶硼酸和碳酸钾加入到去除溶解氧的DMF与水的混合溶液中，再加入四(三苯基膦)钯，加热反应，反应完成后收集有机层，对有机层纯化得到产物2，7-二(4-吡啶基)咔唑；
    (2)将2，7-二(4-吡啶基)咔唑和卤代烃加入到DMF中，氮气保护下反应；反应完成后向反应液中加入丙酮并过滤，滤饼依次用丙酮，二氯甲烷和正己烷多次洗涤得到荧光分子。
  4. 根据权利要求3所述荧光分子的制备方法，其特征在于，步骤(1)中，所述2，7-二溴咔唑，4-吡啶硼酸和碳酸钾按摩尔比1：1.2～1.5：2～3，所述加热反应的温度为70～120℃，加热反应的时间为12～18小时，步骤(2)中，所述2，7-二(4-吡啶基)咔唑和卤代烃按摩尔比1：20～30，所述反应的温度为80～110℃，反应的时间为12～48小时；所述卤代烃为溴乙烷、1-溴丁烷或1-溴辛烷。
  5. 一种层级自组装体，其特征在于，所述层级自组装体中包含权利要求1或2所述的荧光分子及葫芦脲。
  6. 根据权利要求5所述层级自组装体，其特征在于，所述葫芦脲为葫芦[7]脲或葫芦[8]脲。
  7. 根据权利要求5或6所述层级自组装体的制备方法，其特征在于，包括如下步骤：将权利要求1或2所述荧光分子用水配置成水溶液，得到溶液I，将葫芦脲加入到部分溶液I中，配置为葫芦脲-发光分子溶液，得到溶液II，即为层级自组装体。
  8. 根据权利要求7所述层级自组装体的制备方法，其特征在于，将溶液I和溶液II按不同配比进行混合，得到不同配比的混合溶液，即得多个层级自组装体。
  9. 根据权利要求8所述层级自组装体的制备方法，其特征在于，采用葫芦 [7]脲时，层级自组装体中溶液I与溶液II的配比1：0.2-3.0；采用葫芦[8]脲时，层级自组装体中溶液I与溶液II的配比1：0.1-1.5；所述水的pH为0-7。
  10. 权利要求5或6所述层级自组装体在防伪技术中的应用。
PCT/CN2023/092957 2022-05-11 2023-05-09 一种荧光分子、多色体系及其制备方法与应用 Ceased WO2023217124A1 (zh)

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