CN106010508A - Indolizine carboxylic acid type pH fluorescent probe and application thereof - Google Patents

Indolizine carboxylic acid type pH fluorescent probe and application thereof Download PDF

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Publication number
CN106010508A
CN106010508A CN201610349416.3A CN201610349416A CN106010508A CN 106010508 A CN106010508 A CN 106010508A CN 201610349416 A CN201610349416 A CN 201610349416A CN 106010508 A CN106010508 A CN 106010508A
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carboxylic acid
indolizine
fluorescent probe
probe
acid type
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CN106010508B (en
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葛燕青
段桂运
曹晓群
董建
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Taishan Medical University
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    • 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
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—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

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  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)

Abstract

The invention discloses an indolizine carboxylic acid type pH fluorescent probe. The probe is 2-acetylindolizine-7-carboxylic acid, and the chemical structural formula (I) is shown in the specification. The fluorescent probe disclosed by the invention has unique fluorescent selectivity and relatively high sensitivity to pH in a water solution of dimethyl sulfoxide; and compared with an existing probe, the indolizine carboxylic acid type pH fluorescent probe has the remarkable advantages that the probe has a narrow pH relevant range, is not interfered by backgrounds and is applicable to pH detection of a strong acidic environment, and has a great application prospect.

Description

A kind of indolizine carboxylic acids pH fluorescent probe and application thereof
The present invention relates to organic molecule fluorescent probe field, particularly relate in a kind of novel pH fluorescent probe 2-acetyl group Benzazole-7-carboxylic acid and application thereof.
Background technology
PH, as an important indicator of cell health, grows at cell, diffusion, apoptosis, autophagy, and ion transports, and Other cell processes play an important role.Its minor variations just may cause cell function element unrest and serious disease, such as large intestine Cancer, breast carcinoma, cystic fibrosis, neurodegenerative diseases even Alzheimer's disease.But the most conventional glass electrode is surveyed The method of pH is not suitable for the detection of life field pH.
Fluorescent probe selectivity is good, highly sensitive, simple to operate, low cost and can realize monitoring in real time, has made Testing tool for a kind of first-selection is applied to the mensuration of intracellular ph value.Although existing multiple pH fluorescent probe is in the news, but The most deep for the research of internal pH under acid condition.For this, develop the acid pH probe of new type ideal, detection Intracellular hydrionic concentration and distribution have particularly important meaning to the research physiology of cell, pathological process.??
Indolizine compound is because being limited by limited synthetic method, and it reports for work seldom in the application of optical field, itself and conduct The application of pH fluorescent probe has no that document is reported especially.
Summary of the invention
For the deficiencies in the prior art, it is an object of the invention to provide a kind of pH fluorescent probe recruit's indolizine carboxylic acid And application.
The technical scheme is that a kind of indolizine carboxylic acid pH fluorescent probe, its chemical structural formula as the formula (1):
Present invention additionally comprises the application of indolizine carboxylic acid pH fluorescent probe, formula (1) compound is right in the aqueous solution of dimethyl sulfoxide PH has the fluorescence selectivity of uniqueness.
Present invention additionally comprises the synthetic method of indolizine carboxylic acid pH fluorescent probe, in the ethanol solution of 95%, by 2-acetyl Base indolizine-7-carboxylic acid, ethyl ester and sodium hydroxide, according to 1:2 ingredient proportion, back flow reaction 2-5 hour under 80 degree, obtain 2-acetyl Base indolizine-7-carboxylic acid.
The dimethyl sulfoxide solution of preparation indolizine carboxylic acid, in the aqueous solution of the dimethyl sulfoxide being added separately to different pH (two First sulfoxide: water=2:8), tested the selectivity studied different pH by fluorescence spectrum, survey its fluorescence emission spectrum intensity and become Change and find: during pH has 2.6 to be changed to 7.5, at 460 nm, fluorescence intensity substantially weakens, as shown in Figure 1.Therefore, middle nitrogen Indene carboxylic acid has huge application prospect as pH fluorescent probe.
Accompanying drawing explanation
Fig. 1: the fluorescence spectrum figure of the dimethyl sulfoxide aqueous solution (dimethyl sulfoxide: water=2:8) of different pH.
Fig. 2: the nucleus magnetic hydrogen spectrum of fluorescent probe recruit.
The nuclear-magnetism carbon spectrum of Fig. 3: fluorescent probe recruit.
Detailed description of the invention
Embodiment 1: the synthetic schemes of formula (1) compound is shown below:
Concrete synthesis step is as follows:
It is sequentially added into 2.31g(10.0 mmol in 50 mL round-bottomed flasks) 2-acetyl group indolizine-7-carboxylic acid, ethyl ester, 0.80g (20.0 mmol) sodium hydroxide, the ethanol of 20 mL95%, 80 degree of lower back flow reaction 2-5 hour, pour in 300 mL water, dense salt PH to 5-6 is adjusted in acid, separates out a large amount of solid, sucking filtration, is dried to obtain 1.86g yellow solid product, productivity 91.6%.
Nuclear magnetic resonance hydrogen spectruming determining:1H NMR (400 MHz, DMSO-d6):δ12.96 (s, 1H), 8.31 (m, 2H), 8.39 (s, 1H), 7.13 (s, 1H), 7.04(m, 1H),2.51 (s, 3H). 13C NMR (100 MHz, DMSO- d6): 194.37, 166.79, 131.61, 129.65, 126.48, 124.23, 121.21, 118.98, 111.41, 104.44, 28.09.
Such as Fig. 2, shown in Fig. 3.
Embodiment 2:
Taking indolizine carboxylic acid 0.0020g, be dissolved in 10mL dimethyl sulfoxide, obtain probe mother solution, concentration is 10-3M.Take 100 microlitres respectively Probe mother solution, in the aqueous solution of the dimethyl sulfoxide joining 10mL difference pH (dimethyl sulfoxide: water=2:8) to survey its fluorescent emission strong Degree change finds: during pH has 2.6 to be changed to 7.5, at 430 nm, fluorescence intensity is remarkably reinforced, as shown in Figure 1.

Claims (2)

1. an indolizine carboxylic acids pH fluorescent probe, it is characterised in that: it is 2-acetyl group indolizine-7-carboxylic acid, its chemistry Structural formula is as the formula (1):
Formula (1) compound has the fluorescence selectivity of uniqueness in the aqueous solution of dimethyl sulfoxide to pH.
2. the synthetic method of 2-acetyl group indolizine-7-carboxylic acid pH fluorescent probe described in claim 1, it is characterised in that: 95% Ethanol solution in, by 2-acetyl group indolizine-7-carboxylic acid, ethyl ester and sodium hydroxide according to 1:2 ingredient proportion, 80 degree lower refluxes React 2-5 hour, obtain 2-acetyl group indolizine-7-carboxylic acid.
CN201610349416.3A 2016-05-24 2016-05-24 A kind of indolizine carboxylic acids pH fluorescence probes and its application Expired - Fee Related CN106010508B (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106483113A (en) * 2016-10-26 2017-03-08 华南师范大学 1 pyrene formic acid is used as the application of pH fluorescence probe
CN109749734A (en) * 2017-11-07 2019-05-14 泰山医学院 A kind of Ratiometric fluorescent probe can detecte sulfite ion and application
CN110498794A (en) * 2018-05-18 2019-11-26 泰山医学院 The pyridine derived species Pd of imidazo [1,2-a]2+Fluorescence probe and its application
CN113444067A (en) * 2021-06-04 2021-09-28 西华大学 Preparation method and application of benzothiophene carboxylate
CN114276343A (en) * 2020-09-27 2022-04-05 中石化南京化工研究院有限公司 Preparation method of fluorescent probe for detecting trace iron ions in chlorobenzene

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CN103992790A (en) * 2014-05-27 2014-08-20 南京师范大学 Novel pH-responsive fluorescence molecular probe and synthetic method thereof

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WO2002070680A1 (en) * 2001-03-01 2002-09-12 Basf Aktiengesellschaft Method of identifying inhibitors of cdc25
CN102660253A (en) * 2012-03-07 2012-09-12 泰山医学院 Pyrazoline derivative Ni<2+> fluorescence probe and application thereof
CN103980885A (en) * 2014-05-27 2014-08-13 南京师范大学 Novel pH-responsive fluorescent molecular probe and preparation method thereof
CN103992790A (en) * 2014-05-27 2014-08-20 南京师范大学 Novel pH-responsive fluorescence molecular probe and synthetic method thereof

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106483113A (en) * 2016-10-26 2017-03-08 华南师范大学 1 pyrene formic acid is used as the application of pH fluorescence probe
CN109749734A (en) * 2017-11-07 2019-05-14 泰山医学院 A kind of Ratiometric fluorescent probe can detecte sulfite ion and application
CN110498794A (en) * 2018-05-18 2019-11-26 泰山医学院 The pyridine derived species Pd of imidazo [1,2-a]2+Fluorescence probe and its application
CN110498794B (en) * 2018-05-18 2022-02-01 山东第一医科大学(山东省医学科学院) Imidazo [1,2-a ] pyridine derivative Pd2+ fluorescent probe and application thereof
CN114276343A (en) * 2020-09-27 2022-04-05 中石化南京化工研究院有限公司 Preparation method of fluorescent probe for detecting trace iron ions in chlorobenzene
CN114276343B (en) * 2020-09-27 2023-07-07 中国石油化工股份有限公司 Preparation method of fluorescent probe for detecting trace iron ions in chlorobenzene
CN113444067A (en) * 2021-06-04 2021-09-28 西华大学 Preparation method and application of benzothiophene carboxylate
CN113444067B (en) * 2021-06-04 2022-06-07 西华大学 Preparation method and application of benzothiophene carboxylate

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