Synthesis and application of aggregation-induced phosphorescent molecular probe for detecting and imaging aluminum ions in organism

Abstract

The invention provides synthesis and application of a probe for detecting and imaging aluminum ions in a living body, and belongs to the technical field of detection. The invention solves the problem that the low solubility of the probe in an aqueous solution may cause error signals of self-precipitation in living cells in the imaging process, and the sensitivity and accuracy of tracking Al<3+> in a biological system are greately affected. According to the invention, a novel phosphorescent molecular probe is designed and synthesized, the specific detection of aluminum ions is realized by modifying carboxyl on hexathiobenzene molecules, and meanwhile, the imaging performance of the probe on Al<3+> in living cells is further evaluated in a model plant arabidopsis thaliana. According to the invention, a novel phosphorescent molecular probe for specific detection of aluminum ions is designed and synthesized by introducing carboxyl into a hexa(4-hydroxy-1-thiophenyl)benzene (HHPB) molecule. A unique aggregation-induced phosphorescence (AIP) effect is utilized to develop a time-gated luminescence detection method based on long-life emission induced by aluminum ions.

Description

technical field

[0001] The invention belongs to the technical field of detection, and relates to the synthesis and application of an aggregation-induced phosphorescent molecular probe for detection and imaging of aluminum ions in living organisms. Background technique

[0002] With the development of industrialization, the proportion of heavier and toxic metal ions in people's lives and the environment is also increasing, and metal ions play an indispensable role in various biological processes. Accurate measurement of metal ions is of great importance. Significance. As the third most abundant element in the earth's crust, aluminum continues to enter the ecosystem with the increase of acid rain. Current evidence shows that ingestion of aluminum ions produces significant toxicity to organisms such as plants and humans. Currently, the quantification and imaging of toxic metal ions usually rely on the accuracy of fluorescent indicators and specific optical methods. Although ...

Examples

Embodiment 1

[0026] Example 1: Synthesis of functionalized HHPB-6OCH2COONa probe and its photophysical properties

[0027] Introducing carboxyl groups to functionalize hexa(4-hydroxy-1-phenylthio)benzene (HHPB) to obtain {4-[penta-(4-ethoxycarbonylmethoxy-phenylthio)-phenylthio) ]-phenoxy}-sodium acetate (HHPB-6OCH2COONa), realizes the combination of the probe to Al3+ by means of the oxygen supply site of the carboxyl group. And by 1H NMR, 13C NMR and mass spectrometry to prove the pure compound molecules. HHPB-6OCH2COONa solid powder exhibits bright luminescence under ultraviolet light irradiation. It is measured that it can be excited by 468nm ultraviolet-visible light, and emits bright yellow light with a maximum emission of 570nm. The solid powder was dissolved in pH 7.0 10mM HEPES buffer solution to prepare a solution with a concentration of 50 μM. It was observed that the fluorescence of the solution was very weak and almost invisible under ultraviolet light irradiation. It is meas...

Embodiment 2

[0028] Implementation Example 2: Detection of specific aluminum ions based on aggregation-induced phosphorescence probes

[0029] HHPB-6OCH2COONa was used as a phosphorescence probe to detect aluminum ions through the enhancement of phosphorescence caused by the coordination reaction initiated by aluminum ions. To detect aluminum ions in aqueous solution, HHPB-6OCH2COOH was first reacted with sodium hydroxide to convert it into a soluble form of the sodium salt. HHPB-6OCH2COOH contains multiple carboxyl groups, and its sodium salt form combines with aluminum ions to produce a bright yellow precipitate in aqueous solution. HHPB-6OCH2COONa (50μM) emits very weak light when dissolved in water. After adding a certain amount of Al3+ (375μM), the luminescence intensity of HHPB-6OCH2COONa increases by 32 times. Therefore, the dynamic binding equilibrium between HHPB-6OCH2COONa and aluminum ions tends to the overall molar ratio of 1:6. The significant change in PL of HHPB-6OCH2COONa...

Embodiment 3

[0031] Implementation Example 3: Time-gated detection of aluminum ions in serum

[0032] Time-gated luminescence (TGL) technology is an effective method to minimize autofluorescence and scattered light, which is suitable for precise sensing and high-contrast imaging using long-lived emitting probes. The long lifetime of HHPB-6OCH2COONa enabled the development of the first time-gated luminescent detection method for aluminum ions using human serum as a composite matrix. Studies have found that human serum has relatively bright autofluorescence even when excited at a long excitation wavelength of 467nm, but its lifetime is very short, on the order of nanoseconds. The large difference in lifetime between HHPB-6OCH2COONa and the serum substrate allows TGL to collect emission signals from HHPB-6OCH2COONa when an appropriate delay time is applied. When no delay was applied, about 1% serum in volume doubled the PL intensity of HHPB-6OCH2COONa added with a fixed amount of Al3+, but t...

technical field

[0001] The invention belongs to the technical field of detection, and relates to the synthesis and application of an aggregation-induced phosphorescent molecular probe for detection and imaging of aluminum ions in living organisms. Background technique

[0002] With the development of industrialization, the proportion of heavier and toxic metal ions in people's lives and the environment is also increasing, and metal ions play an indispensable role in various biological processes. Accurate measurement of metal ions is of great importance. Significance. As the third most abundant element in the earth's crust, aluminum continues to enter the ecosystem with the increase of acid rain. Current evidence shows that ingestion of aluminum ions produces significant toxicity to organisms such as plants and humans. Currently, the quantification and imaging of toxic metal ions usually rely on the accuracy of fluorescent indicators and specific optical methods. Although ...

Examples

Embodiment 1

[0026] Example 1: Synthesis of functionalized HHPB-6OCH2COONa probe and its photophysical properties

[0027] Introducing carboxyl groups to functionalize hexa(4-hydroxy-1-phenylthio)benzene (HHPB) to obtain {4-[penta-(4-ethoxycarbonylmethoxy-phenylthio)-phenylthio) ]-phenoxy}-sodium acetate (HHPB-6OCH2COONa), realizes the combination of the probe to Al3+ by means of the oxygen supply site of the carboxyl group. And by 1H NMR, 13C NMR and mass spectrometry to prove the pure compound molecules. HHPB-6OCH2COONa solid powder exhibits bright luminescence under ultraviolet light irradiation. It is measured that it can be excited by 468nm ultraviolet-visible light, and emits bright yellow light with a maximum emission of 570nm. The solid powder was dissolved in pH 7.0 10mM HEPES buffer solution to prepare a solution with a concentration of 50 μM. It was observed that the fluorescence of the solution was very weak and almost invisible under ultraviolet light irradiation. It is meas...

Embodiment 2

[0028] Implementation Example 2: Detection of specific aluminum ions based on aggregation-induced phosphorescence probes

[0029] HHPB-6OCH2COONa was used as a phosphorescence probe to detect aluminum ions through the enhancement of phosphorescence caused by the coordination reaction initiated by aluminum ions. To detect aluminum ions in aqueous solution, HHPB-6OCH2COOH was first reacted with sodium hydroxide to convert it into a soluble form of the sodium salt. HHPB-6OCH2COOH contains multiple carboxyl groups, and its sodium salt form combines with aluminum ions to produce a bright yellow precipitate in aqueous solution. HHPB-6OCH2COONa (50μM) emits very weak light when dissolved in water. After adding a certain amount of Al3+ (375μM), the luminescence intensity of HHPB-6OCH2COONa increases by 32 times. Therefore, the dynamic binding equilibrium between HHPB-6OCH2COONa and aluminum ions tends to the overall molar ratio of 1:6. The significant change in PL of HHPB-6OCH2COONa...

Embodiment 3

[0031] Implementation Example 3: Time-gated detection of aluminum ions in serum

[0032] Time-gated luminescence (TGL) technology is an effective method to minimize autofluorescence and scattered light, which is suitable for precise sensing and high-contrast imaging using long-lived emitting probes. The long lifetime of HHPB-6OCH2COONa enabled the development of the first time-gated luminescent detection method for aluminum ions using human serum as a composite matrix. Studies have found that human serum has relatively bright autofluorescence even when excited at a long excitation wavelength of 467nm, but its lifetime is very short, on the order of nanoseconds. The large difference in lifetime between HHPB-6OCH2COONa and the serum substrate allows TGL to collect emission signals from HHPB-6OCH2COONa when an appropriate delay time is applied. When no delay was applied, about 1% serum in volume doubled the PL intensity of HHPB-6OCH2COONa added with a fixed amount of Al3+, but t...

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