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Preparation and application of near-infrared luminescent ruthenium complexes

A technology of binuclear ruthenium complexes and ligands, which is applied in the field of preparation of binuclear ruthenium complexes, can solve problems such as poor solubility and large application restrictions, and achieve the effect of structural stability

Inactive Publication Date: 2020-10-30
BEIJING NORMAL UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

(X.Zhu W.Lu, Y Zhang et al.Imidazole-modified porphyrinas a pH-responsive sensitizer for cancer photodynamic therapy[,Chem.Commun.,2011,47(37),10311; S. Silvi,E C.Constable , C.E.Housecroft et al., Photochemical switching of luminescence and singlet oxygen generation by chemical signal communication, Chem.Commun., 2009, (12), 1484.) Most of the molecules currently reported for singlet oxygen switches used in pH regulation are organic Ligands have poor solubility in aqueous solution, and the practical application is limited

Method used

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  • Preparation and application of near-infrared luminescent ruthenium complexes
  • Preparation and application of near-infrared luminescent ruthenium complexes
  • Preparation and application of near-infrared luminescent ruthenium complexes

Examples

Experimental program
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Effect test

Embodiment 1

[0024] Embodiment 1: Complex [(bpy) 2 Ru(HL 1 )Ru(H 2 L 2 )] (ClO 4 ) 4 The preparation steps:

[0025] (1) Ligand H 2 L 2 According to the literature [P.S.Natarajan, M.

[0026] Schmittel, Inorg. Chem. 2013, 52(15), 8579.] Synthesis.

[0027] (2)[Ru(H 2 L 2 )Cl 3 ] is RuCl 3 ·3H 2 O and ligand H 2 L 2 According to the molar ratio of 1:1, it is obtained by heating under reflux in ethanol.

[0028] (3) Ligand HL 1 and [Ru(bpy) 2 HL 1 ](ClO 4 ) 2 According to the literature [Z.B.Zheng, Z.M.Duan, J.M. Zhangt al., Chromogenic and fluorogenic sensing properties toward cations and anions by a terpyridine / phenylimidazo[4,5-f]phenanthroline hybrid, Sensors Actuators B 2012,169,312; Z.B.Zheng, Y.M.Duan Ma et al., Highly sensitive and selective difunctional ruthenium (II) complex based chemosensor fordihydrogen phosphate anion and ferrous cation, Inorg.Chem.2013,52,2306.] synthesis.

[0029] (4) Complexes [(bpy) 2 Ru(HL 1 )Ru(H 2 L 2 )] (ClO 4 ) 4 Preparation...

Embodiment 2

[0032] Example 2: Determination of UV-Vis absorption spectrum and emission spectrum at different pH and drawing of working curve The acid-base titration of the complex is carried out in Britton-Robinson (abbreviated as BR) buffer solution. BR buffer solution is a mixture of 0.04M glacial acetic acid, 0.04M boric acid and 0.1M sodium chloride. Sodium chloride is used to maintain the ionic strength of the system, thereby reducing the influence of the external environment on the test. Prepare 40ml 3.75×10 -6 The mol / L complex solution to be tested was divided into two parts, one part was adjusted to pH with concentrated sulfuric acid, and the ultraviolet-visible absorption and emission spectra of the solution were measured at pH=0.2-2.0. Another part is adjusted pH with concentrated sodium hydroxide solution, measures the ultraviolet-visible absorption and emission spectrum (excitation wavelength λ of excitation wavelength λ) of solution when pH=2.0-7.0 ex = 505nm). Measure a ...

Embodiment 3

[0040] Example 3: pH switchable singlet oxygen generation

[0041] The detection of singlet oxygen uses anthracene-9,10-dipropionic acid (ADPA) as the singlet oxygen scavenger. Under light conditions, the singlet oxygen produced by the binuclear ruthenium complex interacts with ADPA to reduce the concentration of ADPA, thereby causing a decrease in absorbance.

[0042] Prepare 10mg / mL ADPA standard solution, add 10μL of ADPA standard solution and binuclear ruthenium complex solution in 3mL PBS solution, at 25mW / cm 2 Visible light was irradiated for 10 minutes, and the absorbance decrease of ADPA at 378nm was recorded every 2 minutes. Then 10 mg / mL rose bengal (Rose bengal) was prepared as a standard photosensitizer, and the standard singlet oxygen quantum yield was 0.75. According to the concentration of the binuclear ruthenium complex, the decrease of the absorbance of ADPA can be analyzed to produce the dinuclear ruthenium complex. 1 o 2 s efficiency. Calculation of sin...

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Abstract

The invention discloses a preparation method of a binuclear ruthenium complex with good water solubility and pH response near infrared luminescence and singlet oxygen generation properties of the binuclear ruthenium complex.

Description

technical field [0001] The invention relates to the fields of pH sensing and singlet oxygen generation and regulation, in particular to a preparation method of a binuclear ruthenium complex and its application in the fields of near-infrared phosphorescence sensing induced by different pH and singlet oxygen generation switch. Background technique [0002] The traditional methods for detecting pH include pH meter, pH indicator and pH test paper, etc. The acidity meter used for more accurate pH measurement must use glass electrodes, but glass electrodes may cause mechanical damage due to electrochemical interference, so It is not suitable for the detection of pH in living body. Many life processes in human cells and organelles are closely related to pH. For example, under normal physiological conditions, the pH of the extracellular fluid in the human body is 7.40 ([H + ]=40nmol / L), the pH variation range is generally 0.1-0.2 pH units. Too strong acidity or too strong alkalini...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F15/00C09K11/06G01N21/33G01N21/64
CPCC07F15/0053C09K11/06C09K2211/185G01N21/33G01N21/6428
Inventor 王克志刘慧宇严舒怡洪小燕顾东浩
Owner BEIJING NORMAL UNIVERSITY