Carboxylate radical bridged binuclear iron-sulfur-cluster fluorescent probe, preparation method and application thereof

一种荧光探针、羧酸根的技术，应用在荧光/磷光、化学仪器和方法、硫化染料等方向，达到操作简单、选择性好、荧光变化敏锐的效果

Inactive Publication Date: 2015-11-25
DALIAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Most of their central metals are ruthenium (Ru), cobalt (Co), europium (Eu) and iron (Fe), and most of the fluorophores or chromophores are o-phenanthroline and naphthalene (DaltonTrans.2009,12,2096 -2102; DaltonTrans.2012, 41, 4484-4496; Appl.Organometal.Chem., 2008, 22, 258-261; Analyst, 2013, 138, 278-283; Polym.Chem., 2012, 3, 2640-2648.), while Fluorescent probes of carboxylate-bridged dinuclear iron-sulfur clusters have not been reported yet

Method used

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  • Carboxylate radical bridged binuclear iron-sulfur-cluster fluorescent probe, preparation method and application thereof
  • Carboxylate radical bridged binuclear iron-sulfur-cluster fluorescent probe, preparation method and application thereof
  • Carboxylate radical bridged binuclear iron-sulfur-cluster fluorescent probe, preparation method and application thereof

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Experimental program
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preparation example Construction

[0029] A method for preparing a carboxylate-bridged dinuclear iron-sulfur cluster fluorescent probe, the reaction mechanism is as follows:

[0030]

[0031] (1) Addition reaction

[0032] Addition reaction of 9-anthracenemethylamine and p-methoxycarbonylphenylisocyanate to obtain the corresponding carboxylate;

[0033] (2) Hydrolysis reaction

[0034] Mixing the product solution obtained in step (1) with water and performing a hydrolysis reaction to obtain intermediate 3;

[0035] (3) Neutralization reaction

[0036] The intermediate 3 obtained in step (2) is reacted with a base to obtain a carboxylate;

[0037] (4) Coordination reaction

[0038] The carboxylate salt obtained in step (3) is coordinated with the dinuclear iron precursor 4a or 4b to obtain fluorescent probes 5a and 5b.

Embodiment 1

[0039] Example 1 Synthesis of carboxylate-bridged dinuclear iron-sulfur cluster fluorescent probe 5a

[0040] 0.86g p-methoxycarbonyl phenyl isocyanate was added in 180mL dichloromethane solution containing 9-anthracenemethylamine (1g), stirred at room temperature for 24 hours, filtered, 10mL chloroform washed the filter cake, and then the filter cake was dissolved in ethanol ( 10 mL), 2M sodium hydroxide solution (10 mL) was added thereto, and the temperature was raised to 75° C. to react for 12 hours. Then add 3M hydrochloric acid to the reaction solution to adjust the pH=6, filter with suction, wash the filter cake with 5mL water and ethanol respectively, and finally recrystallize with a mixed solvent of dimethyl sulfoxide-acetone to obtain hydrolyzate 3 (0.92g, 52% ).

[0041] 1 HNMR (400MHz, DMSO-d 6 ):δ11.24(br,1H),8.99(s,1H),8.61(br,1H),8.54(d,J H-H =8Hz,2H),8.11(br,2H),7.72(br,2H),7.54-7.61(m,4H),7.35(br,3H),5.31(br,2H). 13 CNMR (100MHz, DMSO-D 6 ): δ155.08, 141....

Embodiment 2

[0046] Example 2 Synthesis of carboxylate-bridged dinuclear iron-sulfur cluster fluorescent probe 5b

[0047] 4b was used as the dinuclear iron precursor, and the rest of the operation steps were the same as in Example 1 to obtain 5b (105 mg, 58%).

[0048] 1 HNMR (400MHz, CD 2 Cl 2 ):δ8.44(s,1H),8.33(d,J H-H =8Hz,2H),8.01(d,J H-H =8Hz, 2H), 7.46-7.51(m, 4H), 7.14(d, J H-H =8Hz,2H),6.93(d,J H-H =8Hz, 2H), 6.73(s, 1H), 5.33(br, 2H), 5.26(br, 1H), 1.93(t, J H-H =8Hz,6H),1.63(q,J H-H =8Hz,4H),1.46(s,30H).IR(KBr,cm -1 ):3421(m), 3056(w), 2981(m), 2925(s), 1698(s), 1597(s), 1519(s), 1448(w), 1403(s), 1375(m) , 1319(m), 1231(m), 1178(m), 1073(w), 1018(s), 845(s), 778(m), 736(m).

[0049] ESI-HRMS(m / z):[M-PF 6 ] + 873.2506;calcd.valueforC 47 h 57 Fe 2 N 2 o 3 S 2 :873.2509.

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Abstract

The invention provides a carboxylate radical bridged binuclear iron-sulfur-cluster fluorescent probe adopting the structure shown in the general formula I. A preparation method comprises steps as follows: anthracene methylamine and p-methoxycarbonylphenyl isocyanate have an addition reaction to produce substituted methyl benzoate; then corresponding carboxylic acid is obtained through hydrolysis; the obtained carboxylic acid and alkali react to produce carboxylate; the carboxylate is coordinated with a binuclear iron precursor to produce the fluorescent probe. Compared with the prior art, a carboxylate radical bridged binuclear iron-sulfur cluster with a metal complex close to nuclear structures of bio-enzymes is provided for the first time; the metal complex serves as the fluorescent probe, fluorine ion detection selectivity is good, fluorescence titration experiment operation is simple, and fluorescence change is sensitive.

Description

technical field [0001] The invention relates to a class of carboxylate-bridged dinuclear iron-sulfur cluster fluorescent probe complexes and a preparation method and application thereof, which belong to the detection of ions in the field of fine chemical industry. Background technique [0002] There are many types of enzymes in organisms, among which there are several biological enzymes whose central structure is dinuclear iron bridged by carboxylate groups, such as ribonucleotide reductase (RNR) and soluble methane monooxygenase (sMMO), which can Catalytic conversion of some important substrates in organisms plays a very important role in organisms. So simulating the structure and function of these biological enzymes is a challenging task, but also of great significance. (Acc. Chem. Res. 2011, 44, 280-288; Coord. Chem. Rev. 2013, 257, 3-26.). [0003] Anions are ubiquitous in living organisms and play a very important role, among which fluoride ion is one of the indispens...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F15/02C09K11/06G01N21/64
CPCG01N33/182C07F15/02C07F17/02C09B1/00C09B49/00C09K11/06C09K2211/1007C09K2211/1011C09K2211/1014C09K2211/187G01N21/643G01N2021/6439
Inventor 周宇涵曲景平董晓亮
Owner DALIAN UNIV OF TECH
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