- Strong in vitro and vivo cytotoxicity of novel organoplatinum(II) complexes with quinoline-coumarin derivatives
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A series of novel organoplatinum(II) complexes, [PtII(QC1)(H-QC1)Cl] (Pt1), [PtII(QC2)(H-QC2)Cl] (Pt2), [PtII(QC3)(H-QC3)Cl] (Pt3), [PtII(QC4)(H-QC4)Cl]?CH3OH (Pt4), [PtII(QC5)(H-QC5)Cl] (Pt5), [PtII(H-QC6)(DMSO)Cl2] (Pt6), [PtII(H-QC7)(DMSO)Cl2]?H2O (Pt7), [PtII(H-QC8)(DMSO)Cl2] (Pt8), [PtII(H-QC9)(DMSO)Cl2]?CH3OH (Pt9), [PtII(H-QC10)(DMSO)Cl2] (Pt10) and [PtII(H-QC11)(DMSO)Cl2] (Pt11), bearing quinoline-coumarin derivatives (H-QC1?H-QC11) have been first designed. Complexes Pt1–Pt11 selectively displayed obvious cytotoxicities in comparison to cisplatin for A549/DDP (cisplatin-resistant human lung adenocarcinoma) cells and HeLa cervical carcinoma cells, with IC50 values as low as 100 nM?10.33 μM. In addition, Pt4 and Pt5 display a green-colored luminescent properties, targeted mitochondrial membrane and, thereby induced mainly mitochondria-mediated cell apoptosis was in the following order: Pt4 > Pt5. The different anti-cancer activity of quinoline-coumarin complexes Pt4 (100 nM) and Pt5 (250 nM) were correlate with the presence of 3-(2′-quinolyl)-6-hydroxy-coumarin (H-QC4) ligand. The quinoline-coumarin complex Pt4 (2.0 mg/kg per 2 days) also displayed potent in vivo anti-tumor effect after 21 days-treated. In contrast, the H-QC4 ligand highly enhances the anti-tumor activity and selectivity of organoplatinum(II) complexes in comparison to other previously reported coumarin derivatives metal complexes.
- Qin, Qi-Pin,Wang, Zhen-Feng,Huang, Xiao-Ling,Tan, Ming-Xiong,Zou, Bi-Qun,Liang, Hong
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- Colorimetric and fluorescent signaling of Au3+ by desulfurization of thiocoumarin
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We investigated the chemosignaling of Au3+ by the selective desulfurization of thiocoumarin. In the presence of a heavy metal ion chelator N,N,N′,N′-tetrakis-(2-pyridylmethyl)ethylenediamine, thiocoumarin was selectively converted to its oxo analogue by reaction with Au3+, resulting in a pronounced chromogenic and fluorescent signaling. Selective signaling of Au3+ was possible in the presence of common alkali, alkaline earth, and transition metal ions, as well as Au+ in a mixed aqueous environment. The colorimetric determination of Au3+ was possible by the color change from pink to yellowish green of the designed probe. The detection limit for the determination of Au3+ in 50% aqueous acetonitrile was 1.1 × 10-7 M.
- Park, Ji Eun,Choi, Myung Gil,Chang, Suk-Kyu
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- Photoinduced formation of the laser dye coumarin 6 from its dihydro derivatives
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The dihydro form of the laser dye Coumarin 6 and its acylated derivatives undergo photoinduced transformations with Coumarin 6 formation. The reactions go easily both in organic solvents and in polymer films with a high increase of fluorescence. Irreversibility of the reaction provides potential use of the new photosensitive media for optical information recording and sensing technologies.
- Traven, Valerii F.,Cheptsov, Dmitrii A.,Solovjova, Natalya P.,Chibisova, Tatjana A.,Voronov, Ilya I.,Dolotov, Sergei M.,Ivanov, Ivan V.
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- Light-up lipid droplets for the visualization of lipophagy and atherosclerosis by coumarin-derived bioprobe
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Lipid droplets (LDs) are intracellular lipid-metabolism organelles that involved in many physiological processes, metabolic disorders as well as diseases such as atherosclerosis. However, the specific probes that can visually locate abnormal LDs-rich tissues and track LDs-associated behavior to the naked eye with adequate biosafety still are rare. Herein, we develop a new design strategy of LDs-targeted probe based on the solvatochromism of coumarin derivatives. The results revealed that the emission wavelength of coumarin fluorophores gradually red shift in different solvents with increasing polarity, while absorption wavelength almost unchanged. As a result, the enlarged stokes shift of coumarin was emerged from oil to water. Furthermore, properly reducing water solubility and adding electronic donor at the structure of coumarins can enlarge this type of solvatochromism. This discovery was utilized to develop suitable probe for the image of LDs and LDs-rich tissues with high resolution and biosafety. Therefore, LDs-associated behavior was visible to the naked eye during the process of lipophagy and atherosclerosis. We deem that the developed probe here offers a new possibility to accurately diagnosis and analyse LDs-related diseases in clinic and preclinical study.
- Zheng, Jinrong,Qin, Shuheng,Gui, Lijuan,Li, Hua,Fan, Lixue,Yang, Yifei,Chen, Haiyan,Xu, Hui,Yuan, Zhenwei
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supporting information
p. 2385 - 2389
(2021/03/17)
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- Fluorescent 7-Substituted Coumarin Dyes: Solvatochromism and NLO Studies
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The effect of three substituents N,N-diethylamine, carbazole and diphenylamine at the 7 position of coumarin on linear and nonlinear optical properties are studied using absorption and emission solvatochromism, and DFT. By varying the substituent 53?nm red shift is achieved in emission. The polarity plots with regression close to unity revealed good charge transfer in the system. Solvent polarizability and dipolarity are mainly responsible for solvatochromic shift as proved by multilinear regression analysis. General Mulliken Hush analysis shows diphenylamine substituent leads to more charge separation in compound 6c. The hyperpolarizabilities are evaluated by quantum mechanical calculations. Structure of the compounds are optimized at B3LYP/6-31G(d) level and NLO computations are done using range separated hybrid functionals with large basis sets. Second order hyperpolarizability (γ) found 589.27 × 10?36, 841.29 × 10?36 and 1043.00 × 10?36 e.s.u for the compounds 6a, 6b and 6c respectively.
- Bhagwat, Archana A.,Sekar, Nagaiyan
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p. 121 - 135
(2018/11/10)
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- Reinvestigation of the synthesis of “covalent-assembly” type probes for fluoride ion detection. Identification of novel 7-(diethylamino)coumarins with aggregation-induced emission properties
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An unprecedented C-3 functionalization of 4-(diethylamino)salicylaldehyde through a Friedel-Crafts type alkylation reaction has been discovered during the synthesis of “covalent-assembly”-based fluorescent probes for detection of fluoride ions. The resulting Friedel-Crafts adduct was successfully used for the preparation of two novel 8-substituted 7-(diethylamino)coumarin dyes. The photophysical study of these fluorophores has enabled us to highlight their remarkable aggregation-induced emission (AIE) properties characterized by a yellow-orange emission of aggregates in water. Therefore, 4-(tert-butyldimethylsilyloxy)benzyl substituent was identified as a novel AIE-active moiety which could be seen as a possible alternative to popular tetraphenylethylene (TPE).
- Quesneau, Valentin,Roubinet, Beno?t,Renard, Pierre-Yves,Romieu, Anthony
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supporting information
(2019/11/05)
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- Discovery of fluorescent 3-heteroarylcoumarin derivatives as novel inhibitors of anaplastic lymphoma kinase
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Altered expression or hyperactivation of anaplastic lymphoma kinase (ALK), as a consequence of translocations or point mutations, is one of the main oncogenic drivers in non-small cell lung cancer. Using structure-based design and in vitro enzyme assays, we identified 3-heteroarylcoumarin as a new template for the development of novel fluorescent ALK inhibitors. Molecular simulation provided structural insights for the design of 3-heteroarylcoumarin derivatives, which were easily prepared through efficient synthetic approaches including direct C-H cross coupling. Importantly, these coumarin-based ALK inhibitors can be tracked using microscopy techniques: we illustrated the use of the most potent compound in this series, 5a, (ALK/IC50 = 0.51 μM, λemi = 500 nm, φF = 0.29) to monitor its subcellular distribution pattern by confocal fluorescence microscopy.
- Mah, Shinmee,Song, Daesun,Shin, Yongje,Jung, Yongwon,Hong, Sungwoo,Jang, Jaebong,Latif, Muhammad
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p. 186 - 194
(2019/01/11)
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- Synthesis and properties of arsenic(III)-reactive coumarin-appended benzothiazolines: A new approach for inorganic arsenic detection
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The EPA has established a maximum contaminant level (MCL) of 10 ppb for arsenic (As) in drinking water requiring sensitive and selective detection methodologies. To tackle this challenge, we have been active in constructing small molecules that react specifically with As3+ to furnish a new fluorescent species (termed a chemodosimeter). We report in this contribution, the synthesis and spectroscopy of two small-molecule fluorescent probes that we term ArsenoFluors (or AFs) as As-specific chemodosimeters. The AFs (AF1 and AF2) incorporate a coumarin fluorescent reporter coupled with an As-reactive benzothiazoline functional group. AFs react with As3+ to yield the highly fluorescent coumarin-6 dye (C6) resulting in a 20-25-fold fluorescence enhancement at λem ～ 500 nm with detection limits of 0.14-0.23 ppb in tetrahydrofuran (THF) at 298 K. The AFs also react with common environmental As3+ sources such as sodium arsenite in a THF/CHES (N-cyclohexyl-2-aminoethanesulfonic acid) (1:1, pH 9, 298 K) mixture resulting in a modest fluorescence turn-ON (1.5- to 3-fold) due to the quenched nature of coumarin-6 derivatives in high polarity solvents. Bulk analysis of the reaction of the AFs with As3+ revealed that the C6 derivatives and the Schiff-base disulfide of the AFs (SB1 and SB2) are the ultimate end-products of this chemistry with the formation of C6 being the principle photoproduct responsible for the As3+-specific turn-ON. It appears that a likely species that is traversed in the reaction path is an As-hydride-ligand complex that is a putative intermediate in the proposed reaction path.
- Ezeh, Vivian C.,Harrop, Todd C.
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p. 2323 - 2334
(2013/04/10)
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- A fluorescence "turn-on" chemodosimeter for Cu2+ in aqueous solution based on the ion promoted oxidation
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We developed a novel method for Cu2+ detection based on the ion promoted oxidation reaction. Chemodosimeter L (weak fluorescence) can be oxidized into 3-benzothiazoly-7-N,N-diethylaminocoumarin (strong green fluorescence, coumarin 6) by Cu2+ with high selectivity and sensitivity in HEPES (10 mM, pH = 7.4) buffer containing 50% (v/v) water-CH 3CN solution. The Royal Society of Chemistry 2012.
- Li, Junbo,Zeng, Yang,Hu, Qihui,Yu, Xianglin,Guo, Jia,Pan, Zhiquan
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p. 3623 - 3626
(2012/05/20)
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- Direct C-H cross-coupling approach to heteroaryl coumarins
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A Pd-catalyzed direct cross-coupling of 3-bromocoumarins with heteroarenes provided an efficient route to synthesizing 3-heteroarylcoumarins. The reaction scope for the transformation was fairly broad, affording modest to good yields of various 3-heteroarylcoumarin scaffolds, which are privileged structures and prevalent motifs in many biologically active compounds and fluorophores. The Royal Society of Chemistry 2012.
- Min, Minsik,Kim, Bomi,Hong, Sungwoo
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experimental part
p. 2692 - 2698
(2012/04/23)
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- The one-pot synthesis and fluorimetric study of 3-(2′-benzothiazolyl)coumarins
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A novel, piperidene-catalysed, one-pot synthesis of 3-(2′-benzothiazolyl)coumarins was undertaken, starting from salicylaldehydes, ethyl cyanoacetate and o-aminobenzenethiols in ethanol. Salicylaldehydes with electron-donating group gave optimum yields. The novel method is characterized by mild reaction conditions, simple procedure and low waste. All compounds were fluorescent in solution emitting either green light (490?nm) or blue light (440-460?nm). Two typical fluorescence peaks were found in the three-dimensional fluorescence spectra.
- Zhou, Shihai,Jia, Jianhong,Gao, JianRong,Han, Liang,Li, Yujin,Sheng, Weijian
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experimental part
p. 123 - 128
(2010/11/04)
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- Hg2+-selective chromogenic and fluorogenic chemodosimeter based on thiocoumarins
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The highly selective chemodosimetric behavior of thiocoumarins toward Hg2+ ions was investigated; significant chromogenic and fluorogenic signaling of Hg2+ ions occurs from the transformation of thiocoumarin to coumarin by Hg2+
- Choi, Myung Gil,Kim, Youn Hwan,Namgoong, Ji Eun,Chang, Suk-Kyu
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body text
p. 3560 - 3562
(2009/12/02)
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- Synthesis and anti-angiogenesis activity of coumarin derivatives
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A series of 7-diethylaminocoumarin compounds were synthesized and the cytotoxicities were tested against human umbilical vein endothelial cell (HUVEC) and some cancer cells. We found that the introduction of cyano groups at the 4-position will promote the bioactivity. In particular, compounds 9 and 10 strongly inhibited the proliferation of various cancer cell lines, and 12 and 15 showed a high selectivity for HUVEC. Therefore, these coumarin molecules can be utilized as lead compounds to develop potential nontoxic angiogenesis inhibitors and small molecular ligands to target HUVEC.
- Lee, Seokjoon,Sivakumar, Krishnamoorthy,Shin, Woon-Seob,Xie, Fang,Wang, Qian
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p. 4596 - 4599
(2007/10/03)
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- Efficient synthesis of 3-substituted coumarins
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The Mukaiyama's esterification protocol, using 2-chloro-1-methylpyridinium iodide-triethylamine reagent, has been successfully exploited to provide rapid access to a variety of 3-substituted coumarins in satisfactory yields.
- Mashraqui, Sabir H.,Vashi, Dhaval,Mistry, Hitesh D.
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p. 3129 - 3134
(2007/10/03)
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- Preparation, photochemistry, and electronic structures of coumarin laser dye complexes of cyclopentadienylruthenium(II)
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The syntheses and characterization of six new compounds that contain the CpRu+ (Cp = η5-C5H5) moiety bound to a substituted coumarin laser dye are reported. The complexes prepared are of the general form [CpRu(η6-laser dye)]PF6, where laser dye = coumarin-1 (7-(diethylamino)-4-methylcoumarin), coumarin-2 (4,6-dimethyl-7-(ethylamino)coumarin), coumarin-6 (3-(2-benzothiazolyl)-7-(diethylamino)coumarin), coumarin-311 (7-(dimethylamino)-4-methylcoumarin), coumarin-334 (10-acetyl-2,3,6,7-tetrahydro-1H,5H,11H-[1]benzopyrano[6,7,8-ij]quinolizin-11- one), or coumarin-338 (2,3,6,7-tetrahydro-11-oxo-1H,5H,11H-[1]benzopyrano[6,7,8-ij]quinolizine-10- carboxylic acid 1,1-dimethylethyl ester). The structures of all of the new complexes except the complex of coumarin-6 were determined by 1H and 13C NMR spectroscopy and contain the CpRu+ group bound to the benzenoid moiety of the coumarin system. The CpRu+ group binds to the benzothiazole group of the coumarin-6 compound. Photolysis of the complexes in CH3CN solutions results in the formation of CpRu(CH3CN)3+ and the free dye. The complexes of the dyes other than coumarin-6 exhibit low-lying MLCT bands and are not emissive. The coumarin-6 complex retains the low-lying intramolecular charge-transfer band present in the free dye and emits in fluid solution at room temperature with λmax = 532 nm and Φ = 0.11 ± 0.02. The laser dye centered emission band of the complex is red-shifted 25 nm with respect to the free coumarin-6 emission.
- Koefod, Robert S.,Mann, Kent R.
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p. 2285 - 2290
(2008/10/08)
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