scholarly journals FeIII, CuII and ZnII Complexes of the Rigid 9-Oxido-phenalenone Ligand—Spectroscopy, Electrochemistry, and Cytotoxic Properties

2021 ◽  
Vol 22 (8) ◽  
pp. 3976
Author(s):  
Katharina Butsch ◽  
Alexander Haseloer ◽  
Simon Schmitz ◽  
Ingo Ott ◽  
Julia Schur ◽  
...  

The three complexes [Fe(opo)3], [Cu(opo)2], and [Zn(opo)2] containing the non-innocent anionic ligand opo− (opo− = 9-oxido-phenalenone, Hopo = 9-hydroxyphenalonone) were synthesised from the corresponding acetylacetonates. [Zn(opo)2] was characterised using 1H nuclear magnetic resonance (NMR) spectroscopy, the paramagnetic [Fe(opo)3] and [Cu(opo)2] by electron paramagnetic resonance (EPR) spectroscopy. While the EPR spectra of [Cu(opo)2] and [Cu(acac)2] in dimethylformamide (DMF) solution are very similar, a rather narrow spectrum was observed for [Fe(opo)3] in tetrahydrofuran (THF) solution in contrast to the very broad spectrum of [Fe(acac)3] in THF (Hacac = acetylacetone, 2,4-pentanedione; acac− = acetylacetonate). The narrow, completely isotropic signal of [Fe(opo)3] disagrees with a metal-centred S = 5/2 spin system that is observed in the solid state. We assume spin-delocalisation to the opo ligand in the sense of an opo− to FeIII electron transfer. All compounds show several electrochemical opo-centred reduction waves in the range of −1 to −3 V vs. the ferrocene/ferrocenium couple. However, for CuII and FeIII the very first one-electron reductions are metal-centred. Electronic absorption in the UV to vis range are due to π–π* transitions in the opo core, giving Hopo and [Zn(opo)2] a yellow to orange colour. The structured bands ranging from 400 to 500 for all compounds are assigned to the lowest energy π−π* transitions. They show markedly higher intensities and slight shifts for the CuII (brown) and FeIII (red) complexes and we assume admixing metal contributions (MLCT for CuII, LMCT for FeIII). For both complexes long-wavelength absorptions assignable to d–d transitions were detected. Detailed spectroelectrochemical experiments confirm both the electrochemical and the optical assignments. Hopo and the complexes [Cu(opo)2], [Zn(opo)2], and [Fe(opo)3] show antiproliferative activities against HT-29 (colon cancer) and MCF-7 (breast cancer) cell lines in the range of a few µM, comparable to cisplatin under the same conditions.

Polymers ◽  
2021 ◽  
Vol 13 (5) ◽  
pp. 829
Author(s):  
Galina M. Mamardashvili ◽  
Dmitriy A. Lazovskiy ◽  
Ilya A. Khodov ◽  
Artem E. Efimov ◽  
Nugzar Z. Mamardashvili

New coordination oligomers and polymers of Sn(IV)-tetra(4-sulfonatophenyl)porphyrin have been constructed by the chelation reaction of its diaxialphenolates with Cu2+. The structure and properties of the synthesized polyporphyrin arrays were investigated by 1H Nuclear Magnetic Resonance (1H NMR), Infra Red (IR), Ultra Violet - Visible (UV-Vis) and fluorescence spectroscopy, mass spectrometry, Powder X-Rays Diffraction (PXRD), Electron Paramagnetic Resonance (EPR), thermal gravimetric, elemental analysis, and quantum chemical calculations. The results show that the diaxial coordination of bidentate organic ligands (L-tyrazine and diaminohydroquinone) leads to the quenching of the tetrapyrrole chromophore fluorescence, while the chelation of the porphyrinate diaxial complexes with Cu2+ is accompanied by an increase in the fluorescence in the organo-inorganic hybrid polymers formed. The obtained results are of particular interest to those involved in creating new ‘chemo-responsive’ (i.e., selectively interacting with other chemical species as receptors, sensors, or photocatalysts) materials, the optoelectronic properties of which can be controlled by varying the number and connection type of monomeric fragments in the polyporphyrin arrays.


2020 ◽  
Vol 2020 ◽  
pp. 1-9
Author(s):  
Shengxian Zhao ◽  
Yin Cao ◽  
Zhenzhen Cui ◽  
Jiayun Zhang ◽  
Zhixiang Pan ◽  
...  

A series of 2-arylidene-N-(quinolin-6-yl)hydrazine-1-carboxamides 5a–5o were synthesized and characterized. The synthesized compounds (5a–5o) were screened in vitro against three breast cancer cell lines: SKBR3, MDA-MB-231, and MCF-7 cancer cell lines by the MTT assay. According to MTT results, compounds 5k and 5l showed better antiproliferative activities over MCF-7 cell lines with IC50 values of 8.50 and 12.51 μM. Colony formation assay indicated 5k/5l treatment obviously inhibited the growth of MCF-7 cells and 5k/5l-induced cell cycle was arrested in the G2-M phase. Moreover, 5k/5l significantly increased the level of cleaved PARP and induced the apoptosis in MCF-7 cells. In addition, compared to Hela cells, MCF-7 cells were more sensitive to 5k/5l treatment.


1993 ◽  
Vol 07 (05) ◽  
pp. 271-290 ◽  
Author(s):  
SHOEI-SHENG LIN ◽  
JENG-KUANG HUANG ◽  
YING-SHENG HUANG

In this review, the preparation and characterization of the pyrite-type compound RuS 2 and RuSe 2, as well as the mixed anion compositions RuS 2 − x Se x, are systematically reported. Unusual temperature dependence in electrical transport properties characterize these compounds. Electrolyte electroreflectance measurements were used to get a better understanding of their band structure. Long-wavelength optical phonons have been studied by Raman scattering measurements at room temperature. The nature of defect in these compounds were studied by electron paramagnetic resonance (EPR) investigation. A chalcogen point defect model was established to account for the spin S = 1/2 paramagnetic species detected by EPR.


2014 ◽  
Vol 70 (3) ◽  
pp. 540-547 ◽  
Author(s):  
Xiaowen Wang ◽  
Jiahai Ma ◽  
Zhenpeng Wang ◽  
Rongrong Guo ◽  
Xuefeng Hu

The kinetics, environmental influencing factors, products and reaction mechanism of aqueous phototransformation of bisphenol S (BPS), as an alternative to bisphenol A, which is of environmental concern, were investigated. p-Hydroxybenzenesulfonic acid, as the major transformation product was confirmed by gas chromatography – mass spectrometry, electrospray ionization, 1H nuclear magnetic resonance and fluorescence spectrum analysis. A reaction pathway was proposed based on the reactive oxygen species related results by electron paramagnetic resonance and radical traps. The competition of the excited state of BPS between transferring electron to O2 to •O2- and directly oxidizing H2O to •OH was revealed.


1965 ◽  
Vol 20 (6) ◽  
pp. 509-512 ◽  
Author(s):  
A. Haug ◽  
P. Douzou

With orotic acid an EPR triplet state signal (ΔM= ±2) was observed in a non-cracking rigid solvent at 77°K. This triplet state, lying at 470 mμ, has a mean half-life of 0.2 sec and is characterized by a large zero-field splitting.Excitation and phosphorescence spectra of related pyrimidines were measured, too. Besides uracil and cytosine, the excitation peak of these pyrimidines coincides with the large π—π* absorption peak. In the case of uracil and cytosine the excitation peak lies distinctly separated at the long wavelength side of the corresponding absorption peak. This probably indicates a n—π* excitation. The failure to record EPR triplet signals in these pyrimidines is attributed to large zero-field splitting.


2018 ◽  
Vol 2018 ◽  
pp. 1-10 ◽  
Author(s):  
Nur Rahimah Fitrah Mohd Sofyan ◽  
Fariza Juliana Nordin ◽  
Mohd Ridzuan Mohd Abd Razak ◽  
Syahrina Nur ‘Ain Abdul Halim ◽  
Nur Adila Fatin Mohd Khir ◽  
...  

Five silver(I) complexes containing a mixed ligand system of phosphine and thiazolidine were successfully synthesized. The structural information of the complexes was assembled using various spectroscopic techniques such as CHN elemental analysis, Fourier transformed infrared (FTIR), 1H, 13C, and 31P{1H} NMR spectroscopy, and thermogravimetric analysis (TGA). A bidentate phosphine ligand acted as a chelating agent which bond to the silver in 1 : 2 molar ratios. Meanwhile, thiazolidine was attached to the silver in a 1 : 1 molar ratio. The antiplasmodial properties of all synthesized complexes were investigated on chloroquine-resistant P. falciparum parasite via HRP2 assays and cytotoxicity tests on Vero cells. Of all the synthesized complexes, complex 2 showed the highest SI value (more than 12.4) followed by complex 5 (6.6). The potent properties of compounds 2 and 5 were also noted in the in vitro antiproliferative assays involving MDA-MB-231 and MCF-7 breast cancer cell lines as well as HT-29 colon cancer cell line. Complex 2 was selective for MDA-MB-231 cells (GI50 = 1.9 ± 0.3 µM), while complex 5 acted predominantly on breast carcinoma cells (GI50 MDA-MB-231 = 4.7 ± 1.1 µM; MCF-7 = 2.9 ± 0.9 µM) instead of colon carcinoma (HT-29) cells (GI50 = 15.1 ± 1.9 µM).


2006 ◽  
Vol 518 ◽  
pp. 459-464
Author(s):  
A. Milutinović ◽  
M.J. Romčević ◽  
N.Ž Romčević

In Part I of this paper, we used X-ray, far-infrared reflectivity and electron paramagnetic resonance measurements to investigate optical and magnetic properties of Hg1-xMnxSe (x≤0.26) alloys. In Part II, we expand our investigation to Raman spectroscopy and galvanomagnetic measurements. We registered two-mode behaviour of long wavelength optical phonons and described it by modified Genzel’s model. Except modes from the centre of Brillouin zone, there are some of forbidden modes in Raman spectra that originate from the edge of the zone, as well as a mode that corresponds to the maximum of phonon density of states. Modes of unalloyed α–MnSe are registered, too.


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