TY - JOUR A1 - Strauch, Peter A1 - Neumann, Mike A1 - Kelling, Alexandra A1 - Schilde, Uwe T1 - Bis(1,2-dithiosquarato)nickelates(II): Synthesis, Structure, EPR and Thermal Behavior JF - Acta chimica Slovenica N2 - 1,2-Dithiosquaratonickelates are available by direct synthesis from metal salts with dipotassium-1,2-dithiosquarate and the appropriate counter cations. The synthesis and characterization, including mass spectrometry, of a series 1,2-dithiosquaratonickelates(II), [Ni(dtsq)(2)](2-), with several "onium" cations is reported and the X-ray structures of two diamagnetic complexes, (HexPh(3)P)(2)[Ni(dtsq)(2)] and (BuPh3P)(2)[Ni(dtsq)(2)] with sterically demanding counter ions are presented. The diamagnetic nickel complexes have been doped as host lattices with traces of Cu(II) to measure EPR for additional structural information. The thermal behavior of this series is studied by thermogravimetry and differential thermal analysis (TG/DTA). The thermolysis in air as well as under nitrogen atmosphere of these complexes results in nickel oxide nano-particles in all cases, which are characterized by X-ray powder diffraction. KW - 1,2-Dithiosquarate,1,2-Dithiosquaratonickelate KW - X-ray structure KW - TG/DTA KW - Nickel oxide KW - EPR spectroscopy Y1 - 2015 SN - 1318-0207 SN - 1580-3155 VL - 62 IS - 2 SP - 288 EP - 296 PB - Drustvo CY - Ljubljana ER - TY - JOUR A1 - Strauch, Peter A1 - Kossmann, Alexander A1 - Kelling, Alexandra A1 - Schilde, Uwe T1 - EPR on bis(1,2-dithiosquarato)cuprate(II) in the bis(1,2-dithiosquarato)nickelate(II) host lattice - structure and spectroscopy JF - Chemical papers N2 - EPR spectroscopy is a well suited analytical tool to monitor the electronic situation around paramagnetic metal centres as copper(II) and therefore the structural influences on the paramagnetic ion. 1,2-Dithiosquaratometalates are available by direct synthesis from metal salts with dipotassium-1,2-dithiosquarate and the appropriate counter cations. Synthesis and characterisation of bis(benzyltributylammonium)1,2-dithiosquaratonickelate(II), (BzlBu(3)N)(2)[Ni(dtsq)(2)], and bis(benzyltributylammonium)1,2-dithiosquaratocuprate(II), (BzlBu(3)N)(2)[Cu(dtsq)(2)], with benzyltributylammonium as the counter ion is reported and the X-ray structures of two complexes, (BzlBu(3)N)(2)[Ni(dtsq)(2)] and (BzlBu(3)N)(2)[Cu(dtsq)(2)], are presented. Both complexes, crystallising in the monoclinic space group P2(1)/c, are isostructural with only small differences in the coordination sphere due to the different metal ions. The diamagnetic nickel complex is therefore well suited as a host lattice for the paramagnetic Cu(II) complex to measure EPR for additional structural information. (c) 2015 Institute of Chemistry, Slovak Academy of Sciences KW - 1,2-dithiosquarate KW - 1,2-dithiosquaratometalate KW - X-ray structure KW - EPR spectroscopy Y1 - 2016 U6 - https://doi.org/10.1515/chempap-2015-0154 SN - 0366-6352 SN - 1336-9075 VL - 70 SP - 61 EP - 68 PB - De Gruyter CY - Berlin ER - TY - JOUR A1 - Geroldinger, Gerald A1 - Tonner, Matthias A1 - Fudickar, Werner A1 - De Sarkar, Sritama A1 - Dighal, Aishwarya A1 - Monzote, Lianet A1 - Staniek, Katrin A1 - Linker, Torsten A1 - Chatterjee, Mitali A1 - Gille, Lars T1 - Activation of anthracene endoperoxides in leishmania and impairment of mitochondrial functions JF - Molecules N2 - Leishmaniasis is a vector-borne disease caused by protozoal Leishmania. Because of resistance development against current drugs, new antileishmanial compounds are urgently needed. Endoperoxides (EPs) are successfully used in malaria therapy, and experimental evidence of their potential against leishmaniasis exists. Anthracene endoperoxides (AcEPs) have so far been only technically used and not explored for their leishmanicidal potential. This study verified the in vitro efficiency and mechanism of AcEPs against both Leishmania promastigotes and axenic amastigotes (L. tarentolae and L. donovani) as well as their toxicity in J774 macrophages. Additionally, the kinetics and radical products of AcEPs’ reaction with iron, the formation of radicals by AcEPs in Leishmania, as well as the resulting impairment of parasite mitochondrial functions were studied. Using electron paramagnetic resonance combined with spin trapping, photometry, and fluorescence-based oximetry, AcEPs were demonstrated to (i) show antileishmanial activity in vitro at IC50 values in a low micromolar range, (ii) exhibit host cell toxicity in J774 macrophages, (iii) react rapidly with iron (II) resulting in the formation of oxygen- and carbon-centered radicals, (iv) produce carbon-centered radicals which could secondarily trigger superoxide radical formation in Leishmania, and (v) impair mitochondrial functions in Leishmania during parasite killing. Overall, the data of different AcEPs demonstrate that their structures besides the peroxo bridge strongly influence their activity and mechanism of their antileishmanial action. KW - Leishmania KW - endoperoxides KW - EPR spectroscopy KW - mitochondria KW - radicals Y1 - 2018 U6 - https://doi.org/10.3390/molecules23071680 SN - 1420-3049 VL - 23 IS - 7 PB - MDPI CY - Basel ER -