Supplementary data for article: Zianna, A.; Sumar Ristovic, M.; Psomas, G.; Hatzidimitriou, A.; Coutouli-Argyropoulou, E.; Lalia-Kantouri, M. Cadmium(II) Complexes of 5-Nitro-Salicylaldehyde and α -Diimines: Synthesis, Structure and Interaction with Calf-Thymus DNA. Journal of Coordination Chemistry 2015, 68 (24), 4444–4463. https://doi.org/10.1080/00958972.2015.1101075

Supplementary material for: [https://doi.org/10.1080/00958972.2015.1101075]Related to published version: [http://cherry.chem.bg.ac.rs/handle/123456789/2004]Related to accepted version: [http://cherry.chem.bg.ac.rs/handle/123456789/3350

Supplementary material for the article: Ristovic, M. S.; Zianna, A.; Psomas, G.; Hatzidimitriou, A. G.; Coutouli-Argyropoulou, E.; Lalia-Kantouri, M. Interaction of Dinuclear Cadmium(II) 5-Cl-Salicylaldehyde Complexes with Calf-Thymus DNA. Materials Science and Engineering C 2016, 61, 579–590. https://doi.org/10.1016/j.msec.2015.12.054

Supplementary material: [https://doi.org/10.1016/j.msec.2015.12.054]Related to published version: [http://cherry.chem.bg.ac.rs/handle/123456789/2052

Supplementary data for the article: Zianna, A.; Ristović, M. Š.; Psomas, G.; Hatzidimitriou, A.; Coutouli-Argyropoulou, E.; Lalia-Kantouri, M. Cadmium(II) Complexes of 5-Bromo-Salicylaldehyde and α-Diimines: Synthesis, Structure and Interaction with Calf-Thymus DNA and Albumins. Polyhedron 2016, 107, 136–147. https://doi.org/10.1016/j.poly.2016.01.020

Supplementary material for: [https://doi.org/10.1016/j.poly.2016.01.020]Related to published version: [http://cherry.chem.bg.ac.rs/handle/123456789/1923

Supplementary material for the article: Ristovic, M. S.; Zianna, A.; Psomas, G.; Hatzidimitriou, A. G.; Coutouli-Argyropoulou, E.; Lalia-Kantouri, M. Interaction of Dinuclear Cadmium(II) 5-Cl-Salicylaldehyde Complexes with Calf-Thymus DNA. Materials Science and Engineering C 2016, 61, 579–590. https://doi.org/10.1016/j.msec.2015.12.054

Supplementary material: [https://doi.org/10.1016/j.msec.2015.12.054]Related to published version: [http://cherry.chem.bg.ac.rs/handle/123456789/2052

Supplementary data for article: Zianna, A.; Sumar Ristovic, M.; Psomas, G.; Hatzidimitriou, A.; Coutouli-Argyropoulou, E.; Lalia-Kantouri, M. Cadmium(II) Complexes of 5-Nitro-Salicylaldehyde and α -Diimines: Synthesis, Structure and Interaction with Calf-Thymus DNA. Journal of Coordination Chemistry 2015, 68 (24), 4444–4463. https://doi.org/10.1080/00958972.2015.1101075

Supplementary material for: [https://doi.org/10.1080/00958972.2015.1101075]Related to published version: [http://cherry.chem.bg.ac.rs/handle/123456789/2004]Related to accepted version: [http://cherry.chem.bg.ac.rs/handle/123456789/3350

Synthesis and structural characterization of new coordination complexes of bivalent metals with oxygen-donor and nitrogen-donor ligands: investigation of biological properties

The aim of this thesis was the synthesis, characterization and study of the biological activity of new coordination complexes of bivalent transitional metals with ligands substituted salicylaldehydes (X–saloH), 2–hydroxy–phenones (ketoΗ) and α–διιμίνες (bipy, phen, neoc, dpamH). Within this scope, forty-one new coordination compounds of Cu, Ni, Cd and Pd were synthesized and characterized. More specifically, seven copper complexes under the general formula [Cu(X–salo)2(S)x] and [Cu(keto)2(S)x], where S = CH3OH or H2O and x = 0–2, fifteen nickel complexes under the general formula [Νi(5–X–salo)2(CH3OH)2] for the neutral complexes, [Νi(dpamH)2(X–salo)]Υ, (where Υ= Cl ή (NO3)) for the cationic and [Ni4(L)4(μ3–CH3O)4(CH3OH)4]for the tetranuclear nickel cubane type clusters, where HL = 5–CH3–saloH, or ppoH, or bpoH. Moreover fifteen cadmium complexes were synthesized, three of which without the presence of a-diimine and twelve with the presence of a-dimines, with different nuclearity (mononuclear, dinuclear and trinuclear). Finally four palladium complexes under the general formula [Pd(X–salo)2] were synthesized and characterized. Complexes were characterized with Infra-red (ΙR) spectroscopy, ulta-violet visible (UV–vis) spectroscopy and nuclear magnetic resonance (1H–NMR), elemental analysis, room temperature magnetic measurements, molecular conductivity measurements, cyclic voltammetry, thermo-analytic teqniques and X-Ray diffraction analysis. It is important to mention that the ligands (Χ–saloH) present different coordination modes, some of which appeared for the first time in cadmium complexes of this thesis. Additionally, spectroscopic (UV-vis) and physicochemical (viscosity measurements) techniques (as well as cyclic voltammetry for cooper and nickel complexes) have been employed in order to study the binding mode and strength of the complexes to calf–thymus (CT) DNA, while competitive studies with ethidium bromide (EB) performed by fluorescence have revealed the ability of the complexes to displace the DNA–bound EB. In conclusion intercalation is the most possible mode of interaction of all complexes with CT DNA, while for cationic nickel complexes, an electrostatic interaction with CT DNA may exist. The interaction of the complexes with serum albumin proteins (SA) has been studied by fluorescence emission spectroscopy and the determined binding constants exhibit relative high values, indicating their rather tight binding to the SA in order to get transported towards their potential targets and upon arrival complexes have the potential to get released.Σκοπός της παρούσας διατριβής ήταν η σύνθεση, ο χαρακτηρισμός και η μελέτη της βιολογικής δραστικότητας νέων ενώσεων συναρμογής δισθενών μεταβατικών μετάλλων με ligands υποκατεστημένες σαλικυλαλδεΰδες (X–saloH), 2–υδροξυ–φαινόνες (ketoΗ) και α–διιμίνες (bipy, phen, neoc, dpamH). Σε αυτό το πλαίσιο, παρασκευάστηκαν και χαρακτηρίστηκαν σαρανταμία νέες σύμπλοκες ενώσεις των δισθενών μετάλλων Cu, Ni, Cd και Pd. Συγκεκριμένα, παρασκευάστηκαν επτά ενώσεις του χαλκού με γενικούς τύπους [Cu(X–salo)2(S)x] και [Cu(keto)2(S)x], όπου S = CH3OH ή H2O και x = 0–2, δεκαπέντε ενώσεις του νικελίου με γενικούς τύπους [Νi(5–X–salo)2(CH3OH)2] για τις ουδέτερες ενώσεις, [Νi(dpamH)2(X–salo)]Υ, (όπου Υ= Cl ή (NO3)) για τις κατιονικές και [Ni4(L)4(μ3–CH3O)4(CH3OH)4]για τις τετραπυρηνικές τύπου κουβανίου, όπου HL = 5–CH3–saloH, ή ppoH, ή bpoH. Επίσης παρασκευάστηκαν δεκαπέντε ενώσεις του καδμίου, τρεις εκ των οποίων απουσία α–διιμινών ([Cd(5–NO2–salo)2(CH3OH)2], [Cd(5–Br–salo)2(CH3OH)]2 και [Cd(5–Cl–salo)2(CH3OH)]2) και δώδεκα παρουσία α–διιμινών με διαφορετική πυρηνικότητα (μονομερή, διμερή και τριμερή). Τέλος, παρασκευάστηκαν και τέσσερις ενώσεις του παλλαδίου με γενικό τύπο [Pd(X–salo)2]. Ο χαρακτηρισμός των ενώσεων έγινε με φασματοσκοπία υπερύθρου (ΙR), υπεριώδους ορατού (UV–vis) και πυρηνικού μαγνητικού συντονισμού (1H–NMR), στοιχειακές αναλύσεις, μετρήσεις μαγνητικής επιδεκτικότητας σε θερμοκρασία δωματίου, μετρήσεις μοριακής αγωγιμότητας, κυκλική βολταμμετρία, θερμοαναλυτικές μελέτες και κρυσταλλογραφία ακτίνων–Χ. Είναι σημαντικό να τονιστεί ότι τα ligands (Χ–saloH) παρουσιάζουν διάφορους τρόπους συναρμογής, μερικοί εκ των οποίων εμφανίστηκαν για πρώτη φορά σε ενώσεις του καδμίου αυτής της διατριβής. Επιπλέον, η αλληλεπίδραση των ligands και των ενώσεών τους με το CTDNA μελετήθηκε φασματοσκοπικά με τη χρήση φασματοσκοπίας UV–visκαι φασματοσκοπία εκπομπής φθορισμού (μελέτη της ανταγωνιστικής δράσης με το EB), με μετρήσεις ιξώδους, και με κυκλική βολταμμετρία (για τα σύμπλοκα του χαλκού και του νικελίου). Επίσης με φασματοσκοπία φθορισμού ερευνήθηκε η ικανότητα των ligands και των ενώσεών τους να αλληλεπιδρούν με τις αλβουμίνες BSA και HSA. Από τις μελέτες που πραγματοποιήθηκαν συμπεραίνεται ότι ο πιθανότερος τρόπος αλληλεπίδρασης των συμπλόκων με το CTDNA στο σύνολό τους είναι η παρεμβολή. Στα κατιονικά σύμπλοκα του νικελίου, πέραν της παρεμβολής εμφανίζεται και ηλεκτροστατική αλληλεπίδραση με το DNA. Όλες οι ενώσεις που μελετήθηκαν έχουν την ικανότητα να αλληλεπιδρούν με αλβουμίνες ορού αίματος BSA και HSA, με τέτοιο τρόπο ώστε να μπορούν να μεταφερθούν και να απελευθερωθούν από την αλβουμίνη όταν φτάσουν στα κύτταρα στόχους

Copper(II) Complexes of 5–Fluoro–Salicylaldehyde: Synthesis, Characterization, Antioxidant Properties, Interaction with DNA and Serum Albumins

The synthesis, characterization and biological profile (antioxidant capacity, interaction with calf-thymus DNA and serum albumins) of five neutral copper(II) complexes of 5–fluoro–salicylaldehyde in the absence or presence of the N,N’–donor co–ligands 2,2′–bipyridylamine, 2,9–dimethyl–1,10–phenanthroline, 1,10–phenanthroline and 2,2′–bipyridine are presented herein. The compounds were characterized by physicochemical and spectroscopic techniques. The crystal structures of four complexes were determined by single-crystal X-ray crystallography. The ability of the complexes to scavenge 1,1–diphenyl–picrylhydrazyl and 2,2′–azinobis(3–ethylbenzothiazoline–6–sulfonic acid) radicals and to reduce H2O2 was investigated in order to evaluate their antioxidant activity. The interaction of the compounds with calf-thymus DNA possibly takes place via intercalation as suggested by UV–vis spectroscopy and DNA–viscosity titration studies and via competitive studies with ethidium bromide. The affinity of the complexes with bovine and human serum albumins was examined by fluorescence emission spectroscopy revealing the tight and reversible binding of the complexes with the albumins

Palladium(II) Complexes of Substituted Salicylaldehydes: Synthesis, Characterization and Investigation of Their Biological Profile

Five palladium(II) complexes of substituted salicylaldehydes (X-saloH, X = 4-Et2N (for 1), 3,5-diBr (for 2), 3,5-diCl (for 3), 5-F (for 4) or 4-OMe (for 5)) bearing the general formula [Pd(X-salo)2] were synthesized and structurally characterized. The crystal structure of complex [Pd(4-Et2N-salo)2] was determined by single-crystal X-ray crystallography. The complexes can scavenge 1,1-diphenyl-picrylhydrazyl and 2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) radicals and reduce H2O2. They are active against two Gram-positive (Staphylococcus aureus and Bacillus subtilis) and two Gram-negative (Escherichia coli and Xanthomonas campestris) bacterial strains. The complexes interact strongly with calf-thymus DNA via intercalation, as deduced by diverse techniques and via the determination of their binding constants. Complexes interact reversibly with bovine and human serum albumin. Complementary insights into their possible mechanisms of bioactivity at the molecular level were provided by molecular docking calculations, exploring in silico their ability to bind to calf-thymus DNA, Escherichia coli and Staphylococcus aureus DNA-gyrase, 5-lipoxygenase, and membrane transport lipid protein 5-lipoxygenase-activating protein, contributing to the understanding of the role complexes 1–5 can play both as antioxidant and antibacterial agents. Furthermore, in silico predictive tools have been employed to study the chemical reactivity, molecular properties and drug-likeness of the complexes, and also the drug-induced changes of gene expression profile (as protein- and mRNA-based prediction results), the sites of metabolism, the substrate/metabolite specificity, the cytotoxicity for cancer and non-cancer cell lines, the acute rat toxicity, the rodent organ-specific carcinogenicity, the anti-target interaction profiles, the environmental ecotoxicity, and finally the activity spectra profile of the compounds

Synthesis, thermal analysis, and spectroscopic and structural characterizations of tetranuclear nickel(II) cubane-type clusters with 2-hydroxybenzaldehydes or 2-hydroxyphenones

In this study, three novel tetranuclear nickel(II) cubane-type clusters with the general formula [Ni-4(L)(4)(mu(3)-CH3O)(4)(CH3OH)(4)] [L: the anion of 5-methyl-2-hydroxybenzaldehyde (1), 2-hydroxypropiophenone (2), and 2-hydroxybenzophenone (3)] were synthesized and characterized by single-crystal X-ray diffraction analysis. The crystal structure of each compound contains a tetranuclear cubane core [Ni4O4] based on an approximately cubic array of altering nickel and oxygen atoms with intracluster metal-metal separations of 3.04-3.14 . Each Ni(II) atom is surrounded by two oxygen atoms from the ligand (L) and by the mu(3)-CH3O oxygen atom that bridges three Ni atoms of the cubane core. The coordination sphere of Ni is completed with one methanol molecule and making six-coordinate with a distorted octahedral geometry. These complexes were characterized also by spectroscopy (IR and UV-Vis). Simultaneous TG/DTG-DTA techniques were used to analyze their thermal behavior under inert atmosphere, with particular attention to determine their thermal degradation pathways, which was found to be a multi-step decomposition accompanied by the release of the ligand molecules. Finally, the kinetic analysis of the decomposition processes was performed for the first step of complex (3), since only this verifies the requirement of applying an isoconversional method like Kissinger-Akahira-Sunose (KAS). For this step, we found the average value E (a) = 107.8 +/- A 4.5 kJ mol(-1)

Synthesis, thermal analysis, and spectroscopic and structural characterizations of zinc(II) complexes with salicylaldehydes

In this study, three new zinc(II) complexes with 5-substituted salicylaldehyde ligands (X-saloH) (X = 5-chloro, 5-nitro and 5-methyl) with the general formula [Zn(X-salo)(2)(CH3OH)n], (n = 0 or 2) were synthesized. An octahedral geometry was found for both the complexes [Zn(5-NO2-salo)(2)(CH3OH)(2)] and [Zn(5-Cl-salo)(2)(CH3OH)(2)] by single-crystal X-ray diffraction analysis. These complexes were characterized also by spectroscopy (IR and H-1-NMR). Simultaneous TG/DTG-DTA techniques were used to analyze their thermal behavior under inert atmosphere, with particular attention to determine their thermal degradation pathways, which was found to be a multi-step decomposition accompanied by the release of the ligand molecules. Finally, the kinetic analysis of the decomposition processes was performed by applying both the isoconversional Ozawa-Flynn-Wall (OFW) and the Kissinger-Akahira-Sunose (KAS) methods