Zinc(II) Complexes with Dimethyl 2,2 '-Bipyridine-4,5-dicarboxylate: Structure, Antimicrobial Activity and DNA/BSA Binding Study

Two zinc(II) complexes with dimethyl 2,2 '-bipyridine-4,5-dicarboxylate (py-2py) of the general formula [Zn(py-2py)X-2], X = Cl- (1) and Br- (2) were synthesized and characterized by NMR, IR and UV-Vis spectroscopy and single-crystal X-ray diffraction analysis. Complexes 1 and 2 are isostructural and adopt a slightly distorted tetrahedral geometry with values of tetrahedral indices tau(4) and tau'(4) in the range of 0.80-0.85. The complexes were evaluated for their in vitro antimicrobial activity against two bacterial (Pseudomonas aeruginosa and Staphylococcus aureus) and two fungal strains (Candida albicans and Candida parapsilosis), while their cytotoxicity was tested on the normal human lung fibroblast cell line (MRC-5) and the model organism Caenorhabditis elegans. Complex 1 showed moderate activity against both Candida strains. However, this complex was twofold more cytotoxic compared to complex 2. The complexes tested had no effect on the survival rate of C. elegans. Complex 2 showed the ability to inhibit filamentation of C. albicans, while complex 1 was more effective than complex 2 in inhibiting biofilm formation. The interactions of complexes 1 and 2 with calf thymus DNA (ct-DNA) and bovine serum albumin (BSA) were studied to evaluate their binding affinity toward these biomolecules

CCDC 2220148: Experimental Crystal Structure Determination. Crystallographic data for: "Copper(II) and silver(I) complexes with dimethyl 6-(pyrazine-2-yl)pyridine-3,4-dicarboxylate (py-2pz): the influence of the metal ion on the antimicrobial potential of the complex"

TEZMAQ; Space Group: P 1 (2), Cell: a 8.2856(3)Å b 12.1191(5)Å c 19.2393(6)Å, α 82.105(3)° β 86.220(3)° γ 77.071(3)°Crystallographic data (CCDC 2220148) for: Andrejević TP, Aleksić I, Kljun J, Počkaj M, Zlatar M, Vojnović S, Nikodinović-Runić J, Turel I, Đuran M, Glišić B. Copper(II) and silver(I) complexes with dimethyl 6-(pyrazine-2-yl)pyridine-3,4-dicarboxylate (py-2pz): the influence of the metal ion on the antimicrobial potential of the complex. in RSC Advances. 2023;13(7):4376-4393. doi: http://dx.doi.org/10.1039/D2RA07401JArticle: [https://cer.ihtm.bg.ac.rs/handle/123456789/5654]Related crystallographic data (CCDC 2220146): [https://cer.ihtm.bg.ac.rs/handle/123456789/5669]Related crystallographic data (CCDC 2220147): [https://cer.ihtm.bg.ac.rs/handle/123456789/5670]Related crystallographic data (CCDC 2220149): [https://cer.ihtm.bg.ac.rs/handle/123456789/5672]Related crystallographic data (CCDC 2220150): [https://cer.ihtm.bg.ac.rs/handle/123456789/5673]Supplementary information: [https://cer.ihtm.bg.ac.rs/handle/123456789/5674

CCDC 2220146: Experimental Crystal Structure Determination. Crystallographic data for: "Copper(II) and silver(I) complexes with dimethyl 6-(pyrazine-2-yl)pyridine-3,4-dicarboxylate (py-2pz): the influence of the metal ion on the antimicrobial potential of the complex"

TEZLOD : New Structure undergoing enhancement Space Group: P 1 (2), Cell: a 7.7916(6)Å b 8.9848(6)Å c 11.9955(7)Å, α 104.394(6)° β 106.396(6)° γ 104.368(6)°Crystallographic data (CCDC 2220146) for: Andrejević TP, Aleksić I, Kljun J, Počkaj M, Zlatar M, Vojnović S, Nikodinović-Runić J, Turel I, Đuran M, Glišić B. Copper(II) and silver(I) complexes with dimethyl 6-(pyrazine-2-yl)pyridine-3,4-dicarboxylate (py-2pz): the influence of the metal ion on the antimicrobial potential of the complex. in RSC Advances. 2023;13(7):4376-4393. doi: http://dx.doi.org/10.1039/D2RA07401JArticle: [https://cer.ihtm.bg.ac.rs/handle/123456789/5654]Related crystallographic data (CCDC 2220147): [https://cer.ihtm.bg.ac.rs/handle/123456789/5670]Related crystallographic data (CCDC 2220148): [https://cer.ihtm.bg.ac.rs/handle/123456789/5671]Related crystallographic data (CCDC 2220149): [https://cer.ihtm.bg.ac.rs/handle/123456789/5672]Related crystallographic data (CCDC 2220150): [https://cer.ihtm.bg.ac.rs/handle/123456789/5673]Supplementary information: [https://cer.ihtm.bg.ac.rs/handle/123456789/5674

CCDC 2220147: Experimental Crystal Structure Determination. Crystallographic data for: "Copper(II) and silver(I) complexes with dimethyl 6-(pyrazine-2-yl)pyridine-3,4-dicarboxylate (py-2pz): the influence of the metal ion on the antimicrobial potential of the complex"

TEZLUJ : New Structure undergoing enhancement Space Group: P 1 (2), Cell: a 8.2856(3)Å b 12.1191(5)Å c 19.2393(6)Å, α 82.105(3)° β 86.220(3)° γ 77.071(3)°Crystallographic data (CCDC 2220147) for: Andrejević TP, Aleksić I, Kljun J, Počkaj M, Zlatar M, Vojnović S, Nikodinović-Runić J, Turel I, Đuran M, Glišić B. Copper(II) and silver(I) complexes with dimethyl 6-(pyrazine-2-yl)pyridine-3,4-dicarboxylate (py-2pz): the influence of the metal ion on the antimicrobial potential of the complex. in RSC Advances. 2023;13(7):4376-4393. doi: http://dx.doi.org/10.1039/D2RA07401JArticle: [https://cer.ihtm.bg.ac.rs/handle/123456789/5654]Related crystallographic data (CCDC 2220146): [https://cer.ihtm.bg.ac.rs/handle/123456789/5669]Related crystallographic data (CCDC 2220148): [https://cer.ihtm.bg.ac.rs/handle/123456789/5671]Related crystallographic data (CCDC 2220149): [https://cer.ihtm.bg.ac.rs/handle/123456789/5672]Related crystallographic data (CCDC 2220150): [https://cer.ihtm.bg.ac.rs/handle/123456789/5673]Supplementary information: [https://cer.ihtm.bg.ac.rs/handle/123456789/5674

CCDC 2220149: Experimental Crystal Structure Determination. Crystallographic data for: "Copper(II) and silver(I) complexes with dimethyl 6-(pyrazine-2-yl)pyridine-3,4-dicarboxylate (py-2pz): the influence of the metal ion on the antimicrobial potential of the complex"

TEZMEU: Space Group: P 1 (2), Cell: a 7.4731(4)Å b 11.7049(4)Å c 17.6092(8)Å, α 97.285(4)° β 96.617(4)° γ 102.781(4)°Crystallographic data (CCDC 2220149) for: Andrejević TP, Aleksić I, Kljun J, Počkaj M, Zlatar M, Vojnović S, Nikodinović-Runić J, Turel I, Đuran M, Glišić B. Copper(II) and silver(I) complexes with dimethyl 6-(pyrazine-2-yl)pyridine-3,4-dicarboxylate (py-2pz): the influence of the metal ion on the antimicrobial potential of the complex. in RSC Advances. 2023;13(7):4376-4393. doi: http://dx.doi.org/10.1039/D2RA07401JArticle: [https://cer.ihtm.bg.ac.rs/handle/123456789/5654]Related crystallographic data (CCDC 2220146): [https://cer.ihtm.bg.ac.rs/handle/123456789/5669]Related crystallographic data (CCDC 2220147): [https://cer.ihtm.bg.ac.rs/handle/123456789/5670]Related crystallographic data (CCDC 2220148): [https://cer.ihtm.bg.ac.rs/handle/123456789/5671]Related crystallographic data (CCDC 2220150): [Supplementary information: https://cer.ihtm.bg.ac.rs/handle/123456789/5673]Supplementary information: [https://cer.ihtm.bg.ac.rs/handle/123456789/5674

CCDC 2220150: Experimental Crystal Structure Determination. Crystallographic data for: "Copper(II) and silver(I) complexes with dimethyl 6-(pyrazine-2-yl)pyridine-3,4-dicarboxylate (py-2pz): the influence of the metal ion on the antimicrobial potential of the complex"

TEZMIY: Space Group: P 21/n (14), Cell: a 11.0042(12)Å b 12.8657(8)Å c 12.5820(12)Å, α 90° β 115.436(13)° γ 90°Crystallographic data (CCDC 2220150) for: Andrejević TP, Aleksić I, Kljun J, Počkaj M, Zlatar M, Vojnović S, Nikodinović-Runić J, Turel I, Đuran M, Glišić B. Copper(II) and silver(I) complexes with dimethyl 6-(pyrazine-2-yl)pyridine-3,4-dicarboxylate (py-2pz): the influence of the metal ion on the antimicrobial potential of the complex. in RSC Advances. 2023;13(7):4376-4393. doi: http://dx.doi.org/10.1039/D2RA07401JArticle: [https://cer.ihtm.bg.ac.rs/handle/123456789/5654]Related crystallographic data (CCDC 2220146): [https://cer.ihtm.bg.ac.rs/handle/123456789/5669]Related crystallographic data (CCDC 2220147): [https://cer.ihtm.bg.ac.rs/handle/123456789/5670]Related crystallographic data (CCDC 2220148): [https://cer.ihtm.bg.ac.rs/handle/123456789/5671]Related crystallographic data (CCDC 2220149): [https://cer.ihtm.bg.ac.rs/handle/123456789/5672]Supplementary information: [https://cer.ihtm.bg.ac.rs/handle/123456789/5674

Electronic Supplementary Information for: "Copper(II) and silver(I) complexes with dimethyl 6-(pyrazine-2-yl)pyridine-3,4-dicarboxylate (py-2pz): the influence of the metal ion on the antimicrobial potential of the complex"

Dimethyl 6-(pyrazine-2-yl)pyridine-3,4-dicarboxylate (py-2pz) was used as a ligand for the synthesis of new copper(II) and silver(I) complexes, [CuCl2(py-2pz)]2 (1), [Cu(CF3SO3)(H2O)(py-2pz)2]CF3SO3·2H2O (2), [Ag(py-2pz)2]PF6 (3) and {[Ag(NO3)(py-2pz)]·0.5H2O}n (4). The complexes were characterized by spectroscopic and electrochemical methods, while their structures were determined by single crystal X-ray diffraction analysis. The X-ray analysis revealed the bidentate coordination mode of py-2pz to the corresponding metal ion via its pyridine and pyrazine nitrogen atoms in all complexes, while in polynuclear complex 4, the heterocyclic pyrazine ring of one py-2pz additionally behaves as a bridging ligand between two Ag(I) ions. DFT calculations were performed to elucidate the structures of the investigated complexes in solution. The antimicrobial potential of the complexes 1–4 was evaluated against two bacterial (Pseudomonas aeruginosa and Staphylococcus aureus) and two Candida (C. albicans and C. parapsilosis) species. Silver(I) complexes 3 and 4 have shown good antibacterial and antifungal properties with minimal inhibitory concentration (MIC) values ranging from 4.9 to 39.0 μM (3.9–31.2 μg mL−1). All complexes inhibited the filamentation of C. albicans and hyphae formation, while silver(I) complexes 3 and 4 had also the ability to inhibit the biofilm formation process of this fungus. The binding affinity of the complexes 1–4 with calf thymus DNA (ct-DNA) and bovine serum albumin (BSA) was studied by fluorescence emission spectroscopy to clarify the mode of their antimicrobial activity. Catechol oxidase biomimetic catalytic activity of copper(II) complexes 1 and 2 was additionally investigated by using 3,5-di-tert-butylcatechol (3,5-DTBC) and o-aminophenol (OAP) as substrates.1H NMR spectrum of py-2pz S5 1H NMR spectrum of complex 3 S6 1H NMR spectrum of complex 4 S7 Fig. S1 UV-Vis spectra of copper(II) complexes 1 and 2 recorded in DMSO at room temperature. S8 Fig. S2 UV-Vis spectra of silver(I) complexes 3 and 4 in respect to the spectrum of uncoordinated py-2pz recorded in DMSO at room temperature. S9 Fig. S3 Time-dependant UV-Vis spectra of copper(II) complex 2 and silver(I) complex 3 recorded in DMSO/PBS (v/v 2 : 1 and 1 : 42.9 for 2 and 3, respectively) at room temperature. S10 Fig. S4 Cyclic voltammogram of py-2pz ligand at GC electrode in DMSO (c = 1 × 10-3 M) and 0.1 M TBAHP as a supporting electrolyte with a scan rate of 50 mV s-1 . S11 Fig. S5 Graphical representation of the spin density of the high-spin state of 1. Isosurfaces were drawn at 0.003 a.u. with α-spin depicted by blue surfaces. S12 Fig. S6 Inhibition of violacein and prodigiosin production in the presence of complexes 1 – 4 and py-2pz ligand tested on Chromobacterium violaceum CV026 and Serratia marcescens at 100 µg per disc concentration. DMSO was used as a control. S13 Scheme S1 Catechol oxidase (CAO) and phenoxazinone synthase (PHS) activity. S14 Table S1 C. albicans ATCC10231 biofilm inhibition (%) in the presence of silver(I) complexes 3 and 4 in range of subinhibitory concentrations. Table S2 Details of the crystal structure determination for copper(II) complexes 1 and 2 S16 Table S3 Details of the crystal structure determination for silver(I) complexes 3 and 4 S17 Cartesian coordinates of all DFT optimized structures S18.Suplementary information for: Andrejević TP, Aleksić I, Kljun J, Počkaj M, Zlatar M, Vojnović S, Nikodinović-Runić J, Turel I, Đuran M, Glišić B. Copper(II) and silver(I) complexes with dimethyl 6-(pyrazine-2-yl)pyridine-3,4-dicarboxylate (py-2pz): the influence of the metal ion on the antimicrobial potential of the complex. in RSC Advances. 2023;13(7):4376-4393. doi: [http://dx.doi.org/10.1039/D2RA07401J]Article: [https://cer.ihtm.bg.ac.rs/handle/123456789/5654]Related crystallographic data (CCDC 2220146): [https://cer.ihtm.bg.ac.rs/handle/123456789/5669]Related crystallographic data (CCDC 2220147): [https://cer.ihtm.bg.ac.rs/handle/123456789/5670]Related crystallographic data (CCDC 2220148): [https://cer.ihtm.bg.ac.rs/handle/123456789/5671]Related crystallographic data (CCDC 2220149): [https://cer.ihtm.bg.ac.rs/handle/123456789/5672]Related crystallographic data (CCDC 2220150): [https://cer.ihtm.bg.ac.rs/handle/123456789/5673

Synthesis, structural characterization and antimicrobial activity of silver(I) complexes with 1-benzyl-1H-tetrazoles

Herein, we report the synthesis and structural characteristics of three tetrazole-containing compounds, 1-benzyl-1H-tetrazole (bntz), 1-benzyl-1H-tetrazol-5-amine (bntza) and 1-(4-methoxybenzyl)-1H-tetrazol-5-amine (mbntza) and the corresponding silver(I) complexes of the general formula [Ag(NO3-O)(L-N4)(2)](n), L = bntz (1), bntza (2) and mbntza (3). Silver(I) complexes 1-3 and 1-benzyl-1H-tetrazoles have been studied in detail by NMR, IR and UV-Vis spectroscopic methods and the structures of 1 and 2 have been determined by single-crystal X-ray diffraction analysis. The results of these analyses revealed a monodentate coordination of the ligands to Ag(I) ion via the N4 tetrazole nitrogen. The antimicrobial potential of silver(I) complexes 1-3 was evaluated against the broad panel of Gram-positive and Gram-negative bacteria and fungi, displaying their remarkable inhibiting activity with MIC (minimal inhibitory concentration) values in the range 2-8 and 0.16-1.25 mu g/mL (3.8-16.3 and 0.31-2.15 mu M), respectively. On the other hand, 1-benzyl-1H-tetrazoles used for the synthesis of the silver(I) complexes were not active against the investigated strains, suggesting that the activity of the complexes originates from the Ag(I) ion exclusively. Moreover, silver(I) complexes 1-3 have good therapeutic potential, which can be deduced from their moderate cytotoxicity on the human fibroblast cell line MRC5, with IC50 values falling in the range 30-60 mu g/mL (57.7-103.4 mu M).Related to published version: [https://imagine.imgge.bg.ac.rs/handle/123456789/1144]This is the peer-reviewed version of the article: Andrejević, T. P., Nikolić, A. M., Glišić, B., Wadepohl, H., Vojnović, S., Zlatović, M., Petković, M., Nikodinović-Runić, J., Opsenica, I. M., & Djuran, M. (2018). Synthesis, structural characterization and antimicrobial activity of silver(I) complexes with 1-benzyl-1H-tetrazoles. Polyhedron, 154, 325–333. [https://doi.org/10.1016/j.poly.2018.08.001

Supplementary data for the article: Andrejević, T. P.; Nikolić, A. M.; Glišić, B. Đ.; Wadepohl, H.; Vojnovic, S.; Zlatović, M.; Petković, M.; Nikodinovic-Runic, J.; Opsenica, I. M.; Djuran, M. I. Synthesis, Structural Characterization and Antimicrobial Activity of Silver(I) Complexes with 1-Benzyl-1H-Tetrazoles. Polyhedron 2018, 154, 325–333. https://doi.org/10.1016/j.poly.2018.08.001

Supplementary data for: [https://doi.org/10.1016/j.poly.2018.08.001]Research data for this article: [https://www.ccdc.cam.ac.uk/structures/search?id=doi:10.5517/ccdc.csd.cc2046ft&sid=DataCite]Research data for this article: [https://www.ccdc.cam.ac.uk/structures/search?id=doi:10.5517/ccdc.csd.cc2046gv&sid=DataCite]Related to published version: [http://cherry.chem.bg.ac.rs/handle/123456789/2228]Related to accepted version: [http://cherry.chem.bg.ac.rs/handle/123456789/2991

Different coordination abilities of 1,7- and 4,7-phenanthroline in the reactions with copper(II) salts: Structural characterization and biological evaluation of the reaction products

The reactions between equimolar amounts of CuX2 (X = NO3− and CF3SO3−) and two aromatic nitrogen-containing heterocycles differing in the position of nitrogen atoms, 1,7- and 4,7-phenanthroline (1,7- and 4,7-phen), were performed in ethanol/methanol at room temperature. When CuX2 salts were mixed with 4,7-phen, two copper(II) complexes, [Cu(NO3)2(4,7-Hphen)2](NO3)2 (1) and [Cu(CF3SO3)(4,7- phen)2(H2O)2]CF3SO3 (2), were formed. On the other hand, in the reaction of CuX2 salts with 1,7-phen, only 1,7-HphenNO3 (3a/b) and 1,7-HphenCF3SO3 (4) were obtained as the final products. The obtained products 1–4 were characterized by spectroscopic and X-ray diffraction techniques. In the copper(II) complexes 1 and 2, the coordination geometry around the Cu(II) ion is distorted octahedral and square pyramidal, respectively. The antimicrobial potential of the copper(II) complexes 1 and 2 and corresponding compounds used for their synthesis were assessed against four different bacterial species and Candida albicans, displaying moderate growth inhibiting activity. The cytotoxic properties of the investigated complexes were also evaluated against the normal human lung fibroblast cell line (MRC-5) indicating moderate, yet more pronounced cytotoxicity than antimicrobial properties