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In order to discover a new antibiotic drug with better or similar activity of the already existing drugs, a series of novel cobalt(II) complexes with ß-diketonate as ligands is synthesized and tested on four strains of bacteria and four species of fungi. All compounds showed notable antimicrobial activity against all tested strains. More importantly, some cobalt(II) complexes displayed greater activity than ketoconazole. It is important to notice that on the tested strains Mucor mucedo and Penicillium italicum complex 2B showed five times better activity compared to ketoconazole, while complex 2D had two times better activity on Penicillium italicum strain compared to ketoconazole. Moreover, investigations with bovine serum albumin were performed. Investigations showed that the tested complexes have an appropriate affinity for binding to bovine serum albumin. In addition, the molecular docking study was performed to investigate more specifically the sites and binding mode of the tested cobalt(II) complexes with ß-diketonate as ligands to bovine serum albumin, tyrosyl-tRNA synthetase, topoisomerase II DNA gyrase, and cytochrome P450 14 alpha-sterol demethylase. In conclusion, all the results indicated the great prospective of the novel cobalt complexes for some potential clinical applications in the future.
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BACKGROUND: Cobalt, an essential trace element, is vital for maintaining human nervous system function, aiding in DNA synthesis, and contributing to red blood cell production. It is helpful for disease diagnosis and treatment plan evaluation by precisely monitoring its concentration changes in the human body. Despite extensive efforts made, due to its ultra-low concentration, the current limit of detection (LOD) as reported is still inadequate and cannot be satisfied with the precise clinical applications. Therefore, it is crucial to develop novel label-free sensors with high sensitivity and excellent selectivity for detecting trace amounts of Co2+. RESULTS: Here, an ultrasensitive optical fiber SPR sensor was designed and fabricated for label-free detection of Co2+ with ultra-low concentration. It is achieved by modifying the carboxyl-functionalized CQDs on the AuNPs/Au film-coated hetero-core fiber, which can specifically capture the Co2+, leading to changes in the fiber's surface refractive index (RI) and subsequent SPR wavelength shifts in the transmission spectrum. Both the Au film and AuNPs on the fiber are modified with CQDs, leveraging their large surface area to enhance the number of active sites and probes. The sensor exhibits an ultra-high sensitivity of approximately 6.67 × 1019 nm/M, and the LOD is obtained as low as 5.36 × 10-20 M which is several orders of magnitude lower compared to other conventional methods. It is also experimentally demonstrated that the sensor possesses excellent specificity, stability, and repeatability, which may be adapted for detecting real clinical samples. SIGNIFICANCE: The CQDs-functionalized optical fiber SPR sensor exhibits substantial potential for precisely detecting Co2+ of trace amounts, which is especially vital for scarce clinical samples. Additionally, the sensing platform with sample sensor fabrication and measurement configuration introduces a novel, highly sensitive approach to biochemical analysis, particularly adapting for applications involving the detection of trace targets, which could also be employed to detect various biochemical targets by facile modification of CQDs with specific groups or biomolecules.
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Cobalto , Ouro , Limite de Detecção , Nanopartículas Metálicas , Fibras Ópticas , Ressonância de Plasmônio de Superfície , Cobalto/química , Ouro/química , Nanopartículas Metálicas/química , HumanosRESUMO
Two cobalt(II) complexes [CoL1](OTf)2 (1, L1 = 6,6''-di(anilino)-4'-phenyl-2,2':6',2''-terpyridine) and [CoL2](OTf)2·MeOH (2, L2 = 6,6''-di(N,N-dimethylamino)-4'-phenyl-2,2':6',2''-terpyridine) were synthesized and characterized. Crystal structure analyses showed that the spin carries were coordinated by five N atoms from the neutral pentaaza ligands, forming distorted trigonal bipyramidal coordination environments. Ab initio calculations revealed large easy-axial anisotropy in complexes 1 and 2. Magnetic measurements suggest that complexes 1 and 2 are field-induced single-molecule magnets, whose relaxations are mainly predominated by Raman and direct processes.
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Optimal pH is essential for efficient cobalt extraction from polymeric membrane systems, with D2EHPA used as an extractant for Co(II) at pH < 7, achieving 47% efficiency. The pH of piperazine as a stripping agent increases to a concentration of 0.48 M, and the extraction efficiency of Co(II) > 80%. Depending on the functional group of (C4H10N2), the optimal pH for separation was 9.8. The study revealed that pKa value was calculated to predict the ideal pH, and its value was 9.73, which is nearly to the pH, since the pH of the strip concentration and the properties of the membrane affect the extraction of cobalt at 30 °C. The partition ratio indicates the high distribution of the extract in supported ceramic polymer membrane (SCPM). The ceramic component provides mechanical strength and rigidity to the overall membrane structure, allowing it to withstand high pressures and temperatures during operation Study various factors such as the effect of pH on the ionization of the extract; effect of pH on band ionization; effect of pH on the temperature in the extract, effect of pH on the solute, effect of the band at different pH ranges and a comparison was made between the predictive model and experimental data that was proven through mathematical modeling using the MATLAB program.
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A new Co(II) complex, [Co(NCS)2(L)2] (1) has been synthesized based on levamisole (L) as a new ligand. Single-crystal X-ray diffraction analyses confirm that the Co(II) ion is having a distorted tetrahedral coordination geometry in the complex. Notably strong intramolecular Sâ â â S and Sâ â â N interactions has been confirmed by employing Quantum Theory of Atoms in Molecules (QTAIM). These intramolecular interactions occur among the sulfur and nitrogen atoms of the levamisole ligands and also the nitrogen atoms of the thiocyanate. Direct current (dc) magnetic analyses reveal presence of zero field splitting (ZFS) and large magnetic anisotropy on Co(II). Detailed ab initio ligand field theory calculations quantitatively predicted the magnitude of ZFS. Prominent field-induced single-ion magnet (SIM) behavior was observed for 1 from dynamic magnetization measurements. Slow magnetic relaxation follows an Orbach mechanism with the effective energy barrier Ueff=29.6 (7)â K and relaxation time τo=1.4 (4)×10-9â s.
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The title compound, [Co(C3H4N2)(C30H30N10)](BF4)2, is a five-coordinate CoII complex based on the neutral ligands tris-[(1-benzyl-triazol-4-yl)meth-yl]amine (tbta) and imidazole. It exhibits a distorted trigonal bipyramidal geometry in which the equatorial positions are occupied by the three N-atom donors from the triazole rings of the tripodal tbta ligand. The apical amine N-atom donor of tbta and the N-atom donor of the imidazole ligand occupy the axial positions of the coordination sphere. Two tetra-fluoro-borate anions provide charge balance in the crystal.
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Reacting trimesic acid (H3TMA, C9H6O6) with CaCl2 and MCl2 at 110â °C under hydrothermal conditions gave the isostructural heterobimetallic coordination polymers (CPs) catena-poly[[tetraaquazinc(II)]-µ-5-carboxybenzene-1,3-dicarboxylato-[tetraaquacalcium(II)]-µ-5-carboxybenzene-1,3-dicarboxylato], [CaZn(HTMA)2(H2O)8]n, 1, and catena-poly[[tetraaquacobalt(II)]-µ-5-carboxybenzene-1,3-dicarboxylato-[tetraaquacalcium(II)]-µ-5-carboxybenzene-1,3-dicarboxylato], [CaCo(HTMA)2(H2O)8]n, 2. Compounds 1 and 2 crystallize in the monoclinic space group C2/c. The solid-state structures consist of eight-coordinate CaII ions and six-coordinate MII ions. These ions are connected by a doubly deprotonated HTMA2- ligand to create a one-dimensional (1D) zigzag chain. Poly[[decaaquabis(µ3-benzene-1,3,5-tricarboxylato)calcium(II)dizinc(II)] dihydrate], {[CaZn2(TMA)2(H2O)10]·2H2O}n, 3, was found incidentally as a minor by-product during the synthesis of 1 at a temperature of 140â °C. It forms crystals in the orthorhombic space group Ccce. The structure of 3 consists of a two-dimensional (2D) layer composed of [Zn(TMA)] chains that are interconnected by CaII ions. The presence of aromatic carboxylic acid ligands and water molecules, which can form numerous hydrogen bonds and π-π interactions, increases the stability of the three-dimensional (3D) supramolecular architecture of these CPs. Compounds 1 and 2 exhibit thermal stability up to 420â °C, as indicated by the thermogravimetric analysis (TGA) curves. The powder X-ray diffraction (PXRD) data reveal the formation of unidentified phases in methanol and dimethyl sulfoxide, while 1 exhibits chemical stability in a wide range of solvents. The luminescence properties of 1 dispersed in various low molecular weight organic solvents was also examined. The results demonstrate excellent selectivity, sensitivity and recyclability for detecting acetone molecules in aqueous media. Additionally, a possible sensing mechanism is also outlined.
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Two new Cobalt(II) complexes 12 and 13 have been synthesized from 2-[(E)-(3-acetyl-4-hydroxyphenyl)diazenyl]-4-(2-hydroxyphenyl)thiophene-3-carboxylic acid (11) as a novel ligand. These three new compounds were characterized on the basis of their powder X-Ray Diffraction, UV-Vis, IR, NMR, elemental analysis and MS spectral data. DFT/B3LYP mode of calculations were carried out to determine some theorical parameters of the molecular structure of the ligand. The purity of the azoic ligand and the metal complexes were ascertained by TLC and melting points. The analysis of the IR spectra of the polyfunctionalized azo compound 11 and its metal complexes 12 and 13, reveals that the coordination patterns of the ligand are hexadentate and tetradentate respectively. Based on the UV-Vis electronic spectral data and relevant literature reports, the ligand and derived complexes were assigned the E (trans) isomer form. Likewise, octahedral and square-planar geometries were respectively assigned to the cobalt(II) complexes. The broth microdilution method was used for antibacterial assays through the determination of minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC). The ligand 11 displayed moderate antibacterial activity (MIC = 32-128 µg/mL) against Staphylococcus aureus ATCC25923, Escherichia coli ATCC25922, Pseudomonas aeruginosa and Klebsiella pneumoniae 22. The octahedral cobalt(II) complex 12 showed moderate activity against Pseudomonas aeruginosa (MIC = 128 µg/mL) and Klebsiella pneumoniae 22 (MIC = 64 µg/mL) and none against Staphylococcus aureus ATCC25923 and Escherichia coli ATCC25922, whereas the square-planar complex 13 displayed moderate activity only on Klebsiella pneumoniae 22 (MIC = 64 µg/mL).
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The present study synthesized a series of cobalt (II) metal ion frame hybrid candidates (6a-6f) bearing phyto-flavonol galangin with substituted aryl diazenyl coumarins, and further structural confirmation was validated by various spectral techniques, including NMR, ATR-FTIR, UV-vis, HPLC, XRD, etc. Therapeutic potency was investigated via PASS (prediction of activity spectra for substances), molecular docking, molecular dynamics simulation, prediction of toxicity, pharmacokinetics, and drug-likeness scores, along with the highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO), with their energy gaps (ΔEH-L) to locate the most potential therapeutic candidates. The PASS prediction (Pa > Pi score) showed that proposed metal complexes have kinase inhibitors, antioxidative, and antischistosomal activities with potential molecular docking scores (> -7 kcal/mol) against selected targeted enzymes. Further, the MD-simulation (RMSD, RMSF, Rg, and H-bonds) of the most potential docking complex, 'HER2-6d', showed a minimum deviation similar to the standard drug (lapatinib) at 100 ns, indicating that 6d could be a potential noncovalent anticancer inhibitor. In addition, metal complexes possess a non-toxic and ideal drug-ability profiles, and positive electron space in an excited state increases the binding affinity towards target enzymes. Among all six ligands, 6c and 6d were the two most multipotent therapeutic agents from the above analyses. In summary, this could be a feasible approach towards the utilization of phytochemicals in mainstream therapeutic applications, where bioinformatics tools help to select a lead drug candidate at an early stage and guide for higher experimental success by proceeding with potential candidates.Communicated by Ramaswamy H. Sarma.
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In the recent past, there has been an ever-increasing interest in the search for metal-based therapeutic drug candidates for protein misfolding disorders (PMDs) particularly neurodegenerative disorders such as Alzheimer's, Parkinson's, Prion's diseases, and amyotrophic lateral sclerosis. Also, different amyloidogenic variants of human lysozyme (HL) are involved in hereditary systemic amyloidosis. Metallo-therapeutic agents are extensively studied as antitumor agents, however, they are relatively unexplored for the treatment of non-neuropathic amyloidoses. In this work, inhibition potential of a novel ionic cobalt(II) therapeutic agent (CoTA) of the formulation [Co(phen)(H2O)4]+[glycinate]- is evaluated against HL fibrillation. Various biophysical techniques viz., dye-binding assays, dynamic light scattering (DLS), differential scanning calorimetry (DSC), electron microscopy, and molecular docking experiments validate the proposed mechanism of inhibition of HL fibrillation by CoTA. The experimental corroborative results of these studies reveal that CoTA can suppress and slow down HL fibrillation at physiological temperature and pH. DLS and 1-anilino-8-naphthalenesulfonate (ANS) assay show that reduced fibrillation in the presence of CoTA is marked by a significant decrease in the size and hydrophobicity of the aggregates. Fluorescence quenching and molecular docking results demonstrate that CoTA binds moderately to the aggregation-prone region of HL (Kb = 6.6 × 104 M-1), thereby, inhibiting HL fibrillation. In addition, far-UV CD and DSC show that binding of CoTA to HL does not cause any change in the stability of HL. More importantly, CoTA attenuates membrane damaging effects of HL aggregates against RBCs. This study identifies inorganic metal complexes as a therapeutic intervention for systemic amyloidosis.
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Amiloide , Amiloidose , Humanos , Amiloide/química , Muramidase/química , Simulação de Acoplamento Molecular , Amiloidose/tratamento farmacológico , Amiloidose/metabolismo , Difusão Dinâmica da Luz , Agregados ProteicosRESUMO
Electrogenic biofilms in bioelectrochemical systems (BES) are critical in wastewater treatment. Industrial effluents often contain cobalt (Co2+); however, its impact on biofilms is unknown. This study investigated how increasing Co2+ concentrations (0-30 mg/L) affect BES biofilm community dynamics, extracellular polymeric substances, microbial metabolism, electron transfer gene expression, and electrochemical performance. The research revealed that as Co2+ concentrations increased, power generation progressively declined, from 345.43 ± 4.07 mW/m2 at 0 mg/L to 160.51 ± 0.86 mW/m2 at 30 mg/L Co2+. However, 5 mg/L Co2+ had less effect. The Co2+ removal efficiency in the reactors fed with 5 and 10 mg/L concentrations exceeded 99% and 94%, respectively. However, at 20 and 30 mg/L, the removal efficiency decreased substantially, likely because of reduced biofilm viability. FTIR indicated the participation of biofilm functional groups in Co2+ uptake. XPS revealed Co2+ presence in biofilms as CoO and Co(OH)2, indicating precipitation also aided removal. Cyclic voltammetry and electrochemical impedance spectroscopy tests revealed that 5 mg/L Co2+ had little impact on the electrocatalytic activity, while higher concentrations impaired it. Furthermore, at a concentration of 5 mg/L Co2+, there was an increase in the proportion of the genus Anaeromusa-Anaeroarcus, while the genus Geobacter declined at all tested Co2+ concentrations. Additionally, higher concentrations of Co2+ suppressed the expression of extracellular electron transfer genes but increased the expression of Co2+-resistance genes. Overall, this study establishes how Co2+ impacts electrogenic biofilm composition, function, and treatment efficacy, laying the groundwork for the optimized application of BES in remediating Co2+-contaminated wastewater.
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Ácidos Alcanossulfônicos , Fontes de Energia Bioelétrica , Purificação da Água , Cobalto , Elétrons , Biofilmes , Eletrodos , ÍonsRESUMO
Here, we combined magnetometry, multi-frequency electronic paramagnetic resonance, and wave function based ab initio calculations to investigate magnetic properties of two high spin Co(II) complexes Co(BDPRP) (BDPRP=2,6-bis((2-(S)-di(4-R)phenylhydroxylmethyl-1-pyrrolidi-nyl)methyl)pyridine, R=H for 8; R=tBu for 9). Complexesâ 8 and 9 featuring effective D3h symmetry were found to possess D=24.0 and 32.0â cm-1, respectively, in their S=3/2 ground states of 1 e ' ' d x z / y z 4 1 e ' d x y / x 2 - y 2 2 1 a 1 ' d z 2 1 ${{\left(1{{\rm e}}^{{\rm { {^\prime}}}{\rm { {^\prime}}}}\right({d}_{xz/yz}\left)\right)}^{4}{\left(1{{\rm e}}^{{\rm { {^\prime}}}}\right({d}_{{xy/{x}^{2}-y}^{2}}\left)\right)}^{2}{\left(1{{\rm a}}_{1}^{{\rm { {^\prime}}}}\right({d}_{{z}^{2}}\left)\right)}^{1}}$ . Ligand field analyses revealed that the low-lying d-d excited states make either positive or vanishing contributions to D. Hence, total positive D values were measured for 8 and 9, as well as related D3h high spin Co(II) complexes. In contrast, negative D values are usually observed for C3v congeners. In-depth analyses suggested that lowering symmetry from D3h to C3v induces orbital mixing between 1 e d x z / y z ${1{\rm e}\left({d}_{xz/yz}\right)}$ and 2 e d x y / x 2 - y 2 ${2{\rm e}\left({d}_{{xy/{x}^{2}-y}^{2}}\right)}$ and admixes excited state 4 A 2 1 e â 2 e ${{}^{4}{{\rm A}}_{2}\left(1e\to 2e\right)}$ into the ground state. Both factors turn the total D value progressively negative with the increasing distance (δ) of the Co(II) center out of the equatorial plane. Therefore, δ determines the sign and magnitude of final D values of five-coordinate trigonal bipyramidal S=3/2 Co(II) complexes as measured for a series of such species with varying δ.
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Solar-thermal water evaporation is a promising strategy for clean water production, which needs the development of solar-thermal conversion materials with both high efficiency and high stability. Herein, we reported an ultra-stable cobalt(II)-organic assembly NKU-123 with light-generated radicals, exhibiting superior photothermal conversion efficiency and high stability. Under the irradiation of 808â nm light, the temperature of NKU-123 rapidly increases from 25.5 to 215.1 °C in 6â seconds. The solar water evaporator based on NKU-123 achieves a high solar-thermal water evaporation rate of 1.442 and 1.299â kg m-2 h-1 under 1-sun irradiation with a water evaporation efficiency of 97.8 and 87.9 % for pure water and seawater, respectively. A detailed mechanism study revealed that the formation of light-generated radicals leads to an increase of spin density of NKU-123 for enhancing the photothermal effect, which provides insights into the design of highly efficient photothermal materials.
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Response mechanism of the electrode is elucidated in terms of (hydrogen) phosphate accelerating oxidation of CoII to CoIII for the first time. Cyclic voltammetric techniques in conjunction with XRD, XPS and Raman characterizations have demonstrated unambiguously the response of cobalt (II) hydroxide electrode involves a phosphate and hydrogen ion dependent charge transfer process. Phosphate ions induce Co(OH)2 transformed into CoOOH within interlayer adsorption and restored the initial state after reduction. Meanwhile, the in common structural between Co(OH)2 and CoOOH prevents extensive structural convertibility upon cycling, result in the advantage of reversibility in phase transformation. Demonstrated sustainable technique offered the determination of phosphate with robust reproducibility (1000 cycles), long storage stability (6 months) and selectivity (potential interference: Cl-, NO3-, SO42- and HCO3-), achieving a detection limit of 5 × 10-8 M over a wide linear range up to 1.28 mM. Presented work provided insights into the unique selectivity towards phosphate in cobalt based sensors, which may inspire the rational design of Co(OH)2-based electrodes with superior electrochemical performance or extended applications.
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Several cobalt(II) complexes Co1-Co3 bearing pyridine-oxime ligands (L1 = pyridine-2-aldoxime for Co1; L2 = 6-methylpyridine-2-aldoxime for Co2; L3 = phenyl-2-pyridylketoxime for Co3) and picolinaldehyde O-methyl oxime (L4)-supported Co4 were synthesized and well characterized by FT-IR, mass spectrum and elemental analysis. The single-crystal X-ray diffraction of complex Co2 reveals that the cobalt center of CoCl2 is coordinated with two 6-methylpyridine-2-aldoxime ligands binding with Npyridine and Noxime atoms, which feature a distorted octahedral structure. These Co complexes Co1-Co4 displayed extremely high activity toward isoprene polymerization upon activation with small amount of AlClEt2 in toluene, giving polyisoprene with high activity up to 16.3 × 105 (mol of Co)-1(h)-1. And, the generated polyisoprene displayed high molecular weights and narrow molecular distribution with a cis-1,4-enriched selectivity. The type of cobalt complexes, cocatalyst and reaction temperature all have effects on the polymerization activity but not on the microstructure of polymer.
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The natural flavonol quercetin (Q) is found in many vegetables, fruits, and beverages, and it is known as a strong antioxidant. Its metal ion chelation may increase its antioxidant activity. The present study aims to explore the Co(II), Cu(II), and Zn(II) chelating on the antioxidant effectiveness and severe acute respiratory syndrome coronavirus 2 (SARSCoV2) main protease (Mpro) inhibitory of quercetin using Density-functional theory (DFT), molecular docking, and molecular dynamics simulations (MD). DFT calculations at the B3LYP/LanL2DZ reveal that the high antioxidant activity of the metal-chelated quercetin complexes is mainly returned to their lower ionization potentials (IPs) compared with the one of the free quercetin. Molecular docking of quercetin and its Co(II), Cu(II), and Zn(II) chelates into the active binding sites of peroxiredoxin 5 and SARS-CoV-2 main protease (Mpro) were performed using Lamarckian Genetic Algorithm method. The docked quercetin and its metal chelates fit well into the binding site of the target proteins, and their binding affinity is strongly influenced by the type of the chelated metals Co(II), Cu(II), and Zn(II), and molar ratio metal: ligand, i.e. 1:2 and 2:1. Further, the binding stability of QZn2 and QCu2 in peroxiredoxin 5 and SARS-CoV-2 main protease targets is evaluated using MD simulation conducted for 100 ns simulations at natural room temperature conditions, and the obtained results showed that all chelates remain bound to the ligand binding groove of protein except for 1HD2_QZn2 complex. Finally, the adsorption, distribution, metabolism, excretion, and toxicity (ADMET) and drug-likeness properties of quercetin and cobalt(II)-quercetin (QCo2(II)) were investigated.Communicated by Ramaswamy H. Sarma.
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Aims@#The aim of this study was to conduct antimicrobial analysis on novel Schiff base-derived cobalt(II) complexes (Co(L1)2 and Co(L2)2).@*Methodology and results @#Synthesis of Co(II) Schiff base complexes was carried out by reacting Schiff bases with cobalt(II) chloride hexahydrate and spectroscopic analyses were used for characterization. Microbiological assays comprised the determination of the minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC) of tested substances and the evaluation of their antibiofilm activity. A total of 11 bacteria were tested, including multidrug-resistant strains. Investigated compounds performed inhibitory activity against all tested bacteria, with the MIC value of 250 µg/mL and 125 µg/mL just for Escherichia coli ATCC 14169. Results regarding the antibiofilm properties suggest that investigated Schiff’s base complexes have antibiofilm activity in a strain-specific and concentrationdependant manner. @*Conclusion, significance and impact of study: @#The current study showed that the novel complex compounds possess antimicrobial and antibiofilm properties against Gram-positive and Gram-negative bacteria. Since bacterial resistance to currently available antibiotics is rapidly increasing, further studies may provide information about using novel complexes as potential antimicrobial agents.