Anna Pietryczuk

In this study, the structure of the synthesized Zn(II) complex with homovanillic acid (HVA) was investigated using the FT-IR, UV/Vis, and NMR spectroscopic methods, as well as elemental and thermal (TG, DTG, and DSC) analysis. The stoichiometric molar ratio of metal:ligand for the solid form of the complex was established as 1:2, with coordination through the carboxylate group and aromatic ring substituents. The theoretical structural and electronic parameters were calculated by the use of the B3LYP/6-311++G(d,p) method. Antioxidant properties were examined using spectroscopic tests: DPPH (1,1-diphenyl-2-picrylhydrazyl radical), FRAP (ferric reducing antioxidant activity), and ABTS (2,2′-azino-bis-(3-ethylbenzothiazoline-6-sulfonic acid) (diammonium salt radical cation). The Zn(II) complex with HVA showed similar or lower antioxidant properties compared to the ligand, depending on the antioxidant assay. The antimicrobial activity of acid and its complex with Zn(II) against Escherichia coli, Bacillus subtilis, and Candida albicans were also investigated by evaluation of the minimum inhibitory concentration (MIC). The Zn(II) complex shows higher antibacterial and antifungal activity compared to HVA.

This paper presents the results of a study of the effects of the lanthanide ions Ce³⁺, Pr³⁺, Nd³⁺ and Sm³⁺ on the electronic structure and antioxidant and biological (antimicrobial and cytotoxic) properties of p-coumaric acid (p-CAH₂). Structural studies were conducted via spectroscopic methods (FTIR, ATR, UV). Thermal degradation studies of the complexes were performed. The results are presented in the form of TG, DTG and DSC curves. Antioxidant properties were determined via activity tests against DPPH, ABTS and OH radicals. The reducing ability was tested via CUPRAC assays. Minimum inhibitory concentrations (MICs) of the ligand and lanthanide complexes were determined on E. coli, B. subtilis and C. albicans microorganisms. The antimicrobial activity was also determined using the MTT assay. The results were presented as the relative cell viability of C. albicans, P. aeruginosa, E. coli and S. aureus compared to controls and expressed as percentages. In the obtained complexes in the solid phase, lanthanide ions coordinate three ligands in a bidentate chelating coordination mode through the carboxyl group of the acid. Spectroscopic analysis showed that lanthanide ions increase the aromaticity of the pi electron system of the ligand. Thermal analysis showed that the complexes are hydrated and have a higher thermal stability than the ligand. The products of thermal decomposition of the complexes are lanthanide oxides. In the aqueous phase, the metal combines with the ligand in a 1:1 molar ratio. Antioxidant activity tests showed that the complexes have a similar ability to remove free radicals. ABTS and DPPH tests showed that the complexes have twice the ability to neutralise radicals than the ligand, and a much higher ability to remove the hydroxyl radical. The abilities of the complexes and the free ligand to reduce Cu2+ ions in the CUPRAC test are at a similar level. Lanthanide complexes of p-coumaric acid are characterised by a higher antimicrobial capacity than the free ligand against Escherichia coli bacteria, Bacillus subtilis and Candida albicans fungi.

In this study, we investigated the structures of lanthanide (Eu(III), Dy(III), and Gd(III)) complexes with p-coumaric (p-CAH₂) and caffeic (CFAH₃) acids using the FTIR_KBr, FTIR_ATR, and Raman spectroscopic methods. The compositions of the solid phase caffeinates and p-coumarates were obtained on the basis of the amounts of hydrogen and carbon determined using an elemental analysis. The degree of hydration and the thermal decomposition of each compound were examined via a thermal analysis of TG, DTG, and DSC. Antioxidant spectroscopic tests were performed using the DPPH (1,1-diphenyl-2-picrylhydrazyl radical), FRAP (ferric reducing antioxidant activity), and ABTS (2,2’-azino-bis-(3-ethylbenzothiazoline-6-sulfonic acid) (diammonium salt radical cation) methods. The antimicrobial activity of each compound against Escherichia coli, Bacillus subtilis, and Candida albicans was investigated. The electrical properties of the liposomes which mimicked the microbial surfaces formed in the electrolyte containing the tested compounds were also investigated. The above biological properties of the obtained complexes were compared with the activities of p-CAH₂ and CFAH₃. The obtained data suggest that lanthanide complexes are much more thermally stable and have higher antimicrobial and antioxidant properties than the ligands (with the exception of CFAH₃ in the case of antioxidant activity tests). The Gd(III) complexes revealed the highest biological activity among the studied lanthanide complexes.

One of the solutions implemented in order to improve the quality of soils exposed to pesticides is the application of sewage sludge, which is a by-product of wastewater treatment. As an organic substrate, it provides soil with important nutrients, such as nitrogen and phosphorus, and enriches it with organic matter, thanks to which it can be a valuable fertilizer. The aim of the presented research was to evaluate the influence of granulated sewage sludge (GSS) on the biological properties of soil treated with herbicides (MCPA and dicamba) and fungicides (thiophanate-methyl and azoxystrobin). The following aspects were investigated: the activity of selected soil enzymes, the genetic biodiversity of bacteria and fungi, and the abundance of the bacterial gene responsible for ammonia oxidation. A field experiment was conducted, in which granulated sewage sludge (GSS) was applied to soil at a single dose of 3 t/ha. Wheat (Triticum aestivum L.) was sown on the prepared plots. The herbicides (H) and fungicides (F) as well as their mixture (F + H) were applied to the plants in the appropriate growth phases in the doses recommended by the producer. The control was soil without sewage sludge (C). The samples taken were tested for: dehydrogenases, catalases and urease activities, genetic biodiversity structure of bacteria and fungi by TRFLP assay, and the abundance of the bacterial amoA gene by qPCR. On the basis of the obtained results, it was found that the application of pesticides to soil fertilized with sewage sludge influenced the enzymatic activity of soil, and their activity differed depending on the tested enzyme. The activity of URE and DHA on the plots with GSS was higher by approx. 20% and 30%, respectively, as compared to the plots without GSS application. Moreover, both the genetic biodiversity of microorganisms and the abundance of amoA gene differed depending on the variant of the experiment. The GSS treatment of soil significantly influenced the growth of the studied gene as compared to C, and its abundance was 9.15 log¹⁰ gene copies/g DW of soil. Due to the content of nutrients in sewage sludge, it can be a valuable fertilizer in agricultural crops treated with pesticides.

The aim of this study was to determine the effect of humic acid on the growth and metabolism of Candida albicans, a common waterborne pathogenic yeast. At 10–20 mg/L, humic acid caused the greatest increase in biomass and compactness of proteins and monosaccharides, both in cells and in extracellular secretion of the yeast. At higher humic acid concentrations (40–80 mg/L), C. albicans cells still had higher protein levels compared to control, but showed reduced levels of metabolites and inhibited growth, and a significant increase in the activity of antioxidant enzymes, indicating a toxic effect of the humic acid. The increase in protein content in the cells of C. albicans combined with an increase in the activity of antioxidant enzymes may indicate that the studied yeast excels in conditions of high water enrichment with low availability of organic matter. This indicates that Candida albicans is capable of breaking down organic matter that other microorganisms cannot cope with, and for this reason, this yeast uses carbon sources that are not available to other microorganisms. This indicates that this fungus plays an important role in the organic carbon sphere to higher trophic levels, and is common in water polluted with organic matter.

Caffeic acid (CFA) is one of the various natural antioxidants and chemoprotective agents occurring in the human diet. In addition, its metal complexes play fundamental roles in biological systems. Nevertheless, research on the properties of CFA with lanthanide metals is very scarce, and little to no chemical or biological information is known about these particular systems. Most of their properties, including their biological activity and environmental impact, strictly depend on their structure, stability, and solution behaviour. In this work, a multi-analytical-technique approach was used to study these relationships for the Eu(III)/CFA complex. The synthesized metal complex was studied by FT-IR, FT-Raman, elemental, and thermal (TGA) analysis. In order to examine the chemical speciation of the Eu(III)/CFA system in an aqueous solution, several independent potentiometric and spectrophotometric UV-Vis titrations were performed at different M:L (metal:ligand) and pH ratios. The general molecular formula of the synthesized metal complex in the solid state was [Eu(CFA)₃(H₂O)₃]∙2H₂O (M:L ratio 1:3), while in aqueous solution the 1:1 species were observed at the optimum pH of 6 ≤ pH ≤ 10, ([Eu(CFA)] and [Eu(CFA)(OH)]⁻). These results were confirmed by ¹H-NMR experiments and electrospray-ionization mass spectrometry (ESI-MS). To evaluate the interaction of Eu(III)/CFA and CFA alone with cell membranes, electrophoretic mobility assays were used. Various antioxidant tests have shown that Eu(III)/CFA exhibits lower antioxidant activity than the free CFA ligand. In addition, the antimicrobial properties of Eu(III)/CFA and CFA against Escherichia coli, Bacillus subtilis and Candida albicans were investigated by evaluation of the minimum inhibitory concentration (MIC). Eu(III)/CFA shows higher antibacterial activity against bacteria compared to CFA, which can be explained by the highly probable increased lipophilicity of the Eu(III) complex.

Seven derivatives of plant-derived hydroxybenzoic acid (HBA)—including 2,3-dihydroxybenzoic (2,3-DHB, pyrocatechuic), 2,4-dihydroxybenzoic (2,4-DHB, β-resorcylic), 2,5-dihydroxybenzoic (2,5-DHB, gentisic), 2,6-dihydroxybenzoic (2,6-DHB, γ-resorcylic acid), 3,4-dihydroxybenzoic (3,4-DHB, protocatechuic), 3,5-dihydroxybenzoic (3,5-DHB, α-resorcylic), and 3,4,5-trihydroxybenzoic (3,4,5-THB, gallic) acids—were studied for their structural and biological properties. Anti-/pro-oxidant properties were evaluated by using DPPH^• (2,2-diphenyl-1-picrylhydrazyl), ABTS^•+ (2,2-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid), FRAP (ferric-reducing antioxidant power), CUPRAC (cupric-reducing antioxidant power), and Trolox oxidation assays. Lipophilicity was estimated by means of experimental (HPLC) and theoretical methods. The antimicrobial activity against Escherichia coli (E. coli), Pseudomonas aeruginosa (P. aeruginosa), Staphylococcus aureus (S. aureus), Bacillus subtilis (B. subtilis), Salmonella enteritidis (S. enteritidis), and Candida albicans (C. albicans) was studied. The cytotoxicity of HBAs in MCF-7 and MDA-MB-231 cell lines was estimated. Moreover, the structure of HBAs was studied by means of experimental (FTIR, ¹H, and ¹³C NMR) and quantum chemical DFT methods (the NBO and CHelpG charges, electrostatic potential maps, and electronic parameters based on the energy of HOMO and LUMO orbitals). The aromaticity of HBA was studied based on the calculated geometric and magnetic aromaticity indices (HOMA, Aj, BAC, I6, NICS). The biological activity of hydroxybenzoic acids was discussed in relation to their geometry, the electronic charge distribution in their molecules, their lipophilicity, and their acidity. Principal component analysis (PCA) was used in the statistical analysis of the obtained data and the discussion of the dependency between the structure and activity (SAR: structure–activity relationship) of HBAs. This work provides valuable information on the potential application of hydroxybenzoic acids as bioactive components in dietary supplements, functional foods, or even drugs.

The structure of the Zn(II) complex of 5-caffeoylquinic acid (chlorogenic acid, 5-CQA) and the type of interaction between the Zn(II) cation and the ligand were studied by means of various experimental and theoretical methods, i.e., electronic absorption spectroscopy UV/Vis, infrared spectroscopy FT-IR, elemental, thermogravimetric and density functional theory (DFT) calculations at B3LYP/6-31G(d) level. DPPH (2,2-diphenyl-1-picrylhydrazyl), ABTS (2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid), FRAP (ferric reducing antioxidant power), CUPRAC (cupric reducing antioxidant power) and trolox oxidation assays were applied in study of the anti-/pro-oxidant properties of Zn(II) 5-CQA and 5-CQA. The antimicrobial activity of these compounds against Escherichia coli, Pseudomonas aeruginosa, Bacillus subtilis, Staphylococcus aureus, Salmonella enteritidis and Candida albicans was tested. An effect of Zn(II) chelation by chlorogenic acid on the anti-/pro-oxidant and antimicrobial activities of the ligand was discussed. Moreover, the mechanism of the antioxidant properties of Zn(II) 5-CQA and 5-CQA were studied on the basis of the theoretical energy descriptors and thermochemical parameters. Zn(II) chlorogenate showed better antioxidant activity than chlorogenic acid and commonly applied natural (L-ascorbic acid) and synthetic antioxidants (butylated hydroxyanisol (BHA) and butylated hydroxytoluene (BHT)). The pro-oxidant activity of Zn(II) 5-CQA was higher than the ligand and increased with the rise of the compound concentration The type of Zn(II) coordination by the chlorogenate ligand strongly affected the antioxidant activity of the complex.