Development and Validation of an Analytical Method for Determination of Al,Ca, Cd,Fe, Mg and P in Calcium-Rich Materials by ICP OES

Four procedures based on closed-vessel microwave-assisted wet digestion with different oxidative reagents, including HNO₃ (P1), HNO₃ + H₂O₂ (P2), aqua regia (P3) and Lefort aqua regia (P4), for preparation of calcium (Ca)-rich materials prior to determination of total concentrations of Al, Ca, Cd, Fe, Mg and P by inductively coupled optical emission spectrometry (ICP OES) were compared. It was found that digestion with Lefort aqua regia (P4) provided the best results for all examined elements, i.e., precision of 0.30–4.4%, trueness better than 2%, recoveries of added elements between 99.5–101.9%, and limits of detection within 0.08–1.8 ng g⁻¹. Reliability of this procedure was verified by analysis of relevant certified reference materials (CRMs), i.e., Natural Moroccan Phosphate Rock—Phosphorite (BCR-O32). Additionally, selection of appropriate analytical lines for measurements of element concentrations, linear dynamic ranges of calibration curves and matrix effects on the analyte response were extensively investigated. Finally, the selected procedure was successfully applied for routine analysis of other Ca-rich materials, i.e., CRMs such as NIST 1400 (Bone Ash), CTA-AC-1 (Apatite Concentrate Kola Peninsula) and NCS DC70308 (Carbonate Rock), and six natural samples, such as a dolomite, a phosphate rock, an enriched superphosphate fertilizer, pork bones, pork bones after incineration, and after steam gasification.     

Relationship Between Geršgorin‐type Theorems for Certain Subclasses of H‐Matrices

It is well known that the eigenvalue inclusion domain can be obtained by Geršgorin theorem. It is also known that the Geršgorin theorem is equivalent to the statement that each strictly diagonally dominant (SDD) matrix is nonsingular. Similarly, statements about nonsingularity of some classes of matrices, which are generalizations of SDD class, produce new Geršgorin‐type theorems for eigenvalue inclusion domain. In this paper we will consider some subclasses of H‐matrices and corresponding (Geršgorin‐type) eigenvalue inclusion theorems. Finally, we will establish relationship between given inclusion domains.     

ICP-MS Determination of Antimicrobial Metals in Microcapsules

Silver (Ag) and zinc (Zn) are very powerful antimicrobial metals. Therefore, in this research, a high-throughput, sensitive, and rapid method was developed for the determination of Ag and Zn in microcapsules using inductively coupled plasma mass spectrometry (ICP-MS). The sample preparation procedure employed simple microwave digestion of the microcapsules with 55.55% v/v HNO₃ and 44.45% v/v H₂O₂. The method was applied to determine Ag and Zn in microcapsule samples of different sizes (120 and 450 μm) after their preparation with and without chitosan. Prepared microcapsules, after characterization, were bonded to a polymer carrier by sol-gel procedure and the materials were characterized by FTIR spectroscopy and high-resolution optical microscopy. Significant differences were found in Ag and Zn levels between microcapsules samples prepared with and without chitosan. The results have shown that samples with chitosan had up to 20% higher levels of Zn than Ag: 120 μm microcapsules contained 351.50 μg/g of Ag and 85.51 μg/g of Zn, respectively. In contrast, samples prepared without chitosan showed larger overall variability: In microcapsules with a diameter of 120 μm, the amounts of antimicrobial metals were 98.32 μg/g of Ag and 106.75 μg of Zn, respectively. Moreover, 450 μm microcapsules contained 190.98 μg/g of Ag and 121.35 μg/g of Zn. Those quantities are high enough for efficient antimicrobial activity of newly prepared microcapsules, enabling the application of microcapsules in different antimicrobial coatings.     

Effects of Coumarinyl Schiff Bases against Phytopathogenic Fungi,the Soil-Beneficial Bacteria and Entomopathogenic Nematodes: Deeper Insight into the Mechanism of Action

Coumarin derivatives have been reported as strong antifungal agents against various phytopathogenic fungi. In this study, inhibitory effects of nine coumarinyl Schiff bases were evaluated against the plant pathogenic fungi (Fusarium oxysporum f. sp. lycopersici, Fusarium culmorum, Macrophomina phaseolina and Sclerotinia sclerotiourum). The compounds were demonstrated to be efficient antifungal agents against Macrophomina phaseolina. The results of molecular docking on the six enzymes related to the antifungal activity suggested that the tested compounds act against plant pathogenic fungi, inhibiting plant cell-wall-degrading enzymes such as endoglucanase I and pectinase. Neither compound exhibited inhibitory effects against two beneficial bacteria (Bacillus mycoides and Bradyrhizobium japonicum) and two entomopathogenic nematodes. However, compound 9 was lethal (46.25%) for nematode Heterorhabditis bacteriophora and showed an inhibitory effect against acetylcholinesterase (AChE) (31.45%), confirming the relationship between these two activities. Calculated toxicity and the pesticide-likeness study showed that compound 9 was the least lipophilic compound with the highest aquatic toxicity. A molecular docking study showed that compounds 9 and 8 bind directly to the active site of AChE. Coumarinyl Schiff bases are promising active components of plant protection products, safe for the environment, human health, and nontarget organisms.     

A Series of Green Oxovanadium(IV) Precatalysts with O,N and S Donor Ligands in a Sustainable Olefins Oligomerization Process

Designing catalyst systems based on transition metal ions and activators using the principles of green chemistry is a fundamental research goal of scientists due to the reduction of poisonous solvents, metal salts and organic ligands released into the environment. Urgent measures to reduce climate change are in line with the goals of sustainable development and the new restrictive laws ordained by the European Union. In this report, we attempted to use known oxovanadium(IV) green complex compounds with O, N and S donor ligands, i.e., [VO(TDA)phen] • 1.5 H₂O (TDA = thiodiacetate), (phen = 1,10-phenanthroline), oxovanadium(IV) microclusters with 2-phenylpyridine (oxovanadium(IV) cage), [VOO(dipic)(2-phepyH)] • H₂O (dipic = pyridine-2,6-dicarboxylate anion), (2-phepyH = 2-phenylpyridine), [VO(dipic)(dmbipy)] • 2H₂O (dmbipy = 4,4′-dimethoxy-2,2′-dipyridyl) and [VO(ODA)(bipy)] • 2 H₂O (ODA = oxydiacetate), (bipy = 2,2′-bipyridine), as precatalysts in oligomerization reactions of 3-buten-2-ol, 2-propen-1-ol, 2-chloro-2-propen-1-ol and 2,3-dibromo-2-propen-1-ol. The precatalysts, in most cases, turned out to be highly active because the catalytic activity exceeded 1000 g mmol⁻¹·h⁻¹. In addition, the oligomers were characterized by Fourier-transform infrared spectroscopy (FTIR), matrix-assisted laser desorption/ionization (MALDI-TOF-MS), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) techniques.     

Red clover (<Emphasis Type=Italic>Trifolium pratense</Emphasis> L.) honey: volatiles chemical-profiling and unlocking antioxidant and anticorrosion capacity

Headspace solid-phase micro-extraction (HS-SPME) and ultrasonic solvent extraction (USE) were used for red clover honey volatiles extraction. The extracts were analysed using gas chromatography and mass spectrometry (GC-MS). Lilac aldehyde isomers dominated in the headspace (individual range from 7.6 % to 21.4 %) followed by phenylacetaldehyde (10.1–31.2 %) and benzaldehyde (7.0–15.7 %). Higher aliphatic alcohols and hydrocarbons were the predominant constituents of the honey extracts. The honey and its extracts exhibited rather weak anti-radical activity (DPPH assay) and total antioxidant activity (FRAP assay). On the other hand, the honey’s inhibitive properties towards the corrosion of AA 2017A alloy in NaCl solution (potentiodynamic polarisation and potentiostatic pulse measurements) revealed the honey to be a very good anodic inhibitor (efficiency up to 76 %) while the honey extracts (USE) showed better inhibition efficacy.     

Kinetics and mechanism of degradation of Co(II)–<Emphasis Type=Italic>N</Emphasis>-benzyloxycarbonylglycinato complex

The kinetics of multi-step thermal degradation of Co(II) complex with N-benzyloxycarbonyl glycinato ligand [Co(N-Boc-gly)₂(H₂O)₄]·2H₂O, in non-isothermal conditions was studied using isoconversional and non-isoconversional methods. The degradation of complex occurs in three well-separated steps involving the loss of water molecules in first step followed by two degradation steps of dehydrated complex. The dependence of Arrhenius parameters on conversion degree showed that all observed steps of thermal degradation are very complex, involving more than one elementary step, as can be expected for most solid-state heterogeneous reactions with solid reactants and solid and gaseous products. It was shown that step 1, corresponding to the dehydration, involves a series of competitive dehydration steps of differently bound water molecules complicated by diffusion. Second step involves two parallel reactions related to the loss of two identical C₆H₅CH₂O– ligand fragments complicated by the presence of products in gaseous state. Further degradation in step 3 corresponds to complex process with a change in the limiting stage, in this case from the kinetic to the diffusion regime, connected with the presence of gaseous products diffusing through the solid product.     

Synthesis and antioxidant activity of some new coumarinyl-1,3-thiazolidine-4-ones

A series of Schiff's bases (E)-N-2-aryliden-2-(4-methyl-2-oxo-2H-chromen-7-yloxy)acetohydrazides 2a-l and N-(2-(substituted phenyl)-4-oxo-thiazolidin-3-yl)-2-(4-methyl-2-oxo-2H-chromen-7-yloxy)acetamides 3a-l were synthesized and evaluated for their antioxidant activity by the phosphomolybdenum method. Most of the Schiff's bases and thiazolidine-4-ones bearing two hydroxyl groups on the phenyl ring showed excellent antioxidant activity in comparison with ascorbic acid. Preliminary investigation on cytotoxic and antifungal activity was done on some representative samples.