Publications

Gaining insight into Pd/C catalytic systems aimed at locating reactive centers on carbon surfaces, revealing their properties and estimating the number of reactive centers presents a challenging problem. In the present study state-of-the-art experimental techniques involving ultra high resolution SEM/STEM microscopy (1 Å resolution), high brilliance X-ray absorption spectroscopy and theoretical calculations on truly nanoscale systems were utilized to reveal the role of carbon centers in the formation and nature of Pd/C catalytic materials. Generation of Pd clusters in solution from the easily available Pd ₂dba₃ precursor and the unique reactivity of the Pd clusters opened an excellent opportunity to develop an efficient procedure for the imaging of a carbon surface. Defect sites and reactivity centers of a carbon surface were mapped in three-dimensional space with high resolution and excellent contrast using a user-friendly nanoscale imaging procedure. The proposed imaging approach takes advantage of the specific interactions of reactive carbon centers with Pd clusters, which allows spatial information about chemical reactivity across the Pd/C system to be obtained using a microscopy technique. Mapping the reactivity centers with Pd markers provided unique information about the reactivity of the graphene layers and showed that >2000 reactive centers can be located per 1 μm² of the surface area of the carbon material. A computational study at a PBE-D3-GPW level differentiated the relative affinity of the Pd₂ species to the reactive centers of graphene. These findings emphasized the spatial complexity of the carbon material at the nanoscale and indicated the importance of the surface defect nature, which exhibited substantial gradients and variations across the surface area. The findings show the crucial role of the structure of the carbon support, which governs the formation of Pd/C systems and their catalytic activity.

In recent years, the emergence of nickel catalysis and the development of many remarkable synthetic applications have been observed. The key advantages of nickel catalysts include: a) efficient catalysis and the ability to initiate transformations involving usually unreactive substrates; b) the accessibility of Ni⁰/Ni^I/Ni^II/Ni^III oxidation states and radical pathways; c) new reactivity patterns beyond the traditional framework of metal catalysts; d) the facile activation of unsaturated molecules and a variety of transformations involving multiple bonds; and e) opportunities in photocatalytic applications and dual photocatalysis. The present viewpoint briefly summarizes the fundamental aspects of nickel chemistry and highlights promising directions of catalyst development.

Vinyl sulfides represent an important class of compounds in organic chemistry and materials science. Atom-economic addition of thiols to the triple bond of alkynes provides an excellent opportunity for environmentally friendly processes. We have found that well-known and readily available Pd-NHC complex (IMes)Pd(acac)Cl is an efficient catalyst for alkyne hydrothiolation. The reported technique provides a general one-pot approach for the selective preparation of Markovnikov-type vinyl sulfides starting from tertiary, secondary, or primary aliphatic thiols, as well as benzylic and aromatic thiols. In all the studied cases, the products were formed in excellent selectivity and good yields.

Three different types of drug delivery platforms based on imidazolium ionic liquids (ILs) were synthesized in high preparative yields, namely, the models involving (i) ionic binding of drug and IL; (ii) covalent binding of drug and IL; and (iii) dual binding using both ionic and covalent approaches. Seven ionic liquids containing salicylic acid (SA-ILs) in the cation or/and in the anion were prepared, and their cytotoxicity toward the human cell lines CaCo-2 (colorectal adenocarcinoma) and 3215 LS (normal fibroblasts) was evaluated. Cytotoxicity of SA-ILs was significantly higher than that of conventional imidazolium-based ILs and was comparable to the pure salicylic acid. It is important to note that the obtained SA-ILs dissolved in water more readily than salicylic acid, suggesting benefits of possible usage of traditional nonsoluble active pharmaceutical ingredients in an ionic liquid form.

Functionalization of ionic liquids (ILs) with natural amino acids is usually considered as a convenient approach to decrease their toxicity and find new areas of chemical application as sustainable solvents, reagents or catalysts. In the present study, the cytotoxicity of several amino acid-containing ionic liquids (AAILs) with amino acid-based cations and anions was studied towards NIH/3T3 and CaCo-2 cell cultures and compared with the toxicity of conventional imidazolium-based ILs. The presence of an amino acid in the anion did not lead to a significant decrease in toxicity, whereas in the cation it unexpectedly increased the toxicity, as compared with conventional ILs. Exposure to 1-butyl-3-methylimidazolium chloride or 1-butyl-3-methylimidazolium glycinate induced apoptosis in NIH/3T3 cells. The present study gives new insights into biological effects of AAILs and shows that an amino acid residue may make ILs more biologically active. Special attention should be paid to the plausible synergetic effect of a combination of ILs with natural biologically active molecules. The results suggest possible medical application of AAILs rather than involvement as a green and sustainable tool to carry out chemical reactions.

The extraction of peptides was studied in a two-phase ionic liquid (IL)/organic solvent system, which displayed outstanding chain length sensitivity (dipeptide vs tripeptide) and separation ability, even for structurally similar peptides (divaline vs dialanine). The extraction process could be performed under substoichiometric conditions; an IL-to-peptide ratio as low as 3:1 led to a high extraction selectivity of divaline/dialanine = 6. For practical applications, two systems were developed for the extraction of peptides from ILs under heterogeneous and homogeneous conditions, with selectivities of 6 and 3.5, respectively. The developed system has shown excellent recycling properties and was reused several times without any visible changes in the selectivity and extraction efficiency. A nuclear magnetic resonance (NMR) experiment with molecular-level spatial resolution was successfully performed to study the mechanism of the extraction process and to visualize the two-phase system.

Combined experimental and theoretical studies revealed a complex mechanistic picture in which the carboxylic group-assisted proton transfer from acetic acid to an alkyne molecule is the key step in the unique gold-mediated alkyne transformation that leads to the formation of gem-disubstituted vinyl gold complexes. The structures of the complexes were unambiguously established using NMR spectroscopy (in solution) and X-ray diffraction (in the solid state). ESI-MS study of the reaction mixture revealed multiple gold-containing complexes and clusters. Investigation of the MS² fragmentation patterns of the selected ions suggested the involvement of gold acetylides in the transformation. Further treatment of the complexes with protic acid led to the discovery of a novel route for the gold-mediated alkyne hydrothiolation.

Metal complexes with N-heterocyclic carbene ligands (NHC) are ubiquitously used in catalysis, where the stability of the metal–ligand framework is a key issue. Our study shows that Ni-NHC complexes may undergo facile decomposition due to the presence of water in organic solvents (hydrolysis). The ability to hydrolyze Ni(NHC)2X2 complexes decreases in the order of NHC = 1,2,4-triazolium > benzimidazolium ≈ imidazolium. Depending on the ligand and substituents, the half reaction time of the complex decomposition may change from several minutes to hours. The nature of the halogen is also an important factor, and the ability for decomposition of the studied complexes decreases in the order of Cl > Br > I. NMR and MS monitoring revealed that Ni-NHC complexes in the presence of water undergo hydrolysis with Ni–Ccarbene bond cleavage, affording the corresponding N,N′-dialkylated azolium salts and nickel(II) hydroxide. These findings are of great importance for designing efficient and recyclable catalytic systems, because trace water is a common contaminant in routine synthetic applications.

Ubiquitous usage of Pd- and Pt-containing nanoparticles in automotive catalytic converters is an important potential threat to the environment. The unavoidable release of transition metal species to the environment and their contact with water give rise to the poisoning of ecosystems by heavy metal compounds. Electrospray ionization mass spectrometry and the newly-developed fragment partitioning approach show that a variety of metal species may be formed upon contact of metal salts with water. A series of monometallic complexes, homonuclear clusters and heteronuclear clusters of palladium and platinum were detected and characterized. The study has revealed a critical danger of metal contamination due to easy formation of transition metal clusters, which may be much more toxic than corresponding monometallic complexes.

A possible mechanistic pathway related to an enzyme-catalyzed [4+2] cycloaddition reaction was studied by theoretical calculations at density functional (B3LYP, O3LYP, M062X) and semiempirical levels (PM6-DH2, PM6) performed on a model system. The calculations were carried out for the key [4+2] cycloaddition step considering enzyme-catalyzed biosynthesis of Spinosyn A in a model reaction, where a reliable example of a biological Diels-Alder reaction was reported experimentally. In the present study it was demonstrated that the [4+2] cycloaddition reaction may benefit from moving along the energetically balanced reaction coordinate, which enabled the catalytic rate enhancement of the [4+2] cycloaddition pathway involving a single transition state. Modelling of such a system with coordination of three amino acids indicated a reliable decrease of activation energy by ~18.0 kcal/mol as compared to a non-catalytic transformation.

The design of functional organic and hybrid molecular systems has shown outstanding recent growth and is a high priority in the development of new technologies and novel functional materials. Recent advancements in the chemical sciences have provided fascinating opportunities to access the most complex molecular architectures ever possible so far. Herein, we discuss the principles of the structural organization of recently studied molecular systems, basic approaches for their assembly, and challenging directions for their practical applications.

The necessary prerequisites to carry out efficient NMR/MS studies and the important points required to avoid inconsistent measurements are discussed. A comparative assessment of the sensitivity and accuracy of NMR, EI-MS and ESI-MS measurements was carried out to evaluate typical laboratory research performance. Accurate NMR measurements are possible in the 10 ^–1–10^–3 m concentration range, with spectral studies still being possible at concentrations of approximately 10^–4–10^–5 m. EI-MS is more sensitive and can operate at concentrations of 10^–6 m, while commonly available ESI-MS can be efficient up to a concentration of 10^–18 m.