Mariusz Urbaniak

Self-disproportionation of enantiomers via sublimation (SDEvS) is widely observed, yet its mechanistic origin remains elusive. One unresolved question is whether the phenomenon is primarily governed by the intrinsic properties of chiral solids or by differences in sample preparation, which vary considerably across published studies. Here, we systematically compare six representative preparation protocols, including mechanical mixing, grinding, solvent-mediated recrystallization, and the preparation of different crystal compositions, using amides N-acetyl-1-phenylethylamine (1, Ac-PEA), ethyl 2-acetamido-3-phenylpropanoate (2, N-Ac-α-Phe-OEt) and tert-butyl N-(1-phenylethyl)carbamate (3) as model compounds. Despite measurable variations in the extent of enantiomeric enrichment, all preparation methods led to the same qualitative SDE behavior for the investigated systems. Sample preparation therefore acts only as a secondary factor, modulating the efficiency of enantiomeric fractionation without altering its overall direction. These findings demonstrate that sublimation-induced SDE is an emergent property of the chiral solid rather than an artifact of sample history. Our results provide a foundation for comparing data obtained under different experimental protocols and represent an important step toward a unified mechanistic understanding of sublimation-induced SDE.

In this study, a series of novel alkoxylated resorcinarenes were synthesized using secondary and tertiary alcohols under mild catalytic conditions involving iminodiacetic acid. Structural characterization, including single-crystal X-ray diffraction, confirmed the successful incorporation of branched alkyl chains and highlighted the influence of substitution patterns on molecular packing. Notably, detailed mass spectrometric analysis revealed that, under specific conditions, the reaction pathway may shift toward the formation of defined oligomeric species with supramolecular characteristics—an observation that adds a new dimension to the synthetic potential of this system. To complement the chemical analysis, selected derivatives were evaluated for biological activity, focusing on bacterial growth and biofilm formation. Using four clinically relevant strains (Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa, and Bacillus subtilis), we assessed both planktonic proliferation (OD₆₀₀) and biofilm biomass (crystal violet assay). Compound 2c (2-pentanol derivative) consistently promoted biofilm formation, particularly in S. aureus and B. subtilis, while having limited cytotoxic effects. In contrast, compound 2e and the DMSO control exhibited minimal impact on biofilm development. The results suggest that specific structural features of the alkoxy chains may modulate microbial responses, potentially via membrane stress or quorum sensing interference. This work highlights the dual relevance of alkoxylated resorcinarenes as both supramolecular building blocks and modulators of microbial behavior.

The review is devoted to self-disproportionation of enantiomers (SDE) phenomenon which has been observed for many different classes of chiral organic compounds. The SDE phenomenon occurs when the fractionation of an enantioenriched sample due the application of a physicochemical process under achiral conditions results in the variation of the proportion of the enantiomers present across the fractions, though the overall composition in terms of the sample ee remains unchanged. The SDE process can be considered in terms of separating the excess enantiomer from the racemate. The basic terminology related to SDE was described. The formation of the SDE under chromatographic conditions is the result of an association process occurring in a solution of a chiral, non-racemic compound. Information on preferred interactions leading to homo-/heterochiral supramolecules can be provided by quantum chemical calculations, NMR spectroscopy and comparison of crystal structures of the racemic and enantiomeric crystals. Several examples of the chromatographic experiments with different classes of compounds were given in two purposes 1) to highlight the possibility of application SDE during column chromatography as the method for enantiopurification of the chiral, non-racemic compounds; 2) to demonstrate that a standard workup (chromatographic purification, evaporation) can alter the stereochemical outcome of asymmetric reactions

Four compounds with lactone moiety were synthesized from chalcone 1 in three- or four-step synthesis. γ-Bromo-δ-lactone 5 was the only product of bromolactonization of acid 4 whereas bromolactonization of ester 3, apart from lactone 5 also afforded its isomer 6 and two diastereoisomeric δ-hydroxy-γ-lactones 7 and 8. Lactone 8 was also obtained in 88% yield as a product of simultaneous dehalogenation and translactonization of γ-bromo-δ-lactone 5 by Penicillum frequentans AM 359. Chalcone-derived lactones 5–8 were subjected to the tests on antimicrobial activity and the results compared with activity of starting chalcone 1. Obtained lactones 5–8 in most cases limited the growth of tested bacterial and fungal strains. The highest activity was found for δ-hydroxy-γ-lactone 8 which completely inhibited the growth of Staphylococcus aureus, Fusarium graminearum, Aspergillus niger, and Alternaria sp. The introduction of lactone moiety into chalcone scaffold significantly improved antimicrobial activity of the compound: γ-bromo-δ-lactone 6 and δ-hydroxy-γ-lactone 8 were significantly stronger growth inhibitors of S. aureus and F. graminearum. In the case of the latter, a clear positive effect of the lactone function on the antifungal activity was also observed for γ-bromo-δ-lactone 5.

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.

2-(2-Fluoro-4-biphenyl) propionic acid (flurbiprofen), from the phenylalkanoic acid family of nonsteroidal anti-inflammatory drugs (NSAID’s), is currently on the pharmaceutical market as a racemate. This racemic compound was tested for its propensity to undergo the self-disproportionation of enantiomers (SDE) phenomenon by various forms of chromatography (SDEvC), such as routine gravity-driven column chromatography, medium-pressure liquid chromatography (MPLC), preparative thin-layer chromatography (PTLC), and size-exclusion chromatography (SEC), as well as by sublimation (SDEvS). Furthermore, examination by nuclear magnetic resonance (NMR) in various solvents found that flurbiprofen exhibited the phenomenon of self-induced diastereomeric anisochronism (SIDA). By measurement of the diffusion coefficient (D), the longitudinal relaxation time (T₁), and the transverse relaxation time (T₂) using NMR, as well as by electrospray ionization-mass spectrometry (ESI-MS) examinations, the preferred intermolecular association was found to be solvent dependent, e.g., heterochiral association was preferred in toluene, while homochiral association was preferred in more polar solvents. This study also attempted, unsuccessfully, to correlate the NMR measurements of flurbiprofen with chromatographic outcomes for the rationalization and prediction of chromatographic results based on NMR measurements. Because the intermolecular hydrogen bonding of the acid groups in flurbiprofen overwhelmingly predominates over other intermolecular interactions, flurbiprofen seemed to represent a good test case for this idea. The behavior of scalemic samples of flurbiprofen is important, as, although it is currently dispensed as a racemate, clinical applications of the R enantiomer have been investigated. SDEvC and SDEvS both have ramifications for the preparation, handling, and storage of enantioenriched flurbiprofen, and this concern applies to other chiral drugs as well.

Infections due to Gram-negative bacteria Helicobacter pylori may result in humans having gastritis, gastric or duodenal ulcer, and even gastric cancer. Investigation of quantitative changes of soluble biomarkers, correlating with H. pylori infection, is a promising tool for monitoring the course of infection and inflammatory response. The aim of this study was to determine, using an experimental model of H. pylori infection in guinea pigs, the specific characteristics of infrared spectra (IR) of sera from H. pylori infected (40) vs. uninfected (20) guinea pigs. The H. pylori status was confirmed by histological, molecular, and serological examination. The IR spectra were measured using a Fourier-transform (FT)-IR spectrometer Spectrum 400 (PerkinElmer) within the range of wavenumbers 3000–750 cm⁻¹ and converted to first derivative spectra. Ten wavenumbers correlated with H. pylori infection, based on the chi-square test, were selected for a K-nearest neighbors (k-NN) algorithm. The wavenumbers correlating with infection were identified in the W2 and W3 windows associated mainly with proteins and in the W4 window related to nucleic acids and hydrocarbons. The k-NN for detection of H. pylori infection has been developed based on chemometric data. Using this model, animals were classified as infected with H. pylori with 100% specificity and 97% sensitivity. To summarize, the IR spectroscopy and k-NN algorithm are useful for monitoring experimental H. pylori infection and related inflammatory response in guinea pig model and may be considered for application in humans.

Helicobacter pylori infections causing gastroduodenal disorders are a common medical problem. The aim of this study was to determine the specific motives of infrared spectroscopy (IR) spectra of sera from H. pylori-infected and uninfected children applied to investigate quantitatively-selected soluble biomarkers correlated with H. pylori infection in children and presumable consequent delayed growth. Sera from 41 children infected with H. pylori (Hp(+)) and 43 uninfected (Hp(−)) under the care of the Polish Mother’s Hospital in Lodz, Poland, were analyzed. The H. pylori status was confirmed by gastroscopy, ¹³C urea breath testing, and anti-H. pylori IgG antibodies. Infrared spectra were measured using an FTIR/FT-NIR Spectrum 400 spectrometer (PerkinElmer). The IR spectrum was measured in the wavenumber range 3000–750 cm⁻¹ and subjected to mathematical calculation of the first derivative. Based on the chi-square test, 10 wavenumbers of spectra correlating with H. pylori infection were selected for use in designing an artificial neural network. Ten parts of the IR spectra correlating with H. pylori infection were identified in the W2 and W3 windows associated mainly with proteins and the W4 window related to nucleic acids and hydrocarbons. Artificial neural networks for H. pylori infection were developed based on chemometric data. By mathematical modeling, children were classified towards H. pylori infection in conjunction with elevated levels of selected biomarkers in serum potentially related to growth retardation. The study concludes that IR spectroscopy and artificial neural networks may help to confirm H. pylori-driven growth disorders in children.

The C-arylation of Mannich base is used to obtain a series of new arylmethylene resorcinarene derivatives. Initially, aminomethyl derivative as the intermediate is formed in the Mannich reaction of resorcinarene with iminodiacetic acid. Next, activated aromatic rings act as a nucleophile in the reaction with this Mannich base and the arylmethylene derivatives of resorcinarene are prepared. The mixture of isomeric products is obtained for monosubstituted phenyl rings. Reaction with a suitably substituted phenyl ring gives one main product in good yields.