Engine oil is a valuable source of information on the technical condition of the drive unit. Under the influence of many factors, including operating conditions, time, high temperature, and various types of contamination, the oil gradually degrades, which can result in serious engine damage. The subject of the article focuses on an attempt to answer the questions of how engine failure affects the degradation of engine oil and whether we can use this knowledge to detect potential problems in public transport vehicles at an early stage.
View Article and Find Full Text PDFThis study delves into the intricate mechanics of human middle ear implants by examining a lumped parameter model with five degrees of freedom to estimate sound transfer. The ASTM standard, recognized globally as a benchmark, served as a reference for analysis, ensuring test accuracy and providing a comprehensive evaluation framework. To assess the implant's usability, numerical simulations were conducted and compared against both the ASTM standard and the experimental results obtained from temporal bone studies.
View Article and Find Full Text PDFSpectrochim Acta A Mol Biomol Spectrosc
January 2025
Raman Optical Activity combined with Circularly Polarized Luminescence (ROA-CPL) was used in the spectral recognition of glutathione peptide (GSH) and its model post-translational modifications (PTMs). We demonstrate the potential of ROA spectroscopy and CPL probes (EuCl, Na[Eu(DPA)], NaEuEDTA) in the study of unmodified peptide, i.e.
View Article and Find Full Text PDFAims: Corticosteroids are the treatment of choice for many inflammatory diseases but often lead to adverse effects, including hyperglycaemia. This study investigated the mechanisms driving differential effects on glucose control for AZD9567, an oral nonsteroidal selective glucocorticoid receptor modulator vs. prednisolone in 46 patients with type 2 diabetes mellitus.
View Article and Find Full Text PDFRaman optical activity (ROA) spectroscopy exhibits significant potential in the study of (bio)molecules as it encodes information on their molecular structure, chirality, and conformations. Furthermore, the method reveals details on excited electronic states when applied under resonance conditions. Here, we present a combined study of the far from resonance (FFR)-ROA and resonance ROA (RROA) of a single relatively small molecular system.
View Article and Find Full Text PDFCarotenoids tend to form supramolecular aggregates via non-covalent interactions where the chirality of individual molecules is amplified to the macroscopic level. We show that this can also be achieved for non-chiral carotenoid monomers interacting with polysaccharides. The chirality induction in canthaxanthin (CAX), caused by heparin (HP) and hyaluronic acid (HA), was monitored by chiroptical spectroscopy.
View Article and Find Full Text PDFIn living organisms, carotenoids are incorporated in biomembranes, remarkably modulating their mechanical characteristics, fluidity, and permeability. Significant resonance enhancement of Raman optical activity (ROA) signals of carotenoid chiral aggregates makes resonance ROA (RROA), a highly selective tool to study exclusively carotenoid assemblies in model membranes. Hence, RROA is combined with electronic circular dichroism (ECD), dynamic light scattering (DLS), molecular dynamics, and quantum-chemical calculations to shed new light on the carotenoid aggregation in dipalmitoylphosphatidylcholine (DPPC) liposomes.
View Article and Find Full Text PDFThe article presents the effect of pre-sowing Lavatera thuringiaca L. seeds stimulation with He-Ne laser light on the chemical composition (P, S, K, Ca, Mn, Fe, Ni, Cu and Zn content) of ash obtained after combustion of shoots of different ages. Results varied, but it was confirmed that pre-sowing exposure of seeds to this physical factor for 10-min has the most pronounced effect on K, Cu and Mn content increase (6%, 20%, 31% increase respectively) in the ash after the first year of vegetation as well as on Cu, K and Zn content increase (9%, 19%, 22% increase respectively) after the second year of vegetation.
View Article and Find Full Text PDFBiochim Biophys Acta Mol Cell Res
January 2023
Sulfhemoglobinemia is an incurable disease caused by an overdose of sulfur-containing drugs with oxidizing properties. Its diagnosis remains hindered due to the similarity of symptoms to other pathological state - methemoglobinemia, as well as contradictory information on the structure and characteristics of sulfhemoglobin. Herein, we present sulfhemoglobinemia model on living functional human erythrocytes, designed to recreate processes which could take place in a patient body in order to complement missing information and highlight distinctiveness of two hemoglobin (Hb) adducts formed after interaction with sulfur donors.
View Article and Find Full Text PDFSpectrochim Acta A Mol Biomol Spectrosc
November 2022
Chirality transfer (also called induced chirality) is a phenomenon present in chiroptical spectra that manifests itself as a new band or bands of an achiral molecule interacting with a chiral one. In the Raman optical activity (ROA) spectroscopy, the bands of achiral solvents have been recently observed, but the latest papers have shown that they corresponded to the new ECD-Raman (eCP-Raman) effect. Here, we show an unambiguous example of chirality transfer observed in the ROA spectra.
View Article and Find Full Text PDFIn this study, we found that a recently discovered ECD-Raman effect dominated over the natural Raman optical activity in a series of atropisomeric naphthalenediimides, and we investigated the kind of information about the molecular structure that could be obtained from the spectra. The ECD-Raman effect is polarised Raman scattering modulated by electronic circular dichroism. We showed that the spectra significantly depended on the substitution of the solute and/or the change of the solvent.
View Article and Find Full Text PDFResonance Raman Optical Activity (RROA) appeared as a natural extension of the nonresonance branch. It combines the structural sensitivity of chiroptical spectroscopy with the signal enhancement coming from the resonance of molecular electronic transitions with the excitation laser light. However, the idea has been hampered by many technical and theoretical problems that are being clarified only in recent years.
View Article and Find Full Text PDFIntermolecular interactions sensitive to chirality occur in many biological events. We report a complex formation between a versatile vanadium-based probe and a chiral co-ligand monitored the combination of electronic circular dichroism (ECD) and Raman scattering. This "ECD-Raman" effect was discovered relatively recently and can be measured using a Raman optical activity (ROA) spectrometer.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
September 2021
Resonance Raman optical activity (RROA) possesses all aspects of a sensitive tool for molecular detection, but its measurement remains challenging. We demonstrate that reliable recording of RROA of chiral colorful compounds is possible, but only after considering the effect of the electronic circular dichroism (ECD) on the ROA spectra induced by the dissolved chiral compound. We show RROA for a number of model vitamin B derivatives that are chemically similar but exhibit distinctively different spectroscopic behavior.
View Article and Find Full Text PDFThe aim of this paper is to compare the results of kinematic viscosity of lubricating oils measurements at 40 °C, obtained with three different rapid evaluation devices, and the standardized method using an Ubbelohde Capillary viscometer. The following instruments were selected to measure: a mid-FTIR spectrophotometer, a microchannel viscometer, and a Stabinger viscometer. The study material comprised 42 fresh engine oils, all of which are commercially available.
View Article and Find Full Text PDFFuels and their components accumulate in soil, and many soil organisms are exposed to this pollution. Compared to intensive research on the effect of conventional fuel on soil, very few studies have been conducted on soil ecotoxicity of biofuels. Considering the limited information available, the present study evaluated the changes caused by the presence of biodiesel and diesel fuel in soil.
View Article and Find Full Text PDFThis work demonstrates resonance Raman optical activity (RROA) spectra of three truncated vitamin B derivatives modified within the nucleotide loop. Since truncated cobalamins possess sufficiently high rotational strength in the range of ROA excitation (532 nm), it was possible to record their spectra in the resonance condition. They showed several distinct spectral features allowing for the distinguishing of studied compounds, in contrast to other methods, i.
View Article and Find Full Text PDFIn this work, cobalamins with different upper axial substituents and a cobalamin derivative with a ring modification were studied using chiroptical spectroscopies, in particular resonance Raman optical activity (RROA), to shed light on the influence of structural modifications on RROA spectra in these strongly chiral systems in resonance with multiple excited states at 532 nm excitation. We have demonstrated that for these unique systems RROA possesses augmented structural specificity, surpassing resonance Raman spectroscopy and enabling at the same time measurement of cobalamins at fairy low concentrations of ∼10 mol dm. The enhanced structural specificity of RROA is a result of bisignate spectra due to resonance via more than one electronic state.
View Article and Find Full Text PDFCarotenoid microcrystals, extracted from cells of carrot roots and consisting of 95 % of achiral β-carotene, exhibit a very intense chiroptical (ECD and ROA) signal. The preferential chirality of crystalline aggregates that consist mostly of achiral building blocks is a newly observed phenomenon in nature, and may be related to asymmetric information transfer from the chiral seeds (small amount of α-carotene or lutein) present in carrot cells. To confirm this hypothesis, we synthesized several model aggregates from various achiral and chiral carotenoids.
View Article and Find Full Text PDFWe have isolated mixtures of [5]- and [3]-ladderanoic acids 1a and 2a from the biomass of an anammox bioreactor and have separated the acids and their phenacyl esters for the first time by HPLC. The absolute configurations of the naturally occurring acids and their phenacyl esters are assigned as R at the site of side-chain attachment by comparison of experimental specific rotations with corresponding values predicted using quantum chemical (QC) methods. The absolute configurations for 1a and 2a were independently verified by comparison of experimental Raman optical activity spectra with corresponding spectra predicted using QC methods.
View Article and Find Full Text PDFSpectrochim Acta A Mol Biomol Spectrosc
January 2019
This comprehensive study on selected 14 carbohydrates in water solution is an extension of previously published one focused only on solid state analysis. Here, Raman spectroscopy was used as a dedicated method for analysis of carbohydrates in solution, both using a normal effect (RS) and its chiral analogue: Raman Optical Activity spectroscopy (ROA). The compounds were selected as biologically important and representative of all groups: monosaccharides, disaccharides, trisaccharides, cyclodextrines and polysaccharides.
View Article and Find Full Text PDFBiomolecular aggregation is omnipresent in nature and important for metabolic processes or in medical treatment; however, the phenomenon is rather difficult to predict or understand on the basis of computational models. Recently, we found that electronic circular dichroism (ECD) spectroscopy and closely related resonance Raman optical activity (RROA) are extremely sensitive to the aggregation mechanism and structure of the astaxanthin dye. In the present study, molecular dynamics (MD) and quantum chemical (QC) computations (ZIndo/S, TDDFT) are used to link the aggregate structure with ECD spectral shapes.
View Article and Find Full Text PDFTwo enantiomers of 2-methyl-N-(1-thien-2-ylethyl)propane-2-sulfonamide (TSA) were synthesized, and their VCD, ROA, IR, and Raman spectra were registered. The solved (S)-TSA X-ray structure shows a disorder connected to the presence of two TSA conformers differing by a slight rotation of the thiophene ring. Two molecules in the unit cell of the monoclinic P2 crystal form a net of NH···OS and C*H···OS hydrogen bonds.
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