Percorrer por autor "Khmelinskii, Igor"
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- 5-Deazaalloxazine as photosensitizer of singlet oxygen and potential redox-sensitive agentPublication . Insińska-Rak, Małgorzata; Golczak, Anna; Gierszewski, Mateusz; Anwar, Zubair; Cherkas, Volodymyr; Kwiatek, Dorota; Sikorska, Ewa; Khmelinskii, Igor; Burdziński, Gotard; Cibulka, Radek; Mrówczyńska, Lucyna; Kolanowski, Jacek Lukasz; Sikorski, MarekFlavins are a unique class of compounds that combine the features of singlet oxygen generators and redox-dependent fluorophores. From a broad family of flavin derivatives, deazaalloxazines are significantly underdeveloped from the point of view of photophysical properties. Herein, we report photophysics of 5-deazaalloxazine (1a) in water, acetonitrile, and some other solvents. In particular, triplet excited states of 1ain water and in acetonitrile were investigated using ultraviolet-visible (UV-Vis) transient absorption spectroscopy. The measured triplet lifetimes for 1a were all on the microsecond time scale (approximate to 60 mu s) in deoxygenated solutions. The quantum yield of S-1 -> T-1 intersystem crossing for 1ain water was 0.43 based on T1 energy transfer from 1a to indicaxanthin (5) acting as acceptor and on comparative actinometric measurements using benzophenone (6). 1a was an efficient photosensitizer for singlet oxygen in aerated solutions, with quantum yields of singlet oxygen in methanol of about 0.76, compared to acetonitrile similar to 0.74, dichloromethane similar to 0.64 and 1,2-dichloroethane similar to 0.54. Significantly lower singlet oxygen quantum yields were obtained in water and deuterated water (Phi(Delta)similar to 0.42 and 0.44, respectively). Human red blood cells (RBC) were used as a cell model to study the antioxidant capacity in vitro and cytotoxic activity of 1a. Fluorescence-lifetime imaging microscopy (FLIM) data were analyzed by fluorescence lifetime parameters and distribution for different parts of the emission spectrum. Comparison of multidimensional fluorescent properties of RBC under physiological-like and oxidative-stress conditions in the presence and absence of 1a suggests its dual activity as probe and singlet-oxygen generator and opens up a pathway for using FLIM to analyze complex intracellular behavior of flavin-like compounds. These new data on structure-property relationship contribute to the body of information required for a rational design of flavin-based tools for future biological and biochemical applications.
- Absorption spectra of Muler cell intermediate filaments: experimental results and theoretical modelsPublication . Khmelinskii, Igor; Makarov, VladimirExperimental spectra of Muller cell (MC) intermediate filaments (IFs) isolated from porcine retina are reported in this work. The absorption spectra recorded at different MC IF concentrations were used to estimate their absorption cross-sections at different wavelengths. The average absorption cross-section of a single MC IF was ca. (0.97...2.01) x 10(-1) cm(2) in the 650-445 nm spectral range. To interpret these experimental absorption spectra, we made ab initio calculations of the optical spectra of a-helix polypeptides, and also used a simplified theoretical approach that modeled an IF by a conductive wire. The energy spectra of the refractive index, extinction coefficient (absorption cross-section), energy loss and reflectivity functions for different photon polarizations, with strong anisotropy with respect to the system axis, were calculated ab initio for polyglycine a-helix molecule containing 1000 glycine residues. Strong anisotropy of these parameters was explained by photons interacting with different electronic transitions. Note that similarly strong anisotropy was also obtained for the optical absorption cross-sections in the simplified model. Both modeling approaches were used for calculating the absorption cross sections of interest. As a result, the absorption cross-section for photons propagating axially along MC IFs was much larger than their geometrical cross-section. The latter result was explained taking into account the density of electronic states, with numerous electrons contributing to the transition intensity at a given energy. We found that the simple conductive wire model describes the MC IF absorption spectrum better than the ab initio spectra. The latter conclusion was explained by the limitations of ab initio analysis, which only took into account one alpha-helix with 1000 aminoacids, whereas each porcine Muller cell IF is assembled of thousands of protein molecules, reaching the total length of ca. 100 mu m. The presently reported results contribute to the understanding of the quantum mechanism of high-contrast vision of vertebrate eyes. Published by Elsevier B.V.
- Analysis of quantum coherence in biologyPublication . Khmelinskii, Igor; Makarov, Vladimir, IWe reviewed the tools of quantum physics used in modeling of quantum coherence (QC) effects in different systems, including biological systems, which behave as quantum objects in some of their degrees of freedom. In particular, we considered the usage of the effective Hamiltonian (EH), Green's function (GF) and density matrix (DM) methods in the analysis of QC, focusing on QC in biological systems. We discussed the two main mechanisms of loss of quantum state coherence: (i) dephasing of the originally prepared coherent wave package and (ii) population relaxation in the same wave package. Dephasing does not affect the quantum state population, e.g. as in spin-spin relaxation, where dephasing is described by the tau(2) relaxation time. On the other hand, the state population relaxation of the spin wavepackage is attributed to spin-lattice relaxation and is described by the tau(1) relaxation time. Presently we discussed EH and GF formalisms in terms of the complex energy, dependent on intra- and intersystem interactions that induce state population relaxation. We provided a detailed analysis of these approaches for the exciton relaxation dynamics in a glycine polypeptide chain. The same phenomena were described in the DM formalism using the relaxation matrix. We discussed QC in different biological systems, showing that QC is conserved when the interactions of the coherent wavepackage with other degrees of freedom are weak, as otherwise population relaxation causes loss of QC. We believe that our results will be useful for the researchers in the area of quantum biology.
- Application of multidimensional and conventional fluorescence techniques for classification of beverages originating from various berry fruitPublication . Sikorska, Ewa; Wlodarska, Katarzyna; Khmelinskii, IgorThe objectives of this study were to characterize fluorescence of beverages from berry fruit, including chokeberry, blackcurrant, raspberry and strawberry, and to develop classification models based on different types of fluorescence spectra to identify beverages depending on the fruit species. Total fluorescence spectra (excitation-emission matrices, EEMs) and total synchronous fluorescence spectra (TSFS) were recorded for a series of commercial berry fruit beverages. An analysis of EEMs using parallel factor analysis (PARAFAC) revealed four components characterized by the excitation/emission maxima at 275/326, 319/410, 414/600, and 360/460 nm, respectively. Based on the spectral profiles, these components were assigned to various groups of phenolic compounds. Partial least squares discriminant analysis was used to develop the classification models. The analysis was performed on PARAFAC scores, unfolded EEMs (uEEMs), unfolded TSFS (uTSFS), and additionally on conventional emission spectra (EMS) measured at particular excitation wavelengths and single synchronous fluorescence spectra (SFS). The classification models with the same average classification error of 4.86% were obtained for the analysis of both the entire uEEMs and uTSFS. Among models based on the individual spectra, the lowest error of 4.42% was obtained for SFS measured at Delta lambda = 40 nm, and an error of 7.64% was obtained for EMS measured at the excitation wavelength of 360 nm. The classification model based on the PARAFAC scores had the highest error of 15.27%. The present results show good potential of fluorescence as rapid and reagent-free tool for authenticity evaluation of berry beverages.
- Computational modeling of In vitro swelling of mitochondria: A biophysical approachPublication . Makarov, Vladimir I.; Khmelinskii, Igor; Javadov, SabzaliSwelling of mitochondria plays an important role in the pathogenesis of human diseases by stimulating mitochondria-mediated cell death through apoptosis, necrosis, and autophagy. Changes in the permeability of the inner mitochondrial membrane (IMM) of ions and other substances induce an increase in the colloid osmotic pressure, leading to matrix swelling. Modeling of mitochondrial swelling is important for simulation and prediction of in vivo events in the cell during oxidative and energy stress. In the present study, we developed a computational model that describes the mechanism of mitochondrial swelling based on osmosis, the rigidity of the IMM, and dynamics of ionic/neutral species. The model describes a new biophysical approach to swelling dynamics, where osmotic pressure created in the matrix is compensated for by the rigidity of the IMM, i.e., osmotic pressure induces membrane deformation, which compensates for the osmotic pressure effect. Thus, the effect is linear and reversible at small membrane deformations, allowing the membrane to restore its normal form. On the other hand, the membrane rigidity drops to zero at large deformations, and the swelling becomes irreversible. As a result, an increased number of dysfunctional mitochondria can activate mitophagy and initiate cell death. Numerical modeling analysis produced results that reasonably describe the experimental data reported earlier.
- Contrary to consensus, oxidation of ethanol by human alcohol dehydrogenase (ADH) 1A is activated by ATPPublication . Khmelinskii, Igor; Makarov, Vladimir I.Presently we report that enzymatic oxidation of ethanol (EtOH) by ADH1A alcohol dehydrogenase is strongly accelerated in presence of adenosine triphosphate (ATP), by up to the factor of 20 in vitro. This result provides a different look on the role of ATP in functioning of alcohol dehydrogenases (ADH), which until presently were a textbook example of enzymes not requiring ATP and successfully operating without it. However, ATP is available in every living cell and will activate reactions conducted by ADH enzymes in vivo. Therefore, the body of published literature describing properties of numerous ADH enzymes requires a thorough revision.
- Current–voltage characteristics of a Co/Ni bilayer nanofilmPublication . Khmelinskii, Igor; Makarov, VladimirWidespread interest in optical and electrical properties of nanostructured systems began more than 20 years ago. Here, optical and electrical properties of Co/Ni bilayer nanofilms are explored. These optical and electrical properties were described in terms of a common confined wavefunction spanning both Co and Ni layers. The effective relative electron mass parameter f estimated for this bilayer film was about 0.1489. Temperature dependence of the current-voltage characteristics of the Co/Ni bilayer nanofilms was described as that of a Schottky diode with the Schottky barrier height of US = 24 cm-1, very small compared to other semiconducting materials. Therefore, Co/Ni bilayer nanofilms apparently had semiconducting properties, which may approxi-mately be described using Schottky diode theory. Such semiconducting properties of bilayer metal nanofilms could be used in special low-temperature low-consumption electronic devices.
- Discrimination of beer flavours by analysis of volatiles using the mass spectrometer as an electronic nosePublication . Sikorska, Ewa; Chmielewski, Jaroslaw; Gorecki, Tomasz; Khmelinskii, Igor; Sikorski, Marek; De Keukeleire, DenisEntire mass spectra of beer headspace components were used as fingerprints for beer brand classification and differentiation of beer samples stored under various conditions. Chemometric analysis of the mass spectra allowed for the discrimination of beer brands and for the detection of beer aging and photodegradation. The numeric methods used include unsupervised PCA modelling and discrimination using kappa NN, LDA, and D-PLS methods.
- Dissipation of triadimefon on the solid/gas interfacePublication . Silva, José P. da; Silva, Abílio M. da; Khmelinskii, IgorThe dissipation or triadimefon, as pure solid and in the Bayleton 5 commercial formulation, was studied under controlled and natural conditions. Volatilization and photodegradation were shown to be the main dissipation processes. The volatilization results can be described by an empirical model assuming exponential decay of the volatilization rate. The filler of the commercial formulation is determinant for the volatilization but has little effect on the photodegradation rates. The main photoproducts were identified and a reaction mechanism proposed. (C) 2001 Elsevier Science Ltd. All rights reserved.
- Education today: 12 + 5 < 4 - lessons of education reforms in Portugal and beyondPublication . Khmelinskii, Igor; Fonseca, Custódia; Stallinga, PeterSince the adoption of the ‘Lei de Bases…’ of 1984, the quality of education in Portugal is declining, undermined by ‘critical, creative and independent thinking’, implemented by neglecting memorization as a learning tool, as supposedly students should understand things without knowing them. As a consequence, vast majority of students can’t retain any abstract knowledge. They prepare from scratch for their tests and forget everything afterwards. The students never acquire essential primary-school skills such as capacity to do mental calculations, hence the title of this report, comparing contemporary school + university education to pre-1984 primary school of 4 years. The quality of education is further degraded by ‘evaluation’ of teachers at school and university, judged by academic success and degree of satisfaction of their students. With the students objectively incapable to learn, understand or remember, the teachers have a dilemma of either letting such students pass without retained knowledge, skills and competences, or else have their own ‘evaluation’ suffer. As the generations change, students who were ‘passed’ become teachers themselves, still with no retained knowledge and thus no moral authority to fail their own students. Thus, the level of requirements monotonously degrades, with the educational fraud perpetuated in the new generations.