Chain Geometry Determined by the Affine Group

Chain geometry associated with an affine group and with a linear group is studied. In particular, closely related to the respective chain geometries affine partial linear spaces and generalizations of sliced spaces are defined. The automorphisms of thus obtained structures are determined.     

Application of microextraction by packed sorbent to isolation of psychotropic drugs from human serum

A method of microextraction by packed sorbent (MEPS) followed by liquid chromatography with diode array detection has been developed and optimized for the extraction of six tricyclic antidepressants (amitriptyline, nortriptyline, imipramine, desipramine, doxepin, nordoxepin) from human serum. The optimal parameters of MEPS extraction (type of sorbent, volume of sample, composition, and volume of washing and elution solutions) for these drugs in spiked samples were defined. The developed MEPS procedure was validated and then successfully applied to the analysis of serum reference material. The limit of detection (0.02–0.05 μg/mL), intraday (2.7–8.8%) and interday (4.4–11.6%) precision (RSD), and the accuracy of the assay (94.5–108.8%) at three concentration levels—0.2, 0.5, and 0.8 μg/mL—were estimated. The accuracy of the method was evaluated by the analysis of certified reference material. Moreover, the validated procedure was compared with the solid-phase extraction technique. Finally, microextraction by packed sorbent was assessed as a suitable tool in forensic and clinical methods for serum sample preparations.     

Stochastic switching in systems with rare and hidden attractors

Complex biochemical networks are commonly characterised by the coexistence of multiple stable attractors. This endows living systems with plasticity in responses under changing external conditions, thereby enhancing their probability for survival. However, the type of such attractors as well as their positioning can hinder the likelihood to randomly visit these areas in phase space, thereby effectively decreasing the level of multistability in the system. Using a model based on the Hodgkin–Huxley formalism with bistability between a silent state, which is a rare attractor, and oscillatory bursting attractor, we demonstrate that the noise-induced switching between these two stable attractors depends on the structure of the phase space and the disposition of the coexisting attractors to each other.     

On the convergence of zero-point vibrational corrections to nuclear shieldings and shielding anisotropies towards the complete basis set limit in water

ABSTRACT

The method and basis set dependence of zero-point vibrational corrections (ZPVCs) to nuclear magnetic resonance shielding constants and anisotropies has been investigated using water as a test system. A systematic comparison has been made using the Hartree–Fock, second-order Møller–Plesset perturbation theory (MP2), coupled cluster singles and doubles (CCSD), coupled cluster singles and doubles with perturbative triples corrections (CCSD(T)) and Kohn–Sham density functional theory with the B3LYP exchange-correlation functional methods in combination with the second-order vibrational perturbation theory (VPT2) approach for the vibrational corrections. As basis sets, the correlation consistent basis sets cc-pVXZ, aug-cc-pVXZ, cc-pCVXZ and aug-cc-pCVXZ with X = D, T, Q, 5, 6 and the polarisation consistent basis sets aug-pc-n and aug-pcS-n with n = 1, 2, 3, 4 were employed. Our results show that basis set convergence of the vibrational corrections is not monotonic and that very large basis sets are needed before a reasonable extrapolation to the basis set limit can be performed. Furthermore, our results suggest that coupled cluster methods and a decent basis set are required before the error of the electronic structure approach is lower than the inherent error of the VPT2 approximation.     

Analysis of time delay effects on a linear bubble chain system

A chain of vertically rising discrete air bubbles represents a transition phenomenon from individual to continuum behavior in a bubbly liquid. Previous studies have reported that there is a preference for acoustic energy to propagate along the bubble chain and that this behavior could be explained by a coupled-oscillator model. However, it has recently been demonstrated that quantitative results from the coupled-oscillator model do not match experimental data. In this paper, it is shown how adding time delays to the coupled-oscillator model can produce results that are in better agreement with experimental data. In addition, the effects of time delays on the natural frequencies and damping of individual eigenmodes of the vertical bubble chain are also investigated. It was found that adding time delays can dramatically change the damping of the different modes of the system while having less dramatic impact on the natural frequencies of the individual eigenmodes. Counterintuitively, it is found that the effects of time delays appear to be more important when the bubbles are closer together than when they are farther apart.     

Naphthazarin Derivatives in the Light of Intra- and Intermolecular Forces

Our long-term investigations have been devoted the characterization of intramolecular hydrogen bonds in cyclic compounds. Our previous work covers naphthazarin, the parent compound of two systems discussed in the current work: 2,3-dimethylnaphthazarin (1) and 2,3-dimethoxy-6-methylnaphthazarin (2). Intramolecular hydrogen bonds and substituent effects in these compounds were analyzed on the basis of Density Functional Theory (DFT), Møller–Plesset second-order perturbation theory (MP2), Coupled Clusters with Singles and Doubles (CCSD) and Car-Parrinello Molecular Dynamics (CPMD). The simulations were carried out in the gas and crystalline phases. The nuclear quantum effects were incorporated a posteriori using the snapshots taken from ab initio trajectories. Further, they were used to solve a vibrational Schrödinger equation. The proton reaction path was studied using B3LYP, ωB97XD and PBE functionals with a 6-311++G(2d,2p) basis set. Two energy minima (deep and shallow) were found, indicating that the proton transfer phenomena could occur in the electronic ground state. Next, the electronic structure and topology were examined in the molecular and proton transferred (PT) forms. The Atoms In Molecules (AIM) theory was employed for this purpose. It was found that the hydrogen bond is stronger in the proton transferred (PT) forms. In order to estimate the dimers’ stabilization and forces responsible for it, the Symmetry-Adapted Perturbation Theory (SAPT) was applied. The energy decomposition revealed that dispersion is the primary factor stabilizing the dimeric forms and crystal structure of both compounds. The CPMD results showed that the proton transfer phenomena occurred in both studied compounds, as well as in both phases. In the case of compound 2, the proton transfer events are more frequent in the solid state, indicating an influence of the environmental effects on the bridged proton dynamics. Finally, the vibrational signatures were computed for both compounds using the CPMD trajectories. The Fourier transformation of the autocorrelation function of atomic velocity was applied to obtain the power spectra. The IR spectra show very broad absorption regions between 700 cm−1–1700 cm−1 and 2300 cm−1–3400 cm−1 in the gas phase and 600 cm−1–1800 cm−1 and 2200 cm−1–3400 cm−1 in the solid state for compound 1. The absorption regions for compound 2 were found as follows: 700 cm−1–1700 cm−1 and 2300 cm−1–3300 cm−1 for the gas phase and one broad absorption region in the solid state between 700 cm−1 and 3100 cm−1. The obtained spectroscopic features confirmed a strong mobility of the bridged protons. The inclusion of nuclear quantum effects showed a stronger delocalization of the bridged protons.     

Microalgae as a Potential Functional Ingredient: Evaluation of the Phytochemical Profile,Antioxidant Activity and In-Vitro Enzymatic Inhibitory Effect of Different Species

The functional food market has been in a state of constant expansion due to the increasing awareness of the impact of the diet on human health. In the search for new natural resources that could act as a functional ingredient for the food industry, microalgae represent a promising alternative, considering their high nutritional value and biosynthesis of numerous bioactive compounds with reported biological properties. In the present work, the phytochemical profile, antioxidant activity, and enzymatic inhibitory effect aiming at different metabolic disorders (Alzheimer’s disease, Type 2 diabetes, and obesity) were evaluated for the species Porphyridium purpureum, Chlorella vulgaris, Arthorspira platensis, and Nannochloropsis oculata. All the species presented bioactive diversity and important antioxidant activity, demonstrating the potential to be used as functional ingredients. Particularly, P. purpureum and N. oculata exhibited higher carotenoid and polyphenol content, which was reflected in their superior biological effects. Moreover, the species P. purpureum exhibited remarkable enzymatic inhibition for all the analyses.     

Adsorption of urea on a polycrystalline silver electrode; comparison of electrochemical and radiometric methods

The adsorption of urea on a polycrystalline silver electrode was studied by radiometry and impedance spectroscopy. The differential capacity of the silver electrode in 0.01 M NaClO₄ solution containing urea in concentrations from 10^–6 to 5×10^–4 M has been determined. The isotherms of urea adsorption, found from the capacitance and radiometric measurements have been compared. The experimental data were described by the Langmuir isotherm, and the Gibbs energy of adsorption was calculated. The urea adsorption takes place in the entire range of the applied potential. The process is reversible with respect to the electrode potential and the bulk urea concentration.Dedicated to Professor Gyorgy Horanyi on the occasion of his 70th birthday     

Optimization of TLC Detection by Phosphomolybdic Acid Staining for Robust Quantification of Cholesterol and Bile Acids

JPC – Journal of Planar Chromatography – Modern TLC - In this paper we describe a robust and sensitive detection procedure for cholesterol and selected bile acids (cholic acid,...