Optimization and validation of post-column assay for screening of radical scavengers in herbal raw materials and herbal preparations

On-line method, which combines HPLC distribution and post-column reaction, was designed for the search of individual antioxidants. Optimization of the assay was performed evaluating optimal ABTS(+) radical cation concentration in the reactor, reaction time, impact of flow rate, reaction coil length. HPLC-ABTS assay validation in this work was performed by assessing reference antioxidant negative peak areas in radical scavenging chromatogram. Sample free radical scavenging activity is expressed as trolox equivalent antioxidant capacity (TEAC). Optimized and validated method was applied in detection of compounds possessing free radical scavenging ability in complex mixtures. Antioxidant compounds were studied in perilla (Perilla frutescens (L.) Britton var. crispa f. viridis) herbal raw material and its preparations. The HPLC-separated antioxidant compounds were identified using HPLC-photodiode array coupled to mass spectrometer, using a reference mass for determining accurate masses. Radical scavenging characteristics of rosmarinic acid, which is the dominant phenolic compound in medicinal herbal raw material of perilla and its preparations, were confirmed by the calculated TEAC values. Compounds responsible for antioxidant effect in herbal raw materials and herbal preparations were identified, evaluated and compared.     

Numerical analysis of nonlinear model of excited carrier decay

This paper presents a mathematical model for photo-excited carrier decay in a semiconductor. Due to the carrier trapping states and recombination centers in the bandgap, the carrier decay process is defined by the system of nonlinear differential equations. The system of nonlinear ordinary differential equations is approximated by linearized backward Euler scheme. Some a priori estimates of the discrete solution are obtained and the convergence of the linearized backward Euler method is proved. The identifiability analysis of the parameters of deep centers is performed and the fitting of the model to experimental data is done by using the genetic optimization algorithm. Results of numerical experiments are presented.     

Additive splitting methods for elliptic-parabolic problems

Three finite-difference splitting schemes are proposed for numerical solution of the nonlinear 3D parabolic-elliptic problem. Adaptive front-tracking and time-stepping strategies are included into the algorithms. Parallelization of the algorithms is done using the domain decomposition method. The 1D decomposition of the computational domain is used in order to obtain the optimal computational load balancing among processors and to minimize the frequency of data communications. A redistribution of the computational domain among processors is done dynamically during computations.

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Sunto In questo lavoro vengono proposti tre diversi schemi di decomposizione alle differenze finite per la risoluzione numerica di problemi ellittico-parabolici non lineari in 3D. Negli algoritmi sono incluse strategie adattative front-tracking e time-stepping. La parallelizzazione degli algoritmi è realizzata usando il metodo della decomposizione di domini. Viene impiegata la decomposizione 1D del dominio computazionale per ottenere il bilanciameto ottimale del carico computazionale tra i processori e per minizzare la frequenza della comunicazione dei dati. Durante le computazioni, infine, viene realizzata dinamicamente la ridistribuzione dei domini computazionali.

     

Finite volume ADI scheme for hybrid dimension heat conduction problems set in a cross-shaped domain

Lithuanian Mathematical Journal - In this paper, we construct an alternating direction implicit (ADI) type finite volume numerical scheme to solve a nonclassical nonstationary heat conduction...     

A central limit theorem for a weighted power variation of a Gaussian process*

Let ρ be a real-valued function on [0, T], and let LSI(ρ) be a class of Gaussian processes over time interval [0, T], which need not have stationary increments but their incremental variance σ(s, t) is close to the values ρ(|t ? s|) as t → s uniformly in s ∈ (0, T]. For a Gaussian processesGfrom LSI(ρ), we consider a power variation V _n corresponding to a regular partition π _n of [0, T] and weighted by values of ρ(·). Under suitable hypotheses on G, we prove that a central limit theorem holds for V _n as the mesh of π _n approaches zero. The proof is based on a general central limit theorem for random variables that admit a Wiener chaos representation. The present result extends the central limit theorem for a power variation of a class of Gaussian processes with stationary increments and for bifractional and subfractional Gaussian processes.     

The measuring of radon volumetric activity and exhalation rate in ground-level air

The physical and chemical characteristics of radon gas make it a good tracer for use in the application of atmospheric transport models. Radon exhalation rate from soil is one of the most important factors for evaluation of the environmental radon level. For this purpose to find out the volumetric activity of radon in ground-level air the measuring has been made using radon monitor SARAD RTM 2200. Radon volumetric activity and radon exhalation rate in ground-level air and at different depths of soil depending on soil temperature and atmospheric parameters in different seasons of the year was calculated and evaluated in two areas of Vilnius city. It has been established that the volumetric activity of radon and radon exhalation intensity is vertically distributed and the corresponding increase in deeper soil layers, and depends on the specific activity of radium, soil temperature and moisture content, temperature difference between soil and atmospheric temperatures.     

Phytochemical and antioxidant profiles of leaves from different Sorbus L. species

Leaves of Sorbus L. have been used in various traditional medicine systems. Phenolic compounds determine the main pharmacological effects of Sorbus L. In this study, phytochemical and antioxidant profiles of Sorbus anglica, Sorbus aria, Sorbus arranensis, Sorbus aucuparia, Sorbus austriaca, Sorbus caucasica, Sorbus commixta, Sorbus discolor, Sorbus gracilis, Sorbus hostii, Sorbus semi-incisa and Sorbus tianschanica were determined. Twenty four constituents were identified in Sorbus L. species using ultra high performance liquid chromatography coupled to quadruple and time-of-flight mass spectrometers. Post-column FRAP assay identified compounds with reducing activity and revealed significantly greatest total antioxidant activity of 175.30 μmol TE/g DW, 169.20 μmol TE/g DW and 148.11 μmol TE/g DW in S. commixta, S. discolor and S. gracilis leaf samples, respectively, with neochlorogenic and chlorogenic acids being most significant contributors. Characteristic fingerprints of phytochemical and antioxidant profiles could be applied for the quality evaluation of various raw materials of Sorbus L. species.     

Mechanical Properties of Dense Zeolitic Imidazolate Frameworks (ZIFs): A High‐Pressure X‐ray Diffraction,Nanoindentation and Computational Study of the Zinc Framework Zn(Im)2, and its Lithium?Boron Analogue,LiB(Im)4

The dense, anhydrous zeolitic imidazolate frameworks (ZIFs), Zn(Im)₂ ( 1 ) and LiB(Im)₄ ( 2 ), adopt the same zni topology and differ only in terms of the inorganic species present in their structures. Their mechanical properties (specifically the Young’s and bulk moduli, along with the hardness) have been elucidated by using high pressure, synchrotron X‐ray diffraction, density functional calculations and nanoindentation studies. Under hydrostatic pressure, framework 2 undergoes a phase transition at 1.69 GPa, which is somewhat higher than the transition previously reported in 1 . The Young’s modulus (E) and hardness (H) of 1 (E≈8.5, H≈1 GPa) is substantially higher than that of 2 (E≈3, H≈0.1 GPa), whilst its bulk modulus is relatively lower (≈14 GPa cf. ≈16.6 GPa). The heavier, zinc‐containing material was also found to be significantly harder than its light analogue. The differential behaviour of the two materials is discussed in terms of the smaller pore volume of 2 and the greater flexibility of the LiN₄ tetrathedron compared with the ZnN₄ and BN₄ units.     

Flexibility and swing effect on the adsorption of energy-related gases on ZIF-8: combined experimental and simulation study

ZIF-8, a prototypical zeolitic porous coordination polymer, prepared via the self-assembly of tetrahedral atoms (e.g. Zn and Co) and organic imidazolate linkers, presents large cavities which are interconnected by narrow windows that allow, in principle, molecular sieving. However, ZIF-8 shows flexibility due to the swing of the imidazolate linkers, which results in the adsorption of molecules which are too large to fit through the narrow window. In this work, we assess the impact of this flexibility, previously only observed for nitrogen, and the level of agreement between the experimental and simulated isotherms of different energy-related gases on ZIF-8 (CO(2), CH(4) and alkanes). We combine experimental gas adsorption with GCMC simulations, using generic and adjusted force fields and DFT calculations with the Grimme dispersion correction. By solely adapting the UFF force field to reduce the Lennard-Jones parameter ε, we achieve excellent agreement between the simulated and experimental results not only for ZIF-8 but also for ZIF-20, where the transferability of the adapted force field is successfully tested. Regarding ZIF-8, we show that two different structural configurations are needed to properly describe the adsorption performance of this material, demonstrating that ZIF-8 is undergoing a structural change during gas adsorption. DFT calculations with the Grimme dispersion correction are consistent with the GCMC and experimental observations, illustrating the thermodynamics of the CH(4) adsorption sites and confirming the existence of a new adsorption site with a high binding energy within the 4-ring window of ZIF-8.     

Exceptionally low shear modulus in a prototypical imidazole-based metal-organic framework

Using Brillouin scattering, we measured the single-crystal elastic constants (C(ij)'s) of a prototypical metal-organic framework (MOF): zeolitic imidazolate framework (ZIF)-8 [Zn(2-methylimidazolate)(2)], which adopts a zeolitic sodalite topology and exhibits large porosity. Its C(ij)'s under ambient conditions are (in GPa) C(11)=9.522(7), C(12)=6.865(14), and C(44)=0.967(4). Tensorial analysis of the C(ij)'s reveals the complete picture of the anisotropic elasticity in cubic ZIF-8. We show that ZIF-8 has a remarkably low shear modulus G(min) < or approximately 1 GPa, which is the lowest yet reported for a single-crystalline extended solid. Using ab initio calculations, we demonstrate that ZIF-8's C(ij)'s can be reliably predicted, and its elastic deformation mechanism is linked to the pliant ZnN(4) tetrahedra. Our results shed new light on the role of elastic constants in establishing the structural stability of MOF materials and thus their suitability for practical applications.