Electronically excited states of membrane fluorescent probe 4-dimethylaminochalcone. Results of quantum chemical calculations

Quantum-chemical calculations of ground and excited states for membrane fluorescent probe 4-dimethylaminochalcone (DMAC) in vacuum were performed. Optimized geometries and dipole moments for lowest-lying singlet and triplet states were obtained. The nature of these electronic transitions and the relaxation path in the excited states were determined; changes in geometry and charge distribution were assessed. It was shown that in vacuum the lowest existed level is of (n, π*) nature, and the closest to it is the level of (π, π*) nature; the energy gap between them is narrow. This led to an effective (1)(π, π*) →(1)(n, π*) relaxation. After photoexcitation the molecule undergoes significant transformations, including changes in bond orders, pyramidalization angle of the dimethylamino group, and planarity of the molecule. Its dipole moment rises from 5.5 Debye in the ground state to 17.1 Debye in the (1)(π, π*) state, and then falls to 2 Debye in the (1)(n, π*) state. The excited (1)(n, π*) state is a short living state; it has a high probability of intersystem crossing into the (3)(π, π*) triplet state. This relaxation path explains the low quantum yield of DMAC fluorescence in non-polar media. It is possible that (3)(π, π*) is responsible for observed DMAC phosphorescence.     

Cholinesterase sensors based on screen-printed electrodes for detection of organophosphorus and carbamic pesticides

Cholinesterase sensors based on screen-printed electrodes modified with polyaniline, 7,7,8,8-tetracyanoquinodimethane (TCNQ), and Prussian blue have been developed and tested for detection of anticholinesterase pesticides in aqueous solution and in spiked grape juice. The influence of enzyme source and detection mode on biosensor performance was explored. It was shown that modification of the electrodes results in significant improvement of their analytical characteristics for pesticide determination. Thus, the slopes of the calibration curves obtained with modified electrodes were increased twofold and the detection limits of the pesticides were reduced by factors of 1.6 to 1.8 in comparison with the use of unmodified transducers. The biosensors developed make it possible to detect down to 2×10^–8 mol L^–1 chloropyrifos-methyl, 5×10^–8 mol L^–1 coumaphos, and 8×10^–9 mol L^–1 carbofuran in aqueous solution and grape juice. The optimal conditions for grape juice pretreatment were determined to diminish interference from the sample matrix.Abbreviations ChE Cholinesterase - TCNQ 7,7,8,8-Tetracyanoquinodimethane - ChO Choline oxidase - AChE Acetylcholinesterase - BChE Butyrylcholinesterase - BSA Bovine serum albumin - 2-PAM 2-Pyridine aldoxime methiodide     

Certain Probabilistic Aspects of Semistable Laws

We study the extent to which the property of semistability of a random vector in ^d is determined by semistability of its marginals, and the place of semistable laws within the family of type G and sub-stable laws. Similarities and differences between stable and semistable laws are discussed.     

An Asymptotic Model of Seismic Reflection from a Permeable Layer

Analysis of compression wave propagation in a poroelastic medium predicts a peak of reflection from a high-permeability layer in the low-frequency end of the spectrum. An explicit formula expresses the resonant frequency through the elastic moduli of the solid skeleton, the permeability of the reservoir rock, the fluid viscosity and compressibility, and the reservoir thickness. This result is obtained through a low-frequency asymptotic analysis of Biot’s model of poroelasticity. A review of the derivation of the main equations from the Hooke’s law, momentum and mass balance equations, and Darcy’s law suggests an alternative new physical interpretation of some coefficients of the classical poroelasticity. The velocity of wave propagation, the attenuation factor, and the wave number are expressed in the form of power series with respect to a small dimensionless parameter. The absolute value of this parameter is equal to the product of the kinematic reservoir fluid mobility and the wave frequency. Retaining only the leading terms of the series leads to explicit and relatively simple expressions for the reflection and transmission coefficients for a planar wave crossing an interface between two permeable media, as well as wave reflection from a thin highly permeable layer (a lens). Practical applications of the obtained asymptotic formulae are seismic modeling, inversion, and attribute analysis.     

Synthesis and some transformations of new 9-furylnaphtho[2,3-b]furan derivatives

The synthesis of a number of naphtho[2,3-b]furan derivatives, containing a furyl substituent in position 9 by intramolecular cyclization of 2-carboxy and 2-formylbis(5-alkylfur-2-yl)methanes is described. The reactivity of the title compounds in formylation, acetylation, nitration, and oxidation reactions has been investigated. It was shown that nitration of 2-methyl-9-(5-methyl-2-furyl)naphtho[2,3-b]furan-4-yl acetate leads to oxidative furan ring opening rather than to electrophilic substitution.     

Morphometric model of lymphocyte as applied to scanning flow cytometry

The peripheral blood lymphocytes of normal individuals are investigated by methods of specialized light microscopy. Lymphocytes as a whole and T-cell subpopulation are considered. Lymphocyte structure is characterized with reference to polarizing scanning flow cytometry. The lymphocyte and lymphocyte nucleus shapes are analyzed. Linear correlation dependence between sizes of lymphocyte and its nucleus is indicated. A morphometric model of a lymphocyte is constructed using the obtained data. The findings can be used, for instance, as input parameters to solve the direct and inverse light-scattering problems of turbidimetry, nephelometry, and flow cytometry.     

Carathéodory bounds for integer cones

We provide analogues of Carathéodory's theorem for integer cones and apply our bounds to integer programming and to the cutting stock problem. In particular, we provide an NP certificate for the latter, whose existence has not been known so far.     

Aptasensor for Thrombin Based on Carbon Nanotubes‐Methylene Blue Composites

The amperometric and EQCM aptasensors based on DNA aptamers immobilized by avidin‐biotin method or by electrostatic adsorption onto multiwalled carbon nanotube layer contained methylene blue (MB) have been developed and examined for thrombin detection in buffer and in spiked blood serum. The presence of MB increases the binding capacity of the surface layer and enhances the range of thrombin concentrations to be determined. This results in significant improvement of analytical characteristics of thrombin detection. The EQCM aptasensors allowed us to detect 0.3–100 nM and amperometric aptasensors 10–1000 nM of thrombin.