Square‐wave Voltammetry of Two‐step Surface Electrode Mechanisms Coupled with Chemical Reactions – A Theoretical Overview

Square‐wave voltammetry (SWV) of so‐called “surface redox reactions” is seen as a simple and efficient tool to quantify large number of drugs, physiologically active substances and other important chemicals. It also provides elegant methods to get access to relevant kinetic and thermodynamic parameters related to many lipophilic compounds. Moreover, with this technique we can study activity of various enzymes by exploring the “protein‐film voltammetry” set up. In this work, we focus on theoretical SWV features of four complex surface electrode mechanisms, in which the electron exchange between the working electrode and the studied redox substrate takes place in two successive steps. While we present large number of calculated square‐wave voltammograms, we give hints to recognize particular two‐step surface mechanism, but also to distinguish it from other similar mechanisms. We present plenty of relevant aspects of surface two‐step surface EE, two‐step surface ECE and surface catalytic EEC’ mechanisms. Moreover, we present for the first time a series of theoretical results related to two‐step surface EECrev mechanism (i. e. two‐step surface reaction coupled to follow‐up reversible chemical step). The simulated voltammetric patterns presented in this work can bring relevant aspects to resolve some experimental situations met in voltammetry of many redox enzymes and other important substances whose electrochemical transformation occurs in two‐steps.     

Control of optical properties of biotissues: I. spectral properties of the eye sclera

A method for computer modeling of transmission and diffuse reflection of a strongly scattering biotissue is described. Results of calculations of spectral characteristics for a model of the human eye sclera are presented and compared with experiments. The possibility to control optical properties of biotissues is theoretically substantiated and experimentally confirmed. Variations in color indices of biotissues are calculated using theoretical and experimental spectral characteristics obtained for the eye sclera.     

Controlling optical properties of biological tissues: II. Coherent optical methods for studying the tissue structure

Correlation and polarization properties of dynamic speckle fields formed upon scanning in vitro human sclera samples subjected to immersion agents with a focused laser beam were studied. The immersion agent diffusion into the tissue reduces the relative refractive index of structure-forming elements (collagen fibrils) with respect to the base sclera substance and thus stimulates the passage from multiple to single scattering of a probing beam. Experimental data are presented on the evolution of the autocorrelation function of intensity fluctuations and the intensity ratio between polarized and depolarized components of laser radiation passed through a sclera layer due to artificial clarification of the tissue samples analyzed. Possible applications of the developed method to the tissue structure diagnostics are discussed.     

Urea (Polyurea) Greases

The review deals with greases in which organic ureas of various compositions and structures are used as thickeners. The nature of compounds participating in the synthesis of organic ureas and the main types of polyurea thickeners are considered. The physicochemical, tribological, and operation properties of plastic polyurea lubricants are discussed.     

Synthesis of Novel Lipophilic Polyamines via Ugi Reaction and Evaluation of Their Anticancer Activity

Natural polyamines (PAs) are involved in the processes of proliferation and differentiation of cancer cells. Lipophilic synthetic polyamines (LPAs) induce the cell death of various cancer cell lines. In the current paper, we have demonstrated a new method for synthesis of LPAs via the multicomponent Ugi reaction and subsequent reduction of amide groups by PhSiH₃. The anticancer activity of the obtained compounds was evaluated in the A-549, MCF7, and HCT116 cancer cell lines. For the first time, it was shown that the anticancer activity of LPAs with piperazine fragments is comparable with that of aliphatic LPAs. The presence of a diglyceride fragment in the structure of LPAs appears to be a key factor for the manifestation of high anticancer activity. The findings of the study strongly support further research in the field of LPAs and their derivatives.     

Electron paramagnetic resonance and optical spectroscopy of K3Na(CrO4)2 ferroelastics activated by MnO 4 2− molecular impurity ions

Crystals of a proper ferroelastic K₃Na(CrO₄)₂ containing molecular impurity ions MnO ₄ ^2? are studied using electron paramagnetic resonance (EPR) and optical spectroscopy. The EPR spectrum of the Mn⁶⁺ ion contained in the molecular impurity ion MnO ₄ ^2? is identified at low temperatures (T ≤ 20 K). The intensity of this spectrum decreases unusually fast as the temperature increases. A broad IR luminescence band with a vibronic structure well resolved at a temperature of 8 K is revealed. Theoretical treatment of the Mn⁶⁺ ion involved in the molecular impurity ions MnO ₄ ^2? of the K₃Na(CrO₄)₂ ferroelastic crystal suggests that an important role in this case is played by the pseudo-Jahn-Teller. The pseudo-Jahn-Teller effect offers an explanation for the appearance of a fine structure in the vibronic replicas in the luminescence spectrum, on the one hand, and accounts for the fast decrease in the intensity of the EPR spectrum of K₃Na(CrO₄)₂: MnO ₄ ^2? with increasing temperature, on the other.