Novel Antitumor L‐Arabinose Derivative of Indolocarbazole with High Affinity to DNA

Novel indolocarbazole derivative 12‐(α‐L ‐arabinopyranosyl)indolo[2,3‐α]pyrrolo[3,4‐c]carbazole‐5,7‐dione (AIC) demonstrated high potency (at submicromolar concentrations) against the NCI panel of human tumor cell lines and transplanted tumors in vivo. In search of tentative targets for AIC, we found that the drug formed high affinity intercalative complexes with d(AT)₂₀, d(GC)₂₀ and calf thymus DNA (binding constants (1.6×10⁶) M ^?1≤K_a≤(3.3×10⁶) M ^?1). The drug intercalated preferentially into GC pairs of the duplex. Importantly, the concentrations at which AIC formed the intercalative complexes with DNA (C≤1 μM ) were identical to the concentrations that triggered p53‐dependent gene reporter transactivation, the replication block, the inhibition of topoisomerase I‐mediated DNA relaxation and death of HCT116 human colon carcinoma cells. We conclude that the formation of high affinity intercalative complexes with DNA is an important factor for anticancer efficacy of AIC.     

Computer Modeling of Probable Decomposition Reactions: Cyclonitramines

An approach to computer synthesis and retrosynthesis of organic compounds was formulated, and the CASB (Computer-Assisted Structure Building) software for its computer implementation was created. The approach was evaluated by the example of computer generation of probable routes for reactions of homolytic decomposition. Elementary steps of homolysis reactions were modeled with the use of the “retrosynthetic” method. Each elementary reaction describes fragments that should be present in the structure and structural modifications that should be carried out to obtain reaction products. Target fragments are described in terms of production rules by specifying types of atoms, their formal charges and radical states, numbers of adjacent heteroatoms, hybridizations, etc. All possible intermediates of molecular homolysis reactions are generated by the program in a single step and then used in further search for probable pathways of decomposition during subsequent steps until the given maximum number of steps is achieved. Screening of advantageous pathways for these reactions was based on a set of empirical rules. The results obtained by the suggested approach and the corresponding program were illustrated by the example of some cyclic nitramines (RDX and HMX) and demonstrated good agreement with the experiment.     

Diffusion welding of aluminium alloy strengthened by Al2O3 particles through an Al/Cu multilayer foil

In the diffusion welding (DW) of difficult-to-deform materials (such as composites and intermetallics), the application of intermediate multilayer foils (MF), which have alternating layers of elements that form intermetallics, allows for production of a permanent joint under milder conditions. In this paper, the processes occurring in the joint zone (JZ) during DW of Al–5 wt.%Mg+27 wt.%Al₂O₃ composite material through the Al/Cu interlayer were studied. It was shown that, while heating of such a foil, phase transformations that are due to the reaction diffusion of elements, run in it. At MF heating under a continuously applied external load, the materials are plastically deformed. It is established that the intensity of foil plastic deformation at a specified load non-monotonically depends on temperature. It is shown that welding temperature is determined by the temperature at which MF can undergo superplastic flow under the impact of applied pressure. A mechanism of formation for a solid-phase joint of high-strength materials through interlayers based on the MF of intermetallic-forming elements is proposed.     

Development of vibration damping materials based on butyl rubber: A study of the phase equilibrium,rheological, and dynamic properties of compositions

A detailed study of butyl rubber-based vibration damping formulations linking their composition, morphology, phase structure, viscosity, mechanical loss factor, and other characteristics is presented for the first time. High performance of the compositions including aromatic petroleum oil is explained by limited solubility of the plasticizer that leads to the formation of a highly-viscous emulsion (η_20°C ≈ 1000 Pa·s) consisting of a swollen butyl rubber matrix and dispersed oil droplets in the broad composition range. Chalk is found to be the best inorganic filler as its spherical particles provide strong adhesion to the reinforcing layer of aluminum foil. Aiming to eliminate ecologically unfriendly aromatic compounds, a new low-cost binding agent formulation based on butyl rubber mixed with polyisobutylene and highly refined mineral oil is suggested. Being environmentally safe, it possesses high viscosity of 1000–3000 Pa·s, cohesion strength of 3.5–5.0 N/cm, penetration of 4.5–6.0 mm, and mechanical loss factor up to 0.34 at room temperature, which are as good as, or even better than, the properties of currently produced vibration damping materials containing aromatic compounds. New materials can be used in car and aircraft parts for effective vibration isolation.     

The influence of poly(3,4-ethylenedioxythiophene) modification on the transport properties and fuel cell performance of Nafion-117 membranes

Nafion-117/PEDOT composite membranes were synthesized by in situ chemical polymerization of 3,4-ethylenedioxythiophene (EDOT) using ammonium persulfate as an oxidant. The polymerization of EDOT in Nafion membranes for various EDOT/oxidant treatment sequences was studied for the first time. PEDOT introduction leads to a slight decrease in both the ion-exchange capacity and water uptake of the composite membranes, as well as to an increase in cationic transport. Membranes initially treated with an oxidant exhibit better conductivity and lower hydrogen permeability. The effect of both modification of Nafion-117 membranes by PEDOT and hot-pressing of hydrogen-oxygen membrane-electrode assemblies (MEAs) on the performance of proton-exchange membrane fuel cells was studied. The maximum power density of the fabricated MEAs increases 1.5-fold: from 510 (for a pristine Nafion-117 membrane) to 810 mW cm⁻² (for a membrane modified by PEDOT). The current density at a voltage of 0.4 V reaches 1248 and 2246 mA cm⁻², respectively.     

Role of Chiral Configuration in the Photoinduced Interaction of D- and L-Tryptophan with Optical Isomers of Ketoprofen in Linked Systems

The study of the L- and D-amino acid properties in proteins and peptides has attracted considerable attention in recent years, as the replacement of even one L-amino acid by its D-analogue due to aging of the body is resulted in a number of pathological conditions, including Alzheimer’s and Parkinson’s diseases. A recent trend is using short model systems to study the peculiarities of proteins with D-amino acids. In this report, the comparison of the excited states quenching of L- and D-tryptophan (Trp) in a model donor–acceptor dyad with (R)- and (S)-ketoprofen (KP-Trp) was carried out by photochemically induced dynamic nuclear polarization (CIDNP) and fluorescence spectroscopy. Quenching of the Trp excited states, which occurs via two mechanisms: prevailing resonance energy transfer (RET) and electron transfer (ET), indeed demonstrates some peculiarities for all three studied configurations of the dyad: (R,S)-, (S,R)-, and (S,S)-. Thus, the ET efficiency is identical for (S,R)- and (R,S)-enantiomers, while RET differs by 1.6 times. For (S,S)-, the CIDNP coefficient is almost an order of magnitude greater than for (R,S)- and (S,R)-. To understand the source of this difference, hyperpolarization of (S,S)-and (R,S)- has been calculated using theory involving the electron dipole–dipole interaction in the secular equation.     

The Formation of Mn-Ce Oxide Catalysts for CO Oxidation by Oxalate Route: The Role of Annealing Conditions

Catalysis Letters - A series of Mn-Ce oxide catalysts with Mn:Ce?=?1 was synthesized by oxalate route under different annealing conditions. The physicochemical properties were...     

Surface Structure,Spectroscopic and Photocatalytic Activity Study of Polyaniline/TiO2 Nanocomposites

PANI （polyaniline） as a promising conducting polymer and photosensitizer has been used to prepare PANI/TiO2 （polyaniline/TiO2） nanocomposite as photocatalyst. TiO2 nanoparticles with size of 5-100 nm were encapsulated by PANI via the ＂in situ＂ polymerization of aniline on the surface of TiO2 nanoparticles. IR, SEM, EPR techniques were used to characterize the mechanism of electron interaction in PANI/TiO2 nanocomposite. The resulting PANI-modified TiO2 composites exhibit significantly higher photocatalytic activity than that of neat PANI on degradation of MB （methylen blue） aqueous solution under UV irradiation.     

Search for New Three-, Four-Component Petasis,Passerini, Hantzsch,Kabachnic-Fields,Ugi Reactions with Organic Compounds of Phosphorus,Arsenic, Antimony and Bismuth

It is discovered a new three-, four-component Petasis, Passerini, Hantzsch, Kabachnic-Fields, Ugi reactions with of arsine, stibine and bismuthine in organometallic chemistry. Modifications were replaced to a nitrogen atom of classical reactions of atoms of phosphorus, arsenic, antimony and bismuth. It has been proposed a new mechanism for possible reactions.     

The antioxidant activity of Californian red wines does not correlate with wine age

A range of physico‐chemical properties of 21 Californian red wines from 1 to 28 years old were correlated with wine age. The level of monomeric phenolics and low molecular‐weight phenolic oligomers decreased with age, while the level of high molecular‐weight phenolics increased. On the other hand, total phenols given by the Folin–Ciocalteau method, antioxidant capacity determined using a controlled chain reaction of methyl linoleate and the intensity of the anodic peak determined by cyclic voltammetry (CV) did not show any significant correlation with wine age. Total phenols and the shapes of CV traces were more dependent on the grape variety and the particular viticultural and wine‐making practices rather than on wine age. At the same time, young and aged wines showed a pronounced difference in the shape of [O₂] traces recorded during the oxidation of methyl linoleate in a micellar solution inhibited by wine addition. Possible reasons why the antioxidant activity of red wines does not correlate with wine age are discussed. Copyright © 2006 Society of Chemical Industry