Acid-Catalyzed Reactions of 2,3-Epoxy Derivatives of Citral with Alcohols

Acid-catalyzed reactions of 2,3-epoxy derivatives of citral (which is a widely spread naturally occurring unsaturated aldehyde) with alcohols were studied under conditions of heterogeneous catalysis and in fluorosulfonic acid. A number of new products were obtained, and possible mechanisms of their formation were proposed.     

Dynamic imaging of single DNA-protein interactions using atomic force microscopy

Atomic force microscopy (AFM) imaging of static DNA-protein complexes, in air and in liquid, can be used to directly obtain quantitative and qualitative information on the structure of different complexes. For example, DNA length, the location of preferential binding sites for proteins and bending of DNA as a result of the complexation can all be measured. Recording consecutive AFM images of DNA and protein molecules under conditions that they are still able to move and interact, or dynamic AFM imaging, however, can reveal information on the dynamic aspects of the interactions between these molecules. Here, an overview is given of the technical challenges that need to be considered for successful dynamic AFM imaging studies of individual DNA-protein interactions. Necessary technical improvements to the AFM set-up and the development of new sample preparation methods are described in this paper.     

A novel heterocyclic system — dihydro-2H-1,5,2,4-dioxadiazine. 2,4-Dimethyldihydro-2H-1,5,2,4-dioxadiazine hydrochloride: synthesis and NMR study

The first representative of a novel heterocyclic system, namely, 2,4-dimethyldihydro-2H-1,5,2,4-dioxadiazine hydrochloride, was synthesized.     

Investigation of the chemical heterogeneity of polyphenylenes using the condensation of methyl aryl ketones as a model reaction

The chemical heterogeneity of polyphenylenes obtained by trimerization poiycycio-condensation of acetylaromatic compounds has been investigated by GLC-MS analysis of the products of trimerization cyclocondensation of acetophenone. The mechanism for the formation of side products of the reaction is discussed. The presence of dypnone fragments in the polyphenylene structure results in a decrease in the thermal stability of these polymers.Deceased March, 1993.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1595–1601, September, 1993.     

Synthesis and structure of 5,5-dialkyl-3-arylamino-2-thiohydantoins

The reaction of arylhydrazides of -alkyl--chlorocarboxylic acids with thiocyanate ions gave intermediate thiocyanates which rearranged to isothiocyanates on heating and the latter cyclized to 5,5-dialkyl-3-arylamino-2-thiohydantoins.Institute of Technical Chemistry, Urals Branch, Russian Academy of Sciences, Perm' 614000. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 898–903, July, 1997.     

Serum Chloride Optical Sensors Based on Dynamic Quenching of the Fluorescence of Photo-Immobilized Lucigenin

This article describes the preparation and performance of an optical sensor for continuous measurement of chloride at extracellular (serum) levels (20–200mM). The sensor is based on dynamic quenching of the fluorescence of lucigenin which was photo-immobilized on a hydrogel. Quenching occurs via a collisional mechanism, and the decrease in fluorescence intensity on exposure to 100mM chloride typically is –60%. It allows the determination of chloride in the 1 to 200mM concentration range, with a precision of ±3mM at 120mM. Bromide, iodide and salicylate act as interferents, while the effect of pH and oxygen is negligibly small. The sensor displays strong fluorescence intensity, excellent reproducibility, long-term stability, response times in the order of 2–5min, and is used in a commercial serum and blood chloride analyzer.Received January 21, 2003; accepted April 6, 2003 Published online July 28, 2003     

The effect of polyamine homologation on the transport and cytotoxicity properties of polyamine-(DNA-intercalator) conjugates

An efficient five-step synthetic method was developed to access a homologous series of spermidine-acridine and spermidine-anthracene conjugates. The derivatives were comprised of a spermidine fragment covalently tethered at its N4 position to either an acridine or anthracene nucleus via an aliphatic chain (e.g., spermidine-[aliphatic tether]-acridine). The distance separating the spermidine and aromatic nucleus was altered by using different tethers comprised of four or five methylene units, respectively. These ligands (2-5) were shown to inhibit human DNA topoisomerase-II (TOPO-II) activity at 10 microM. Enzymatic activity was assessed as the ability to unknot (decatenate) and cleave kinetoplast DNA (kDNA). Polyamine conjugation did not disrupt the ability of the acridine-spermidine conjugates 2 and 3 to inhibit TOPO-II activity as compared with the 9-aminoacridine and 9-(N-butyl)aminoacridine controls (at 10 microM). In general, the acridine derivatives (2 and 3) showed higher TOPO-II inhibitory activity than their anthracene counterparts (4 and 5). However, this trend was reversed in a whole cell assay with L1210 (murine leukemia) cells, wherein the anthracene analogues were more potent than their acridine counterparts. In this regard the qualitative enzyme-based assay did not predict the trends in the corresponding IC(50) values. Within either series insertion of an additional methylene unit did not significantly alter activity. While the appended spermidine unit did not disrupt TOPO II inhibition by the tethered DNA intercalator, it did provide an alternative mode of entry into the cell as demonstrated by spermidine protection assays. These results were compared with a spermine-intercalator analogue. Of all the conjugates tested the N(4)-(4-(9-aminoacridinyl)butyl)spermine hexahydrochloride (conjugate 16)resulted in the highest degree of L1210 cell rescue upon cotreatment of the cells with exogenous spermidine. It was concluded that the monoalkylated spermine motif present in 16 holds promise as a better vector than its N4 monoalkylated spermidine counterpart.     

Simulating Unstable States during the Coumarin Adsorption on a Mercury Electrode

Dependences of differential capacitance C on potential E of a stationary electrode (hanging mercury drop) in aqueous 0.1 M NaF solutions containing 4.6 × 10^–4 to 3 × 10^–3 M C₉H₆O₂ are obtained using an automatic impedancemeter. At coumarin concentrations below 0.001 M and potential slowly scanned near –1.1 V (SCE) the capacitance is unstable, which results in differently-shaped C vs. E curves in this potential range. The obtained results are attributed to nonequilibrium phase transitions in the adsorption layer, during which the orientation of coumarin molecules at the electrode surface alters. These phenomena are explained semiquantitatively on the basis of a developed theory.     

Problems of Quantitative Spectroscopic Measurements in Heterogeneous Catalysis: Molar Absorption Coefficients of Vibrations in Adsorbed Substances

Published data on the molar absorption coefficients and integral intensities A ₀ of vibrations in physically and chemically adsorbed molecules are reviewed. Analysis of published data shows that bonds characterized by high values of the dipole momentum derivative with respect to the normal coordinate change during adsorption toward decreasing this derivative, whereas bonds characterized by a low value of the derivative change toward increasing the derivative. Thus, adsorption results in a decrease in the difference in values of the dipole momentum derivative with respect to the normal coordinate of different bonds compared with the same bonds in the individual molecules. In addition, the interval of changing the molar absorption coefficients for the surface complexes are at least two orders of magnitude lower than that for the same bonds in the molecules in the gas phase. A series for the degree of easiness in detecting complexes on the catalyst surface (the series of decreasing the molar absorption coefficient) is proposed.     

Synthesis and transformations of metallacycles. 23. Cp2TiCl2-Catalyzed cyclometallation of fullerene C60 with EtAlCl2

1-Ethyl-2,3-fullerenoaluminacyclopropanes (EtAl)_n(²-C₆₀) were synthesized by the reaction of fullerene C₆₀ with an excess of EtAlCl₂ in the presence of Mg and using Cp₂TiCl₂ as the catalyst in a THF--toluene solution at 20 °C. Deuterolysis of fullerenoaluminacyclopropanes afforded a mixture of deuteriofullerenes C₆₀D_m, where m = 6--12.