A 13-membered crown ether with an azoxy subunit in the macrocycle: Synthesis and X-ray structure

The presented azoxy compound is an example of a new crown ether analogue. It has been synthesized by the reduction of an open chain dinitro compound with stannite under strongly alkaline conditions. A method for the separation of the azo and azoxy compounds formed simultaneously has been proposed. The structures of two crystallographically independent molecules of compound2 have been determined. In spite of the small size of the macroring in compound2, the phenyl residues around the azoxy group have atrans orientation. Supplementary Data relating to this article have been deposited with the British Library as Supplementary Publication No. 82157 (11 pages).     

Aggregation behavior of p-n-alkylbenzamidinium chloride surfactants

The aggregation behavior of a novel class of surfactants, p-n-alkylbenzamidinium chlorides, has been investigated. The thermodynamics of aggregation of p-n-decylbenzamidinium chloride mixed with cationic and anionic cosurfactants has been studied using isothermal titration calorimetry. For mixtures of p-n-decylbenzamidinium chloride with n-alkyltrimethylammonium chlorides, the aggregation process is enthalpically more favorable than for the pure n-alkyltrimethylammonium chlorides, probably caused by diminished headgroup repulsion due to charge delocalization in the amidinium headgroup. A critical aggregation concentration between 3 and 4 mM has been extrapolated for p-n-decylbenzamidinium chloride at 40 degrees C, around two times lower than that of similar surfactants without charge delocalization in the headgroup and well comparable to that of similar surfactants with charge delocalization in the headgroup. In mixtures of p-n-decylbenzamidinium chloride with either sodium n-alkylsulfates or sodium dodecylbenzenesulfonate, evidence is found for the formation of bilayer aggregates by the pseudo-double-tailed catanionic surfactants composed of p-n-decylbenzamidinium and the anionic surfactant. These aggregates are solubilized to mixed micelles by excess free anionic surfactant at the measured critical aggregation concentration.     

Studies on the Distribution of Phenoxyacetic Acid in Two-Phase Systems: <Emphasis Type="Italic">n</Emphasis>-Aliphatic Hydrocarbon – Water

Summary. Phenoxyacetic acid distribution in two-phase systems n-aliphatic hydrocarbon (C₅–C₈) – water and its dimerization in organic phase were investigated. The values of distribution coefficient (D _HR), distribution constant (K _D), and dimerization constant (K _dim) of acid were obtained. The empirical correlations of these quantities with Hildebrand solubility parameter of organic solvents were established. The influence of pH of the aqueous phase as well as the polarity of the applied organic solvents on phenoxyacetic acid physical chemistry in the two-phase systems was described.     

Mapping of possible prion protein self-interaction domains using peptide arrays

Background  

The common event in transmissible spongiform encephalopathies (TSEs) or prion diseases is the conversion of host-encoded protease sensitive cellular prion protein (PrP^C) into strain dependent isoforms of scrapie associated protease resistant isoform (PrP^Sc) of prion protein (PrP). These processes are determined by similarities as well as strain dependent variations in the PrP structure. Selective self-interaction between PrP molecules is the most probable basis for initiation of these processes, potentially influenced by chaperone molecules, however the mechanisms behind these processes are far from understood. We previously determined that polymorphisms do not affect initial PrP^C to PrP^Sc binding but rather modulate a subsequent step in the conversion process. Determining possible sites of self-interaction could elucidate which amino acid(s) or amino acid sequences contribute to binding and further conversion into other isoforms. To this end, ovine – and bovine PrP peptide-arrays consisting of 15-mer overlapping peptides were probed with recombinant sheep PrP^C fused to maltose binding protein (MBP-PrP).     

Simultaneous propane dehydrogenation andco2hydrogenation overCrOx/SiO2catalyst

Summary Single reverse water-gas shift (RWGS) and dehydrogenation of propane with CO₂(DH-CO₂) reactions in the presence and absence of the CrO_x/SiO₂ catalyst have been studied between 673 and 873 K. It was found that the CrO_x/SiO₂ catalyst is active both in the dehydrogenation of propane and in the RWGS reactions. The obtained results suggest that the dehydrogenation of propane to propene in the presence of CO₂on CrO_x/SiO₂can be facilitated by the RWGS reaction.</o:p>     

4,5‐Di­hydro‐3‐methyl‐5‐(4‐methyl­phenyl)‐1H‐pyrazole‐1‐carboxamidinium acetate acetone hemisolvate

The X‐ray structure analysis of the unexpected product of the reaction between 4‐(4‐methyl­phenyl)­but‐3‐en‐2‐one and amino­guanidine revealed the title compound, C₁₂H₁₇N₄⁺·C₂H₃O₂^?·0.5C₃H₆O, consisting of a protonated amidine moiety joined to a substituted pyrazoline ring at the N1 atom. The amidine group is protonated and the positive charge is delocalized over the three C—N bonds in a similar manner to that found in guanidinium salts. The amidinium moiety of the cation is linked to the acetate anions through four N—H?O hydrogen bonds, with N?O distances of 2.749 (4), 2.848 (4), 2.904 (4) and 2.911 (4) Å. The pyrazoline ring adopts a flattened envelope conformation and the substituted phenyl ring is oriented perpendicular to the attached heterocycle. The acetone solvate molecule lies across a twofold rotation axis.     

Isoperichoric focusing field-flow fractionation and thin layer isoperichoric focusing based on coupling of gradient generated by primary field with secondary field action: general principles and performances

The primary field forces can generate spatially oriented gradient of the effective property of a continuum or pseudo-continuum fluid (carrier liquid). When this gradient is coupled with the action of a secondary field of identical or different nature the isoperichoric focused zones of the dispersed species can appear. Consequently, they can be separated according to differences responding to the property gradient of the carrier liquid. This concept can be applied under static (non-flow) conditions in thin layer focusing as well as under dynamic conditions with the elution due to the carrier liquid flow in focusing field-flow fractionation. The gradient established by the action of the primary field and the concentration distribution of the isoperichoric focused zone formed by the coupled effect of the gradient and of the primary or secondary field are described theoretically. The rigorous relationship describing the shape of the focused zone is compared with the approximate solutions. The performances of the proposed principle were evaluated by model calculations. Potential experimental configurations considering the implementation of the static and dynamic conditions are discussed. The generalized isoperichoric focusing theory can be applied to describe the particular processes operating in analytical and preparative focusing separations of the particles of various, but especially of biological origin.     

REDUCED PHOTOINACTIVATION OF 10-DODECYL ACRIDINE ORANGE-SENSITIZED YEAST CELLS AT HIGH FLUENCE RATES MEASUREMENTS AND COMPUTER SIMULATIONS

Abstract-During the development of a photodamage cell sorter several photosensitizers were tested for their ability to photoinactivate more than 90% of the sensitized cells after a brief irradiation with a fluence of 10 kJ/m². In pilot experiments, yeast cells sensitized with 10-dodecyl acridine orange (DAO) were effectively photoinactivated after receiving a fluence of 10 kJ/m² delivered in 8 s. However, when the same fluence was delivered in 3 μ s during passage through a focused laser beam in the cell sorter, all cells survived.
Computer simulations of the relevant photophysical and chemical reactions inside the irradiated cell were used to investigate the cause of this phenomenon. The results indicated that the absence of photoinactivation by DAO, after flash irradiations, was caused by the combined effects of (1) limited oxygen diffusion into the cell and (2) a reduced number of collisions between photosensitizer triplet and oxygen molecules during the irradiation due to saturation of the intracellular photosensitizer triplet concentration. The contributions of triplet-triplet annihilation and triplet quenching by ground state photosensitizer molecules were found to be minimal and not significant. These findings indicate that Type II photosensitizers are incapable of rapid selective photoinactivation in cell sorters.     

All-trans-1-acyloxy-1,3-pentadiene-5 ols as reactive dienes in new intramolecular diels-alder reactions

The high reactivity of the $\text{all-trans}$-1-acyloxy-1,3-pentadiene-5-ols as dienes in intramolecular Diels-Alder reactions with maleic anhydride and fumaric acid ethylester monochloride is discussed.     

1‐Methyl‐1H‐imidazo[4,5‐f]quinolin‐6‐ium chloride monohydrate

The title compound, C₁₁H₁₀N₃⁺·Cl^?·H₂O, belongs to the N1‐methyl‐substituted imidazo­[4,5‐f]­quinoline family, in which the heterocyclic ring is protonated at the pyridine rather than at the imidazole N atom. The mol­ecule as a whole is almost exactly planar. The molecular structure has been compared with that of the 2‐amino analogue described in the literature, and it was found that the extra amino group of the latter is involved in conjugation with the adjacent double bond, i.e. the conjugation does not extend over the entire heterocyclic system. The cation of the title compound forms a strong hydrogen bond with the Cl^? anion and the anions are interconnected by the water solvent mol­ecule.