Raman spectroscopic study of the molecular structure of the uranyl mineral zippeite from Jáchymov (Joachimsthal), Czech Republic

Raman spectra at 298 and 77K and infrared spectra of the uranyl sulfate mineral zippeite from Jáchymov (Joachimsthal), Czech Republic, K(0.6)(H(3)O)0.4[(UO(2))6(SO(4))3(OH)7].8H2O, were studied. Observed bands were tentatively attributed to the (UO(2))2+ and (SO(4))2- stretching and bending vibrations, the OH stretching vibrations of water molecules, hydroxyls and oxonium ions, and H(2)O, oxonium, and delta U-OH bending vibrations. Empirical relations were used for the calculation of U-O bond lengths in uranyl R (A)=f(nu(3) or nu(1)(UO(2))2+). Calculated U-O bond lengths are in agreement with U-O bond lengths from the single crystal structure analysis and those inferred for uranyl anion sheet topology of uranyl pentagonal dipyramidal coordination polyhedra. The number of observed bands supports the conclusion from single crystal structure analysis that at least two symmetrically distinct U6+ (in uranyls) and S6+ (in sulfates), water molecules and hydroxyls may be present in the crystal structure of the zippeite studied. Strong to very weak hydrogen bonds present in the crystal structure of zippeite studied were inferred from the IR spectra.     

Microwave assisted fluorination: an improved method for side chain fluorination of substituted 1-arylethanones

A two-step, one-pot microwave (MW) assisted fluorination of 1-arylethanones to their corresponding 1-aryl-2-fluoroethanones has been developed. The first step utilises Selectfluor™ as a fluorinating agent in methanol forming 1-aryl-2-fluoroethanones and their corresponding dimethyl acetals. In the second step, water is added and Selectfluor™ acts as a Lewis acid in the hydrolytic cleavage of the dimethyl acetals. Compared to the thermal synthesis, the MW assisted method leads to a reduction in reaction time both in the fluorination and for the dimethyl acetal cleavage. Moreover, the one-pot procedure reduces reagent and solvent consumption. The method is best suited for the preparation of 1-aryl-2-fluoroethanones containing substituents that deactivates electrophilic aromatic substitution, however highly electron deficient ketones such as 1-(3,5-dinitrophenyl)ethanone reacts more slowly. Reactions using electron rich aromatic ketones had a low regioselectivity, and also produced fluoroaromatic products.     

Irregularity strength of digraphs

It is an elementary exercise to show that any non-trivial simple graph has two vertices with the same degree. This is not the case for digraphs and multigraphs. We consider generating irregular digraphs from arbitrary digraphs by adding multiple arcs. To this end, we define an irregular labeling of a digraph D to be an arc-labeling of the digraph such that the ordered pairs of the sums of the in-labels and out-labels at each vertex are all distinct. We define the strength of D to be the smallest of the maximum labels used across all irregular labelings. Similar definitions for graphs have been studied extensively and a different formulation of digraph irregularity was given in [H. Hackett, Irregularity strength of graphs and digraphs, Masters Thesis, University of Louisville, 1995]. Here we continue the study of irregular labelings of digraphs. We give a general lower bound on and determine exactly for tournaments, directed paths and cycles and the orientation of the path where all vertices have either in-degree 0 or out-degree 0. We also determine the irregularity strength of a union of directed cycles and a union of directed paths, the latter which requires a new result pertaining to finding circuits of given lengths containing prescribed vertices in the complete symmetric digraph with loops.     

Dynamic measurement of the electron velocity distribution in rarefied,weakly ionized argon

An experimental technique for the diagnosis of rarefied ionized gases has been developed. The source of the ionized gas is formed by the region behind the reflected shock in a shock tube from which it is expanded through a nozzle. This flow is sampled by an adjustable skimmer forming a molecular beam. The velocity of the electrons on the centerline of the beam is analyzed in a magnetic field and registered by an electron multiplier. By sweeping the intensity of the field during the test time the whole range of the velocity distribution is scanned. The geometric dimensions of nozzle and skimmer together with the characteristic of the analyzer allow to neglect the divergence of the flow in the evaluation of the distribution. Comparisons of evaluated electron temperatures show good agreement with a theoretically predicted temperature decay in an expansion flow.     

Separation of uranium from complex nuclear reaction product mixtures

A solvent extraction procedure for rapid separation of uranium from complex nuclear reaction product mixtures is suggested. The procedure has been tested in batch experiments with tracer amounts of representative elements. It has also been tested with fission products and uranium tracer using the continuous chemical separation system SISAK at the Mainz TRIGA reactor.     

Fungal extractives—VI : Structure of lactaral,a new sesquiterpene furan-3-aldehyde from Lactarius,by spectroscopic methods

The structure of a new sesquiterpene furan-3-aldehyde from Lactarius vellereus and L. pergamenus has been elucidated by means of IR, UV ¹H- and ¹³C-NMR spectroscopy and computer simulation of the ¹H-NMR spectrum.     

Influence of pH and Salt on the Photocrosslinking in Polyelectrolyte Thymine‐Containing Films

Photocrosslinking of thymine‐based water‐soluble polymer films was investigated at varying preparation conditions. Adding salt or decreasing the pH of the solution from which the films were cast resulted in the decreased efficiency of photoimmobilization, while increasing the pH was found to increase the photoimmobilization efficiency. A mechanistic rationale for the observed effects is proposed.     

On H‐immersions

For a fixed multigraph H, possibly containing loops, with V(H) = {h₁,…, h_k}, we say a graph G is H‐linked if for every choice of k vertices v₁,…,v_k in G, there exists a subdivision of H in G such that v_i represents h_i (for all i). An H‐immersion in G is similar except that the paths in G, playing the role of the edges of H, are only required to be edge disjoint. In this article, we extend the notion of an H‐linked graph by determining minimum degree conditions for a graph G to contain an H‐immersion with a bounded number of vertex repetitions on any choice of k vertices. In particular, we extend results found in [2,3,5]. © 2007 Wiley Periodicals, Inc. J Graph Theory 57: 245–254, 2008     

Congruent melting of binary compounds with non-negligible vapour pressure

The sulfaguanidine—water (SG-H₂O) system is a binary system with non-negligible vapour pressure which presents a monohydrate. The phase diagram of this system is drawn from DTA experimental results, using the temperature-specific volume-molar fraction (T-v-x) model which was described in part I of this work. The melting of the monohydrate (SG, H₂O) is found to be congruent. Isochoric sections are drawn; they make it possible to determine the limits of the two eutectic invariant planes. The composition and specific volume of the vapour phase at the eutectic equilibrium of theSG-SG, H₂O subsystem are given. The triple line solid-liquid-vapour of the one-component phase diagram of the monohydrate is drawn. The experimental results are consistent with the congruent melting of the monohydrate. These results also show that the solid, liquid and vapour phase at the triple line have not the same composition.