(TMTSF)2(2,5-Tcnqbr2): Structure and Physical Properties

The 2:1 charge-transfer salt (TMTSF)₂(2,5-TCNQBr2) has been prepared and its physical properties investigated. Its crystal structure consists of segregated stacks of TMTSF donors (ring-over-bond overlap pattern; mean interplanar spacing of 3.6A) and chains of edge-on and disordered 2,5-TCNQBr2 acceptors. Infrared data are suggestive of unit charge on the 2,5-TCNQBr2 molecule and, therefore, half charge on the TMTSF donor. Resistivity data are successfully interpreted on the basis of a percolation construction. Magnetic data are also presented.     

Betti numbers of Stanley–Reisner rings determine hierarchical Markov degrees

There are two seemingly unrelated ideals associated with a simplicial complex Δ: one is the Stanley–Reisner ideal I _Δ , the monomial ideal generated by minimal non-faces of Δ, well-known in combinatorial commutative algebra; the other is the toric ideal I _M(Δ) of the facet subring of Δ, whose generators give a Markov basis for the hierarchical model defined by Δ, playing a prominent role in algebraic statistics. In this note we show that the complexity of the generators of I _M(Δ) is determined by the Betti numbers of I _Δ . The unexpected connection between the syzygies of the Stanley–Reisner ideal and degrees of minimal generators of the toric ideal provide a framework for further exploration of the connection between the model and its many relatives in algebra and combinatorics.     

Palladium-catalyzed allylic cross-coupling reactions of primary and secondary homoallylic electrophiles

The Pd(0)-catalyzed allylic cross-coupling of homoallylic tosylate substrates using boronic acids and pinacol esters is reported. The reaction uses 2-(4,5-dihydro-2-oxazolyl)quinoline (quinox) as a ligand and is performed at ambient temperature. The scope of the reaction is broad in terms of both the boronate transmetalating reagent and the substrate and includes secondary tosylates. Mechanistic studies support an alkene-mediated S(N)2-type stereoinvertive oxidative addition of unactivated primary and secondary alkyl tosylates.     

Parametric ranked set sampling

Ranked set sampling was introduced by McIntyre (1952,Australian Journal of Agricultural Research,3, 385–390) as a cost-effective method of selecting data if observations are much more cheaply ranked than measured. He proposed its use for estimating the population mean when the distribution of the data was unknown. In this paper, we examine the advantage, if any, that this method of sampling has if the distribution is known, for a specific family of distributions. Specifically, we consider estimation of and for the family of random variables with cdf's of the formF(x–/). We find that the ranked set sample does provide more information about both and than a random sample of the same number of observations. We examine both maximum likelihood and best linear unbiased estimation of and , as well as methods for modifying the ranked set sampling procedure to provide even better estimation.This paper has been prepared with partial support from the United States Environmental Protection Agency under Cooperative Agreement Number CR821801-01-0. The contents have not been subjected to Agency review and therefore do not necessarily reflect the views or policies of the Agency and no official endorsement should be inferred.     

THE PHOTOTOXICITY OF PHENYLHEPTATRIYNE: OXYGEN-DEPENDENT HEMOLYSIS OF HUMAN ERYTHROCYTES AND INACTIVATION OF Escherichia coli

Abstract— Phenylheptatriyne (PHT) plus near-ultraviolet light(320–400 nm; NUV) hemolyzed human erythrocytes in an oxygen dependent manner. When the phototoxicity of PHT plus NUV was tested with a series of Escherichia coli strains carrying all four possible combinations of genes controlling excision proficiency ( uvrA6 vs uvrA ⁺) and catalase activity (HPII, katF vs katF *), the membrane was found to be an important lethal target. Consistent with this observation. PHT plus NUV did not induce histidine independent ( his-4 ⁺) mutations in the four tester strains (RT7h-RT10h). Using tester strain RT10h, it was shown that there was no inactivation by PHT plus NUV in nitrogen. Results of experiments with an E. coli fatty acid auxotroph (K1060) treated with PHT plus NUV are also consistent with membrane proteins being the chief targets for attack. Radicals were formed during the photolysis of PHT plus NUV in aqueous solutions, both in the presence of air and under nitrogen. Since PHT plus NUV did not hemolyze erythrocytes or inactivate E. coli cells under nitrogen, these radicals are not cytotoxic.     

High-performance liquid chromatographic monitoring of metabolic products resulting from the treatment of mouse hepatoma cells with N6-cycloalkylated nucleosides.

High-performance liquid chromatography was used to analyze cell lysates and growth medium of mouse hepatoma cells, separately treated with N6-cyclopropyl-, N6-cyclobutyl-, and N6-cyclopentyladenosines, in an effort to gain insight into the mechanism by which these modified nucleosides exert their cytotoxic effect(s). The corresponding 5'-monophosphate of the respective modified nucleoside was detected in the separate cell lysate samples. Both the modified nucleoside and its corresponding 5'-monophosphate were detected in the separate growth medium samples and their relative concentrations therein were determined. These results indicate that the cytotoxicity of these N6-cycloalkylated nucleosides may be attributed to their 5'-monophosphates within the cells.     

Solvation equilibria in very concentrated electrolyte solutions

A stepwise hydration-equilibrium model for aqueous electrolytes is developed and shown to give a good quantitative account of osmotic coefficients of strong, highly soluble electrolytes up to concentrations of 20–30 m. The main parameters needed are two equilibrium constants describing the stepwise hydration and the number of hydration sites. Choice of ion-size parameter has only a minor effect.This paper was presented at the symposium, The Physical Chemistry of Aqueous Systems, held at the University of Pittsburgh, Pittsburgh, Pennsylvania, June 12–14, 1972, in honor of the 70th birthday of Professor H. S. Frank.Contribution from the Diffusion Research Unit, Research School of Physical Sciences, Australian National University, Canberra, A.C.T., Australia and the University of New England, Armidale, N. S. W., Australia.     

Enthalpies of dilution of urea solutions in six polar solvents at several temperatures

Using the isothermal displacement calorimeter, enthalpies of dilution are obtained for solutions of urea in water, methanol, ethanol, formamide, N,N-dimethyl-formamide, and dimethyl sulfoxide. The results are discussed in terms of solute-solvent and solute-solute interactions.Now Diane Beaumont.