Synthesis of two naphthoquinone antibiotics, dehydroherbarin and 6-deoxybostrycoidin

The synthesis of two naphthoquinone antibiotics, dehydroherbarin (7) and 6-deoxybostrycoidin (5), was accomplished by reaction of 3-acetonyl-2-bromomethyl-6,8-dimethoxy-1,4-naphthoquinone (23) with either triethylamine or ammonia, respectively. This is the first report on their synthesis.     

Enhanced aromaticity of the transition structures for the diels-alder reactions of quinodimethanes: evidence from ab initio and DFT computations

The Diels-Alder reactions of various quinodimethanes with ethylene are studied by means of ab initio molecular orbital and density functional theory (DFT) to show the effect of aromaticity on the reaction path. The calculations reveal that these reactions are both kinetically and thermodynamically much more favored than the prototype butadiene-ethylene Diels-Alder reaction due to the aromatization process in the transition state (TS) and product. A progressive aromaticity gain is noticed during the reaction, and hence the partial pi-delocalized peripheral diene ring function is coupled with the six-electron sigma,pi-delocalized cyclic unit resulting in an enhanced aromaticity of the TS. The magnetic criteria such as magnetic susceptibility exaltation and nucleus independent chemical shift provide definitive evidence for and fully support the aromatization process and the aromaticity of the TS. The extent of sigma-pi delocalization and the bond make-break at the TS are consistent with each other, and this is strongly influenced by the adjacent pi-aromatization process. Moreover, the aromaticity trends in the resulting TSs and products parallel the activation and reaction energies; the extent of aromatization increases with increasing reaction rate and exothermicity. This confirms that aromaticity is the driving factor governing cycloadditions involving quinodimethanes.     

Bayesian analysis of blood glucose time series from diabetes home monitoring

This paper describes the application of a novel Bayesian estimation technique to extract the structural components, i.e., trend and daily patterns, from blood glucose level time series coming from home monitoring of insulin dependent diabetes mellitus patients. The problem is formulated through a set of stochastic equations, and is solved in a Bayesian framework by using a Markov chain Monte Carlo technique. The potential of the method is illustrated by analyzing data coming from the home monitoring of a 14-year old male patient.     

Synthesis of biaryls via intermolecular radical addition of heteroaryl and aryl bromides onto arenes

Tris(trimethylsilyl)silane (TTMSS) and azobisisobutironitrile (AIBN) promoted the easy intermolecular arylation of aryl and heteroaryl bromides under thermal conditions via a radical pathway.     

Synthesis of an orange anthrathiophene pigment isolated from a Japanese bryozoan

A short, regiospecific synthesis of the naturally occurring anthrathiophene 1 from naphthazarin (7) is described.     

The Tausk Controversy on the Foundations of Quantum Mechanics: Physics, Philosophy, and Politics

In 1966 the Brazilian physicist Klaus Tausk (b. 1927) circulated a preprint from the International Centre for Theoretical Physics in Trieste, Italy, criticizing Adriana Daneri,Angelo Loinger,and Giovanni Maria Prosperi’s theory of 1962 on the measurement problem in quantum mechanics. A heated controversy ensued between two opposing camps within the orthodox interpretation of quantum theory, represented by Léon Rosenfeld and Eugene P.Wigner. The controversy went well beyond the strictly scientific issues, however, reflecting philosophical and political commitments within the context of the Cold War, the relationship between science in developed and Third World countries, the importance of social skills, and personal idiosyncrasies.     

Isolation from pig liver microsomes, identification by electrospray tandem mass spectrometry and in vitro immunosuppressive activity of a rapamycin tris-epoxide metabolite

It was demonstrated that rapamycin is metabolized in vitro by pig liver microsomes under the influence of the cytochrome P450-dependent mixed function oxygenase system to a rapamycin tris-epoxide metabolite, as demonstrated by electrospray tandem mass spectrometry. The in vitro immunosuppressive activity of this metabolite was found to be lower than that of rapamycin, probably because the rapamycin effector sector was structurally modified. The effector region of rapamycin was recognized to include the conjugated double bonds of this compound and metabolic reactions affecting this region may change the binding affinity of the rapamycin-FKBP binary complex towards another pharmacological receptor bound to the binary complex. Moreover, metabolic modifications in the effector region are probably able to induce a change in the binding affinities of the rapamycin-FKBP binary complex, including the pipecolic acid moiety and the lactone function of the parent drug.     

Lawlike Reversibility, Factlike Irreversibility. The Symmetry of Time in Physics

Mehlberg's and Lewis' phrases in the title aptlyrender Boltzmann's and Gibbs' views. Statisticalcorrelation of physical events expresses theirinteration or propagated causality. Information, as(retarded) cognizance or as (advanced) organization, istied a la Reichenbach with Aristole's efficient or finalcauses. Correspondence between the classical and thequantal transition formulas is discussed, and CPT invariance of nonseparabilityemphasized.