Electronic absorption spectra of tetrahedral oxoanions: Ferrate(VI) ion

Summary The polarized electronic absorption spectrum of [FeO₄]^2– has been measured at liquid helium temperature using single crystals of K₂CrO₄ doped with the ferrate(VI) ion and a new band has been observed at 9112 cm^–1. An interpretation of the spectrum in the 9000-22000 cm^–1 range is given by considering the possible ligand field transition under the crystal site perturhation.     

Two 17‐hydroxy‐9(10→5)‐abeo‐estr‐4‐ene‐3,10‐diones

(5S,9S,17S)‐17‐Hydroxy‐9(10→5)‐abeo‐estr‐4‐ene‐3,10‐dione, C₁₈H₂₆O₃, (II), and (5R,9R,17S)‐17‐hydroxy‐9(10→5)‐abeo‐estr‐4‐ene‐3,10‐dione, C₁₈H₂₆O₃, (III), are equimolecular products of the Fe^II‐induced transposition of 10β‐hydro­peroxy‐17β‐hydroxyestr‐4‐en‐3‐one, (I). With respect to reagent mol­ecules, the configuration at C9 is retained for (II) while it is inverted in (III). The conformations of the five‐ and six‐membered rings are compared.     

Orlicz spaces with a o–O type structure

We study non reflexive Orlicz spaces \(L^\varPsi \) and their Morse subspace \(M^\varPsi \), i.e. the closure of \(L^\infty \) in \(M^\varPsi \) to determine when \((M^\varPsi ,L^\varPsi )\) can be described as having an o–O type structure with respect to an equivalent norm on \(L^\varPsi \). Examples of classes of Young functions for which the answer is affirmative are provided, but also examples are given to show that this is not possible for all non-reflexive Orlicz spaces. An equivalent expression of the distance in \(L^\varPsi \) to \(M^\varPsi \), induced by the new norm, is also provided.

     

Modification in the side chain of solomonsterol A: discovery of cholestan disulfate as a potent pregnane-X-receptor agonist

Seven synthetic analogues of the PXR (pregnane-X-receptor) potent natural agonist solomonsterol A were prepared by total synthesis. Their activity toward PXR was assessed by transactivation and RT-PCR assays. The study discloses cholestan disulfate (8) as a new, simplified agonist of PXR. By in vitro studies on hepatic cells we have demonstrated that this compound is a potent PXR agonist and functional characterization in human macrophages and hepatic stellate cells provided evidence that cholestan disulfate (8) has the ability to modulate the immune response triggered by bacterial endotoxin as well as to counter-activate hepatic stellate cell activation induced by thrombin. Because inhibition of immune-driven circuits might have relevance in the treatment of inflammation and liver fibrosis, the present data support the development of cholestan disulfate (8) in preclinical models of inflammatory diseases.     

Chaos in the square billiard with a modified reflection law

The purpose of this paper is to study the dynamics of a square billiard with a non-standard reflection law such that the angle of reflection of the particle is a linear contraction of the angle of incidence. We present numerical and analytical arguments that the nonwandering set of this billiard decomposes into three invariant sets, a parabolic attractor, a chaotic attractor, and a set consisting of several horseshoes. This scenario implies the positivity of the topological entropy of the billiard, a property that is in sharp contrast with the integrability of the square billiard with the standard reflection law.     

Efficient synthesis of N-methoxyindoles via alkylative cycloaddition of nitrosoarenes with alkynes

[reaction: see text] N-Methoxyindoles are produced in moderate to excellent yields from the reaction between nitrosoarenes and alkynes in the presence of K2CO3/(CH3)2SO4. Terminal alkynes with conjugating substituents afford 3-substituted N-methoxyindoles exclusively. The analogous reactions with methyl propiolate provide a one-step preparation of phytoalexin analogues from Wasabi.     

Surface‐initiated atom transfer radical polymerization grafting of poly(2,2,2‐trifluoroethyl methacrylate) from flat silicon wafer surfaces

Poly(2,2,2‐trifluoroethyl methacrylate) (PTFEMA), a partially fluorinated polymer, was directly grafted from silicon wafer surfaces by a surface‐initiated atom‐transfer radical polymerization (ATRP). The polymer layer thickness increased linearly with monomer conversion and molecular weight of free polymers in solution. The thickness was mainly determined by the experimental conditions such as activator/deactivator ratio, monomer/catalyst ratio, and monomer concentration. PTFEMA layers of more than 100‐nm thick were obtained. The grafted PTFEMA chains were “living” and allowed the extension of a second block of PMMA. X‐ray photoelectron spectroscopy study showed that the chemical compositions at the surfaces agreed well with their theoretical values. A novel surface‐attachable difunctional initiator was also synthesized and applied to the grafting of PTFEMA. The grafting density was doubled using this difunctional initiator, from 0.48 to 0.86 chains/nm². © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1252–1262, 2006