Über das «pK» elektronisch angeregter Azulenium-Kationen

It is shown that azulenium cations in the first electronically excited state S₁ are stronger acids than in the ground state S₀. Their apparent pK″*, obtained from the H₀-dependence of the quenching of the azulenium cation S₁ → S₀ fluorescence does not correspond to a true acid-base equilibrium in the electronically excited state S₁. The pK″* values are kinetically controlled, the rate of reprotonation of azulene in the S₁ state being too low to compete with the internal conversion to S₀.     

Die Zusammensetzung der Neutrallipide aus normalen Hirnen alter Menschen

The chemical composition of lipids from six human brains (60–73 years) is reported. The total lipids out of cortex, white matter, diencephalon and cerebellum, pons, and medulla oblongata have been isolated and the neutral lipids have been separated in cerebrosides, sphingomyelines, and lecithins. The highest amount of pure lipids is found in the white matter, the lowest in the cortex. The relation of neutral lipids to acid lipids as well as the amount of cholesterol are about equal for all regions. The white matter shows more cerebrosides and sphingomyelines than the cortex, the opposite being the case for lecithins. The differences are strongly significant. The fatty acids out of the different pure lipid fractions have been analysed as esters by gas chromatography. Stearic and lignoceric acid, and cerebronic and hydroxy nervonic acid respectively are main components of cerebrosides, with only little differences for the different brain regions. The fatty acids of sphingomyelines consist mainly of stearic and nervonic acid; in the white matter these two acids are present about in the same quantity, whereas stearic acid dominates in the cortex and the other sections. Lecithins contain above all palmitic and oleic acid. The amount of the latter in the white matter is higher than that of palmitic acid.     

State-specific rotational energy transfer in OH (A 2Σ+, v′=0) by some combustion-relevant collision partners

State-to-state rotational energy transfer (RET) co-efficients were determined for inelastic collisions of OH (A ²⁺, v=0) with N₂, CO₂, and H₂O at 300 K. The experimental procedure described previously allows the direct evaluation of state-specific RET coefficients from time-resolved laser-induced fluorescence (LIF) measurements without any assumptions on the RET. The results show strikingly different RET behaviour for the three collision partners. The data can serve as a basis for a comparison with dynamic collision models.A. Jörg is now with IBM Corporation, Frankfurt, Fed. Rep. Germany     

Pharmacomodulation of a ligand targeting the HBV capsid hydrophobic pocket

Hepatitis B virus (HBV) is a small enveloped retrotranscribing DNA virus and an important human pathogen. Its capsid-forming core protein (Cp) features a hydrophobic pocket proposed to be central notably in capsid envelopment. Indeed, mutations in and around this pocket can profoundly modulate, and even abolish, secretion of enveloped virions. We have recently shown that Triton X-100, a detergent used during Cp purification, binds to the hydrophobic pocket with micromolar affinity. We here performed pharmacomodulation of pocket binders through systematic modifications of the three distinct chemical moieties composing the Triton X-100 molecule. Using NMR and ITC, we found that the flat aromatic moiety is essential for binding, while the number of atoms of the aliphatic chain modulates binding affinity. The hydrophilic tail, in contrast, is highly tolerant to changes in both length and type. Our data provide essential information for designing a new class of HBV antivirals targeting capsid–envelope interactions.

Small-molecule binding to the Hepatitis B virus core protein hydrophobic pocket, a possible strategy for targeting viral particle assembly.     

Magnetic proximity effect in EuO-Cs interface

In the surface of the ferromagnetic insulator EuO is covered with a small amount of cesium, the photoelectric magnetization curves P(H) show magnetic saturation in contrast to those of the pure surface. The proximity of the Cs film causes the paramagnetism of the clean EuO surface to disappear.