Rubrenolide, total synthesis and revision of its reported stereochemical structure

In this paper the synthesis of the natural product rubrenolide is presented. Due to an error in the original proposed stereochemical structure of rubrenolide, the synthesis was not straightforward. Application of the photo-induced rearrangement of an appropriate epoxy diazomethyl ketone gave access to the precursor lactone with an ee of 91%. Coupling of this lactone with (4S)-2,2-dimethyl-[1,3]-dioxolane-4-carbaldehyde gave, after some additional steps, the final product that was identical with an authentic sample of the natural product.     

Excited States and Charge Separation in Membranes of the Green Sulfur Bacterium Prosthecochloris aestuarii

Time-resolved absorbance changes were measured in isolated membranes, depleted of chlorosomes, and in the Fenna-Matthews-Olson (FMO) complex of the green sulfur bacterium Prosthecochloris aestuarri. The isolated FMO complex showed a biphasic decay of excited bacteriochlorophyll a (BChl a) with time constants of about 80 and 1400 ps. Approximately the same time constants were observed upon excitation of isolated membranes together with a component of about 30 ps. It is concluded that the efficiency of energy transfer from the FMO to the core complex is very low, in agreement with earlier measurements of the efficiency of charge separation. The 30 ps decay component is ascribed to trapping of the excitation energy from the core BChl a by the reaction center.     

Fractionation of ethylene/1‐pentene copolymers using a combination of SEC‐FTIR and SEC‐HPer DSC

The short chain branching distribution (SCBD) and thermal properties of ethylene/1‐pentene copolymers were studied using SEC‐FTIR and SEC‐HPer DSC. The copolymers, synthesized with Cp₂ZrCl₂/MAO, were fractionated using size exclusion chromatography (SEC). The infrared analysis of the fractions showed that the copolymers had—on average—higher 1‐pentene concentration in the low molecular weight range. Furthermore, the thermal properties of the SEC deposits of these copolymers on a Germanium disc were studied using high performance differential scanning calorimetry (HPer DSC). Single SEC separations were used to accumulate fractions in the microgram range that were directly analyzed with regard to their thermal properties, thus allowing us to study SCBD as well as thermal behavior simultaneously. When these fractions (with masses ranging from 10–80 μg) were analyzed using HPer DSC, good melting and crystallization temperature distributions were obtained, proving that HPer DSC can be used as a complementary method to SEC‐FTIR. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2956–2965, 2007     

Cobalt(II) Complexes of Nitrile‐Functionalized Ionic Liquids

A series of nitrile‐functionalized ionic liquids were found to exhibit temperature‐dependent miscibility (thermomorphism) with the lower alcohols. Their coordinating abilities toward cobalt(II) ions were investigated through the dissolution process of cobalt(II) bis(trifluoromethylsulfonyl)imide and were found to depend on the donor abilities of the nitrile group. The crystal structures of the cobalt(II) solvates [Co(C₁C_1CNPyr)₂(Tf₂N)₄] and [Co(C₁C_2CNPyr)₆][Tf₂N]₈, which were isolated from ionic‐liquid solutions, gave an insight into the coordination chemistry of functionalized ionic liquids. Smooth layers of cobalt metal could be obtained by electrodeposition of the cobalt‐containing ionic liquids.     

Transverse mode coupling in an optical resonator

Small-angle scattering due to mirror surface roughness is shown to couple the optical modes and deform the transmission spectra in a frequency-degenerate optical cavity. A simple model based on a random scattering matrix clearly visualizes the mixing and avoided crossings between multiple transverse modes. These effects are visible only in the frequency-domain spectra; cavity ringdown experiments are unaffected by changes in the spatial coherence, as they probe just the intracavity photon lifetime.     

Molecular simulations of the adsorption of cycloalkanes in MFI-type silica

A new force field for the simulation of the adsorption of cycloalkanes in nanoporous silica affords a significant improvement over any previously employed force field. The simulated isotherms reproduce the most salient features in the experimental isotherms extremely well. The study of cyclo-pentane, -hexane, and -heptane adsorption in MFI-type silica indicates an inflection for cyclopentane but not for cyclohexane at intermediate pressure. If corroborated by experiments, such an inflection point would afford an excellent calibration point for further force field developments. At low pressures, mixture isotherms of cyclohexane and n-hexane show a temperature dependence on the selectivity in accordance with recent results by J. P. Fox and S. P. Bates, J. Phys. Chem., 2004, 108, 17136. This dependence is caused by a difference in temperature dependence of the Henry coefficient for both molecules. At high pressures entropy effects due to packing always favor the sorption of n-hexane. Furthermore, the influence of the flexibility of the zeolite framework on the adsorption of these rather bulky molecules is investigated. It is found that this influence of the flexibility on the adsorption of cyclohexane is as small as with n-alkanes.     

Resonant cars spectroscopy of s-tetrazine vapour

CARS experiments on s-tetrazine vapour show that the electronic resonance enhancement in the Q-branch is most effective for the lower J values. This suggests that the radiationless relaxation rate in the excited state increases with rotational quantum number. Delayed picosecond CARS experiments indicate that the rotation-vibration coupling for the 1008 cm^?1 ground-state vibrational mode is approximately 2 MHz.