Synthesis of 1,3‐Bis(tetracyano‐2‐azulenyl‐3‐butadienyl)azulenes by the [2+2] Cycloaddition–Retroelectrocyclization of 1,3‐Bis(azulenylethynyl)azulenes with Tetracyanoethylene

1,3‐Bis(azulenylethynyl)azulene derivatives 9–14 have been prepared by palladium‐catalyzed alkynylation of 1‐ethynylazulene 8 with 1,3‐diiodoazulene 1 or 1,3‐diethynylazulene 2 with the corresponding haloazulenes 3–7 under Sonogashira–Hagihara conditions. Bis(alkynes) 9–14 reacted with tetracyanoethylene (TCNE) in a formal [2+2] cycloaddition–retroelectrocyclization reaction to afford the corresponding new bis(tetracyanobutadiene)s (bis(TCBDs)) 15–20 in excellent yields. The redox behavior of bis(TCBD)s 15–20 was examined by using CV and differential pulse voltammetry (DPV), which revealed their reversible multistage reduction properties under the electrochemical conditions. Moreover, a significant color change of alkynes 9–14 and TCBDs 15–20 was observed by visible spectroscopy under the electrochemical reduction conditions.     

Coverage-dependent sticking probability and desorption kinetics of water molecules on Rh(111)

The adsorption and desorption kinetics of water molecules on Rh(111) were investigated using temperature programed desorption (TPD). Water molecules on Rh(111) show coverage-dependent sticking probability; the initial sticking probability is estimated to be 0.46. In the desorption process, a dilute gaslike phase and two-dimensional islands of water coexist on the surface. Based on the model proposed by Kreuzer and Payne [Surf. Sci.200, L433 (1988)], the apparent fractional-order TPD spectra can be interpreted as first-order desorption from the coexistence of two phases on which the sticking probabilities are different. Based on this, the previous estimation of pre-exponential factors assuming half-order desorption [A. Beniya et al., J. Chem. Phys.125, 054717 (2006)] should be revised.     

Geometrical isomerization of fac/mer-Mo(CO)3(phosphite)3 and cis/trans-Mo(CO)4(phosphite)2 catalyzed by Me3SiOSO2CF3

Geometrical isomerization of fac-Mo(CO)₃L₃ (L = P(OPh)₃, P(OMe)₃, P(OEt)₃) to the mer form and that of cis-Mo(CO)₄L₂ (L = P(OPh)₃, P(OMe)₃, PPh₂(OMe)) to the trans form were observed in CH₂Cl₂ at room temperature in the presence of a catalytic amount of Me₃SiOSO₂CF₃ (TMSOTf). Crossover experiments suggest that a ligand dissociation is not involved in the isomerization. A catalytic cycle involving an interaction of the silicon atom in Me₃Si⁺ with one oxygen in P(OR)₃ ligands has been proposed. The first isolation and the X-ray structure analysis were attained for mer-Mo(CO)₃{P(OPh)₃}₃ through the TSMOTf-assisted isomerization of fac-Mo(CO)₃{P(OPh)₃}₃.     

Kinetic and geometric isotope effects originating from different adsorption potential energy surfaces: cyclohexane on Rh(111)

Novel isotope effects were observed in desorption kinetics and adsorption geometry of cyclohexane on Rh(111) by the use of infrared reflection absorption spectroscopy, temperature programmed desorption, photoelectron spectroscopy, and spot-profile-analysis low energy electron diffraction. The desorption energy of deuterated cyclohexane (C(6)D(12)) is lower than that of C(6)H(12). In addition, the work function change by adsorbed C(6)D(12) is smaller than that by adsorbed C(6)H(12). These results indicate that C(6)D(12) has a shallower adsorption potential than C(6)H(12) (vertical geometric isotope effect). The lateral geometric isotope effect was also observed in the two-dimensional cyclohexane superstructures as a result of the different repulsive interaction between interfacial dipoles. The observed isotope effects should be ascribed to the quantum nature of hydrogen involved in the C-H···metal interaction.     

Docosahexaenoic acid and eicosapentaenoic acid induce changes in the physical properties of a lipid bilayer model membrane

We investigated the effect of fatty acids such as stearic acid (SA, 18:0), oleic acid (OA, 18:1), eicosapentaenoic acid (EPA, 20:5), and docosahexaenoic acid (DHA, 22:6) on a dipalmitoylphosphatidylcholine (DPPC) bilayer by determining the phase transition temperature, fluorescence anisotropy of 1,6-diphenyl-1,3,5-hexatriene (DPH), and detergent insolubility. Treatment with unsaturated fatty acid broadened and shifted the phase transitions of the DPPC bilayer to a lower temperature. The phase transition temperature and the value of fluorescence anisotropy of DPH at 37 degrees C decreased progressively with increasing treatment amounts of unsaturated fatty acid. A large amount of the DPPC bilayer treated with unsaturated fatty acid was dissolved in Triton X-100, obtaining a low level of detergent insolubility. These modifications of the bilayer physical properties were most pronounced with DHA and EPA treatment. These data show that unsaturated fatty acids, particularly DHA and EPA, induce a marked change in the lipid bilayer structure. The composition of fatty acids in the DPPC bilayer was similar after treatment with various unsaturated fatty acids, suggesting that the different actions of unsaturated fatty acids are attributed to change in the molecular structure (e.g., kinked conformation by double bonds). We further explored the change in physical properties induced by fatty acids dispersed in a water-in-oil-in-water multiple emulsion and found that unsaturated fatty acids acted efficiently on the DPPC bilayer, even when incorporated in emulsion form.     

Fast enantiomeric analysis of a complex essential oil with an innovative multidimensional gas chromatographic system

The present research is focussed on the evaluation of a recently developed high performance multidimensional gas chromatographic (MDGC) system employed in the fast analysis of a series of chiral compounds contained in rosemary essential oil. The heart of the MDGC system consists in a simple transfer device for the rapid sequential re-injection of analyte "heart-cuts" from the first to the second dimension. The transfer system has no temperature restrictions, presents very low dead volumes and achieves multidimensional analysis through a pressure-balance mechanism. The MDGC set-up is characterized by two GC ovens (enabling independent temperature programming) and the possibility of mass spectrometric (MS) and/or flame ionization detection (FID). Multiple-cut conventional and fast MDGC-FID methods were developed and the results obtained compared, in order to evaluate the effectiveness of the system. In this respect, the rapid method provided the same analytical result in a greatly reduced time (approximately five times less). Furthermore, quali/quantitative data reproducibilty was very good. Fast MDGC was achieved by using micro-bore (0.1mm I.D.) columns in both dimensions.