Contribution à la phytochimie du genre Gentiana,VI. Etude des xanthones dans les feuilles de Gentiana bavarica L.

Ten tetraoxygenated xanthones (1-hydroxy-3, 7, 8-trimethoxyxanthone I; 1, 7-dihydroxy-3, 8-dimethoxyxanthone II; 1, 7, 8-trihydroxy-3-methoxyxanthone III; 1, 3, 7, 8-tetrahydroxyxanthone IV; 3, 7, 8-trimethoxyxanthone-1-O-primeveroside V; 7-hydroxy-3, 8-dimethoxyxanthone-1-O-primeveroside VI; 1, 8-dihydroxy-3-methoxyxanthone-7-O-acetylrutinoside VII; 7, 8-dihydroxy-3-methoxyxanthone-1-O-primeveroside VIII; 3, 7, 8-trihydroxyxanthone-1-O-primeveroside IX; 3, 7, 8-trihydroxyxanthone-1-O-glucoside X) have been isolated from leaves of Gentiana bavarica L . by means of column chromatography on polyamid. Among these xanthones, VI, VII, VIII and IX were not encountered before in nature.     

Synthèse des pseudocyphellarines A et B,deux depsides du lichen Pseudocyphellaria endochrysea

Synthesis of Pseudocyphellarins A and B, Two Depsides from the Lichen Pseudocyphellaria endochrysea The total synthesis of the depsides pseudocyphellarin A (= 3-hydroxy-4-methoxycarbonyl-2,5,6-trimethyl-phenyl 3-formyl-2,4-dihydroxy-5,6-dimethylbenzoate; 11 ) and pseudocyphellarin B (3-hydroxy-4-methoxycarbonyl-2,5,6-trimethylphenyl 2,4-dihydroxy-3-hydroxymethyl-5,6-dimethyl benzoate; 12 ) is described.     

The Early Steps of Molecule-to-Material Conversion in Chemical Vapor Deposition (CVD): A Case Study

Transition metal complexes with β-diketonate and diamine ligands are valuable precursors for chemical vapor deposition (CVD) of metal oxide nanomaterials, but the metal-ligand bond dissociation mechanism on the growth surface is not yet clarified in detail. We address this question by density functional theory (DFT) and ab initio molecular dynamics (AIMD) in combination with the Blue Moon (BM) statistical sampling approach. AIMD simulations of the Zn β-diketonate-diamine complex Zn(hfa)₂TMEDA (hfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate; TMEDA = N,N,N′,N′-tetramethylethylenediamine), an amenable precursor for the CVD of ZnO nanosystems, show that rolling diffusion of this precursor at 500 K on a hydroxylated silica slab leads to an octahedral-to-square pyramidal rearrangement of its molecular geometry. The free energy profile of the octahedral-to-square pyramidal conversion indicates that the process barrier (5.8 kcal/mol) is of the order of magnitude of the thermal energy at the operating temperature. The formation of hydrogen bonds with surface hydroxyl groups plays a key role in aiding the dissociation of a Zn-O bond. In the square-pyramidal complex, the Zn center has a free coordination position, which might promote the interaction with incoming reagents on the deposition surface. These results provide a valuable atomistic insight on the molecule-to-material conversion process which, in perspective, might help to tailor by design the first nucleation stages of the target ZnO-based nanostructures.     

First-principles study of aqueous hydroxide solutions

Car-Parrinello molecular dynamics simulations have been carried out for aqueous NaOH and KOH solutions under ambient conditions over a wide range of concentrations. From these simulations, we have observed a continuous change of the water structure with added hydroxide, characterized by a significant shift of the second peak of the OO radial distribution functions to shorter distances. At the highest concentration investigated, the normal tetrahedral coordination of pure water is completely missing, a result that is consistent with a recent neutron diffraction experiment. The added hydroxide also gives rise to some unique spectroscopic features, including a "free" O-H stretch, a broadening of the normal water OH stretching band, and a large blue shift of both the librational band and the low-frequency translation. These results are in good agreement with the experimental data. Finally, it was demonstrated that the structural and dynamical behavior is inextricably linked to the formation of compact hydroxide-water complexes.     

Opening the Pandora's jar of molecule‐to‐material conversion in chemical vapor deposition: Insights from theory

First‐principles modeling can be a powerful tool for the understanding and optimization of bottom‐up processes for nanomaterials fabrication, such as chemical vapor deposition (CVD), a key technology for the development of advanced systems and devices. Molecule‐to‐material conversion by CVD involves complex chemical phenomena, which are often obscure and still largely unexplored. A proper modeling would require high level of accuracy, large sized models and should include both temperature effects and statistical sampling of reactive events. By presenting a few selected examples, this perspective surveys such problems and discusses currently available approaches for their solution. Possible strategies for future advances in the field are also highlighted. © 2013 Wiley Periodicals, Inc.     

A Novel Allenic Epoxycyclohexane and Related Compounds from Eutypa lata (Pers: F.) Tul

The novel allenic epoxycyclohexanes 1 , and related compounds 2 and 3 have been isolated from the culture medium of Eutypa lata. Their structures were established by combination of spectroscopic and chemical techniques. Biogenetic origin and biological activity of these compounds are also discussed.     

Isolement et identification de l'évernine dans la «mousse de chêne» (Evernia prunastri (L.) Ach.). 2e Communication

Isolation and identification of evernine in ‘Oakmosse’ (Evernia prunastri (L. ) Ach.). A new depside, evernin ( 1 ), has been found in the lichen Evernia Prunastri (L. ) Ach. The determination of the structure and the spectral parameters of 1 , especially the ¹³C-NMR. spectrum, are described.     

Isolement et identification de composés phénoliques et monoterpéniques de la mousse de chêne (Evernia prunastri (L.) Ach.)

The composition of different oakmoss extracts was investigated by combined gas chromatography/mass spectrometry. A series of 38 compounds – especially phenol derivatives and monoterpenes – was identified, 22 of which have not yet been reported as constituents of oakmoss.     

First principles studies on boron sites in zeolites

A systematic computational investigation on protonated and nonprotonated boron-containing zeolites (boralites), performed by using different periodic density functional theory approximations, is presented. Both minimum energy structures and finite temperature behavior of model boron sodalites were analyzed. All of the adopted computational schemes agree in predicting an acid site composed of a silanol Si-OH group loosely linked to a planar BO(3) structure in the protonated system and a BO(4) tetrahedral site in the sodium-containing zeolite. Calculated structural and vibrational properties are in line with experimental data. Comparisons of the protonated boralite site with Al and Ga zeolitic acid sites are discussed as well. Results indicate that this class of mild acid catalysts is characterized by significant framework flexibility and pronounced thermal effects due to the loosely bound acid site.