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The formation of highly organized structures based on two ligands with pyridyl functionalities, 4,4'-bipyridine (BPY) and 1,4-di(4,4''-pyridyl) benzene (BPYB), and Cu adatoms on the Cu(111) surface has been studied with low temperature and variable temperature scanning tunneling microscopy (STM) and first-principles calculations. We show that the formation of a highly organized adlayer built from adatom-molecule and molecule-molecule units strongly depends on the number of mobile Cu atoms on the surface. While a high concentration of Cu adatoms (high adatom/BPY ratio, ≥1) leads systematically to the formation of organometallic nanolines, their absence (low adatom/BPY ratio, ≈0) gives a compact self-assembled molecular network, and more specifically hydrogen-bond networks (HBN) with BPY molecules organized in a T-shaped fashion. Alternatively, an intermediate concentration of Cu adatoms (0 < adatom/BPY < 1) allows the formation of a well-organized and compact structure where both organometallic and HBN components coexist. Although STM images cannot clearly reveal the presence of Cu adatoms within the organometallic moiety, the bonding of BPY to a single or two Cu adatoms can be clearly identified by scanning tunneling spectroscopy (STS), and is supported by Density Functional Theory (DFT) results. Additional STM simulations suggest that the relative position of the Cu adatom with respect to the organic ligands just above has a significant impact on its detection by STM. This study exemplifies the prominent role of metallic adatoms on the formation of a complex organometallic network and should open more rational practices to optimize the formation of these supramolecular networks.

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Two new spirostanol saponins ( 1 and 2) were isolated from the roots of Smilax medica, together with the known smilagenin 3-O-beta-D-glucopyranoside (3). Their structures were determined by spectroscopic methods including 1D- and 2D-NMR experiments. Compounds 1 and 2 exhibited antifungal activity against the human pathogenic yeasts Candida albicans, C. glabrata and C. tropicalis (MICs between 6.25 and 50 microg/mL) whereas 3 was inactive.

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From the rhizomes of Dioscorea cayenensis Lam.-Holl (Dioscoreaceae), the new 26- O- beta- D-glucopyranosyl-22-methoxy-3 beta,26-dihydroxy-25( R)-furost-5-en-3- O- alpha- L-rhamnopyranosyl-(1-->4)- alpha- L-rhamnopyranosyl-(1-->4)-[ alpha- L-rhamnopyranosyl-(1-->2)]- beta- D-glucopyranoside ( 1) was isolated together with the known dioscin ( 2) and diosgenin 3- O- alpha- L-rhamnopyranosyl-(1-->4)- alpha- L-rhamnopyranosyl-(1-->4)-[ alpha- L-rhamnopyranosyl-(1-->2)]- beta- D-glucopyranoside ( 3). Their structures were established on the basis of spectral data. Compound 2 exhibited antifungal activity against the human pathogenic yeasts Candida albicans, C. glabrata and C. tropicalis (MICs of 12.5, 12.5 and 25 micro g/mL, respectively) whereas 3 showed weak activity and 1 was inactive.

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The aim of this review is to update current knowledge on the betulinic, ursolic and echinocystic acids and their natural and semisynthetic analogs, focussing on their cytotoxic and anti-HIV activities. Then, the last results of the authors' team on unusual semisynthetic derivatives of these triterpenoids will be presented in order to establish structure/activity relationships.

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A pore network is used as a model of a porous medium with hierarchical and single level organization of the pores. A microscopic diffusion or adsorption process is introduced that permits the study of both temporal evolution and effective properties of transport. The relationships between the model parameters and the measurable quantities are derived. The transport in media with a hierarchical organization of pores is shown to be qualitatively different from that in media lacking this organization. The question of experimental distinction between the two types of pore organization is also studied. We show that mercury intrusion porosimetry (MIP) measurements furnish valuable information about the pore organization in a sample, but that the exact deconvolution of the real pore size distribution from the experimental data is not straightforward. Our work provides indications for a correct interpretation of MIP results. Qualitative comparison with experiments show the pertinence of hierarchical models.

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Modern soil and litter samples from southeastern Cameroon, collected along a continuous forest-savanna transect were analysed for pollen content to define modern pollen-vegetation relationships. The pollen results, completed and compared with botanical inventories, leaf area index and basal area measurements performed in the same area, clearly registered the physiognomy, the main floristic composition and floral richness of the two sampled ecosystems. Distortions were observed between sampled vegetations and their pollen rain, related to important differences in pollen production and dispersal of plant species: this is a general feature in many tropical regions. The pollen data in the area studied reflected well the recent transgression of forest versus savanna. This permitted us to define inside the forest ecosystem more successional vegetation communities than the botanical surveys allowed.