Labdane Diterpenoids from Salvia tingitana Etl. Synergize with Clindamycin against Methicillin-Resistant Staphylococcus aureus

Quorum-sensing (QS) is a regulatory mechanism in bacterial communication, important for pathogenesis control. The search for small molecules active as quorum-sensing inhibitors (QSI) that can synergize with antibiotics is considered a good strategy to counteract the problem of antibiotic resistance. Here the antimicrobial labdane diterpenoids sclareol (1) and manool (2) extracted from Salvia tingitana were considered as potential QSI against methicillin-resistant Staphylococcus aureus. Only sclareol showed synergistic activity with clindamycin. The quantification of these compounds by LC–MS analysis in the organs and in the calli of S. tingitana showed that sclareol is most abundant in the flower spikes and is produced by calli, while manool is the major labdane of the roots, and is abundant also in the leaves. Other metabolites of the roots were abietane diterpenoids, common in Salvia species, and pentacyclic triterpenoids, bearing a γ-lactone moiety, previously undescribed in Salvia. Docking simulations suggested that 1 and 2 bind to key residues, involved in direct interactions with DNA. They may prevent accessory gene regulator A (AgrA) binding to DNA or AgrA activation upon phosphorylation, to suppress virulence factor expression. The antimicrobial activity of these two compounds probably achieves preventing upregulation of the accessory gene regulator (agr)-regulated genes.     

Electrospray ionization mass spectrometry for identification and structural characterization of pregnane glycosides

Pregnane glycosides are a class of naturally occurring substances characterized by some interesting biological activities and widely distributed in the plant kingdom and in some marine organisms. Their toxicity and use in herbal drugs and folk medicines has generated great interest in the chemical characterization of these molecules. In the study reported here the potential of electrospray ionization mass spectrometry (ESI-MS) in the identification and structural characterization of pregnane glycosides was examined. ESI-MS/MS and ESI-MS(n) analyses were performed on 27 different compounds employing two mass spectrometers equipped with a triple-quadrupole or an ion-trap analyzer. The data illustrate the ability of the ESI techniques in the identification of pregnane glycosides, including the nature of the pregnane core, the kind of ester substituents, the types of sugar residues (hexose, deoxyhexose, dideoxyhexose, O-methyldeoxyhexose and O-methyldideoxyhexose), and the primary structure of the saccharide chain. From these data, a generalized fragmentation pathway was proposed by comparing the spectra acquired for all the compounds. Interestingly, similar results were obtained from the two instruments, thus demonstrating that detailed analyses of product ion spectra obtained using a triple-quadrupole mass spectrometer led to structural information comparable to those obtainable in MSn experiments using an ion trap. Different and complementary information was deduced by fragmenting the [M+H]+ or the [M+Na]+ ions, or the protonated aglycone [Agl+H]+ generated by in-source fragmentation. The present evidence clearly suggests that, in order to obtain a complete characterization of pregnane glycosides by MS, all three of these species should be accurately analyzed.     

Bioactive modification of silicon surface using self-assembled hydrophobins from Pleurotus ostreatus

A crystalline silicon surface can be made biocompatible and chemically stable by a self-assembled biofilm of proteins, the hydrophobins (HFBs) purified from the fungus Pleurotus ostreatus. The protein-modified silicon surface shows an improvement in wettability and is suitable for immobilization of other proteins. Two different proteins were successfully immobilized on the HFBs-coated chips: the bovine serum albumin and an enzyme, a laccase, which retains its catalytic activity even when bound on the chip. Variable-angle spectroscopic ellipsometry (VASE), water contact angle (WCA), and fluorescence measurements demonstrated that the proposed approach in silicon surface bioactivation is a feasible strategy for the fabrication of a new class of hybrid devices.     

Finite-time stabilization of impulsive dynamical linear systems

Finite-time stabilization of a special class of hybrid systems, namely impulsive dynamical linear systems (IDLS), is tackled in this paper. IDLS exhibit jumps in the state trajectory which can be either time-driven (time-dependent IDLS) or subordinate to specific state values (state-dependent IDLS). Sufficient conditions for finite-time stabilization of IDLS are provided. Such results require solving feasibility problems which involve Differential–Difference Linear Matrix Inequalities (D/DLMIs), which can be numerically solved in an efficient way, as illustrated by the proposed examples.     

A new norkaurane‐γ‐lactone from Parinari sprucei

The title tetracyclic diterpenoid, 10,13,16,17‐tetra­hydroxy‐9‐methyl‐15‐oxo‐20‐norkaurane‐18,10‐carbolactone hemihydrate, C₂₀H₂₈O₆·0.5H₂O, is a plant metabolite from Parinari sprucei, part of the Venezuelan Amazon flora. The asymmetric unit consists of two nearly identical mol­ecules of the diterpenoid and one mol­ecule of water. Some of the geometric parameters reflect steric strain in the mol­ecule. The extended structure is characterized by hydrogen bonds and weaker hydrogen‐mediated interactions, which involve all of the hydroxy groups and propagate in sheets that coincide with the (002) family of planes. The water mol­ecule acts as a double hydrogen‐bond donor and single acceptor and thus plays a critical role in the pattern of intermolecular interactions.     

Incompressible Elastic Bodies with Non-Convex Energy under Dead-Load Surface Tractions

In this paper we study the equilibrium deformations of an incompressible elastic body with a non-convex strain energy function which is subjected to a homogeneous distribution of dead-load tractions. To determine the stable solutions we consider the mixtures of the phases which minimize the total energy density. In the special case of a trilinear material we discuss the stability of the equilibrium phases in detail. Finally, we show that multiphase solutions are possible when the surface loads correspond to a critical simple shear and we sketch their possible forms. This revised version was published online in July 2006 with corrections to the Cover Date.     

Anti-angiogenic activity of Entada africana root

Entada africana roots are used in African traditional medicine for various diseases including inflammation. This application may be mediated through anti-angiogenic effects. Thus, in this study the anti-angiogenic activity of E. africana root extracts (n-hexane, chloroform, chloroform/methanol and methanol) was preliminarily evaluated by the quantitative determination of endogenous alkaline phosphatase in zebrafish embryos. A bioactivity-guided fractionation of chloroform/methanol extract yielded apigenin and robinetin as the main constituents from the most active fractions. In addition, a marked reduction on capillary formation was evidenced in chick chorioallantoic membrane after treatment with the active fractions or isolated compounds. Results obtained in this study suggest that the anti-angiogenic effects of E. africana root may account for its use in inflammatory diseases and other related pathological conditions.     

Recoverable PEG-supported copper catalyst for highly stereocontrolled nitroaldol condensation

A new poly(ethylene glycol)-modified DAT2-Cu(OAc)2 complex smoothly catalyzes a base-free nitroaldol condensation in a highly enantioselective manner (ee up to 93%) also in reagent-grade solvent and in the presence of air. Effective recovery and recycling (up to five runs) of supported catalysts are documented.