Complex and chaotic response of a non-linear oscillator with an isothermal gas spring

In this paper we study the dynamics of a non-linear one-degree-of-freedom system subjected to an external harmonic excitation, representing a simplified model for the synchronous hydraulic oscillations that can occur in the draft tube of Francis turbines at partial loads. The application of different typical numerical techniques has shown the existence of multiple coexisting periodic solutions, and the non-periodic bounded solutions which exhibit deterministic chaotic behaviour. The relevant strange attractor has been defined and the loss of memory associated with an exponential divergence in time of close initial conditions resulting in chaotic dynamics have been found and measured. A partial classification of qualitatively different dynamical behaviours for the system has been outlined in the control parameter space.

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Sommario In questo articolo viene studiata la dinamica di un sistema non-lineare ad un singolo grado di liberta' soggetto ad una forzante armonica esterna, rappresentante un modello semplificato per le oscillazioni idrauliche sincrone che hanno luogo nei diffusori delle turbine tipo Francis a carico parziale. Applicando differenti tecniche numeriche, viene mostrata l'esistenza di soluzioni periodiche multiple, oltre che soluzioni non-periodiche limitate con tipico comportamento caotico deterministico. L'attrattore strano corrispondente e' stato definito e caratterizzato: la perdita di memoria associata alla divergenza esponenziale di orbite inizialmente vicine, tipica della dinamica caotica, e' stata individuata e calcolata numericamente. Una prima parziale classificazione dei vari comportamenti dinamici per il sistema viene evidenziata attraverso la rappresentazione nello spazio parametrico.

     

Stereochemical control of skeletal diversity

[reaction: see text]. Substrates having appendages that pre-encode skeletal information (sigma-elements) can be converted into products having distinct skeletons using a common set of reaction conditions. The sequential use of the Ugi 4CC-IMDA reaction, followed by allylation, hydrolysis, and acylation of a chiral amino alcohol appendage (sigma-element), leads to substrates for a ROM/RCM or RCM reaction. The stereochemistry of the sigma-element and not its constitution controls the outcome of the pathway selected. This work illustrates the potential of linking stereochemical control to the challenging problem of skeletal diversity.     

The LILITH approach to organic synthesis planning

The general basis of the LILITH program is outlined. The size of the possible solution space is reduced by enhancing convergence, simplification and ordering. Complexity distance, relevant bond sets and ordering for bond-forming sequences are described. The evaluation of reactivity is the second main aspect in organic synthesis planning. Properties involving the ground state (native bond polarity) and the excited state (group-similar interference) contribute to the prediction of reactivity.     

Catalysis of Ugi four component coupling reactions by rare earth metal triflates

Substoichiometric quantities of scandium and ytterbium triflate increase the yield of Ugi four component coupling reactions of aromatic aldehydes 2- to 7-fold. These rare earth metal triflates enhance the reaction yields primarily via activation of the imine intermediate of this multicomponent reaction.     

Formation of an aminoacyl-S-enzyme intermediate is a key step in the biosynthesis of chloramphenicol

Herein we report the first biochemical characterization of an enzyme involved in the biosynthesis of chloramphenicol that provides new insights into the origins of the antibiotic.     

Multienzymatic preparation of (−)-[3-(oxiran-2-yl)phenyl]methanol and (−)-3-(oxiran-2-yl)benzoic acid

The cascade use of enzymatic activities allows for the preparation of enantiomerically pure epoxides. In particular, using whole-cell biocatalysts we can prepare both (?)-[3-(oxiran-2-yl)phenyl]methanol and (?)-3-(oxiran-2-yl)benzoic acid in one-pot, two or three steps procedure. The yield is quantitative and enantiomeric purity greater than 95%. The selected biocatalysts contain a styrene monoxygenase from Pseudomonas fluorescens ST and a naphthalene dihydrodiol dehydrogenase from P. fluorescens N3, cloned and expressed in Escherichia coli.     

Effects of lipopolysaccharide-induced inflammation on expression of growth-associated genes by corticospinal neurons

Background  

Inflammation around cell bodies of primary sensory neurons and retinal ganglion cells enhances expression of neuronal growth-associated genes and stimulates axonal regeneration. We have asked if inflammation would have similar effects on corticospinal neurons, which normally show little response to spinal cord injury. Lipopolysaccharide (LPS) was applied onto the pial surface of the motor cortex of adult rats with or without concomitant injury of the corticospinal tract at C4. Inflammation around corticospinal tract cell bodies in the motor cortex was assessed by immunohistochemistry for OX42 (a microglia and macrophage marker). Expression of growth-associated genes c-jun, ATF3, SCG10 and GAP-43 was investigated by immunohistochemistry or in situ hybridisation.     

Investigation of the configurational stabilities of chiral isocyanoacetates in multicomponent reactions

Isocyanoacetates are uniquely reactive compounds characterized by an ambivalent isocyano functional group and an enolizable α-carbon. It is widely believed that chiral α-substituted isocyanoacetates are configurationally unstable in some synthetically useful isocyanide-based multicomponent reactions. Herein, we demonstrate that chiral isocyanoacetates can be used with minimal to negligible epimerization in a variety of canonical Ugi four-component condensations as well as Joullié-Ugi three-component condensations, reactions that are particularly useful for constructing complex peptide structures in a single synthetic operation.