Rationally designed inhibitors as tools for comparing the mechanism of squalene-hopene cyclase with oxidosqualene cyclase

The inhibition of squalene-hopene cyclase (SHC) (E.C. 5.4.99.-), an enzyme of bacterial membranes catalyzing the formation of pentacyclic sterol-like triterpenes, was studied by using different classes of compounds originally developed as inhibitors of oxidosqualene cyclase (OCS) (E.C. 5.4.99.7), the enzyme of eukaryotes responsible for the formation of tetracyclic precursors of sterols. The mechanism of cyclization of squalene by SHC, beginning with a protonation of the 2,3 double bond by an acidic residue of the enzyme, followed by a series of electrophilic additions of the carbocationic intermediates to the double bonds, is similar to the mechanism of cyclization of 2,3-oxidosqualene by OSC. The inhibitors studied included: (i) analogs of the carbocationic intermediates formed during cyclization, such as aza-analogs of squalene and 2,3-oxidosqualene; (ii) affinity-labeling inhibitors bearing a methylidene reactive group; and (iii) vinyldioxidosqualenes and vinylsulfide derivatives of the substrates. Comparison of the results obtained with the two enzymes, SHC and OSC, showed that many of the most effective inhibitors of OSC were also able to inhibit SHC, while some derivatives acted as specific inhibitors. Differences could be easily explained on the basis of the different substrate specificity of the two enzymes.     

Synthesis and catalytic activity of optically active polymers containing oxime groups

Optically active polymers containing oxime groups have been prepared: (i) by partial quaternization of poly(4-vinyl pyridine) (P4VP) with phenacyloxime bromide and with (+)-(S)-1-bromo-2-methylbutane; and (ii) by reaction of the copolymer from 4VP and (+)-(S)-5-methyl-1-hepten-3-one with hydroxylamine. These polymers have been used as catalysts for the esterolysis of esters of p-nitrophenol with non-chiral and with chiral acids. The kinetic parameters of the catalytic process are markedly dependent on the structure of polymer and substrate. A moderate chiral discrimination of the antipodes of p-nitrophenyl 2-methylbutanoate is observed with the catalyst obtained from the copolymer of 4VP with (+)-(S)-5-methyl-1-hepten-3-one.     

How the risk of failure in lifetime of tempered glass depends on the size of NiS inclusions and heat soak test duration

The probability of breakage in service lifetime of heat-tempered glass panes contaminated by nickel sulfide inclusions is estimated with a multiscale micromechanically motivated statistical theory, which considers the effects of the heat soak test (HST). Short and long HSTs differently affect the phase transformation of NiS of diverse chemical composition, whose increase in volume can break the glass. The main hypothesis, corroborated by experiments, is that there is a lower limit for the size of NiS stones below which no crack can be initiated from the volumetric expansion. The catastrophic propagation of nucleated fractures in the long term is modeled through a rescaled critical stress intensity factor, which accounts for the subcritical crack propagation and the slow phase transformation of NiS. A parametric analysis evidences how the failure probability is strongly affected by these parameters, depending on the holding time in the HST. Tailored experimental activity is suggested for the proper calibration of the model.     

Dipyridamole technetium-99m Sestamibi imaging in the diagnosis of syndrome X

In a middle-aged woman with anginal chest pain and a normal-appearing angiogram, dypiridamole technetium-99m Sestamibi scintigraphy, a noninvasive method, provided the diagnosis of syndrome X and was used in follow-up to monitor the course of disease.     

Sensitivity analysis of the rice model WARM in Europe: Exploring the effects of different locations,climates and methods of analysis on model sensitivity to crop parameters

Sensitivity analysis studies how the variation in model outputs can be due to different sources of variation. This issue is addressed, in this study, as an application of sensitivity analysis techniques to a crop model in the Mediterranean region. In particular, an application of Morris and Sobol' sensitivity analysis methods to the rice model WARM is presented. The output considered is aboveground biomass at maturity, simulated at five rice districts of different countries (France, Greece, Italy, Portugal, and Spain) for years characterized by low, intermediate, and high continentality. The total effect index of Sobol' (that accounts for the total contribution to the output variation due a given parameter) and two Morris indices (mean μ and standard deviation σ of the ratios output changes/parameter variations) were used as sensitivity metrics. Radiation use efficiency (RUE), optimum temperature (T_opt), and leaf area index at emergence (LAI_ini) ranked in most of the combinations site × year as first, second and third most relevant parameters. Exceptions were observed, depending on the sensitivity method (e.g. LAI_ini resulted not relevant by the Morris method), or site-continentality pattern (e.g. with intermediate continentality in Spain, LAI_ini and T_opt were second and third ranked; with low continentality in Portugal, RUE was outranked by T_opt). Low σ values associated with the most relevant parameters indicated limited parameter interactions. The importance of sensitivity analyses by exploring site × climate combinations is discussed as pre-requisite to evaluate either novel crop-modelling approaches or the application of known modelling solutions to conditions not explored previously. The need of developing tools for sensitivity analysis within the modelling environment is also emphasized.     

Optimal controllers for spatially invariant systems with delayed communication requirements

We consider the problem of optimal design of semi-decentralized controllers for a special class of spatially distributed systems. This class includes spatially invariant and distributed discrete-time systems with an inherent temporal delay in the interaction of neighboring sites. We consider the problem of optimal design of distributed controllers that have the same information passing delay structure as the plant. We show how for stable plants, the YJBK parameterization of such stabilizing controllers yields a convex parameterization for this class. We then show how the optimal problem can be solved.     

A genetic expectation-maximization method for unsupervised change detection in multitemporal SAR imagery

In this paper, we present a novel, automatic and unsupervised change-detection approach to the analysis of single-channel single-polarization multitemporal SAR images. The statistical parameters of the changed and unchanged classes, which are assumed to follow a generalized Gaussian (GG) distribution in the analysed log-ratio image, are explicitly estimated by the expectation-maximization (EM) algorithm initialized with a robust strategy based on genetic algorithms (GAs). In addition, the proposed approach integrates two further processing capabilities. The first one intends to cope with the problem of the automatic detection of multiple changes in the scene. This is carried out by modelling the log-ratio image histogram with a multimodal GG mixture whose number of components is estimated basing on the Bayesian information criterion (BIC). The second processing capability allows exploitation of spatial contextual information in the change detection process through a Markovian formulation. Results obtained on both simulated and real data are reported and discussed.     

Functional properties of reduced moisture fruits as ingredients in food systems

Fruit pieces of some species have been processed to be used as ingredients in various food systems, either by partial dehydration alone or by osmosis and partial dehydration, to achieve different levels of water activity and solids contents in the final products.

The relationships existing among processing, phase composition after processing and functional properties of the products have been assessed within a useful range of water content and water activity.

The functional properties are expressed as diagrams relating the phase composition (soluble solids, insoluble solids and water) to the range of consistencies obtainable at various water activities. These diagrams provide a useful tool for preparing fruit ingredients suitable for specific food systems.     

NADPH-dependent D-aldose reductases and xylose fermentation in Fusarium oxysporum

Two aldose (xylose) reductases (ARI and ARII) from Fusarium oxysporum were purified and characterized. The native ARI was a monomer with M(r) 41000, pI 5.2 and showed a 52-fold preference for NADPH over NADH, while ARII was homodimeric with a subunit of M(r) 37000, pI 3.6 and a 60-fold preference for NADPH over NADH. In this study, the influence of aeration and the response to the addition of electron acceptors on xylose fermentation by F. oxysporum were also studied. The batch cultivation of F. oxysporum on xylose was performed under aerobic, anaerobic and oxygen-limited conditions in stirred tank reactors. Oxygen limitation had considerable influence on xylose metabolism. Under anaerobic conditions (0 vvm), xylitol was the main product with a maximum yield of 0.34 mole of xylitol/mole of xylose while the maximum ethanol yield (1.02 moles of ethanol/mole of xylose) was obtained under aerobic conditions (0.3 vvm). When the artificial electron acceptor acetoin was added to an anaerobic batch fermentation of xylose by F. oxysporum, the ethanol yield increased while xylitol excretion was also decreased.     

Biotransformation of Waste Bile Acids: A New Possible Sustainable Approach to Anti-Fungal Molecules for Crop Plant Bioprotection?

Phytopathogenic fungi are among the main causes of productivity losses in agriculture. To date, synthetic chemical pesticides, such as hydroxyanilides, anilinopyrimidines and azole derivatives, represent the main treatment tools for crop plant defence. However, the large and uncontrolled use of these substances has evidenced several side effects, namely the resistance to treatments, environmental damage and human health risks. The general trend is to replace chemicals with natural molecules in order to reduce these side effects. Moreover, the valorisation of agri-food industry by-products through biotransformation processes represents a sustainable alternative to chemical synthesis in several sectors. This research is aimed at comparing the anti-phytopathogenic activity of waste bovine and porcine bile with secosteroids obtained by biotransformation of bile acids with Rhodococcus strains. The ultimate goal is to apply these natural products on food crops affected by phytopathogenic fungi.