Direct and Enantioselective Vinylogous Michael Addition of α‐Alkylidenepyrazolinones to Nitroolefins Catalyzed by Dual Cinchona Alkaloid Thioureas

While several protocols exist for the asymmetric functionalization of pyrazolinones at the α‐position relying on nucleophilic addition or annulation procedures, use of α‐alkylidene electron‐rich analogues in asymmetric vinylogous coupling to carbon electrophiles is substantially an uncharted domain. We now report, for the first time, that alkylidenepyrazolinones carrying an enolizable carbon at the γ‐position efficiently participate in direct and asymmetric, catalytic vinylogous Michael‐type additions to nitroolefins providing the expected adducts in high yields, with complete γ‐site selectivity and with extraordinary levels of enantio‐, diastereo‐, and geometrical selectivities. Both enantiomeric adducts were equally accessed by employing a quasi‐enantiomeric quinine‐ or quinidine‐based thiourea catalyst pair.

     

Computer simulations reveal complex distribution of haemodynamic forces in a mouse retina model of angiogenesis

There is currently limited understanding of the role played by haemodynamic forces on the processes governing vascular development. One of many obstacles to be overcome is being able to measure those forces, at the required resolution level, on vessels only a few micrometres thick. In this paper, we present an in silico method for the computation of the haemodynamic forces experienced by murine retinal vasculature (a widely used vascular development animal model) beyond what is measurable experimentally. Our results show that it is possible to reconstruct high-resolution three-dimensional geometrical models directly from samples of retinal vasculature and that the lattice-Boltzmann algorithm can be used to obtain accurate estimates of the haemodynamics in these domains. We generate flow models from samples obtained at postnatal days (P) 5 and 6. Our simulations show important differences between the flow patterns recovered in both cases, including observations of regression occurring in areas where wall shear stress (WSS) gradients exist. We propose two possible mechanisms to account for the observed increase in velocity and WSS between P5 and P6: (i) the measured reduction in typical vessel diameter between both time points and (ii) the reduction in network density triggered by the pruning process. The methodology developed herein is applicable to other biomedical domains where microvasculature can be imaged but experimental flow measurements are unavailable or difficult to obtain.     

Mapping carbon and water vapor fluxes in a chaparral ecosystem using vegetation indices derived from AVIRIS

Using simple models derived from spectral reflectance, we mapped the patterns of ecosystem CO₂ and water fluxes in a semi-arid site in southern California during a period of extreme disturbance, marked by drought and fire. Employing a combination of low (∼ 2 km) and high (∼ 16 km) altitude images from the hyperspectral Airborne Visible Infrared Imaging Spectrometer (AVIRIS), acquired between April 2002 and September 2003, and ground data collected from an automated tram system, several vegetation indices were calculated for Sky Oaks field station, a FLUXNET and SpecNet site located in northern San Diego County (CA, USA). Based on the relationships observed between the fluxes measured by the eddy covariance tower and the vegetation indices, net CO₂ and water vapor flux maps were derived for the region around the flux tower. Despite differences in the scale of the images (from ∼ 2 m to 16 m pixel size) as well as marked differences in environmental conditions (drought in 2002, recovery in early 2003, and fire in mid 2003), net CO₂ and water flux modeled from AVIRIS-derived reflectance indices (NDVI, PRI and WBI) effectively tracked changes in tower fluxes across both drought and fire, and readily revealed spatial variation in fluxes within this landscape. After an initial period of net carbon uptake, drought and fire caused the ecosystem to lose carbon to the atmosphere during most of the study period. Our study shows the power of integrating optical and flux data in LUE models to better understand factors driving surface-atmosphere carbon and water vapor flux cycles, one of the main goals of SpecNet.     

Municipal-treated wastewater reuse for plant nurseries irrigation

Results of an experiment aimed at assessing the possibility of reusing reclaimed wastewater for nursery ornamental plants are presented. Tests were carried out in Pistoia (Italy). A pilot plant for tertiary treatment (filtration and peracetic acid + UV disinfection) of the local wastewater treatment plant (WWTP) effluent was set up. An experimental plot with six containerized ornamental species was irrigated with the tertiary effluent and growth and physiological parameters were monitored. A control plot irrigated with fertigated water (nutrient-enriched groundwater) was also set up in order to compare the plants response to different kinds of irrigation water. The refinery treatment by filtration and disinfection with Peracetic Acid (PAA) and UV together was very effective in bacteria removal. The value of 2 MPN of Total Coliforms in 100 ml set by Italian law (until June 2003) for unrestricted irrigation was constantly satisfied. Agronomic results indicate no major limitations to the use of a tertiary effluent as an irrigation source in an ornamental plant nursery. The nutrient content of the tertiary effluent was able to maintain good plant growth as well as fertigated water for most of the tested species.     

Bioinspired Nacre‐Like Alumina with a Metallic Nickel Compliant Phase Fabricated by Spark‐Plasma Sintering

Many natural materials present an ideal “recipe” for the development of future damage‐tolerant lightweight structural materials. One notable example is the brick‐and‐mortar structure of nacre, found in mollusk shells, which produces high‐toughness, bioinspired ceramics using polymeric mortars as a compliant phase. Theoretical modeling has predicted that use of metallic mortars could lead to even higher damage‐tolerance in these materials, although it is difficult to melt‐infiltrate metals into ceramic scaffolds as they cannot readily wet ceramics. To avoid this problem, an alternative (“bottom‐up”) approach to synthesize “nacre‐like” ceramics containing a small fraction of nickel mortar is developed. These materials are fabricated using nickel‐coated alumina platelets that are aligned using slip‐casting and rapidly sintered using spark‐plasma sintering. Dewetting of the nickel mortar during sintering is prevented by using NiO‐coated as well as Ni‐coated platelets. As a result, a “nacre‐like” alumina ceramic displaying a resistance‐curve toughness up to ≈16 MPa m^½ with a flexural strength of ≈300 MPa is produced.     

Use of Geophysical Techniques for the Localization of the Restricting Zones of Permeability in the Bottom of Basin： Forecasting the Zones of Clogging

Measurements of dielectric parameters followed by permeability tests are performed on soil samples of infiltration basin. The dielectric parameters are obtained by TDR （time domain reflectrometry） measurements from which it is found that the measurement of the permittivity, the electrical conductivity and the relaxation time of compacted soil allows the mapping of the values of the coefficient of permeability at the surface of an infiltration basin. With the distribution of the coefficient of permeability, the areas of water stagnation can be detected before the basin filling. The study proves that the TDR measurements for the detection of these zones can be used for the management of infiltration basins for sustainable working and their remediation can be undertaken before the rainy seasons.     

Pd/SiO2 as Heterogeneous Catalyst for the Heck Reaction: Evidence for a Sensitivity to the Surface Structure of Supported Particles

The contact of Pd(AcO)₂ in solution with thiouric tethered to a silica led to the formation of supported nanoparticles (ca. 2 nm in size) active in the Heck reaction, quite sensitive to the palladium leaching. A stable supported phase was obtained by subsequent calcination, but the catalytic activity resulted strongly dependent on the calcination temperature. Such a behaviour was related to differences in the surface structure of the supported particles, as those monitored by IR spectroscopy of CO adsorbed on catalysts reduced at various temperatures.     

Model building and assessment of the impact of covariates for disease prevalence mapping in low-resource settings: to explain and to predict

This paper provides statistical guidance on the development and application of model-based geostatistical methods for disease prevalence mapping. We illustrate the different stages of the analysis, from exploratory analysis to spatial prediction of prevalence, through a case study on malaria mapping in Tanzania. Throughout the paper, we distinguish between predictive modelling, whose main focus is on maximizing the predictive accuracy of the model, and explanatory modelling, where greater emphasis is placed on understanding the relationships between the health outcome and risk factors. We demonstrate that these two paradigms can result in different modelling choices. We also propose a simple approach for detecting over-fitting based on inspection of the correlation matrix of the estimators of the regression coefficients. To enhance the interpretability of geostatistical models, we introduce the concept of domain effects in order to assist variable selection and model validation. The statistical ideas and principles illustrated here in the specific context of disease prevalence mapping are more widely applicable to any regression model for the analysis of epidemiological outcomes but are particularly relevant to geostatistical models, for which the separation between fixed and random effects can be ambiguous.     

Limit behaviour of masonry arches in the presence of finite displacements

A procedure is proposed for the calculation of the equilibrium paths of a masonry arch with elastic abutments. The elasticity of the abutments implies the existence of a non-linear, non-trivial equilibrium path, with the development of three hinges from the beginning of the load history. The shape of the equilibrium path suggests that shallow masonry arches should be classified in three different ways according to the nature of their failure load. In the first class a fourth hinge can develop as the live load is increased, and a classical failure load is reached when a four-hinge mechanism occurs. In the second case the equilibrium path shows a limit point, and finally it is possible to have a monotonically increasing equilibrium path, with no limit point or bifurcation point. If the arch is very shallow, only these two latter possibilities must be examined, and the presence of non-rigid abutments can cause instability of the arch. This instability phenomenon could be particularly important for flying buttresses of cathedrals, if they were built along rivers, or more generally on elastic soil.     

New processes in the environmental chemistry of nitrite: nitration of phenol upon nitrite photoinduced oxidation

The role of nitrite as an environmental factor has been widely recognized. Nitrite is a relevant source of *OH in the atmosphere, both in the gas phase via photolysis of gaseous HNO2 and in atmospheric hydrometeors by photolysis of NO2-. In aqueous systems, *OH production through nitrite photolysis can be negligible due to the competition for light absorption by dissolved Fe(III), colloidal iron oxides, and nitrate. These photoexcited oxidants interact with NO2- and HNO2 to form *NO2, either directly or via formation of *OH. As a consequence, nitrite and nitrous acid may act as *NO2 rather than *OH sources. The radical *NO2 is involved in the nitration of many aromatic compounds, of which phenol is a model in this work. Kinetic measurements using 2-propanol as *OH scavenger show that the direct production of *OH by aqueous Fe(III) species decreases as pH increases. At slightly acidic and neutral pH values, oxidation of nitrite occurs by direct electron transfer to photoexcited Fe(III)aq species or colloidal iron oxides, in addition to the *OH-mediated oxidation of NO2-. The reported findings suggest a completely new role of nitrite in aquatic environments.