S(N)/S(N)' competition: selective access to new 10-fluoro artemisinins

In this paper, we report a simple route to accede to a new family of C-10 fluorinated derivatives of artemisinin 7. We demonstrated that nucleophilic substitution of the allylic bromide 6 with alcohols can occur at carbon 10 (compounds 7) under solvolytic conditions (S(N)'/S(N) ratio, 87:13). Furthermore, using the particular properties of hexafluoroisopropanol (HFIP), we are able to increase the selectivity of the substitution. Primary alcohols are completely selective for allylic substitution. With amines as nucleophiles, selectivity of substitution is dependent on their nucleophilicity, but attack at carbon 16 was always favored. However, the S(N)'/S(N) ratio could be slightly increased by adding HFIP, which is able to modulate their nucleophilicity through hydrogen bonding. In preliminary in vitro assessments, these new compounds, 7, exhibited a satisfying activity against malaria.     

A New Cell for Electrical Conductivity Measurement on Saturated Samples at Upper Crust Conditions

Electrical resistivity soundings are used by geophysicists to determine the structure and composition of the Earth’s crust and mantle and to explore natural resources (ore, oil, gas, water). Their interpretations in terms of composition and in-situ physical conditions depend mainly on laboratory measurements of electrical conductivity of rocks at simulated crustal conditions of temperature, pressure, saturation and pore pressures. These measurements present a numbers of limitations, in particular, in the case where conductive pore fluids are present, as in the case of deep reservoir conditions, where temperature exceeds 250 °C. Here, we present a new cell capable of measuring electrical conductivity of large saturated samples at confining pressure up to 200 MPa, pore pressure up to 50 MPa, and temperature up to 500 °C. The measurement cell has been developed in a commercial, internally heated, gas pressure apparatus (Paterson press). It is based on the concept of “guard ring” electrode, which is adapted to samples that are jacketed by a very conductive, metallic material. Numerical modeling of the current flow in the electrical cell allowed defining the optimal cell geometry. Calibration tests have been performed on Fontainebleau sandstones saturated with electrolytes of different conductivities, up to 350 °C. The resulting electrical formation factor and temperature dependence of electrical conductivity are in very good agreement with previous studies. This new cell will improve the exploration and exploitation of deep fluid reservoirs, as in unconventional, high enthalpy geothermal fields. In particular, the investigations address possible effects of fluid-rock interactions on electrical resistivity of a reservoir host rock.     

Characterizing changes in MR images with color-coded Jacobians

Image registration is the process of establishing spatial correspondence between two images or between two image volumes. Registration can be achieved by rigid, elastic, or a combination of rigid and elastic transforms that attempt to bring the two images into coincidence. A rigid transform accounts for differences in positioning and an elastic transform describes deformations due to differences in tissue properties, temporal changes due to growth or atrophy, or differences between individuals. Deformation-based morphometry uses the resulting deformation fields from these transforms to evaluate differences between the images being registered. Three methods of registration were evaluated: rigid (affine) transformation, elastic optical flow transformation, and elastic spline transformation. All three methods produce vector deformation fields that map each point in one image to a point in the other image. A 12-color map of the transformation Jacobian was used to represent local volume changes. Using the three registration methods, color-mapped Jacobians were determined using a simulated three-dimensional block with known translation, rotation, expansion, contraction, and intensity modulations. Color-coded Jacobians were also generated for experimentally measured magnetic resonance image volumes of water-filled balloons and 7-year-old twin boys. Color-coded Jacobians overlaid on anatomical images provide a convenient method to identify regional tissue expansion and contraction.     

P-type nitrogen-doped ZnO nanoparticles stable under ambient conditions

Zinc oxide is considered as a very promising material for optoelectronics. However, to date, the difficulty in producing stable p-type ZnO is a bottleneck, which hinders the advent of ZnO-based devices. In that context, nitrogen-doped zinc oxide receives much attention. However, numerous reviews report the controversial character of p-type conductivity in N-doped ZnO, and recent theoretical contributions explain that N-doping alone cannot lead to p-typeness in Zn-rich ZnO. We report here that the ammonolysis at low temperature of ZnO(2) yields pure wurtzite-type N-doped ZnO nanoparticles with an extraordinarily large amount of Zn vacancies (up to 20%). Electrochemical and transient spectroscopy studies demonstrate that these Zn-poor nanoparticles exhibit a p-type conductivity that is stable over more than 2 years under ambient conditions.     

Combined effect of γ-irradiation and bacterial-fermented dextrose on microbiological quality of refrigerated pork sausages

The objective of this study was to evaluate the effect of a concentrated fermented dextrose (FD), a natural antimicrobial product, combined with low dose γ-irradiation (1.5 kGy) on the microbiological quality of fresh pork sausages. Fresh pork sausages containing the FD (0.25%, 0.5% and 0.75%) were prepared in a meat pilot plant and were irradiated using a UC-15A irradiator equipped with a ⁶⁰Cobalt source. The γ-irradiation treatment alone was able to reduce the initial psychrophilic and mesophilic bacteria by more than 2 log CFU/g and kept the lactobacillus population under the detection limit (100 CFU/g). Results also showed that the FD alone was able to extend the shelf life of the sausages from 5 days up to 13 days. At day 13, the FD or irradiation alone showed 2 log CFU/g less mesophilic bacteria than the control. After combining FD and irradiation another reduction of the microbial count of 1 log CFU/g was observed. When combining the irradiation treatment with the FD results it showed a reduced growth rate of the psychrophilic and mesophilic bacteria compared to both treatments alone. This study demonstrated that FD with low dose gamma irradiation act in synergy to reduce the multiplication of the total bacterial flora in fresh sausages.     

A general rule for disk and hemisphere partition into equal-area cells

A new general rule is presented to define procedures in order to cut a disk or a hemisphere into an imposed number of equal-area cells. The system has several degrees of freedom that can be fixed, for instance, by enforcing the cells aspect ratios. Therefore, the cells can have very comparable forms, i.e. close to the square. This kind of method is effectively useful because it is not possible to build exact dense uniform distributions of points on the sphere. However, it will be shown that it is easy to cover the sphere, the hemisphere or the disk with equal-area cells. This capability makes easy, for instance, the implementation of stratified sampling in Monte Carlo methods. Moreover, the use of different azimuthal projections allows to link problems initially stated either on the hemisphere or within the circle.     

Interactions of NO2 with amine-functionalized SBA-15: effects of synthesis route

SBA-15 mesoporous silica was modified using (3-aminopropyl)trimethoxysilane (APTMS) following co-condensation or grafting methods and then used as a NO(2) adsorbent at room temperature. The samples were characterized before and after exposure to NO(2) by SEM-EDX, N(2) adsorption at 77 K, potentiometric titration, thermal analysis, and FTIR spectroscopy. Even though, regardless of the synthesis route, the addition of propylamine groups leads to a significant enhancement in the amount of NO(2) adsorbed (from 21 to 124 mg(NO(2))/g), a higher retention of NO(2) and NO (released as a result of surface reactions) was measured on the grafted silica than on all of the co-condensed samples. In the case of the latter materials, improvements in both NO(2) adsorption capacity and NO retention were found for the samples treated with NaOH. This behavior is related to the higher reactivity of deprotonated propylamine groups (formed during NaOH treatment) with NO(2), the presence of silanol groups, and the residual amount of sodium present in the samples. The mechanism of NO(2) adsorption on propylamine groups involves the formation of nitramine and/or nitrosamine. Analysis of the spent materials indicates that the porosity of co-condensed materials is not affected to the same extent by adsorption of NO(2) as that of the grafted silica.     

Experiment and theory of low-pressure nitrogen adsorption in organic layers supported or grafted on inorganic adsorbents: toward a tool to characterize surfaces of hybrid organic/inorganic systems

We report experimental nitrogen adsorption isotherms of organics-coated silicas, which exhibit a low-pressure desorption branch that does not meet the adsorption branch upon emptying of the pores. To address the physical origin of such a hysteresis loop, we propose an equilibrium thermodynamic model that enables one to explain this phenomenon. The present model assumes that, upon adsorption, a small amount of nitrogen molecules penetrate within the organic layer and reach adsorption sites that are located on the inorganic surface, between the grafted or adsorbed organic molecules. The number of accessible adsorption sites thus varies with the increasing gas pressure, and then we assume that it stays constant upon desorption. Comparison with experimental data shows that our model captures the features of nitrogen adsorption on such hybrid organic/inorganic materials. In particular, in addition to predicting the shape of the adsorption isotherm, the model is able to estimate, with a reasonable number of adjustable parameters, the height of the low-pressure hysteresis loop and to assess in a qualitative fashion the local density of the organic chains at the surface of the material.