Femtosecond electronic relaxation of excited metalloporphyrins in the gas phase

A systematic study of the ultrafast decay of metalloporphyrins containing various transition metals with partially filled 3d shells and zinc (3d filled) is reported here after excitation in the second excited state of the system (Soret band). Both time-of-flight mass spectrometry and velocity map imaging have been used for detection. A general biexponential decay with a short time constant tau1 approximately 100 fs is observed for the transition metal porphyrins, followed by a tau2 approximately 1 ps time decay. This evolution is interpreted as a porphyrin-to-metal charge transfer, tau1, followed by a back transfer, tau2, which leads to an excited state (d,d*) localized on the metal. These conclusions stem from the different behaviors of zinc and the transition metal porphyrins. A porphyrin-to-metal charge transfer model is chosen to describe the relaxation mechanism, based upon the fact that transition metalloporphyrins can accept electrons on the metal site, in contrast to zinc porphyrins.     

Micro-actuators: when artificial muscles made of nematic liquid crystal elastomers meet soft lithography

The production, via soft lithography, of micron-sized thermoresponsive pillars made of side-on nematic LCE leads to the formation of surface-responsive structures. The individual, monodisperse pillars, when cut out from the surface, behave as micro-actuators, showing contraction of around 35% at the nematic to isotropic phase transition.     

Adsorption of simple gases in MCM-41 materials: the role of surface roughness

This paper reports the development and testing of atomistic models of silica MCM-41 pores. Model A is a regular cylindrical pore having a constant section. Model B has a surface disorder that reproduces the morphological features of a pore obtained from an on-lattice simulation that mimics the synthesis process of MCM-41 materials. Both models are generated using a similar procedure, which consists of carving the pore out of an atomistic silica block. The differences between the two models are analyzed in terms of small angle neutron scattering spectra as well as adsorption isotherms and isosteric heat curves for Ar at 87 K and Xe at 195 K. As expected for capillary condensation in regular nanopores, the Ar and Xe adsorption/desorption cycles for model A exhibit a large hysteresis loop having a symmetrical shape, i.e., with parallel adsorption and desorption branches. The features of the adsorption isotherms for model B strongly depart from those observed for model A. Both the Ar and Xe adsorption branches for model B correspond to a quasicontinuous pore filling that involves coexistence within the pore of liquid bridges and gas nanobubbles. As in the case of model A, the Ar adsorption isotherm for model B exhibits a significant hysteresis loop; however, the shape of the loop is asymmetrical with a desorption branch much steeper than the adsorption branch. In contrast, the adsorption/desorption cycle for Xe in model B is quasicontinuous and quasireversible. Comparison with adsorption and neutron scattering experiments suggests that model B is too rough at the molecular scale but reproduces reasonably the surface disorder of real MCM-41 at larger length scales. In contrast, model A is smooth at small length scales in agreement with experiments but seems to be too ordered at larger length scales.     

Electrochemically triggered open and closed Pacman bis-metalloporphyrins

A new type of very compact Pacman bis-porphyrin scaffold has been obtained in which a calix[4]arene spacer provides both cofacial preorganization and flexibility. Changes in the distance between the two tetrapyrrolic macrocycles can be triggered by electrochemistry, where closed and open conformers can be interconverted in a handclapping motion.     

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.