Analysis of the local structure of phosphorus-substituted LAMOX oxide ion conductors

The effect of partial substitution of molybdenum by phosphorus on the global and local structural arrangement of the fast oxide-ion conductor La(2)Mo(2)O(9) (LAMOX) has been studied by X-ray powder diffraction as well as (139)La and (31)P solid state NMR. The diffraction patterns show that La(2)Mo(2-y)P(y)O(9-y/2) forms a solid solution at low phosphorus concentrations, and that there is a structural phase transition upon increasing phosphorus concentration. This phase transition is also reflected in (139)La and (31)P NMR spectra. The possibility to excite (31)P multiple-quantum coherences of one of the (31)P NMR signals gives evidence of an accumulation of phosphorus atoms on neighbouring Mo-type sites already before formation of three-dimensional precipitates. On the basis of our X-ray and NMR results we propose a possible structural arrangement of the compound La(2)Mo(2-y)P(y)O(9-y/2) that explains the experimental observations by crystal twinning.     

Divergent Synthesis of Molecular Winch Prototypes

We report the synthesis of conceptually new prototypes of molecular winches with the ultimate aim to investigate the work performed by a single ruthenium-based molecular motor anchored on a surface by probing its ability to pull a load upon electrically-driven directional rotation. According to a technomimetic design, the motor was embedded in a winch structure, with a long flexible polyethylene glycol chain terminated by an azide hook to connect a variety of molecular loads. The structure of the motor was first derivatized by means of two sequential cross-coupling reactions involving a penta(4-halogenophenyl)cyclopentadienyl hydrotris(indazolyl)borate ruthenium(II) precursor and the resulting benzylamine derivative was next exploited as key intermediate in the divergent synthesis of a family of nanowinch prototypes. A one-pot method involving sequential peptide coupling and Cu-catalyzed azide-alkyne cycloaddition was developed to yield four loaded nanowinches, with load fragments encompassing triptycene, fullerene and porphyrin moieties.     

Uptake and release kinetics of 22 polar organic chemicals in the Chemcatcher passive sampler

The Chemcatcher passive sampler, which uses Empore? disks as sampling phase, is frequently used to monitor polar organic chemicals in river water and effluents. Uptake kinetics need to be quantified to calculate time-weighted average concentrations from Chemcatcher field deployments. Information on release kinetics is needed if performance reference compounds (PRCs) are used to quantify the influence of environmental conditions on the uptake. In a series of uptake and elimination experiments, we used Empore? SDB disks (poly(styrenedivinylbenzene) copolymer modified with sulfonic acid groups) as a sampling phase and 22 compounds with a logK _ow (octanol–water partitioning coefficient) range from ?2.6 to 3.8. Uptake experiments were conducted in river water or tap water and lasted up to 25 days. Only 1 of 22 compounds (sulfamethoxazole) approached equilibrium in the uptake trials. Other compounds showed continuing non-linear uptake, even after 25 days. All compounds could be released from SDB disks, and desorption was proportionally higher in disks loaded for shorter periods. Desorption showed two-phase characteristics, and desorption was proportionally higher for passively sorbed compounds compared to actively loaded compounds (active loading was performed by pulling spiked river water over SDB disks using vacuum). We hypothesise that the two-phase kinetics and better retention of actively loaded compounds—and compounds loaded for a longer period—may be caused by slow diffusion of chemicals within the polymer. As sorption and desorption did not show isotropic kinetics, it is not possible to develop robust PRCs for adsorbent material like SDB disks.     

Detection of genetically modified corn (Bt176) in spiked cow blood samples by polymerase chain reaction and immunoassay methods

The fate of DNA and protein transgenic sequences in products derived from animals fed transgenic crops has recently raised public interest. Sensitive molecular tests targeting the Bt176 genetic construct and the transgenic Cry1Ab protein were developed to determine whether plant sequences, especially transgenic sequences, are present in animal products. A protocol for total DNA extraction and purification from cow whole blood samples was first drawn up and assessed by spiking with known amounts of DNA from Bt176 maize. The limit of detection for transgenic sequences (35S promoter and Bt176-specific junction sequence) was determined by both the polymerase chain reaction-enzyme-linked immunosorbent assay (PCR-ELISA) and the 5'-nuclease PCR assay. Four additional PCR systems were built to substantiate the results. The first detects a mono-copy maize-specific sequence (ADH promoter). Two others target multi-copy sequences from plant nucleus (26S rRNA gene) and chloroplast (psaB gene). The last one, used as a positive control, targets a mono-copy animal sequence (alpha(s1)-casein gene). Both methods detected a minimum spiking at 25 copies of Bt176 maize/mL in 10 mL whole blood samples. The sandwich ELISA kit used detected down to 1 ng transgenic Cry1Ab protein/mL spiked whole blood.     

Electrocapillary at contact: potential-dependent adhesion between a gold electrode and a mica surface

Using the electrochemical surface forces apparatus, we investigated adhesion (from pull-off measurements) between gold and mica as the potential of the gold surface was changed externally. Measurements were performed at different concentrations of KClO(4) in a potential window where the gold electrode is ideally polarizable. At applied potentials where the gold-mica interactions are repulsive, we obtain double layer forces that are predictable by the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory of colloid stability but deviate from the theory at short range. At applied potentials where the gold-mica interactions are attractive, we observed a very strong dependence of adhesion on the applied potential, a result that cannot be directly related to DLVO theory. We show, however, that an approach based on electrocapillary thermodynamics can be employed to model the potential dependence of adhesion seen in our measurements. This electrocapillary approach presents evidence of charging at the gold-mica interface and stresses the relation between the charge within and outside of the contact area.     

Photochemical Processes Involved in a Biopolymer Doped by Chromium(VI) during Hologram Recording

This paper is devoted to the study of the photochemical processes occurring during hologram formation in a biopolymer, agar doped by chromium(VI). The evolution of both the absorbing chromium species and the polymer allowed elucidating the reactions taking place during irradiation in conditions representative of hologram formation. As previously observed with dichromated poly(vinyl alcohol) (PVA), polymer containing hydroxyl groups as agar, irradiation of dichromated agar provoked a two step reduction of chromium species and the crosslinking of the host polymer. But agar has a rather complex chemical structure and the photoproducts formed along the polymeric chains throughout the photoredox process were different in agar and in PVA. The photostability of the matrix, that has been proven, coupled with the possibility to record good quality holograms, allowed us to propose dichromated agar as a new natural photosensitive biomaterial.     

Effect of surface roughness and chemical composition on the wetting properties of silicon-based substrates

The article reports on the wetting properties of silicon-based materials as a function of their roughness and chemical composition. The investigated surfaces consist of hydrogen-terminated and chemically modified atomically flat crystalline silicon, porous silicon and silicon nanowires. The hydrogenated surfaces are functionalized with 1-octadecene or undecylenic acid under thermal conditions. The changes occurring upon surface functionalization are characterized using Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS) spectroscopy and water contact angle measurements. By increasing the surface roughness, the static water contact angle increases. The combination of high surface roughness with chemical functionalization with water repellent coating (1-octadecene) enables reaching superhydrophobicity (water contact angle greater than 150°) for silicon nanowires.     

The Aqueous Ca2+ System,in Comparison with Zn2+, Fe3 +, and Al3 +: An Ab Initio Molecular Dynamics Study

Herein, we report on the structure and dynamics of the aqueous Ca²⁺ system studied by using ab initio molecular dynamics (AIMD) simulations. Our detailed study revealed the formation of well‐formed hydration shells with characteristics that were significantly different to those of bulk water. To facilitate a robust comparison with state‐of‐the‐art X‐ray absorption fine structure (XAFS) data, we employ a 1st principles MD‐XAFS procedure and directly compare simulated and experimental XAFS spectra. A comparison of the data for the aqueous Ca²⁺ system with those of the recently reported Zn²⁺, Fe³⁺, and Al³⁺ species showed that many of their structural characteristics correlated well with charge density on the cation. Some very important exceptions were found, which indicated a strong sensitivity of the solvent structure towards the cation′s valence electronic structure. Average dipole moments for the 2nd shell of all cations were suppressed relative to bulk water.     

Osteopontin: A Uranium Phosphorylated Binding‐Site Characterization

Herein, we describe the structural investigation of one possible uranyl binding site inside a nonstructured protein. This approach couples spectroscopy, thermodynamics, and theoretical calculations (DFT) and studies the interaction of uranyl ions with a phosphopeptide, thus mimicking a possible osteopontin (OPN) hydroxyapatite growth‐inhibition site. Although thermodynamical aspects were investigated by using time‐resolved laser fluorescence spectroscopy (TRLFS) and isothermal titration calorimetry (ITC), structural characterization was performed by extended X‐ray absorption fine structure (EXAFS) at the U L_III‐edge combined with attenuated total reflection Fourier transform infrared (ATR‐FTIR) spectroscopy. From the vibrational and fluorescence spectra, several structural models of a UO₂²⁺/peptide complex were developed and subsequently refined by using theoretical calculations to fit the experimental EXAFS obtained. The structural effect of the pH value was also considered under acidic to moderately acidic conditions (pH 1.5–5.5). Most importantly, the uranyl/peptide coordination environment was similar to that of the native protein.