Free charge carrier repartition over the surface of photosensitive materials: Why and how to manage?

The free charge carrier repartition over the surface of the photosensitive solids can be efficiently managed by selective elimination of the “parasite” free charge carriers (FCCs) from the exited body. This makes it possible to “correct” the natural FCC repartition law represented by the well-known fifty-fifty ratio (1 generated electron in conduction band versus 1 hole formed in valence band) and to better protect the FCCs against recombination. The chemical design principles of the FCC selective photo-generators (FCCP-Ss) were formulated. The functioning mechanism of the hole selective nanocomposite photo-generators (Sh⁺-FCCPs) was examined. This type of active materials generating mainly the most powerful oxidation agents (OH⁰ radicals) is suitable for application in oxidation photocatalysis, microbiological object sterilization, and self-cleaning surface development.     

57Fe Mössbauer spectra and magnetic data from the kagomé antiferromagnet H3O-jarosite

⁵⁷Fe Mössbauer spectra are presented from (H₃O)Fe₃(SO₄)₂(OH)₆ (or H₃O-jarosite), which is a model kagomé antiferromagnet which features geometrical frustration and spin-glass-like behaviour. Dynamic scaling of the freezing temperature as a function of frequency is observed over a large frequency range, which indicates the presence of a spin-glass transition. A fast relaxation model between “up” and “down” states, separated by an energy gap, is presented to account for the shape of the Mössbauer spectra below the freezing temperature. From a calculation of the Electric Field Gradient tensor, it is suggested that H₃O-jarosite is an XY-Heisenberg antiferromagnet, where the Fe³⁺ moments lie in the kagomé planes.     

Crystallization of polyamide confined in sub‐micrometer droplets dispersed in a molten polyethylene matrix

The crystallization of submicrometer PA6 droplets dispersed in an ethylene‐1‐octene copolymer matrix, using PE‐g‐MA as a compatibilizer agent, is investigated. This system shows a nonconventional mechanical behavior at high temperatures. Up to ～100 °C above the final melting temperature of the ethylene‐1‐octene copolymer matrix, the system shows good thermal and mechanical properties including dimensional stability. Because of the dispersed phase morphology of the system, so‐called fractionated/homogeneous crystallization takes place leading to an extra supercooling of PA6: ～50 °C compared to the bulk PA6 crystallization temperature. Thus—though this is most probably just of interest for small‐scale research—the system can be processed at lowered temperatures while still providing exceptional high‐temperature properties. While the matrix is in the melt state when crystallization of the dispersed PA6 phase occurs, the possibility of matrix induced crystallization is absent, contrary to almost all of the ‘dispersed droplets in a matrix’ systems reported so far. The kinetics of this phenomenon is investigated in detail by DSC: the existence of fractionated/homogeneous crystallization is shown to be related to the lack of active nuclei in the dispersed droplets by means of self‐seeding experiments. The occurrence of extensive cold crystallization of PA6 in the confined environment is studied as is the crystallization kinetics, including the characterization of its time dependences showing its sporadic nature. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 815–825, 2006     

Parallel extraction columns and parallel analytical columns coupled with liquid chromatography/tandem mass spectrometry for on-line simultaneous quantification of a drug candidate and its six metabolites in dog plasma.

A method with parallel extraction columns and parallel analytical columns (PEC-PAC) for on-line high-flow liquid chromatography/tandem mass spectrometry (LC/MS/MS) was developed and validated for simultaneous quantification of a drug candidate and its six metabolites in dog plasma. Two on-line extraction columns were used in parallel for sample extraction and two analytical columns were used in parallel for separation and analysis. The plasma samples, after addition of an internal standard solution, were directly injected onto the PEC-PAC system for purification and analysis. This method allowed the use of one of the extraction columns for analyte purification while the other was being equilibrated. Similarly, one of the analytical columns was employed to separate the analytes while the other was undergoing equilibration. Therefore, the time needed for re-conditioning both extraction and analytical columns was not added to the total analysis time, which resulted in a shorter run time and higher throughput. Moreover, the on-line column extraction LC/MS/MS method made it possible to extract and analyze all seven analytes simultaneously with good precision and accuracy despite their chemical class diversity that included primary, secondary and tertiary amines, an alcohol, an aldehyde and a carboxylic acid. The method was validated with the standard curve ranging from 5.00 to 5000 ng/mL. The intra- and inter-day precision was no more than 8% CV and the assay accuracy was between 95 and 107%.     

Photo‐Rheometry/NIR Spectrometry: An in situ Technique for Monitoring Conversion and Viscoelastic Properties during Photopolymerization

Summary: A suitable rheometer for simultaneous dynamic mechanical analysis (DMA) and NIR (Near Infra‐Red) in situ analysis during UV curing was developed. The conversion and viscoelastic properties of a dimethacrylate/styrene‐based system were investigated. The results were plotted against both irradiation time and total average conversion. For the same conversion, a lower intensity delays the reaction but does not affect the viscoelastic properties.

A device for simultaneous photo‐rheology and NIR spectroscopy experiments.     

The crystalline state as a dynamic system: IR microspectroscopy under electrochemical control for a [NiFe] hydrogenase

Controlled formation of catalytically-relevant states within crystals of complex metalloenzymes represents a significant challenge to structure–function studies. Here we show how electrochemical control over single crystals of [NiFe] hydrogenase 1 (Hyd1) from Escherichia coli makes it possible to navigate through the full array of active site states previously observed in solution. Electrochemical control is combined with synchrotron infrared microspectroscopy, which enables us to measure high signal-to-noise IR spectra in situ from a small area of crystal. The output reports on active site speciation via the vibrational stretching band positions of the endogenous CO and CN⁻ ligands at the hydrogenase active site. Variation of pH further demonstrates how equilibria between catalytically-relevant protonation states can be deliberately perturbed in the crystals, generating a map of electrochemical potential and pH conditions which lead to enrichment of specific states. Comparison of in crystallo redox titrations with measurements in solution or of electrode-immobilised Hyd1 confirms the integrity of the proton transfer and redox environment around the active site of the enzyme in crystals. Slowed proton-transfer equilibria in the hydrogenase in crystallo reveals transitions which are only usually observable by ultrafast methods in solution. This study therefore demonstrates the possibilities of electrochemical control over single metalloenzyme crystals in stabilising specific states for further study, and extends mechanistic understanding of proton transfer during the [NiFe] hydrogenase catalytic cycle.

Electrochemically-coupled IR microspectroscopy of single crystals provides insight into proton-coupled electron transfer in [NiFe] hydrogenase.     

Numerical Prediction of Two-Phase Flow through a Tube Bundle Based on Reduced-Order Model and a Void Fraction Correlation

Predicting the void fraction of a two-phase flow outside of tubes is essential to evaluate the thermohydraulic behaviour in steam generators. Indeed, it determines two-phase mixture properties and affects two-phase mixture velocity, which enable evaluating the pressure drop of the system. The two-fluid model for the numerical simulation of two-phase flows requires interaction laws between phases which are not known and/or reliable for a flow within a tube bundle. Therefore, the mixture model, for which it is easier to implement suitable correlations for tube bundles, is used. Indeed, by expressing the relative velocity as a function of slip, the void fraction model of Feenstra et al. and Hibiki et al. developed for upward cross-flow through horizontal tube bundles is introduced and compared. With the method suggested in this paper, the physical phenomena that occur in tube bundles are taken into consideration. Moreover, the tube bundle is modelled using a porous media approach where the Darcy–Forchheimer term is usually defined by correlations found in the literature. However, for some tube bundle geometries, these correlations are not available. The second goal of the paper is to quickly compute, in quasi-real-time, this term by a non-intrusive parametric reduced model based on Proper Orthogonal Decomposition. This method, named Bi-CITSGM (Bi-Calibrated Interpolation on the Tangent Subspace of the Grassmann Manifold), consists in interpolating the spatial and temporal bases by ITSGM (Interpolation on the Tangent Subspace of the Grassmann Manifold) in order to define the solution for a new parameter. The two developed methods are validated based on the experimental results obtained by Dowlati et al. for a two-phase cross-flow through a horizontal tube bundle.     

Kinetic resolution of sulfur-stereogenic sulfoximines by Pd(ii)–MPAA catalyzed C–H arylation and olefination

A direct Pd(ii)-catalyzed kinetic resolution of heteroaryl-enabled sulfoximines through an ortho-C–H alkenylation/arylation of arenes has been developed. The coordination of the sulfoximine pyridyl-motif and the chiral amino acid MPAA ligand to the Pd(ii)-catalyst controls the enantio-discriminating C(aryl)–H activation. This method provides access to a wide range of enantiomerically enriched unreacted aryl-pyridyl-sulfoximine precursors and C(aryl)–H alkenylation/arylation products in good yields with high enantioselectivity (up to >99% ee), and selectivity factor up to >200. The coordination preference of the directing group, ligand effect, geometry constraints, and the transient six-membered concerted-metalation–deprotonation species dictate the stereoselectivity; DFT studies validate this hypothesis.

A Pd/MPAA catalysed KR of heteroaryl substituted sulfoximines through C–H alkenylation and arylation (up to >99% ee) is developed. In-depth DFT studies uncover the salient features.