Anomalous small-angle X-ray scattering from charged soft matter

A review of recent applications of Anomalous Small-Angle X-ray Scattering (ASAXS) to charged soft matter systems is presented. Although the potential of ASAXS was realized in the eighties [1], applications to soft matter systems became feasible in recent years thanks to the technical developments at the synchrotron sources. Examples include both stiff chain and flexible polyelectrolytes, colloidal brush-like polyelectrolytes, DNA, RNA, and polysaccharides where the counterion profile could be determined with high precision and compared with theoretical models. In addition, ASAXS has also been found useful for microstructure characterization in soft materials. Finally, the present capability for ASAXS studies is illustrated by an example involving a surfactant micellar system

Sum Rules for Multi-Photon Spectroscopy of Ions in Finite Symmetry

Models describing one- and two-photon transitions for ions in crystalline environments are unified and extended to the case of parity-allowed and parity- forbidden p-photon transitions. The number of independent parameters for characterizing the polarization dependence is shown to depend on an ensemble of properties and rules which combine symmetry considerations and physical models.Comment: 16 pages, Tex fil

Gradients of orientation, composition and hydration of proteins for efficient light collection by the cornea of the horseshoe crab

The lateral eyes of the horseshoe crab, Limulus polyphemus, are the largest compound eyes within recent Arthropoda. While this visual system has been extensively described before, the precise mechanism allowing vision has remained controversial. Correlating quantitative refractive index (RI) mapping and detailed structural analysis, we demonstrate how gradients of RI in the cornea result from the hierarchical organization of chitin-protein fibers, heterogeneity in protein composition and bromine doping, as well as spatial variation in water content. Combining the realistic cornea structure and measured RI gradients with full-wave optical modelling and ray-tracing approaches, we show that the light collection mechanism depends on both refraction-based graded index (GRIN) optics and total internal reflection. The optical properties of the cornea are governed by different mechanisms at different hierarchical levels, demonstrating the remarkable versatility of arthropod cuticle.One-sentence summary Structural hierarchy and protein hydration determine the optical performance of the cornea of L. polyphemus.Competing Interest StatementTS and MAKAR are employed by TELIGHT. All other authors declare that they have no competing interests

Impact of Crystal Structure and Particles Shape on the Photoluminescence Intensity of CdSe/CdS Core/Shell Nanocrystals

To study the influence of the chemical and crystalline composition of core/shell NCs on their photoluminescence (PL) the mean structural profile of a large ensemble of NCs has to be retrieved in atomic resolution. This can be achieved by retrieving the chemical profile of core/shell NCs using anomalous small angle x-ray scattering (ASAXS) in combination with the analysis of powder diffraction data recorded by wide angle x-ray scattering (WAXS). In the current synchrotron based study, we investigate CdSe/CdS core/shell NCs with different core dimensions by recording simultaneously ASAXS and WAXS spectra. The CdS shells are grown epitaxial on nominal spherical CdSe cores with core diameters from around 3.5–5.5 nm. Three different CdSe shell thicknesses are realized by depositing around 4, 6, and 8 monolayers (MLs) of CdSe. We reveal that the epitaxial core/shell structure depicts a chemical sharp interface, even after a post growth annealing step. With increasing NC diameter, however, the CdSe/CdS NCs deviate significantly from a spherical shape. Instead an elliptical particle shape with pronounced surface facets for the larger core/shell NCs is found. In combination with the powder diffraction data we could relate this anisotropic shape to a mixture of crystal phases within the CdSe core. The smallest CdSe cores exhibit a pure hexagonal wurtzite crystal structure, whereas the larger ones also possess a cubic zincblende phase fraction. This mixed crystal phase fractions lead to a non-spherical shell growth with different thicknesses along specific crystallographic directions: The long axes are terminated by basal crystal faces parallel either to the a- or c-axis, the short axes by “tilted” pyramidal planes. By combining these structural data with the measured PL quantum yield values, we can clearly connect the optical output of the NCs to their shape and to their shell thickness. Above 6 ML CdS shell-thickness no further increase of the PL can be observed, but for large aspect ratio values the PL is significantly decreased. The gained understanding of the internal crystal structure on CdSe/CdS NCs is general applicable for a precise tuning of the optical properties of crystalline core/shell NCs

Crystal Phase Transitions in the Shell of PbS CdS Core Shell Nanocrystals Influences Photoluminescence Intensity

ABSTRACT We reveal the existence of two different crystalline phases, i.e., the metastable rock salt and the equilibrium zinc blende phase within the CdS shell of PbS CdS core shell nanocrystals formed by cationic exchange. The chemical composition profile of the core shell nanocrystals with different dimensions is determined by means of anomalous small angle X ray scattering with subnanometer resolution and is compared to X ray diffraction analysis. We demonstrate that the photoluminescence emission of PbS nanocrystals can be drastically enhanced by the formation of a CdS shell. Especially, the ratio of the two crystalline phases in the shell significantly influences the photoluminescence enhancement. The highest emission was achieved for chemically pure CdS shells below 1 nm thickness with a dominant metastable rock salt phase fraction matching the crystal structure of the PbS core. The metastable phase fraction decreases with increasing shell thickness and increasing Exchange times. The photoluminescence intensity depicts a constant decrease with decreasing metastable rock salt phase fraction but Shows an abrupt drop for shells above 1.3 nm thickness. We relate this effect to two different transition mechanisms for changing from the metastable rock salt phase to the equilibrium zinc blende phase depending on the shell thicknes

Kinetic arrest and glass-glass transitions in short-ranged attractive colloids

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Microstructure and rheology near an attractive colloidal glass transition

International audienceMicrostructure and rheological properties of a thermally reversible short-ranged attractive colloidal system are studied in the vicinity of the attractive glass transition line. At high volume fractions, the static structure factor changes very little but the low frequency shear moduli varies over several orders of magnitude across the transition. From the frequency dependence of shear moduli, fluid-attractive glass and repulsive glass-attractive glass transitions are identified