Sub‐microsecond‐resolved multi‐speckle X‐ray photon correlation spectroscopy with a pixel array detector

Small‐angle X‐ray photon correlation spectroscopy (XPCS) measurements spanning delay times from 826 ns to 52.8 s were performed using a photon‐counting pixel array detector with a dynamic range of 0–3 (2 bits). Fine resolution and a wide dynamic range of time scales was achieved by combining two modes of operation of the detector: (i) continuous mode, where data acquisition and data readout are performed in parallel with a frame acquisition time of 19.36 µs, and (ii) burst mode, where 12 frames are acquired with frame integration times of either 2.56 µs frame^?1 or 826 ns frame^?1 followed by 3.49 ms or 1.16 ms, respectively, for readout. The applicability of the detector for performing multi‐speckle XPCS was demonstrated by measuring the Brownian dynamics of 10 nm‐radius gold and 57 nm‐radius silica colloids in water at room temperature. In addition, the capability of the detector to faithfully record one‐ and two‐photon counts was examined by comparing the statistical distribution of photon counts with expected probabilities from the negative binomial distribution. It was found that in burst mode the ratio of 2 s to 1 s is markedly smaller than predicted and that this is attributable to pixel‐response dead‐time.     

Palladium-catalyzed coupling of pyrazole triflates with arylboronic acids

[reaction: see text] A general protocol for the palladium-mediated Suzuki coupling reaction of pyrazole triflates and aryl boronic acids has been developed. The use of additional dppf ligand was determined to increase product yields allowing for the use of a broad range of reaction substrates.     

Molecular Mixed‐Metal Manganese Oxido Cubanes as Precursors to Heterogeneous Oxygen Evolution Catalysts

Well‐defined mixed‐metal [CoMn₃O₄] and [NiMn₃O₄] cubane complexes were synthesized and used as precursors for heterogeneous oxygen evolution reaction (OER) electrocatalysts. The discrete clusters were dropcasted onto glassy carbon (GC) and indium tin oxide (ITO) electrodes, and the OER activities of the resulting films were evaluated. The catalytic surfaces were analyzed by various techniques to gain insight into the structure‐function relationships of the electrocatalysts’ heterometallic composition. Depending on preparation conditions, the Co‐Mn oxide was found to change metal composition during catalysis, while the Ni–Mn oxides maintained the NiMn₃ ratio. XAS studies provided structural insights indicating that the electrocatalysts are different from the molecular precursors, but that the original NiMn₃O₄ cubane‐like geometry was maintained in the absence of thermal treatment ( 2‐Ni ). In contrast, the thermally generated 3‐Ni develops an oxide‐like extended structure. Both 2‐Ni and 3‐Ni undergo structural changes upon electrolysis, but they do not convert into the same material. The observed structural motifs in these heterogeneous electrocatalysts are reminiscent of the biological oxygen‐evolving complex in Photosystem II, including the MMn₃O₄ cubane moiety. The reported studies demonstrate the use of discrete heterometallic oxide clusters as precursors for heterogeneous water oxidation catalysts of novel composition and the distinct behavior of two sets of mixed metal oxides.     

NMR of human saliva protein/wine tannin complexes. Towards deciphering astringency with physico-chemical tools

In the present work, we used NMR (chemical shift variations and diffusion measurement) to determine the affinity and the number of sites of four different 4-8 procyanidin dimers for a model PRP peptide. A number of three binding sites has been identified for every tannin, but significant affinity differences are highlighted from one to another dimer (a factor 10 approximately) that could be related to their specific 3D-structure.     

Relationship between structural and stress relaxation in a block-copolymer melt

The relationship between structural relaxation on molecular length scales and macroscopic stress relaxation was explored in a disordered block-copolymer melt. Experiments show that the structural relaxation time, measured by x-ray photon correlation spectroscopy is larger than the terminal stress relaxation time, measured by rheology, by factors as large as 100. We demonstrate that the structural relaxation data are dominated by the diffusion of intact micelles while the stress relaxation data are dominated by contributions due to disordered concentration fluctuations.     

Estimation of surface snow properties using combined millimeter-wave backscatter and near-infrared reflectance measurements

Knowledge of surficial snow properties such as grain size, surface roughness, and free-water content provides clues to the metamorphic state of snow on the ground, which in turn yields information on weathering processes and climatic activity. Remote sensing techniques using combined concurrent measurements of near-infrared passive reflectance and millimeter-wave radar backscatter show promise in estimating the above snow parameters. Near-infrared reflectance is strongly dependent on snow grain size and free-water content, while millimeter-wave backscatter is primarily dependent on free-water content and, to some extent, on the surface roughness. A neural-network based inversion algorithm has been developed that optimally combines near-infrared and millimeter-wave measurements for accurate estimation of the relevant snow properties. The algorithm uses reflectances at wavelengths of 1160 nm, 1260 nm and 1360 nm, as well as co-polarized and cross-polarized backscatter at a frequency of 95 GHz. The inversion algorithm has been tested using simulated data, and is seen to perform well under noise-free conditions. Under noise-added conditions, a signal-to-noise ratio of 32 dB or greater ensures acceptable errors in snow parameter estimation.