Assemblies of 3.5 nm PbS nanoparticles (NPs) nucleate in three dominant superlattice polymorphs: amorphous, body-centered-cubic (bcc) and face-centered-cubic (fcc) phase. This superlattice relationship can be controlled by the inter-NP distance without changing the NP size. Upon increase of inter-NP distance, the packing density decreases, and the capping molecules at NP surfaces change in structure and accordingly modify the surface energy. The driving force for NP assembly develops from an entropic maximization to a reduction of total free energy through multiple interactions between surface molecules and NPs and resulting variation of surface molecules. Upon long-term aging and additional thermal treatment, fcc undergoes a tetragonal distortion and subsequently transforms to bcc phase, and simultaneously, the NPs embedded in supercrystals reduce surface energy primarily in {200} facets. Linking molecule-NP interactions with a series of changes of packing density and surface lattice spacings of NPs allows for an interpretation of principles governing the nucleation, structure stability, and transformation of PbS NP-assembled supercrystals.

Growing hypoxic and anoxic areas in coastal environments reduce fish habitat, but the interactions and impact on fish in these areas are poorly understood. Using "natural tag" properties of otoliths, we found significant correlations between the extent of Baltic Sea hypoxia and Mn/Ca ratios in regions of cod (Gadus morhua) otoliths corresponding to year 1 of life; this is associated with elevated bottom water dissolved manganese that increases with hypoxia. Elevated Mn/Ca ratios were also found in other years of life but with less frequency. We propose that cod exhibiting enhanced Mn/Ca ratios were exposed to dissolved manganese from hypoxia-induced redox dynamics in nursery areas. Neolithic (4500 B.P.) cod otoliths (n = 12) had low levels of Mn/Ca ratios, consistent with low hypoxia, but a single otolith dated to the younger Iron Age had a distinct growth band with an elevated Mn/Ca ratio. Sr/Ca patterns reflecting changes in environmental salinity and temperature were similar in both modern and Stone Age otoliths, indicating consistent migration habits across time, and Ba/Sr ratios in modern cod otoliths indicate increasing use of a more saline habitat with age. Using elemental ratios, numerous existing archival collections of otoliths could provide the means to reconstruct hypoxia exposure histories and major patterns of fish movement near "dead zones" globally.otolith chemistry | life-history tracers

The strain state of epitaxial La0.5Sr0.5MnO3 thin films on BaTiO3 are dynamically tuned by temperature and substrate bias. The resistivity of the La0.5Sr0.5MnO3 thin films is particularly sensitive to changes in structure. Fractional changes in magnetization and resistivity as a function of temperature reveal a direct correlation with fractional changes in the structure, as measured by out-of-plane x-ray diffraction. Fractional changes in resistivity, as large as 30%, are observed for strain induced by the structural phase transitions of the BaTiO3 substrate, and a 12% change is induced by an inverse piezoelectric effect at room temperature.

Pulsed laser deposition (PLD) of homoepitaxial SrTiO(3) 001 was studied with in situ x-ray specular reflectivity and surface diffuse x-ray scattering. Unlike prior reflectivity-based studies, these measurements access both time and length scales of the evolution of the surface morphology during growth. In particular, we show that this technique allows direct measurements of the diffusivity for both inter- and intralayer transport. Our results explicitly limit the possible role of island breakup, demonstrate the key roles played by nucleation and coarsening in PLD, and place an upper bound on the Ehrlich-Schwoebel barrier for downhill interlayer diffusion.

We grew SrTiO3 on SrTiO3 [001] by pulsed laser deposition, while observing x-ray diffraction at the (00 1 2 ) position. The drop ∆I in the x-ray intensity following a laser pulse contains information about plume-surface interactions. Kinematic theory predicts ∆I I = −4σ(1 − σ), so that ∆I I depends only on the amount of deposited material σ. In contrast, we observed experimentally that | ∆I I | < 4σ(1 − σ), and that ∆I I depends on the phase of x-ray growth oscillations. The combined results suggest a fast smoothing mechanism that depends on surface step-edge density.