Reef-building corals and their aragonite (CaCO3) skeletons support entire reef ecosystems, yet their formation mechanism is poorly understood. Here we used synchrotron spectromicroscopy to observe the nanoscale mineralogy of fresh, forming skeletons from six species spanning all reef-forming coral morphologies: Branching, encrusting, massive, and table. In all species, hydrated and anhydrous amorphous calcium carbonate nanoparticles were precursors for skeletal growth, as previously observed in a single species. The amorphous precursors here were observed in tissue, between tissue and skeleton, and at growth fronts of the skeleton, within a low-density nano- or microporous layer varying in thickness from 7 to 20 µm. Brunauer-Emmett-Teller measurements, however, indicated that the mature skeletons at the microscale were space-filling, comparable to single crystals of geologic aragonite. Nanoparticles alone can never fill space completely, thus ion-by-ion filling must be invoked to fill interstitial pores. Such ion-by-ion diffusion and attachment may occur from the supersaturated calcifying fluid known to exist in corals, or from a dense liquid precursor, observed in synthetic systems but never in biogenic ones. Concomitant particle attachment and ion-by-ion filling was previously observed in synthetic calcite rhombohedra, but never in aragonite pseudohexagonal prisms, synthetic or biogenic, as observed here. Models for biomineral growth, isotope incorporation, and coral skeletons’ resilience to ocean warming and acidification must take into account the dual formation mechanism, including particle attachment and ion-by-ion space filling.

We use tunable, vacuum ultraviolet laser-based angle-resolved photoemission spectroscopy and density functional theory calculations to study the electronic properties of Dirac semimetal candidate cubic PtBi2. In addition to bulk electronic states we also find surface states in PtBi2 which is expected as PtBi2 was theoretical predicated to be a candidate Dirac semimetal. The surface states are also well reproduced from DFT band calculations. Interestingly, the topological surface states form Fermi contours rather than double Fermi arcs that were observed in Na3Bi. The surface bands forming the Fermi contours merge with bulk bands in proximity of the Dirac points projections, as expected. Our data confirms existence of Dirac states in PtBi2 and reveals the fragility of the Fermi arcs in Dirac semimetals. Because the Fermi arcs are not topologically protected in general, they can be deformed into Fermi contours, as proposed by [Kargarian et al., PNAS 113, 8648 (2016)].Our results demonstrate validity of this theory in PtBi2. arXiv:1904.03138v1 [cond-mat.mtrl-sci]

The mature skeletons of hard corals, termed stony or scleractinian corals, are made of aragonite (CaCO 3 ). During their formation, particles attaching to the skeleton's growing surface are calcium carbonate, transiently amorphous. Here we show that amorphous particles are observed frequently and reproducibly just outside the skeleton, where a calicoblastic cell layer envelops and deposits the forming skeleton. The observation of particles in these locations, therefore, is consistent with nucleation and growth of particles in intracellular vesicles. The observed extraskeletal particles range in size between 0.2 and 1.0 μm and contain more of the amorphous precursor phases than the skeleton surface or bulk, where they gradually crystallize to aragonite. This observation was repeated in three diverse genera of corals, Acropora sp., Stylophora pistillatadifferently sensitive to ocean acidification (OA)and Turbinaria peltata, demonstrating that intracellular particles are a major source of material during the additive manufacturing of coral skeletons. Thus, particles are formed away from seawater, in a presumed intracellular calcifying fluid (ICF) in closed vesicles and not, as previously assumed, in the extracellular calcifying fluid (ECF), which, unlike ICF, is partly open to seawater. After particle attachment, the growing skeleton surface remains exposed to ECF, and, remarkably, its crystallization rate varies significantly across genera. The skeleton surface layers containing amorphous pixels vary in thickness across genera: ∼2.1 μm in Acropora, 1.1 μm in Stylophora, and 0.9 μm in Turbinaria. Thus, the slowcrystallizing Acropora skeleton surface remains amorphous and soluble longer, including overnight, when the pH in the ECF drops. Increased skeleton surface solubility is consistent with Acropora's vulnerability to OA, whereas the Stylophora skeleton surface layer crystallizes faster, consistent with Stylophora's resilience to OA. Turbinaria, whose response to OA has not yet been tested, is expected to be even more resilient than Stylophora, based on the present data.

Glycine, the simplest amino acid, is considered a promising functional biomaterial owing to its excellent biocompatibil-ity and strong out-of-plane piezoelectricity. Practical applications require glycine films to be manufactured with their...