Experimental Characterization of Defect-Induced Phonon Lifetime Shortening.

We present the first direct experimental measurement of defect-induced lifetime shortening of acoustic surface phonons. Defects are found to contribute a temperature-independent component to the linewidths of Rayleigh wave phonons on a Ni(111) surface. We also characterized the increase in phonon scattering with both surface defect density and phonon wave vector. A quantitative estimate of the scattering rate between phonon modes and surface line defects is extracted from the experimental data for the first time.

Single-molecular diffusivity and long jumps of large organic molecules: CoPc on Ag(100).

Energy dissipation and the transfer rate of adsorbed molecules do not only determine the rates of chemical reactions but are also a key factor that often dictates the growth of organic thin films. Here, we present a study of the surface dynamical motion of cobalt phthalocyanine (CoPc) on Ag(100) in reciprocal space based on the helium spin-echo technique in comparison with previous scanning tunnelling microscopy studies. It is found that the activation energy for lateral diffusion changes from 150 meV at 45-50 K to ≈100 meV at 250-350 K, and that the process goes from exclusively single jumps at low temperatures to predominantly long jumps at high temperatures. We thus illustrate that while the general diffusion mechanism remains similar, upon comparing the diffusion process over widely divergent time scales, indeed different jump distributions and a decrease of the effective diffusion barrier are found. Hence a precise molecular-level understanding of dynamical processes and thin film formation requires following the dynamics over the entire temperature scale relevant to the process. Furthermore, we determine the diffusion coefficient and the atomic-scale friction of CoPc and establish that the molecular motion on Ag(100) corresponds to a low friction scenario as a consequence of the additional molecular degrees of freedom.

2D Helium Atom Diffraction from a Microscopic Spot.

A method for measuring helium atom diffraction with micron-scale spatial resolution is demonstrated in a scanning helium microscope (SHeM) and applied to study a micron-scale spot on the (100) plane of a lithium fluoride (LiF) crystal. The positions of the observed diffraction peaks provide an accurate measurement of the local lattice spacing, while a combination of close-coupled scattering calculations and Monte Carlo ray-tracing simulations reproduce the main variations in diffracted intensity. Subsequently, the diffraction results are used to enhance image contrast by measuring at different points in reciprocal space. The results open up the possibility for using helium microdiffraction to characterize the morphology of delicate or electron-sensitive materials on small scales. These include many fundamentally and technologically important samples which cannot be studied in conventional atom scattering instruments, such as small grain size exfoliated 2D materials, polycrystalline samples, and other surfaces that do not exhibit long-range order.

Evolution, diversity, and disparity of the tiger shark lineage Galeocerdo in deep time.

Sharks have a long and rich fossil record that consists predominantly of isolated teeth due to the poorly mineralized cartilaginous skeleton. Tiger sharks (Galeocerdo), which represent apex predators in modern oceans, have a known fossil record extending back into the early Eocene (ca. 56 Ma) and comprise 22 recognized extinct and one extant species to date. However, many of the fossil species remain dubious, resulting in a still unresolved evolutionary history of the tiger shark genus. Here, we present a revision of the fossil record of Galeocerdo by examining the morphological diversity and disparity of teeth in deep time. We use landmark-based geometric morphometrics to quantify tooth shapes and qualitative morphological characters for species discrimination. Employing this combined approach on fossil and extant tiger shark teeth, our results only support six species to represent valid taxa. Furthermore, the disparity analysis revealed that diversity and disparity are not implicitly correlated and that Galeocerdo retained a relatively high dental disparity since the Miocene despite its decrease from four to one species. With this study, we demonstrate that the combined approach of quantitative geometric morphometric techniques and qualitative morphological comparisons on isolated shark teeth provides a useful tool to distinguish between species with highly similar tooth morphologies.

Motion of water monomers reveals a kinetic barrier to ice nucleation on graphene.

The interfacial behaviour of water remains a central question to fields as diverse as protein folding, friction and ice formation. While the properties of water at interfaces differ from those in the bulk, major gaps in our knowledge limit our understanding at the molecular level. Information concerning the microscopic motion of water comes mostly from computation and, on an atomic scale, is largely unexplored by experiment. Here, we provide a detailed insight into the behaviour of water monomers on a graphene surface. The motion displays remarkably strong signatures of cooperative behaviour due to repulsive forces between the monomers, enhancing the monomer lifetime ( ≈ 3 s at 125 K) in a free-gas phase that precedes the nucleation of ice islands and, in turn, provides the opportunity for our experiments to be performed. Our results give a molecular perspective on a kinetic barrier to ice nucleation, providing routes to understand and control the processes involved in ice formation.

Inter-adsorbate forces and coherent scattering in helium spin-echo experiments.

In studies of dynamical systems, helium atoms scatter coherently from an ensemble of adsorbates as they diffuse on the surface. The results give information on the co-operative behaviour of interacting adsorbates and thus include the effects of both adsorbate-substrate and adsorbate-adsorbate interactions. Here, we discuss a method to disentangle the effects of interactions between adsorbates from those with the substrate. The result gives an approximation to observations that would be obtained if the scattering was incoherent. Information from the experiment can therefore be used to distinguish more clearly between long-range inter-adsorbate forces and the short range effects arising from the local lattice potential and associated thermal excitations. The method is discussed in the context of a system with strong inter-adsorbate interactions, sodium atoms diffusing on a copper (111) surface.

Alkali metal adsorption on metal surfaces: new insights from new tools.

The adsorption of sodium on Ru(0001) is studied using 3He spin-echo spectroscopy (HeSE), molecular dynamics simulations (MD) and density functional theory (DFT). In the multi-layer regime, an analysis of helium reflectivity, gives an electron-phonon coupling constant of λ = 0.64 ± 0.06. At sub-monolayer coverage, DFT calculations show that the preferred adsorption site changes from hollow site to top site as the supercell increases and the effective coverage, θ, is reduced from 0.25 to 0.0625 adsorbates per substrate atom. Energy barriers and adsorption geometries taken from DFT are used in molecular dynamics calculations to generate simulated data sets for comparison with measurements. We introduce a new Bayesian method of analysis that compares measurement and model directly, without assuming analytic lineshapes. The value of adsorbate-substrate energy exchange rate (friction) in the MD simulation is the sole variable parameter. Experimental data at a coverage θ = 0.028 compares well with the low-coverage DFT result, giving an effective activation barrier Eeff = 46 ± 4 meV with a friction γ = 0.3 ps-1. Better fits to the data can be achieved by including additional variable parameters, but in all cases, the mechanism of diffusion is predominantly on a Bravais lattice, suggesting a single adsorption site in the unit cell, despite the close packed geometry.

Micro-computed tomography imaging reveals the development of a unique tooth mineralization pattern in mackerel sharks (Chondrichthyes; Lamniformes) in deep time.

The cartilaginous fishes (Chondrichthyes) have a rich fossil record which consists mostly of isolated teeth and, therefore, phylogenetic relationships of extinct taxa are mainly resolved based on dental characters. One character, the tooth histology, has been examined since the 19th century, but its implications on the phylogeny of Chondrichthyes is still in debate. We used high resolution micro-CT images and tooth sections of 11 recent and seven extinct lamniform sharks to examine the tooth mineralization processes in this group. Our data showed similarities between lamniform sharks and other taxa (a dentinal core of osteodentine instead of a hollow pulp cavity), but also one feature that has not been known from any other elasmobranch fish: the absence of orthodentine. Our results suggest that this character resembles a synapomorphic condition for lamniform sharks, with the basking shark, Cetorhinus maximus, representing the only exception and reverted to the plesiomorphic tooth histotype. Additionally, †Palaeocarcharias stromeri, whose affiliation still is debated, shares the same tooth histology only known from lamniform sharks. This suggests that †Palaeocarcharias stromeri is member of the order Lamniformes, contradicting recent interpretations and thus, dating the origin of this group back at least into the Middle Jurassic.

A middle - late Eocene neoselachian assemblage from nearshore marine deposits, Mahajanga Basin, northwestern Madagascar.

We report here the first neoselachian fossil fauna from Eocene nearshore marine deposits of the Mahajanga Basin, northwestern Madagascar. The fauna includes seven species of shark: Nebrius blankenhorni, Brachycarcharias koerti, Galeocerdo eaglesomei, two species of Carcharhinus (one of which is described as a new species), Physogaleus, Rhizoprionodon and Sphyrna. Three species of rays were also recovered: Pristis, Myliobatis and an undetermined dasyatid ray. This fauna represents the first Cenozoic neoselachian fossil record from the Eocene of Madagascar and broadens our understanding of their evolutionary and biogeographic history in the southern hemisphere during this time. Although the diversity of the genera and species of the fauna is very low, the age and similarity of genera to those in Congo, west Africa, Arabia, Asia, Europe, and North, Central, and South America suggests that these genera were broadly distributed and diverse within the shallow marine settings of the Tethyan and southern provinces during middle and late Eocene.

On the need of providing tooth morphology in descriptions of extant elasmobranch species.

Elasmobranchii is a clade of chondrichthyans (cartilaginous fishes) that comprises sharks, skates and rays represented today by approximately 1,200 species. Chondrichthyans have a long evolutionary history dating back to the Late Ordovician (ca. 450 million years ago [Mya]) based on isolated dermal denticles (Janvier 1996). Other remains such as articulated skeletons and teeth are known from the Lower Devonian (ca. 410 Mya: Mader 1986; Miller et al. 2003). The fossil record of modern elasmobranchs (Neoselachii) can be traced back to the Early Permian (ca. 290 Mya) and is represented by isolated teeth (Ivanov 2005), with fossils of crown group sharks and rays appearing in Lower Jurassic (ca. 200 Mya) rocks (e.g., Cappetta 2012). Since their appearance in the geological record, elasmobranchs are mainly represented by isolated teeth, whereas articulated skeletons are very rare and restricted to a small number of fossil localities (e.g., Cappetta 2012). The scarcity of skeletal remains in their fossil record is due to their poorly mineralized cartilaginous skeleton that requires special taphonomical conditions to be preserved. Elasmobranch teeth, in contrast, are composed of highly mineralized tissues (hydroxyapatite) that have a strong preservation potential (Shimada 2006). In addition, elasmobranchs replace their teeth continuously over the course of their life span (polyphyodonty) and therefore shed thousands of teeth in their lifetime (Reif et al. 1978; Schnetz et al. 2016) leading to large numbers of potential fossils. These morphologically highly diverse isolated teeth constitute much of the rich fossil record of elasmobranchs, and largely form the basis of our understanding of elasmobranch diversity and evolution through geological time.

Tooth mineralization and histology patterns in extinct and extant snaggletooth sharks, Hemipristis (Carcharhiniformes, Hemigaleidae)-Evolutionary significance or ecological adaptation?

Shark jaws exhibit teeth that are arranged into distinct series and files and display great diversities in shapes and structures, which not only is related to their function (grasping, cutting, crushing) during feeding, but also bear a strong phylogenetic signal. So far, most research on the relationship between shark teeth and feeding ecology and systematics focused on the external tooth morphology only. Although the tooth histology of sharks has been examined since the early 19th century, its functional and systematic implications are still ambiguous. Shark teeth normally consist of either a porous, cellular dentine, osteodentine (in lamniform sharks and some batoids) or a dense layer of orthodentine (known from different sharks). Sharks of the order Carcharhiniformes, comprising ca. 60% of all extant shark species, are known to have orthodont teeth, with a single exception-the snaggletooth shark, Hemipristis elongata. High resolution micro-CT images of jaws and teeth from selected carcharhiniform sharks (including extant and fossil snaggletooth sharks) and tooth sections of teeth of Hemipristis, other carcharhiniform and lamniform sharks, have revealed that (1) Hemipristis is indeed the only carcharhiniform shark filling its pulp cavity with osteodentine in addition to orthodentine, (2) the tooth histology of Hemipristis elongata differs from the osteodont histotype, which evolved in lamniform sharks and conversely represents a modified orthodonty, and (3) this modified orthodonty was already present in extinct Hemipristis species but the mineralization sequence has changed over time. Our results clearly show the presence of a third tooth histotype-the pseudoosteodont histotype, which is present in Hemipristis. The unique tooth histology of lamniform sharks might provide a phylogenetic signal for this group, but more research is necessary to understand the phylogenetic importance of tooth histology in sharks in general.

Potent and Highly Selective Inhibitors of the Proteasome Trypsin-like Site by Incorporation of Basic Side Chain Containing Amino Acid Derived Sulfonyl Fluorides.

A unique category of basic side chain containing amino acid derived sulfonyl fluorides (SFs) has been synthesized for incorporation into new proteasome inhibitors targeting the trypsin-like site of the 20S proteasome. Masking the former α-amino functionality of the amino acid starting derivatives as an azido functionality allowed an elegant conversion to the corresponding amino acid derived sulfonyl fluorides. The inclusion of different SFs at the P1 site of a proteasome inhibitor resulted in 14 different peptidosulfonyl fluorides (PSFs) having a high potency and an excellent selectivity for the proteolytic activity of the ß2 subunit over that of the ß5 subunit. The results of this study strongly indicate that a free N-terminus of PSFs inhibitors is crucial for high selectivity toward the trypsin-like site of the 20S proteasome. Nevertheless, all compounds are slightly more selective for inhibition of the constitutive over the immunoproteasome.

Polarisation in spin-echo experiments: Multi-point and lock-in measurements.

Spin-echo instruments are typically used to measure diffusive processes and the dynamics and motion in samples on ps and ns time scales. A key aspect of the spin-echo technique is to determine the polarisation of a particle beam. We present two methods for measuring the spin polarisation in spin-echo experiments. The current method in use is based on taking a number of discrete readings. The implementation of a new method involves continuously rotating the spin and measuring its polarisation after being scattered from the sample. A control system running on a microcontroller is used to perform the spin rotation and to calculate the polarisation of the scattered beam based on a lock-in amplifier. First experimental tests of the method on a helium spin-echo spectrometer show that it is clearly working and that it has advantages over the discrete approach, i.e., it can track changes of the beam properties throughout the experiment. Moreover, we show that real-time numerical simulations can perfectly describe a complex experiment and can be easily used to develop improved experimental methods prior to a first hardware implementation.

Mass Transport in Surface Diffusion of van der Waals Bonded Systems: Boosted by Rotations?

Mass transport at a surface is a key factor in heterogeneous catalysis. The rate is determined by excitation across a translational barrier and depends on the energy landscape and the coupling to the thermal bath of the surface. Here we use helium spin-echo spectroscopy to track the microscopic motion of benzene adsorbed on Cu(001) at low coverage (θ ∼ 0.07 ML). Specifically, our combined experimental and computational data determine both the absolute rate and mechanism of the molecular motion. The observed rate is significantly higher by a factor of 3.0 ± 0.1 than is possible in a conventional, point-particle model and can be understood only by including additional molecular (rotational) coordinates. We argue that the effect can be described as an entropic contribution that enhances the population of molecules in the transition state. The process is generally relevant to molecular systems and illustrates the importance of the pre-exponential factor alongside the activation barrier in studies of surface kinetics.

Energy Dissipation during Diffusion at Metal Surfaces: Disentangling the Role of Phonons versus Electron-Hole Pairs.

Helium spin echo experiments combined with ab initio based Langevin molecular dynamics simulations are used to quantify the adsorbate-substrate coupling during the thermal diffusion of Na atoms on Cu(111). An analysis of trajectories within the local density friction approximation allows the contribution from electron-hole pair excitations to be separated from the total energy dissipation. Despite the minimal electronic friction coefficient of Na and the relatively small mass mismatch to Cu promoting efficient phononic dissipation, about (20±5)% of the total energy loss is attributable to electronic friction. The results suggest a significant role of electronic nonadiabaticity in the rapid thermalization generally relied upon in adiabatic diffusion theories.

Coupling between diffusion and orientation of pentacene molecules on an organic surface.

The realization of efficient organic electronic devices requires the controlled preparation of molecular thin films and heterostructures. As top-down structuring methods such as lithography cannot be applied to van der Waals bound materials, surface diffusion becomes a structure-determining factor that requires microscopic understanding. Scanning probe techniques provide atomic resolution, but are limited to observations of slow movements, and therefore constrained to low temperatures. In contrast, the helium-3 spin-echo (HeSE) technique achieves spatial and time resolution on the nm and ps scale, respectively, thus enabling measurements at elevated temperatures. Here we use HeSE to unveil the intricate motion of pentacene admolecules diffusing on a chemisorbed monolayer of pentacene on Cu(110) that serves as a stable, well-ordered organic model surface. We find that pentacene moves along rails parallel and perpendicular to the surface molecules. The experimental data are explained by admolecule rotation that enables a switching between diffusion directions, which extends our molecular level understanding of diffusion in complex organic systems.

Miocene Shark and Batoid Fauna from Nosy Makamby (Mahajanga Basin, Northwestern Madagascar).

Madagascar is well known for producing exceptional fossils. However, the record for selachians remains relatively poorly known. Paleontological reconnaissance on the island of Nosy Makamby, off northwest Madagascar, has produced a previously undescribed assemblage of Miocene fossils. Based on isolated teeth, ten taxonomic groups are identified: Otodus, Carcharhinus, Galeocerdo, Rhizoprionodon, Sphyrna, Hemipristis, Squatina, Rostroraja, Himantura and Myliobatidae. Six are newly described from Madagascar for the Cenozoic (Galeocerdo, Rhizoprionodon, Sphyrna, Squatina, Rostroraja and Himantura). In association with these specimens, remains of both invertebrates (e.g., corals, gastropods, bivalves) and vertebrates (e.g., bony fish, turtles, crocodylians, and sirenian mammals) were also recovered. The sedimentary facies are highly suggestive of a near-shore/coastal plain depositional environment. This faunal association shares similarities to contemporaneous sites reported from North America and Europe and gives a glimpse into the paleoenvironment of Madagascar's Miocene, suggesting that this region was warm, tropical shallow-water marine.

Design of experiments to optimize an in vitro cast to predict human nasal drug deposition.

BACKGROUND: Previous studies showed nasal spray in vitro tests cannot predict in vivo deposition, pharmacokinetics, or pharmacodynamics. This challenge makes it difficult to assess deposition achieved with new technologies delivering to the therapeutically beneficial posterior nasal cavity. In this study, we determined best parameters for using a regionally divided nasal cast to predict deposition. Our study used a model suspension and a design of experiments to produce repeatable deposition results that mimic nasal deposition patterns of nasal suspensions from the literature. METHODS: The seven-section (the nozzle locator, nasal vestibule, front turbinate, rear turbinate, olfactory region, nasopharynx, and throat filter) nylon nasal cast was based on computed tomography images of healthy humans. It was coated with a glycerol/Brij-35 solution to mimic mucus. After assembling and orienting, airflow was applied and nasal spray containing a model suspension was sprayed. After disassembling the cast, drug depositing in each section was assayed by HPLC. The success criteria for optimal settings were based on nine in vivo studies in the literature. The design of experiments included exploratory and half factorial screening experiments to identify variables affecting deposition (angles, airflow, and airflow time), optimization experiments, and then repeatability and reproducibility experiments. RESULTS: We found tilt angle and airflow time after actuation affected deposition the most. The optimized settings were flow rate of 16 L/min, postactuation flow time of 12 sec, a tilt angle of 23°, nozzle angles of 0°, and actuation speed of 5 cm/sec. Neither cast nor operator caused significant variation of results. CONCLUSION: We determined cast parameters to produce results resembling suspension nasal sprays in the literature. The results were repeatable and unaffected by operator or cast. These nasal spray parameters could be used to assess deposition from new devices or formulations. For human deposition studies using radiolabeled formulations, this cast could show that radiolabel deposition represents drug deposition. Our methods could also be used to optimize settings for other casts.