Seis-ing up the Super-Morrison formation sauropods.

The Upper Jurassic Morrison Formation sauropods Diplodocus (formerly "Seismosaurus") hallorum and Supersaurus vivianae are quantifiably the largest dinosaurian taxa from the formation, as well as being among the largest dinosaurs in the world. Their extreme body size (in particular body length, c. 50+ m) has fascinated the paleontological community since their discoveries and has sparked an ongoing discussion on the trends and limits of Morrison Formation sauropod body size. Although not an undeviating proxy, often the largest and skeletally most mature specimens are among the rarest (as exemplified in Triceratops). While their body size has no phylogenetic bearing, the extreme size and potential eco and biological significance of these two sauropod taxa are frequently discussed. Whether these rare and titanically proportioned sauropod specimens are large-bodied, senescent or both is an often-repeating rhetoric. To definitively make maturational inferences about these taxa, we osteohistologically sampled the holotype of D. hallorum (NMMNH P-25079) and the second known specimen of S. vivianae (WDC DMJ-021). Our age-determinant and maturational assessments indicate that both specimens were skeletally mature at their respective age of death. Retrocalculation methods for D. hallorum NMMNH P-25079 produce a maximum age-at-death estimation of 60 years, whereas S. vivianae WDC DMJ-021 lived well past skeletal maturity-so much so that reliable retrocalculated ages cannot be accurately determined at this time. Additionally, the rarity of such large sauropods within the Morrison Formation might be more parsimoniously explained as relating to their maturity as opposed to representing aberrant taxa on the Morrison landscape.

Direct measurement of Ni incorporation into Fe3O4(001).

The normal incidence X-ray standing wave (NIXSW) technique has been used to follow the evolution of the adsorption geometry of Ni adatoms on the Fe3O4(001)-(√2 × âˆš2)R45° surface as a function of temperature. Two primary surface region sites are identified: a bulk-continuation tetrahedral site and a sub-surface octahedral site, the latter site being preferred at higher annealing temperatures. The ease of incorporation is linked to the presence of subsurface cation vacancies in the (√2 × âˆš2)R45° reconstruction and is consistent with the preference for octahedral coordination observed in the spinel compound NiFe2O4.

Probing the interplay between geometric and electronic structure in a two-dimensional K-TCNQ charge transfer network.

Scanning tunnelling microscopy (STM), low energy electron diffraction (LEED), ultraviolet and soft X-ray photoelectron spectroscopy (UPS and SXPS) have been used to characterise the formation of a coadsorption phase of TCNQ and K on Ag(111), while the normal incident X-ray standing waves (NIXSW) technique has been used to obtain quantitative structural information. STM and LEED show that an ordered incommensurate phase is formed in which the K atoms are surrounded by four TCNQ molecules in a 'windmill' motif, characteristic of other metal/TCNQ phases, in which the nominal TCNQ : K stoichiometry is 1 : 1. UPS and SXPS data indicate the TCNQ is in a negatively-charged state. NIXSW results show that the carbon core of the TCNQ is essentially planar at a height above the Ag(111) surface closely similar to that found without coadsorbed K. In the presence of TCNQ the height of the K ions above the surface is significantly larger than on clean Ag(111), and the ions occupy sites above 'holes' in the TCNQ network. NIXSW data also show that the N atoms in the molecules must occupy sites with at least two different heights above the surface, which can be reconciled by a tilt or twist of the TCNQ molecules, broadly similar to the geometry that occurs in bulk TCNQ/K crystals.

How does your crystal grow? A commentary on Burton, Cabrera and Frank (1951) 'The growth of crystals and the equilibrium structure of their surfaces'.

The key ideas presented in the classic paper 'The growth of crystals and the equilibrium structure of their surfaces' by W. K. Burton, N. Cabrera and F. C. Frank, published in Philosophical Transactions A in 1951, are summarized and put in the context of both the state of knowledge at the time of publication and the considerable amount of work since that time that has built on and developed these ideas. Many of these developments exploit the huge increase in the capabilities of computer modelling that complement the original analytic approach of the paper. The dearth of relevant experimental data at the time of the original publication has been transformed by the application of increasingly sophisticated modern methods of surface science. This commentary was written to celebrate the 350th anniversary of the journal Philosophical Transactions of the Royal Society.

Ordered growth of vanadyl phthalocyanine (VOPc) on an iron phthalocyanine (FePc) monolayer.

The growth and characterisation of a non-planar phthalocyanine (vanadyl phthalocyanine, VOPc) on a complete monolayer (ML) of a planar phthalocyanine (Iron(II) phthalocyanine, FePc) on an Au(111) surface, has been investigated using ultra-high vacuum (UHV) scanning tunnelling microscopy (STM) and low energy electron diffraction (LEED). The surface mesh of the initial FePc monolayer has been determined and shown to correspond to an incommensurate overlayer, not commensurate as previously reported. Ordered islands of VOPc, with (1 × 1) epitaxy, grow on the FePc layer at submonolayer coverages. The individual VOPc molecules occupy sites directly atop the underlying FePc molecules, indicating that significant intermolecular bonding must occur. It is proposed that this interaction implies that the V[double bond, length as m-dash]O points down into the surface, allowing a Fe-O bond to form. The detailed appearance of the STM images of the VOPc molecules is consistent with previous studies in other VOPc growth studies in which this molecular orientation has been proposed.

Quantitative adsorbate structure determination for quasicrystals using x-ray standing waves.

The quantitative structure determination of adsorbed species on quasicrystal surfaces has so far appeared to present insurmountable problems. The normal incidence standing x-ray wave field technique offers a simple solution, without extensive data sets or large computations. Its application to quasicrystals raises several conceptual difficulties that are related to the phase problem in x-ray diffraction. We demonstrate their solution for the case of Si atoms adsorbed on the decagonal Co-rich modification of the Al-Co-Ni quasicrystal to determine the local structure, comprising 6-atom clusters in particular hollow sites.

Headbutting through time: A review of this hypothesized behavior in "dome-headed" fossil taxa.

Headbutting is a combative behavior most popularly portrayed and exemplified in the extant bighorn sheep (Ovis canadensis). When behaviorally proposed in extinct taxa, these organisms are oft depicted Ovis-like as having used modified cranial structures to combatively slam into one another. The combative behavioral hypothesis of headbutting has a long and rich history in the vertebrate fossil literature (not just within Dinosauria), but the core of this behavioral hypothesis in fossil terrestrial vertebrates is associated with an enlarged osseous cranial dome-an osteological structure with essentially no current counterpart. One confounding issue found in the literature is that while the term "headbutting" sounds simplistic enough, little terminology has been used to describe this hypothesized behavior. And pertinent to this special issue, potential brain trauma and the merits of such proposed pugilism have been assessed largely from the potential deformation of the overlying osseous structure; despite the fact that extant taxa readily show that brain damage can and does occur without osteological compromise. Additionally, the extant taxa serving as the behavioral counterpart for comparison are critical, not only because of the combative behaviors and morphologies they display, but also the way they engage in such behavior. Sheep (Ovis), warthogs (Phacochoerus), and bison (Bison) all engage in various forms of "headbutting", but the cranial morphologies and the way each engages in combat is markedly different. To hypothesize that an extinct organism engaged in headbutting like an extant counterpart in theory implies specific striking:contacting surfaces, speed, velocity, and overall how that action was executed. This review examines the history and usage of the headbutting behavioral hypothesis in these dome-headed fossil taxa, their respective extant behavioral counterparts, and proposes a protocol for specific behavioral terms relating to headbutting to stem future confusion. We also discuss the disparate morphology of combative cranial structures in the fossil record, and the implications of headbutting-induced brain injury in extinct taxa. Finally, we conclude with some potential implications for artistic reconstructions of fossil taxa regarding this behavioral repertoire.

Structure Determination of F4TCNQ on Ag(111): A Systematic Trend in Metal Adatom Incorporation.

A structure determination of the commensurate phase formed by 7,7,8,8-tetracyano-2,3,5,6-tetrafluoroquinodimethane (F4TCNQ) absorbed on Ag(111) is reported. Initial characterization was performed using low-energy electron diffraction and synchrotron radiation photoelectron spectroscopy, with quantitative structural data being provided by normal incident X-ray standing waves (NIXSW) and surface X-ray diffraction (SXRD). NIXSW data show the F4TCNQ molecule to adopt a "twisted" conformation on the surface, previously found to be associated with metal adatom incorporation into a 2d-metal-organic framework for F4TCNQ on Au(111), Ag(100), and Cu(111). SXRD results provide direct evidence of the presence of Ag adatoms that are found to occupy near-bridge or fcc hollow sites with respect to the underlying surface, at an adsorption height of 2.69 ± 0.10 Å. The results show a consistent pattern of behavior for F4TCNQ adsorption on the (111) surfaces of Cu, Ag, and Au.

Does F4TCNQ Adsorption on Cu(111) Form a 2D-MOF?

The results of a quantitative experimental structural investigation of the adsorption phases formed by 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanoquinodimethane (F4TCNQ) on Cu(111) are reported. A particular objective was to establish whether Cu adatoms are incorporated into the molecular overlayer. A combination of normal incidence X-ray standing waves, low-energy electron diffraction, scanning tunneling microscopy, and X-ray photoelectron spectroscopy measurements, complemented by dispersion-inclusive density functional theory calculations, demonstrates that F4TCNQ on Cu(111) does cause Cu adatoms to be incorporated into the overlayer to form a two-dimensional metal-organic framework (2D-MOF). This conclusion is shown to be consistent with the behavior of F4TCNQ adsorption on other coinage metal surfaces, despite an earlier report concluding that the adsorption structure on Cu(111) is consistent with the absence of any substrate reconstruction.

Donor-Acceptor Co-Adsorption Ratio Controls the Structure and Electronic Properties of Two-Dimensional Alkali-Organic Networks on Ag(100).

The results are presented of a detailed combined experimental and theoretical investigation of the influence of coadsorbed electron-donating alkali atoms and the prototypical electron acceptor molecule 7,7,8,8-tetracyanoquinodimethane (TCNQ) on the Ag(100) surface. Several coadsorption phases were characterized by scanning tunneling microscopy, low-energy electron diffraction, and soft X-ray photoelectron spectroscopy. Quantitative structural data were obtained using normal-incidence X-ray standing wave (NIXSW) measurements and compared with the results of density functional theory (DFT) calculations using several different methods of dispersion correction. Generally, good agreement between theory and experiment was achieved for the quantitative structures, albeit with the prediction of the alkali atom heights being challenging for some methods. The adsorption structures depend sensitively on the interplay of molecule-metal charge transfer and long-range dispersion forces, which are controlled by the composition ratio between alkali atoms and TCNQ. The large difference in atomic size between K and Cs has negligible effects on stability, whereas increasing the ratio of K/TCNQ from 1:4 to 1:1 leads to a weakening of molecule-metal interaction strength in favor of stronger ionic bonds within the two-dimensional alkali-organic network. A strong dependence of the work function on the alkali donor-TCNQ acceptor coadsorption ratio is predicted.

The first occurrence of an avian-style respiratory infection in a non-avian dinosaur.

Other than repaired fractures, osteoarthritis, and periosteal reaction, the vertebrate fossil record has limited evidence of non-osseous diseases. This difficulty in paleontological diagnoses stems from (1) the inability to conduct medical testing, (2) soft-tissue pathologic structures are less likely to be preserved, and (3) many osseous lesions are not diagnostically specific. However, here reported for the first time is an avian-style respiratory disorder in a non-avian dinosaur. This sauropod presents irregular bony pathologic structures stemming from the pneumatic features in the cervical vertebrae. As sauropods show well-understood osteological correlates indicating that respiratory tissues were incorporated into the post-cranial skeleton, and thus likely had an 'avian-style' form of respiration, it is most parsimonious to identify these pathologic structures as stemming from a respiratory infection. Although several extant avian infections produce comparable symptoms, the most parsimonious is airsacculitis with associated osteomyelitis. From actinobacterial to fungal in origin, airsacculitis is an extremely prevalent respiratory disorder in birds today. While we cannot pinpoint the specific infectious agent that caused the airsacculitis, this diagnosis establishes the first fossil record of this disease. Additionally, it allows us increased insight into the medical disorders of dinosaurs from a phylogenetic perspective and understanding what maladies plagued the "fearfully great lizards".

Direct Experimental Evidence for Substrate Adatom Incorporation into a Molecular Overlayer.

While the phenomenon of metal substrate adatom incorporation into molecular overlayers is generally believed to occur in several systems, the experimental evidence for this relies on the interpretation of scanning tunneling microscopy (STM) images, which can be ambiguous and provides no quantitative structural information. We show that surface X-ray diffraction (SXRD) uniquely provides unambiguous identification of these metal adatoms. We present the results of a detailed structural study of the Au(111)-F4TCNQ system, combining surface characterization by STM, low-energy electron diffraction, and soft X-ray photoelectron spectroscopy with quantitative experimental structural information from normal incidence X-ray standing wave (NIXSW) and SXRD, together with dispersion-corrected density functional theory (DFT) calculations. Excellent agreement is found between the NIXSW data and the DFT calculations regarding the height and conformation of the adsorbed molecule, which has a twisted geometry rather than the previously supposed inverted bowl shape. SXRD measurements provide unequivocal evidence for the presence and location of Au adatoms, while the DFT calculations show this reconstruction to be strongly energetically favored.

Face-dependent bond lengths in molecular chemisorption: the formate species on Cu(111) and Cu(110).

Many previous structural studies of molecular adsorbates on metal surfaces indicate that the local coordination and bonding is closely similar to that in organometallic compounds, implying that the metallic substrate has no significant influence. Here we show that such an influence is detectable for one model system, namely, the formate species, HCOO, adsorbed on the atomically rough and smooth (110) and (111) surfaces of Cu, leading to a statistically significant difference (0.09±0.05 Å) in the Cu-O chemisorption bond length. The effect is reproduced in density functional theory calculations.

V2O3(0001) surface termination: phase equilibrium.

Complementary but independent medium-energy and low-energy ion scattering studies of the (0001) surfaces of V(2)O(3) films grown on Pd(111), Au(111) and Cu(3)Au(100) reveal a reconstructed full O(3)-layer termination creating a VO(2) surface trilayer. This structure is fully consistent with previous calculations based on thermodynamic equilibrium at the surface during growth, but contrasts with previous suggestions that the surface termination comprises a complete monolayer of vanadyl (V=O) species.

The structure of furan reaction products on Pd(111).

Previous experimental studies of the interaction of molecular furan, C(4)H(4)O, with Pd(111) have led to the conclusion that partial dissociation leads to two coadsorbed reaction products, CO and a C(3)H(3) species. Using density functional theory (DFT), a range of possible molecular conformation and adsorption sites of the C(3)H(3) species have been explored and the lowest energy structures, and associated C 1s photoelectron core-level binding energy shifts (CLSs), have been determined. Comparison of these CLS values with published experimental measurements allows one possible conformation to be rejected. New simulations of the C 1s scanned-energy mode photoelectron diffraction (PhD) spectra for several of lowest-energy structures found in DFT are compared with the results of an earlier experimental study. The lowest energy structure found in DFT is not consistent with the PhD data, suggesting that energy barriers to achieve the associated conformation cannot be overcome in the dissociation process. Through consideration of the results of both methods, the most probable surface structures are discussed.

Uracil on Cu(110): a quantitative structure determination by energy-scanned photoelectron diffraction.

The local adsorption site of the nucleobase uracil on Cu(110) has been determined quantitatively by energy-scanned photoelectron diffraction (PhD). Qualitative inspection of the O 1s and N 1s soft x-ray photoelectron spectra, PhD modulation spectra, and O K-edge near-edge x-ray adsorption fine structure indicate that uracil bonds to the surface through its nitrogen and oxygen constituent atoms, each in near atop sites, with the molecular plane essentially perpendicular to surface and aligned along the close packed [110] azimuth. Multiple scattering simulations of the PhD spectra confirm and refine this geometry. The Cu-N bondlength is 1.96 ± 0.04 Å, while the Cu-O bondlengths of the two inequivalent O atoms are 1.93 ± 0.04 Å and 1.96 ± 0.04 Å, respectively. The molecule is twisted out of the [110]direction by 11 ± 5°.

New insight on the role of localisation in the electronic structure of the Si(111)(7 × 7) surfaces.

New angle-resolved photoelectron spectroscopy (ARPES) data, recorded at several different photon energies from the Si(111)(7 × 7) surface, show that the well-known S1 and S2 surface states that lie in the bulk band gap are localised at specific (adatom and rest atom) sites on the reconstructed surface. The variations in the photoemission intensity from these states as a function of polar and azimuthal emission angle, and incident photon energy, are not consistent with Fermi surface mapping but are well-described by calculations of the multiple elastic scattering in the final state. This localisation of the most shallowly bound S1 state is consistent with the lack of significant dispersion, with no evidence of Fermi surface crossing, implying that the surface is not, as has been previously proposed, metallic in character. Our findings highlight the importance of final state scattering in interpreting ARPES data, an aspect that is routinely ignored and can lead to misleading conclusions.

Height-related trends in stomatal sensitivity to leaf-to-air vapour pressure deficit in a tall conifer.

Stomatal responses to leaf-to-air vapour pressure deficit (LVPD), leaf water potential components, and cuticular properties were characterized for Douglas-fir (Pseudotsuga menziesii) foliage collected from tree tops along a height gradient from 5 m to 58 m in order to explore height-related trends in stomatal sensitivity to LVPD and to investigate the role of bulk leaf turgor and leaf cuticle thickness in determining stomatal behaviour. There were three distinct phases in the response of stomatal conductance (g(s)) to changes in LVPD. At low LVPD, g(s) increased with increasing LVPD (phase one). During the second phase, g(s) was maximal at low to intermediate LVPD and during the third phase g(s) declined steadily as LVPD increased. The responsiveness of g(s) to LVPD exhibited a height-related pattern such that maximum g(s) (g(s-max)) occurred at progressively greater LVPD with increasing height (r2=0.55, P=0.006). Bulk leaf osmotic potential at full turgor decreased with height (r2=0.77, P=0.00016), and LVPD at g(s-max) and at maximum crown conductance (g(c-max)) in the field were significantly correlated with leaf turgor (r2=0.92, P=0.0093). Cuticle thickness increased by 0.044 microm for every metre increase in height (r2=0.78, P=0.00015). The observed trends in the response of g(s) to LVPD along a height gradient, and their consistency with height-related trends in foliar osmotic potential suggest that osmotic adjustment at the tops of tall trees influences the relationship between g(s) and LVPD.

Methoxy species on Cu(110): understanding the local structure of a key catalytic reaction intermediate.

Partial oxidation of methanol to formaldehyde over Cu(110) is one of the most studied catalytic reactions in surface science, yet the local site of the reaction intermediate, methoxy, remains unknown. Using a combination of experimental scanned-energy mode photoelectron diffraction, and density functional theory, a consistent structural solution is presented in which all methoxy species occupy twofold coordinated "short-bridge" adsorption sites. The results are consistent with previously-published scanning tunnelling microscopy images and theoretical calculations of the reaction mechanism.

STM study of molecule double-rows in mixed self-assembled monolayers of alkanethiols.

Using scanning tunnelling microscopy (STM), we have studied mixed self-assembled monolayers of linear alkanethiol molecules. Nonanedithiol (C9S2), nonanethiol (C9S), decanethiol (C10S), and dodecanethiol (C12S) were inserted into a self-assembled octanethiol (C8S) host matrix monolayer on an Au(111) surface using a two-step method. Quasi-one-dimensional double-row structures were found in the ordered, close-packed domains of the C8S matrix for each mixed monolayer system. These close-packed domains coexist with ordered striped phase domains (for C9S and C10S) or with a disordered phase (for C9S2 and C12S). Results from high-resolution images suggest that the double-rows are composed of inserted non-nearest-neighbor substitutional molecules, the ordering of which may be a result of locally induced surface stress.