Small molecule binding to surface-supported single-site transition-metal reaction centres.

Despite dominating industrial processes, heterogeneous catalysts remain challenging to characterize and control. This is largely attributable to the diversity of potentially active sites at the catalyst-reactant interface and the complex behaviour that can arise from interactions between active sites. Surface-supported, single-site molecular catalysts aim to bring together benefits of both heterogeneous and homogeneous catalysts, offering easy separability while exploiting molecular design of reactivity, though the presence of a surface is likely to influence reaction mechanisms. Here, we use metal-organic coordination to build reactive Fe-terpyridine sites on the Ag(111) surface and study their activity towards CO and C2H4 gaseous reactants using low-temperature ultrahigh-vacuum scanning tunnelling microscopy, scanning tunnelling spectroscopy, and atomic force microscopy supported by density-functional theory models. Using a site-by-site approach at low temperature to visualize the reaction pathway, we find that reactants bond to the Fe-tpy active sites via surface-bound intermediates, and investigate the role of the substrate in understanding and designing single-site catalysts on metallic supports.

Room temperature strain-induced Landau levels in graphene on a wafer-scale platform.

Graphene is a powerful playground for studying a plethora of quantum phenomena. One of the remarkable properties of graphene arises when it is strained in particular geometries and the electrons behave as if they were under the influence of a magnetic field. Previously, these strain-induced pseudomagnetic fields have been explored on the nano- and micrometer-scale using scanning probe and transport measurements. Heteroepitaxial strain, in contrast, is a wafer-scale engineering method. Here, we show that pseudomagnetic fields can be generated in graphene through wafer-scale epitaxial growth. Shallow triangular nanoprisms in the SiC substrate generate strain-induced uniform fields of 41 T, enabling the observation of strain-induced Landau levels at room temperature, as detected by angle-resolved photoemission spectroscopy, and confirmed by model calculations and scanning tunneling microscopy measurements. Our work demonstrates the feasibility of exploiting strain-induced quantum phases in two-dimensional Dirac materials on a wafer-scale platform, opening the field to new applications.

Imaging the real space structure of the spin fluctuations in an iron-based superconductor.

Spin fluctuations are a leading candidate for the pairing mechanism in high temperature superconductors, supported by the common appearance of a distinct resonance in the spin susceptibility across the cuprates, iron-based superconductors and many heavy fermion materials. The information we have about the spin resonance comes almost exclusively from neutron scattering. Here we demonstrate that by using low-temperature scanning tunnelling microscopy and spectroscopy we can characterize the spin resonance in real space. We show that inelastic tunnelling leads to the characteristic dip-hump feature seen in tunnelling spectra in high temperature superconductors and that this feature arises from excitations of the spin fluctuations. Spatial mapping of this feature near defects allows us to probe non-local properties of the spin susceptibility and to image its real space structure.

Acoustic buffeting by infrasound in a low vibration facility.

Measurement instruments and fabrication tools with spatial resolution on the atomic scale require facilities that mitigate the impact of vibration sources in the environment. One approach to protection from vibration in a building's foundation is to place the instrument on a massive inertia block, supported on pneumatic isolators. This opens the questions of whether or not a massive floating block is susceptible to acoustic forces, and how to mitigate the effects of any such acoustic buffeting. Here this is investigated with quantitative measurements of vibrations and sound pressure, together with finite element modeling. It is shown that a particular concern, even in a facility with multiple acoustic enclosures, is the excitation of the lowest fundamental acoustic modes of the room by infrasound in the low tens of Hz range, and the efficient coupling of the fundamental room modes to a large inertia block centered in the room.

Dispersing artifacts in FT-STS: a comparison of set point effects across acquisition modes.

Fourier-transform scanning tunnelling spectroscopy (FT-STS), or quasiparticle interference, has become an influential tool for the study of a wide range of important materials in condensed matter physics. However, FT-STS in complex materials is often challenging to interpret, requiring significant theoretical input in many cases, making it crucial to understand potential artifacts of the measurement. Here, we compare the most common modes of acquiring FT-STS data and show through both experiment and simulations that artifact features can arise that depend on how the tip height is stabilized throughout the course of the measurement. The most dramatic effect occurs when a series of dI/dV maps at different energies are acquired with simultaneous constant current feedback; here a feature that disperses in energy appears that is not observed in other measurement modes. Such artifact features are similar to those arising from real physical processes in the sample and are susceptible to misinterpretation.

Pronounced polarization-induced energy level shifts at boundaries of organic semiconductor nanostructures.

Organic semiconductor devices rely on the movement of charge at and near interfaces, making an understanding of energy level alignment at these boundaries an essential element of optimizing materials for electronic and optoelectronic applications. Here we employ low temperature scanning tunneling microscopy and spectroscopy to investigate a model system: two-dimensional nanostructures of the prototypical organic semiconductor, PTCDA (3,4,9,10-perylenetetracarboxylic dianhydride) adsorbed on NaCl (2 ML)/Ag(111). Pixel-by-pixel scanning tunneling spectroscopy allows mapping of occupied and unoccupied electronic states across these nanoislands with sub-molecular spatial resolution, revealing strong electronic differences between molecules at the edges and those in the centre, with energy level shifts of up to 400 meV. We attribute this to the change in electrostatic environment at the boundaries of clusters, namely via polarization of neighbouring molecules. The observation of these strong shifts illustrates a crucial issue: interfacial energy level alignment can differ substantially from the bulk electronic structure in organic materials.

Long- versus Short-Range Scattering in Doped Epitaxial Graphene.

Tuning the electronic properties of graphene by adatom deposition unavoidably introduces disorder into the system, which directly affects the single-particle excitations and electrodynamics. Using angle-resolved photoemission spectroscopy (ARPES) we trace the evolution of disorder in graphene by thallium adatom deposition and probe its effect on the electronic structure. We show that the signatures of quasiparticle scattering in the photoemission spectral function can be used to identify thallium adatoms, although charged, as efficient short-range scattering centers. Employing a self-energy model for short-range scattering, we are able to extract a δ-like scattering potential δ = -3.2 ± 1 eV. Therefore, isolated charged scattering centers do not necessarily act just as good long-range (Coulomb) scatterers but can also act as efficient short-range (δ-like) scatterers; in the case of thallium, this happens with almost equal contributions from both mechanisms.

Quantifying many-body effects by high-resolution Fourier transform scanning tunneling spectroscopy.

High-resolution Fourier transform scanning tunneling spectroscopy (FT-STS) is used to study many-body effects on the surface state of Ag(111). Our results reveal a kink in the otherwise parabolic band dispersion of the surface electrons and an increase in the quasiparticle lifetime near the Fermi energy Ef. The experimental data are accurately modeled with the T-matrix formalism for scattering from a single impurity, assuming that the surface electrons are dressed by the electron-electron and electron-phonon interactions. We confirm the latter as the interaction responsible for the deviations from bare dispersion. We further show how FT-STS can be used to simultaneously extract real and imaginary parts of the self-energy for both occupied and unoccupied states with a momentum and energy resolution competitive with angle-resolved photoemission spectroscopy. From our quantitative analysis of the data we extract a Debye energy of ℏΩD=14±1 meV and an electron-phonon coupling strength of λ=0.13±0.02, consistent with previous results. This proof-of-principle measurement advances FT-STS as a method for probing many body effects, which give rise to a rich array of material properties.

Scanning tunneling spectroscopy of superconducting LiFeAs single crystals: evidence for two nodeless energy gaps and coupling to a bosonic mode.

The superconducting compound LiFeAs is studied by scanning tunneling microscopy and spectroscopy. A gap map of the unreconstructed surface indicates a high degree of homogeneity in this system. Spectra at 2 K show two nodeless superconducting gaps with Δ(1)=5.3±0.1 meV and Δ(2)=2.5±0.2 meV. The gaps close as the temperature is increased to the bulk T(c), indicating that the surface accurately represents the bulk. A dip-hump structure is observed below T(c) with an energy scale consistent with a magnetic resonance recently reported by inelastic neutron scattering.

Detecting 2009 pandemic influenza A (H1N1) virus infection: availability of diagnostic testing led to rapid pandemic response.

Diagnostic tests for detecting emerging influenza virus strains with pandemic potential are critical for directing global influenza prevention and control activities. In 2008, the Centers for Disease Control and Prevention received US Food and Drug Administration approval for a highly sensitive influenza polymerase chain reaction (PCR) assay. Devices were deployed to public health laboratories in the United States and globally. Within 2 weeks of the first recognition of 2009 pandemic influenza H1N1, the Centers for Disease Control and Prevention developed and began distributing a new approved pandemic influenza H1N1 PCR assay, which used the previously deployed device platform to meet a >8-fold increase in specimen submissions. Rapid antigen tests were widely used by clinicians at the point of care; however, test sensitivity was low (40%-69%). Many clinical laboratories developed their own pandemic influenza H1N1 PCR assays to meet clinician demand. Future planning efforts should identify ways to improve availability of reliable testing to manage patient care and approaches for optimal use of molecular testing for detecting and controlling emerging influenza virus strains.

Strain-induced pseudo-magnetic fields greater than 300 tesla in graphene nanobubbles.

Recent theoretical proposals suggest that strain can be used to engineer graphene electronic states through the creation of a pseudo-magnetic field. This effect is unique to graphene because of its massless Dirac fermion-like band structure and particular lattice symmetry (C3v). Here, we present experimental spectroscopic measurements by scanning tunneling microscopy of highly strained nanobubbles that form when graphene is grown on a platinum (111) surface. The nanobubbles exhibit Landau levels that form in the presence of strain-induced pseudo-magnetic fields greater than 300 tesla. This demonstration of enormous pseudo-magnetic fields opens the door to both the study of charge carriers in previously inaccessible high magnetic field regimes and deliberate mechanical control over electronic structure in graphene or so-called "strain engineering."

High Q optical fiber tips for NC-AFM in liquid.

Non-contact atomic force microscopy is rapidly expanding from ultra-high vacuum to include the study of surfaces and biomolecules in liquids by high resolution imaging and force spectroscopy. This is despite the additional frequency shift noise due to the inherently low Q factor of the cantilever oscillating in a liquid. In this paper we present a tip based on an optical fiber which can operate in liquid with Q factors in excess of 100 using a 'diving bell' arrangement which allows only a small portion of the tip to be submerged. We demonstrate stable imaging and force spectroscopy using this set-up. The tips are based on scanning near-field optical microscopy tips and, when used with NC-AFM, provide a method of combining both high resolution mechanical and fluorescence studies of biomolecules and cells.

Determination of the local contact potential difference of PTCDA on NaCl: a comparison of techniques.

There has been increasing focus on the use of Kelvin probe force microscopy (KPFM) for the determination of local electronic structure in recent years, especially in systems where other methods, such as scanning tunnelling microscopy/spectroscopy, may be intractable. We have examined three methods for determining the local apparent contact potential difference (CPD): frequency modulation KPFM (FM-KPFM), amplitude modulation KPFM (AM-KPFM), and frequency shift-bias spectroscopy, on a test system of 3,4,9,10-perylene tetracarboxylic dianhydride (PTCDA) on NaCl, an example of an organic semiconductor on a bulk insulating substrate. We will discuss the influence of the bias modulation on the apparent CPD measurement by FM-KPFM compared to the DC-bias spectroscopy method, and provide a comparison of AM-KPFM, AM-slope detection KPFM and FM-KPFM imaging resolution and accuracy. We will also discuss the distance dependence of the CPD as measured by FM-KPFM for both the PTCDA organic deposit and the NaCl substrate.

Molecular dewetting on insulators.

Recent attention given to the growth and morphology of organic thin films with regard to organic electronics has led to the observation of dewetting (a transition from layer(s) to islands) of molecular deposits in many of these systems. Dewetting is a much studied phenomenon in the formation of polymer and liquid films, but its observation in thin films of the 'small' molecules typical of organic electronics requires additional consideration of the structure of the interface between the molecular film and the substrate. This review covers some key concepts related to dewetting and molecular film growth. In particular, the origins of different growth modes and the thickness dependent interactions which give rise to dewetting are discussed in terms of surface energies and the disjoining pressure. Characteristics of molecular systems which may lead to these conditions, including the formation of metastable interface structures and commensurate-incommensurate phase transitions, are also discussed. Brief descriptions of some experimental techniques which have been used to study molecular dewetting are given as well. Examples of molecule-on-insulator systems which undergo dewetting are described in some detail, specifically perylene derivatives on alkali halides, C(60) on alkali halides, and the technologically important system of pentacene on SiO(2). These examples point to some possible predicting factors for the occurrence of dewetting, most importantly the formation of an interface layer which differs from the bulk crystal structure.

Strain induced dewetting of a molecular system: bimodal growth of PTCDA on NaCl.

Submonolayer coverages of the molecule 3,4,9,10-perylene tetracarboxylic dianhydride (PTCDA) deposited on NaCl(001) surfaces were imaged with high resolution noncontact-atomic force microscopy. Two island types were observed: monolayer islands with a p3x3 epitaxy at low coverage and a mixture of these and bulklike crystallites at higher coverage. The transition between the pure monolayer islands and mixed islands occurs at approximately 0.85 ML, corresponding to a complete p3x3 layer. Calculations show the p3x3 epitaxy to be incompatible with a multilayer crystal of PTCDA. Consequently, the growth of additional layers results in an adaptation of the interface structure forcing a dewetting transition.

Monitoring of concordance in growth hormone therapy.

Concordance with growth hormone (GH) therapy in 75 children was objectively assessed using data on GP prescriptions over 12 months. 23% missed >2 injections/week. Lower concordance was associated with longer duration on GH therapy (p<0.005), lack of choice of delivery device (p<0.005) and short prescription durations (p<0.005), and predicted lower height velocities (p<0.05).

Comment on 'Temperature dependence of the energy dissipation in dynamic force microscopy'.

A recent article in this journal by Roll et al (2008 Nanotechnology 19 045703) presents experimental results of the temperature dependence of dissipation in dynamic force microscopy which they use to elucidate the mechanisms of such a dissipation signal in the PTCDA on KBr system. We argue here that dissipation results are often highly dependent upon the tip structure, and urge caution in the interpretation of single sets of experimental data.

Nucleation and submonolayer growth of C60 on KBr.

Noncontact atomic force microscopy has been applied to the prototypical molecule-insulator system C60 on KBr to study nucleation and submonolayer growth. Overview images reveal an island growth mode with unusual branching structures. Simultaneous molecular and atomic resolution on the C60 and KBr surfaces, respectively, was obtained revealing a coincident 8x3 superstructure. Also, a 21+/-3 pm apparent height difference was observed in atomic force microscopy topographies between some first layer molecules. One of the initial nucleation sites of the C60 islands was determined by observation of loosely bound molecules at kink sites in monatomic KBr steps, in conjunction with the observation that islands form preferentially at step edges.

Detection of molecular diversity in Bacillus atrophaeus by amplified fragment length polymorphism analysis.

Phenotypically, Bacillus atrophaeus is indistinguishable from the type strain of Bacillus subtilis except by virtue of pigment production on certain media. Several pigmented variants of B. subtilis have been reclassified as B. atrophaeus, but several remain ambiguous in regard to their taxonomic placement. In this study, we examined strains within the American Type Culture Collection originally deposited as Bacillus globigii, B. subtilis var. niger, or Bacillus niger using 16S rRNA gene sequencing and amplified fragment length polymorphism (AFLP) analysis to determine the level of molecular diversity among these strains and their relationship with closely related taxa. The 16S rRNA gene sequences revealed little variation with one base substitution between the B. atrophaeus type strain ATCC 49337 and the other pigmented bacilli. AFLP analysis produced high-quality DNA fingerprints with sufficient polymorphism to reveal strain-level variation. Cluster analysis of Dice similarity coefficients revealed that three strains, ATCC 31028, ATCC 49760, and ATCC 49822, are much more closely related to B. atrophaeus than to B. subtilis and should be reclassified as B. atrophaeus. A very closely related cluster of B. atrophaeus strains was also observed; this cluster was genetically distinct from the type strain. The level of variation between the two groups was approximately the same as the level of variation observed between members of the two B. subtilis subspecies, subtilis and spizizenii. It is proposed that the cluster of strains typified by ATCC 9372 be designated a new subspecies, B. atrophaeus subsp. globigii.

The Mental Adjustment to Cancer (MAC) scale: replication and refinement in 632 breast cancer patients.

BACKGROUND: Assessment of adjustment of patients in cancer treatment trials is becoming more common and increasingly regarded as a useful outcome measure. The widely used Mental Adjustment to Cancer (MAC) Scale was designed to measure Fighting Spirit (FS), Anxious Preoccupation (AP), Helpless-hopelessness (HH) and Fatalism. METHODS: Questionnaire responses from 632 breast cancer patients were randomly divided into two groups, one for exploratory analyses and possible scale refinement, and the other for validation purposes. RESULTS: Estimates of reliability (Cronbach's alpha) were satisfactory for two scales, FS (alpha = 0.85) and HH (alpha = 0.81), but lower for AP (alpha = 0.65) and Fatalism (alpha = 0.64). Exploratory factor analysis suggested that the MAC Scale might be measuring six independent constructs including two related to Fighting Spirit (Positive Orientation to the Illness, Minimizing the Illness), two related to Fatalism (Fatalism-revised, Loss of Control), a construct we have named Angst, and an unchanged HH construct. Scales developed to measure these constructs were satisfactorily replicated in confirmatory analyses but some reliabilities were lower than desirable. The general structure of the MAC Scale remained little changed despite the division of two scales and the suggested removal of six items. The refined scales correlated with the Hospital Anxiety and Depression scale and the Medical Coping Modes Questionnaire, indicating good concurrent validity. CONCLUSIONS: While reasonable reliability of the original scales persists through analyses of the MAC Scale, the original factor structure could not be reproduced. Six refined constructs with strong construct validity were identified within the overall domain of mental adjustment to cancer.