Imaging Soft Materials with Scanning Tunneling Microscopy

By modifying freeze-fracture replication, a standard electron microscopy fixation technique, for use with the scanning tunneling microscope (STM), a variety of soft, non-conductive biomaterials can be imaged at high resolution in three dimensions. Metal replicas make near ideal samples for STM in comparison to the original biological materials. Modifications include a 0.1 μm backing layer of silver and mounting the replicas on a fine-mesh silver filters to enhance the rigidity of the metal replica. This is required unless STM imaging is carried out in vacuum; otherwise, a liquid film of contamination physically connects the STM tip with the sample. This mechanical coupling leads to exaggerated height measurements; the enhanced rigidity of the thicker replica eliminates much of the height amplification. Further improvement was obtained by imaging in a dry nitrogen atmosphere. Calibration and reproducibility were tested with replicas of well characterized bilayers of cadmium arachidate on mica that provide regular 5.5 nm steps. We have used the STM/replica technique to examine the ripple shape and amplitude in the P/J. phase of dimyristoylpbospbatidyl-choline (DMPC) in water. STM images were analyzed using a cross-correlation averaging program to eliminate the effects of noise and the finite size and shapes of the metal grains that make up the replica. The correlation averaging allowed us to develop a composite ripple profile averaged over hundreds of individual ripples and different samples. The STM/replica technique is sufficiently general that it can be used to examine a variety of hydrated lipid and protein samples at a lateral resolution of about 1 nm and a vertical resolution of about 0.3 run

Sensitivity of shelf sea marine ecosystems to temporal resolution of meteorological forcing

Phytoplankton phenology and the length of the growing season have implications that cascade through trophic levels and ultimately impact the global carbon flux to the seafloor. Coupled hydrodynamic‐ecosystem models must accurately predict timing and duration of phytoplankton blooms in order to predict the impact of environmental change on ecosystem dynamics. Meteorological conditions, such as solar irradiance, air temperature and wind‐speed are known to strongly impact the timing of phytoplankton blooms. Here, we investigate the impact of degrading the temporal resolution of meteorological forcing (wind, surface pressure, air and dew point temperatures) from 1‐24 hours using a 1D coupled hydrodynamic‐ecosystem model at two contrasting shelf‐sea sites: one coastal intermediately stratified site (L4) and one offshore site with constant summer stratification (CCS). Higher temporal resolutions of meteorological forcing resulted in greater wind stress acting on the sea surface increasing water column turbulent kinetic energy. Consequently, the water column was stratified for a smaller proportion of the year producing a delayed onset of the spring phytoplankton bloom by up to 6 days, often earlier cessation of the autumn bloom, and shortened growing season of up to 23 days. Despite opposing trends in gross primary production between sites, a weakened microbial loop occurred with higher meteorological resolution due to reduced dissolved organic carbon production by phytoplankton caused by differences in resource limitation: light at CCS and nitrate at L4. Caution should be taken when comparing model runs with differing meteorological forcing resolutions. Recalibration of hydrodynamic‐ecosystem models may be required if meteorological resolution is upgraded

On the density-potential mapping in time-dependent density functional theory

The key questions of uniqueness and existence in time-dependent density functional theory are usually formulated only for potentials and densities that are analytic in time. Simple examples, standard in quantum mechanics, lead however to non-analyticities. We reformulate these questions in terms of a non-linear Schr\"odinger equation with a potential that depends non-locally on the wavefunction.Comment: 8 pages, 2 figure

Surfactant-aided exfoliation of molydenum disulphide for ultrafast pulse generation through edge-state saturable absorption

We use liquid phase exfoliation to produce dispersions of molybdenum disulphide (MoS2) nanoflakes in aqueous surfactant solutions. The chemical structures of the bile salt surfactants play a crucial role in the exfoliation and stabilization of MoS2. The resultant MoS2 dispersions are heavily enriched in single and few (<6) layer flakes with large edge to surface area ratio. We use the dispersions to fabricate free-standing polymer composite wide-band saturable absorbers to develop mode-locked and Q- switched fibre lasers, tunable from 1535-1565 and 1030-1070 nm, respectively. We attribute this sub-bandgap optical absorption and its nonlinear saturation behaviour to edge-mediated states introduced within the material band-gap of the exfoliated MoS2 nanoflakes.Comment: 6 pages, 5 figure

The NASA Ames Research Center one- and two-dimensional stratospheric models. Part 2: The two-dimensional model

The two-dimensional model of stratospheric constituents is presented in detail. The derivation of pertinent transport parameters and the numerical solution of the species continuity equations, including a technique for treating the stiff differential equations that represent the chemical kinetic terms, and appropriate methods for simulating the diurnal variations of the solar zenith angle and species concentrations are discussed. Predicted distributions of tracer constituents (ozone, carbon 14, nitric acid) are compared with observed distributions

A Spitzer IRAC Census of the Asymptotic Giant Branch Populations in Local Group Dwarfs. II. IC 1613

We present Spitzer Space Telescope IRAC photometry of the Local Group dwarf irregular galaxy IC 1613. We compare our 3.6, 4.5, 5.8, and 8.0 micron photometry with broadband optical photometry and find that the optical data do not detect 43% and misidentify an additional 11% of the total AGB population, likely because of extinction caused by circumstellar material. Further, we find that a narrowband optical carbon star study of IC 1613 detects 50% of the total AGB population and only considers 18% of this population in calculating the carbon to M-type AGB ratio. We derive an integrated mass-loss rate from the AGB stars of 0.2-1.0 x 10^(-3) solar masses per year and find that the distribution of bolometric luminosities and mass-loss rates are consistent with those for other nearby metal-poor galaxies. Both the optical completeness fractions and mass-loss rates in IC 1613 are very similar to those in the Local Group dwarf irregular, WLM, which is expected given their similar characteristics and evolutionary histories.Comment: Accepted by ApJ, 26 pages, 10 figures, version with high-resolution figures available at: http://webusers.astro.umn.edu/~djackson

Texture-specific Si isotope variations in Barberton Greenstone Belt cherts record low temperature fractionations in early Archean seawater

Sedimentary cherts are unusually abundant in early Archean (pre-3.0 Ga) sequences, suggesting a silica cycle that was profoundly different than the modern system. Previously applied for the purpose of paleothermometry, Si isotopes in ancient cherts can offer broader insight into mass fluxes and mechanisms associated with silica concentration, precipitation, diagenesis, and metamorphism. Early Archean cherts contain a rich suite of sedimentological and petrographic textures that document a history of silica deposition, cementation, silicification, and recrystallization. To add a new layer of insight into the chemistry of early cherts, we have used wavelength-dispersive spectroscopy and then secondary ion mass spectrometry (SIMS) to produce elemental and Si and O isotope ratio data from banded black-and-white cherts from the Onverwacht Group of the Barberton Greenstone Belt, South Africa. This geochemical data is then interpreted in the framework of depositional and diagenetic timing of silica precipitation provided by geological observations. SIMS allows the comparison of Si and O isotope ratios of distinct silica phases, including black carbonaceous chert beds and bands (many including well-defined sedimentary grains), white relatively pure chert bands including primary silica granules, early cavity-filling cements, and later quartz-filled veins. Including all chert types and textures analyzed, the δ^(30)Si dataset spans a range from −4.78‰ to +3.74‰, with overall mean 0.20‰, median 0.51‰, and standard deviation 1.30‰ (n = 1087). Most samples have broadly similar δ^(30)Si distributions, but systematic texture-specific δ^(30)Si differences are observed between white chert bands (mean +0.60‰, n = 750), which contain textures that represent primary and earliest diagenetic silica phases, and later cavity-filling cements (mean −1.41‰, n = 198). We observed variations at a ∼100 μm scale indicating a lack of Si isotope homogenization at this scale during diagenesis and metamorphism, although fractionations during diagenetic phase transformations may have affected certain textures. We interpret these systematic variations to reflect fractionation during silica precipitation as well as isotopically distinct fluids from which later phases originated. SIMS δ^(18)O values fall in a range from 16.39‰ to 23.39‰ (n = 381), similar to previously published data from bulk gas source mass spectrometry of Onverwacht cherts. We observed only limited examples of texture-related variation in δ^(18)O and did not observe correlation of δ^(18)O with δ^(30)Si trends. This is consistent with hypotheses that Si isotope ratios are more resistant to alteration under conditions of rock-buffered diagenesis (Marin-Carbonne et al., 2011). Our results indicate that low temperature processes fractionated silicon isotopes in early Archean marine basins, a behavior that probably precludes the application of chert δ^(30)Si as a robust paleothermometer. The values we observe for facies that sedimentological and petrographic observations indicate formed as primary and earliest diagenetic silica precipitates from seawater are more ^(30)Si-rich than that expected for bulk silicate Earth. This is consistent with the hypothesis that the silicon isotope budget is balanced by the coeval deposition of ^(30)Si-enriched cherts and ^(30)Si-depleted iron formation lithologies. Precipitation of authigenic clay minerals in both terrestrial and marine settings may have also comprised a large ^(30)Si-depleted sink, with the corollary of an important non-carbonate alkalinity sink consuming cations released by silicate weathering