Work functions, ionization potentials, and in-between: Scaling relations based on the image charge model

We revisit a model in which the ionization energy of a metal particle is associated with the work done by the image charge force in moving the electron from infinity to a small cut-off distance just outside the surface. We show that this model can be compactly, and productively, employed to study the size dependence of electron removal energies over the range encompassing bulk surfaces, finite clusters, and individual atoms. It accounts in a straightforward manner for the empirically known correlation between the atomic ionization potential (IP) and the metal work function (WF), IP/WF$\sim$2. We formulate simple expressions for the model parameters, requiring only a single property (the atomic polarizability or the nearest neighbor distance) as input. Without any additional adjustable parameters, the model yields both the IP and the WF within $\sim$10% for all metallic elements, as well as matches the size evolution of the ionization potentials of finite metal clusters for a large fraction of the experimental data. The parametrization takes advantage of a remarkably constant numerical correlation between the nearest-neighbor distance in a crystal, the cube root of the atomic polarizability, and the image force cutoff length. The paper also includes an analytical derivation of the relation of the outer radius of a cluster of close-packed spheres to its geometric structure.Comment: Original submission: 8 pages with 7 figures incorporated in the text. Revised submission (added one more paragraph about alloy work functions): 18 double spaced pages + 8 separate figures. Accepted for publication in PR

MRI sensing based on the displacement of paramagnetic ions from chelated complexes

We introduce a mechanism for ion sensing by MRI in which analytes compete with paramagnetic ions for binding to polydentate chelating agents. Displacement of the paramagnetic ions results in alteration of solvent interaction parameters and consequent changes in relaxivity and MRI contrast. The MRI changes can be tuned by the choice of chelator. As an example, we show that calcium-dependent displacement of Mn[superscript 2+] ions bound to EGTA and BAPTA results in a T[subscript 1]-weighted MRI signal increase, whereas displacement from calmodulin results in a signal decrease. The changes are ion selective and can be explained using relaxivity theory. The ratio of T[subscript 2] to T[subscript 1] relaxivity is also calcium-dependent, indicating the feasibility of “ratiometric” analyte detection, independent of the probe concentration. Measurement of paramagnetic ion displacement effects could be used to determine analyte ion concentrations with spatial resolution in opaque specimens.National Institutes of Health (U.S.) (grant DP2-OD2441)National Institutes of Health (U.S.) (grant R01-GM65519)McGovern Institute for Brain Research at MIT. Neurotechnology (MINT) Progra

Variant of the <i>FLNC</i> gene nucleotide sequence in a family with different phenotypic manifestations of left ventricular non-compaction

Left ventricular non-compaction is a heterogeneous heart disease with various phenotypic and clinical manifestations. The article presents the results of clinical, instrumental and molecular genetic investigations of a family with diagnosed left ventricular non-compaction (LVNC) with different clinical and phenotypic manifestations. As a result of a molecular genetic testing, all family members with the LVNC phenotype were found to have a likely pathogenic variant in the FLNC gene. Variants in this gene are associated with a number of cardiomyopathies: dilated, hypertrophic, and restrictive. In the international scientific literature, isolated clinical cases of LVNC development with variants of the FLNC gene nucleotide sequence are presented. In our work, we present a case report of LVNC with a variety of clinical manifestations within the same family

Seasonal variations in pore water and sediment geochemistry of littoral lake sediments (Asylum Lake, MI, USA)

BACKGROUND: Seasonal changes in pore water and sediment redox geochemistry have been observed in many near-surface sediments. Such changes have the potential to strongly influence trace metal distribution and thus create seasonal fluctuations in metal mobility and bioavailability. RESULTS: Seasonal trends in pore water and sediment geochemistry are assessed in the upper 50 cm of littoral kettle lake sediments. Pore waters are always redox stratified, with the least compressed redox stratification observed during fall and the most compressed redox stratification observed during summer. A 2-step sequential sediment extraction yields much more Fe in the first step, targeted at amorphous Fe(III) (hydr)oxides (AEF), then in the second step, which targets Fe(II) monosulfides. Fe extracted in the second step is relatively invariant with depth or season. In contrast, AEF decreases with sediment depth, and is seasonally variable, in agreement with changes in redox stratification inferred from pore water profiles. A 5-step Tessier extraction scheme was used to assess metal association with operationally-defined exchangeable, carbonate, iron and manganese oxide (FMO), organic/sulfide and microwave-digestible residual fractions in cores collected during winter and spring. Distribution of metals in these two seasons is similar. Co, As, Cd, and U concentrations approach detection limits. Fe, Cu and Pb are mostly associated with the organics/sulfides fraction. Cr and Zn are mostly associated with FMO. Mn is primarily associated with carbonates, and Co is nearly equally distributed between the FMO and organics/sulfide fractions. CONCLUSION: This study clearly demonstrates that near-surface lake sediment pore water redox stratification and associated solid phase geochemistry vary significantly with season. This has important ramifications for seasonal changes in the bioavailability and mobility of trace elements. Without rate measurements, it is not possible to quantify the contribution of various processes to natural organic matter degradation. However, the pore water and solid phase data suggest that iron reduction and sulfate reduction are the dominant pathways in the upper 50 cm of these sediments

The effect of tidal forcing on biogeochemical processes in intertidal salt marsh sediments

<p>Abstract</p> <p>Background</p> <p>Early diagenetic processes involved in natural organic matter (NOM) oxidation in marine sediments have been for the most part characterized after collecting sediment cores and extracting porewaters. These techniques have proven useful for deep-sea sediments where biogeochemical processes are limited to aerobic respiration, denitrification, and manganese reduction and span over several centimeters. In coastal marine sediments, however, the concentration of NOM is so high that the spatial resolution needed to characterize these processes cannot be achieved with conventional sampling techniques. In addition, coastal sediments are influenced by tidal forcing that likely affects the processes involved in carbon oxidation.</p> <p>Results</p> <p>In this study, we used in situ voltammetry to determine the role of tidal forcing on early diagenetic processes in intertidal salt marsh sediments. We compare ex situ measurements collected seasonally, in situ profiling measurements, and in situ time series collected at several depths in the sediment during tidal cycles at two distinct stations, a small perennial creek and a mud flat. Our results indicate that the tides coupled to the salt marsh topography drastically influence the distribution of redox geochemical species and may be responsible for local differences noted year-round in the same sediments. Monitoring wells deployed to observe the effects of the tides on the vertical component of porewater transport reveal that creek sediments, because of their confinements, are exposed to much higher hydrostatic pressure gradients than mud flats.</p> <p>Conclusion</p> <p>Our study indicates that iron reduction can be sustained in intertidal creek sediments by a combination of physical forcing and chemical oxidation, while intertidal mud flat sediments are mainly subject to sulfate reduction. These processes likely allow microbial iron reduction to be an important terminal electron accepting process in intertidal coastal sediments.</p

Neural Correlates of Behavioural Olfactory Sensitivity Changes Seasonally in European Starlings

Possibly due to the small size of the olfactory bulb (OB) as compared to rodents, it was generally believed that songbirds lack a well-developed sense of smell. This belief was recently revised by several studies showing that various bird species, including passerines, use olfaction in many respects of life. During courtship and nest building, male European starlings (Sturnus vulgaris) incorporate aromatic herbs that are rich in volatile compounds (e.g., milfoil, Achillea millefolium) into the nests and they use olfactory cues to identify these plants. Interestingly, European starlings show seasonal differences in their ability to respond to odour cues: odour sensitivity peaks during nest-building in the spring, but is almost non-existent during the non-breeding season.This study used repeated in vivo Manganese-enhanced MRI to quantify for the first time possible seasonal changes in the anatomy and activity of the OB in starling brains. We demonstrated that the OB of the starling exhibits a functional seasonal plasticity of certain plant odour specificity and that the OB is only able to detect milfoil odour during the breeding season. Volumetric analysis showed that this seasonal change in activity is not linked to a change in OB volume. By subsequently experimentally elevating testosterone (T) in half of the males during the non-breeding season we showed that the OB volume was increased compared to controls.By investigating the neural substrate of seasonal olfactory sensitivity changes we show that the starlings' OB loses its ability during the non-breeding season to detect a natural odour of a plant preferred as green nest material by male starlings. We found that testosterone, applied during the non-breeding season, does not restore the discriminatory ability of the OB but has an influence on its size

Conference of Soviet and American Jurists on the Law of the Sea and the Protection of the Marine Environment

Included in the papers for the Conference of Soviet and American Jurists on the Law of the Sea and the Protection of the Marine Environment: Introduction by Milton Katz and Richard R. Baxter, p. 1 Freedom of Scientific Research in the World Ocean by A.F. Vysotsky, p. 7 The International Law of Scientific Research in the Oceans by Richard R. Baxter, p. 27 Responsibility and Liability for Harm to the Marine Environment by Robert E. Stein, p. 41 Liability for Marine Environment Pollution Damage in Contemporary International Sea Law by A. L. Makovsky, p. 59 Protection of the Marine Environment from Pollution by Richard A. Frank, p. 73 The Freedom of Navigation and the Problem of Pollution of the Marine Environment by V. A. Kiselev, p. 93 The Freedom of Navigation Under International Law by William E. Butler, p. 107 International Fisheries Management Without Global Agreement: United States Policies and Their Impact on the Soviet Union by H. Gary Knight, p. 119 Some Biological Background for International Legal Acts on Rational Utilization of the Living Resources of the World Ocean by P. A. Moiseev, p. 143 An International Regime for the Seabed Beyond National Jurisdiction by Thomas M. Franck, p. 151 Settlement of Disputes Under the Law of Ocean Use, with Particular Reference to Environmental Protection by John Lawrence Hargrove, p. 18

Elevated creatine kinase activity in primary hepatocellular carcinoma

BACKGROUND: Inconsistent findings have been reported on the occurrence and relevance of creatine kinase (CK) isoenzymes in mammalian liver cells. Part of this confusion might be due to induction of CK expression during metabolic and energetic stress. METHODS: The specific activities and isoenzyme patterns of CK and adenylate kinase (AdK) were analysed in pathological liver tissue of patients undergoing orthotopic liver transplantation. RESULTS: The brain-type, cytosolic BB-CK isoenzyme was detected in all liver specimens analysed. Conversely, CK activity was strongly increased and a mitochondrial CK (Mi-CK) isoenzyme was detected only in tissue samples of two primary hepatocellular carcinomas (HCCs). CONCLUSION: The findings do not support significant expression of CK in normal liver and most liver pathologies. Instead, many of the previous misconceptions in this field can be explained by interference from AdK isoenzymes. Moreover, the data suggest a possible interplay between p53 mutations, HCC, CK expression, and the growth-inhibitory effects of cyclocreatine in HCC. These results, if confirmed, could provide important hints at improved therapies and cures for HCC

Quantifying bioirrigation using ecological parameters: a stochastic approach†

Irrigation by benthic macrofauna has a major influence on the biogeochemistry and microbial community structure of sediments. Existing quantitative models of bioirrigation rely primarily on chemical, rather than ecological, information and the depth-dependence of bioirrigation intensity is either imposed or constrained through a data fitting procedure. In this study, stochastic simulations of 3D burrow networks are used to calculate mean densities, volumes and wall surface areas of burrows, as well as their variabilities, as a function of sediment depth. Burrow networks of the following model organisms are considered: the polychaete worms Nereis diversicolor and Schizocardium sp., the shrimp Callianassa subterranea, the echiuran worm Maxmuelleria lankesteri, the fiddler crabs Uca minax, U. pugnax and U. pugilator, and the mud crabs Sesarma reticulatum and Eurytium limosum. Consortia of these model organisms are then used to predict burrow networks in a shallow water carbonate sediment at Dry Tortugas, FL, and in two intertidal saltmarsh sites at Sapelo Island, GA. Solute-specific nonlocal bioirrigation coefficients are calculated from the depth-dependent burrow surface areas and the radial diffusive length scale around the burrows. Bioirrigation coefficients for sulfate obtained from network simulations, with the diffusive length scales constrained by sulfate reduction rate profiles, agree with independent estimates of bioirrigation coefficients based on pore water chemistry. Bioirrigation coefficients for O(2 )derived from the stochastic model, with the diffusion length scales constrained by O(2 )microprofiles measured at the sediment/water interface, are larger than irrigation coefficients based on vertical pore water chemical profiles. This reflects, in part, the rapid attenuation with depth of the O(2 )concentration within the burrows, which reduces the driving force for chemical transfer across the burrow walls. Correction for the depletion of O(2 )in the burrows results in closer agreement between stochastically-derived and chemically-derived irrigation coefficient profiles