Controlling the Kondo Effect in CoCu_n Clusters Atom by Atom

Clusters containing a single magnetic impurity were investigated by scanning tunneling microscopy, spectroscopy, and ab initio electronic structure calculations. The Kondo temperature of a Co atom embedded in Cu clusters on Cu(111) exhibits a non-monotonic variation with the cluster size. Calculations model the experimental observations and demonstrate the importance of the local and anisotropic electronic structure for correlation effects in small clusters.Comment: 4 pages, 4 figure

Gamma-Ray Spectral States of Galactic Black Hole Candidates

OSSE has observed seven transient black hole candidates: GRO J0422+32, GX339-4, GRS 1716-249, GRS 1009-45, 4U 1543-47, GRO J1655-40, and GRS 1915+105. Two gamma-ray spectral states are evident and, based on a limited number of contemporaneous X-ray and gamma-ray observations, these states appear to be correlated with X-ray states. The former three objects show hard spectra below 100 keV (photon number indices Gamma < 2) that are exponentially cut off with folding energy ~100 keV, a spectral form that is consistent with thermal Comptonization. This "breaking gamma-ray state" is the high-energy extension of the X-ray low, hard state. In this state, the majority of the luminosity is above the X-ray band, carried by photons of energy ~100 keV. The latter four objects exhibit a "power-law gamma-ray state" with a relatively soft spectral index (Gamma ~ 2.5-3) and no evidence for a spectral break. For GRO J1655-40, the lower limit on the break energy is 690 keV. GRS 1716-249 exhibits both spectral states, with the power-law state having significantly lower gamma-ray luminosity. The power-law gamma-ray state is associated with the presence of a strong ultrasoft X-ray excess (kT ~ 1 keV), the signature of the X-ray high, soft (or perhaps very high) state. The physical process responsible for the unbroken power law is not well understood, although the spectra are consistent with bulk-motion Comptonization in the convergent accretion flow.Comment: 27 pages, 3 figures, uses aaspp.sty and psfig.st

Phase II trial of dexverapamil and epirubicin in patients with non-responsive metastatic breast cancer.

Agents capable of reversing P-glycoprotein-associated multidrug resistance have usually failed to enhance chemotherapy activity in patients with solid tumours. Based on its toxicity profile and experimental potency, dexverapamil, the R-enantiomer of verapamil, is considered to be promising for clinical use as a chemosensitizer. The purpose of this early phase II trial was to evaluate the effects of dexverapamil on epirubicin toxicity, activity and pharmacokinetics in patients with metastatic breast cancer. A two-stage design was applied. Patients first received epirubicin alone at 120 mg m(-2) i.v. over 15 min, repeated every 21 days. Patients with refractory disease continued to receive epirubicin at the same dose and schedule but supplemented with oral dexverapamil 300 mg every 6 h x 13 doses. The Gehan design was applied to the dexverapamil/epirubicin cohort of patients. Thirty-nine patients were entered on study, 25 proceeded to receive epirubicin plus dexverapamil. Dexverapamil did not increase epirubicin toxicity. The dose intensity of epirubicin was similar when used alone or with dexverapamil. In nine intrapatient comparisons, the area under the plasma concentration-time curve (AUC) of epirubicin was significantly reduced by dexverapamil (mean 2968 vs 1901 microg ml[-1] h[-1], P= 0.02). The mean trough plasma levels of dexverapamil and its major metabolite nor-dexverapamil were 1.2 and 1.5 microM respectively. The addition of dexverapamil to epirubicin induced partial responses in 4 of 23 patients evaluable for tumour response (17%, CI 5-39%, s.e.P 0.079). The remissions lasted 3, 8, 11 and 11+ months. These data suggest that the concept of enhancing chemotherapy activity by adding chemosensitizers may function not only in haematological malignancies but also in selected solid tumours. An increase in the AUC and toxicity of cytotoxic agents does not seem to be a prerequisite for chemosensitizers to enhance anti-tumour activity

Deciphering the dynamics of inorganic carbon export from intertidal salt marshes using high-frequency measurements

© The Author(s), 2018. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Marine Chemistry 206 (2018): 7-18, doi:10.1016/j.marchem.2018.08.005.The lateral export of carbon from coastal marshes via tidal exchange is a key component of the marsh carbon budget and coastal carbon cycles. However, the magnitude of this export has been difficult to accurately quantify due to complex tidal dynamics and seasonal cycling of carbon. In this study, we use in situ, high-frequency measurements of dissolved inorganic carbon (DIC) and water fluxes to estimate lateral DIC fluxes from a U.S. northeastern salt marsh. DIC was measured by a CHANnelized Optical Sensor (CHANOS) that provided an in situ concentration measurement at 15-min intervals, during periods in summer (July – August) and late fall (December). Seasonal changes in the marsh had strong effects on DIC concentrations, while tidally-driven water fluxes were the fundamental vehicle of marsh carbon export. Episodic events, such as groundwater discharge and mean sea water level changes, can impact DIC flux through altered DIC concentrations and water flow. Variability between individual tides within each season was comparable to mean variability between the two seasons. Estimated mean DIC fluxes based on a multiple linear regression (MLR) model of DIC concentrations and high-frequency water fluxes agreed reasonably well with those derived from CHANOS DIC measurements for both study periods, indicating that high-frequency, modeled DIC concentrations, coupled with continuous water flux measurements and a hydrodynamic model, provide a robust estimate of DIC flux. Additionally, an analysis of sampling strategies revealed that DIC fluxes calculated using conventional sampling frequencies (hourly to two-hourly) of a single tidal cycle are unlikely to capture a representative mean DIC flux compared to longer-term measurements across multiple tidal cycles with sampling frequency on the order of tens of minutes. This results from a disproportionately large amount of the net DIC flux occurring over a small number of tidal cycles, while most tides have a near-zero DIC export. Thus, high-frequency measurements (on the order of tens of minutes or better) over the time period of interest are necessary to accurately quantify tidal exports of carbon species from salt marshes.This work was funded by NSF Graduate Research Fellowship Program, NSF Ocean Sciences Postdoctoral Fellowship (OCE-1323728), Link FoundationOcean Engineering and Instrumentation Fellowship, National Institute of Science and Technology (NIST no. 60NANB10D024), the USGS LandCarbon and Coastal & Marine Geology Programs, NSF Chemical Oceanography Program (OCE-1459521), NSF Ocean Technology and Interdisciplinary Coordination program (OCE-1233654) and NOAA Science Collaborative (NA09NOS4190153)

Intertidal salt marshes as an important source of inorganic carbon to the coastal ocean

© The Author(s), 2016. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Limnology and Oceanography 61 (2016): 1916–1931, doi:10.1002/lno.10347.Dynamic tidal export of dissolved inorganic carbon (DIC) to the coastal ocean from highly productive intertidal marshes and its effects on seawater carbonate chemistry are thoroughly evaluated. The study uses a comprehensive approach by combining tidal water sampling of CO2 parameters across seasons, continuous in situ measurements of biogeochemically-relevant parameters and water fluxes, with high-resolution modeling in an intertidal salt marsh of the U.S. northeast region. Salt marshes can acidify and alkalize tidal water by injecting CO2 (DIC) and total alkalinity (TA). DIC and TA generation may also be decoupled due to differential effects of marsh aerobic and anaerobic respiration on DIC and TA. As marsh DIC is added to tidal water, the buffering capacity first decreases to a minimum and then increases quickly. Large additions of marsh DIC can result in higher buffering capacity in ebbing tide than incoming tide. Alkalization of tidal water, which mostly occurs in the summer due to anaerobic respiration, can further modify buffering capacity. Marsh exports of DIC and alkalinity may have complex implications for the future, more acidified ocean. Marsh DIC export exhibits high variability over tidal and seasonal cycles, which is modulated by both marsh DIC generation and by water fluxes. The marsh DIC export of 414 g C m−2 yr−1, based on high-resolution measurements and modeling, is more than twice the previous estimates. It is a major term in the marsh carbon budget and translates to one of the largest carbon fluxes along the U.S. East Coast.USGS Coastal & Marine Geology Program; U.S. National Science Foundation Grant Number: OCE-1459521; NOAA Science Collaborative Grant Number: NA09NOS4190153; USGS LandCarbon Progra