We report that the Kondo effect exerted by a magnetic ion depends on its chemical environment. A cobalt phthalocyanine molecule adsorbed on an Au111 surface exhibited no Kondo effect. Cutting away eight hydrogen atoms from the molecule with voltage pulses from a scanning tunneling microscope tip allowed the four orbitals of this molecule to chemically bond to the gold substrate. The localized spin was recovered in this artificial molecular structure, and a clear Kondo resonance was observed near the Fermi surface. We attribute the high Kondo temperature (more than 200 kelvin) to the small on-site Coulomb repulsion and the large half-width of the hybridized d-level.
12Tunnel field effect transistors (TFETs) based on vertical stacking of two dimensional materials are 13 of interest for low-power logic devices. The monolayer transition metal dichalcogenides (TMDs) 14 with sizable band gaps show promise in building p-n junctions (couples) for TFET applications.
We have studied the organometallic intermediate of a surface-supported Ullmann coupling reaction from 4, 4″-dibromo-p-terphenyl to poly(para-phenylene) by scanning tunneling microscopy/spectroscopy and density functional theory calculations. Our study reveals at a single-molecular level that the intermediate consists of biradical terphenyl (ph)(3) units that are connected by single Cu atoms through C-Cu-C bridges. Upon further increasing the temperature, the neighboring biradical (ph)(3) units are coupled by C-C bonds forming poly(para-phenylene) oligomers while the Cu atoms are released.
At elevated levels, homocysteine (Hcy, 1) is a risk factor for cardiovascular diseases, Alzheimer's disease, neural tube defects, and osteoporosis. Both 1 and cysteine (Cys, 3) are linked to neurotoxicity. The biochemical mechanisms by which 1 and 3 are involved in disease states are relatively unclear. Herein, we describe simple methods for detecting either Hcy or Cys in the visible spectral region with the highest selectivity reported to date without using biochemical techniques or preparative separations. Simple methods and readily available reagents allow for the detection of Cys and Hcy in the range of their physiologically relevant levels. New HPLC postcolumn detection methods for biological thiols are reported. The potential biomedical relevance of the chemical mechanisms involved in the detection of 1 is described.
Background:Cohort studies in North America and western Europe have reported increased risk of mortality associated with long-term exposure to fine particles (PM2.5), but to date, no such studies have been reported in China, where higher levels of exposure are experienced.Objectives:We estimated the association between long-term exposure to PM2.5 with nonaccidental and cause-specific mortality in a cohort of Chinese men.Methods:We conducted a prospective cohort study of 189,793 men 40 y old or older during 1990–91 from 45 areas in China. Annual average PM2.5 levels for the years 1990, 1995, 2000, and 2005 were estimated for each cohort location using a combination of satellite-based estimates, chemical transport model simulations, and ground-level measurements developed for the Global Burden of Disease (GBD) 2013 study. A Cox proportional hazards regression model was used to estimate hazard ratios (HR) for nonaccidental cardiovascular disease (CVD), chronic obstructive pulmonary disease (COPD), and lung-cancer mortality. We also assessed the shape of the concentration–response relationship and compared the risk estimates with those predicted by Integrated Exposure-Response (IER) function, which incorporated estimates of mortality risk from previous cohort studies in western Europe and North America.Results:The mean level of PM2.5 exposure during 2000–2005 was 43.7 μg/m3 (ranging from 4.2 to 83.8 μg/m3). Mortality HRs (95% CI) per 10-μg/m3 increase in PM2.5 were 1.09 (1.08, 1.09) for nonaccidental causes; 1.09 (1.08, 1.10) for CVD, 1.12 (1.10, 1.13) for COPD; and 1.12 (1.07, 1.14) for lung cancer. The HR estimate from our cohort was consistently higher than IER predictions.Conclusions:Long-term exposure to PM2.5 was associated with nonaccidental, CVD, lung cancer, and COPD mortality in China. The IER estimator may underestimate the excess relative risk of cause-specific mortality due to long-term exposure to PM2.5 over the exposure range experienced in China and other low- and middle-income countries. https://doi.org/10.1289/EHP1673
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