Adsorption of Hydrogen on Neutral and Charged Fullerene: Experiment and Theory

Helium droplets are doped with fullerenes (either C60 or C70) and hydrogen (H2 or D2) and investigated by high-resolution mass spectrometry. In addition to pure helium and hydrogen cluster ions, hydrogen-fullerene complexes are observed upon electron ionization. The composition of the main ion series is (H2)nHCm+ where m = 60 or 70. Another series of even-numbered ions, (H2)nCm+, is slightly weaker in stark contrast to pure hydrogen cluster ions for which the even-numbered series (H2)n+ is barely detectable. The ion series (H2)nHCm+ and (H2)nCm+ exhibit abrupt drops in ion abundance at n = 32 for C60 and 37 for C70, indicating formation of an energetically favorable commensurate phase, with each face of the fullerene ion being covered by one adsorbate molecule. However, the first solvation layer is not complete until a total of 49 H2 are adsorbed on C60+; the corresponding value for C70+ is 51. Surprisingly, these values do not exhibit a hydrogen-deuterium isotope effect even though the isotope effect for H2/D2 adsorbates on graphite exceeds 6%. We also observe doubly charged fullerene-deuterium clusters; they, too, exhibit abrupt drops in ion abundance at n = 32 and 37 for C60 and C70, respectively. The findings imply that the charge is localized on the fullerene, stabilizing the system against charge separation. Density functional calculations for C60-hydrogen complexes with up to five hydrogen atoms provide insight into the experimental findings and the structure of the ions. The binding energy of physisorbed H2 is 57 meV for H2C60+ and (H2)2C60+, and slightly above 70 meV for H2HC60+ and (H2)2HC60+. The lone hydrogen in the odd-numbered complexes is covalently bound atop a carbon atom but a large barrier of 1.69 eV impedes chemisorption of the H2 molecules. Calculations for neutral and doubly charged complexes are presented as well

Methane Adsorption on Aggregates of Fullerenes: Site-Selective Storage Capacities and Adsorption Energies

Methane adsorption on positively charged aggregates of C60 is investigated by both mass spectrometry and computer simulations. Calculated adsorption energies of 118–281 meV are in the optimal range for high‐density storage of natural gas. Groove sites, dimple sites, and the first complete adsorption shells are identified experimentally and confirmed by molecular dynamics simulations, using a newly developed force field for methane–methane and fullerene–methane interaction. The effects of corrugation and curvature are discussed and compared with data for adsorption on graphite, graphene, and carbon nanotubes

One Third of Patients before Endoprosthesis Implantation Show an Oral Focus as Potential Source of Infectious Complication: The Value of Pre-Operative Dental Risk Stratification in a German Cohort

Objective: The aim of this cross-sectional cohort study was to evaluate a comprehensive dental examination and referral concept for patients prior to endoprosthesis (EP) implantation in an interdisciplinary setting. Methods: Patients, who were prepared for EP surgery in the clinic for orthopaedics, were referred to the dental clinic for a dental examination. Thereby, dental and periodontal treatment need, radiographic and temporomandibular joint findings were assessed. Based on oral and radiographic investigation, a risk classification for potential source of prosthetic infection was performed. If potential oral foci of EP infection were present (e.g., apically radiolucent teeth, severe periodontitis or additional inflammatory findings), patients were classified as at high risk for EP infection with oral origin. Those individuals were allocated to their family dentist or special clinic for dental treatment prior to EP surgery. Results: A total of 311 patients were included (mean age: 67.84 10.96 years, 51% male). A dental treatment need of 33% was found, while the periodontal treatment need was 83%. Thirty-one percent of patients showed at least one apical radiolucency (a sign of chronic infection/inflammation). Furthermore, additional findings such as radiographic signs of sinusitis maxillaris were found in 24% of patients. Temporomandibular disease was probable in 17% of individuals. One-third (34%) were assigned to the high risk group for an EP infection with oral origin. Conclusion: German patients before EP have a high periodontal treatment need and show frequently (34%) a potential oral focus of infection, underlining the necessity of including dental examination and risk stratification as part of the pre-operative assessment prior to EP implantation. Therefore, an approach as applied in this study appears reasonable for those individuals

An accurate determination of the Avogadro constant by counting the atoms in a 28Si crystal

The Avogadro constant links the atomic and the macroscopic properties of matter. Since the molar Planck constant is well known via the measurement of the Rydberg constant, it is also closely related to the Planck constant. In addition, its accurate determination is of paramount importance for a definition of the kilogram in terms of a fundamental constant. We describe a new approach for its determination by "counting" the atoms in 1 kg single-crystal spheres, which are highly enriched with the 28Si isotope. It enabled isotope dilution mass spectroscopy to determine the molar mass of the silicon crystal with unprecedented accuracy. The value obtained, 6.02214084(18) x 10^23 mol^-1, is the most accurate input datum for a new definition of the kilogram.Comment: 4 pages, 5 figures, 3 table

Bond dissociation of the dipeptide dialanine and its derivative alanine anhydride induced by low energy electrons

Dissociative electron attachment to dialanine and alanine anhydride has been studied in the gas phase utilizing a double focusing two sector field mass spectrometer. We show that low-energy electrons (i.e., electrons with kinetic energies from near zero up to 13 eV) attach to these molecules and subsequently dissociate to form a number of anionic fragments. Anion efficiency curves are recorded for the most abundant anions by measuring the ion yield as a function of the incident electron energy. The present experiments show that as for single amino acids (M), e.g., glycine, alanine, valine, and proline, the dehydrogenated closed shell anion (M–H)− is the most dominant reaction product. The interpretation of the experiments is aided by quantum chemical calculations based on density functional theory, by which the electrostatic potential and molecular orbitals are calculated and the initial electron attachment process prior to dissociation is investigate

Neuron-specific alterations in signal transduction pathways associated with Alzheimer's disease

The hallmarks of sporadic Alzheimer's disease (AD) are extracellular amyloid deposits, intracellular neurofibrillary tangles (NFTs), and neuronal death. Hyperphosphorylation of tau is a key factor in the generation of NFTs. Mitogen activated protein kinase 1 (MAPK1) and protein kinase C beta (PRKCB) are thought to play a role in hyperphosphorylation, and PRCKB is thought to be involved in hypoxic stress and vascular dysfunction, and to trigger MAPK phosphorylation pathways. We performed single-cell analyses of neurons with different vulnerabilities to AD-related changes. Using quantitative PCR (qPCR), we measured the levels of MAPK1 and PRKCB transcript in CA1 (high vulnerability), CA2 pyramidal cells from the hippocampus, granule cells from the cerebellum (low vulnerability), and neurons from the brain stem (nucleus tractus spinalis nervi trigemini, characterized by early neurophysiological deficits) at progressive Braak stages compared to age-matched controls. The highly vulnerable CA1 pyramidal neurons were characterized by age- and disease-unrelated increases in PRCKB levels and by age- and disease-related increases in MAPK1 levels. In contrast, low PRKCB levels were found in CA2 pyramidal neurons, and MAPK1 levels were elevated in controls and intermediate AD stages. Both PRKCB and MAPK1 were increased in the late AD stages. MAPK1 and PRKCB levels were low in the brainstem and cerebellum. We propose that alterations in the expression of these two genes occur early in the pathogenesis of AD in a region-specific manner. In addition, multiple signal transduction pathways need to be affected to result in AD instead of physiological aging