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

Ordered Phases of Ethylene Adsorbed on Charged

In spite of extensive investigations of ethylene adsorbed on graphite, bundles of nanotubes, and crystals of fullerenes, little is known about the existence of commensurate phases; they have escaped detection in almost all previous work. Here we present a combined experimental and theoretical study of ethylene adsorbed on free C60 and its aggregates. The ion yield of measured by mass spectrometry reveals a propensity to form a structurally ordered phase on monomers, dimers and trimers of C60 in which all sterically accessible hollow sites over carbon rings are occupied. Presumably the enhancement of the corrugation by the curvature of the fullerene surface favors this phase which is akin to a hypothetical 1 × 1 phase on graphite. Experimental data also reveal the number of molecules in groove sites of the C60 dimer through tetramer. The identity of the sites, adsorption energies and orientations of the adsorbed molecules are determined by molecular dynamics calculations based on quantum chemical potentials, as well as density functional theory. The decrease in orientational order with increasing temperature is also explored in the simulations whereas in the experiment it is impossible to vary the temperature

Structures, energetics, and dynamics of helium adsorbed on isolated fullerene ions

Helium adsorbed on C60+ and C70+ exhibits phenomena akin to helium on graphite. Mass spectra suggest that commensurate layers form when all carbon hexagons and pentagons are occupied by one He each, but that the solvation shell does not close until 60 He atoms are adsorbed on C60+, or 62 on C70+. Molecular dynamics simulations of C 60Hen+ at 4 K show that the commensurate phase is solid. Helium added to C60He32+ will displace some atoms from pentagonal sites, leading to coexistence of a registered layer of immobile atoms interlaced with a nonregistered layer of mobile atomsThis work was supported by MICINN projects FIS2010-15127, ACI2008-0777, CTQ2010-17006, Consolider-Ingenio CSD2007-00010, CAM program NANOBIOMAGNET S2009/MAT1726, the Austrian Science Fund, Wien (FWF, projects P19073, L633, and I200 N29), the European Commission, Brussels (ITS-LEIF), and the European COST Action CM0702

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

Genome-wide association and HLA fine-mapping studies identify risk loci and genetic pathways underlying allergic rhinitis

Allergic rhinitis is the most common clinical presentation of allergy, affecting 400 million people worldwide, with increasing incidence in westernized countries1,2. To elucidate the genetic architecture and understand the underlying disease mechanisms, we carried out a meta-analysis of allergic rhinitis in 59,762 cases and 152,358 controls of European ancestry and identified a total of 41 risk loci for allergic rhinitis, including 20 loci not previously associated with allergic rhinitis, which were confirmed in a replication phase of 60,720 cases and 618,527 controls. Functional annotation implicated genes involved in various immune pathways, and fine mapping of the HLA region suggested amino acid variants important for antigen binding. We further performed genome-wide association study (GWAS) analyses of allergic sensitization against inhalant allergens and nonallergic rhinitis, which suggested shared genetic mechanisms across rhinitis-related traits. Future studies of the identified loci and genes might identify novel targets for treatment and prevention of allergic rhinitis

Genetic association study of QT interval highlights role for calcium signaling pathways in myocardial repolarization.

The QT interval, an electrocardiographic measure reflecting myocardial repolarization, is a heritable trait. QT prolongation is a risk factor for ventricular arrhythmias and sudden cardiac death (SCD) and could indicate the presence of the potentially lethal mendelian long-QT syndrome (LQTS). Using a genome-wide association and replication study in up to 100,000 individuals, we identified 35 common variant loci associated with QT interval that collectively explain ∼8-10% of QT-interval variation and highlight the importance of calcium regulation in myocardial repolarization. Rare variant analysis of 6 new QT interval-associated loci in 298 unrelated probands with LQTS identified coding variants not found in controls but of uncertain causality and therefore requiring validation. Several newly identified loci encode proteins that physically interact with other recognized repolarization proteins. Our integration of common variant association, expression and orthogonal protein-protein interaction screens provides new insights into cardiac electrophysiology and identifies new candidate genes for ventricular arrhythmias, LQTS and SCD

New Frontiers-class Uranus Orbiter: Exploring the feasibility of achieving multidisciplinary science with a mid-scale mission

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Multi-ancestry genome-wide association study of 21,000 cases and 95,000 controls identifies new risk loci for atopic dermatitis

Genetic association studies have identified 21 loci associated with atopic dermatitis risk predominantly in populations of European ancestry. To identify further susceptibility loci for this common, complex skin disease, we performed a meta-analysis of >15 million genetic variants in 21,399 cases and 95,464 controls from populations of European, African, Japanese and Latino ancestry, followed by replication in 32,059 cases and 228,628 controls from 18 studies. We identified ten new risk loci, bringing the total number of known atopic dermatitis risk loci to 31 (with new secondary signals at four of these loci). Notably, the new loci include candidate genes with roles in the regulation of innate host defenses and T cell function, underscoring the important contribution of (auto)immune mechanisms to atopic dermatitis pathogenesis