3,347 research outputs found
Adsorption of Cu, Ag, and Au atoms on graphene including van der Waals interactions
We performed a systematic density functional study of the adsorption of
copper, silver, and gold adatoms on graphene, especially accounting for van der
Waals interactions by the vdW-DF and the PBE+D2 methods. In particular, we
analyze the preferred adsorption site (among top, bridge, and hollow positions)
together with the corresponding distortion of the graphene sheet and identify
diffusion paths. Both vdW schemes show that the coinage metal atoms do bind to
the graphene sheet and that in some cases the buckling of the graphene can be
significant. The results for silver are at variance with those obtained with
GGA, which gives no binding in this case. However, we observe some quantitative
differences between the vdW-DF and the PBE+D2 methods. For instance the
adsorption energies calculated with the PBE+D2 method are systematically higher
than the ones obtained with vdW-DF. Moreover, the equilibrium distances
computed with PBE+D2 are shorter than those calculated with the vdW-DF method
Performance of ab initio and density functional methods for conformational equilibria of CnH2n+2 alkane isomers (n=2-8)
Conformational energies of n-butane, n-pentane, and n-hexane have been
calculated at the CCSD(T) level and at or near the basis set limit.
Post-CCSD(T) contribution were considered and found to be unimportant. The data
thus obtained were used to assess the performance of a variety of density
functional methods. Double-hybrid functionals like B2GP-PLYP and B2K-PLYP,
especially with a small Grimme-type empirical dispersion correction, are
capable of rendering conformational energies of CCSD(T) quality. These were
then used as a `secondary standard' for a larger sample of alkanes, including
isopentane and the branched hexanes as well as key isomers of heptane and
octane. Popular DFT functionals like B3LYP, B3PW91, BLYP, PBE, and PBE0 tend to
overestimate conformer energies without dispersion correction, while the M06
family severely underestimates GG interaction energies. Grimme-type dispersion
corrections for these overcorrect and lead to qualitatively wrong conformer
orderings. All of these functionals also exhibit deficiencies in the conformer
geometries, particularly the backbone torsion angles. The PW6B95 and, to a
lesser extent, BMK functionals are relatively free of these deficiencies.
Performance of these methods is further investigated to derive conformer
ensemble corrections to the enthalpy function, , and the Gibbs
energy function, , of these alkanes. While
is only moderately sensitive to the level of theory, exhibits more pronounced sensitivity. Once again, double hybrids
acquit themselves very well.Comment: J. Phys. Chem. A, revised [Walter Thiel festschrift
Elastic and vibrational properties of alpha and beta-PbO
The structure, electronic and dynamic properties of the two layered alpha
(litharge) and beta (massicot) phases of PbO have been studied by density
functional methods. The role of London dispersion interactions as leading
component of the total interaction energy between layers has been addressed by
using the Grimme's approach, in which new parameters for Pb and O atoms have
been developed. Both gradient corrected and hybrid functionals have been
adopted using Gaussian-type basis sets of polarized triple zeta quality for O
atoms and small core pseudo-potential for the Pb atoms. Basis set superposition
error (BSSE) has been accounted for by the Boys-Bernardi correction to compute
the interlayer separation. Cross check with calculations adopting plane waves
that are BSSE free have also been performed for both structures and vibrational
frequencies. With the new set of proposed Grimme's type parameters structures
and dynamical parameters for both PbO phases are in good agreement with
experimental data.Comment: 8 pages, 5 figure
Eccrine porocarcinoma of the head: An important differential diagnosis in the elderly patient
Background: Eccrine porocarcinoma is a rare malignant tumor of the sweat gland, characterized by a broad spectrum of clinicopathologic presentations. Surprisingly, unlike its benign counterpart eccrine poroma, eccrine porocarcinoma is seldom found in areas with a high density of eccrine sweat glands, like the palms or soles. Instead, eccrine porocarcinoma frequently occurs on the lower extremities, trunk and abdomen, but also on the head, resembling various other skin tumors, as illustrated in the patients described herein. Observations: We report 5 cases of eccrine porocarcinoma of the head. All patients were initially diagnosed as having epidermal or melanocytic skin tumors. Only after histopathologic examination were they classified as eccrine porocarcinoma, showing features of epithelial tumors with abortive ductal differentiation. Characteristic clinical, histopathologic and immunohistochemical findings of eccrine porocarcinomas are illustrated. Conclusion: Eccrine porocarcinomas are potentially fatal adnexal malignancies, in which extensive metastatic dissemination may occur. Porocarcinomas are commonly overlooked, or misinterpreted as squamous or basal cell carcinomas as well as other common malignant and even benign skin tumors. Knowledge of the clinical pattern and histologic findings, therefore, is crucial for an early therapeutic intervention, which can reduce the risk of tumor recurrence and serious complications. Copyright (c) 2008 S. Karger AG, Basel
Direct observation of a highly spin-polarized organic spinterface at room temperature
The design of large-scale electronic circuits that are entirely
spintronics-driven requires a current source that is highly spin-polarised at
and beyond room temperature, cheap to build, efficient at the nanoscale and
straightforward to integrate with semiconductors. Yet despite research within
several subfields spanning nearly two decades, this key building block is still
lacking. We experimentally and theoretically show how the interface between Co
and phthalocyanine molecules constitutes a promising candidate. Spin-polarised
direct and inverse photoemission experiments reveal a high degree of spin
polarisation at room temperature at this interface. We measured a magnetic
moment on the molecules's nitrogen pi orbitals, which substantiates an
ab-initio theoretical description of highly spin-polarised charge conduction
across the interface due to differing spinterface formation mechanims in each
spin channel. We propose, through this example, a recipe to engineer simple
organic-inorganic interfaces with remarkable spintronic properties that can
endure well above room temperature
What is the Role of Acid-Acid Interactions in Asymmetric Phosphoric Acid Organocatalysis? A Detailed Mechanistic Study using Interlocked and Non-Interlocked Catalysts
Organocatalysis has revolutionized asymmetric synthesis. However, the supramolecular interactions of organocatalysts in solution are often neglected, although the formation of catalyst aggregates can have a strong impact on the catalytic reaction. For phosphoric acid based organocatalysts, we have now established that catalyst-catalyst interactions can be suppressed by using macrocyclic catalysts, which react predominantly in a monomeric fashion, while they can be favored by integration into a bifunctional catenane, which react mainly as phosphoric acid dimers. For acyclic phosphoric acids, we found a strongly concentration dependent behavior, involving both monomeric and dimeric catalytic pathways. Based on a detailed experimental analysis, DFT-calculations and a direct NMR-based observation of the catalyst aggregates, we could demonstrate that intermolecular acid-acid interactions have a drastic influence on the reaction rate and stereoselectivity of the asymmetric transfer-hydrogenation catalyzed by chiral phosphoric acids
Asymmetric triplex metallohelices with high and selective activity against cancer cells
Small cationic amphiphilic α-helical peptides are emerging as agents for the treatment of cancer and infection, but they are costly and display unfavourable pharmacokinetics. Helical coordination complexes may offer a three-dimensional scaffold for the synthesis of mimetic architectures. However, the high symmetry and modest functionality of current systems offer little scope to tailor the structure to interact with specific biomolecular targets, or to create libraries for phenotypic screens. Here, we report the highly stereoselective asymmetric self-assembly of very stable, functionalized metallohelices. Their anti-parallel head-to-head-to-tail ‘triplex’ strand arrangement creates an amphipathic functional topology akin to that of the active sub-units of, for example, host-defence peptides and p53. The metallohelices display high, structure-dependent toxicity to the human colon carcinoma cell-line HCT116 p53++, causing dramatic changes in the cell cycle without DNA damage. They have lower toxicity to human breast adenocarcinoma cells (MDA-MB-468) and, most remarkably, they show no significant toxicity to the bacteria methicillin-resistant Staphylococcus aureus and Escherichia coli.
At a glanc
Reversible, Opto-Mechanically Induced Spin-Switching in a Nanoribbon-Spiropyran Hybrid Material
It has recently been shown that electronic transport in zigzag graphene
nanoribbons becomes spin-polarized upon application of an electric field across
the nanoribbon width. However, the electric fields required to experimentally
induce this magnetic state are typically large and difficult to apply in
practice. Here, using both first-principles density functional theory (DFT) and
time-dependent DFT, we show that a new spiropyran-based, mechanochromic polymer
noncovalently deposited on a nanoribbon can collectively function as a dual
opto-mechanical switch for modulating its own spin-polarization. These
calculations demonstrate that upon mechanical stress or photoabsorption, the
spiropyran chromophore isomerizes from a closed-configuration ground-state to a
zwitterionic excited-state, resulting in a large change in dipole moment that
alters the electrostatic environment of the nanoribbon. We show that the
electronic spin-distribution in the nanoribbon-spiropyran hybrid material can
be reversibly modulated via noninvasive optical and mechanical stimuli without
the need for large external electric fields. Our results suggest that the
reversible spintronic properties inherent to the nanoribbon-spiropyran material
allow the possibility of using this hybrid structure as a resettable,
molecular-logic quantum sensor where opto-mechanical stimuli are used as inputs
and the spin-polarized current induced in the nanoribbon substrate is the
measured output.Comment: Accepted by Nanoscal
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